[go: up one dir, main page]

WO2014014109A1 - Composition formant une couche de passivation, substrat semi-conducteur ayant une couche de passivation, procédé de fabrication d'un substrat semi-conducteur ayant une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire, et cellule solaire - Google Patents

Composition formant une couche de passivation, substrat semi-conducteur ayant une couche de passivation, procédé de fabrication d'un substrat semi-conducteur ayant une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire, et cellule solaire Download PDF

Info

Publication number
WO2014014109A1
WO2014014109A1 PCT/JP2013/069699 JP2013069699W WO2014014109A1 WO 2014014109 A1 WO2014014109 A1 WO 2014014109A1 JP 2013069699 W JP2013069699 W JP 2013069699W WO 2014014109 A1 WO2014014109 A1 WO 2014014109A1
Authority
WO
WIPO (PCT)
Prior art keywords
passivation
passivation layer
composition
layer
forming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/069699
Other languages
English (en)
Japanese (ja)
Other versions
WO2014014109A9 (fr
Inventor
修一郎 足立
吉田　誠人
野尻　剛
倉田　靖
田中　徹
明博 織田
剛 早坂
服部　孝司
三江子 松村
敬司 渡邉
真年 森下
浩孝 濱村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201380038207.1A priority Critical patent/CN104488089A/zh
Priority to JP2014525893A priority patent/JPWO2014014109A1/ja
Publication of WO2014014109A1 publication Critical patent/WO2014014109A1/fr
Publication of WO2014014109A9 publication Critical patent/WO2014014109A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a composition for forming a passivation layer, a semiconductor substrate with a passivation layer, a method for manufacturing a semiconductor substrate with a passivation layer, a solar cell element, a method for manufacturing a solar cell element, and a solar cell.
  • n-type diffusion layer is uniformly formed by performing several tens of minutes at 800 ° C. to 900 ° C.
  • n-type diffusion layers are formed not only on the front surface, which is the light receiving surface, but also on the side surface and the back surface. Therefore, side etching is performed to remove the n-type diffusion layer formed on the side surface.
  • the n-type diffusion layer formed on the back surface needs to be converted into a p + -type diffusion layer. For this reason, by applying an aluminum paste containing aluminum powder and a binder to the entire back surface and heat-treating (baking) it, the n-type diffusion layer is converted into a p + -type diffusion layer and an aluminum electrode is formed. Get ohmic contact.
  • the aluminum electrode formed from the aluminum paste has low conductivity.
  • the aluminum electrode generally formed on the entire back surface must have a thickness of about 10 ⁇ m to 20 ⁇ m after heat treatment (firing).
  • silicon and aluminum have different thermal expansion rates, a large internal stress is generated in the silicon substrate during the heat treatment (firing) and cooling in the silicon substrate on which the aluminum electrode is formed, leading to the grain boundaries. Cause damage, increase of crystal defects and warpage.
  • a point contact method has been proposed in which an aluminum paste is applied to a part of the surface of a silicon substrate to partially form a p + -type diffusion layer and an aluminum electrode (for example, Japanese Patent No. 3107287). (See the publication).
  • an aluminum paste is applied to a part of the surface of a silicon substrate to partially form a p + -type diffusion layer and an aluminum electrode.
  • back surface In the case of a solar cell having a point contact structure on the surface opposite to the light receiving surface (hereinafter also referred to as “back surface”), it is necessary to suppress the recombination rate of minority carriers on the surface of the portion other than the aluminum electrode. is there.
  • a SiO 2 film or the like has been proposed as a passivation layer (see, for example, JP-A-2004-6565).
  • Such a passivation effect is generally called a field effect, and an aluminum oxide (Al 2 O 3 ) film or the like has been proposed as a material having a negative fixed charge (see, for example, Japanese Patent No. 4767110).
  • Such a passivation layer is generally formed by a method such as an ALD (Atomic Layer Deposition) method or a CVD (Chemical Vapor Deposition) method (for example, Journal of Applied Physics, 104 (2008), 113703-1). 113703-7).
  • composition for forming a passivation layer tends to cause printing bleeding when applied on a semiconductor substrate, it is difficult to form a passivation layer having a desired pattern shape on the semiconductor substrate.
  • printing bleeding refers to a phenomenon in which a composition for forming a passivation layer applied on a semiconductor substrate spreads.
  • the composition for formation of a passivation layer will be formed with the pattern which opened the opening part (contact part) locally.
  • the dimensions of the opening may be, for example, a diameter of 0.5 mm or less and a pitch of 2 mm or less. In order to form a pattern uniformly, the printing bleeding of the composition for forming a passivation layer is significantly suppressed. Is required.
  • the present invention has been made in view of the above-described conventional problems, and has excellent storage stability, and a passivation layer can be formed into a desired shape while suppressing printing bleeding by a simple method. It is an object of the present invention to provide a composition for forming a passivation layer capable of forming a passivation layer having an excellent effect on a semiconductor substrate.
  • the present invention also provides a semiconductor substrate with a passivation layer obtained by using the composition for forming a passivation layer, formed in a desired shape and having a passivation layer having an excellent passivation effect, a method for manufacturing a semiconductor substrate with a passivation layer, a solar It is an object to provide a battery element, a method for manufacturing a solar battery element, and a solar battery.
  • a composition for forming a passivation layer comprising a compound represented by the following general formula (I), a filler, a liquid medium, and a resin.
  • M contains at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf.
  • R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • m represents an integer of 1 to 5.
  • composition for forming a passivation layer according to ⁇ 1> further comprising a compound represented by the following general formula (II).
  • each R 2 independently represents an alkyl group having 1 to 8 carbon atoms.
  • n represents an integer of 0 to 3.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group.
  • R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • ⁇ 3> The above ⁇ 1> or ⁇ 1>, wherein the filler contains at least one particle selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, silicon nitride, aluminum oxide, zirconium oxide, and silicon carbide.
  • the filler contains at least one particle selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, silicon nitride, aluminum oxide, zirconium oxide, and silicon carbide.
  • composition for forming a passivation layer according to any one of ⁇ 1> to ⁇ 3>, wherein the filler has a volume average particle diameter of 0.01 ⁇ m to 50 ⁇ m.
  • composition for forming a passivation layer according to any one of ⁇ 1> to ⁇ 4>, wherein the filler includes glass particles.
  • ⁇ 6> The composition for forming a passivation layer according to ⁇ 5>, wherein the glass particles have a glass softening point of 300 ° C to 1000 ° C.
  • the total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) is 0.1% by mass to 80% by mass, and the content of the filler is 0.1%.
  • a semiconductor substrate in which a p-type layer and an n-type layer are pn-joined, and a passivation layer formation according to any one of ⁇ 1> to ⁇ 8> provided on the entire surface or a part of the semiconductor substrate A solar cell element having a passivation layer, which is a heat-treated product of the composition for use, and an electrode provided on at least one of the p-type layer and the n-type layer.
  • the passivation layer forming composition according to any one of the above items ⁇ 1> to ⁇ 8> is applied to the entire surface or a part of a semiconductor substrate in which a p-type layer and an n-type layer are pn-junctioned. Forming a composition layer; heat-treating the composition layer to form a passivation layer; and forming an electrode on at least one of the p-type layer and the n-type layer.
  • the manufacturing method of the solar cell element which has.
  • a solar cell comprising the solar cell element according to ⁇ 11> above and a wiring material disposed on an electrode of the solar cell element.
  • a passivation layer having a superior passivation effect on a semiconductor substrate, which is excellent in storage stability and can be formed into a desired shape by suppressing printing bleeding by a simple method.
  • a possible composition for forming a passivation layer can be provided.
  • the present invention also provides a semiconductor substrate with a passivation layer obtained by using the composition for forming a passivation layer, formed in a desired shape and having a passivation layer having an excellent passivation effect, a method for manufacturing a semiconductor substrate with a passivation layer, a solar A battery element, a method for manufacturing a solar battery element, and a solar battery can be provided.
  • the term “process” includes not only an independent process but also an after-use if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • the term “layer” includes a configuration of a shape formed in part in addition to a configuration of a shape formed on the entire surface when observed as a plan view.
  • composition for forming a passivation layer of the present invention contains a compound represented by the following general formula (I) (hereinafter also referred to as “specific metal alkoxide compound”), a filler, a liquid medium, and a resin.
  • the composition for forming a passivation layer may further contain other components as necessary. With this configuration, a composition for forming a passivation layer that has an excellent passivation effect, excellent storage stability, and can suppress printing bleeding is obtained, and the passivation layer is formed into a desired shape by a simple method. be able to.
  • M contains at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf.
  • R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • m represents an integer of 1 to 5.
  • the composition for forming a passivation layer is applied to a semiconductor substrate to form a composition layer having a desired shape, and this is heat-treated (fired) to form a passivation layer having an excellent passivation effect in a desired shape.
  • the method of the present invention is a simple and highly productive method that does not require a vapor deposition apparatus or the like. Further, the passivation layer can be formed in a desired shape without requiring a complicated process such as mask processing.
  • the passivation effect of a semiconductor substrate refers to an effective lifetime of minority carriers in a semiconductor substrate on which a passivation layer is formed by using a device such as Nippon Semi-Lab Co., Ltd., WT-2000PVN, etc. It can be evaluated by measuring by the method.
  • the effective lifetime ⁇ is expressed by the following equation (A) by the bulk lifetime ⁇ b inside the semiconductor substrate and the surface lifetime ⁇ s of the semiconductor substrate surface.
  • ⁇ s becomes long, resulting in a long effective lifetime ⁇ .
  • the bulk lifetime ⁇ b is increased and the effective lifetime ⁇ is increased. That is, by measuring the effective lifetime ⁇ , the interface characteristics between the passivation layer and the semiconductor substrate and the internal characteristics of the semiconductor substrate such as dangling bonds can be evaluated.
  • the composition for forming a passivation layer contains at least one compound represented by the general formula (I) (hereinafter also referred to as “specific metal alkoxide compound”).
  • the specific metal alkoxide compound is an alkoxide containing at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf.
  • a metal oxide formed by heat-treating (firing) a passivation layer forming composition containing a specific metal alkoxide compound has defects of metal atoms or oxygen atoms and is likely to generate fixed charges.
  • this fixed charge is generated near the interface of the semiconductor substrate, the concentration of minority carriers can be reduced, and as a result, the carrier recombination rate at the interface is suppressed, and an excellent passivation effect is achieved. Conceivable.
  • the bonding mode in the passivation layer is examined. be able to. Further, by measuring an X-ray diffraction spectrum (XRD, X-ray diffraction), the crystal phase near the interface of the passivation layer can be confirmed. Furthermore, the fixed charge of the passivation layer can be evaluated by the CV method (CapacitanceitVoltage measurement).
  • M includes at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf. From the viewpoint of the passivation effect, M is composed of Nb, Ta, and Y. It is preferably at least one selected from the group, and more preferably Nb. Further, from the viewpoint of making the fixed charge density of the passivation layer negative, M is preferably at least one selected from the group consisting of Nb, Ta, VO, and Hf.
  • each R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
  • the alkyl group is more preferable.
  • the alkyl group represented by R 1 may be linear or branched. Specific examples of the alkyl group represented by R 1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, hexyl, octyl, 2- Examples thereof include an ethylhexyl group and a 3-ethylhexyl group.
  • aryl group represented by R 1 examples include a phenyl group. Specific examples of the aryl group represented by R 1 include a phenyl group.
  • the alkyl group and aryl group represented by R 1 may have a substituent. Examples of the substituent for the alkyl group include a halogen atom, an amino group, a hydroxyl group, a carboxyl group, a sulfone group, and a nitro group.
  • R 1 is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, from the viewpoint of storage stability and a passivation effect.
  • m represents an integer of 1 to 5. From the viewpoint of storage stability, m is preferably 5 when M is Nb, m is preferably 5 when M is Ta, and M is VO. M is preferably 3, m is preferably 3 when M is Y, and m is preferably 4 when M is Hf.
  • M is preferably at least one selected from the group consisting of Nb, Ta and Y, and the fixed charge density of the passivation layer is increased. From the viewpoint of making it negative, M is preferably at least one selected from the group consisting of Nb, Ta, VO, and Hf. From the viewpoint of storage stability and a passivation effect, R 1 has 1 carbon atom. It is preferably an unsubstituted alkyl group of 1 to 4, and m is preferably an integer of 1 to 3 from the viewpoint of storage stability.
  • Compounds represented by the general formula (I) are niobium methoxide, niobium ethoxide, niobium isopropoxide, niobium n-propoxide, niobium n-butoxide, niobium t-butoxide, niobium isobutoxide, tantalum methoxide, tantalum.
  • tantalum isopropoxide, tantalum n-propoxide, tantalum n-butoxide, tantalum t-butoxide, tantalum isobutoxide, yttrium methoxide, yttrium ethoxide, yttrium isopropoxide, yttrium n-propoxide, yttrium n- Butoxide, yttrium t-butoxide, yttrium isobutoxide, vanadium methoxide oxide, vanadium ethoxide oxide, vanadium isopropoxide oxide, vanadium n-propoxide oxide Vanadium n-butoxide oxide, vanadium t-butoxide oxide, vanadium isobutoxide oxide, hafnium methoxide, hafnium ethoxide, hafnium isopropoxide, hafnium n-propoxide, hafnium n-butoxide, hafnium me
  • niobium ethoxide can be mentioned, among others niobium ethoxide, niobium n-propoxide, niobium n-butoxide, tantalum ethoxide, tantalum n-propoxide, tantalum n-butoxide, yttrium isopropoxide, yttrium n-butoxide, etc. Can be mentioned.
  • niobium ethoxide, niobium n-propoxide, niobium n-butoxide, tantalum ethoxide, tantalum n-propoxide, tantalum n-butoxide, vanadium ethoxide oxide, vanadium n-propoxy Preference is given to oxides, vanadium n-butoxide oxide, hafnium ethoxide, hafnium n-propoxide and hafnium n-butoxide.
  • a prepared product or a commercially available product may be used as the compound represented by the general formula (I).
  • Commercially available products include, for example, pentamethoxyniobium, pentaethoxyniobium, penta-i-propoxyniobium, penta-n-propoxyniobium, penta-i-butoxyniobium, penta-n-butoxyniobium from High Purity Chemical Laboratory, Inc.
  • Penta-sec-butoxy niobium pentamethoxy tantalum, pentaethoxy tantalum, penta-i-propoxy tantalum, penta-n-propoxy tantalum, penta-i-butoxy tantalum, penta-n-butoxy tantalum, penta-sec-butoxy tantalum , Penta-t-butoxytantalum, vanadium (V) trimethoxide oxide, vanadium (V) triethoxy oxide, vanadium (V) tri-i-propoxide oxide, vanadium (V) tri-n-propoxide oxide, vanadium (V Tri-i-butoxide oxide, vanadium (V) tri-n-butoxide oxide, vanadium (V) tri-sec-butoxide oxide, vanadium (V) tri-t-butoxide oxide, tri-i-propoxy yttrium, tri-n -Butoxy yttrium, tetramethoxy
  • a halide of a specific metal (M) and an alcohol are reacted in the presence of an inert organic solvent, and ammonia or an amine compound is used to further extract the halogen.
  • Known methods such as a method of adding (Japanese Patent Laid-Open No. 63-227593 and Japanese Patent Laid-Open No. 3-291247) can be used.
  • the compound represented by the general formula (I) may be a compound in which a chelate structure is formed by mixing with a compound having a specific structure having two carbonyl groups described later.
  • the number of carbonyl groups to be chelated is not particularly limited, but when M is Nb, the number of carbonyl groups to be chelated is preferably 1 to 5, and when M is Ta, the number of carbonyl groups to be chelated is The number of carbonyl groups to be chelated is preferably 1 to 3 when M is VO, and the number of carbonyl groups to be chelated is 1 to 3 when M is Y. It is preferable that when M is Hf, the number of carbonyl groups to be chelated is preferably 1 to 4.
  • a chelate structure in the compound represented by the general formula (I) can be confirmed by a commonly used analysis method. For example, it can be confirmed using an infrared spectrum, a nuclear magnetic resonance spectrum, a melting point, or the like.
  • the content of the specific metal alkoxide compound contained in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the content of the specific metal alkoxide compound can be 0.1% by mass to 80% by mass in the composition for forming a passivation layer, and 0.5% by mass to 70% by mass from the viewpoint of storage stability and a passivation effect.
  • the content is preferably 1% by mass, more preferably 1% by mass to 60% by mass, and still more preferably 1% by mass to 50% by mass.
  • the composition for forming a passivation layer contains at least one filler.
  • the printability can be improved.
  • the improvement of printability means reduction of printing bleeding (a phenomenon in which the composition for forming a passivation layer applied on a substrate spreads).
  • the passivation effect can be improved by including a filler in the composition for forming a passivation layer.
  • the reason for this can be considered as follows. That is, when a composition for forming a passivation layer containing no filler is applied to a semiconductor substrate and subjected to heat treatment (firing), the formed passivation layer tends to be dense while the thickness of the passivation layer tends to be thin. At this time, if there is a defect such as a void in the passivation layer, moisture or impurities may adhere to the semiconductor substrate from the location, and the effective lifetime of the semiconductor substrate may be reduced.
  • the composition for forming a passivation layer contains a filler, so that the fillers are networked by sintering or the like during heat treatment (firing), function as a protective film for the semiconductor substrate, and reduce the effective lifetime. It is thought to suppress.
  • the function as a protective layer for the semiconductor substrate is particularly effective for a semiconductor substrate having an uneven structure such as a texture. That is, by forming the network layer derived from the filler, it is considered that the uneven structure portion existing on the surface of the semiconductor substrate can be protected by the passivation layer, and the passivation effect is improved.
  • the filler preferably contains at least one particle selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, silicon nitride, aluminum oxide, zirconium oxide, and silicon carbide.
  • a filler may be used alone or in combination of two or more.
  • at least one particle selected from the group consisting of silicon dioxide, aluminum hydroxide, and zirconium oxide as a filler is preferable that it contains at least one kind of particles selected from the group consisting of silicon dioxide and aluminum hydroxide.
  • the composition for forming a passivation layer contains particles of silicon dioxide, it does not react with a specific metal alkoxide compound even during heat treatment (firing) and is stably present in the composition for forming a passivation layer.
  • the point which is excellent in the storage stability of the composition for formation of a passivation layer is mentioned.
  • the filler is preferably glass particles.
  • the glass particles include those containing at least one selected from the group consisting of silicon dioxide, boron oxide, bismuth oxide, aluminum oxide, zinc oxide, titanium oxide, and calcium oxide.
  • the composition for forming a passivation layer contains glass particles as a filler, a passivation layer having an excellent passivation effect can be formed.
  • This can be considered, for example, as follows.
  • the glass particles in the composition for forming a passivation layer are softened during the heat treatment (firing) treatment, so that the glass particles are partly or wholly networked, and a heat treatment product (firing product) of a specific metal alkoxide compound. It is considered that it functions as a protective film for the passivation layer, and suppresses a decrease in effective lifetime. At this time, the lower the softening point of the glass particles, the more easily the above effect can be obtained.
  • the softening point is too low, the viscosity of the molten glass becomes too low during the heat treatment (firing), and the passivation layer is formed on the semiconductor substrate. In some cases, it is difficult to form a passivation layer in a desired shape.
  • the softening point of the glass particles is 300 ° C. to 1000 ° C. from the viewpoints of the ability to form a network between the glass particles, the viscosity of the glass after melting, the prevention of bleeding of the passivation layer, and the lifetime. Is preferably 350 ° C., more preferably 350 ° C. to 800 ° C., and still more preferably 350 ° C. to 750 ° C.
  • the crystallization temperature of the glass particles is 450 ° C. or more from the viewpoints of the ability to form a network between glass particles, the viscosity of the glass after melting, the prevention of bleeding of the passivation layer, and the lifetime.
  • the temperature is preferably 950 ° C, more preferably 450 ° C to 900 ° C, and still more preferably 480 ° C to 900 ° C.
  • the volume average particle diameter of the filler is not particularly limited, and the particle diameter when the volume-based integrated value in the particle size distribution is 50% (hereinafter also simply referred to as “particle diameter”, sometimes abbreviated as “D50%”). Is preferably 0.01 ⁇ m to 50 ⁇ m, more preferably 0.01 ⁇ m to 30 ⁇ m, still more preferably 0.01 ⁇ m to 20 ⁇ m, and particularly preferably 0.01 to 10 ⁇ m. By setting D50% of the filler to 0.01 ⁇ m or more, viscosity characteristics suitable for printing can be imparted to the composition for forming a passivation layer, and printing unevenness and printing bleeding tend to be further suppressed.
  • the printing unevenness refers to a phenomenon in which the thickness of the composition layer varies depending on a location, which is caused when a part of the screen plate is badly separated when the screen plate is separated from the semiconductor substrate.
  • the particle diameter of the filler is measured by a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter, LS 13, 320).
  • a laser diffraction / scattering particle size distribution analyzer Beckman Coulter, LS 13, 320.
  • the refractive index of the solvent is set to 1.48
  • the refractive index of the filler is set to the value of each substance (for example, 1.57 in the case of aluminum hydroxide particles). From the particle size distribution measured under the above conditions, the particle size (D50%) when the volume-based integrated value is 50% is calculated.
  • the above measurement method calculates the particle diameter from the particle size distribution of the filler as a raw material, but the particle diameter of the filler can also be measured using the composition for forming a passivation layer of the present invention.
  • 1 g of the composition for forming a passivation layer and 9 g of terpineol as a solvent are mixed to obtain a particle size measurement sample.
  • a laser diffraction / scattering particle size distribution measuring apparatus (Beckman Coulter, LS 13, 320) is used as described above.
  • 0.05 g to 0.50 g of the particle size measurement sample is used, and this is measured by dispersing it in 125 ml of a solvent (terpineol).
  • the content of the filler in the composition for forming a passivation layer is not particularly limited. From the viewpoint of suppressing printing unevenness and printing bleeding, the filler content in the composition for forming a passivation layer is preferably 0.1% by mass to 50% by mass, and preferably 1% by mass to 50% by mass. Is more preferable, and it is still more preferable that it is 2 mass%-45 mass%.
  • the composition for forming a passivation layer contains at least one liquid medium (solvent or dispersion medium). Thereby, the liquid physical properties (viscosity, surface tension, etc.) of the composition for forming a passivation layer can be adjusted to a required range depending on the application method when applying to a semiconductor substrate or the like.
  • liquid medium examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, Ketone solvents such as dipropyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, diisopropyl Ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxan
  • the liquid medium preferably contains at least one selected from the group consisting of a terpene solvent, an ester solvent, and an alcohol solvent from the viewpoints of impartability to a semiconductor substrate and pattern formation, and is selected from the group consisting of terpene solvents. More preferably, it contains at least one of the above.
  • the content of the liquid medium in the composition for forming a passivation layer is determined in consideration of impartability, pattern formability, or storage stability.
  • the content of the liquid medium is preferably 5% by mass to 98% by mass in the total mass of the composition for forming a passivation layer, from the viewpoint of the impartability of the composition and the pattern formability. More preferably, it is 95 mass%.
  • the composition for forming a passivation layer contains at least one resin.
  • a resin By including a resin, the shape stability of the composition layer formed by applying the composition for forming the passivation layer on the semiconductor substrate is further improved, and the passivation layer is desired in the region where the composition layer is formed. It can be selectively formed in the shape.
  • the type of resin is not particularly limited.
  • the resin is preferably a resin whose viscosity can be adjusted within a range where a good pattern can be formed.
  • Specific examples of the resin include polyvinyl alcohol, polyacrylamide, polyacrylamide derivatives, polyvinylamide, polyvinylamide derivatives, polyvinylpyrrolidone, polyethylene oxide, polyethylene oxide derivatives, polysulfonic acid, polyacrylamide alkylsulfonic acid, cellulose, and cellulose derivatives (carboxymethylcellulose).
  • Cellulose ethers such as hydroxyethyl cellulose and ethyl cellulose
  • gelatin gelatin derivatives, starch, starch derivatives, sodium alginate, sodium alginate derivatives, xanthan, xanthan derivatives, guar gum, guar gum derivatives, scleroglucan, scleroglucan derivatives, tragacanth, Tragacanth derivative, dextrin, dextrin derivative, (meta)
  • crylic acid resin (meth) acrylic acid ester resin (alkyl (meth) acrylate resin, dimethylaminoethyl (meth) acrylate resin, etc.), butadiene resin, styrene resin, siloxane resin, and copolymers thereof.
  • (meth) acrylic acid means at least one of “acrylic acid” and “methacrylic acid”
  • (meth) acrylate means at least one of “acrylate” and “methacrylate”. means.
  • a neutral resin having no acidic or basic functional group it is preferable to use a neutral resin having no acidic or basic functional group, and even when the content is small, viscosity and From the viewpoint of adjusting thixotropy, it is more preferable to use a cellulose derivative such as ethyl cellulose.
  • the molecular weight of the resin is not particularly limited, and it is preferable to adjust appropriately in view of a desired viscosity as the composition for forming a passivation layer.
  • the weight average molecular weight of the resin is preferably 1,000 to 10,000,000, and more preferably 1,000 to 5,000,000, from the viewpoints of storage stability and pattern formation.
  • the weight average molecular weight of resin is calculated
  • the content of the resin in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the resin content is preferably 0.1% by mass to 50% by mass in the total mass of the composition for forming a passivation layer.
  • the resin content is more preferably 0.2% by mass to 25% by mass, and more preferably 0.5% by mass to 20% by mass. Is more preferable, and 0.5 to 15% by mass is particularly preferable.
  • the total content of the liquid medium and the resin in the composition for forming a passivation layer is 5% by mass to 98% by mass from the viewpoint of improving storage stability, pattern forming property, and printability. Preferably there is.
  • composition for forming a passivation layer may contain at least one compound represented by the general formula (II) (hereinafter also referred to as “organoaluminum compound”).
  • organoaluminum compound When the composition for forming a passivation layer contains an organoaluminum compound, the passivation effect can be further improved. This can be considered as follows.
  • the organoaluminum compound includes compounds called aluminum alkoxide, aluminum chelate and the like, and preferably has an aluminum chelate structure in addition to the aluminum alkoxide structure. Further, as described in Nippon Seramikkusu Kyokai Gakujitsu Ronbunshi, vol. 97, pp369-399 (1989), the organoaluminum compound becomes aluminum oxide (Al 2 O 3 ) by heat treatment (firing). At this time, since the formed aluminum oxide is likely to be in an amorphous state, a four-coordinate aluminum oxide layer is easily formed in the vicinity of the interface with the semiconductor substrate, and may have a large negative fixed charge due to the four-coordinate aluminum oxide. It is considered possible. At this time, it is considered that a passivation layer having an excellent passivation effect can be formed by compounding with an oxide derived from a specific metal alkoxide compound having a fixed charge.
  • each R 2 independently represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group represented by R 2 may be linear or branched. Specific examples of the alkyl group represented by R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, hexyl, octyl, 2- Examples thereof include an ethylhexyl group and a 3-ethylhexyl group.
  • the alkyl group represented by R 2 is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms from the viewpoint of storage stability and a passivation effect, and is an unsubstituted alkyl group having 1 to 4 carbon atoms. More preferably.
  • n represents an integer of 0 to 3. n is preferably an integer of 1 to 3 and more preferably 1 or 3 from the viewpoint of storage stability.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group. From the viewpoint of storage stability, at least one of X 2 and X 3 is preferably an oxygen atom.
  • R 3 , R 4 and R 5 in the general formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group represented by R 3 , R 4 and R 5 may be linear or branched.
  • the alkyl group represented by R 3 , R 4 and R 5 may have a substituent or may be unsubstituted, and is preferably unsubstituted.
  • the alkyl group represented by R 3 , R 4 and R 5 is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • alkyl group represented by R 3 , R 4 and R 5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and a hexyl group.
  • R 3 and R 4 in the general formula (II) are preferably each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms. Or it is more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • R 5 in the general formula (II) is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms from the viewpoint of storage stability and a passivation effect, and is preferably a hydrogen atom or 1 to 4 carbon atoms.
  • the unsubstituted alkyl group is more preferable.
  • the compound represented by the general formula (II) is a compound in which n is 1 to 3 and R 5 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms from the viewpoint of storage stability. It is preferable.
  • the compound represented by the general formula (II) is a compound in which n is 0, R 2 is each independently an alkyl group having 1 to 4 carbon atoms, and n is from the viewpoint of storage stability and a passivation effect. 1 to 3, R 2 is each independently an alkyl group having 1 to 4 carbon atoms, at least one of X 2 and X 3 is an oxygen atom, and R 3 and R 4 are each independently a hydrogen atom Alternatively, it is preferably an alkyl group having 1 to 4 carbon atoms, and R 5 is at least one selected from the group consisting of compounds each independently being a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 2 is each independently an unsubstituted alkyl group having 1 to 4 carbon atoms
  • n is 1 to 3
  • R 2 is each independently an unsubstituted alkyl group having 1 to 4 carbon atoms
  • at least one of X 2 and X 3 is an oxygen atom
  • R 3 or R 4 bonded to the oxygen atom is A group consisting of a compound having a C 1-4 alkyl group, and when X 2 or X 3 is a methylene group, R 3 or R 4 bonded to the methylene group is a hydrogen atom
  • R 5 is a hydrogen atom It is at least one selected from more.
  • aluminum trialkoxide which is an organoaluminum compound represented by the general formula (II) and n is 0, include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, trisec-butoxyaluminum, monosec-butoxy -Diisopropoxyaluminum, tri-t-butoxyaluminum, tri-n-butoxyaluminum and the like.
  • organoaluminum compound represented by the general formula (II) where n is 1 to 3 include aluminum ethyl acetoacetate diisopropylate and tris (ethylacetoacetate) aluminum.
  • organoaluminum compound represented by the general formula (II) and n being 1 to 3 a prepared product or a commercially available product may be used.
  • commercially available products include Kawaken Fine Chemical Co., Ltd. trade names, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, and the like.
  • the organoaluminum compound represented by the general formula (II) and n is 1 to 3 can be prepared by mixing an aluminum trialkoxide and a compound having a specific structure having two carbonyl groups.
  • a commercially available aluminum chelate compound may also be used.
  • the compound having a specific structure having two carbonyl groups is at least one selected from the group consisting of ⁇ -diketone compounds, ⁇ -ketoester compounds, and malonic acid diesters from the viewpoints of reactivity and storage stability. preferable.
  • ⁇ -diketone compounds include acetylacetone, 3-methyl-2,4-pentanedione, 2,3-pentanedione, 3-ethyl-2,4-pentanedione, and 3-butyl-2,4-pentane.
  • Examples include dione, 2,2,6,6-tetramethyl-3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, and the like.
  • ⁇ -ketoester compounds include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isobutyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, pentyl acetoacetate, isopentyl acetoacetate, hexyl acetoacetate, acetoacetic acid n-octyl, heptyl acetoacetate, 3-pentyl acetoacetate, ethyl 2-acetylheptanoate, ethyl 2-butylacetoacetate, ethyl 4,4-dimethyl-3-oxovalerate, ethyl 4-methyl-3-oxovalerate Ethyl 2-ethylacetoacetate, ethyl hexylacetoacetate, methyl 4-methyl-3-oxovalerate, isopropyl acetoacetate, e
  • malonic acid diester examples include dimethyl malonate, diethyl malonate, dipropyl malonate, diisopropyl malonate, dibutyl malonate, di-t-butyl malonate, dihexyl malonate, t-butylethyl malonate, methyl malonate
  • examples include diethyl, diethyl ethylmalonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl sec-butylmalonate, diethyl isobutylmalonate, diethyl 1-methylbutylmalonate, and the like.
  • the number of aluminum chelate structures is not particularly limited as long as it is 1 to 3. Among these, 1 or 3 is preferable from the viewpoint of storage stability, and 1 is more preferable from the viewpoint of solubility.
  • the number of aluminum chelate structures can be controlled, for example, by appropriately adjusting the ratio of mixing aluminum trialkoxide and a compound having a specific structure having two carbonyl groups. Moreover, you may select suitably the compound which has a desired structure from a commercially available aluminum chelate compound.
  • aluminum ethyl acetoacetate diisopropylate is more preferably used.
  • an aluminum chelate structure in the organoaluminum compound can be confirmed by a commonly used analysis method. For example, it can be confirmed using an infrared spectrum, a nuclear magnetic resonance spectrum, a melting point, or the like.
  • the organoaluminum compound may be liquid or solid and is not particularly limited. From the viewpoint of the passivation effect and storage stability, an organoaluminum compound having favorable stability at room temperature (25 ° C.) and good solubility or dispersibility is preferable. By using such a specific organoaluminum compound, the homogeneity of the formed passivation layer can be further improved, and a desired passivation effect can be stably obtained.
  • the content of the organoaluminum compound can be appropriately selected as necessary.
  • the total content of the specific metal alkoxide compound and the organoaluminum compound may be 0.1% by mass to 80% by mass in the composition for forming a passivation layer from the viewpoint of storage stability and a passivation effect. It is preferably 1% by mass to 50% by mass, more preferably 0.1% by mass to 45% by mass, further preferably 0.5% by mass to 45% by mass, and 1% by mass to 40% by mass. It is particularly preferable that the content is% by mass.
  • the composition for forming a passivation layer may contain an acidic compound or a basic compound.
  • the content of the acidic compound or the basic compound is 1% by mass or less in the composition for forming a passivation layer, respectively. It is preferable that the content is 0.1% by mass or less.
  • Examples of acidic compounds include Bronsted acid and Lewis acid. Specific examples include inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as acetic acid.
  • Examples of basic compounds include Bronsted bases and Lewis bases. Specifically, examples of the basic compound include inorganic bases such as alkali metal hydroxides and alkaline earth metal hydroxides; organic bases such as trialkylamine and pyridine.
  • the semiconductor substrate with a passivation layer of the present invention includes a semiconductor substrate and a passivation layer (baked product layer) that is a heat treatment product of the composition for forming a passivation layer provided on the entire surface or a part of the semiconductor substrate.
  • the semiconductor substrate with a passivation layer exhibits an excellent passivation effect by having a passivation layer that is a heat-treated product layer (baked product layer) of the composition for forming a passivation layer.
  • the semiconductor substrate is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • the semiconductor substrate include those obtained by doping (diffusing) p-type impurities or n-type impurities into silicon, germanium, or the like.
  • the semiconductor substrate is preferably a silicon substrate.
  • the semiconductor substrate may be a p-type semiconductor substrate or an n-type semiconductor substrate.
  • the surface on which the passivation layer is formed is a semiconductor substrate having a p-type layer.
  • the p-type layer on the semiconductor substrate is a p-type layer derived from the p-type semiconductor substrate
  • the p-type layer is formed on the n-type semiconductor substrate or the p-type semiconductor substrate as a p-type diffusion layer or a p + -type diffusion layer. It may be a thing.
  • the thickness of the semiconductor substrate is not particularly limited and can be appropriately selected according to the purpose.
  • the thickness of the semiconductor substrate can be 50 ⁇ m to 1000 ⁇ m, preferably 75 ⁇ m to 750 ⁇ m.
  • the thickness of the passivation layer formed on the semiconductor substrate is not particularly limited and can be appropriately selected depending on the purpose.
  • the average thickness of the passivation layer is preferably 5 nm to 50 ⁇ m, preferably 10 nm to 30 ⁇ m, and more preferably 15 nm to 20 ⁇ m.
  • the semiconductor substrate with a passivation layer can be applied to solar cell elements, light emitting diode elements, and the like.
  • a solar cell element and a solar cell excellent in conversion efficiency can be obtained by applying a semiconductor substrate with a passivation layer to a solar cell element.
  • the passivation layer may be provided on either the light receiving surface side or the back surface side of the solar cell element.
  • the passivation layer may be provided on the side surface side of the solar cell element.
  • the method for producing a semiconductor substrate with a passivation layer according to the present invention includes a step of forming the composition layer by applying the composition for forming a passivation layer on the entire surface or a part of the semiconductor substrate, and heat-treating the composition layer ( Firing) to form a passivation layer.
  • the manufacturing method may further include other steps as necessary.
  • the composition for forming a passivation layer of the present invention By using the composition for forming a passivation layer of the present invention, printing bleeding can be suppressed and the passivation layer can be formed into a desired shape by a simple method. Moreover, the passivation layer excellent in the passivation effect can be more uniformly formed on the application surface of the semiconductor substrate by using the composition for forming a passivation layer of the present invention.
  • the semiconductor substrate with a passivation layer those described for the semiconductor substrate with a passivation layer can be used, and those that can be suitably used are also the same.
  • the method for producing a semiconductor substrate with a passivation layer preferably further includes a step of applying an alkaline aqueous solution on the semiconductor substrate before the step of forming the composition layer. That is, it is preferable to wash the surface of the semiconductor substrate with an alkaline aqueous solution before applying the composition for forming a passivation layer on the semiconductor substrate. By washing with an alkaline aqueous solution, organic substances, particles, and the like present on the surface of the semiconductor substrate can be removed, and the passivation effect is further improved.
  • RCA cleaning and the like As a method of cleaning with an alkaline aqueous solution, generally known RCA cleaning and the like can be exemplified. For example, by immersing the semiconductor substrate in a mixed solution of ammonia water and hydrogen peroxide water and treating at 60 ° C. to 80 ° C., organic substances and particles can be removed from the surface of the semiconductor substrate, and the semiconductor substrate can be cleaned.
  • the washing time is preferably 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes.
  • the method for forming the composition layer by applying the passivation layer forming composition on the semiconductor substrate there is no particular limitation on the method for forming the composition layer by applying the passivation layer forming composition on the semiconductor substrate.
  • a method for applying a composition for forming a passivation layer on a semiconductor substrate using a known application method or the like can be mentioned.
  • the application method include screen printing, an ink jet method, a dispenser method, and the like. From the viewpoint of productivity, screen printing is preferable.
  • the application amount of the composition for forming a passivation layer can be appropriately selected according to the purpose.
  • the application amount of the composition for forming a passivation layer can be appropriately adjusted so that the thickness of the formed passivation layer becomes a desired thickness described later.
  • the viscosity of the composition for forming a passivation layer can be 0.01 Pa ⁇ s to 10,000 Pa ⁇ s.
  • the viscosity of the composition for forming a passivation layer is preferably 0.1 Pa ⁇ s to 1000 Pa ⁇ s. The viscosity is measured using a rotary shear viscometer at 25 ° C. and a shear rate of 1.0 s ⁇ 1 .
  • the composition for forming a passivation layer has thixotropy.
  • thixotropic index is calculated by dividing the shear viscosity eta 2 of the shear viscosity eta 1 at a shear rate of 1.0 s -1 at a shear rate of 10s -1 ( ⁇ 1 / ⁇ 2 ) is 1. It is preferably from 05 to 100, more preferably from 1.1 to 50.
  • the shear viscosity is measured at a temperature of 25 ° C. using a rotary shear viscometer equipped with a cone plate (diameter 50 mm, cone angle 1 °).
  • a passivation layer is formed on a semiconductor substrate by heat-treating (baking) the composition layer formed by the composition for forming a passivation layer to form a heat-treated material layer (baked material layer) derived from the composition layer.
  • the heat treatment (firing) condition of the composition layer is the heat treatment product of the compound represented by the general formula (I) contained in the composition layer and the compound represented by the general formula (II) contained as necessary. If it can convert into the metal oxide or composite oxide which is (baked product), it will not be restrict
  • the heat treatment (firing) temperature is preferably 300 ° C.
  • the heat treatment (firing) temperature here means the maximum temperature in the furnace used for the heat treatment (firing).
  • the heat treatment (firing) time can be appropriately selected according to the heat treatment (firing) temperature and the like.
  • the heat treatment (firing) time can be 0.1 to 10 hours, and preferably 0.1 to 5 hours.
  • the heat treatment (firing) time here means the holding time at the maximum temperature.
  • the heat treatment (firing) can be performed using a diffusion furnace (for example, ACCURON CQ-1200, Hitachi Kokusai Electric Inc.).
  • the atmosphere in which the heat treatment (firing) is performed is not particularly limited, and can be performed in the air.
  • the thickness of the passivation layer produced by the method for producing a semiconductor substrate with a passivation layer is not particularly limited and can be appropriately selected according to the purpose.
  • the average thickness of the passivation layer is preferably 5 nm to 50 ⁇ m, more preferably 10 nm to 30 ⁇ m, and still more preferably 15 nm to 20 ⁇ m.
  • the average thickness of the passivation layer is calculated as an arithmetic average value obtained by measuring the thickness at three points by an ordinary method using an interference film thickness meter (for example, F20 film thickness measurement system, Filmetrics Co., Ltd.).
  • a method of manufacturing a semiconductor substrate with a passivation layer includes: a composition layer comprising a composition for forming a passivation layer, after the composition for forming a passivation layer is applied to the semiconductor substrate and before the step of forming the passivation layer by heat treatment (firing). You may further have the process of drying-processing. By including the step of drying the composition layer, a passivation layer having a more uniform passivation effect can be formed.
  • the step of drying the composition layer is not particularly limited as long as at least a part of the liquid medium contained in the composition for forming a passivation layer can be removed.
  • the drying treatment can be, for example, a heat treatment at 30 ° C. to 250 ° C. for 1 minute to 60 minutes, and is preferably a heat treatment at 40 ° C. to 220 ° C. for 3 minutes to 40 minutes.
  • the drying treatment may be performed under normal pressure or under reduced pressure.
  • the manufacturing method of the semiconductor substrate with a passivation layer is a method of degreasing a composition layer made of the composition for forming a passivation layer after applying the composition for forming a passivation layer and before the step of forming the passivation layer by heat treatment (firing). You may have further the process to do.
  • a passivation layer having a more uniform passivation effect can be formed.
  • the step of degreasing the composition layer is not particularly limited as long as at least a part of the resin contained in the composition for forming a passivation layer can be removed.
  • the degreasing treatment can be, for example, a heat treatment at 250 ° C. to 450 ° C. for 10 minutes to 120 minutes, and is preferably a heat treatment at 300 ° C. to 400 ° C. for 3 minutes to 60 minutes.
  • the degreasing treatment is preferably performed in the presence of oxygen, and more preferably performed in the air.
  • the solar cell element of the present invention is a passivation that is a heat treatment product of a semiconductor substrate in which a p-type layer and an n-type layer are pn-junction, and the passivation layer forming composition provided on the entire surface or part of the semiconductor substrate.
  • the solar cell element may further include other components as necessary.
  • a solar cell element is excellent in conversion efficiency by having the passivation layer formed from the composition for passivation layer formation of this invention.
  • the semiconductor substrate to which the composition for forming a passivation layer is applied is not particularly limited, and can be appropriately selected from those usually used according to the purpose. What was demonstrated by the semiconductor substrate with a passivation layer can be used, and what can be used conveniently is also the same.
  • the surface of the semiconductor substrate on which the passivation layer is provided may be any of the light receiving surface, the back surface, and the side surface of the solar cell element.
  • the thickness of the passivation layer formed on the semiconductor substrate is not particularly limited and can be appropriately selected depending on the purpose.
  • the average thickness of the passivation layer is preferably 5 nm to 50 ⁇ m, preferably 10 nm to 30 ⁇ m, and more preferably 15 nm to 20 ⁇ m.
  • the shape and size of the solar cell element and for example, a square with a side of 125 to 156 mm is preferable.
  • the composition layer is formed by applying the passivation layer forming composition to the entire surface or a part of a semiconductor substrate in which a p-type layer and an n-type layer are pn-junctioned.
  • the manufacturing method of the solar cell element may further include other steps as necessary.
  • the composition for forming a passivation layer By using the composition for forming a passivation layer, it is possible to produce a solar cell element that suppresses printing bleeding and is excellent in conversion efficiency by a simple method. Furthermore, the passivation layer can be formed on the semiconductor substrate so as to have a desired shape, and the productivity of the solar cell element is excellent.
  • an electrode on at least one of a p-type layer and an n-type layer in a semiconductor substrate a commonly used method can be employed.
  • it can be manufactured by applying an electrode forming paste such as a silver paste or an aluminum paste to a desired region of a semiconductor substrate and performing a heat treatment (firing) as necessary.
  • the surface of the semiconductor substrate on which the passivation layer is provided may be a p-type layer or an n-type layer. Among these, a p-type layer is preferable from the viewpoint of conversion efficiency.
  • the details of the method for forming a passivation layer using the composition for forming a passivation layer are the same as the method for manufacturing a semiconductor substrate with a passivation layer described above, and the preferred embodiments are also the same.
  • the thickness of the passivation layer formed on the semiconductor substrate is not particularly limited and can be appropriately selected according to the purpose.
  • the average thickness of the passivation layer is preferably 5 nm to 50 ⁇ m, more preferably 10 nm to 30 ⁇ m, and still more preferably 15 nm to 20 ⁇ m.
  • FIG. 1 is a sectional view schematically showing an example of a method for producing a solar cell element having a passivation layer according to this embodiment.
  • this process diagram does not limit the present invention at all.
  • the p-type semiconductor substrate 1 is washed with an alkaline aqueous solution to remove organic substances, particles and the like on the surface of the p-type semiconductor substrate 1. Thereby, the passivation effect improves more.
  • an alkaline aqueous solution generally known RCA cleaning or the like can be used.
  • the surface of the p-type semiconductor substrate 1 is subjected to alkali etching or the like to form irregularities (also referred to as texture) on the surface.
  • alkali etching an etching solution composed of NaOH and IPA (isopropyl alcohol) can be used.
  • an n + -type diffusion layer 2 is formed with a depth of submicron order, A pn junction is formed at the boundary with the p-type bulk portion.
  • a method for diffusing phosphorus for example, a method of performing several tens of minutes at 800 ° C. to 1000 ° C. in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen can be cited.
  • the n + -type diffusion layer 2 is formed not only on the light receiving surface (front surface) but also on the back surface and side surfaces (not shown) as shown in FIG. Is formed.
  • a PSG (phosphosilicate glass) layer 3 is formed on the n + -type diffusion layer 2. Therefore, side etching is performed to remove the side PSG layer 3 and the n + -type diffusion layer 2.
  • the PSG layer 3 on the light receiving surface and the back surface is removed using an etching solution such as hydrofluoric acid. Further, as shown in FIG. 1 (5), the back surface is separately etched to remove the n + -type diffusion layer 2 on the back surface.
  • an antireflection film 4 such as silicon nitride is formed on the n + type diffusion layer 2 on the light receiving surface by a PECVD (Plasma Enhanced Chemical Vapor Deposition) method or the like at a thickness of about 90 nm.
  • PECVD Pulsma Enhanced Chemical Vapor Deposition
  • the passivation layer forming composition of the present invention is applied to a part of the back surface by screen printing or the like, and after drying, heat treatment (baking) at a temperature of 400 ° C. to 900 ° C. To form a passivation layer 5.
  • FIG. 5 an example of the formation pattern of the passivation layer 5 in the back surface is shown as a schematic plan view.
  • FIG. 7 is an enlarged schematic plan view of a portion A in FIG.
  • FIG. 8 is an enlarged schematic plan view of a portion B in FIG.
  • the passivation layer 5 on the back surface has a dot shape except for a portion where the back surface output extraction electrode 7 is formed in a later step.
  • the p-type semiconductor substrate 1 is formed with an exposed pattern.
  • the pattern of the dot-shaped openings is defined by the dot diameter (L a ) and the dot interval (L b ), and is preferably arranged regularly.
  • Dot diameter (L a) and the dot interval (L b) can be arbitrarily set, in view of the recombination-inhibiting passivation effect and minority carriers, it is preferable that L a is L b at 5 [mu] m ⁇ 2 mm is 10 [mu] m ⁇ 3 mm More preferably, L a is 10 ⁇ m to 1.5 mm and L b is 20 ⁇ m to 2.5 mm, and more preferably L a is 20 ⁇ m to 1.3 mm and L b is 30 ⁇ m to 2 mm.
  • FIG. 4 is a schematic plan view showing an example of the light receiving surface of the solar cell element.
  • the light receiving surface electrode includes a light receiving surface current collecting electrode 8 and a light receiving surface output extraction electrode 9.
  • the width of the light receiving surface current collecting electrode 8 is preferably 10 ⁇ m to 250 ⁇ m
  • the width of the light receiving surface output extraction electrode 9 is preferably 100 ⁇ m to 2 mm.
  • two light receiving surface output extraction electrodes 9 are provided.
  • the number of light receiving surface output extraction electrodes 9 may be three or four. it can.
  • FIG. 9 is a schematic plan view showing an example of the back surface of the solar cell element.
  • the width of the back surface output extraction electrode 7 is not particularly limited, and the width of the back surface output extraction electrode 7 is preferably 100 ⁇ m to 10 mm from the viewpoint of the connectivity of the wiring material in the subsequent manufacturing process of the solar cell.
  • the light receiving surface and the back surface After applying the electrode paste to each of the light receiving surface and the back surface, after drying, the light receiving surface and the back surface are both heat-treated (fired) at a temperature of about 450 ° C. to 900 ° C. in the atmosphere, and the light receiving surface collecting electrode 8 is applied to the light receiving surface. And the light receiving surface output extraction electrode 9 and the back surface collecting electrode 6 and the back surface output extraction electrode 7 are formed on the back surface, respectively.
  • the glass particles contained in the silver electrode paste forming the light receiving surface electrode react with the antireflection film 4 (fire through),
  • the light-receiving surface electrode (light-receiving surface current collecting electrode 8, light-receiving surface output extraction electrode 9) and the n + -type diffusion layer 2 are electrically connected (ohmic contact).
  • the aluminum in the aluminum electrode paste diffuses into the semiconductor substrate 1 by heat treatment (firing). , P + -type diffusion layer 10 is formed.
  • composition for forming a passivation layer of the present invention it is possible to form a passivation layer that can suppress printing bleeding and can be formed into a desired shape, and by improving the passivation effect, solar power with excellent power generation performance A battery element can be manufactured.
  • FIG. 2 is a cross-sectional view showing another example of a method for manufacturing a solar cell element having a passivation layer according to this embodiment, and the n + -type diffusion layer 2 on the back surface is removed by an etching process.
  • the solar battery cell can be manufactured in the same manner as in FIG. 1 except that the back surface is further flattened.
  • a technique such as immersing the back surface of the semiconductor substrate in a mixed solution of nitric acid, hydrofluoric acid and acetic acid or a potassium hydroxide solution can be used.
  • FIG. 3 is a cross-sectional view showing a process diagram illustrating another example of a method for manufacturing a solar cell element having a passivation layer according to the present embodiment. This method is the same as the method shown in FIG. 1 until the step of forming the texture structure, the n + -type diffusion layer 2 and the antireflection film 4 on the semiconductor substrate 1 (FIGS. 19 (19) to (24)).
  • FIG. 6 an example of the formation pattern of the passivation layer in the back surface is shown as a schematic plan view.
  • dot-like openings are arranged on the entire back surface, and dot-like openings are also arranged on the portion where the back-surface output extraction electrode is formed in a later step.
  • a p + -type diffusion layer 10 is formed by diffusing aluminum from the portion, and then etched with hydrochloric acid or the like to form a heat-treated product layer (baked product layer) derived from the aluminum paste formed on the p + -type diffusion layer 10 A method of removing can be used.
  • a silver electrode paste containing glass particles is applied to the light receiving surface by screen printing or the like, and a silver electrode paste containing glass particles is applied to the back surface by screen printing or the like.
  • the silver electrode paste on the light receiving surface is applied in a pattern according to the shape of the light receiving surface electrode shown in FIG. 4, and the silver electrode paste on the back surface is applied in a pattern according to the shape of the back electrode shown in FIG.
  • the light receiving surface and the back surface are heat-treated (fired) at a temperature of about 450 ° C. to 900 ° C. in air, as shown in FIG.
  • a light receiving surface collecting electrode 8 and a light receiving surface output extraction electrode 9 are formed on the light receiving surface, and a back surface collecting electrode 11 and a back surface output extraction electrode 7 are formed on the back surface, respectively.
  • the light receiving surface electrode and the n + -type diffusion layer 2 are electrically connected on the light receiving surface, and the back surface collecting electrode 11 and the back surface output extraction electrode 7 formed by vapor deposition are electrically connected on the back surface.
  • the solar cell includes the above-described solar cell element and a wiring material provided on the electrode of the solar cell element.
  • FIG. 10 is a diagram for explaining an example of a method for manufacturing a solar cell.
  • the solar cell includes at least one of the solar cell elements 12 and is configured by arranging the wiring material 13 on the output extraction electrode of the solar cell element. If necessary, the solar cell is formed by connecting a plurality of solar cell elements via a wiring material 13, further sealing with a sealing material 14, and overlapping a glass plate 16 and a back sheet 15.
  • the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in this field.
  • composition 1 for forming a passivation layer 5.0 g of ethyl cellulose (Nihon Kasei Co., Ltd., ETHOCEL 200 cps, hereinafter sometimes abbreviated as “EC”) as a resin, and terpineol (Nippon Terpene Chemical Co., Ltd., hereinafter abbreviated as “TPO”) as a liquid medium 95.0 g) was mixed and stirred at 150 ° C. for 1 hour to prepare an ethylcellulose solution.
  • EC ethyl cellulose
  • TPO terpineol
  • niobium ethoxide (Wako Pure Chemical Industries, Ltd.) as a compound represented by the general formula (I)
  • silicon dioxide particles Nippon Aerosil Co., Ltd., hydrophobic fumed silica “AEROSIL RY 200” as a filler.
  • the particle diameter (D50%) is 20 nm) 10.0 g
  • the ethylcellulose solution 30.0 g, and the terpineol 35.0 g were mixed to prepare a composition 1 for forming a passivation layer.
  • Table 1 summarizes the composition and the like.
  • the shear viscosity of the composition 1 for forming a passivation layer prepared above was measured immediately after preparation (within 12 hours) and after storage at 25 ° C. for 30 days, respectively.
  • the shear viscosity was measured by mounting a cone plate (diameter 50 mm, cone angle 1 °) on Anton Paar, MCR301, at a temperature of 25 ° C. and a shear rate of 1.0 s ⁇ 1 .
  • the shear viscosity at 25 ° C. was 35.6 Pa ⁇ s immediately after preparation, and 36.2 Pa ⁇ s after storage at 25 ° C. for 30 days.
  • the change rate of the shear viscosity after storage for 30 days is “A” when the change rate is less than 10%, “B” when the change rate is 10% or more and less than 30%, and “C” when the change rate is 30% or more. ". If evaluation is A and B, it is favorable as the storage stability of the composition for forming a passivation layer. Table 2 shows the values of the shear viscosity immediately after preparation and the evaluation results of storage stability.
  • a semiconductor substrate having a mirror-shaped single crystal p-type silicon substrate 50 mm square, thickness 625 ⁇ m, hereinafter referred to as substrate A
  • substrate B Two types of single crystal p-type silicon substrates (50 mm square, thickness 180 ⁇ m, hereinafter referred to as substrate B) on which a texture structure was formed were used.
  • the composition 1 for forming a passivation layer prepared as described above was continuously printed 10 times on each of the substrate A and the substrate B. Visually confirmed that 9 sheets had no printing unevenness.
  • “A” is the case where printing unevenness is not visually observed during printing is 9 or more out of 10 sheets
  • “B” is the case of 8 or less and 6 or more
  • the case of 5 or less is “ Evaluated as “C”. If evaluation is A and B, it is favorable as printing unevenness of the composition for forming a passivation layer.
  • the uneven printing refers to a phenomenon in which the thickness of the composition layer varies depending on the location, which is caused when a part of the screen plate is badly separated when the screen plate is separated from the silicon substrate.
  • the prepared composition 1 for forming a passivation layer was printed on the entire surface of the substrate A and the substrate B in a pattern shown in FIG.
  • the dot-shaped opening pattern used in the evaluation has a dot diameter (L a ) of 368 ⁇ m and a dot interval (L b ) of 0.5 mm.
  • substrate B which provided the composition 1 for passivation layer formation were heated at 150 degreeC for 3 minute (s), and were dried by evaporating a liquid medium.
  • the substrate A and the substrate B were heat-treated (fired) at a temperature of 700 ° C. for 10 minutes, and then allowed to cool at room temperature (25 ° C.).
  • the dot diameter (L a ) of the dot-shaped opening in the passivation layer formed on the substrate after heat treatment (firing) was measured.
  • the dot diameter (L a ) was measured at 10 points, and the average value was calculated.
  • the dot diameter (L a ) was 348 ⁇ m, and for substrate B, it was 340 ⁇ m.
  • the dot diameter (L a ) (368 ⁇ m) immediately after printing is less than 10% when the dot diameter (L a ) reduction rate after heat treatment (firing) is less than 10%.
  • printing bleeding refers to a phenomenon in which a composition for forming a passivation layer applied on a semiconductor substrate spreads.
  • the effective lifetime of the evaluation substrate obtained above was measured at room temperature (25 ° C.) by the reflected microwave photoconductive decay method using a lifetime measuring device (Nippon Semi-Lab Co., Ltd., WT-2000PVN).
  • the effective lifetime of the region to which the composition for forming a passivation layer was applied was 380 ⁇ s.
  • a single crystal p-type semiconductor substrate (125 mm square, thickness 200 ⁇ m) was prepared, and texture structures were formed on the light receiving surface and the back surface by alkali etching.
  • a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen treatment was performed at a temperature of 900 ° C. for 30 minutes to form n + -type diffusion layers on the light receiving surface, the back surface, and the side surfaces.
  • side etching was performed to remove the side PSG layer and the n + -type diffusion layer, and the PSG layer on the light-receiving surface and the back surface was removed using an etching solution containing hydrofluoric acid.
  • the back surface was separately etched to remove the n + -type diffusion layer on the back surface. Thereafter, an antireflection film made of silicon nitride was formed on the n + -type diffusion layer on the light-receiving surface with a thickness of about 90 nm by PECVD.
  • the passivation layer forming composition 1 prepared above was applied to the back surface in the pattern of FIGS. 5, 7 and 8, and then dried at a temperature of 150 ° C. for 5 minutes, and a diffusion furnace (ACCURON CQ-1200,
  • the passivation layer 5 was formed by performing a heat treatment (firing) with a maximum temperature of 700 ° C. and a holding time of 10 minutes in the atmosphere using Hitachi Kokusai Electric).
  • the back surface passivation layer 5 is formed in a pattern in which the p-type semiconductor substrate is exposed in a dot shape except for a portion where the back surface output extraction electrode is formed in a later step.
  • the pattern of the dot-shaped openings has the same shape as that used in the printing bleeding evaluation, the dot diameter (L a ) is 368 ⁇ m, and the dot interval (L b ) is 0.5 mm.
  • a commercially available silver electrode paste (PV-16A, DuPont) was printed on the light receiving surface with the pattern shown in FIG. 4 by screen printing.
  • the electrode pattern is composed of a light receiving surface (output) current collecting electrode 8 with a width of 120 ⁇ m and a light receiving surface output extraction electrode 9 with a width of 1.5 mm, and printed so that the thickness after heat treatment (firing) is 20 ⁇ m Conditions (screen plate mesh, printing speed and printing pressure) were adjusted as appropriate. This was heated at a temperature of 150 ° C. for 5 minutes to evaporate the liquid medium, thereby performing a drying treatment.
  • the printing conditions (screen plate mesh, printing speed, and printing pressure) of the silver electrode paste were appropriately adjusted so that the thickness of the back surface output extraction electrode 7 after heat treatment (firing) was 20 ⁇ m.
  • the aluminum electrode paste was printed on the entire surface other than the back surface output extraction electrode 7 to form a back surface current collecting electrode pattern.
  • the printing conditions of the aluminum electrode paste were appropriately adjusted so that the thickness of the back surface collecting electrode 8 after heat treatment (firing) was 30 ⁇ m.
  • a heat treatment was performed at a temperature of 150 ° C. for 5 minutes, and the liquid medium was evaporated to perform a drying process.
  • a wiring member (soldered rectangular wire for solar cell, product name: SSA-TPS 0.2 ⁇ 1.5) (20) Specifications of Sn-Ag-Cu lead-free solder plated to a maximum thickness of 20 ⁇ m per side on a copper wire with a thickness of 0.2mm x width 1.5mm, Hitachi Metals [(former) Hitachi Cable Co., Ltd.] and using a tab wire connection device (NTS-150-M, Tabbing & Stringing Machine, NPC) to melt the solder under conditions of a maximum temperature of 250 ° C. and a holding time of 10 seconds.
  • the wiring material was connected to the light receiving surface output extraction electrode 9 and the back surface output extraction electrode 7.
  • glass plate 16 / sealing material 14 / wiring material 13 are layered in the order of solar cell element 12 / sealing material 14 / back sheet 15, and this layered body is laminated using a vacuum laminator (LM-50 ⁇ 50, NPC Corporation) to make a part of the wiring member
  • the solar cell 1 was produced by vacuum lamination at a temperature of 140 ° C. for 5 minutes so as to be exposed.
  • the evaluation of the power generation performance of the produced solar cell was performed using pseudo-sunlight (WXS-155S-10, Wacom Denso Co., Ltd.) and voltage-current (IV) evaluation measuring instrument (IV CURVE TRACER MP-180, This was performed in combination with a measuring device of Eihiro Seiki Co., Ltd.). Jsc (short circuit current), Voc (open voltage), F. F. (Form factor) and ⁇ (conversion efficiency) were obtained by measuring in accordance with JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005), respectively. The obtained measured value was converted into a relative value with the measured value of the solar cell (solar cell C1) produced in Comparative Example 1 shown later as 100.0.
  • Example 2 22.5 g of tantalum (V) methoxide, 12.5 g of silicon dioxide particles (AEROSIL RY 200, particle diameter (D50%) is 20 nm), 30.0 g of the ethylcellulose solution prepared in Example 1, and 35. of terpineol.
  • a composition 2 for forming a passivation layer was prepared by mixing 0 g. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 2 was evaluated, the printability (printing unevenness and printing bleeding), and the effective lifetime were measured. Furthermore, the solar cell element 2 and the solar cell 2 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • Example 3 10.0 g of niobium ethoxide, 20.0 g of aluminum hydroxide particles (HP-360, Showa Denko KK, particle size (D50%) is 3.2 ⁇ m, purity 99.0% by mass), aluminum ethyl acetoacetate di 7.5 g of isopropylate (Kawaken Fine Chemical Co., Ltd., trade name: ALCH), 30.0 g of the ethylcellulose solution prepared in Example 1, and 26.5 g of terpineol were mixed to obtain composition 3 for forming a passivation layer. Prepared.
  • Example 2 Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 3 was evaluated, the printability (printing unevenness and printing blur) was evaluated, and the effective lifetime was measured. Furthermore, the solar cell element 3 and the solar cell 3 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • Example 4 Silicon (SiO 2) 1.5 parts dioxide, (2 O 3 B) 13.5 parts of boron oxide, bismuth oxide (Bi 2 O 3) 83.0 parts of aluminum oxide (Al 2 O 3) 1.5 parts, A glass composed of 0.5 part of zinc oxide (ZnO) (hereinafter sometimes abbreviated as “G01”) was prepared.
  • the obtained glass G01 had a softening point of 420 ° C. and a crystallization temperature of over 650 ° C.
  • glass G01 particles having a particle diameter (D50%) of 1.5 ⁇ m were obtained.
  • the shape was substantially spherical.
  • the glass particle shape was determined by observing using a TM-1000 scanning electron microscope manufactured by Hitachi High-Technologies Corporation.
  • the average particle diameter of the glass was calculated using a Beckman Coulter, LS 13, 320 type laser scattering diffraction particle size distribution analyzer (measurement wavelength: 632 nm).
  • the softening point of the glass was obtained from a differential heat (DTA) curve using a Shimadzu Corporation, DTG-60H type differential heat / thermogravimetric measuring device.
  • a composition for forming a passivation layer by mixing 24.5 g of vanadium (V) oxytriethoxide, 10.5 g of glass G01 particles, 30.0 g of the ethylcellulose solution prepared in Example 1, and 35.0 g of terpineol. 4 was prepared. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 4 was evaluated, the printability (printing unevenness and printing bleeding), and the effective lifetime were measured. Furthermore, the solar cell element 4 and the solar cell 4 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • Example 5 25.0 g of yttrium ethoxide, 10.0 g of aluminum hydroxide particles (particle diameter (D50%) is 3.2 ⁇ m), 30.0 g of the ethylcellulose solution prepared in Example 1, and 35.0 g of terpineol were mixed.
  • a passivation layer forming composition 5 was prepared. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 5 was evaluated, the printability (printing unevenness and printing blur) was evaluated, and the effective lifetime was measured. Furthermore, the solar cell element 5 and the solar cell 5 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • Example 6 14.5 g of hafnium ethoxide, 8.0 g of silicon dioxide particles (AEROSIL RY 200, particle size (D50%) is 20 nm), 12.5 g of aluminum ethyl acetoacetate diisopropylate (ALCH), prepared in Example 1
  • the composition 6 for forming a passivation layer was prepared by mixing 30.0 g of the ethyl cellulose solution and 35.0 g of terpineol. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 6 was evaluated, the printability (printing unevenness and printing blur) was evaluated, and the effective lifetime was measured. Furthermore, the solar cell element 6 and the solar cell 6 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • Example 7 Silicon dioxide (SiO 2 ) 49.0 parts, boron oxide (B 2 O 3 ) 16.0 parts, aluminum oxide (Al 2 O 3 ) 13.5 parts, zinc oxide (ZnO) 8.5 parts, titanium oxide ( A glass composed of TiO 2 ) 7.5 and calcium oxide (CaO) 5.5 (hereinafter sometimes abbreviated as “G02”) was prepared.
  • the obtained glass G02 had a softening point of 800 ° C. and a crystallization temperature of over 650 ° C.
  • glass G02 particles having a particle diameter (D50%) of 1.5 ⁇ m were obtained.
  • the shape of the glass G02 particles was substantially spherical.
  • composition 7 for forming a passivation layer was prepared by mixing. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 7 was evaluated, the printability (printing unevenness and printing blur) was evaluated, and the effective lifetime was measured. Furthermore, the solar cell element 7 and the solar cell 7 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • Example 8 A composition 8 for forming a passivation layer was prepared by mixing 19.0 g of tantalum methoxide, 16.0 g of glass G01 particles, 30.0 g of the ethylcellulose solution prepared in Example 1, and 35.0 g of terpineol. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition 8 was evaluated, the printability (printing unevenness and printing bleeding), and the effective lifetime were measured. Furthermore, the solar cell element 8 and the solar cell 8 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • a passivation layer made of aluminum oxide (Al 2 O 3 ) was formed using an ALD (Atomic Layer Deposition) method without using a composition for forming a passivation layer.
  • the film forming conditions were adjusted using an atomic layer deposition apparatus so that the Al 2 O 3 layer had a thickness of 20 nm.
  • the thickness of the layer after film formation was measured using the interference type film thickness meter (F20 film thickness measuring system, Filmetrics Co., Ltd.).
  • the substrate for effective lifetime measurement, the solar cell element C1, and the solar cell C1 were prepared by the above-described method, and the effective lifetime was measured and the power generation performance of the solar cell C1 was evaluated.
  • the kind of semiconductor substrate used for each evaluation, the film formation pattern, the light-receiving surface, and the electrode formation method of a back surface are the same as Example 1.
  • Example 2 In the preparation of the composition for forming a passivation layer in Example 1, it is composed of niobium ethoxide, a liquid medium (TPO), and a resin (EC) as shown in Table 1 without using silicon dioxide particles as a filler. A composition C2 for forming a passivation layer was prepared. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition C2, evaluation of printability (print unevenness and print bleeding), and measurement of effective lifetime were performed. Further, a solar cell element C2 and a solar cell C2 were produced in the same manner as in Example 1, and the power generation performance was evaluated.
  • TPO liquid medium
  • EC resin
  • composition for forming a passivation layer in Example 1 is composed of vanadium ethoxide, a liquid medium (TPO), and a resin (EC) as shown in Table 1 without using silicon dioxide particles as a filler.
  • a composition C3 for forming a passivation layer was prepared. Thereafter, in the same manner as in Example 1, the storage stability of the passivation layer forming composition C3 was evaluated, the printability (printing unevenness and printing bleeding) was evaluated, and the effective lifetime was measured.
  • the effective lifetime and the power generation performance of the solar cell evaluated in Examples 1 to 8 are almost the same as those measured in Comparative Example 1.
  • the ALD method It can be seen that a passivation layer having an excellent passivation effect comparable to that of aluminum oxide (Al 2 O 3 ) is formed.
  • Comparative Example 2 and Comparative Example 3 it was found that the storage stability and printability of the composition for forming a passivation layer were significantly reduced. This is due to the fact that no filler is contained in the composition for forming a passivation layer, so that the storage stability is deteriorated by causing phase separation between the liquid medium and a specific metal alkoxide compound in the composition for forming a passivation layer. It is considered that the printability deteriorated due to the decrease in the thixotropy of the composition for forming a passivation layer and the passivation layer.
  • the power generation performance of the solar cells C2 and C3 produced in Comparative Example 2 and Comparative Example 3 was also significantly lower than that of Comparative Example 1.
  • This above printability deteriorates, i.e. the progression of the bleeding printing, dot-shaped opening in the printed pattern of the passivation layer forming composition (dot diameter L a is 368Myuemu) is at almost disappeared and will, after step It is considered that when the aluminum electrode paste was printed and heat-treated (fired), the area of the ohmic contact portion formed between the back surface collecting electrode and the semiconductor substrate was greatly reduced.
  • a passivation film used for a solar cell element including aluminum oxide and niobium oxide and having a silicon substrate.
  • niobium oxide / aluminum oxide a mass ratio (niobium oxide / aluminum oxide) between the niobium oxide and the aluminum oxide is 30/70 to 90/10.
  • ⁇ 3> The passivation film according to ⁇ 1> or ⁇ 2>, in which a total content of the niobium oxide and the aluminum oxide is 90% by mass or more.
  • the passivation film according to any one of ⁇ 1> to ⁇ 4> which is a heat-treated product of a coating type material including an aluminum oxide precursor and a niobium oxide precursor.
  • a p-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
  • An n-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
  • a first electrode formed on the surface of the n-type impurity diffusion layer on the light-receiving surface side of the silicon substrate;
  • a passivation film comprising aluminum oxide and niobium oxide formed on the back surface of the silicon substrate and having a plurality of openings;
  • a second electrode forming an electrical connection with the surface on the back side of the silicon substrate through the plurality of openings;
  • a solar cell element comprising:
  • a p-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
  • An n-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
  • a first electrode formed on the surface of the n-type impurity diffusion layer on the light-receiving surface side of the silicon substrate;
  • a p-type impurity diffusion layer formed on a part or all of the back side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate;
  • a passivation film comprising aluminum oxide and niobium oxide formed on the back surface of the silicon substrate and having a plurality of openings;
  • a second electrode that forms an electrical connection with the surface of the p-type impurity diffusion layer on the back side of the silicon substrate through the plurality of openings;
  • a solar cell element comprising:
  • An n-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
  • a p-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
  • a second electrode formed on the back side of the silicon substrate;
  • a passivation film formed on the light-receiving surface side surface of the silicon substrate and including a plurality of openings and containing aluminum oxide and niobium oxide;
  • a first electrode formed on the surface of the p-type impurity diffusion layer on the light-receiving surface side of the silicon substrate and forming an electrical connection with the surface on the light-receiving surface side of the silicon substrate through the plurality of openings;
  • a solar cell element comprising:
  • ⁇ 10> The solar cell element according to any one of ⁇ 7> to ⁇ 9>, wherein a mass ratio of niobium oxide to aluminum oxide (niobium oxide / aluminum oxide) in the passivation film is 30/70 to 90/10.
  • ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a total content of the niobium oxide and the aluminum oxide in the passivation film is 90% by mass or more.
  • ⁇ 12> a silicon substrate;
  • a passivation film having a long carrier lifetime of a silicon substrate and having a negative fixed charge can be realized at low cost.
  • a coating type material for realizing the formation of the passivation film can be provided.
  • a highly efficient solar cell element using the passivation film can be realized at low cost.
  • a silicon substrate with a passivation film having a long carrier lifetime and a negative fixed charge can be realized at low cost.
  • the passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and niobium oxide.
  • the fixed charge amount of the film can be controlled by changing the composition of the passivation film.
  • the mass ratio of niobium oxide and aluminum oxide is 30/70 to 80/20 from the viewpoint that the negative fixed charge can be stabilized. Further, the mass ratio of niobium oxide and aluminum oxide is more preferably 35/65 to 70/30 from the viewpoint that the negative fixed charge can be further stabilized. Further, the mass ratio of niobium oxide and aluminum oxide is preferably 50/50 to 90/10 from the viewpoint that both improvement of carrier lifetime and negative fixed charge can be achieved.
  • the mass ratio of niobium oxide to aluminum oxide in the passivation film is measured by energy dispersive X-ray spectroscopy (EDX), secondary ion mass spectrometry (SIMS), and high frequency inductively coupled plasma mass spectrometry (ICP-MS). be able to.
  • Specific measurement conditions are as follows. Dissolving the passivation film in acid or alkaline aqueous solution, atomizing this solution and introducing it into Ar plasma, measuring the wavelength and intensity by spectroscopically analyzing the light emitted when the excited element returns to the ground state, Element qualification is performed from the obtained wavelength, and quantification is performed from the obtained intensity.
  • the total content of niobium oxide and aluminum oxide in the passivation film is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of maintaining good characteristics. As the components of niobium oxide and aluminum oxide in the passivation film increase, the effect of negative fixed charges increases.
  • the total content of niobium oxide and aluminum oxide in the passivation film can be measured by combining thermogravimetric analysis, fluorescent X-ray analysis, ICP-MS, and X-ray absorption spectroscopy. Specific measurement conditions are as follows.
  • the ratio of inorganic components can be calculated by thermogravimetric analysis, the ratio of niobium and aluminum can be calculated by fluorescent X-ray or ICP-MS analysis, and the ratio of oxide can be examined by X-ray absorption spectroscopy.
  • components other than niobium oxide and aluminum oxide may be included as organic components from the viewpoint of improving the film quality and adjusting the elastic modulus.
  • the presence of the organic component in the passivation film can be confirmed by elemental analysis and measurement of the FT-IR of the film.
  • the content of the organic component in the passivation film is more preferably less than 10% by mass, further preferably 5% by mass or less, and particularly preferably 1% by mass or less in the passivation film.
  • the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a niobium oxide precursor. Details of the coating type material will be described next.
  • the coating material of the present embodiment includes an aluminum oxide precursor and a niobium oxide precursor, and is used for forming a passivation film for a solar cell element having a silicon substrate.
  • the aluminum oxide precursor can be used without particular limitation as long as it produces aluminum oxide.
  • As the aluminum oxide precursor it is preferable to use an organic aluminum oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and chemically stable.
  • organic aluminum oxide precursors include aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , High Purity Chemical Research Laboratory SYM-AL04, and the like.
  • the niobium oxide precursor can be used without particular limitation as long as it produces niobium oxide.
  • the niobium oxide precursor it is preferable to use an organic niobium oxide precursor from the viewpoint of uniformly dispersing niobium oxide on the silicon substrate and chemically stable.
  • organic niobium oxide precursors include niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), High Purity Chemical Laboratory Nb-05, etc. be able to.
  • a passivation film is formed by forming a coating type material containing an organic niobium oxide precursor and an organic aluminum oxide precursor using a coating method or a printing method, and then removing organic components by a subsequent heat treatment (firing). Can be obtained. Therefore, as a result, a passivation film containing an organic component may be used.
  • FIGS. 12 to 15 are cross-sectional views showing first to fourth configuration examples of the solar cell element using the passivation film on the back surface of the present embodiment.
  • silicon substrate (crystalline silicon substrate, semiconductor substrate) 101 used in this embodiment mode either single crystal silicon or polycrystalline silicon may be used. Further, as the silicon substrate 101, either p-type crystalline silicon or n-type crystalline silicon may be used. From the standpoint of exerting the effects of the present embodiment, p-type crystalline silicon is more suitable.
  • the single crystal silicon or polycrystalline silicon used for the silicon substrate 101 may be arbitrary, but single crystal silicon or polycrystalline silicon having a resistivity of 0.5 ⁇ ⁇ cm to 10 ⁇ ⁇ cm is preferable.
  • a light receiving surface antireflection film 103 such as a silicon nitride (SiN) film, and a first electrode 105 (light receiving surface side electrode, first surface electrode, upper surface electrode) using silver (Ag) or the like. , A light receiving surface electrode) is formed.
  • the light receiving surface antireflection film 103 may also have a function as a light receiving surface passivation film. By using the SiN film, both functions of the light receiving surface antireflection film and the light receiving surface passivation film can be provided.
  • the solar cell element of the present embodiment may or may not have the light-receiving surface antireflection film 103.
  • the light receiving surface of the solar cell element is preferably formed with a concavo-convex structure (texture structure) in order to reduce the reflectance on the surface, but the solar cell element of the present embodiment has a texture structure. It may or may not have.
  • a BSF (Back Surface Field) layer 104 which is a layer doped with a group III element such as aluminum or boron, is formed on the back side (lower side, second side, back side in the figure) of the silicon substrate 101.
  • the solar cell element of this embodiment may or may not have the BSF layer 104.
  • a second surface made of aluminum or the like is used on the back surface side of the silicon substrate 101 to make contact (electrical connection) with the BSF layer 104 (or the surface on the back surface side of the silicon substrate 101 when the BSF layer 104 is not provided). Electrodes 106 (back side electrode, second side electrode, back side electrode) are formed.
  • a contact region (a surface on the back side of the silicon substrate 101 when the BSF layer 104 is not provided) and the second electrode 106 are electrically connected (
  • a passivation film (passivation layer) 107 containing aluminum oxide and niobium oxide is formed in a portion excluding the opening OA).
  • the passivation film 107 of this embodiment can have a negative fixed charge. With this fixed charge, electrons which are minority carriers among the carriers generated in the silicon substrate 101 by light are bounced back to the surface side. For this reason, a short circuit current increases and it is anticipated that photoelectric conversion efficiency will improve.
  • the second electrode 106 is formed on the entire surface of the contact region (opening OA) and the passivation film 107.
  • the second electrode 106 is formed only in the region (opening OA).
  • the second electrode 106 may be formed only in part on the contact region (opening OA) and the passivation film 107. Even with the solar cell element having the configuration shown in FIG. 13, the same effect as in FIG. 12 (first configuration example) can be obtained.
  • the BSF layer 104 is formed only on a part of the back surface side including the contact region (opening OA portion) with the second electrode 106, and FIG. 12 (first configuration example). Thus, it is not formed on the entire back surface side. Even with the solar cell element having such a configuration (FIG. 14), the same effect as that of FIG. 12 (first configuration example) can be obtained. Further, according to the solar cell element of the third configuration example of FIG. 14, the BSF layer 104, that is, the impurity is doped at a higher concentration than the silicon substrate 101 by doping a group III element such as aluminum or boron. Since there are few areas, it is possible to obtain higher photoelectric conversion efficiency than that in FIG. 12 (first configuration example).
  • FIG. 15 a fourth configuration example shown in FIG. 15 will be described.
  • the second electrode 106 is formed on the entire surface of the contact region (opening OA) and the passivation film 107, but in FIG. 15 (fourth configuration example), the contact The second electrode 106 is formed only in the region (opening OA).
  • the second electrode 106 may be formed only in part on the contact region (opening OA) and the passivation film 107. Even with the solar cell element having the configuration shown in FIG. 15, the same effect as in FIG. 14 (third configuration example) can be obtained.
  • the second electrode 106 when the second electrode 106 is applied by a printing method and baked at a high temperature to form the entire surface on the back side, a convex warpage tends to occur in the temperature lowering process. Such warpage may cause damage to the solar cell element, which may reduce the yield. Further, the problem of warpage increases as the silicon substrate becomes thinner. The cause of this warp is that stress is generated because the thermal expansion coefficient of the second electrode 106 made of metal (for example, aluminum) is larger than that of the silicon substrate, and the shrinkage in the temperature lowering process is correspondingly large.
  • metal for example, aluminum
  • the electrode structure tends to be symmetrical vertically. This is preferable because stress due to the difference in thermal expansion coefficient is unlikely to occur. However, in that case, it is preferable to provide a separate reflective layer.
  • a texture structure is formed on the surface of the silicon substrate 101 shown in FIG.
  • the texture structure may be formed on both sides of the silicon substrate 101 or only on one side (light receiving side).
  • the damaged layer of the silicon substrate 101 is removed by immersing the silicon substrate 101 in a heated potassium hydroxide or sodium hydroxide solution.
  • a texture structure is formed on both surfaces or one surface (light receiving surface side) of the silicon substrate 101 by dipping in a solution containing potassium hydroxide and isopropyl alcohol as main components. Note that, as described above, the solar cell element of the present embodiment may or may not have a texture structure, and thus this step may be omitted.
  • a phosphorus diffusion layer (n + layer) is formed as the diffusion layer 102 by thermal diffusion of phosphorus oxychloride (POCl 3 ) or the like on the silicon substrate 101.
  • the phosphorus diffusion layer can be formed, for example, by applying a coating-type doping material solution containing phosphorus to the silicon substrate 101 and performing heat treatment. After the heat treatment, the phosphorous glass layer formed on the surface is removed with an acid such as hydrofluoric acid, whereby a phosphorous diffusion layer (n + layer) is formed as the diffusion layer 102.
  • the method for forming the phosphorus diffusion layer is not particularly limited.
  • the phosphorus diffusion layer may be formed so that the depth from the surface of the silicon substrate 101 is in the range of 0.2 ⁇ m to 0.5 ⁇ m, and the sheet resistance is in the range of 40 ⁇ / ⁇ to 100 ⁇ / ⁇ (ohm / square). preferable.
  • a BSF layer 104 on the back surface side is formed by applying a coating-type doping material solution containing boron, aluminum or the like to the back surface side of the silicon substrate 101 and performing heat treatment.
  • a coating-type doping material solution containing boron, aluminum or the like for the application, methods such as screen printing, inkjet, dispensing, spin coating and the like can be used.
  • the BSF layer 104 is formed by removing a layer of boron glass, aluminum, or the like formed on the back surface with hydrofluoric acid, hydrochloric acid, or the like.
  • the method for forming the BSF layer 104 is not particularly limited.
  • the BSF layer 104 is formed so that the concentration range of boron, aluminum, etc.
  • the solar cell element of the present embodiment may or may not have the BSF layer 104, and thus this step may be omitted.
  • the diffusion layer 102 on the light-receiving surface and the BSF layer 104 on the back surface are formed using a coating-type doping material solution
  • the above-described doping material solution is applied to both sides of the silicon substrate 101 to diffuse.
  • the phosphorous diffusion layer (n + layer) and the BSF layer 104 as the layer 102 may be formed in a lump, and then phosphorous glass, boron glass, or the like formed on the surface may be removed all at once.
  • a silicon nitride film as the light-receiving surface antireflection film 103 is formed on the diffusion layer 102.
  • the method for forming the light receiving surface antireflection film 103 is not particularly limited.
  • the light-receiving surface antireflection film 103 is preferably formed to have a thickness in the range of 50 to 100 nm and a refractive index in the range of 1.9 to 2.2.
  • the light-receiving surface antireflection film 103 is not limited to a silicon nitride film, and may be a silicon oxide film, an aluminum oxide film, a titanium oxide film, or the like.
  • the surface antireflection film 103 such as an silicon nitride film can be formed by a method such as plasma CVD or thermal CVD, and is preferably formed by plasma CVD that can be formed in a temperature range of 350 ° C. to 500 ° C.
  • the passivation film 107 contains aluminum oxide and niobium oxide.
  • an aluminum oxide precursor typified by an organometallic decomposition coating material from which aluminum oxide can be obtained by heat treatment (firing), and niobium oxide obtained by heat treatment (firing). It is formed by applying a material (passivation material) containing a niobium oxide precursor typified by a commercially available organometallic decomposition coating type material and heat-treating (firing).
  • the formation of the passivation film 107 can be performed as follows, for example.
  • the above coating material is spin-coated on one side of a 725 ⁇ m thick 8-inch (20.32 cm) p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been previously removed with hydrofluoric acid having a concentration of 0.049% by mass
  • pre-baking is performed on a hot plate at 120 ° C. for 3 minutes. Thereafter, heat treatment is performed at 650 ° C. for 1 hour in a nitrogen atmosphere. In this case, a passivation film containing aluminum oxide and niobium oxide is obtained.
  • the thickness of the passivation film 107 formed by the above method is usually about several tens of nanometers as measured by an ellipsometer.
  • the coating type material is applied to a predetermined pattern including the contact area (opening OA) by a method such as screen printing, offset printing, inkjet printing, or dispenser printing.
  • the above-mentioned coating type material is pre-baked in the range of 80 ° C. to 180 ° C. after evaporation to evaporate the solvent, and then at 600 ° C. to 1000 ° C. for 30 minutes to 3 hours in a nitrogen atmosphere or in air. It is preferable to perform a degree of heat treatment (annealing) to form a passivation film 107 (oxide film).
  • the opening (contact hole) OA is preferably formed in a dot shape or a line shape on the BSF layer 104.
  • the mass ratio of niobium oxide to aluminum oxide is preferably 30/70 to 90/10, and preferably 30/70 to 80/20. More preferably, it is more preferably 35/65 to 70/30. Thereby, the negative fixed charge can be stabilized. Further, the mass ratio of niobium oxide and aluminum oxide is preferably 50/50 to 90/10 from the viewpoint that both improvement of carrier lifetime and negative fixed charge can be achieved.
  • the total content of niobium oxide and aluminum oxide is preferably 80% by mass or more, and more preferably 90% by mass or more.
  • the first electrode 105 which is an electrode on the light receiving surface side is formed.
  • the first electrode 105 is formed by forming a paste mainly composed of silver (Ag) on the light-receiving surface antireflection film 103 by screen printing and performing a heat treatment (fire through).
  • the shape of the 1st electrode 105 may be arbitrary shapes, for example, may be a known shape which consists of a finger electrode and a bus-bar electrode.
  • the second electrode 106 which is an electrode on the back side is formed.
  • the second electrode 106 can be formed by applying a paste containing aluminum as a main component using screen printing or a dispenser and heat-treating it.
  • the shape of the second electrode 106 is preferably the same shape as the shape of the BSF layer 104, a shape covering the entire back surface, a comb shape, a lattice shape, or the like.
  • the paste for forming the first electrode 105 and the second electrode 106, which are the electrodes on the light receiving surface side, is first printed, and then heat-treated (fire-through), whereby the first electrode 105 and the second electrode 106 are formed.
  • the two electrodes 106 may be formed together.
  • the BSF layer 104 is formed in a contact portion between the second electrode 106 and the silicon substrate 101 in a self-alignment manner. Is formed.
  • the BSF layer 104 may be separately formed by applying a coating-type doping material solution containing boron, aluminum, or the like to the back side of the silicon substrate 101 and heat-treating it. .
  • the diffusion layer 102 is formed by a layer doped with a group III element such as boron
  • the BSF layer 104 is formed by doping a group V element such as phosphorus.
  • a leakage current flows through a portion where the inversion layer formed at the interface due to the negative fixed charge and the metal on the back surface are in contact with each other, and the conversion efficiency may be difficult to increase.
  • FIG. 16 is a cross-sectional view illustrating a configuration example of a solar cell element using the light-receiving surface passivation film of the present embodiment.
  • the diffusion layer 102 on the light receiving surface side is p-type doped with boron, and collects holes on the light receiving surface side and electrons on the back surface side of the generated carriers. For this reason, it is preferable that the passivation film 107 having a negative fixed charge is on the light receiving surface side.
  • an antireflection film made of SiN or the like may be further formed by CVD or the like.
  • the passivation material (a-1) is spin-coated on one side of a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been removed in advance with a hydrofluoric acid having a concentration of 0.049% by mass.
  • Pre-baking was performed on the plate at 120 ° C. for 3 minutes.
  • the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film through a metal mask by vapor deposition, thereby manufacturing a capacitor having a metal-insulator-semiconductor (MIS) structure.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from an ideal value of ⁇ 0.81V to + 0.32V. From this shift amount, it was found that the passivation film obtained from the passivation material (a-1) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 7.4 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (a-1) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to a heat treatment (firing) at 650 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured using a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 530 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (firing) the passivation material (a-1) showed a certain degree of passivation performance and a negative fixed charge.
  • Reference Example 1-2 Similar to Reference Example 1-1, a commercially available organometallic decomposition coating material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High-Purity Chemical Laboratory, SYM-AL04, concentration 2. 3 mass%] and a commercially available organometallic decomposable coating type material [High Purity Chemical Laboratory, Nb-05, concentration 5 mass%] from which niobium oxide (Nb 2 O 5 ) can be obtained by heat treatment (firing). Passivation materials (a-2) to (a-7) shown in Table 3 were prepared by mixing at different ratios.
  • each of the passivation materials (a-2) to (a-7) was applied to one side of a p-type silicon substrate, and heat treatment (firing) was performed to produce a passivation film.
  • the voltage dependence of the capacitance of the obtained passivation film was measured, and the fixed charge density was calculated therefrom.
  • the carrier lifetime is also increased after heat treatment (firing). Since it showed a certain value, it was suggested that it functions as a passivation film. It was found that all the passivation films obtained from the passivation materials (a-2) to (a-7) stably show negative fixed charges and can be suitably used as a passivation for a p-type silicon substrate. .
  • the passivation material (c-1) is spin-coated on one side of a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been removed in advance with a hydrofluoric acid having a concentration of 0.049% by mass.
  • Pre-baking was performed at 120 ° C. for 3 minutes on the plate.
  • heat treatment was performed at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and niobium oxide. When the film thickness was measured with an ellipsometer, it was 50 nm.
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film through a metal mask by vapor deposition, thereby manufacturing a capacitor having a metal-insulator-semiconductor (MIS) structure.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from an ideal value of ⁇ 0.81 V to +4.7 V. From this shift amount, it was found that the passivation film obtained from the passivation material (c-1) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 3.2 ⁇ 10 12 cm ⁇ 2 .
  • the passivation material (c-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain silicon.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured using a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 330 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (sintering) the passivation material (c-1) exhibited a certain degree of passivation performance and a negative fixed charge.
  • the passivation material (c-2) is spin-coated on one side of a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been removed in advance with a hydrofluoric acid having a concentration of 0.049% by mass.
  • Pre-baking was performed at 120 ° C. for 3 minutes on the plate.
  • heat treatment was performed at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and niobium oxide. When the film thickness was measured by an ellipsometer, it was 14 nm.
  • a plurality of 1 mm diameter aluminum electrodes are deposited on the passivation film through a metal mask to form a MIS (Metal-Insulator-Semiconductor) capacitor.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A).
  • Vfb flat band voltage
  • LCR meter HP, 4275A
  • Vfb flat band voltage
  • the passivation film obtained from the passivation material (c-2) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 0.8 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (c-2) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (firing) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured with a lifetime measuring device (Kobelco Research Institute Co., Ltd., RTA-540). As a result, the carrier lifetime was 200 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • each of the passivation materials (b-1) to (b-7) was applied to one side of a p-type silicon substrate and heat-treated (fired) to produce a passivation film, Using this, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • the passivation film obtained from the passivation materials (b-1) to (b-6) has a large carrier lifetime and has a function as a passivation.
  • the niobium oxide / aluminum oxide ratios were 10/90 and 20/80, the fixed charge density values varied greatly, and a negative fixed charge density could not be stably obtained. It was confirmed that a negative fixed charge density can be realized by using niobium oxide.
  • a negative fixed charge is stably generated because a passivation film showing a positive fixed charge is obtained in some cases. It turns out that it has not reached to show.
  • a passivation film exhibiting a fixed charge can be used as a passivation for an n-type silicon substrate.
  • a negative fixed charge density could not be obtained with the passivation material (b-7) containing 100% by mass of aluminum oxide.
  • a passivation material (d-3) As a passivation material (d-3), a commercially available organometallic decomposition coating material [having high purity chemical laboratory Hf-05, concentration 5 mass%] from which hafnium oxide (HfO 2 ) can be obtained by heat treatment (firing) is used. Got ready.
  • each of the passivation materials (d-1) to (d-3) is applied to one side of a p-type silicon substrate, and then heat-treated (fired) to produce a passivation film. Using this, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • the passivation material was applied to both sides of the p-type silicon substrate, and the carrier lifetime was measured using a sample obtained by heat treatment (firing). The results obtained are summarized in Table 5.
  • the passivation films obtained from the passivation materials (d-1) to (d-3) have a small carrier lifetime and an insufficient function as a passivation. It also showed a positive fixed charge.
  • the passivation film obtained from the passivation material (d-3) had a negative fixed charge, but its value was small. It was also found that the carrier lifetime was relatively small and the function as a passivation was insufficient.
  • an SiN film produced by plasma CVD was formed as the light-receiving surface antireflection film 103 on the light-receiving surface side.
  • the passivation material (a-1) prepared in Reference Example 1-1 was applied to the region excluding the contact region (opening OA) on the back surface side of the silicon substrate 101 by the inkjet method. Thereafter, heat treatment was performed to form a passivation film 107 having an opening OA.
  • a sample using the passivation material (c-1) prepared in Reference Example 1-3 was separately prepared as the passivation film 107.
  • a paste mainly composed of silver was screen-printed in the shape of predetermined finger electrodes and bus bar electrodes.
  • a paste mainly composed of aluminum was screen-printed on the entire surface.
  • heat treatment fire-through
  • electrodes first electrode 105 and second electrode 106
  • aluminum is diffused into the opening OA on the back surface to form the BSF layer 104.
  • the fire-through process in which the SiN film is not perforated is described, but the opening OA is first formed in the SiN film by etching or the like, and then the silver electrode is formed. You can also.
  • the passivation film 107 is not formed in the above manufacturing process, aluminum paste is printed on the entire back surface, and the p + layer 114 corresponding to the BSF layer 104 and the electrode 116 corresponding to the second electrode.
  • the characteristic evaluation was performed on the entire surface to form a solar cell element having the structure shown in FIG.
  • characteristic evaluation was performed according to JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005). The results are shown in Table 6.
  • the solar cell element having the passivation film 107 including the niobium oxide and aluminum oxide layers has both increased short-circuit current and open-circuit voltage as compared with the solar cell element not having the passivation film 107, and the conversion efficiency ( It was found that the photoelectric conversion efficiency was improved by 1% at the maximum.
  • a passivation film for use in a solar cell element having a silicon substrate comprising aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
  • ⁇ 2> The passivation film according to ⁇ 1>, wherein a mass ratio of the oxide of the vanadium group element to the aluminum oxide (vanadium group element oxide / aluminum oxide) is 30/70 to 90/10.
  • ⁇ 3> The passivation film according to ⁇ 1> or ⁇ 2>, in which a total content of the oxide of the vanadium group element and the aluminum oxide is 90% or more.
  • the oxide of the vanadium group element includes any of oxides of two or three kinds of vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide. Any one of ⁇ 1> to ⁇ 3> The passivation film according to claim 1.
  • ⁇ 5> Heat treatment of a coating-type material comprising: a precursor of aluminum oxide; and a precursor of an oxide of at least one vanadium group element selected from the group consisting of a precursor of vanadium oxide and a precursor of tantalum oxide.
  • the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
  • a p-type impurity diffusion layer formed on part or all of the second surface side of the silicon substrate and doped with an impurity at a higher concentration than the silicon substrate,
  • the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
  • n-type impurity diffusion layer formed on a part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate, The solar cell element according to ⁇ 9>, wherein the second electrode is electrically connected to the n-type impurity diffusion layer through an opening of the passivation film.
  • ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a mass ratio of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 30/70 to 90/10 .
  • ⁇ 12> The solar cell element according to any one of ⁇ 7> to ⁇ 11>, wherein the total content of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 90% or more.
  • the oxide of the vanadium group element includes an oxide of two or three vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide, ⁇ 7> to ⁇ 12>
  • the solar cell element according to any one of the above.
  • ⁇ 14> a silicon substrate;
  • a passivation film having a long carrier lifetime of a silicon substrate and having a negative fixed charge can be realized at low cost.
  • a coating type material for realizing the formation of the passivation film can be provided.
  • a low-cost and highly efficient solar cell element using the passivation film can be realized.
  • a silicon substrate with a passivation film having a long carrier lifetime and a negative fixed charge can be realized at low cost.
  • the passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide. It is what was included.
  • the amount of fixed charges possessed by the passivation film can be controlled by changing the composition of the passivation film.
  • the vanadium group element is a Group 5 element in the periodic table, and is an element selected from vanadium, niobium, and tantalum.
  • the mass ratio of the oxide of vanadium group element to aluminum oxide is preferably 35/65 to 90/10, from the viewpoint that the negative fixed charge can be stabilized, and is preferably 50/50 to 90/10. More preferably.
  • the mass ratio of vanadium group element oxide and aluminum oxide in the passivation film is determined by energy dispersive X-ray spectroscopy (EDX), secondary ion mass spectrometry (SIMS), and high frequency inductively coupled plasma mass spectrometry (ICP-MS). ) Can be measured. Specific measurement conditions are as follows in the case of ICP-MS, for example. Dissolving the passivation film in acid or alkaline aqueous solution, atomizing this solution and introducing it into Ar plasma, measuring the wavelength and intensity by spectroscopically analyzing the light emitted when the excited element returns to the ground state, Element qualification is performed from the obtained wavelength, and quantification is performed from the obtained intensity.
  • EDX energy dispersive X-ray spectroscopy
  • SIMS secondary ion mass spectrometry
  • ICP-MS high frequency inductively coupled plasma mass spectrometry
  • the total content of the vanadium group element oxide and aluminum oxide in the passivation film is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of maintaining good characteristics.
  • the components other than the oxide of vanadium group elements and aluminum oxide in the passivation film increase, the effect of negative fixed charges increases.
  • components other than vanadium group oxide and aluminum oxide may be contained as organic components from the viewpoint of improving the film quality and adjusting the elastic modulus.
  • the presence of the organic component in the passivation film can be confirmed by elemental analysis and measurement of the FT-IR of the film.
  • vanadium oxide As the oxide of the vanadium group element, it is preferable to select vanadium oxide (V 2 O 5 ) from the viewpoint of obtaining a larger negative fixed charge.
  • the passivation film may include two or three vanadium group oxides selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide as the vanadium group element oxide.
  • the passivation film is preferably obtained by heat-treating a coating-type material, and can be obtained by forming a coating-type material using a coating method or a printing method, and then removing organic components by heat treatment. More preferred. That is, the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a vanadium group element oxide precursor. Details of the coating type material will be described later.
  • the coating type material of the present embodiment is a coating type material used for a passivation film for a solar cell element having a silicon substrate, and includes a precursor of aluminum oxide, a precursor of vanadium oxide, and a precursor of tantalum oxide. And a precursor of an oxide of at least one vanadium group element selected from the group.
  • a precursor of the oxide of the vanadium group element contained in the coating material a precursor of vanadium oxide (V 2 O 5 ) is selected from the viewpoint of the negative fixed charge of the passivation film formed from the coating material. It is preferable.
  • the coating type material is composed of two or three vanadium group elements selected from the group consisting of vanadium oxide precursors, niobium oxide precursors and tantalum oxide precursors as vanadium group oxide precursors. An oxide precursor may also be included.
  • the aluminum oxide precursor can be used without particular limitation as long as it produces aluminum oxide.
  • As the aluminum oxide precursor it is preferable to use an organic aluminum oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and a chemically stable viewpoint.
  • Examples of the organic aluminum oxide precursor include aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , Kojundo Chemical Laboratory Co., Ltd., SYM-AL04.
  • the precursor of the oxide of the vanadium group element can be used without particular limitation as long as it generates an oxide of the vanadium group element.
  • the vanadium group element oxide precursor is preferably an organic vanadium group oxide oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and chemically stable. .
  • organic vanadium oxide precursors examples include vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13), High Purity Chemical Laboratory, V-02 can be mentioned.
  • organic tantalum oxide precursors include tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12), Kojundo Chemical Laboratory, Ta-10-P Can be mentioned.
  • organic niobium oxide precursors examples include niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), High Purity Chemical Laboratory, Nb-05. Can be mentioned.
  • a passivation film By forming a coating type material containing an organic vanadium group oxide precursor and an organic aluminum oxide precursor using a coating method or a printing method, and then removing the organic components by a heat treatment, A passivation film can be obtained. Therefore, as a result, a passivation film containing an organic component may be used.
  • the content of the organic component in the passivation film is more preferably less than 10% by mass, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the solar cell element (photoelectric conversion device) of the present embodiment includes the passivation film (insulating film, protective insulating film) described in the above embodiment in the vicinity of the photoelectric conversion interface of the silicon substrate, that is, aluminum oxide and vanadium oxide. And at least one oxide of a vanadium group element selected from the group consisting of tantalum oxide. By containing aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, the carrier lifetime of the silicon substrate can be extended and negative fixed charges can be obtained. And the characteristics (photoelectric conversion efficiency) of the solar cell element can be improved.
  • Passivation of passivation material (a2-1) on one side of a 725 ⁇ m thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) with natural oxide film removed beforehand with hydrofluoric acid at a concentration of 0.49% by mass It was applied and placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing vanadium oxide and vanadium oxide [vanadium oxide / aluminum oxide 63/37 (mass%)]. It was 51 nm when the film thickness was measured with the ellipsometer. When the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
  • the passivation material (a2-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 650 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured with a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the carrier lifetime was 380 ⁇ s.
  • the decrease in carrier lifetime (from 400 ⁇ s to 380 ⁇ s) was within ⁇ 10%, and the decrease in carrier lifetime was small.
  • the passivation film obtained by heat-treating (sintering) the passivation material (a2-1) showed a certain degree of passivation performance and a negative fixed charge.
  • Reference Example 2-2 Similar to Reference Example 2-1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2 3 mass%] and a commercially available organometallic thin film coating type material [Vitamin Purity Laboratory, V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) can be obtained by heat treatment, Passivation materials (a2-2) to (a2-7) shown in Table 7 were prepared by mixing at different ratios.
  • each of the passivation materials (a2-2) to (a2-7) was applied to one side of a p-type silicon substrate and heat-treated (fired) to produce a passivation film.
  • the voltage dependence of the capacitance of the obtained passivation film was measured, and the fixed charge density was calculated therefrom.
  • the carrier lifetime was measured using a sample obtained by applying a passivation material to both sides of a p-type silicon substrate and performing heat treatment (firing).
  • the passivation materials (a2-2) to (a2-7) are all negative after the heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film. It was found that all the passivation films obtained from the passivation materials (a2-2) to (a2-7) stably show negative fixed charges and can be suitably used as a passivation for a p-type silicon substrate. .
  • the passivation material (b2-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (firing) the passivation material (b2-1) exhibits a certain degree of passivation performance and a negative fixed charge.
  • the passivation material (b2-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere. A sample in which both surfaces of the substrate were covered with a passivation film was produced. The carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 170 ⁇ s. For comparison, the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by curing the passivation material (b2-2) exhibited a certain degree of passivation performance and a negative fixed charge.
  • Each of the passivation materials (c2-1) to (c2-6) is a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ) from which a natural oxide film has been removed in advance with hydrofluoric acid having a concentration of 0.49% by mass.
  • (Cm) was spin-coated on one side, placed on a hot plate, and pre-baked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and tantalum oxide. Using this passivation film, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • each of the passivation materials (c2-1) to (c2-6) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
  • the passivation materials (c2-1) to (c2-6) are all negative after heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film.
  • Al oxide (Al 2 O 3 ) As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d2-1) having a concentration of 5% by mass.
  • Al (OCH (CH 3 ) 2 ) 3 As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d2-1) having a concentration of 5% by mass.
  • the passivation material (d2-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to a heat treatment (firing) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 610 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating the passivation material (d2-1) exhibited a certain degree of passivation performance and a negative fixed charge.
  • the passivation material (d2-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere. A sample in which both surfaces of the substrate were covered with a passivation film was produced. The carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 250 ⁇ s. For comparison, the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat treatment (firing) the passivation material (d2-2) exhibits a certain degree of passivation performance and a negative fixed charge.
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
  • aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing)
  • heat treatment (firing) Niobium oxide (Nb 2 O) by commercially available organometallic thin film coating type material (VCO, Ltd., high purity chemical research laboratory V-02, concentration 2 mass%) from which vanadium oxide (V 2 O 5 ) is obtained, and heat treatment (firing) 5 )
  • a commercially available organometallic thin film coating type material [Co-development High Purity Chemical Laboratory, Nb-05, concentration 5 mass%] obtained is mixed to obtain a passivation material (e2-2) which is a coating type material. Prepared (see Table 9).
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), heat treatment (firing) Niobium oxide (Nb) by commercially available organometallic thin film coating material [Tapurio Chemical Lab. Ta-10-P, concentration 10% by mass] from which tantalum oxide (Ta 2 O 5 ) can be obtained, and heat treatment (firing) 2 O 5 ), a commercially available organometallic thin film coating material [High Purity Chemical Laboratory Nb-05, concentration 5 mass%] is mixed to form a passivation material (e2-3) which is a coating material Was prepared (see Table 9).
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
  • aluminum oxide Al 2 O 3
  • heat treatment firing
  • Tantalum oxide Ti 2 O 5
  • heat treatment Niobium oxide
  • Nb 2 O 5 Niobium oxide
  • a commercially available organometallic thin film coating type material [High purity chemical research laboratory Nb-05, concentration 5 mass%] was mixed to prepare a passivation material (e2-4) as a coating type material (see Table 9).
  • Each of the passivation materials (e2-1) to (e2-4) was 725 ⁇ m thick and 8 inches thick with the natural oxide film removed beforehand with hydrofluoric acid having a concentration of 0.49% by mass, as in Reference Example 2-1. It was spin-coated on one side of a p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm), placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 650 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and two or more vanadium group element oxides.
  • each of the passivation materials (e2-1) to (e2-4) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
  • each of the passivation materials (f2-1) to (f2-9) was applied to one side of a p-type silicon substrate, and then heat treatment (firing) was performed to form a passivation film. This was used to measure the voltage dependence of the capacitance, and the fixed charge density was calculated therefrom.
  • a SiN film was formed on the light receiving surface side by plasma CVD as the light receiving surface antireflection film 103.
  • the passivation material (a2-1) prepared in Reference Example 2-1 was applied to the region excluding the contact region (opening OA) on the back surface side of the silicon substrate 101 by an inkjet method. Thereafter, heat treatment was performed to form a passivation film 107 having an opening OA.
  • a sample using the passivation material (c2-1) prepared in Reference Example 2-5 was separately prepared as the passivation film 107.
  • a paste mainly composed of silver was screen-printed in the shape of predetermined finger electrodes and bus bar electrodes.
  • a paste mainly composed of aluminum was screen-printed on the entire surface.
  • heat treatment fire-through
  • electrodes first electrode 105 and second electrode 106
  • aluminum is diffused into the opening OA on the back surface to form the BSF layer 104.
  • the fire-through process in which the SiN film is not perforated is described.
  • the opening OA is first formed in the SiN film by etching or the like, and then the silver electrode is formed. You can also
  • the passivation film 107 is not formed in the above manufacturing process, aluminum paste is printed on the entire back surface, and the p + layer 114 corresponding to the BSF layer 104 and the electrode 116 corresponding to the second electrode. was formed on the entire surface to form a solar cell element having the structure of FIG.
  • characteristic evaluation a short circuit current, an open circuit voltage, a fill factor, and conversion efficiency
  • the characteristic evaluation was performed according to JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005). The results are shown in Table 11.
  • the solar cell element having the passivation film 107 has both a short-circuit current and an open-circuit voltage that are increased as compared with the solar electronic element not having the passivation film 107, and the conversion efficiency (photoelectric conversion efficiency) is 0 at the maximum. It was found to improve by 6%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Photovoltaic Devices (AREA)
PCT/JP2013/069699 2012-07-19 2013-07-19 Composition formant une couche de passivation, substrat semi-conducteur ayant une couche de passivation, procédé de fabrication d'un substrat semi-conducteur ayant une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire, et cellule solaire Ceased WO2014014109A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201380038207.1A CN104488089A (zh) 2012-07-19 2013-07-19 钝化层形成用组合物、带钝化层的半导体基板、带钝化层的半导体基板的制造方法、太阳能电池元件、太阳能电池元件的制造方法及太阳能电池
JP2014525893A JPWO2014014109A1 (ja) 2012-07-19 2013-07-19 パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP2012-160336 2012-07-19
JP2012160336 2012-07-19
JP2012-218389 2012-09-28
JP2012218389 2012-09-28
JP2013011934 2013-01-25
JP2013-011934 2013-01-25
JP2013-040153 2013-02-28
JP2013038895 2013-02-28
JP2013-038895 2013-02-28
JP2013040153 2013-02-28

Publications (2)

Publication Number Publication Date
WO2014014109A1 true WO2014014109A1 (fr) 2014-01-23
WO2014014109A9 WO2014014109A9 (fr) 2014-06-19

Family

ID=49948929

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/069699 Ceased WO2014014109A1 (fr) 2012-07-19 2013-07-19 Composition formant une couche de passivation, substrat semi-conducteur ayant une couche de passivation, procédé de fabrication d'un substrat semi-conducteur ayant une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire, et cellule solaire

Country Status (4)

Country Link
JP (1) JPWO2014014109A1 (fr)
CN (1) CN104488089A (fr)
TW (1) TW201412758A (fr)
WO (1) WO2014014109A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111816574A (zh) * 2020-05-29 2020-10-23 济宁东方芯电子科技有限公司 一种uv膜模板及利用uv膜模板实现洁净玻璃钝化的方法
WO2022075456A1 (fr) * 2020-10-08 2022-04-14 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022075457A1 (fr) * 2020-10-08 2022-04-14 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022138385A1 (fr) * 2020-12-21 2022-06-30 昭和電工マテリアルズ株式会社 Composition pour former une électrode, élément de cellule solaire et électrode empilée d'aluminium/argent
WO2022176519A1 (fr) * 2021-02-16 2022-08-25 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022176520A1 (fr) * 2021-02-16 2022-08-25 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022181732A1 (fr) * 2021-02-24 2022-09-01 昭和電工マテリアルズ株式会社 Élément de cellule solaire et cellule solaire
WO2022181730A1 (fr) * 2021-02-24 2022-09-01 昭和電工マテリアルズ株式会社 Élément de cellule solaire et cellule solaire
WO2022181731A1 (fr) * 2021-02-24 2022-09-01 昭和電工マテリアルズ株式会社 Élément de cellule solaire et cellule solaire
CN115332364A (zh) * 2022-08-10 2022-11-11 西南交通大学 太阳能电池钝化涂覆料、制备方法及钝化方法
WO2025055982A1 (fr) * 2023-09-13 2025-03-20 理想晶延半导体设备(上海)股份有限公司 Cellule découpée, module et procédé de revêtement de passivation pour surface découpée latérale de cellule

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101810892B1 (ko) * 2016-09-13 2017-12-20 동우 화인켐 주식회사 터치 센서 및 이를 포함하는 터치 스크린 패널
CN108565341B (zh) * 2018-05-04 2021-07-16 宝德照明集团有限公司 一种硅异质结太阳能电池及其制备方法
CN108831955B (zh) * 2018-06-08 2020-08-11 海门名驰工业设计有限公司 一种硅太阳能电池及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03188938A (ja) * 1989-08-18 1991-08-16 Hitachi Ltd 無機ポリマ薄膜の形成方法
JP2000294817A (ja) * 1999-04-09 2000-10-20 Dainippon Printing Co Ltd 太陽電池モジュ−ル用表面保護シ−トおよびそれを使用した太陽電池モジュ−ル
JP2004359532A (ja) * 2003-04-09 2004-12-24 Jsr Corp タンタル酸化物膜形成用組成物、タンタル酸化物膜およびその製造方法
JP2008019285A (ja) * 2006-07-10 2008-01-31 Sekisui Chem Co Ltd 金属含有ポリマーの製造方法、金属含有ポリマー、感光性樹脂組成物及び半導体素子
JP2011216845A (ja) * 2010-03-18 2011-10-27 Ricoh Co Ltd 絶縁膜形成用インク、絶縁膜の製造方法及び半導体装置の製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328260A (en) * 1981-01-23 1982-05-04 Solarex Corporation Method for applying antireflective coating on solar cell
US4411703A (en) * 1981-01-23 1983-10-25 Solarex Corporation Composition for applying antireflective coating on solar cell
US4496398A (en) * 1982-01-20 1985-01-29 Solarex Corporation Antireflective coating composition
JP3783673B2 (ja) * 2002-03-06 2006-06-07 東レ株式会社 プラズマディスプレイの製造方法
KR101528382B1 (ko) * 2007-10-17 2015-06-12 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 단면 후면 컨택 태양 전지용 유전성 코팅물
JP2011517327A (ja) * 2008-03-04 2011-06-02 ダウ・コーニング・コーポレイション シリコーン組成物、シリコーン接着剤、被覆基材及び積層基材
KR20120037364A (ko) * 2009-07-01 2012-04-19 세키스이가가쿠 고교가부시키가이샤 도전성 페이스트용 바인더 수지, 도전성 페이스트 및 태양 전지 소자
JP5633346B2 (ja) * 2009-12-25 2014-12-03 株式会社リコー 電界効果型トランジスタ、半導体メモリ、表示素子、画像表示装置及びシステム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03188938A (ja) * 1989-08-18 1991-08-16 Hitachi Ltd 無機ポリマ薄膜の形成方法
JP2000294817A (ja) * 1999-04-09 2000-10-20 Dainippon Printing Co Ltd 太陽電池モジュ−ル用表面保護シ−トおよびそれを使用した太陽電池モジュ−ル
JP2004359532A (ja) * 2003-04-09 2004-12-24 Jsr Corp タンタル酸化物膜形成用組成物、タンタル酸化物膜およびその製造方法
JP2008019285A (ja) * 2006-07-10 2008-01-31 Sekisui Chem Co Ltd 金属含有ポリマーの製造方法、金属含有ポリマー、感光性樹脂組成物及び半導体素子
JP2011216845A (ja) * 2010-03-18 2011-10-27 Ricoh Co Ltd 絶縁膜形成用インク、絶縁膜の製造方法及び半導体装置の製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111816574A (zh) * 2020-05-29 2020-10-23 济宁东方芯电子科技有限公司 一种uv膜模板及利用uv膜模板实现洁净玻璃钝化的方法
WO2022075456A1 (fr) * 2020-10-08 2022-04-14 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022075457A1 (fr) * 2020-10-08 2022-04-14 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022138385A1 (fr) * 2020-12-21 2022-06-30 昭和電工マテリアルズ株式会社 Composition pour former une électrode, élément de cellule solaire et électrode empilée d'aluminium/argent
WO2022176519A1 (fr) * 2021-02-16 2022-08-25 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022176520A1 (fr) * 2021-02-16 2022-08-25 昭和電工マテリアルズ株式会社 Composition pour formation d'électrode, élément de cellule solaire, et électrode stratifiée aluminium/argent
WO2022181732A1 (fr) * 2021-02-24 2022-09-01 昭和電工マテリアルズ株式会社 Élément de cellule solaire et cellule solaire
WO2022181730A1 (fr) * 2021-02-24 2022-09-01 昭和電工マテリアルズ株式会社 Élément de cellule solaire et cellule solaire
WO2022181731A1 (fr) * 2021-02-24 2022-09-01 昭和電工マテリアルズ株式会社 Élément de cellule solaire et cellule solaire
CN115332364A (zh) * 2022-08-10 2022-11-11 西南交通大学 太阳能电池钝化涂覆料、制备方法及钝化方法
CN115332364B (zh) * 2022-08-10 2024-08-13 西南交通大学 太阳能电池钝化涂覆料、制备方法及钝化方法
WO2025055982A1 (fr) * 2023-09-13 2025-03-20 理想晶延半导体设备(上海)股份有限公司 Cellule découpée, module et procédé de revêtement de passivation pour surface découpée latérale de cellule

Also Published As

Publication number Publication date
TW201412758A (zh) 2014-04-01
WO2014014109A9 (fr) 2014-06-19
JPWO2014014109A1 (ja) 2016-07-07
CN104488089A (zh) 2015-04-01

Similar Documents

Publication Publication Date Title
WO2014014109A1 (fr) Composition formant une couche de passivation, substrat semi-conducteur ayant une couche de passivation, procédé de fabrication d'un substrat semi-conducteur ayant une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire, et cellule solaire
WO2014014110A9 (fr) Composition servant à former une couche de passivation, substrat semi-conducteur comprenant une couche de passivation, procédé de production d'un substrat semi-conducteur comprenant une couche de passivation, élément de cellule solaire, procédé de production d'un élément de cellule solaire, et cellule solaire
JP6295952B2 (ja) 太陽電池素子及びその製造方法、並びに太陽電池モジュール
US9714262B2 (en) Composition for forming passivation layer, semiconductor substrate having passivation layer, method of producing semiconductor substrate having passivation layer, photovoltaic cell element, method of producing photovoltaic cell element and photovoltaic cell
JP6350278B2 (ja) 太陽電池素子、太陽電池素子の製造方法及び太陽電池モジュール
JP6330661B2 (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板及びその製造方法、並びに太陽電池素子及びその製造方法
WO2014010745A1 (fr) Élément de cellule solaire et son procédé de fabrication
JP6269484B2 (ja) 電界効果型パッシベーション層形成用組成物、電界効果型パッシベーション層付半導体基板、電界効果型パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法及び太陽電池
JP6295953B2 (ja) 太陽電池素子及びその製造方法、並びに太陽電池モジュール
JP6176249B2 (ja) パッシベーション層付半導体基板及びその製造方法
WO2016002901A1 (fr) Composition de formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de production de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire
JP2015115488A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法及び太陽電池
JP2017188537A (ja) 太陽電池素子及びその製造方法並びに太陽電池
JP2017188536A (ja) 太陽電池素子及び太陽電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13820396

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014525893

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13820396

Country of ref document: EP

Kind code of ref document: A1