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WO2016002901A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2016002901A1
WO2016002901A1 PCT/JP2015/069192 JP2015069192W WO2016002901A1 WO 2016002901 A1 WO2016002901 A1 WO 2016002901A1 JP 2015069192 W JP2015069192 W JP 2015069192W WO 2016002901 A1 WO2016002901 A1 WO 2016002901A1
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Prior art keywords
passivation layer
composition
forming
semiconductor substrate
solar cell
Prior art date
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PCT/JP2015/069192
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English (en)
Japanese (ja)
Inventor
剛 早坂
吉田　誠人
野尻　剛
倉田　靖
田中　徹
真年 森下
児玉　俊輔
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to KR1020177002522A priority Critical patent/KR20170026538A/ko
Priority to JP2016531454A priority patent/JP6658522B2/ja
Priority to CN201580035295.9A priority patent/CN106471626A/zh
Publication of WO2016002901A1 publication Critical patent/WO2016002901A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • 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
    • 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
    • H10F71/129—Passivating
    • 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 and a manufacturing method thereof, a solar cell element and a manufacturing method thereof, and a solar cell.
  • a p-type silicon substrate having a texture structure is prepared so as to promote the light confinement effect and achieve high efficiency.
  • several tens of minutes are performed at 800 ° C. to 900 ° C. in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen to form an n-type diffusion layer uniformly on the p-type silicon substrate.
  • phosphorus oxychloride POCl 3
  • nitrogen and oxygen to form an n-type diffusion layer uniformly on the p-type silicon substrate.
  • n-type diffusion layers are formed not only on the surface of the p-type silicon substrate, but also on the side and back surfaces.
  • n-type diffusion layer formed on the side surface of the p-type silicon substrate needs to be converted into a p + -type diffusion layer. Therefore, an n-type diffusion layer is converted into a p + -type diffusion layer by applying an aluminum paste containing aluminum powder and a binder to the entire back surface of the p-type silicon substrate, and heat-treating (baking) the aluminum paste. The ohmic contact is obtained by forming.
  • the aluminum electrode formed from the aluminum paste has low conductivity.
  • the aluminum electrode formed on the entire back surface of the p-type silicon substrate usually has a thickness of about 10 ⁇ m to 20 ⁇ m after heat treatment (firing).
  • the thermal expansion coefficient differs greatly between silicon and aluminum, 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, and the grain boundary Cause damage, crystal defect growth, and warping.
  • Japanese Patent No. 3107287 proposes a point contact technique in which an aluminum paste is applied to a part of the silicon substrate surface to partially form a p + -type diffusion layer and an aluminum electrode. Yes.
  • 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.
  • back surface passivation layer for that purpose, Japanese Patent Application Laid-Open No. 2004-6565 proposes a SiO 2 film or the like. As a passivation effect by forming such a SiO 2 film, there is an effect of terminating the dangling bonds of silicon atoms in the back surface layer portion of the silicon substrate and reducing the surface state density causing recombination.
  • Such a passivation effect is generally called a field effect, and an aluminum oxide (Al 2 O 3 ) film or the like is proposed in Japanese Patent No. 4767110 as a material having a negative fixed charge.
  • Such a passivation layer is generally formed by ALD (Atomic Layer Deposition) method, CVD (Chemical Vapor Deposition) method, etc. as described in Journal of Applied Physics, 104 (2008), 113703-1 to 113703-7. It is formed by the method.
  • One embodiment of the present invention has been made in view of the above-described conventional problems, and is for forming a passivation layer capable of forming a passivation layer excellent in pattern formability and excellent in a passivation effect by a simple method. It is an object to provide a composition. Moreover, one embodiment of the present invention is obtained using a composition for forming a passivation layer, and a semiconductor substrate with a passivation layer comprising a passivation layer having an excellent passivation effect, a method for manufacturing the same, and a solar cell having excellent conversion efficiency It is an object to provide a battery element, a manufacturing method thereof, and a solar battery.
  • a composition for forming a passivation layer comprising a compound represented by the following general formula (I) and water.
  • M represents at least one selected from the group consisting of Al, Nb, Ta, VO, Y, and Hf.
  • R 1 independently represents an alkyl group or an aryl group.
  • m represents an integer of 1 to 5.
  • M represents at least one selected from the group consisting of Al, Nb, Ta, VO, Y, and Hf.
  • R 1 independently represents an alkyl group or an aryl group.
  • m represents an integer of 1 to 5.
  • each R 2 independently represents an alkyl group.
  • n represents an integer of 1 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.
  • composition for forming a passivation layer according to any one of ⁇ 1> to ⁇ 3>, wherein M in the compound represented by the general formula (I) is Nb.
  • thixotropic ratios shear rate shear rate of shear viscosity .eta.1 at 0.1s -1 is calculated by dividing the shear viscosity .eta.2 at 10.0s -1 ( ⁇ 1 / ⁇ 2) it is,
  • the ratio (M1 / M2) calculated by dividing the mass M1 when heated at 150 ° C. for 3 hours by the mass M2 when not heated is 0.0001 to 0.7
  • the thixo ratio ( ⁇ 1 / ⁇ 2) calculated by dividing the shear viscosity ⁇ 1 at a shear rate of 0.1 s ⁇ 1 at 25 ° C. by the shear viscosity ⁇ 2 at a shear rate of 10.0 s ⁇ 1 is 1.05
  • ⁇ 8> a semiconductor substrate;
  • a passivation layer which is a heat treatment product of the composition for forming a passivation layer according to any one of ⁇ 1> to ⁇ 7>, provided on at least a part of at least one surface of the semiconductor substrate;
  • a semiconductor substrate with a passivation layer A semiconductor substrate with a passivation layer.
  • ⁇ 9> forming a composition layer by applying the passivation layer forming composition according to any one of ⁇ 1> to ⁇ 7> to at least a part of at least one surface of the semiconductor substrate; Heat-treating the composition layer to form a passivation layer; The manufacturing method of the semiconductor substrate with a passivation layer which has this.
  • a semiconductor substrate having a pn junction part in which a p-type layer and an n-type layer are pn-junction;
  • a passivation layer which is a heat treatment product of the composition for forming a passivation layer according to any one of ⁇ 1> to ⁇ 7>, provided on at least a part of at least one surface of the semiconductor substrate;
  • An electrode disposed on at least one of the p-type layer and the n-type layer;
  • a solar cell element having
  • ⁇ 11> The passivation according to any one of ⁇ 1> to ⁇ 7>, wherein at least part of at least one surface of a semiconductor substrate having a pn junction formed by pn junction of a p-type layer and an n-type layer is provided.
  • a composition for forming a passivation layer capable of forming a passivation layer having an excellent pattern forming property and an excellent passivation effect by a simple technique.
  • a semiconductor substrate with a passivation layer obtained using a composition for forming a passivation layer and having a passivation layer having an excellent passivation effect, a method for manufacturing the same, and an excellent conversion efficiency are obtained.
  • a solar cell element, a manufacturing method thereof, and a solar cell can be provided.
  • the composition for forming a passivation layer of the present invention a semiconductor substrate with a passivation layer and a method for producing the same, a solar cell element and a method for producing the same, and a mode for carrying out the solar cell will be described in detail.
  • the present invention is not limited to the following embodiments.
  • the components including element steps and the like) are not essential unless otherwise specified.
  • the same applies to numerical values and ranges thereof, and the present invention is not limited thereto.
  • the term “process” is not limited to an independent process, and is included in this term if the purpose of the process is achieved even when 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 types of substances present in the composition unless there is a specific indication when there are a plurality of types of substances corresponding to the respective components 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.
  • the first passivation layer forming composition of the present embodiment includes a compound represented by the following general formula (I) (hereinafter also referred to as “compound of formula (I)”) and water. Moreover, the 2nd composition for passivation layer formation of this embodiment contains the hydrolyzate of a compound of Formula (I).
  • the first composition for forming a passivation layer and the second composition for forming a passivation layer may be collectively referred to simply as a composition for forming a passivation layer.
  • the composition for forming a passivation layer of the present embodiment may further contain other components as necessary. When the composition for forming a passivation layer according to this embodiment contains the above-described components, it is possible to form a passivation layer having excellent pattern forming properties and excellent passivation effect by a simple method.
  • M represents at least one selected from the group consisting of Al, Nb, Ta, VO, Y, and Hf.
  • R 1 independently represents an alkyl group or an aryl group.
  • m represents an integer of 1 to 5.
  • the first composition for forming a passivation layer contains a compound of formula (I) and water, and water is allowed to act on the compound of formula (I), thereby thixo the composition for forming a passivation layer.
  • the ratio is improved.
  • the second composition for forming a passivation layer contains a hydrolyzate of the compound of formula (I), and the hydrolyzate is prepared by allowing water to act on the compound of formula (I).
  • the second passivation layer forming composition has water acting on the compound of formula (I), so that the thixo ratio of the passivation layer forming composition is as follows. Will improve. As a result, it is surmised that the composition for forming a passivation layer of this embodiment is excellent in pattern formability.
  • the composition for forming a passivation layer of the present embodiment is formed by applying water to the compound of formula (I) to improve its thixotropy and applying the composition for forming a passivation layer on a semiconductor substrate.
  • the shape stability of the composition layer is further improved, and the passivation layer can be formed in a desired shape in the region where the composition layer is formed.
  • At least one of a thixotropic agent and a resin to be described later (hereinafter, at least one of the thixotropic agent and the resin is referred to as a thixotropic agent or the like) in order to express a desired thixotropic property. Even if a thixotropic agent or the like is used, the amount of addition can be reduced as compared with the conventional passivation layer forming composition.
  • the thixotropic agent When forming a passivation layer using a composition for forming a passivation layer containing a thixotropic agent composed of an organic substance, the thixotropic agent is thermally decomposed and scattered from the passivation layer through a degreasing process. Become. However, a thermal decomposition product such as a thixotropic agent may remain as an impurity in the passivation layer even after the degreasing step, and the remaining thermal decomposition product such as a thixotropic agent may cause deterioration of the characteristics of the passivation layer.
  • the thixotropic agent when forming a passivation layer using a composition for forming a passivation layer containing a thixotropic agent composed of an inorganic substance, the thixotropic agent does not scatter and remains in the passivation layer even after a heat treatment (firing) step. The remaining thixotropic agent may cause deterioration of the characteristics of the passivation layer.
  • water or a hydrolyzate of the compound of formula (I) behaves as a thixotropic agent when water acts on the compound of formula (I).
  • Water is more likely to scatter from the passivation layer than a conventional thixotropic agent or the like in a heat treatment (firing) step or the like that is performed when the passivation layer is formed using the passivation layer forming composition. For this reason, it is difficult to cause a decrease in the passivation effect of the passivation layer due to the presence of the residue in the passivation layer.
  • the passivation effect of a semiconductor substrate is obtained by reflecting the effective lifetime of minority carriers in the semiconductor substrate on which the passivation layer is formed using a reflection microwave photoconductive decay method using a device such as WT-2000PVN manufactured by Nippon Semi-Lab. It can evaluate by measuring by.
  • 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 first composition for forming a passivation layer contains at least one compound of formula (I).
  • the second composition for forming a passivation layer contains at least one hydrolyzate of the compound of formula (I).
  • a passivation layer having an excellent passivation effect can be formed when the composition for forming a passivation layer of the present embodiment contains at least one compound of formula (I) or a hydrolyzate thereof. The reason can be considered as follows.
  • a metal oxide formed by heat-treating (firing) a composition for forming a passivation layer containing a compound of formula (I) or a hydrolyzate thereof has defects of metal atoms or oxygen atoms, and generates a fixed charge. It will be easier. When this fixed charge generates charge near the interface of the semiconductor substrate, the concentration of minority carriers can be reduced. As a result, the carrier recombination rate at the interface is suppressed, and an excellent passivation effect is achieved. Conceivable.
  • the cross section of the semiconductor substrate is subjected to electron energy loss spectroscopy (EELS, Electron Energy Loss Spectroscopy) using a scanning transmission electron microscope (STEM, Scanning Transmission Electron Microscope). It can be evaluated by examining the binding mode in the analysis of). 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 a CV method (Capacitance Voltage measurement).
  • M is at least one selected from the group consisting of Al, Nb, Ta, VO, Y, and Hf.
  • the passivation effect, the pattern forming property of the composition for forming a passivation layer, and the passivation From the viewpoint of workability in preparing the layer forming composition, M is preferably at least one selected from the group consisting of Al, Nb, Ta, and Y, and thixo of the passivation layer forming composition. From the viewpoint of properties, Nb is more preferable.
  • each R 1 independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Is more preferable, and an alkyl group having 1 to 4 carbon atoms is still more preferable.
  • the alkyl group represented by R 1 may be linear or branched.
  • alkyl group represented by R 1 examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, A hexyl group, an octyl group, an ethylhexyl group, etc. can be mentioned.
  • aryl group represented by R 1 include a phenyl group.
  • the alkyl group and aryl group represented by R 1 may have a substituent, and examples of the substituent include a methyl group, an ethyl group, an i-propyl group, an amino group, a hydroxy group, a carboxy group, a sulfo group. Group, nitro group and the like.
  • R 1 is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, from the viewpoints of reactivity with water and a passivation effect. preferable.
  • m represents an integer of 1 to 5.
  • m is preferably 3 when M is Al, m is preferably 5 when M is Nb, and M is Ta.
  • m is preferably 5
  • m is preferably 3 when m is VO
  • m is preferably 3 when M is Y
  • M is Hf.
  • m is preferably 4.
  • M is at least one selected from the group consisting of Al, Nb, Ta and Y, R 1 is an unsubstituted alkyl group having 1 to 4 carbon atoms, and m is It is preferably an integer of 1 to 5, more preferably M is Nb, R 1 is an unsubstituted alkyl group having 1 to 4 carbon atoms, and m is 5.
  • the state of the compound of formula (I) may be solid or liquid at 25 ° C.
  • the compound of formula (I) is: It is preferably liquid at 25 ° C.
  • the compounds of formula (I) are specifically aluminum methoxide, aluminum ethoxide, aluminum i-propoxide, aluminum n-propoxide, aluminum n-butoxide, aluminum t-butoxide, aluminum i-butoxide, niobium methoxide.
  • a prepared product or a commercially available product may be used as the compound of formula (I).
  • commercially available products include pentamethoxyniobium, pentaethoxyniobium, penta-i-propoxyniobium, penta-n-propoxyniobium, penta-i-butoxyniobium and penta-n-butoxyniobium from High Purity Chemical Laboratory Co., Ltd.
  • 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
  • the compound of formula (I) is prepared by reacting a specific metal (M) halide with an alcohol in the presence of an inert organic solvent, and further adding ammonia or amines to extract the halogen (specialty).
  • a specific metal (M) halide with an alcohol in the presence of an inert organic solvent, and further adding ammonia or amines to extract the halogen (specialty).
  • Known manufacturing methods such as Japanese Utility Model Laid-Open No. 63-227593 and Japanese Patent Laid-Open No. 3-291247) can be used.
  • a part of the compound of the formula (I) may be contained in the passivation layer forming composition of the present embodiment as a compound having a chelate structure formed by mixing with a compound having a specific structure having two carbonyl groups described later. Good.
  • 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 compound of formula (I) contained in the first composition for forming a passivation layer can be appropriately selected as necessary.
  • the content of the compound of the formula (I) can be 0.1% by mass to 80% by mass in the first composition for forming a passivation layer from the viewpoint of reactivity with water and a passivation effect. It is preferably 5% by mass to 70% by mass, more preferably 1% by mass to 60% by mass, and still more preferably 1% by mass to 50% by mass.
  • the content of the hydrolyzate of the compound of formula (I) contained in the second passivation layer forming composition can be appropriately selected as necessary.
  • the content of the hydrolyzate of the compound of formula (I) can be 0.1% by mass to 80% by mass in the second composition for forming a passivation layer from the viewpoint of the passivation effect, and 0.5% by mass.
  • % To 70% by mass preferably 1% to 60% by mass, and more preferably 1% to 50% by mass.
  • the hydrolyzate of the compound of formula (I) refers to a hydrolysis product of the compound of formula (I) obtained by adding water to the compound of formula (I). In the hydrolyzate of the compound, the compound of formula (I) that has not reacted with water may remain, or water that has not reacted with the compound of formula (I) may remain.
  • the first composition for forming a passivation layer contains water.
  • the composition for forming a passivation layer having excellent pattern forming properties is obtained. The reason can be considered as follows.
  • the hydrolyzate of the compound of formula (I), which is a metal compound formed by reacting water with the compound of formula (I) is considered to form a network with the metal compounds. Further, it is considered that this network is easily broken when the composition for forming a passivation layer is flowing, and is re-formed when the composition becomes stationary again. This network increases the viscosity when the composition for forming a passivation layer is stationary, and decreases the viscosity when the composition is flowing. As a result, it is considered that the composition for forming a passivation layer develops thixotropy necessary for pattern formation.
  • a passivation layer having excellent pattern forming properties By using a composition for forming a passivation layer having excellent pattern forming properties, a passivation layer having a desired shape can be formed. This makes it possible to manufacture an excellent semiconductor substrate with a passivation layer, a solar cell element, and a solar cell.
  • the water state may be solid or liquid. From the viewpoint of miscibility with the compound of formula (I), water is preferably a liquid.
  • the content rate of water contained in the first composition for forming a passivation layer can be appropriately selected as necessary.
  • the water content can be 0.01% by mass or more in the first passivation layer forming composition. It is preferably at least mass%, more preferably at least 0.05 mass%, and even more preferably at least 0.1 mass%.
  • the water content may be 0.01% by mass to 80% by mass in the first composition for forming a passivation layer from the viewpoint of pattern formability and passivation effect, and may be 0.03% by mass to It is preferably 70% by mass, more preferably 0.05% by mass to 60% by mass, and still more preferably 0.1% by mass to 50% by mass.
  • the second composition for forming a passivation layer may contain water.
  • the content rate of water contained in the second composition for forming a passivation layer can be appropriately selected as necessary.
  • the water content can be 0.01% by mass or more in the second passivation layer forming composition. It is preferably at least mass%, more preferably at least 0.05 mass%, and even more preferably at least 0.1 mass%.
  • the water content can be 0.01% by mass to 80% by mass in the second composition for forming a passivation layer and 0.03% by mass to 70% by mass from the viewpoint of pattern formability and passivation effect. %, More preferably 0.05% by mass to 60% by mass, and still more preferably 0.1% by mass to 50% by mass.
  • the amount of water that has acted on the compound of formula (I) in the composition for forming a passivation layer can be calculated from the amount of alcohol liberated from the compound of formula (I).
  • alcohol that is, R 1 OH is liberated from the compound of formula (I).
  • the amount of this liberated alcohol is proportional to the number of functional groups of the compound of formula (I) on which water has acted. Therefore, by measuring the amount of this liberated alcohol, the amount of water acting on the compound of formula (I) can be calculated. The measurement of the amount of alcohol liberated can be confirmed, for example, using gas chromatography mass spectrometry (GC-MS).
  • GC-MS gas chromatography mass spectrometry
  • the content of alcohol contained in the composition for forming a passivation layer, that is, free R 1 OH is preferably 0.5% by mass to 70% by mass, more preferably 1% by mass to 60% by mass, and more preferably 1% by mass to 50% by mass. More preferred is mass%.
  • composition for forming a passivation layer of the present embodiment may contain at least one compound represented by the following general formula (II) (hereinafter referred to as “organoaluminum compound”).
  • each R 2 independently represents an alkyl group.
  • n represents an integer of 1 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.
  • 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. Also, Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi, vol. 97, pp 369-399 (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 as a result of compounding with the compound derived from the formula (I) having a fixed charge or an oxide derived from the hydrolyzate thereof.
  • the passivation effect is further enhanced by the respective effects in the passivation layer.
  • the compound (I) or the hydrolyzate thereof and the organoaluminum compound are heat-treated (fired), whereby the metal (M) and aluminum (Al) contained in the compound (I) are mixed. It is considered that the reactivity as a composite metal alkoxide and physical properties such as vapor pressure are improved, the denseness of the passivation layer as a heat-treated product (baked product) is improved, and as a result, the passivation effect is further enhanced.
  • each R 2 independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more 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 group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, A hexyl group, an octyl group, an ethylhexyl group, etc. can be mentioned.
  • 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 1 to 3. n is preferably 1 or 3 from the viewpoint of storage stability, and more preferably 1 from the viewpoint of solubility.
  • 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. 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 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, hexyl group, octyl group, and ethylhexyl group. be able to.
  • R 3 and R 4 are each independently preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms, and preferably a hydrogen atom or 1 to 4 carbon atoms.
  • the unsubstituted alkyl group is more preferable.
  • R 5 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 a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms. More preferably.
  • the organoaluminum compound is preferably a compound in which n is an integer of 1 to 3, and R 5 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the organoaluminum compound is such that n is an integer of 1 to 3, R 2 is each independently an alkyl group having 1 to 4 carbon atoms, and at least X 2 and X 3 A compound in which one is an oxygen atom, R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable.
  • n is an integer of 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 an alkyl group having 1 to 4 carbon atoms
  • X 2 or X 3 is a methylene group
  • R 3 or R 4 bonded to the methylene group is a hydrogen atom. More preferably, R 5 is a hydrogen atom.
  • organoaluminum compound represented by the general formula (II), where n is an integer of 1 to 3 include aluminum ethyl acetoacetate di-propylate and tris (ethyl acetoacetate) aluminum. .
  • organoaluminum compound represented by the general formula (II) and n being an integer of 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.
  • An organoaluminum compound represented by the general formula (II) and n is an integer of 1 to 3 is prepared by mixing the aluminum trialkoxide and a compound having a specific structure having two carbonyl groups described later. be able to.
  • a commercially available aluminum chelate compound may also be used.
  • the aluminum trialkoxide is mixed with a compound having a specific structure having two carbonyl groups, at least a part of the alkoxide group of the aluminum trialkoxide is substituted with the compound having the specific structure to form an aluminum chelate structure.
  • a liquid medium may be present, and heat treatment, addition of a catalyst, and the like may be performed.
  • the stability of the organoaluminum compound to hydrolysis and polymerization reaction is improved, and the storage stability of the composition for forming a passivation layer containing this is further improved. To do.
  • 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 viewpoint of reactivity and storage stability. preferable.
  • Specific examples of the compound having a specific structure having two carbonyl groups include acetylacetone, 3-methyl-2,4-pentanedione, 2,3-pentanedione, 3-ethyl-2,4-pentanedione, 3- Butyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione ⁇ -diketone compounds such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, i-but
  • the number of aluminum chelate structures can be controlled, for example, by appropriately adjusting the mixing ratio of the 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.
  • organoaluminum compounds from the viewpoint of the passivation effect and the compatibility with the solvent contained as necessary, specifically, at least selected from the group consisting of aluminum ethyl acetoacetate di i-propylate and tri i-propoxy aluminum One is preferably used, and aluminum ethyl acetoacetate di i-propylate 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, the homogeneity of the formed passivation layer is further improved by using an organoaluminum compound having good stability at room temperature (25 ° C.) and solubility or dispersibility. A desired passivation effect can be stably obtained.
  • the content of the organoaluminum compound is not particularly limited.
  • the content of the organoaluminum compound when the total content of the compound of formula (I) or a hydrolyzate thereof and the organoaluminum compound is 100% by mass is 0.5% by mass to 80% by mass. It is preferably 1% by mass to 75% by mass, more preferably 2% by mass to 70% by mass, and particularly preferably 3% by mass to 70% by mass.
  • the content of the organoaluminum compound in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the content of the organoaluminum compound may be 0.1% by mass to 60% by mass in the composition for forming a passivation layer, and 0.5% by mass to 55% by mass from the viewpoint of storage stability and a passivation effect. It is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 45% by mass.
  • the composition for forming a passivation layer of this embodiment may contain a liquid medium (solvent or dispersion medium).
  • a liquid medium solvent or dispersion medium
  • the viscosity can be easily adjusted, the impartability can be further improved, and a more uniform passivation layer can be formed.
  • the liquid medium is not particularly limited and can be appropriately selected as necessary. Among these, a liquid medium capable of dissolving the compound of formula (I) and the organoaluminum compound added as necessary to give a uniform solution is preferable, and more preferably containing at least one organic solvent.
  • a liquid medium means a medium in a liquid state at room temperature (25 ° C.).
  • liquid medium examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl i-propyl ketone, methyl-n-butyl ketone, methyl i-butyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, Ketone solvents such as diethyl ketone, di-n-propyl ketone, di-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diethyl ether, methyl ethyl ether, methyl -N-propyl ether, di-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol
  • 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 viewpoint of impartability to a semiconductor substrate and pattern formation, and is selected from the group consisting of a terpene solvent. More preferably, it contains at least one selected from the above.
  • the content of the liquid medium is determined in consideration of the imparting property, pattern forming property, and storage stability.
  • the content of the liquid medium is preferably 5% by mass to 98% by mass with respect to the total mass of the composition for forming a passivation layer, from the viewpoint of impartability of the composition and pattern formability, and is preferably 10% by mass to More preferably, it is 95 mass%.
  • the composition for forming a passivation layer of the present embodiment may further contain at least one resin.
  • the composition stability of the composition layer formed by applying the composition for forming a passivation layer of this embodiment on a semiconductor substrate is further improved, and the composition layer is formed as a passivation layer.
  • the region can be formed in a desired 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 when the composition for forming a passivation layer of the present embodiment is applied on a semiconductor substrate.
  • 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. . These resins are used singly or in combination of two or more.
  • (meth) acryl represents acryl or methacryl
  • (meth) acrylate represents acrylate or methacrylate.
  • the molecular weight of these resins is not particularly limited, and it is preferable to adjust appropriately in view of the 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 viewpoint 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 composition for forming a passivation layer of this embodiment is excellent in thixotropy, it is not necessary to develop thixotropy with a resin.
  • the content of the resin contained in the composition for forming a passivation layer of the present embodiment is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, It is particularly preferable that the resin is substantially not contained.
  • the composition for forming a passivation layer of the present embodiment can further contain other components that are usually used in the field as necessary, in addition to the components described above.
  • the composition for forming a passivation layer of this embodiment 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.
  • acidic compounds include Bronsted acid and Lewis acid.
  • inorganic acids such as hydrochloric acid and nitric acid
  • organic acids such as acetic acid
  • basic compounds include Bronsted bases and Lewis bases.
  • examples of the basic compound include inorganic bases such as alkali metal hydroxides and alkaline earth metal hydroxides, and organic bases such as trialkylamine and pyridine.
  • examples of other components include plasticizers, dispersants, surfactants, thixotropic agents, other metal alkoxide compounds, and high-boiling materials.
  • plasticizers dispersants, surfactants, thixotropic agents, other metal alkoxide compounds, and high-boiling materials.
  • the shape stability of the composition layer formed by applying the composition for forming a passivation layer of the present embodiment on a semiconductor substrate is further improved, and the passivation layer is formed. It can be formed in a desired shape in the region where the composition layer is formed.
  • thixotropic agent examples include fatty acid amides, polyalkylene glycol compounds, organic fillers, and inorganic fillers.
  • polyalkylene glycol compound examples include compounds represented by the following general formula (III).
  • R 6 and R 7 each independently represent a hydrogen atom or an alkyl group, and R 8 represents an alkylene group.
  • n is an arbitrary integer of 3 or more.
  • R 8 in the presence of a plurality of (O-R 8) may or may not be the same.
  • Examples of the fatty acid amide include compounds represented by the following general formulas (1), (2), (3) and (4).
  • R 9 CONH 2 (1) R 9 CONH-R 10 -NHCOR 9 (2) R 9 NHCO—R 10 —CONHR 9 (3) R 9 CONH—R 10 —N (R 11 ) 2 ... (4)
  • R 9 and R 11 each independently represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and R 10 represents 1 to 10 carbon atoms. Represents an alkylene group. R 9 and R 11 may be the same or different.
  • organic filler examples include acrylic resin, cellulose resin, and polystyrene resin.
  • the inorganic filler examples include particles such as silicon dioxide, aluminum hydroxide, aluminum nitride, silicon nitride, aluminum oxide, zirconium oxide, silicon carbide, and glass.
  • the volume average particle diameter of the organic filler or inorganic filler is preferably 0.01 ⁇ m to 50 ⁇ m.
  • the volume average particle diameter of the filler can be measured by a laser diffraction scattering method.
  • metal alkoxide compounds include titanium alkoxide, zirconium alkoxide, silicon alkoxide and the like.
  • the composition for forming a passivation layer according to the present embodiment does not require a thixotropic agent for imparting thixotropy, shape stability, or the like, or can reduce the amount of use thereof.
  • a thixotropic agent for imparting thixotropy, shape stability, or the like.
  • the mass after the heat treatment compared with the mass before the heat treatment is compared with the conventional composition for forming a passivation layer containing a thixotropic agent or the like.
  • the rate is low. This is because water is likely to be scattered from the composition for forming a passivation layer as compared with a conventional thixotropic agent or the like by heat treatment at 150 ° C. for 3 hours.
  • the composition for forming a passivation layer of the present embodiment is calculated by dividing the mass M1 when heated at 150 ° C. for 3 hours by the mass M2 when not heated (M1 / M2). ) Is 0.0001 to 0.7, and the shear viscosity ⁇ 1 at a shear rate of 0.1 s ⁇ 1 at 25 ° C. in the solid content range is the shear viscosity ⁇ 2 at a shear rate of 10.0 s ⁇ 1
  • the thixo ratio ( ⁇ 1 / ⁇ 2) calculated by dividing is preferably 1.05 to 100, and more preferably 1.1 to 50. The shear viscosity is measured at a temperature of 25 ° C.
  • the ratio (M1 / M2) is preferably 0.0005 to 0.6, and more preferably 0.001 to 0.5.
  • the composition for forming a passivation layer of this embodiment is calculated by dividing the shear viscosity ⁇ 1 at 25 ° C. at a shear rate of 0.1 s ⁇ 1 by the shear viscosity ⁇ 2 at a shear rate of 10.0 s ⁇ 1.
  • the thixo ratio ( ⁇ 1 / ⁇ 2) is preferably 1.05 to 100, and more preferably 1.1 to 50.
  • the composition for forming a passivation layer of the present embodiment has a ratio (M1 / M2) calculated by dividing the mass M1 when heated at 150 ° C. for 3 hours by the mass M2 when not heated. It is preferably 0.0001 to 0.7, more preferably 0.0005 to 0.6, and still more preferably 0.001 to 0.5.
  • a high boiling point material may be used as a material together with or instead of the resin.
  • the high boiling point material is preferably a compound that is easily vaporized when heated and does not need to be degreased.
  • the high boiling point material is particularly preferably a high boiling point material having a high viscosity capable of maintaining a printed shape after printing and coating.
  • An example of a material that satisfies these conditions is isobornylcyclohexanol.
  • Isobornyl cyclohexanol is commercially available as “Telsolve MTPH” (Nippon Terpene Chemical Co., Ltd., trade name). Isobornyl cyclohexanol has a high boiling point of 308 ° C. to 318 ° C. When it is removed from the composition layer, it does not need to be degreased by heat treatment (firing) like a resin, but is vaporized by heating. Can be eliminated. For this reason, most of the solvent and isobornyl cyclohexanol contained in the composition for forming a passivation layer as necessary can be removed in the drying step after coating on the semiconductor substrate.
  • the content of the high boiling point material is preferably 3% by mass to 95% by mass in the total mass of the passivation layer forming composition. It is more preferably 5% by mass to 90% by mass, and further preferably 7% by mass to 80% by mass.
  • the composition for forming a passivation layer of the present embodiment contains at least one oxide selected from the group consisting of Al, Nb, Ta, V, Y, and Hf (hereinafter referred to as “specific oxide”). May be. Since the specific oxide is an oxide generated by heat-treating (sintering) the compound of formula (I), the passivation layer formed from the composition for forming a passivation layer containing the specific oxide has an excellent passivation effect. Is expected to be played.
  • the viscosity of the composition for forming a passivation layer of the present embodiment is not particularly limited, and can be appropriately selected according to a method for applying to the semiconductor substrate.
  • the viscosity of the composition for forming a passivation layer may be 0.01 Pa ⁇ s to 100,000 Pa ⁇ s.
  • the viscosity of the composition for forming a passivation layer is preferably 0.1 Pa ⁇ s to 10,000 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 passivation layer formation of this embodiment can be produced by mixing the compound of formula (I), water, and an organoaluminum compound, a liquid medium, a resin, and the like, which are included as necessary, by a commonly used mixing method.
  • the components contained in the composition for forming a passivation layer of the present embodiment, and the content of each component include thermal analysis such as TG / DTA, spectral analysis such as NMR and IR, and chromatographic analysis such as HPLC and GPC. Can be used to confirm.
  • the semiconductor substrate with a passivation layer of the present embodiment includes a semiconductor substrate and a passivation layer that is a heat treatment product of the composition for forming a passivation layer of the present embodiment provided on at least a part of at least one surface of the semiconductor substrate.
  • the semiconductor substrate with a passivation layer of the present embodiment exhibits an excellent passivation effect by having a passivation layer that is a heat-treated product of the composition for forming a passivation layer of the present embodiment.
  • the semiconductor substrate is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • Examples of the semiconductor substrate include those obtained by doping (diffusing) p-type impurities or n-type impurities into silicon, germanium, or the like. Of these, a silicon substrate is preferable.
  • the semiconductor substrate may be a p-type semiconductor substrate or an n-type semiconductor substrate. Among these, from the viewpoint of the passivation effect, it is preferable that 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.
  • 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 thickness 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 formed passivation layer was measured by measuring the thickness at three points by an ordinary method using an interference film thickness meter (for example, Filmetrics F20 film thickness measurement system), and the arithmetic average value thereof Calculated.
  • the semiconductor substrate with a passivation layer of the present embodiment can be applied to a solar cell element, a light emitting diode element, or the like.
  • the solar cell element excellent in conversion efficiency can be obtained by applying to a solar cell element.
  • the method for manufacturing a semiconductor substrate with a passivation layer of the present embodiment includes a step of forming the composition layer by applying the passivation layer forming composition of the present embodiment to at least a part of at least one surface of the semiconductor substrate; Forming a passivation layer by heat-treating (sintering) the composition layer.
  • the manufacturing method may further include other steps as necessary.
  • the method for manufacturing a semiconductor substrate with a passivation layer of this embodiment 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 passivation layer forming composition of the present embodiment 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.
  • a cleaning method using an alkaline aqueous solution a generally known cleaning method using RCA cleaning or the like can be exemplified.
  • 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 of the present embodiment on the semiconductor substrate is not particularly limited.
  • a method of applying the passivation layer forming composition of the present embodiment on a semiconductor substrate using a known coating method can be exemplified.
  • Specific examples include an immersion method, a screen printing method, an inkjet method, a dispenser method, a spin coating method, a brush coating method, a spray method, a doctor blade method, and a roll coating method.
  • a screen printing method, an inkjet method, and the like are preferable.
  • the application amount of the composition for forming a passivation layer of the present embodiment can be appropriately selected according to the purpose.
  • the thickness of the passivation layer to be formed can be appropriately adjusted so as to have a desired thickness.
  • 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 (fired material layer) derived from the composition layer. can do.
  • the heat treatment (firing) conditions of the composition layer are the compound (I) contained in the composition layer and, if necessary, the organoaluminum compound, a metal oxide or composite oxide that is the heat treated product (firing product). There is no particular limitation as long as it can be converted to.
  • the heat treatment (firing) temperature is preferably 300 ° C.
  • the heat treatment (firing) time can be appropriately selected according to the heat treatment (firing) temperature and the like. For example, it can be 0.1 to 10 hours, and preferably 0.2 to 5 hours.
  • the passivation layer is formed before the step of forming the passivation layer by heat treatment (firing). You may further have the process of carrying out the drying process of the composition layer which consists of a composition for medical purposes. 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 capable of removing at least a part of water contained in the composition for forming a passivation layer and at least a part of a liquid medium that may be contained in the composition for forming a passivation layer.
  • 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 method for manufacturing a semiconductor substrate with a passivation layer is applied before the step of forming the passivation layer by heat treatment (firing) after applying the composition for forming a passivation layer.
  • the step of degreasing the composition layer is not particularly limited as long as at least part of the resin that may be 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 3 minutes to 120 minutes, preferably a heat treatment at 250 ° C. to 450 ° C. for 10 minutes to 120 minutes, and 300 ° C. to 400 ° C. for 3 minutes. A heat treatment of ⁇ 60 minutes is also preferable.
  • the degreasing treatment is preferably performed in the presence of oxygen, and more preferably performed in the air.
  • the solar cell element according to the present embodiment is provided on at least a part of a semiconductor substrate having a pn junction part in which a p-type layer and an n-type layer are pn-junction, and at least one surface of the semiconductor substrate.
  • a passivation layer which is a heat treatment product of the passivation layer forming composition, and an electrode disposed on at least one of the p-type layer and the n-type layer.
  • the solar cell element of this embodiment may further have other components as necessary.
  • the solar cell element of this embodiment is excellent in conversion efficiency by having the passivation layer formed from the composition for forming a passivation layer of this embodiment.
  • the semiconductor substrate to which the composition for forming a passivation layer of this embodiment is applied is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • the semiconductor substrate those described in the section of the semiconductor substrate with a passivation layer of the present embodiment can be used, and those that can be suitably used are also the same.
  • the surface of the semiconductor substrate on which the passivation layer of this embodiment is provided is preferably the back 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 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 passivation layer of the present embodiment is formed on at least a part of at least one surface of a semiconductor substrate having a pn junction formed by pn junction of a p-type layer and an n-type layer. Applying a composition for forming a composition layer, heat-treating (firing) the composition layer to form a passivation layer, and on at least one of the p-type layer and the n-type layer And a step of disposing an electrode.
  • the manufacturing method of the solar cell element of this embodiment may further have other processes as needed.
  • a solar cell element excellent in conversion efficiency can be produced by a simple method.
  • an electrode can be manufactured by applying a paste for forming an electrode 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 of this embodiment 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 of the present embodiment are the same as those of the method for manufacturing a semiconductor substrate with a passivation layer described above, and the preferred embodiments are also the same.
  • FIG. 1 is a cross-sectional view schematically showing an example of a method for producing a solar cell element having a passivation layer according to the present 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.
  • a cleaning method using an alkaline aqueous solution a method using generally known RCA cleaning and the like can be mentioned.
  • 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 (i-propyl alcohol) can be used.
  • an n + -type diffusion layer 2 is formed with a thickness on the order of submicrons, 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 Pullasma Enhanced Chemical Vapor Deposition
  • the passivation layer forming composition of the present embodiment 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 300 ° C. to 900 ° C. ) To form a passivation layer 5.
  • FIG. 5 an example of the formation pattern of the passivation layer 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 back surface passivation layer 5 is formed in a dot shape except for the portion where the back surface output extraction electrode 7 is formed in a later step.
  • the pattern 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.
  • the dot diameter (L a ) and the dot interval (L b ) can be set arbitrarily, but from the viewpoint of suppressing the passivation effect and minority carrier recombination, L a should be 5 ⁇ m to 2 mm and L b should be 10 ⁇ m to 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.
  • the dot diameter (L a ) and the dot interval (L b ) are more regularly arranged in this dot-like opening pattern. For this reason, a preferable dot-shaped opening pattern can be formed by suppressing minority carrier recombination, and the power generation efficiency of the solar cell element is improved.
  • a passivation layer having a desired shape is formed by applying the passivation layer forming composition to a portion where the passivation layer is to be formed (portion other than the dot-shaped opening) and heat-treating (sintering).
  • the passivation layer forming composition can be applied to the entire surface including the dot-shaped opening, and the passivation layer in the dot-shaped opening can be selectively removed by laser, photolithography, etc. after heat treatment (firing).
  • the passivation layer forming composition can be selectively applied by previously masking a portion such as a dot-shaped opening where the passivation layer forming composition is not desired to be applied with a mask material.
  • 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. In order to secure a light receiving area, it is necessary to suppress the formation area of these light receiving surface electrodes.
  • the width of the light receiving surface current collecting electrode 8 is preferably 10 ⁇ m to 250 ⁇ m, and the width of the light receiving surface output extraction electrode 9 is preferably 100 ⁇ m to 2 mm.
  • 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, but 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 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.
  • the passivation layer forming composition of the present embodiment which is excellent in pattern formability, a passivation layer excellent in the passivation effect can be formed by a simple method, and a solar cell element excellent in power generation performance is obtained. 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. After that, the solar cell element 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)).
  • a composition for forming a passivation layer is applied.
  • 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.
  • p + -type diffusion layer 10 Form.
  • a method of treating at a temperature around 1000 ° C. in a gas containing boron trichloride (BCl 3 ) can be used.
  • the method of gas diffusion is the same as in the case of using phosphorus oxychloride, the p + -type diffusion layer 10 is formed on the light receiving surface, the back surface, and the side surface of the substrate. It is necessary to take measures such as masking the portions other than the openings to prevent boron from diffusing into unnecessary portions of the p-type semiconductor substrate 1.
  • the aluminum paste is applied to the dot-shaped opening, and this is heat-treated (fired) at a temperature of 450 ° C. to 900 ° C. It is possible to use a technique in which aluminum is diffused from the opening to form the p + -type diffusion layer 10 and then a heat treatment product layer (baked product layer) made of an aluminum paste on the p + -type diffusion layer 10 is etched with hydrochloric acid or the like. it can.
  • the aluminum electrode 11 for backside current collection is formed by physically depositing aluminum on the entire backside.
  • a silver electrode paste containing glass particles forming the light receiving surface collecting electrode 8 and the light receiving surface output extraction electrode 9 is applied to the light receiving surface by screen printing or the like.
  • a silver electrode paste containing glass particles for forming the back surface output extraction electrode 7 is applied 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 both 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 output extraction electrode 7 is formed on the back surface.
  • 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 aluminum electrode 11 and the back surface output extraction electrode 7 formed by vapor deposition are electrically connected on the back surface. Is done.
  • the solar cell of the present embodiment includes at least one of the solar cell elements of the present embodiment, and is configured by arranging a wiring material on the electrode of the solar cell element. That is, the solar cell of this embodiment has the solar cell element and a wiring material disposed on the electrode of the solar cell element.
  • the solar cell of the present embodiment is further configured by connecting a plurality of solar cell elements via a wiring material and further sealing with a sealing material as necessary.
  • the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in the technical field.
  • composition 1 for forming a passivation layer 6.074 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2), terpineol (Nippon Terpene Chemical Co., Ltd., sometimes abbreviated as TPO) After mixing 16.930 g of 5.930 g and isobornylcyclohexanol (Nippon Terpene Chemical Co., Ltd., sometimes abbreviated as tersolve) and kneading for 5 minutes, 1.412 g of pure water is added and kneading is further performed for 5 minutes. Then, a composition 1 for forming a passivation layer was prepared.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2
  • the shear viscosity of the composition 1 for forming a passivation layer prepared above was attached to a rotary shear viscometer (AntonPaar, MCR301) with a cone plate (diameter 50 mm, cone angle 1 °) at a temperature of 25 ° C. Measurements were made under conditions of speeds of 0.1 s ⁇ 1 and 10.0 s ⁇ 1 , respectively.
  • the shear viscosity ( ⁇ 1 ) at a shear rate of 0.1 s ⁇ 1 was 47400 Pa ⁇ s
  • the shear viscosity ( ⁇ 2 ) at a shear rate of 10.0 s ⁇ 1 was 4250 Pa ⁇ s.
  • the thixo ratio ( ⁇ 1 / ⁇ 2 ) when the shear rate was 0.1 s ⁇ 1 and 10.0 s ⁇ 1 was 11.2.
  • a single crystal p-type silicon substrate (50 mm square, thickness 770 ⁇ m, hereinafter simply referred to as a silicon substrate) is used as the semiconductor substrate. did.
  • the prepared composition 1 for forming a passivation layer was printed on the entire surface of the silicon substrate except for the dot-shaped openings with the pattern shown in FIG. 8 using a screen printing method.
  • the dot-like opening pattern used in the evaluation has a dot diameter (L a ) of 714 ⁇ m, a dot interval (L b ) of 2.0 mm, a dot diameter (L a ) of 535 ⁇ m, and a dot interval (L b ).
  • the silicon substrate provided with the composition 1 for forming a passivation layer was heated at 150 ° C. for 5 minutes to dry the liquid medium by evaporating.
  • the silicon substrate was heat-treated (baked) at a temperature of 700 ° C. for 10 minutes and then allowed to cool at room temperature (25 ° C.).
  • the heat treatment (firing) was performed using a diffusion furnace (ACCURON CQ-1200, Hitachi Kokusai Electric Co., Ltd.) under atmospheric conditions under conditions of a maximum temperature of 700 ° C. and a holding time of 10 minutes.
  • the dot diameter (L a ) of the dot-shaped opening in the passivation layer formed on the substrate after heat treatment (firing) was measured, and the dot diameter (L a ) was measured at 10 points. The average value was calculated.
  • the change rate of the dot diameter (L a ) after heat treatment (firing) is less than 15% A, B is 15% or more and less than 30% B, 30% or more was evaluated as C. If evaluation is A or B, the pattern formability of the composition for forming a passivation layer is good.
  • the prepared composition 1 for forming a passivation layer was printed on the entire surface of a silicon substrate using a screen printing method. Then, the silicon substrate provided with the composition 1 for forming a passivation layer was heated at 150 ° C. for 5 minutes to dry the liquid medium by evaporating. Thereafter, the other surface of the silicon substrate was printed and dried. Next, the silicon substrate was heat-treated (baked) at a temperature of 700 ° C. for 10 minutes and then allowed to cool at room temperature (25 ° C.). The heat treatment (firing) was performed using a diffusion furnace (ACCURON CQ-1200, Hitachi Kokusai Electric Co., Ltd.) in an air atmosphere at a maximum temperature of 700 ° C. and a holding time of 10 minutes.
  • a diffusion furnace ACCURON CQ-1200, Hitachi Kokusai Electric Co., Ltd.
  • the effective lifetime of the evaluation substrate obtained above was measured by a reflected microwave photoconductive decay method at room temperature (25 ° C.) using a lifetime measuring device (Nippon Semi-Lab Co., Ltd., WT-2000PVN).
  • the effective lifetime of the region to which the passivation layer forming composition was applied was 325 ⁇ 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 20 minutes to form n + -type diffusion layers on the light receiving surface, the back surface, and the side surface.
  • 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 1 was formed by performing heat treatment (baking) under the conditions of a maximum temperature of 700 ° C. and a holding time of 10 minutes in an atmospheric atmosphere using Hitachi Kokusai Electric). 5, 7, and 8, the back surface passivation layer 1 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 the smallest one used in the evaluation of pattern formability, the dot diameter (L a ) is 178 ⁇ 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 collecting electrode having a width of 120 ⁇ m and a light receiving surface output extraction electrode having a width of 1.5 mm, and printing conditions (for the screen plate) so that the thickness after heat treatment (firing) is 20 ⁇ m.
  • the 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.
  • a wiring member (solder-plated rectangular wire for solar cell, product name: SSA-TPS 0.2 ⁇ 1.5 (20 ), A copper wire with a thickness of 0.2 mm and a width of 1.5 mm is plated with Sn-Ag-Cu lead-free solder with a maximum thickness of 20 ⁇ m per side, Hitachi Metals, Ltd.) Using the device (NTS-150-M, Tabbing & Stringing Machine, NPC, Inc.) and melting the solder under the conditions of a maximum temperature of 250 ° C. and a holding time of 10 seconds, the wiring member and the light receiving surface output extraction electrode and The back surface output extraction electrode was connected.
  • 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. (Curve 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 R1) produced in Reference Example 1 shown later as 100.0.
  • Example 2 Aluminum ethyl acetoacetate di-i-propylate (Kawaken Fine Chemical Co., Ltd., trade name: ALCH) was added to the composition for forming a passivation layer. Specifically, the content of each component was 2.997 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2), and 5.910 g of terpineol.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2
  • Example 2 In the same manner as in Example 1 except that the isobornylcyclohexanol was changed to 16.700 g, aluminum ethyl acetoacetate di-i-propylate was changed to 3.010 g, and pure water was changed to 1.404 g. Composition 2 was prepared. Thereafter, in the same manner as in Example 1, evaluation of the thixotropy, evaluation of pattern formation, and evaluation of effective lifetime of the composition 2 for forming a passivation layer were performed. Further, in the same manner as in Example 1, the solar cell element 2 and the solar cell 2 were produced, and the power generation performance was evaluated.
  • Example 3 In Example 1, aluminum sec-butoxide (Kawaken Fine Chemical Co., Ltd., trade name: ASBD) was added to the composition for forming a passivation layer. Specifically, the content of each component is 3.181 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2), and 6.004 g of terpineol. A composition 3 for forming a passivation layer was prepared in the same manner as in Example 1 except that 16.822 g of isobornylcyclohexanol, 3.214 g of aluminum sec-butoxide, and 3.447 g of pure water were changed.
  • Example 1 Evaluation of the thixotropy, evaluation of pattern formation, and evaluation of effective lifetime of the composition 3 for forming a passivation layer were performed. Furthermore, it carried out similarly to Example 1, the solar cell element 3 and the solar cell 3 were produced, and electric power generation performance was evaluated.
  • Example 4 In Example 1, the blending amount was changed. Specifically, pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2) is contained in 5.986 g, and terpineol is contained in 5.889 g.
  • a composition 4 for forming a passivation layer was prepared in the same manner as in Example 1, except that 16.638 g of isobornylcyclohexanol and 0.999 g of pure water were changed. Thereafter, in the same manner as in Example 1, evaluation of the thixotropy of the composition 4 for forming a passivation layer, evaluation of pattern formation, and evaluation of effective lifetime were performed. Further, in the same manner as in Example 1, the solar cell element 4 and the solar cell 4 were produced, and the power generation performance was evaluated.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 )
  • Example 5 In Example 2, the blending amount was changed. Specifically, the content of each component was 3.057 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2), and 6.272 g of terpineol. In the same manner as in Example 1, except that 17.740 g of isobornylcyclohexanol, 3.121 g of aluminum ethyl acetoacetate di-i-propylate, and 1.072 g of pure water were changed. Composition 5 was prepared.
  • Example 1 Thereafter, in the same manner as in Example 1, evaluation of thixotropy, pattern formation, and effective lifetime of the composition 5 for forming a passivation layer were performed. Further, in the same manner as in Example 1, the solar cell element 5 and the solar cell 5 were produced, and the power generation performance was evaluated.
  • Example 6 In Example 3, the blending amount was changed. Specifically, the content of each component was 2.816 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2), and 5.763 g of terpineol.
  • a composition 6 for forming a passivation layer was prepared in the same manner as in Example 1 except that 16.239 g of isobornylcyclohexanol, 2.795 g of aluminum sec-butoxide, and 0.956 g of pure water were changed. did.
  • Example 1 Thereafter, in the same manner as in Example 1, evaluation of the thixotropy of the composition 6 for forming a passivation layer, evaluation of pattern formation, and evaluation of effective lifetime were performed. Further, in the same manner as in Example 1, the solar cell element 6 and the solar cell 6 were produced, and the power generation performance was evaluated.
  • Example 1 In the preparation of the passivation layer forming composition in Example 2, pure water was not used. Specifically, the content of each component was 2.928 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.2), and 6.489 g of terpineol.
  • a passivation layer forming composition R1 was prepared in the same manner as in Example 1 except that 17.535 g of isobornylcyclohexanol and 2.950 g of aluminum ethyl acetoacetate di-propylate were changed.
  • Example 2 Thereafter, in the same manner as in Example 1, evaluation of the thixotropy of the composition R1 for forming a passivation layer, evaluation of pattern formation, and evaluation of effective lifetime were performed. Further, in the same manner as in Example 1, a solar cell element R1 and a solar cell R1 were produced, and the power generation performance was evaluated.
  • Example 2 In the preparation of the composition for forming a passivation layer in Example 2, the compound represented by the formula (I) was not used. Specifically, the content of each component was changed to 6.419 g of terpineol, 17.217 g of isobornylcyclohexanol, 3.268 g of aluminum ethyl acetoacetate di-i-propylate, and 1.495 g of pure water.
  • a composition R2 for forming a passivation layer was prepared in the same manner as in Example 1 except that. Thereafter, in the same manner as in Example 1, evaluation of the thixotropy, pattern formation, and effective lifetime of the passivation layer forming composition R2 were performed. Further, in the same manner as in Example 1, a solar cell element R2 and a solar cell R2 were produced, and the power generation performance was evaluated.
  • Example 1 In the preparation of the composition for forming a passivation layer in Example 1, the compound represented by the formula (I) was not used. Specifically, passivation was performed in the same manner as in Example 1 except that the content of each component was changed to 6.015 g of terpineol, 16.815 g of isobornylcyclohexanol, and 1.423 g of pure water. A layer forming composition C1 was prepared. Thereafter, in the same manner as in Example 1, evaluation of the thixotropy, pattern formation, and effective lifetime of the passivation layer forming composition C1 were performed. Further, in the same manner as in Example 1, a solar cell element C1 and a solar cell C1 were produced, and power generation performance was evaluated.
  • Table 1 shows the composition of each composition for forming a passivation layer.
  • Table 2 shows the evaluation results of the thixo ratio, the pattern forming property, the effective lifetime, and the power generation performance of the solar cell of the compositions for forming a passivation layer implemented in Examples 1 to 6, Reference Examples 1 and 2, and Comparative Example 1. Show. It was found that the passivation layer forming compositions prepared in Examples 1 to 6 have good thixotropy and pattern formability.
  • the power generation performance of the produced solar cell tended to be relatively high when the composition for forming a passivation layer containing the compound of formula (I) and water was used. This is because, as described above, the composition for forming a passivation layer contains the compound of formula (I) and water, so that the pattern formability is improved and the dot diameter defining the pattern of the passivation layer at the time of solar cell production This is probably because the size of (L a ) was maintained and the contact area ratio between the aluminum electrode paste and the semiconductor substrate was maintained.
  • the power generation performance of the produced solar cell tended to be relatively high when the passivation layer forming composition containing both the compound of formula (I) and the organoaluminum compound was used.
  • the passivation layer forming composition containing both the compound of formula (I) and the organoaluminum compound was used.
  • a composite oxide of metal and aluminum derived from the compound of formula (I) is formed by heat treatment (firing). It is considered that the passivation effect is further improved by forming a denser passivation layer having a large negative fixed charge.
  • the power generation performance of the solar cell produced in Comparative Example 1 was found to be lower than those of Reference Examples 1 and 2 and Examples 1-6.
  • the passivation layer forming composition C1 does not contain the compound of formula (I), and a sufficient passivation effect was not obtained from the film formed by heat-treating (firing) them. It is done.
  • the entire disclosure of Japanese Patent Application No. 2014-138951 filed on July 4, 2014 is incorporated herein by reference.
  • all the documents, patent applications, and technical standards described in this specification are the same as when individual documents, patent applications, and technical standards are specifically and individually described to be incorporated by reference. Which is incorporated herein by reference.

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Abstract

L'invention concerne une première composition de formation d'une couche de passivation, qui contient un composé représenté par la formule générale (I) et de l'eau ; et une seconde composition de formation d'une couche de passivation, qui contient un produit d'hydrolyse d'un composé représenté par la formule générale (I). M(OR1)m formule générale (I) (Dans la formule générale (I), M représente au moins une substance choisie dans le groupe constitué par Al, Nb, Ta, VO, Y et Hf ; chaque R1 représente indépendamment un groupe alkyle ou un groupe aryle ; et m représente un nombre entier de 1 à 5.)
PCT/JP2015/069192 2014-07-04 2015-07-02 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 Ceased WO2016002901A1 (fr)

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KR1020177002522A KR20170026538A (ko) 2014-07-04 2015-07-02 패시베이션층 형성용 조성물, 패시베이션층이 형성된 반도체 기판 및 그의 제조 방법, 태양 전지 소자 및 그의 제조 방법, 및 태양 전지
JP2016531454A JP6658522B2 (ja) 2014-07-04 2015-07-02 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、太陽電池素子及びその製造方法、並びに太陽電池
CN201580035295.9A CN106471626A (zh) 2014-07-04 2015-07-02 钝化层形成用组合物、带钝化层半导体基板及制法、太阳能电池元件及制法及太阳能电池

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WO2014014115A1 (fr) * 2012-07-19 2014-01-23 日立化成株式会社 Substrat semi-conducteur à couche de passivation et son procédé de fabrication
WO2014014110A1 (fr) * 2012-07-19 2014-01-23 日立化成株式会社 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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018003142A1 (fr) * 2016-06-28 2018-01-04 日立化成株式会社 Composition pour formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire

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CN106471626A (zh) 2017-03-01
JPWO2016002901A1 (ja) 2017-04-27

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