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WO2016002902A1 - Procede de production d'une composition pour la formation d'une couche de passivation, substrat semi-conducteur pourvu d'une couche de passivation, procede de fabrication de celui-ci, element de cellule solaire, procede de fabrication de celui-ci et cellule solaire - Google Patents

Procede de production d'une composition pour la formation d'une couche de passivation, substrat semi-conducteur pourvu d'une couche de passivation, procede de fabrication de celui-ci, element de cellule solaire, procede de fabrication de celui-ci et cellule solaire Download PDF

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WO2016002902A1
WO2016002902A1 PCT/JP2015/069193 JP2015069193W WO2016002902A1 WO 2016002902 A1 WO2016002902 A1 WO 2016002902A1 JP 2015069193 W JP2015069193 W JP 2015069193W WO 2016002902 A1 WO2016002902 A1 WO 2016002902A1
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Prior art keywords
passivation layer
composition
forming
semiconductor substrate
layer
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Japanese (ja)
Inventor
田中　徹
吉田　誠人
野尻　剛
倉田　靖
真年 森下
児玉　俊輔
剛 早坂
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Resonac Corp
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Hitachi Chemical Co Ltd
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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
    • 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 method for manufacturing a composition for forming a passivation layer, a semiconductor substrate with a passivation layer and its manufacturing method, a solar cell element and its manufacturing method, and a solar cell.
  • a texture structure is formed on the front surface (light-receiving surface and / or back surface) of the p-type silicon substrate so as to promote the light confinement effect and increase the efficiency.
  • a treatment for several tens of minutes is 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 surface of the p-type silicon substrate. .
  • the n-type diffusion layer formed on the side surface of the p-type silicon substrate is removed by side etching or the like.
  • the n-type diffusion layer formed on the back surface of the p-type silicon substrate needs to be converted into a p + -type diffusion layer. Therefore, an aluminum paste containing aluminum powder and a binder is applied to the entire back surface, and this is heat-treated (fired) to convert the n-type diffusion layer into a p + -type diffusion layer called BSF (Back Surface Field). At the same time, an ohmic contact is obtained by forming an aluminum electrode.
  • BSF Back Surface Field
  • an aluminum electrode formed from an aluminum paste has low conductivity.
  • the aluminum electrode generally formed on the entire back surface must have a thickness of about 10 ⁇ m to 20 ⁇ m after heat treatment (firing).
  • 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.
  • the Al—Si alloy formed at the interface between the BSF or the aluminum electrode and silicon has light absorption, this alloy layer is a major factor for reducing the power generation efficiency.
  • 3107287 discloses a point contact technique in which an aluminum paste is applied to a part of a silicon substrate surface to partially form a p + -type diffusion layer and an aluminum electrode. Proposed.
  • 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.
  • Thin Solid Films, 517 (2009), 6327-6330 and Chinese Physics Letters, 26 (2009), 088102-1 to 088102-4 include sol-gel. A method by law has been proposed.
  • 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 method for producing a composition.
  • one embodiment of the present invention is a semiconductor substrate with a passivation layer obtained using the composition for forming a passivation layer manufactured by the manufacturing method, and having a passivation layer having an excellent passivation effect, a manufacturing method thereof, and It aims at providing the solar cell element which has the outstanding conversion efficiency, the manufacturing method of a solar cell element, and a solar cell.
  • a method for producing a composition for forming a passivation layer comprising the following steps (1) and (2).
  • (1) A step of mixing a compound represented by the following general formula (I) and a liquid medium to produce a mixed composition.
  • M (OR 1 ) m (I)
  • 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.
  • a method for producing a composition for forming a passivation layer comprising the following steps (3) and (4).
  • (3) A step of preparing a water-containing liquid medium by mixing a liquid medium and water.
  • (4) A step of preparing a water-containing composition by mixing the water-containing liquid medium and a compound represented by the following general formula (I).
  • 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.
  • ⁇ 6> The method for producing a passivation layer forming composition according to any one of ⁇ 1> to ⁇ 5>, wherein the liquid medium includes a compound represented by the following general formula (III).
  • ⁇ 8> a semiconductor substrate;
  • a passivation layer which is provided on at least a part of at least one surface of the semiconductor substrate and is a heat treatment product of the passivation layer forming composition manufactured by the manufacturing method according to any one of ⁇ 1> to ⁇ 7>.
  • a semiconductor substrate with a passivation layer When, A semiconductor substrate with a passivation layer.
  • 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 provided on at least a part of at least one surface of the semiconductor substrate and is a heat treatment product of the passivation layer forming composition manufactured by the manufacturing method according to any one of ⁇ 1> to ⁇ 7>.
  • An electrode disposed on at least one of the p-type layer and the n-type layer;
  • a solar cell element having
  • ⁇ 11> The production 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.
  • a method for producing 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.
  • the solar cell element which has the outstanding conversion efficiency, the manufacturing method of a solar cell element, and a solar cell can be provided.
  • the manufacturing method of the composition for forming a passivation layer of the present invention, the semiconductor substrate with a passivation layer and the manufacturing method thereof, the solar cell element and the manufacturing method thereof, and the form 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 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 is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
  • 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 method for producing the first passivation layer forming composition of the present embodiment includes the following steps (1) and (2).
  • the manufacturing method (henceforth a 2nd manufacturing method) of the 2nd composition for passivation layer formation of this embodiment includes the process of following (3) and following (4).
  • the first manufacturing method and the second manufacturing method may be collectively referred to as the manufacturing method of this embodiment.
  • 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 composition for forming a passivation layer produced by the production method of the present embodiment contains the compound of formula (I) and water, and the passivation layer is formed by allowing water to act on the compound of formula (I).
  • the thixo ratio of the forming composition is improved.
  • the composition for forming a passivation layer produced by the production method of the present embodiment is excellent in pattern formability.
  • the composition for forming a passivation layer produced by the production method of this embodiment is improved in its thixotropy by allowing water to act on the compound of formula (I), and the composition for forming a passivation layer is imparted on a semiconductor substrate.
  • the shape stability of the formed 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. Therefore, in the composition for forming a passivation layer produced by the production method of the present embodiment, at least one of a thixotropic agent and a resin described later (hereinafter, at least one of the thixotropic agent and the resin is thixotropic) in order to express desired thixotropic properties.
  • the amount added can be reduced as compared with the conventional passivation layer forming composition.
  • the thixotropic agent is thermally decomposed and scattered from the passivation layer through a degreasing process.
  • 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 contacted portion is hydrolyzed and a hydrolyzate is formed as disclosed in JP-A-10-139788.
  • This hydrolyzate may aggregate and easily form a solid, and it may be difficult for the compound of formula (I) itself to be uniformly dispersed in an organic solvent or the like. Therefore, in order to make it difficult to cause aggregation of the hydrolyzate, it is preferable to mix water in a state where the compound (I) is uniformly dispersed in a high-viscosity liquid medium to obtain a mixed composition.
  • the hydrolyzate is not easily aggregated in a high-viscosity liquid medium.
  • a composition for forming a passivation layer with less mixing unevenness is provided. Furthermore, since uniform gelation proceeds as a whole including the liquid medium, a paste having a large thixotropy can be obtained.
  • the liquid medium and water are mixed and hydrated in the liquid medium, and then the hydrated liquid medium and the compound of formula (I) are mixed. You may mix.
  • the presence of the liquid medium prevents direct contact between the compound of formula (I) and water, and the generation of hydrolyzate can be suppressed. Therefore, in the second production method, a composition for forming a passivation layer with less mixing unevenness is provided. Furthermore, since uniform gelation proceeds as a whole including the liquid medium, a paste having a large thixotropy can be obtained.
  • the passivation effect of a semiconductor substrate refers to an effective lifetime of minority carriers in a semiconductor substrate on which a passivation layer is formed by using reflected light photoconductive attenuation using a device such as Nippon Semi-Lab Co., Ltd. or WT-2000PVN. It can be evaluated by measuring by the method.
  • the effective lifetime ⁇ is expressed by the following equation (A) by the bulk lifetime ⁇ b inside the semiconductor substrate and the surface lifetime ⁇ s on the surface of the semiconductor substrate.
  • A the effective lifetime ⁇
  • the surface state density on the surface of the semiconductor substrate is small, ⁇ 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.
  • a metal oxide formed by heat-treating (firing) a composition for forming a passivation layer produced using a compound of formula (I) has defects of metal atoms or oxygen atoms and tends to generate fixed charges. Conceivable. This fixed charge can generate a charge in the vicinity of the interface with the semiconductor substrate, thereby reducing the concentration of minority carriers. As a result, the carrier recombination rate at the interface is suppressed, and an excellent passivation effect is achieved. it is conceivable that.
  • 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.
  • EELS Electron Energy Loss Spectroscopy
  • STEM scanning transmission electron microscope
  • M represents at least one selected from the group consisting of Al, Nb, Ta, VO, Y, and Hf. Two or more types of M may be contained in the compound of the formula (I).
  • 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, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, t-butyl, hexyl, and octyl. Group, 2-ethylhexyl group, 3-ethylhexyl group and the like.
  • Specific examples of the aryl group represented by R 1 include a phenyl group.
  • the alkyl group and aryl group represented by R 1 may have a substituent, and examples of the substituent of the alkyl group include an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • 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 Nb, Ta, VO and Hf, R 1 is an unsubstituted alkyl group having 1 to 4 carbon atoms, and m is An integer of 1 to 5 is preferable.
  • the state of the compound of formula (I) may be solid or liquid at 25 ° C. From the viewpoint of storage stability of the composition for forming a passivation layer, miscibility with water, and miscibility in the case where a compound represented by formula (II) described later is used in combination, the compound of formula (I) is liquid at 25 ° C. It is preferable that
  • 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) triethoxide oxide, vanadium (V) tri-i-propoxide oxide, vanadium (V) tri-n-propoxide oxide, vanadium( ) 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 an amine compound 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 an amine compound 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.
  • At least a part of the compound of formula (I) may be contained in the composition for forming a passivation layer as a compound having a chelate structure formed by mixing with a compound having a specific structure having two carbonyl groups described later.
  • the number of carbonyl groups to be chelated is not particularly limited, but when M is Al, the number of carbonyl groups to be chelated is preferably 1 to 3, and when M is Nb, the number of carbonyl groups to be chelated is The number of carbonyl groups to be chelated is preferably 1 to 5 when M is Ta, and the number of carbonyl groups to be chelated is 1 to 3 when M is VO.
  • M is Y
  • the number of carbonyl groups to be chelated is preferably 1 to 3
  • M is Hf the number of carbonyl groups to be chelated is preferably 1 to 4. .
  • a chelate structure in the compound of formula (I) can be confirmed by a commonly used analytical 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 the formula (I) contained in the composition for forming a passivation layer produced by the production method of the present embodiment can be appropriately selected as necessary.
  • the content of the compound of formula (I) can be 0.1% by mass to 80% by mass in the composition for forming a passivation layer from the viewpoint of reactivity with water and a passivation effect, and 0.5% by mass. It is preferably ⁇ 70% by mass, more preferably 1% by mass to 60% by mass, and still more preferably 1% by mass to 50% by mass.
  • 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 is a compound called aluminum chelate or 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 by compounding with an oxide derived from the compound of formula (I) having a fixed charge.
  • the combination of the compound of formula (I) and the organoaluminum compound is considered to increase the passivation effect due to the respective effects in the passivation layer.
  • a heat treatment (firing) is performed in a state where the compound of formula (I) and the organoaluminum compound are mixed, thereby generating a composite metal alkoxide of metal (M) and aluminum (Al) contained in the compound of formula (I).
  • physical properties such as reactivity and 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, Examples thereof include a hexyl group, an octyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, and the like.
  • 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 of the alkyl group represented by R 3 , R 4 and R 5 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a sec-butyl group.
  • R 3 , R 4 and R 5 may have a substituent or may be unsubstituted, and is preferably unsubstituted.
  • R 3 and R 4 in the general formula (II) are preferably each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms. Or it is more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • R 5 in the general formula (II) is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms from the viewpoint of storage stability and a passivation effect, and is preferably a hydrogen atom or 1 to 4 carbon atoms.
  • the unsubstituted alkyl group is more preferable.
  • the 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 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 each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is an integer of 1 to 3
  • R 2 is each independently an alkyl group having 1 to 4 carbon atoms
  • 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
  • R 5 is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • a certain compound 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 oxygen
  • R 3 or R 4 bonded to the oxygen atom is an alkyl group having 1 to 4 carbon atoms
  • R 3 or R 4 bonded to the methylene group is It is a compound which is a hydrogen atom and R 5 is a hydrogen atom.
  • organoaluminum compound represented by the general formula (II) examples include aluminum ethyl acetoacetate diisopropylate and tris (ethyl acetoacetate) aluminum.
  • organoaluminum compound represented by the general formula (II) a prepared product or a commercially available product may be used.
  • commercially available products include trade names of Kawaken Fine Chemical Co., Ltd., ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, and the like.
  • the organoaluminum compound represented by the general formula (II) can be prepared by mixing an aluminum trialkoxide and a compound having a specific structure having two carbonyl groups described later.
  • a commercially available aluminum chelate compound may also be used.
  • the aluminum trialkoxide and a compound having a specific structure having two carbonyl groups are mixed, 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, or the like may be performed.
  • 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.
  • ⁇ -diketone compounds include acetylacetone, 3-methyl-2,4-pentanedione, 2,3-pentanedione, 3-ethyl-2,4-pentanedione, and 3-butyl-2,4-pentane.
  • Examples include dione, 2,2,6,6-tetramethyl-3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, and the like.
  • ⁇ -ketoester compounds include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, i-butyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, acetoacetate n-pentyl, i-pentyl acetoacetate, n-hexyl acetoacetate, n-octyl acetoacetate, n-heptyl acetoacetate, 3-pentyl acetoacetate, ethyl 2-acetylheptanoate, ethyl 2-methylacetoacetate, 2-butylacetate Ethyl acetate, ethyl hexyl acetoacetate, ethyl 4,4-dimethyl-3-oxovalerate, ethyl 4-methyl-3-oxox
  • malonic acid diester examples include dimethyl malonate, diethyl malonate, di-n-propyl malonate, di-i-propyl malonate, di-n-butyl malonate, di-t-butyl malonate, and malon.
  • 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 compatibility with the solvent contained as necessary, specifically, selected from the group consisting of aluminum ethyl acetoacetate di-i-propylate and tri-i-propoxyaluminum It is preferable to use at least one selected from the group consisting of aluminum ethyl acetoacetate di-i-propylate.
  • an aluminum chelate structure in the organoaluminum compound can be confirmed by a commonly used analysis method. For example, it can confirm based on an infrared spectroscopy spectrum, a nuclear magnetic resonance spectrum, and melting
  • 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 is preferably 0.1% by mass to 80% by mass when the total content of the compound of formula (I) and the organoaluminum compound is 100% by mass, % To 80% by weight is more preferable, 1% to 75% by weight is further preferable, 2% to 70% by weight is particularly preferable, and 3% to 70% by weight is preferable. Is very preferred.
  • the storage stability of the composition for forming a passivation layer tends to be improved. Moreover, it exists in the tendency for the passivation effect to improve by making an organoaluminum compound 80 mass% or less.
  • 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 produced by the first production method contains an organoaluminum compound
  • the organoaluminum compound is mixed with the compound of formula (I) and a liquid medium in the step (1), or (2) What is necessary is just to mix with a water-containing composition after the process of this.
  • the composition for forming a passivation layer produced by the second production method contains an organoaluminum compound
  • the organoaluminum compound is mixed with the compound of formula (I) and a water-containing liquid medium in the step (4), or (4 It suffices to be mixed with the water-containing composition after the step of).
  • the liquid medium used in the production method of the present embodiment is not particularly limited as long as the liquid medium has a shear viscosity at 25.0 ° C. of 0.1 Pa ⁇ s or more.
  • a high-boiling material high-boiling material
  • the shear viscosity of the liquid medium is measured using a rotary shear viscometer equipped with a cone plate (diameter 50 mm, cone angle 1 °) at a temperature of 25.0 ° C. and a shear rate of 10 s ⁇ 1 .
  • an aggregate of the compound of formula (I) may be generated in the water-containing composition when the mixed composition and water are mixed.
  • the shear viscosity of the mixed composition in which such aggregation does not occur is preferably 0.1 Pa ⁇ s or more under the conditions of 25.0 ° C. and a shear rate of 10 s ⁇ 1 . More preferably, it is 0.2 Pa ⁇ s.
  • the shear viscosity of the mixed composition refers to a value measured in the same manner as the shear viscosity of the liquid medium.
  • the liquid medium used in the present embodiment is not particularly limited as long as it satisfies such conditions and can uniformly disperse the compound of formula (I). Specific examples include isobornylcyclohexanol represented by chemical formula (III).
  • Isobornylcyclohexanol represented by the chemical formula (III) does not need to be easily dispersed (vaporized) and degreased when heated, and can maintain the shape of the passivation layer forming composition after printing or coating.
  • High boiling point material with viscosity is not needed to be easily dispersed (vaporized) and degreased when heated, and can maintain the shape of the passivation layer forming composition after printing or coating.
  • Isobornyl cyclohexanol is commercially available as “Telsolve MTPH” (Nippon Terpene Chemical Co., Ltd., trade name). Isobornylcyclohexanol has a high boiling point of 308 ° C to 318 ° C, and when it is removed from the composition layer, it does not need to be degreased by heat treatment (firing) like a resin, but is scattered (vaporized) by heating. Can be eliminated. For this reason, most of the isobornylcyclohexanol contained in the composition for forming a passivation layer is dried in a drying step after applying the composition for forming a passivation layer produced by the manufacturing method of the present embodiment on a semiconductor substrate. Can be removed.
  • the content of the liquid medium in the composition for forming a passivation layer produced by the production method of the present embodiment is preferably 3% by mass to 95% by mass in the total mass of the composition for forming a passivation layer. It is more preferably from 90% by mass, and further preferably from 7% by mass to 80% by mass.
  • the composition for forming a passivation layer produced by the production method of the present embodiment may contain an organic solvent. Since the composition for forming a passivation layer contains an organic solvent, the adjustment of the viscosity becomes easier, the applicability of the composition for forming a passivation layer to a semiconductor substrate is further improved, and a more uniform passivation layer is formed. can do. It does not restrict
  • an organic solvent that can dissolve the compound of formula (I) and an organoaluminum compound added as necessary to give a uniform solution is preferable, and more preferably includes at least one organic solvent.
  • the organic solvent means an organic substance having a shear viscosity at 25.0 ° C. of less than 0.1 Pa ⁇ s.
  • the shear viscosity of the organic solvent is a value measured in the same manner as the shear viscosity of the liquid medium.
  • organic solvents 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, and methyl-n-hexyl.
  • Ketone solvents such as ketone, 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, dii-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethyl Glycol di-n-propyl ether, ethylene glycol di n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n
  • Protic polar solvent methylene chloride, chloroform, dichloroethane, benzene, toluene, xylene, hexane, octane, ethylbenzene, 2-ethylhexanoic acid and other hydrophobic organic solvents, methanol, ethanol, n-propanol, i-propanol, n- Butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octan
  • the organic solvent preferably contains at least one selected from the group consisting of a terpene solvent, an ester solvent and an alcohol solvent from the viewpoints of imparting the passivation layer forming composition to the semiconductor substrate and patterning properties. More preferably, it contains at least one selected from the group consisting of solvents.
  • the content of the organic solvent is determined in consideration of the impartability of the composition for forming a passivation layer to a semiconductor substrate, pattern formability, and storage stability.
  • the content of the organic solvent is preferably 5% by mass to 98% by mass and more preferably 10% by mass to 95% by mass in the total mass of the composition for forming a passivation layer.
  • the composition for forming a passivation layer produced by the production method of the present embodiment may further contain at least one resin.
  • the shape stability of the composition layer formed by applying the composition for forming a passivation layer on a semiconductor substrate is further improved, and the passivation layer is formed in the region where the composition layer is formed. It 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 in which a good pattern can be formed when the composition for forming a passivation layer is applied onto 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.
  • step (2) the mixed composition and water are mixed to produce a water-containing composition.
  • step (3) the liquid medium and water are mixed to create a hydrous liquid medium.
  • the water state may be solid or liquid. From the viewpoint of miscibility with the mixed composition, water is preferably a liquid.
  • the addition ratio of water to the mixed composition is 50 mol% to 2000 mol when the total of the compound of formula (I) and the organoaluminum compound used as necessary is 100 mol%. It is preferably mol%, more preferably 100 mol% to 1800 mol%, and still more preferably 150 mol% to 1500 mol%.
  • the addition rate of water to the liquid medium is 50 mol% to 2000 mol when the total of the compound of formula (I) and the organoaluminum compound used as necessary is 100 mol%. %, More preferably from 100 mol% to 1800 mol%, and even more preferably from 150 mol% to 1500 mol%.
  • the composition for forming a passivation layer produced by the production method of the present embodiment can further contain other components that are usually used in the field as necessary.
  • other components include plasticizers, dispersants, surfactants, thixotropic agents, other metal alkoxide compounds other than the compound of formula (I), and high-boiling materials.
  • at least one selected from thixotropic agents may be included.
  • the shape stability of the composition layer formed by applying the composition for forming a passivation layer on a semiconductor substrate is further improved, and the passivation layer is formed from the composition. It can be formed in a desired shape in the region where the layer is formed.
  • the content of the thixotropic agent is preferably 5% by mass or less, more preferably 3% by mass or less, and it is preferably used within a range that does not affect the present invention.
  • 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 (IV).
  • 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 (V), (VI), (VII) and (VIII).
  • 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 0.10 ⁇ 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 viscosity of the composition for forming a passivation layer produced by the production method of the present embodiment is not particularly limited, and can be appropriately selected depending on the method for applying 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 passivation layer forming composition has a thixo ratio ( ⁇ 1 / ⁇ 2) calculated by dividing the shear viscosity ⁇ 1 at a shear rate of 0.1 s ⁇ 1 by the shear viscosity ⁇ 2 at a shear rate of 10 s ⁇ 1 . ) Is preferably from 1.05 to 100, more preferably from 1.1 to 50.
  • the shear viscosity is measured at a temperature of 25 ° C. using a rotary shear viscometer equipped with a cone plate (diameter 50 mm, cone angle 1 °).
  • the thixo ratio ( ⁇ 1 / ⁇ 3) calculated as above is preferably 1.05 to 100, more preferably 1.1 to 50.
  • the mixing method used in the step (1) for preparing the mixed composition by mixing the compound of formula (I) and the liquid medium is not particularly limited, and a commonly used mixing method can be applied. it can.
  • the mixing method used in the step (2) of mixing the mixture composition and water to prepare the water-containing composition there is no particular limitation on the mixing method used in the step (2) of mixing the mixture composition and water to prepare the water-containing composition, and a commonly used mixing method can be applied.
  • the mixing method used in the step (3) in which a liquid medium and water are mixed to produce a water-containing liquid medium, and a commonly used mixing method can be applied.
  • the mixing method used in the step (4) there is no particular limitation on the mixing method used in the step (4) in which the water-containing liquid medium and the compound of formula (I) are mixed to prepare the water-containing composition, and a commonly used mixing method is applied. can do.
  • the kind of component contained in the composition for forming a passivation layer, and the content of each component are determined by thermal analysis such as TG / DTA, spectral analysis such as NMR and IR, and chromatographic analysis such as HPLC and GPC. Can be confirmed.
  • the semiconductor substrate with a passivation layer of the present embodiment is a heat treatment product of a composition for forming a passivation layer provided on at least a part of a semiconductor substrate and at least one surface of the semiconductor substrate, and manufactured by the manufacturing method of the present embodiment.
  • the semiconductor substrate with a passivation layer of the present embodiment has an excellent passivation effect by having a passivation layer that is a heat-treated product of the composition for forming a passivation layer.
  • the semiconductor substrate is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • 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 composition layer is formed by applying the passivation layer forming composition manufactured by the manufacturing method according to 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 method for manufacturing a semiconductor substrate with a passivation layer of this embodiment may further include other steps as necessary.
  • a passivation layer having an excellent passivation effect is obtained by using the composition for forming a passivation layer manufactured by the manufacturing method of the present embodiment. It can be formed by a simple method.
  • 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 composition for forming a passivation layer on the semiconductor substrate. By washing with an alkaline aqueous solution, organic substances, particles, and the like present on the surface of the semiconductor substrate can be removed, and the passivation effect is further improved.
  • 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 a composition layer by applying a passivation layer forming composition on a semiconductor substrate there is no particular limitation on the method for forming a composition layer by applying a passivation layer forming composition on a semiconductor substrate.
  • the method of providing the said composition for passivation layer formation on a semiconductor substrate using a well-known coating method etc. can be mentioned.
  • Specific examples include dipping method, screen printing, ink jet method, dispenser method, spin coating method, brush coating, spray method, doctor blade method, roll coating method and the like.
  • a screen printing method, an inkjet method, and the like are preferable.
  • the application amount of the composition for forming a passivation layer can be appropriately selected according to the purpose.
  • the thickness of the passivation layer to be formed can be appropriately adjusted so as to be a desired thickness described later.
  • 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).
  • the method is not particularly limited as long as it can be converted into a method.
  • 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 manufacturing method of the semiconductor substrate with a passivation layer according to the present embodiment is obtained by applying the passivation layer forming composition to the semiconductor substrate and then forming the passivation layer by a heat treatment (firing) before the step of forming the passivation layer. You may have further the process of drying-processing the composition layer which becomes. By having the process of drying the composition layer, a passivation layer having a more uniform passivation effect can be formed.
  • the step of drying the composition layer is not particularly limited as long as at least a part of the water and the liquid medium contained in the composition for forming a passivation layer can be removed.
  • the drying treatment can be, for example, a heat treatment at 30 ° C. to 250 ° C. for 1 minute to 60 minutes, and is preferably a heat treatment at 40 ° C. to 220 ° C. for 3 minutes to 40 minutes.
  • the drying treatment may be performed under normal pressure or under reduced pressure.
  • the 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 300 ° C. to 400 ° C. for 3 minutes to 60 minutes.
  • the degreasing treatment is preferably performed in the presence of oxygen, and more preferably performed in the air.
  • the solar cell element of the present embodiment is provided on at least a part of 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, and the passivation layer A passivation layer, which is a heat-treated product of the forming composition, and an electrode disposed on at least one of the p-type layer and the n-type layer.
  • the solar cell element may further include 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 formation of the passivation layer manufactured by the manufacturing method of this embodiment.
  • the semiconductor substrate to which the composition for forming a passivation layer is applied is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • 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 provided with the passivation layer is preferably the back surface of the solar cell element.
  • the thickness of the passivation layer provided 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 manufacturing method of the solar cell element of this embodiment is manufactured by the manufacturing method of this embodiment on at least a part of at least one surface of a semiconductor substrate having a pn junction part in which a p-type layer and an n-type layer are pn-junctioned.
  • a step of forming a composition layer by applying a composition for forming a passivation layer, a step of heat-treating (firing) the composition layer to form a passivation layer, and a step of forming the p-type layer and the n-type layer. Forming an electrode on at least one of the layers.
  • the method for manufacturing the solar cell element may further include other steps as necessary.
  • the solar cell element excellent in conversion efficiency can be manufactured by a simple method by using the composition for forming a passivation layer manufactured by the manufacturing method of this embodiment. .
  • 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 is provided may be a p-type layer or an n-type layer. Among these, a p-type layer is preferable from the viewpoint of conversion efficiency.
  • the details of the method for forming a passivation layer using the composition for forming a passivation layer are the same as the method for manufacturing a semiconductor substrate with a passivation layer described above, and the preferred embodiments are also the same.
  • 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-propanol) can be used.
  • an n + -type diffusion layer 2 is formed with a thickness on the order of submicrons, and p A pn junction is formed at the boundary with the mold 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 made of silicon nitride or the like is provided on the n + type diffusion layer 2 on the light receiving surface by a PECVD (Plasma Enhanced Chemical Vapor Deposition) method or the like with a thickness of about 90 nm. .
  • PECVD Pulsma Enhanced Chemical Vapor Deposition
  • a passivation layer forming composition produced by the production method of the present embodiment is applied to a part of the back surface by screen printing or the like, and after drying, a temperature of 300 ° C. to 900 ° C. Heat treatment (baking) is performed at a temperature to form the 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 arbitrarily set, but from the viewpoint of the passivation effect and the suppression of recombination of minority carriers, L a is 5 ⁇ m to 2 mm and L b is 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, 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. This makes it possible to form a more preferable dot-shaped opening pattern effective for suppressing recombination of minority carriers, thereby improving the power generation efficiency of the solar cell element.
  • 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 produced by the production method 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 the power generation performance is excellent.
  • a solar cell element can be manufactured.
  • FIG. 2 is a cross-sectional view schematically showing another example of a method for manufacturing a solar cell element having a passivation layer according to the present embodiment, and the n + -type diffusion layer 2 on the back surface is etched.
  • a solar cell element can be manufactured in the same manner as in FIG. 1 except that the back surface is further planarized after being removed by the treatment.
  • 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 shows process drawing which shows typically another example of the manufacturing method of the solar cell element which has a passivation layer which concerns on this embodiment as sectional drawing. This method is the same as the method shown in FIG. 1 until the step of forming the texture structure, the n + -type diffusion layer 2 and the antireflection film 4 on the semiconductor substrate 1 (FIGS. 19 (19) to (24)).
  • FIG. 6 shows a schematic plan view of another example of the formation pattern of the passivation layer on the back surface.
  • 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 4.927 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21) and 28.536 g of isobornylcyclohexanol (Nippon Terpene Chemical Co., Ltd.) Taken and kneaded. Thereto, 1.725 g of purified water was added and kneaded. A highly viscous mixture was obtained.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21
  • isobornylcyclohexanol Nippon Terpene Chemical Co., Ltd.
  • composition 1 was prepared.
  • 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 s -1 respectively.
  • the shear viscosity ( ⁇ 1) at a shear rate of 0.1 s ⁇ 1 was 252 Pa ⁇ s
  • the shear viscosity ( ⁇ 2) at a shear rate of 10 s ⁇ 1 was 21.1 Pa ⁇ s.
  • the thixo ratio ( ⁇ 1 / ⁇ 2) when the shear rate was 0.1 s ⁇ 1 and 10 s ⁇ 1 was 11.9.
  • 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, and the liquid medium was scattered to perform a drying process.
  • 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.
  • the dot diameter (L a ) was measured at 10 points, and 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. Thereafter, the silicon substrate provided with the composition 1 for forming a passivation layer was heated at 150 ° C. for 5 minutes, and the liquid medium was scattered to perform a drying process. Thereafter, printing and drying were performed on the other surface of the silicon substrate. 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.) under atmospheric conditions under conditions of 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 composition for forming a passivation layer was applied was 1250 ⁇ s.
  • Example 2 5.177 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), 33.985 g of isobornylcyclohexanol (Nippon Terpene Chemical Co., Ltd.), 5.166 g of aluminum ethyl acetoacetate diisopropylate (Kawaken Fine Chemical Co., Ltd., trade name: ALCH) and 5.171 g of terpineol (Nippon Terpene Chemical Co., Ltd.) were weighed and kneaded.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21
  • isobornylcyclohexanol Nippon Terpene Chemical Co., Ltd.
  • ALCH aluminum ethyl acetoacetate diiso
  • 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 2 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 120 ⁇ m wide light receiving surface current collecting electrode and a 1.5 mm wide light receiving surface output extraction electrode, and printing conditions (screen plate mesh) so that the thickness after heat treatment (firing) is 20 ⁇ m. , Printing speed and printing pressure) were appropriately adjusted. This was heated at a temperature of 150 ° C. for 5 minutes, and the liquid medium was scattered to perform a drying process.
  • the printing conditions (screen plate mesh, printing speed and printing pressure) of the silver electrode paste and the aluminum electrode paste are set so that the thickness of the back surface output extraction electrode and the back surface collecting electrode after heat treatment (firing) is 20 ⁇ m. Adjusted accordingly. After printing each electrode paste, it was heated for 5 minutes at a temperature of 150 ° C., and the liquid medium was scattered to perform a drying treatment.
  • a wiring member soldder-plated rectangular wire for solar cell, product name: SSA-TPS 0.2 ⁇ 1.5 (20 ), Sn-Ag-Cu lead-free solder plated to a maximum thickness of 20 ⁇ m per side on a copper wire of thickness 0.2mm x width 1.5mm (Hitachi Metals Co., Ltd.), and a tab wire connection device ( By using NTS-150-M, Tabbing & Stringing Machine, NPC Corporation, and melting the solder under the conditions of a maximum temperature of 250 ° C. and a holding time of 10 seconds, the above wiring member, light receiving surface output extraction electrode and back surface output The extraction electrode was connected.
  • glass plate 16 / sealing material 14 / wiring material 13 are connected in the order of solar cell element 12 / sealing material 14 / back sheet 15, and a part of the wiring member is laminated using a vacuum laminator (LM-50 ⁇ 50, NPC Corporation). Was laminated for 5 minutes at a temperature of 140 ° C. so as to expose the solar cell 1.
  • a vacuum laminator LM-50 ⁇ 50, NPC Corporation
  • 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 Eff (conversion efficiency) were measured in accordance with JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005), respectively.
  • Example 3 4.483 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), 36.025 g of isobornylcyclohexanol (Nippon Terpene Chemical Co., Ltd.), 4.496 g of aluminum ethyl acetoacetate diisopropylate (Kawaken Fine Chemical Co., Ltd., trade name: ALCH) and 13.114 g of terpineol (Nippon Terpene Chemical Co., Ltd.) were weighed and kneaded.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21
  • isobornylcyclohexanol Nippon Terpene Chemical Co., Ltd.
  • Example 2 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 2, the solar cell element 2 and the solar cell 2 were produced, and the power generation performance was evaluated.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21
  • ⁇ Comparative Example 3> 5.042 g of pentaethoxyniobium (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21) and 10.021 g of terpineol (Nippon Terpene Chemical Co., Ltd.) were weighed and mixed. . To this, 2.016 g of purified water was added and mixed. A white mass formed.
  • pentaethoxyniobium Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21
  • aluminum ethyl acetoacetate diisopropylate Korean Fine Chemical Co., Ltd., trade name: ALCH
  • i-propanol (Wako Pure Chemical Industries, Ltd.) was weighed and mixed and kneaded for 5 minutes to prepare a passivation layer forming composition 9. Thereafter, the thixotropy of the passivation layer forming composition 9 was evaluated in the same manner as in Example 1. Moreover, although application by screen printing was attempted, since the application could not be performed, evaluation of pattern formation and evaluation of effective lifetime could not be performed.
  • Table 1 summarizes the components used in each step in each example and comparative example.
  • compounds (I), (II) and (III) are each a compound represented by general formula (I), a compound represented by general formula (II) and a compound represented by general formula (III).
  • EtOH and IPA represent ethanol and i-propanol, respectively. “-” Indicates that the corresponding process was not performed.
  • Table 3 summarizes the measurement results of shear viscosity, pattern formability, and effective lifetime measurement results in each example and comparative example. In the table, “-” indicates that the corresponding item was not evaluated.
  • Table 4 summarizes the evaluation results of the solar cells produced in Example 2 and Comparative Example 1.

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Abstract

L'invention concerne un procédé de fabrication d'une composition pour la formation d'une couche de passivation, qui comprend une étape de préparation d'une composition mixte consistant à mélanger un milieu liquide et le composé représenté par la formule générale (I), et une étape de préparation d'une composition contenant de l'eau qui consiste à mélanger de l'eau avec la composition mélangée. Formule générale (I) : M(OR1)m (dans la formule générale (I), M représente au moins un composant choisi dans le groupe constitué par Al, Nb, Ta, VO, Y et Hf ; les R1 représentent chacun un groupe alkyle ou un groupe aryle ; et m représente un nombre entier compris entre 1 et 5).
PCT/JP2015/069193 2014-07-04 2015-07-02 Procede de production d'une composition pour la formation d'une couche de passivation, substrat semi-conducteur pourvu d'une couche de passivation, procede de fabrication de celui-ci, element de cellule solaire, procede de fabrication de celui-ci et cellule solaire Ceased WO2016002902A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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