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WO2014014111A1 - Élément de cellule photovoltaïque , sa fabrication ainsi que module de cellule voltaïque - Google Patents

Élément de cellule photovoltaïque , sa fabrication ainsi que module de cellule voltaïque Download PDF

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Publication number
WO2014014111A1
WO2014014111A1 PCT/JP2013/069701 JP2013069701W WO2014014111A1 WO 2014014111 A1 WO2014014111 A1 WO 2014014111A1 JP 2013069701 W JP2013069701 W JP 2013069701W WO 2014014111 A1 WO2014014111 A1 WO 2014014111A1
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Prior art keywords
passivation
solar cell
oxide
passivation layer
forming
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Ceased
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PCT/JP2013/069701
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English (en)
Japanese (ja)
Inventor
明博 織田
吉田　誠人
野尻　剛
倉田　靖
田中　徹
修一郎 足立
剛 早坂
服部　孝司
三江子 松村
敬司 渡邉
真年 森下
浩孝 濱村
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to JP2014525895A priority Critical patent/JP6350278B2/ja
Priority to CN201380038079.0A priority patent/CN104471718A/zh
Publication of WO2014014111A1 publication Critical patent/WO2014014111A1/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
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • 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 solar cell element, a method for manufacturing a solar cell element, and a solar cell module.
  • n-type diffusion layer is uniformly formed by performing several tens of minutes at 800 ° C. to 900 ° C.
  • n-type diffusion layers are formed not only on the front surface, which is the light receiving surface, but also on the side surface and the back surface. Therefore, side etching is performed to remove the n-type diffusion layer formed on the side surface.
  • the n-type diffusion layer formed on the back surface needs to be converted into a p + -type diffusion layer. For this reason, by applying an aluminum paste containing aluminum particles and a binder to the entire back surface and heat-treating (baking) it, the n-type diffusion layer is converted into a p + -type diffusion layer and an aluminum electrode is formed. Get ohmic contact.
  • the aluminum electrode formed from the aluminum paste has low conductivity. Therefore, in order to reduce the sheet resistance, the aluminum electrode formed on the entire back surface usually must have a thickness of about 10 ⁇ m to 20 ⁇ m after heat treatment (firing). Furthermore, since the thermal expansion coefficient of silicon and aluminum differ greatly, a silicon substrate on which an aluminum electrode is formed generates a large internal stress in the process of heat treatment (firing) and cooling, resulting in damage to grain boundaries, Causes defects to grow and warp.
  • a point contact method has been proposed in which an aluminum paste is applied to a part of the surface of a silicon substrate to partially form a p + -type diffusion layer and an aluminum electrode (for example, Japanese Patent No. 3107287). (See the publication).
  • an SiO 2 film or the like has been proposed as a passivation layer for the back surface (see, for example, JP-A-2004-6565).
  • 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 has been proposed as a material having a negative fixed charge (see, for example, Japanese Patent No. 4767110).
  • Such a passivation layer is generally formed by a method such as an ALD (Atomic Layer Deposition) method or a CVD (Chemical Vapor Deposition) method (for example, Journal of Applied Physics, 104 (2008), 113703-1). 113703-7).
  • the present invention has been made in view of the above-described conventional problems, has a high conversion efficiency, and suppresses a decrease in conversion efficiency over time, a simple manufacturing method thereof, and a solar battery module. It is an issue to provide.
  • a semiconductor substrate having a light receiving surface, a back surface opposite to the light receiving surface, and a side surface; A light-receiving surface electrode disposed on the light-receiving surface; A back electrode disposed on the back surface; At least one selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3 and HfO 2 disposed on at least one of the light receiving surface, the back surface and the side surface.
  • a solar cell element having
  • the composition for forming a passivation layer is composed of Nb 2 O 5 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3 , HfO 2 and a compound represented by the following general formula (I).
  • M contains at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf.
  • R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • m represents an integer of 0 to 5.
  • the passivation layer forming composition contains at least one niobium compound selected from the group consisting of Nb 2 O 5 and a compound in which M in the general formula (I) is Nb, and the passivation layer.
  • R 2 each independently represents an alkyl group having 1 to 8 carbon atoms.
  • n represents an integer of 0 to 3.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group.
  • R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • n in the general formula (II) is an integer of 1 to 3
  • R 5 is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • composition for forming a passivation layer contains at least one aluminum compound selected from the group consisting of Al 2 O 3 and the compound represented by the general formula (II).
  • the liquid medium includes at least one selected from the group consisting of a hydrophobic organic solvent, an aprotic organic solvent, a terpene solvent, an ester solvent, an ether solvent, and an alcohol solvent. Battery element.
  • ⁇ 12> forming a light receiving surface electrode on the light receiving surface of the semiconductor substrate; Forming a back electrode on the back surface of the semiconductor substrate opposite to the light receiving surface; From at least one of the light receiving surface, the back surface and the side surface, Nb 2 O 5 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3 , HfO 2 and a compound represented by the following general formula (I) Forming a composition layer by applying a composition for forming a passivation layer containing at least one compound selected from the group consisting of: Heat-treating the composition layer to form a passivation layer;
  • the method for producing a solar cell element according to any one of the above ⁇ 1> to ⁇ 11> comprising:
  • M contains at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf.
  • R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • m represents an integer of 0 to 5.
  • the composition for forming a passivation layer further contains at least one aluminum compound selected from the group consisting of compounds represented by Al 2 O 3 and the following general formula (II).
  • the manufacturing method of the solar cell element of description is not limited to:
  • R 2 each independently represents an alkyl group having 1 to 8 carbon atoms.
  • n represents an integer of 0 to 3.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group.
  • R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • ⁇ 14> The method for producing a solar cell element according to ⁇ 12> or ⁇ 13>, wherein the temperature of the heat treatment is 400 ° C. or higher.
  • step of forming the composition layer includes applying the composition for forming a passivation layer by a screen printing method or an inkjet method.
  • a battery element manufacturing method is
  • ⁇ 16> The solar cell element according to any one of ⁇ 1> to ⁇ 11>, A wiring material disposed on the electrode of the solar cell element; A solar cell module.
  • the present invention it is possible to provide a solar cell element that has excellent conversion efficiency and suppresses a decrease in conversion efficiency over time, a simple manufacturing method thereof, and a solar cell module.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • a numerical range indicated 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 notice 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 solar cell element of the present invention includes a light receiving surface, a back surface opposite to the light receiving surface, a semiconductor substrate having a side surface, a light receiving surface electrode disposed on the light receiving surface, and a back surface disposed on the back surface.
  • An electrode disposed on at least one of the light receiving surface, the back surface, and the side surface, and selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3, and HfO 2.
  • a passivation layer containing at least one compound hereinafter also referred to as “specific metal oxide”, and a metal element contained in each specific metal oxide is also referred to as “specific metal element”).
  • the solar cell element may further include other components as necessary.
  • a solar cell element having a passivation layer containing a specific metal oxide on at least one of a light receiving surface, a back surface, and a side surface of a semiconductor substrate has excellent conversion efficiency and suppresses a decrease in conversion efficiency over time. .
  • This is considered to be because, for example, since the passivation layer contains a specific metal oxide, an excellent passivation effect is exhibited and the lifetime of carriers in the semiconductor substrate is extended, so that high efficiency can be achieved.
  • the passivation layer containing the specific metal oxide the passivation effect is maintained, and a decrease in conversion efficiency over time can be suppressed.
  • the deterioration of the solar cell characteristics over time can be evaluated by the solar cell characteristics after being left for a predetermined time in a constant temperature and humidity chamber.
  • the reason why the passivation layer containing a specific metal oxide on at least one of the light receiving surface, the back surface, and the side surface of the semiconductor substrate has an excellent passivation effect can be considered as follows. That is, by providing a passivation layer containing a specific metal oxide on the surface of the semiconductor substrate, a fixed charge is generated near the interface with the semiconductor substrate due to defects of a specific metal element or oxygen atom in the specific metal oxide. Is considered to exist. This fixed charge generates an electric field in the vicinity of the interface of the semiconductor substrate, so that band bending occurs and the concentration of minority carriers can be reduced. As a result, since the carrier recombination rate at the interface is suppressed, it is considered that an excellent passivation effect is exhibited.
  • the fixed charge possessed by the specific metal oxide can be evaluated by the CV method (Capacitance Voltage measurement).
  • the surface state density of a passivation layer formed by heat-treating a composition for forming a passivation layer which will be described later, is evaluated by a CV method
  • the value is larger than that of a passivation layer formed by an ALD method or a CVD method.
  • the passivation layer included in the solar cell element of the present invention has a large electric field effect, a decrease in the concentration of minority carriers, and a surface lifetime ⁇ s increases. Therefore, the surface state density is not a relative problem.
  • the passivation effect of a semiconductor substrate refers to an effective lifetime of minority carriers in a semiconductor substrate on which a passivation layer is formed by using a device such as Nippon Semi-Lab Co., Ltd., WT-2000PVN, etc. It can be evaluated by measuring by the method.
  • the effective lifetime ⁇ is expressed by the following equation (A) by the bulk lifetime ⁇ b inside the semiconductor substrate and the surface lifetime ⁇ s of the semiconductor substrate surface.
  • ⁇ s becomes long, resulting in a long effective lifetime ⁇ .
  • the bulk lifetime ⁇ b is increased and the effective lifetime ⁇ is increased. That is, by measuring the effective lifetime ⁇ , the interface characteristics between the passivation layer and the semiconductor substrate and the internal characteristics of the semiconductor substrate such as dangling bonds can be evaluated.
  • the solar cell element includes a semiconductor substrate having a light receiving surface and a back surface opposite to the light receiving surface.
  • 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. Further, 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 (that is, at least one of the light receiving surface, the back surface, and the side surface) is a semiconductor substrate that is a p-type layer.
  • the p-type layer on the semiconductor substrate is a p-type layer derived from the p-type semiconductor substrate
  • the p-type layer is formed on the n-type semiconductor substrate or the p-type semiconductor substrate as a p-type diffusion layer or a p + -type diffusion layer. It may be a thing.
  • the p-type layer and the n-type layer are preferably pn-junctioned. That is, when the semiconductor substrate is a p-type semiconductor substrate, an n-type layer is preferably formed on the light-receiving surface or the back surface of the semiconductor substrate. When the semiconductor substrate is an n-type semiconductor substrate, a p-type layer is preferably formed on the light-receiving surface or the back surface of the semiconductor substrate.
  • the method for forming the p-type layer or the n-type layer on the semiconductor substrate is not particularly limited, and can be appropriately selected from commonly used methods.
  • 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 shape and size of the semiconductor substrate are not limited, and for example, a square with a side of 125 mm to 156 mm can be used.
  • the solar cell element of the present invention has a light receiving surface electrode disposed on the light receiving surface and a back electrode disposed on the back surface opposite to the light receiving surface of the semiconductor substrate.
  • the light receiving surface electrode has a function of collecting current on the light receiving surface of the semiconductor substrate.
  • the back electrode has a function of outputting a current to the outside, for example.
  • the material of the light-receiving surface electrode is not particularly limited, and examples thereof include silver, copper, and aluminum.
  • the thickness of the light-receiving surface electrode is not particularly limited, and is preferably 0.1 ⁇ m to 50 ⁇ m from the viewpoint of conductivity and homogeneity.
  • the material of the back electrode is not particularly limited, and examples thereof include silver, copper, and aluminum.
  • the material of the back electrode is preferably aluminum from the viewpoint of forming the back electrode and forming a p + -type diffusion layer by diffusing aluminum atoms in the semiconductor substrate.
  • the thickness of the back electrode is not particularly limited, and is preferably 0.1 ⁇ m to 50 ⁇ m from the viewpoint of conductivity and substrate warpage.
  • the light-receiving surface electrode and the back surface electrode can be produced by a commonly used method.
  • the light-receiving surface electrode and the back electrode are manufactured by applying an electrode forming paste such as a silver paste, an aluminum paste, or a copper paste to a desired region of a semiconductor substrate, and performing a heat treatment (firing) as necessary. Can do.
  • the solar cell element of the present invention has a passivation layer containing a specific metal oxide on at least one of the light receiving surface, the back surface, and the side surface of the semiconductor substrate. Furthermore, the passivation layer may contain Al 2 O 3 .
  • the passivation layer may be provided on a part or the entire surface of the at least one surface, and is preferably provided in a region other than the electrode. The electrode may be formed so as to overlap with the passivation layer.
  • the average 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 from the viewpoint of the passivation effect.
  • the average thickness of the passivation layer is calculated as an arithmetic average value by measuring the thickness at five points by an ordinary method using an interference film thickness meter (for example, F20 film thickness measurement system manufactured by Filmetrics).
  • the content of the specific metal oxide contained in the passivation layer is preferably 0.1% by mass to 100% by mass from the viewpoint of obtaining a sufficient passivation effect, and 1% by mass to 100% by mass. Is more preferably 10% by mass to 100% by mass.
  • the content rate of the specific metal oxide contained in the passivation layer is measured by the following method.
  • the ratio of the inorganic substance is calculated from the thermogravimetric analysis method using atomic absorption spectrometry, inductively coupled plasma emission spectrometry, thermogravimetric analysis, X-ray photoelectric spectroscopy, or the like.
  • the ratio of the compound of the specific metal element in the inorganic substance is calculated by atomic absorption spectrometry, inductively coupled plasma emission spectrometry, etc., and further the specific metal element in the compound by X-ray photoelectric spectroscopy, X-ray absorption spectroscopy, etc.
  • the ratio of the specific metal oxide is calculated.
  • the passivation layer may further contain an inorganic oxide other than the specific metal oxide.
  • inorganic oxides are preferably compounds having a fixed charge. Specifically, aluminum oxide, silicon oxide, titanium oxide, gallium oxide, zirconium oxide, boron oxide, indium oxide, phosphorus oxide, zinc oxide, lanthanum oxide , Praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, etc. From this viewpoint, it is preferably at least one selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, neodymium oxide and aluminum oxide, and preferably contains at least aluminum oxide. Preferred.
  • the content of other inorganic oxides in the passivation layer is preferably 80% by mass or less, and more preferably 60% by mass or less.
  • the content of other inorganic oxides contained in the passivation layer can be measured in the same manner as the above-described method for measuring the content of the specific metal oxide.
  • the density of the passivation layer from the viewpoint of temporal stability of the passivation effect, preferably 1.0g / cm 3 ⁇ 8.0g / cm 3, more preferably 2.0g / cm 3 ⁇ 6.0g / cm 3, 3 More preferably, it is 0.0 g / cm 3 to 5.0 g / cm 3 .
  • the density of the passivation layer is calculated from the area and thickness of the passivation layer and the mass of the passivation layer. Specifically, the density of the passivation layer is measured using a pressure floating method or a temperature floating method.
  • the passivation layer of the solar cell element of the present invention is a heat-treated product of the composition for forming a passivation layer.
  • the composition for forming a passivation layer is not particularly limited as long as it can form a passivation layer containing a specific metal oxide by heat treatment (firing), and even if the specific metal oxide itself is included, the specific metal
  • the precursor used as an oxide may be included.
  • the specific metal oxide and its precursor are also referred to as a specific metal compound.
  • the composition for forming a passivation layer includes the specific metal oxides (Nb 2 O 5 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3 and HfO 2 ), and the specific It is preferable to include at least one compound selected from the group consisting of compounds represented by the following general formula (I) (hereinafter also referred to as compounds of formula (I)) as the metal oxide precursor.
  • M contains at least one metal element selected from the group consisting of Nb, Ta, V, Y, and Hf.
  • R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • m represents an integer of 0 to 5.
  • each R 1 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
  • the alkyl group is more preferable.
  • the alkyl group represented by R 1 may be linear or branched. Specific examples of the alkyl group represented by R 1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, hexyl, octyl, 2- An ethylhexyl group etc. can be mentioned.
  • aryl group represented by R 1 examples include a phenyl group.
  • the alkyl group and aryl group represented by R 1 may have a substituent.
  • substituent for the alkyl group include a halogen atom, an amino group, a hydroxyl group, a carboxyl group, a sulfone group, and a nitro group.
  • substituent for the aryl group include a halogen atom, a methyl group, an ethyl group, an isopropyl group, an amino group, a hydroxyl group, a carboxyl group, a sulfone group, and a nitro group.
  • R 1 is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, from the viewpoint of storage stability and a passivation effect.
  • m represents an integer of 0 to 5.
  • m is preferably an integer of 1 to 5 from the viewpoint of storage stability.
  • M contains at least one metal element selected from the group consisting of Nb, Ta and Y from the viewpoint of the passivation effect.
  • M preferably contains at least one metal element selected from the group consisting of Nb, Ta, V, and Hf, and Nb, Ta, VO And at least one selected from the group consisting of Hf.
  • R 1 is more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms from the viewpoint of storage stability and a passivation effect.
  • m is preferably an integer of 1 to 5.
  • the state of the compound represented by the general formula (I) may be solid or liquid.
  • the compound represented by the general formula (I) is at room temperature (25 ° C.). And is preferably a liquid.
  • Compounds represented by the general formula (I) are niobium, niobium methoxide, niobium ethoxide, niobium isopropoxide, niobium n-propoxide, niobium n-butoxide, niobium t-butoxide, niobium isobutoxide, tantalum methoxide, Tantalum ethoxide, tantalum, tantalum isopropoxide, tantalum n-propoxide, tantalum n-butoxide, tantalum t-butoxide, tantalum isobutoxide, yttrium, yttrium methoxide, yttrium ethoxide, yttrium isopropoxide, yttrium n-propoxy Yttrium n-butoxide, yttrium t-butoxide, yttrium isobutoxide, vanadium, van
  • Propoxide and yttrium n-butoxide are preferred. From the viewpoint of obtaining a negative fixed charge density, niobium ethoxide, niobium n-propoxide, niobium n-butoxide, tantalum ethoxide, tantalum n-propoxide, tantalum n-butoxide, vanadium ethoxide oxide, vanadium n-propoxy Preference is given to oxides, vanadium n-butoxide oxide, hafnium ethoxide, hafnium n-propoxide and hafnium n-butoxide.
  • a prepared product or a commercially available product may be used as the compound represented by the general formula (I).
  • Commercially available products include, for example, pentamethoxyniobium, pentaethoxyniobium, penta-i-propoxyniobium, penta-n-propoxyniobium, penta-i-butoxyniobium, penta-n-butoxyniobium from High Purity Chemical Laboratory, Inc.
  • Penta-sec-butoxy niobium pentamethoxy tantalum, pentaethoxy tantalum, penta-i-propoxy tantalum, penta-n-propoxy tantalum, penta-i-butoxy tantalum, penta-n-butoxy tantalum, penta-sec-butoxy tantalum , Penta-t-butoxytantalum, vanadium (V) trimethoxide oxide, vanadium (V) triethoxy oxide, vanadium (V) tri-i-propoxide oxide, vanadium (V) tri-n-propoxide oxide, vanadium (V Tri-i-butoxide oxide, vanadium (V) tri-n-butoxide oxide, vanadium (V) tri-sec-butoxide oxide, vanadium (V) tri-t-butoxide oxide, tri-i-propoxy yttrium, tri-n -Butoxy yttrium, tetramethoxy
  • the preparation method includes an inert organic compound and a halide of a specific metal element (M) contained in the compound of formula (I).
  • a known production method such as a method of reacting in the presence of a solvent and adding ammonia or an amine compound to further extract halogen (Japanese Patent Laid-Open Nos. 63-227593 and 3-291247) can be used. .
  • the content of the compound of the formula (I) contained in the composition for forming a passivation layer 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 storage stability and a passivation effect, and 0.5% by mass to 70% by mass.
  • the content is preferably 1% by mass, more preferably 1% by mass to 60% by mass, and still more preferably 1% by mass to 50% by mass.
  • a chelating reagent chelating agent
  • EDTA ethylenediaminetetraacetic acid
  • bipyridine heme
  • naphthyridine benzimidazolylmethylamine
  • oxalic acid malonic acid
  • succinic acid glutaric acid, adipic acid, tartaric acid, maleic acid, phthalic acid and the like
  • succinic acid succinic acid
  • glutaric acid adipic acid
  • tartaric acid maleic acid
  • phthalic acid phthalic acid
  • malonic acid diesters examples thereof include ⁇ -diketone compounds, ⁇ -ketoester compounds, and malonic acid diesters.
  • chelating agents include acetylacetone, 3-methyl-2,4-pentanedione, 2,3-pentanedione, 3-ethyl-2,4-pentanedione, and 3-butyl-2,4-pentanedione.
  • ⁇ -diketone compounds such as 2,2,6,6-tetramethyl-3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione; Methyl acetate, ethyl acetoacetate, propyl acetoacetate, isobutyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, pentyl acetoacetate, isopentyl acetoacetate, hexyl acetoacetate, n-octyl acetoacetate, heptyl acetoacetate, acetoacetic acid 3 -Pentyl, ethyl 2-acetylheptanoate, ethyl 2-butylacetoacetate, 4,4-dimethyl-3 Ethyl oxovalerate, ethyl 4-methyl-3-oxovalerate
  • the presence of the chelate structure can be confirmed by a commonly used analysis method. For example, it can be confirmed using an infrared spectrum, a nuclear magnetic resonance spectrum or a melting point.
  • the specific metal alkoxide compound may be used in a state of hydrolysis and dehydration condensation polymerization.
  • the reaction can proceed in the presence of water and a catalyst.
  • water and catalyst may be distilled off.
  • Catalysts include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, boric acid, phosphoric acid, hydrofluoric acid; and formic acid, acetic acid, propionic acid, butyric acid, oleic acid, linoleic acid, salicylic acid, benzoic acid, phthalic acid, oxalic acid And organic acids such as lactic acid and succinic acid.
  • bases such as ammonia and an amine, as a catalyst.
  • the composition for forming a passivation layer may contain other precursors of a specific metal oxide other than the compound of formula (I).
  • the other precursor of a specific metal oxide will not be restrict
  • other precursors of specific metal oxides include niobic acid, niobium chloride, niobium monoxide, niobium carbide, niobium hydroxide, tantalum acid, tantalum chloride, tantalum pentabromide, vanadium oxychloride, Divanadium oxide, oxobis (2,4-pentanedionato) vanadium, yttrium chloride, yttrium nitrate, yttrium oxalate, yttrium stearate, yttrium carbonate, yttrium naphthenate, yttrium propionate, yttrium nitrate, yttrium
  • the composition for forming a passivation layer may further contain at least one selected from other inorganic oxides other than the specific metal compound and precursors thereof (hereinafter also referred to as other inorganic compounds).
  • Other inorganic compounds include aluminum oxide, silicon oxide, titanium oxide, gallium oxide, zirconium oxide, boron oxide, indium oxide, phosphorus oxide, zinc oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, oxide Examples include europium, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and precursors thereof.
  • the other inorganic compound is at least one selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, neodymium oxide, aluminum oxide, and precursors thereof.
  • a precursor of aluminum oxide a compound represented by the following general formula (II) is preferable.
  • each R 2 independently represents an alkyl group having 1 to 8 carbon atoms.
  • n represents an integer of 0 to 3.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group.
  • R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • a plurality of groups represented by the same symbol may be the same or different.
  • each R 2 independently represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group represented by R 2 may be linear or branched. Specific examples of the alkyl group represented by R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, hexyl, octyl, 2- 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 0 to 3. n is preferably an integer of 1 to 3 and more preferably 1 or 3 from the viewpoint of storage stability.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group. From the viewpoint of storage stability, at least one of X 2 and X 3 is preferably an oxygen atom.
  • R 3 , R 4 and R 5 in the general formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group represented by R 3 , R 4 and R 5 may be linear or branched.
  • the alkyl group represented by R 3 , R 4 and R 5 may have a substituent or may be unsubstituted, and is preferably unsubstituted.
  • the alkyl group represented by R 3 , R 4 and R 5 is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • alkyl group represented by R 3 , R 4 and R 5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and a hexyl group.
  • R 3 and R 4 in the general formula (II) are preferably each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms. Or it is more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • R 5 in the general formula (II) is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms from the viewpoint of storage stability and a passivation effect, and is preferably a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. It is more preferably an unsubstituted alkyl group.
  • 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 from the viewpoint of storage stability. Is preferred.
  • the compound represented by the general formula (II) is a compound in which n is 0, R 2 is each independently an alkyl group having 1 to 4 carbon atoms, and n is from the viewpoint of storage stability and a passivation effect. 1 to 3, R 2 is each independently an alkyl group having 1 to 4 carbon atoms, at least one of X 2 and X 3 is an oxygen atom, and R 3 and R 4 are each independently a hydrogen atom Alternatively, it is preferably an alkyl group having 1 to 4 carbon atoms, and R 5 is at least one selected from the group consisting of compounds having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is 0, R 2 is an unsubstituted alkyl group having 1 to 4 carbon atoms, and n is 1 to 3, 2 is an unsubstituted alkyl group having 1 to 4 carbon atoms, at least one of X 2 and X 3 is an oxygen atom, and R 3 or R 4 bonded to the oxygen atom is an alkyl group having 1 to 4 carbon atoms And when X 2 or X 3 is a methylene group, at least one selected from the group consisting of compounds wherein R 3 or R 4 bonded to the methylene group is a hydrogen atom and R 5 is a hydrogen atom is there.
  • organoaluminum compound (aluminum trialkoxide) represented by the general formula (II) where n is 0 include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-2-butoxyaluminum, mono-2-butoxy -Diisopropoxyaluminum, tri-t-butoxyaluminum, tri-n-butoxyaluminum and the like.
  • organoaluminum compound represented by the general formula (II), wherein n is 1 to 3 include aluminum ethyl acetoacetate diisopropylate [(ethyl acetoacetate) aluminum isopropoxide)], tris (ethyl Acetoacetate) aluminum and the like.
  • organoaluminum compound represented by the general formula (II) and n being 1 to 3 a prepared product or a commercially available product may be used.
  • commercially available products include Kawaken Fine Chemical Co., Ltd. trade names, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, and the like.
  • a chelating reagent chelating agent
  • the chelating reagent examples include the above-mentioned chelating reagents, and compounds having a specific structure having two carbonyl groups such as a ⁇ -diketone compound, a ⁇ -ketoester compound, and a malonic acid diester are preferable.
  • an alkoxide structure and a 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 thermal and chemical stability of the organoaluminum compound is improved, and the transition to aluminum oxide during heat treatment is suppressed. it is conceivable that. As a result, the transition to thermodynamically stable crystalline aluminum oxide is suppressed, and it is considered that amorphous aluminum oxide is easily formed.
  • the state of the metal oxide in the formed passivation layer can be confirmed by measuring an X-ray diffraction spectrum (XRD, X-ray diffraction). For example, it can be confirmed that the XRD has an amorphous structure by not showing a specific reflection pattern.
  • the composition for forming a passivation layer contains an organoaluminum compound
  • the aluminum oxide in the passivation layer obtained by heat treatment (firing) preferably has an amorphous structure.
  • the aluminum oxide is in an amorphous state, aluminum deficiency or oxygen deficiency is likely to occur, fixed charges are likely to be generated in the passivation layer, and a large passivation effect is likely to be obtained.
  • An organoaluminum compound represented by the general formula (II) and n is 1 to 3 is prepared by mixing an aluminum trialkoxide in which n is 0 and a compound having a specific structure having two carbonyl groups. Can do. Examples of the compound having a specific structure having two carbonyl groups include the chelating reagent. A commercially available aluminum chelate compound may also be used. When the aluminum trialkoxide and the chelating reagent are mixed, at least a part of the alkoxide group of the aluminum trialkoxide is substituted with a compound having a specific structure to form an aluminum chelate structure. At this time, if necessary, a solvent may be present, or heat treatment or addition of a catalyst 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 number of aluminum chelate structures is not particularly limited as long as it is 1 to 3. Among these, from the viewpoint of storage stability, it is preferably 1 or 3, and more preferably 1.
  • the number of aluminum chelate structures can be controlled, for example, by appropriately adjusting the mixing ratio of the aluminum trialkoxide and the compound having a specific structure having the two carbonyl groups. Moreover, you may select suitably the compound which has a desired structure from a commercially available aluminum chelate compound.
  • the compounds represented by the general formula (II) from the viewpoint of the passivation effect and the compatibility with the solvent contained as necessary, specifically, it consists of aluminum ethyl acetoacetate diisopropylate and triisopropoxyaluminum. It is preferable to use at least one selected from the group, and it is more preferable to use aluminum ethyl acetoacetate diisopropylate.
  • 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 aluminum compound is The content is preferably 0.1% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass. From the viewpoint of further improving the passivation effect, the content of the aluminum compound with respect to the total amount of the specific metal compound, the compound represented by the general formula (II) and Al 2 O 3 is 0.1% by mass to 99.9%.
  • the content is preferably 1% by mass, more preferably 1% by mass to 99% by mass, and still more preferably 2% to 70% by mass.
  • the composition of the metal oxide in the passivation layer obtained by heat-treating the composition for forming a passivation layer includes Nb 2 O 5 —Al 2 O 3 , Al Binary complex oxides such as 2 O 3 —Ta 2 O 5 , Al 2 O 3 —Y 2 O 3 , Al 2 O 3 —V 2 O 5 , Al 2 O 3 —HfO 2 ; and Nb 2 O 5 —Al 2 O 3 —Ta 2 O 5 , Al 2 O 3 —Y 2 O 3 —Ta 2 O 5 , Nb 2 O 5 —Al 2 O 3 —V 2 O 5 , Al 2 O 3 —HfO 2 —Ta And ternary complex oxides such as 2 O 5 .
  • the composition for forming a passivation layer preferably contains at least one niobium compound selected from the group consisting of Nb 2 O 5 and a compound in which M in the general formula (I) is Nb.
  • the content of the niobium compound in the composition for forming a passivation layer is 0.1% by mass to 99.9% by mass in terms of Nb 2 O 5. It is preferably 1% by mass to 99% by mass, more preferably 30% by mass to 85% by mass.
  • the composition of the metal oxide in the passivation layer obtained by heat-treating the composition for forming the passivation layer includes Nb 2 O 5 —Al 2 O 3 , Nb Binary complex oxides such as 2 O 5 —Ta 2 O 5 , Nb 2 O 5 —Y 2 O 3 , Nb 2 O 5 —V 2 O 5 , Nb 2 O 5 —HfO 2 ; and Nb 2 O 5 —Al 2 O 3 —Ta 2 O 5 , Nb 2 O 5 —Y 2 O 3 —Ta 2 O 5 , Nb 2 O 5 —Al 2 O 3 —V 2 O 5 , Nb 2 O 5 —HfO 2 —Ta And ternary complex oxides such as 2 O 5 . It is.
  • the composition for forming a passivation layer is applied to a semiconductor substrate to form a composition layer having a desired shape, and the composition layer is heat-treated (fired) to form a passivation layer having an excellent passivation effect. be able to.
  • the composition for forming a passivation layer is excellent in storage stability over time because the occurrence of problems such as gelation is suppressed.
  • the composition for forming a passivation layer preferably contains 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 uniform heat treatment layer can be formed.
  • the liquid medium is not particularly limited as long as it can dissolve or disperse the specific metal compound, and can be appropriately selected as necessary.
  • 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 isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, Ketone solvents such as dipropyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, diisopropyl Ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol dimethyl ether
  • Aprotic polar solvents such as methylene chloride, chloroform, dichloroethane, benzene, toluene, xylene, hexane, octane, ethylbenzene, 2-ethylhexanoic acid, methyl isobutyl ketone, methyl ethyl ketone; methanol, ethanol, n-propanol , Isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentano , T-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-oct
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono -Glycol monoether solvents such as n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether; terpinene, terpineol, myrcene, alloocimene, limonene, dipentene, pinene, carvone , Oshimen Terpene solvents such as phellandrene; and water.
  • These liquid media are used alone or in combination of two or more.
  • the liquid medium is at least selected from the group consisting of a hydrophobic organic solvent, an aprotic organic solvent, a terpene solvent, an ester solvent, an ether solvent, and an alcohol solvent from the viewpoint of impartability to a semiconductor substrate and pattern formation.
  • 1 type is preferably included, more preferably at least one selected from the group consisting of terpene solvents, ester solvents, and alcohol solvents, and more preferably at least one selected from the group consisting of terpene solvents. Further preferred.
  • the content of the liquid medium in the composition for forming a passivation layer is determined in consideration of applicability, pattern formability, and storage stability.
  • the content of the liquid medium is preferably 5% by mass to 98% by mass in the composition for forming a passivation layer, from the viewpoint of impartability of the composition for forming a passivation layer and pattern formability. More preferably, it is 95% by mass.
  • the composition for forming a passivation layer preferably contains 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 selectively formed in a desired shape.
  • the type of resin is not particularly limited. Among these, when the composition for forming a passivation layer is applied on a semiconductor substrate, a resin capable of adjusting the viscosity within a range in which a good pattern can be formed is preferable.
  • the resin include polyvinyl alcohol, polyacrylamide, polyacrylamide derivatives, polyvinyl amide, polyvinyl amide derivatives, polyvinyl pyrrolidone, polyethylene oxide, polyethylene oxide derivatives, polysulfonic acid, acrylamide alkyl sulfonic acid, cellulose, cellulose derivatives (carboxymethyl cellulose, Hydroxyethyl cellulose, cellulose ethers such as 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,
  • (meth) acrylic acid means at least one of “acrylic acid” and “methacrylic acid”
  • (meth) acrylate means at least one of “acrylate” and “methacrylate”. means.
  • a neutral resin having no acidic or basic functional group it is preferable to use a neutral resin having no acidic or basic functional group, and even when the content is small, viscosity and From the viewpoint of adjusting thixotropy, it is more preferable to use a cellulose derivative such as ethyl cellulose.
  • the molecular weight of the resin is not particularly limited, and is preferably adjusted appropriately in view of a desired viscosity as the passivation layer forming composition.
  • the weight average molecular weight of the resin is preferably from 100 to 10,000,000, more preferably from 1,000 to 5,000,000, from the viewpoints of storage stability and pattern formability.
  • the weight average molecular weight of resin is calculated
  • the calibration curve is approximated by a cubic equation using a standard polystyrene 5 sample set (PStQuick MP-H, PStQuick B [Tosoh Corporation, trade name]).
  • PStQuick MP-H PStQuick B [Tosoh Corporation, trade name]
  • 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 30% by mass in the composition for forming a passivation layer.
  • the resin content is more preferably 1% by mass to 25% by mass, and further preferably 1.5% by mass to 20% by mass.
  • the content is preferably 1.5% by mass to 10% by mass.
  • the content ratio between the specific metal compound and the resin can be appropriately selected as necessary.
  • the content ratio of the resin to the total amount of the specific metal compound (resin / specific metal compound) is preferably 0.001 to 1000, preferably 0.01 to 100. It is more preferable that the ratio is 0.1 to 1.
  • the composition for forming a passivation layer may contain an acidic compound or a basic compound.
  • the content of the acidic compound or the basic compound is 1% by mass or less in the composition for forming a passivation layer, respectively. It is preferable that the content is 0.1% by mass or less.
  • acidic compounds include Bronsted acid and Lewis acid. Specific examples include inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as acetic acid.
  • Examples of basic compounds include Bronsted bases and Lewis bases.
  • examples of basic compounds include inorganic bases such as alkali metal hydroxides and alkaline earth metal hydroxides, and trialkyls. Examples thereof include organic bases such as amine and pyridine.
  • the composition for forming a passivation layer contains, as necessary, various additives such as a thickener, a wetting agent, a surfactant, inorganic particles, a resin containing silicon atoms, and a thixotropic agent. Also good.
  • inorganic particles examples include silica (silicon oxide), clay, silicon carbide, silicon nitride, montmorillonite, bentonite, and carbon black. Among these, it is preferable to use a filler containing silica as a component.
  • clay refers to a layered clay mineral, and specific examples include kaolinite, imogolite, montmorillonite, smectite, sericite, illite, talc, stevensite, and zeolite.
  • the composition for forming a passivation layer contains inorganic particles, the impartability of the composition for forming a passivation layer tends to be improved.
  • the surfactant examples include nonionic surfactants, cationic surfactants, and anionic surfactants. Among these, nonionic surfactants or cationic surfactants are preferred because impurities such as heavy metals are not brought into the semiconductor device. Furthermore, examples of the nonionic surfactant include a silicon surfactant, a fluorine surfactant, and a hydrocarbon surfactant. When the composition for forming a passivation layer contains a surfactant, the thickness and composition uniformity of the composition layer formed from the composition for forming a passivation layer tend to be improved.
  • Examples of the resin containing silicon atom include terminal lysine-modified silicone, alternating copolymer of polyamide and silicone, side chain alkyl-modified silicone, side chain polyether-modified silicone, terminal alkyl-modified silicone, silicone-modified pullulan, silicone-modified acrylic, etc. can do.
  • the thickness and composition uniformity of the composition layer formed from the passivation layer forming composition tend to be improved.
  • thixotropic agents include polyether compounds, fatty acid amides, fumed silica, hydrogenated castor oil, urea urethane amide, polyvinyl pyrrolidone, oily gelling agents and the like.
  • the composition for forming a passivation layer contains a thixotropic agent, fine line formability (when applying the composition for forming a passivation layer and when drying the composition layer, the expansion of the line width of the linear pattern is suppressed. Tend to improve).
  • the polyether compound include polyethylene glycol, polypropylene glycol, poly (ethylene-propylene) glycol copolymer and the like.
  • the viscosity of the composition for forming a passivation layer 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 can be 0.01 Pa ⁇ s to 10,000 Pa ⁇ s.
  • the viscosity of the composition for forming a passivation layer is preferably 0.1 Pa ⁇ s to 1000 Pa ⁇ s.
  • the viscosity is measured at 25 ° C. and a shear rate of 1.0 s ⁇ 1 using a rotary shear viscometer.
  • the shear viscosity of the composition for forming a passivation layer is not particularly limited. Among them from the viewpoints of pattern formability, thixotropic ratio calculated by dividing the shear viscosity eta 1 at shear viscosity eta 2 at a shear rate of 10s -1 at a shear rate of 1.0s -1 ( ⁇ 1 / ⁇ 2 ) is 1. It is preferably from 05 to 100, more preferably from 1.1 to 50. The shear viscosity is measured at a temperature of 25 ° C. using a rotary shear viscometer equipped with a cone plate (diameter 50 mm, cone angle 1 °).
  • a specific metal compound and a liquid medium or the like contained as necessary can be mixed and produced by a commonly used method.
  • the kind of component contained in the said composition for passivation layer formation and content of each component are thermal analysis, such as TG / DTA; Spectrum analysis, such as NMR and IR; Chromatographic analysis, such as HPLC and GPC; Can be used to confirm.
  • the method for manufacturing a solar cell element of the present invention includes a step of forming a light receiving surface electrode on a light receiving surface of a semiconductor substrate, a step of forming a back electrode on the back surface opposite to the light receiving surface of the semiconductor substrate, From at least one of the light receiving surface, the back surface, and the side surface, Nb 2 O 5 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3 , HfO 2 and the compound represented by the general formula (I) Providing a composition for forming a passivation layer containing at least one compound selected from the group consisting of forming a composition layer; and heat-treating the composition layer to form a passivation layer; Have The method for manufacturing a solar cell element of the present invention may further include other steps as necessary. What was demonstrated by the solar cell element is applicable about the composition for formation of a passivation layer.
  • a passivation layer having an excellent passivation effect can be formed on the semiconductor substrate. Further, the passivation layer can be formed with high productivity by a simple method that does not require a vapor deposition apparatus or the like. Therefore, according to the said method, the solar cell element excellent in conversion efficiency can be manufactured by a simple method.
  • a commonly used method can be employed. For example, it can be formed by applying an electrode forming paste such as a silver paste or an aluminum paste to a desired region of a semiconductor substrate and performing a heat treatment (firing) as necessary.
  • an electrode forming paste such as a silver paste or an aluminum paste
  • the step of forming the light receiving surface electrode and the step of forming the back surface electrode include a step of forming the composition layer by applying the composition for forming a passivation layer to at least one of the light receiving surface, the back surface, and the side surface of the semiconductor substrate. It may be before or after. Further, the heat treatment (firing) for forming the electrode and the heat treatment (firing) for forming the passivation layer from the composition layer may be performed collectively or separately as independent steps.
  • the semiconductor substrate can be washed by immersing the semiconductor substrate in a mixed solution of ammonia water and hydrogen peroxide solution and treating at 60 ° C. to 80 ° C. to remove organic substances and particles.
  • the washing time is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 5 minutes.
  • a method for applying a composition for forming a passivation layer on a semiconductor substrate using a known application method or the like can be mentioned.
  • Specific examples include a printing method such as an immersion method and a screen printing method, a spin coating method, a brush coating method, a spray method, a doctor blade method, a roll coating method, and an ink jet method.
  • the screen printing method and the ink jet method are preferable, and the screen printing method is more preferable.
  • the amount of the passivation layer forming composition applied to the semiconductor substrate can be appropriately selected depending on the purpose.
  • the thickness of the passivation layer to be formed can be appropriately adjusted so as to have 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 (baked material layer) derived from the composition layer. be able to.
  • the composition for forming a passivation layer contains a specific metal compound and other optional metal compounds (such as organoaluminum compounds), the specific metal oxide and other inorganic oxides that are heat-treated products (fired products) If it can be converted into (aluminum oxide (Al 2 O 3 ) or the like), the heat treatment (firing) conditions of the composition layer are not particularly limited.
  • the heat treatment (firing) conditions that can form an amorphous specific metal oxide having no crystal structure are preferable.
  • the passivation layer is composed of an amorphous specific metal oxide, the passivation layer can effectively have a negative charge, and a more excellent passivation effect can be obtained.
  • the heat treatment (firing) temperature is preferably 400 ° C. or higher, more preferably 400 ° C. to 900 ° C., and still more preferably 600 ° C. to 800 ° C.
  • the heat treatment (firing) temperature here means the maximum temperature in the furnace used for the heat treatment (firing).
  • the heat treatment (firing) time can be appropriately selected according to the heat treatment (firing) temperature and the like. For example, it can be 5 seconds to 10 hours, and is preferably 10 seconds to 5 hours.
  • the heat treatment (firing) time here means the holding time at the maximum temperature.
  • the heat treatment (firing) can be performed using a diffusion furnace (for example, ACCURON CQ-1200, Hitachi Kokusai Electric Inc .; 206A-M100, Koyo Thermo System Co., Ltd., etc.).
  • the atmosphere in which the heat treatment (firing) is performed is not particularly limited, and can be performed in the air.
  • a step of drying the composition layer may be further included before the step of heat-treating (sintering) the composition layer to form the passivation layer.
  • the step of drying the composition layer is not particularly limited as long as at least a part of the liquid medium that may be contained in the passivation layer forming composition can be removed.
  • the drying treatment can be, for example, a heat treatment at 30 ° C. to 250 ° C. for 10 seconds to 60 minutes, preferably a heat treatment at 40 ° C. to 220 ° C. for 30 seconds to 10 minutes.
  • the drying treatment may be performed under normal pressure or under reduced pressure.
  • FIG. 1 illustrates, as a cross-sectional view, a process diagram 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 usage method of the present invention.
  • an n + -type diffusion layer 2 is formed in the vicinity of the surface, and an antireflection film 3 is formed on the surface.
  • the antireflection film 3 a silicon nitride film, a titanium oxide film, or the like is known.
  • a surface protective film such as silicon oxide may be present between the antireflection film 3 and the p-type semiconductor substrate 1.
  • the passivation layer according to the present invention may be used as a surface protective film. In that case, although not shown, an antireflection film may be further laminated on the passivation layer to form a two-layer structure.
  • the passivation layer according to the present invention is formed on the light receiving surface, high conversion efficiency is achieved even in a solar cell (not shown) having a general structure in which an aluminum electrode is formed on the entire back surface, instead of a point contact structure as described later. It can be realized.
  • a material for forming the back electrode 5 such as an aluminum electrode paste is applied to a partial region of the back surface, and then heat-treated (fired) to form the back electrode 5, and p A p + type diffusion layer 4 is formed by diffusing aluminum atoms in the type semiconductor substrate 1.
  • the electrode-forming paste is applied to the light-receiving surface side, and then heat-treated (fired) to form the light-receiving surface electrode 7.
  • the electrode-forming paste By using those containing glass particles having a fire-through property as an electrode forming paste, it reaches through the antireflective film 3, as shown in FIG. 1 (c), on the n + -type diffusion layer 2, the light-receiving surface
  • the electrode 7 can be formed to obtain an ohmic contact.
  • the composition for passivation layer formation is provided by screen printing etc. on the p-type layer of the back surface other than the area
  • the passivation layer 6 is formed by heat-treating (baking) the composition layer formed on the p-type layer. By forming the passivation layer 6 on the p-type layer on the back surface, a solar cell element having excellent power generation efficiency can be manufactured.
  • the back electrode made of aluminum or the like can have a point contact structure, and the warpage of the substrate can be reduced.
  • FIG. 1D shows a method of forming a passivation layer only on the back surface portion, but in addition to the back surface of the p-type semiconductor substrate 1, a passivation layer forming composition is also applied to the side surface, and this is subjected to heat treatment (
  • the passivation layer 6 may be further formed on the side surface (edge) of the semiconductor substrate 1 by baking (not shown). Thereby, the solar cell element excellent in power generation efficiency can be manufactured.
  • the passivation layer 6 may be formed by forming the passivation layer forming composition of the present invention only on the side surface without forming the passivation layer on the back surface, and performing heat treatment (firing). When the composition for forming a passivation layer of the present invention is used in a place where there are many crystal defects such as side surfaces, the effect is particularly great.
  • an electrode such as aluminum may be formed on the entire surface by vapor deposition or the like, and it is necessary to perform heat treatment (firing) at a high temperature. No electrode may be formed on the entire surface.
  • FIG. 2 illustrates, as a cross-sectional view, a process diagram schematically showing another example of a method for manufacturing a solar cell element having a passivation layer according to the present embodiment.
  • FIG. 2 shows the heat treatment of the aluminum electrode paste after forming the p + type diffusion layer using the aluminum electrode paste or the p type diffusion layer forming composition capable of forming the p + type diffusion layer by thermal diffusion treatment.
  • the process drawing including the process of removing the heat-treated product of the product or the p + -type diffusion layer forming composition will be described as a cross-sectional view.
  • the p-type diffusion layer forming composition can be configured to include, for example, an acceptor element-containing material and a glass component.
  • an n + -type diffusion layer 2 is formed in the vicinity of the surface of the p-type semiconductor substrate 1, and an antireflection film 3 is formed on the surface.
  • an antireflection film 3 a silicon nitride film, a titanium oxide film, or the like is known.
  • the p + -type diffusion layer 4 is formed by applying a p + -type diffusion layer forming composition to a partial region of the back surface and then performing heat treatment.
  • a heat treatment product 8 of a composition for forming a p + type diffusion layer is formed on the p + type diffusion layer 4.
  • an aluminum electrode paste may be used instead of the p-type diffusion layer forming composition.
  • an aluminum electrode 8 is formed on the p + type diffusion layer 4.
  • the heat-treated product 8 or the aluminum electrode 8 of the p-type diffusion layer forming composition formed on the p + -type diffusion layer 4 is removed by a technique such as etching.
  • the electrode forming paste is selectively applied to the light receiving surface (front surface) and a part of the back surface, and then heat-treated, and the light receiving surface electrode 7 is applied to the light receiving surface (front surface).
  • the back electrode 5 is formed on the back surface.
  • the electrode forming paste for forming the back electrode 5 is not limited to the aluminum electrode paste, but a lower electrode such as a silver electrode paste. An electrode paste capable of forming a resistive electrode can also be used. As a result, the power generation efficiency can be further increased.
  • the composition for passivation layer formation of this invention is provided on the p-type layer of the back surface other than the area
  • the application can be performed by a method such as screen printing.
  • the passivation layer 6 is formed by heat-treating (firing) the composition layer formed on the p + -type diffusion layer 4. By forming the passivation layer 6 on the p-type layer, a solar cell element excellent in power generation efficiency can be manufactured.
  • FIG. 2E shows a method of forming a passivation layer only on the back surface portion.
  • a passivation layer forming composition is applied to the side surface and heat treatment (firing). ) To further form a passivation layer on the side surface (edge) of the p-type semiconductor substrate 1 (not shown).
  • the solar cell element excellent in power generation efficiency can be manufactured.
  • the passivation layer forming composition of the present invention may be applied only to the side surface, and this may be heat-treated (fired) to form a passivation layer.
  • the composition for forming a passivation layer of the present invention is used in a place where there are many crystal defects such as side surfaces, the effect is particularly great.
  • an electrode such as aluminum may be formed on the entire surface by vapor deposition or the like, or heat treatment (firing) is performed at a high temperature.
  • An unnecessary electrode may be formed on the entire surface.
  • a p-type semiconductor substrate having an n + -type diffusion layer formed on the light-receiving surface has been described.
  • an n-type semiconductor substrate having a p + -type diffusion layer formed on the light-receiving surface is described.
  • a solar cell element can be produced.
  • an n + type diffusion layer is formed on the back side.
  • the solar cell module of this invention has the above-mentioned solar cell element and the wiring material arrange
  • the solar cell module includes at least one of the solar cell elements, and is configured by arranging a wiring material such as a tab wire on the electrode of the solar cell element. If necessary, the solar cell may be constituted by connecting a plurality of solar cell elements via a wiring material and further sealing with a sealing material.
  • the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in the industry. There is no restriction
  • Example 1> (Preparation of a composition for forming a passivation layer) Al 2 O 3 thin film coating material (High purity chemical research institute “SYM-Al04”, Al 2 O 3 : 2% by mass, xylene: 87% by mass, 2-propanol: 5% by mass, stabilizer: 6% by mass %) And Nb 2 O 5 thin film coating material (High Purity Chemical Research Institute “Nb-05”, Nb 2 O 5 : 5% by mass, n-butyl acetate: 56% by mass, stabilizer : 16.5 mass%, viscosity modifier: 22.5 mass%) was mixed to prepare a composition 1 for forming a passivation layer.
  • Al 2 O 3 thin film coating material High purity chemical research institute “SYM-Al04”, Al 2 O 3 : 2% by mass, xylene: 87% by mass, 2-propanol: 5% by mass, stabilizer: 6% by mass %
  • Nb 2 O 5 thin film coating material High Purity Chemical Research Institute
  • a single crystal p-type silicon substrate (SUMCO, 50 mm square, thickness: 625 ⁇ m) having a mirror-shaped surface was used.
  • the silicon substrate was cleaned by immersing it at 70 ° C. for 5 minutes using an RCA cleaning solution (Kanto Chemical Co., Ltd., Frontier Cleaner-A01), and pre-processing was performed. Thereafter, a spin coater (Mikasa Co., “MS-100”) is used on the entire surface of one surface of the silicon substrate pretreated with the composition 1 for forming a passivation layer obtained above at 30 rpm at 4000 rpm (min ⁇ 1 ). It was given on condition of second. Then, it dried at 150 ° C.
  • the effective lifetime ( ⁇ s) of the region where the passivation layer of the evaluation substrate obtained above is formed is reflected at room temperature (25 ° C.) using a lifetime measurement device (Nippon Semi-Lab Co., Ltd., WT-2000PVN). It was measured by the microwave photoconductive decay method. The effective lifetime was 480 ⁇ s.
  • the density was calculated from the mass and average thickness of the passivation layer. The density was 3.2 g / cm 3 .
  • an aluminum electrode PVG solutions, PVG-AD-02
  • a silver electrode DuPont, PV159A
  • a solar cell element was produced by heat treatment (firing) at 700 ° C. using a tunnel-type firing furnace (Noritake Co., Ltd.).
  • the produced solar cell element was put in a constant temperature and humidity chamber at 50 ° C. and 80% RH, and power generation characteristics after storage for 1 month were evaluated.
  • the results are shown in Table 3.
  • the rate of change in conversion efficiency after storage of the solar cell element conversion efficiency ⁇ 2 [%] after storage relative to conversion efficiency ⁇ 1 before storage was 99.7%.
  • Example 2> (Preparation of a composition for forming a passivation layer) Ta 2 O 5 thin film coating material (High Purity Chemical Laboratory, “Ta-10-P”, Ta 2 O 5 : 10% by mass, n-octane: 9% by mass, n-butyl acetate: 60% by mass, Stabilizer: 21% by mass) was used as composition 2 for forming a passivation layer.
  • Ta-10-P High Purity Chemical Laboratory
  • Ta 2 O 5 10% by mass
  • n-octane 9% by mass
  • n-butyl acetate 60% by mass
  • Stabilizer 21% by mass
  • a substrate for evaluation was produced in the same manner as in Example 1 except that the composition 2 for forming a passivation layer prepared above was used, and evaluated in the same manner as in Example 1.
  • the effective lifetime was 450 ⁇ s.
  • the thickness of the passivation layer was 75 nm, and the density was 3.6 g / cm 3 .
  • a solar cell element was produced in the same manner as in Example 1 except that the passivation layer forming composition 2 was used instead of the passivation layer forming composition 1, and the power generation characteristics were evaluated.
  • HfO 2 thin film coating material High Purity Chemical Laboratory, “Hf-05”, HfO 2 content: 5% by mass, isoamyl acetate: 73% by mass, n-octane: 10% by mass, isopropyl alcohol: 5% by mass , Stabilizer: 7% by mass
  • HfO 2 thin film coating material High Purity Chemical Laboratory, “Hf-05”, HfO 2 content: 5% by mass, isoamyl acetate: 73% by mass, n-octane: 10% by mass, isopropyl alcohol: 5% by mass , Stabilizer: 7% by mass
  • An evaluation substrate was prepared in the same manner as in Example 1 except that the passivation layer forming composition 3 prepared above was used, and evaluated in the same manner as in Example 1.
  • the effective lifetime was 380 ⁇ s.
  • the thickness of the passivation layer was 71 nm and the density was 3.2 g / cm 3 .
  • a solar cell element was produced in the same manner as in Example 1 except that the passivation layer forming composition 3 was used instead of the passivation layer forming composition 1, and power generation characteristics were evaluated.
  • Y 2 O 3 thin film coating material High Purity Chemical Laboratory, “Y-03”, Y 2 O 3 : 3% by mass, 2-ethylhexanoic acid: 12.5% by mass, n-butyl acetate: 22. 5% by mass, ethyl acetate: 8% by mass, terpin oil: 45% by mass, viscosity modifier: 9% by mass
  • Y-03 Y 2 O 3 thin film coating material
  • An evaluation substrate was prepared in the same manner as in Example 1 except that the passivation layer forming composition 4 prepared above was used, and evaluation was performed in the same manner as in Example 1.
  • the effective lifetime was 390 ⁇ s.
  • the thickness of the passivation layer was 68 nm and the density was 2.8 g / cm 3 .
  • a solar cell element was produced in the same manner as in Example 1 except that the passivation layer forming composition 4 was used instead of the passivation layer forming composition 1, and the power generation characteristics were evaluated.
  • Ethyl acetoacetate aluminum diisopropylate (“ALCH” manufactured by Kawaken Fine Chemical Co., Ltd.), pentaethoxyniobium (Hokuko Chemical Co., Ltd.), acetylacetone (Wako Pure Chemical Industries, Ltd.), xylene (Wako Pure Chemical Industries, Ltd.), 2-Propanol (Wako Pure Chemical Industries, Ltd.) and terpineol (Nippon Terpene Chemical Co., Ltd.) were mixed at the orientation ratio shown in Table 1, and used as the passivation layer forming composition 5.
  • a passivation layer was formed on a pretreated silicon substrate and evaluated in the same manner as in Example 1 except that the composition 5 for forming a passivation layer prepared above was used.
  • the effective lifetime was 420 ⁇ s.
  • the thickness of the passivation layer was 94 nm and the density was 2.6 g / cm 3 .
  • a solar cell element was produced in the same manner as in Example 1 except that the passivation layer forming composition 5 was used instead of the passivation layer forming composition 1, and power generation characteristics were evaluated.
  • Example 1 An evaluation substrate and a solar cell element were produced in the same manner as in Example 1, except that the passivation layer forming composition 1 was not applied. The effective lifetime of the evaluation substrate was measured and evaluated. The effective lifetime was 20 ⁇ s.
  • a colorless and transparent composition C2 was prepared by mixing 2.00 g of Al 2 O 3 particles (High Purity Chemical Laboratory Co., Ltd., average particle size 1 ⁇ m), 1.98 g of terpineol, and 3.98 g of ethyl cellulose solution.
  • a substrate for evaluation was produced in the same manner as in Example 1 except that the composition C2 prepared above was used, and evaluated in the same manner as in Example 1.
  • the effective lifetime was 21 ⁇ s.
  • the thickness of the passivation layer was 2.1 ⁇ m, and the density was 1.4 g / cm 3 .
  • the thickness could not be measured with an interference type film thickness meter, it was measured with a stylus type step meter (AmBios, XP-2). Specifically, a part of the substrate was scraped off with a spatula, and the level difference between the applied portion and the scraped portion was measured under the conditions of a speed of 0.1 mm / s and a needle load of 0.5 mg. The measurement was performed three times, and the average value was calculated as the thickness.
  • a solar cell element was produced in the same manner as in Example 1 except that the composition C2 was used instead of the composition 1 for forming a passivation layer, and power generation characteristics were evaluated.
  • a colorless and transparent composition C3 was prepared by mixing 2.01 g of tetraethoxysilane, 1.99 g of terpineol, and 4.04 g of an ethylcellulose solution prepared in the same manner as in Comparative Example 2.
  • An evaluation substrate was prepared in the same manner as in Example 1 except that the composition C3 prepared above was used, and evaluated in the same manner as in Example 1. The effective lifetime was 23 ⁇ s.
  • the thickness of the passivation layer was 85 nm and the density was 2.1 g / cm 3 .
  • a solar cell element was produced in the same manner as in Example 1 except that the composition C3 was used instead of the composition 1 for forming a passivation layer, and power generation characteristics were evaluated.
  • the solar cell element of the present invention has a passivation layer having an excellent passivation effect, and thus exhibits high conversion efficiency and suppresses deterioration of solar cell characteristics over time. Furthermore, it turns out that the passivation layer of the solar cell element of this invention can be formed in a desired shape by a simple process.
  • a passivation film used for a solar cell element including aluminum oxide and niobium oxide and having a silicon substrate.
  • niobium oxide / aluminum oxide a mass ratio (niobium oxide / aluminum oxide) between the niobium oxide and the aluminum oxide is 30/70 to 90/10.
  • ⁇ 3> The passivation film according to ⁇ 1> or ⁇ 2>, in which a total content of the niobium oxide and the aluminum oxide is 90% by mass or more.
  • the passivation film according to any one of ⁇ 1> to ⁇ 4> which is a heat-treated product of a coating type material including an aluminum oxide precursor and a niobium oxide precursor.
  • a p-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
  • An n-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
  • a first electrode formed on the surface of the n-type impurity diffusion layer on the light-receiving surface side of the silicon substrate;
  • a passivation film comprising aluminum oxide and niobium oxide formed on the back surface of the silicon substrate and having a plurality of openings;
  • a second electrode forming an electrical connection with the surface on the back side of the silicon substrate through the plurality of openings;
  • a solar cell element comprising:
  • a p-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
  • An n-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
  • a first electrode formed on the surface of the n-type impurity diffusion layer on the light-receiving surface side of the silicon substrate;
  • a p-type impurity diffusion layer formed on a part or all of the back side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate;
  • a passivation film comprising aluminum oxide and niobium oxide formed on the back surface of the silicon substrate and having a plurality of openings;
  • a second electrode that forms an electrical connection with the surface of the p-type impurity diffusion layer on the back side of the silicon substrate through the plurality of openings;
  • a solar cell element comprising:
  • An n-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
  • a p-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
  • a second electrode formed on the back side of the silicon substrate;
  • a passivation film formed on the light-receiving surface side surface of the silicon substrate and including a plurality of openings and containing aluminum oxide and niobium oxide;
  • a first electrode formed on the surface of the p-type impurity diffusion layer on the light-receiving surface side of the silicon substrate and forming an electrical connection with the surface on the light-receiving surface side of the silicon substrate through the plurality of openings;
  • a solar cell element comprising:
  • ⁇ 10> The solar cell element according to any one of ⁇ 7> to ⁇ 9>, wherein a mass ratio of niobium oxide to aluminum oxide (niobium oxide / aluminum oxide) in the passivation film is 30/70 to 90/10.
  • ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a total content of the niobium oxide and the aluminum oxide in the passivation film is 90% by mass or more.
  • ⁇ 12> a silicon substrate;
  • a passivation film having a long carrier lifetime of a silicon substrate and having a negative fixed charge can be realized at low cost.
  • a coating type material for realizing the formation of the passivation film can be provided.
  • a highly efficient solar cell element using the passivation film can be realized at low cost.
  • a silicon substrate with a passivation film having a long carrier lifetime and a negative fixed charge can be realized at low cost.
  • the passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and niobium oxide.
  • the fixed charge amount of the film can be controlled by changing the composition of the passivation film.
  • the mass ratio of niobium oxide and aluminum oxide is 30/70 to 80/20 from the viewpoint that the negative fixed charge can be stabilized. Further, the mass ratio of niobium oxide and aluminum oxide is more preferably 35/65 to 70/30 from the viewpoint that the negative fixed charge can be further stabilized. Further, the mass ratio of niobium oxide and aluminum oxide is preferably 50/50 to 90/10 from the viewpoint that both improvement of carrier lifetime and negative fixed charge can be achieved.
  • the mass ratio of niobium oxide to aluminum oxide in the passivation film is measured by energy dispersive X-ray spectroscopy (EDX), secondary ion mass spectrometry (SIMS), and high frequency inductively coupled plasma mass spectrometry (ICP-MS). be able to.
  • Specific measurement conditions are as follows. Dissolving the passivation film in acid or alkaline aqueous solution, atomizing this solution and introducing it into Ar plasma, measuring the wavelength and intensity by spectroscopically analyzing the light emitted when the excited element returns to the ground state, Element qualification is performed from the obtained wavelength, and quantification is performed from the obtained intensity.
  • the total content of niobium oxide and aluminum oxide in the passivation film is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of maintaining good characteristics. As the components of niobium oxide and aluminum oxide in the passivation film increase, the effect of negative fixed charges increases.
  • the total content of niobium oxide and aluminum oxide in the passivation film can be measured by combining thermogravimetric analysis, fluorescent X-ray analysis, ICP-MS, and X-ray absorption spectroscopy. Specific measurement conditions are as follows.
  • the ratio of inorganic components can be calculated by thermogravimetric analysis, the ratio of niobium and aluminum can be calculated by fluorescent X-ray or ICP-MS analysis, and the ratio of oxide can be examined by X-ray absorption spectroscopy.
  • components other than niobium oxide and aluminum oxide may be included as organic components from the viewpoint of improving the film quality and adjusting the elastic modulus.
  • the presence of the organic component in the passivation film can be confirmed by elemental analysis and measurement of the FT-IR of the film.
  • the content of the organic component in the passivation film is more preferably less than 10% by mass, further preferably 5% by mass or less, and particularly preferably 1% by mass or less in the passivation film.
  • the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a niobium oxide precursor. Details of the coating type material will be described next.
  • the coating material of the present embodiment includes an aluminum oxide precursor and a niobium oxide precursor, and is used for forming a passivation film for a solar cell element having a silicon substrate.
  • the aluminum oxide precursor can be used without particular limitation as long as it produces aluminum oxide.
  • As the aluminum oxide precursor it is preferable to use an organic aluminum oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and chemically stable.
  • organic aluminum oxide precursors include aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , High Purity Chemical Research Laboratory SYM-AL04, and the like.
  • the niobium oxide precursor can be used without particular limitation as long as it produces niobium oxide.
  • the niobium oxide precursor it is preferable to use an organic niobium oxide precursor from the viewpoint of uniformly dispersing niobium oxide on the silicon substrate and chemically stable.
  • organic niobium oxide precursors include niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), High Purity Chemical Laboratory Nb-05, etc. be able to.
  • a passivation film is formed by forming a coating type material containing an organic niobium oxide precursor and an organic aluminum oxide precursor using a coating method or a printing method, and then removing organic components by a subsequent heat treatment (firing). Can be obtained. Therefore, as a result, a passivation film containing an organic component may be used.
  • FIGS. 6 to 9 are cross-sectional views showing first to fourth configuration examples of the solar cell element using a passivation film on the back surface of the present embodiment.
  • silicon substrate (crystalline silicon substrate, semiconductor substrate) 101 used in this embodiment mode either single crystal silicon or polycrystalline silicon may be used. Further, as the silicon substrate 101, either p-type crystalline silicon or n-type crystalline silicon may be used. From the standpoint of exerting the effects of the present embodiment, p-type crystalline silicon is more suitable.
  • the single crystal silicon or polycrystalline silicon used for the silicon substrate 101 may be arbitrary, but single crystal silicon or polycrystalline silicon having a resistivity of 0.5 ⁇ ⁇ cm to 10 ⁇ ⁇ cm is preferable.
  • a light receiving surface antireflection film 103 such as a silicon nitride (SiN) film, and a first electrode 105 (light receiving surface side electrode, first surface electrode, upper surface electrode) using silver (Ag) or the like. , A light receiving surface electrode) is formed.
  • the light receiving surface antireflection film 103 may also have a function as a light receiving surface passivation film. By using the SiN film, both functions of the light receiving surface antireflection film and the light receiving surface passivation film can be provided.
  • the solar cell element of the present embodiment may or may not have the light-receiving surface antireflection film 103.
  • the light receiving surface of the solar cell element is preferably formed with a concavo-convex structure (texture structure) in order to reduce the reflectance on the surface, but the solar cell element of the present embodiment has a texture structure. It may or may not have.
  • a BSF (Back Surface Field) layer 104 which is a layer doped with a group III element such as aluminum or boron, is formed on the back side (lower side, second side, back side in the figure) of the silicon substrate 101.
  • the solar cell element of this embodiment may or may not have the BSF layer 104.
  • a second surface made of aluminum or the like is used on the back surface side of the silicon substrate 101 to make contact (electrical connection) with the BSF layer 104 (or the surface on the back surface side of the silicon substrate 101 when the BSF layer 104 is not provided). Electrodes 106 (back side electrode, second side electrode, back side electrode) are formed.
  • the contact region (the surface on the back surface side of the silicon substrate 101 when the BSF layer 104 is not provided) and the second electrode 106 are electrically connected.
  • a passivation film (passivation layer) 107 containing aluminum oxide and niobium oxide is formed in a portion excluding the opening OA).
  • the passivation film 107 of this embodiment can have a negative fixed charge. With this fixed charge, electrons which are minority carriers among the carriers generated in the silicon substrate 101 by light are bounced back to the surface side. For this reason, a short circuit current increases and it is anticipated that photoelectric conversion efficiency will improve.
  • the second electrode 106 is formed on the entire surface of the contact region (opening OA) and the passivation film 107.
  • the second electrode 106 is formed only in the region (opening OA).
  • the second electrode 106 may be formed only in part on the contact region (opening OA) and the passivation film 107. Even with the solar cell element having the configuration shown in FIG. 7, the same effect as that of FIG. 6 (first configuration example) can be obtained.
  • the BSF layer 104 is formed only on a part of the back surface side including the contact region (opening OA portion) with the second electrode 106, and FIG. 6 (first configuration example). Thus, it is not formed on the entire back surface side. Even with the solar cell element having such a configuration (FIG. 8), the same effect as in FIG. 6 (first configuration example) can be obtained. Further, according to the solar cell element of the third configuration example of FIG. 8, impurities are doped at a higher concentration than the silicon substrate 101 by doping the BSF layer 104, that is, a group III element such as aluminum or boron. Since the area is small, it is possible to obtain higher photoelectric conversion efficiency than that in FIG. 6 (first configuration example).
  • FIG. 9 a fourth configuration example shown in FIG. 9 will be described.
  • the second electrode 106 is formed on the entire surface of the contact region (opening OA) and the passivation film 107, but in FIG. 9 (fourth configuration example), the contact is formed.
  • the second electrode 106 is formed only in the region (opening OA).
  • the second electrode 106 may be formed only in part on the contact region (opening OA) and the passivation film 107. Even with the solar cell element having the configuration shown in FIG. 9, the same effect as that of FIG. 8 (third configuration example) can be obtained.
  • the second electrode 106 when the second electrode 106 is applied by a printing method and baked at a high temperature to form the entire surface on the back side, a convex warpage tends to occur in the temperature lowering process. Such warpage may cause damage to the solar cell element, which may reduce the yield. Further, the problem of warpage increases as the silicon substrate becomes thinner. The cause of this warp is that stress is generated because the thermal expansion coefficient of the second electrode 106 made of metal (for example, aluminum) is larger than that of the silicon substrate, and the shrinkage in the temperature lowering process is correspondingly large.
  • metal for example, aluminum
  • the electrode structure tends to be symmetrical vertically. This is preferable because stress due to the difference in thermal expansion coefficient is not easily generated. However, in that case, it is preferable to provide a separate reflective layer.
  • a texture structure is formed on the surface of the silicon substrate 101 shown in FIG.
  • the texture structure may be formed on both sides of the silicon substrate 101 or only on one side (light receiving side).
  • the damaged layer of the silicon substrate 101 is removed by immersing the silicon substrate 101 in a heated potassium hydroxide or sodium hydroxide solution.
  • a texture structure is formed on both surfaces or one surface (light receiving surface side) of the silicon substrate 101 by dipping in a solution containing potassium hydroxide and isopropyl alcohol as main components. Note that, as described above, the solar cell element of the present embodiment may or may not have a texture structure, and thus this step may be omitted.
  • a phosphorus diffusion layer (n + layer) is formed as the diffusion layer 102 by thermal diffusion of phosphorus oxychloride (POCl 3 ) or the like on the silicon substrate 101.
  • the phosphorus diffusion layer can be formed, for example, by applying a coating-type doping material solution containing phosphorus to the silicon substrate 101 and performing heat treatment. After the heat treatment, the phosphorous glass layer formed on the surface is removed with an acid such as hydrofluoric acid, whereby a phosphorous diffusion layer (n + layer) is formed as the diffusion layer 102.
  • the method for forming the phosphorus diffusion layer is not particularly limited.
  • the phosphorus diffusion layer may be formed so that the depth from the surface of the silicon substrate 101 is in the range of 0.2 ⁇ m to 0.5 ⁇ m, and the sheet resistance is in the range of 40 ⁇ / ⁇ to 100 ⁇ / ⁇ (ohm / square). preferable.
  • a BSF layer 104 on the back surface side is formed by applying a coating-type doping material solution containing boron, aluminum or the like to the back surface side of the silicon substrate 101 and performing heat treatment.
  • a coating-type doping material solution containing boron, aluminum or the like for the application, methods such as screen printing, inkjet, dispensing, spin coating and the like can be used.
  • the BSF layer 104 is formed by removing a layer of boron glass, aluminum, or the like formed on the back surface with hydrofluoric acid, hydrochloric acid, or the like.
  • the method for forming the BSF layer 104 is not particularly limited.
  • the BSF layer 104 is formed so that the concentration range of boron, aluminum, etc.
  • the solar cell element of the present embodiment may or may not have the BSF layer 104, and thus this step may be omitted.
  • the diffusion layer 102 on the light-receiving surface and the BSF layer 104 on the back surface are formed using a coating-type doping material solution
  • the above-described doping material solution is applied to both sides of the silicon substrate 101 to diffuse.
  • the phosphorous diffusion layer (n + layer) and the BSF layer 104 as the layer 102 may be formed in a lump, and then phosphorous glass, boron glass, or the like formed on the surface may be removed all at once.
  • a silicon nitride film as the light-receiving surface antireflection film 103 is formed on the diffusion layer 102.
  • the method for forming the light receiving surface antireflection film 103 is not particularly limited.
  • the light-receiving surface antireflection film 103 is preferably formed to have a thickness in the range of 50 to 100 nm and a refractive index in the range of 1.9 to 2.2.
  • the light-receiving surface antireflection film 103 is not limited to a silicon nitride film, and may be a silicon oxide film, an aluminum oxide film, a titanium oxide film, or the like.
  • the surface antireflection film 103 such as an silicon nitride film can be formed by a method such as plasma CVD or thermal CVD, and is preferably formed by plasma CVD that can be formed in a temperature range of 350 ° C. to 500 ° C.
  • the passivation film 107 contains aluminum oxide and niobium oxide.
  • an aluminum oxide precursor typified by an organometallic decomposition coating material from which aluminum oxide can be obtained by heat treatment (firing), and niobium oxide obtained by heat treatment (firing). It is formed by applying a material (passivation material) containing a niobium oxide precursor typified by a commercially available organometallic decomposition coating type material and heat-treating (firing).
  • the formation of the passivation film 107 can be performed as follows, for example.
  • the above coating material is spin-coated on one side of a 725 ⁇ m thick 8-inch (20.32 cm) p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been previously removed with hydrofluoric acid having a concentration of 0.049% by mass
  • pre-baking is performed on a hot plate at 120 ° C. for 3 minutes. Thereafter, heat treatment is performed at 650 ° C. for 1 hour in a nitrogen atmosphere. In this case, a passivation film containing aluminum oxide and niobium oxide is obtained.
  • the thickness of the passivation film 107 formed by the above method is usually about several tens of nanometers as measured by an ellipsometer.
  • the coating type material is applied to a predetermined pattern including the contact area (opening OA) by a method such as screen printing, offset printing, inkjet printing, or dispenser printing.
  • the above-mentioned coating type material is pre-baked in the range of 80 ° C. to 180 ° C. after evaporation to evaporate the solvent, and then at 600 ° C. to 1000 ° C. for 30 minutes to 3 hours in a nitrogen atmosphere or in air. It is preferable to perform a degree of heat treatment (annealing) to form a passivation film 107 (oxide film).
  • the opening (contact hole) OA is preferably formed in a dot shape or a line shape on the BSF layer 104.
  • the mass ratio of niobium oxide to aluminum oxide is preferably 30/70 to 90/10, and preferably 30/70 to 80/20. More preferably, it is more preferably 35/65 to 70/30. Thereby, the negative fixed charge can be stabilized. Further, the mass ratio of niobium oxide and aluminum oxide is preferably 50/50 to 90/10 from the viewpoint that both improvement of carrier lifetime and negative fixed charge can be achieved.
  • the total content of niobium oxide and aluminum oxide is preferably 80% by mass or more, and more preferably 90% by mass or more.
  • the first electrode 105 which is an electrode on the light receiving surface side is formed.
  • the first electrode 105 is formed by forming a paste mainly composed of silver (Ag) on the light-receiving surface antireflection film 103 by screen printing and performing a heat treatment (fire through).
  • the shape of the 1st electrode 105 may be arbitrary shapes, for example, may be a known shape which consists of a finger electrode and a bus-bar electrode.
  • the second electrode 106 which is an electrode on the back side is formed.
  • the second electrode 106 can be formed by applying a paste containing aluminum as a main component using screen printing or a dispenser and heat-treating it.
  • the shape of the second electrode 106 is preferably the same shape as the shape of the BSF layer 104, a shape covering the entire back surface, a comb shape, a lattice shape, or the like.
  • the paste for forming the first electrode 105 and the second electrode 106, which are the electrodes on the light receiving surface side, is first printed, and then heat-treated (fire-through), whereby the first electrode 105 and the second electrode 106 are formed.
  • the two electrodes 106 may be formed together.
  • the BSF layer 104 is formed in a contact portion between the second electrode 106 and the silicon substrate 101 in a self-alignment manner. Is formed.
  • the BSF layer 104 may be separately formed by applying a coating-type doping material solution containing boron, aluminum, or the like to the back side of the silicon substrate 101 and heat-treating it. .
  • the diffusion layer 102 is formed by a layer doped with a group III element such as boron
  • the BSF layer 104 is formed by doping a group V element such as phosphorus.
  • a leakage current flows through a portion where the inversion layer formed at the interface due to the negative fixed charge and the metal on the back surface are in contact with each other, and the conversion efficiency may be difficult to increase.
  • FIG. 10 is a cross-sectional view showing a configuration example of a solar cell element using the light-receiving surface passivation film of the present embodiment.
  • the diffusion layer 102 on the light receiving surface side is p-type doped with boron, and collects holes on the light receiving surface side and electrons on the back surface side of the generated carriers. For this reason, it is preferable that the passivation film 107 having a negative fixed charge is on the light receiving surface side.
  • an antireflection film made of SiN or the like may be further formed by CVD or the like.
  • the passivation material (a-1) is spin-coated on one side of a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been removed in advance with a hydrofluoric acid having a concentration of 0.049% by mass.
  • Pre-baking was performed on the plate at 120 ° C. for 3 minutes.
  • the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film through a metal mask by vapor deposition, thereby manufacturing a capacitor having a metal-insulator-semiconductor (MIS) structure.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from an ideal value of ⁇ 0.81V to + 0.32V. From this shift amount, it was found that the passivation film obtained from the passivation material (a-1) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 7.4 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (a-1) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to a heat treatment (firing) at 650 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured using a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 530 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (firing) the passivation material (a-1) showed a certain degree of passivation performance and a negative fixed charge.
  • Reference Example 1-2 Similar to Reference Example 1-1, a commercially available organometallic decomposition coating material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High-Purity Chemical Laboratory, SYM-AL04, concentration 2. 3 mass%] and a commercially available organometallic decomposable coating type material [High Purity Chemical Laboratory, Nb-05, concentration 5 mass%] from which niobium oxide (Nb 2 O 5 ) can be obtained by heat treatment (firing). Passivation materials (a-2) to (a-7) shown in Table 4 were prepared by mixing at different ratios.
  • each of the passivation materials (a-2) to (a-7) was applied to one side of a p-type silicon substrate, and heat treatment (firing) was performed to produce a passivation film.
  • the voltage dependence of the capacitance of the obtained passivation film was measured, and the fixed charge density was calculated therefrom.
  • the carrier lifetime is also increased after heat treatment (firing). Since it showed a certain value, it was suggested that it functions as a passivation film. It was found that all the passivation films obtained from the passivation materials (a-2) to (a-7) stably show negative fixed charges and can be suitably used as a passivation for a p-type silicon substrate. .
  • the passivation material (c-1) is spin-coated on one side of a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been removed in advance with a hydrofluoric acid having a concentration of 0.049% by mass.
  • Pre-baking was performed at 120 ° C. for 3 minutes on the plate.
  • heat treatment was performed at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and niobium oxide. When the film thickness was measured with an ellipsometer, it was 50 nm.
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film through a metal mask by vapor deposition, thereby manufacturing a capacitor having a metal-insulator-semiconductor (MIS) structure.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from an ideal value of ⁇ 0.81 V to +4.7 V. From this shift amount, it was found that the passivation film obtained from the passivation material (c-1) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 3.2 ⁇ 10 12 cm ⁇ 2 .
  • the passivation material (c-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain silicon.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured using a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 330 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (sintering) the passivation material (c-1) exhibited a certain degree of passivation performance and a negative fixed charge.
  • the passivation material (c-2) is spin-coated on one side of a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ cm to 12 ⁇ cm) from which a natural oxide film has been removed in advance with a hydrofluoric acid having a concentration of 0.049% by mass.
  • Pre-baking was performed at 120 ° C. for 3 minutes on the plate.
  • heat treatment was performed at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and niobium oxide. When the film thickness was measured by an ellipsometer, it was 14 nm.
  • a plurality of 1 mm diameter aluminum electrodes are deposited on the passivation film through a metal mask to form a MIS (Metal-Insulator-Semiconductor) capacitor.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A).
  • Vfb flat band voltage
  • LCR meter HP, 4275A
  • Vfb flat band voltage
  • the passivation film obtained from the passivation material (c-2) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 0.8 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (c-2) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (firing) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured with a lifetime measuring device (Kobelco Research Institute Co., Ltd., RTA-540). As a result, the carrier lifetime was 200 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • each of the passivation materials (b-1) to (b-7) was applied to one side of a p-type silicon substrate and heat-treated (fired) to produce a passivation film, Using this, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • the passivation film obtained from the passivation materials (b-1) to (b-6) has a large carrier lifetime and has a function as a passivation.
  • the niobium oxide / aluminum oxide ratios were 10/90 and 20/80, the fixed charge density values varied greatly, and a negative fixed charge density could not be stably obtained. It was confirmed that a negative fixed charge density can be realized by using niobium oxide.
  • a negative fixed charge is stably generated because a passivation film showing a positive fixed charge is obtained in some cases. It turns out that it has not reached to show.
  • a passivation film exhibiting a fixed charge can be used as a passivation for an n-type silicon substrate.
  • a negative fixed charge density could not be obtained with the passivation material (b-7) containing 100% by mass of aluminum oxide.
  • a passivation material (d-3) As a passivation material (d-3), a commercially available organometallic decomposition coating material [having high purity chemical laboratory Hf-05, concentration 5 mass%] from which hafnium oxide (HfO 2 ) can be obtained by heat treatment (firing) is used. Got ready.
  • each of the passivation materials (d-1) to (d-3) is applied to one side of a p-type silicon substrate, and then heat-treated (fired) to produce a passivation film. Using this, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • the passivation films obtained from the passivation materials (d-1) to (d-3) have a small carrier lifetime and an insufficient function as a passivation. It also showed a positive fixed charge.
  • the passivation film obtained from the passivation material (d-3) had a negative fixed charge, but its value was small. It was also found that the carrier lifetime was relatively small and the function as a passivation was insufficient.
  • an SiN film produced by plasma CVD was formed as the light-receiving surface antireflection film 103 on the light-receiving surface side.
  • the passivation material (a-1) prepared in Reference Example 1-1 was applied to the region excluding the contact region (opening OA) on the back surface side of the silicon substrate 101 by the inkjet method. Thereafter, heat treatment was performed to form a passivation film 107 having an opening OA.
  • a sample using the passivation material (c-1) prepared in Reference Example 1-3 was separately prepared as the passivation film 107.
  • a paste mainly composed of silver was screen-printed in the shape of predetermined finger electrodes and bus bar electrodes.
  • a paste mainly composed of aluminum was screen-printed on the entire surface.
  • heat treatment fire-through
  • electrodes first electrode 105 and second electrode 106
  • aluminum is diffused into the opening OA on the back surface to form the BSF layer 104.
  • the fire-through process in which the SiN film is not perforated is described, but the opening OA is first formed in the SiN film by etching or the like, and then the silver electrode is formed. You can also.
  • the passivation film 107 is not formed in the above manufacturing process, aluminum paste is printed on the entire back surface, and the p + layer 114 corresponding to the BSF layer 104 and the electrode 116 corresponding to the second electrode.
  • the characteristic evaluation was performed on the entire surface to form a solar cell element having the structure shown in FIG.
  • characteristic evaluation was performed according to JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005). The results are shown in Table 7.
  • the solar cell element having the passivation film 107 including the niobium oxide and aluminum oxide layers has both increased short-circuit current and open-circuit voltage as compared with the solar cell element not having the passivation film 107, and the conversion efficiency ( It was found that the photoelectric conversion efficiency was improved by 1% at the maximum.
  • a passivation film for use in a solar cell element having a silicon substrate comprising aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
  • ⁇ 2> The passivation film according to ⁇ 1>, wherein a mass ratio of the oxide of the vanadium group element to the aluminum oxide (vanadium group element oxide / aluminum oxide) is 30/70 to 90/10.
  • ⁇ 3> The passivation film according to ⁇ 1> or ⁇ 2>, in which a total content of the oxide of the vanadium group element and the aluminum oxide is 90% or more.
  • the oxide of the vanadium group element includes any of oxides of two or three kinds of vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide. Any one of ⁇ 1> to ⁇ 3> The passivation film according to claim 1.
  • ⁇ 5> Heat treatment of a coating-type material comprising: a precursor of aluminum oxide; and a precursor of an oxide of at least one vanadium group element selected from the group consisting of a precursor of vanadium oxide and a precursor of tantalum oxide.
  • the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
  • a p-type impurity diffusion layer formed on part or all of the second surface side of the silicon substrate and doped with an impurity at a higher concentration than the silicon substrate,
  • the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
  • n-type impurity diffusion layer formed on a part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate, The solar cell element according to ⁇ 9>, wherein the second electrode is electrically connected to the n-type impurity diffusion layer through an opening of the passivation film.
  • ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a mass ratio of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 30/70 to 90/10 .
  • ⁇ 12> The solar cell element according to any one of ⁇ 7> to ⁇ 11>, wherein the total content of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 90% or more.
  • the oxide of the vanadium group element includes an oxide of two or three vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide, ⁇ 7> to ⁇ 12>
  • the solar cell element according to any one of the above.
  • ⁇ 14> a silicon substrate;
  • a passivation film having a long carrier lifetime of a silicon substrate and having a negative fixed charge can be realized at low cost.
  • a coating type material for realizing the formation of the passivation film can be provided.
  • a low-cost and highly efficient solar cell element using the passivation film can be realized.
  • a silicon substrate with a passivation film having a long carrier lifetime and a negative fixed charge can be realized at low cost.
  • the passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide. It is what was included.
  • the amount of fixed charges possessed by the passivation film can be controlled by changing the composition of the passivation film.
  • the vanadium group element is a Group 5 element in the periodic table, and is an element selected from vanadium, niobium, and tantalum.
  • the mass ratio of the oxide of vanadium group element to aluminum oxide is preferably 35/65 to 90/10, from the viewpoint that the negative fixed charge can be stabilized, and is preferably 50/50 to 90/10. More preferably.
  • the mass ratio of vanadium group element oxide and aluminum oxide in the passivation film is determined by energy dispersive X-ray spectroscopy (EDX), secondary ion mass spectrometry (SIMS), and high frequency inductively coupled plasma mass spectrometry (ICP-MS). ) Can be measured. Specific measurement conditions are as follows in the case of ICP-MS, for example. Dissolving the passivation film in acid or alkaline aqueous solution, atomizing this solution and introducing it into Ar plasma, measuring the wavelength and intensity by spectroscopically analyzing the light emitted when the excited element returns to the ground state, Element qualification is performed from the obtained wavelength, and quantification is performed from the obtained intensity.
  • EDX energy dispersive X-ray spectroscopy
  • SIMS secondary ion mass spectrometry
  • ICP-MS high frequency inductively coupled plasma mass spectrometry
  • the total content of the vanadium group element oxide and aluminum oxide in the passivation film is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of maintaining good characteristics.
  • the components other than the oxide of vanadium group elements and aluminum oxide in the passivation film increase, the effect of negative fixed charges increases.
  • components other than vanadium group oxide and aluminum oxide may be contained as organic components from the viewpoint of improving the film quality and adjusting the elastic modulus.
  • the presence of the organic component in the passivation film can be confirmed by elemental analysis and measurement of the FT-IR of the film.
  • vanadium oxide As the oxide of the vanadium group element, it is preferable to select vanadium oxide (V 2 O 5 ) from the viewpoint of obtaining a larger negative fixed charge.
  • the passivation film may include two or three vanadium group oxides selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide as the vanadium group element oxide.
  • the passivation film is preferably obtained by heat-treating a coating-type material, and can be obtained by forming a coating-type material using a coating method or a printing method, and then removing organic components by heat treatment. More preferred. That is, the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a vanadium group element oxide precursor. Details of the coating type material will be described later.
  • the coating type material of the present embodiment is a coating type material used for a passivation film for a solar cell element having a silicon substrate, and includes a precursor of aluminum oxide, a precursor of vanadium oxide, and a precursor of tantalum oxide. And a precursor of an oxide of at least one vanadium group element selected from the group.
  • a precursor of the oxide of the vanadium group element contained in the coating material a precursor of vanadium oxide (V 2 O 5 ) is selected from the viewpoint of the negative fixed charge of the passivation film formed from the coating material. It is preferable.
  • the coating type material is composed of two or three vanadium group elements selected from the group consisting of vanadium oxide precursors, niobium oxide precursors and tantalum oxide precursors as vanadium group oxide precursors. An oxide precursor may also be included.
  • the aluminum oxide precursor can be used without particular limitation as long as it produces aluminum oxide.
  • As the aluminum oxide precursor it is preferable to use an organic aluminum oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and a chemically stable viewpoint.
  • Examples of the organic aluminum oxide precursor include aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , Kojundo Chemical Laboratory Co., Ltd., SYM-AL04.
  • the precursor of the oxide of the vanadium group element can be used without particular limitation as long as it generates an oxide of the vanadium group element.
  • the vanadium group element oxide precursor is preferably an organic vanadium group oxide oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and chemically stable. .
  • organic vanadium oxide precursors examples include vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13), High Purity Chemical Laboratory, V-02 can be mentioned.
  • organic tantalum oxide precursors include tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12), Kojundo Chemical Laboratory, Ta-10-P Can be mentioned.
  • organic niobium oxide precursors examples include niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), High Purity Chemical Laboratory, Nb-05. Can be mentioned.
  • a passivation film By forming a coating type material containing an organic vanadium group oxide precursor and an organic aluminum oxide precursor using a coating method or a printing method, and then removing the organic components by a heat treatment, A passivation film can be obtained. Therefore, as a result, a passivation film containing an organic component may be used.
  • the content of the organic component in the passivation film is more preferably less than 10% by mass, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the solar cell element (photoelectric conversion device) of the present embodiment includes the passivation film (insulating film, protective insulating film) described in the above embodiment in the vicinity of the photoelectric conversion interface of the silicon substrate, that is, aluminum oxide and vanadium oxide. And at least one oxide of a vanadium group element selected from the group consisting of tantalum oxide. By containing aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, the carrier lifetime of the silicon substrate can be extended and negative fixed charges can be obtained. And the characteristics (photoelectric conversion efficiency) of the solar cell element can be improved.
  • Passivation of passivation material (a2-1) on one side of a 725 ⁇ m thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) with natural oxide film removed beforehand with hydrofluoric acid at a concentration of 0.49% by mass It was applied and placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing vanadium oxide and vanadium oxide [vanadium oxide / aluminum oxide 63/37 (mass%)]. It was 51 nm when the film thickness was measured with the ellipsometer. When the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film by vapor deposition through a metal mask, and a capacitor having a MIS (metal-insulator-semiconductor) structure was fabricated.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from an ideal value of ⁇ 0.81 V to +0.02 V. From this shift amount, it was found that the passivation film obtained from the passivation material (a2-1) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 5.2 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (a2-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 650 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured with a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the carrier lifetime was 380 ⁇ s.
  • the decrease in carrier lifetime (from 400 ⁇ s to 380 ⁇ s) was within ⁇ 10%, and the decrease in carrier lifetime was small.
  • the passivation film obtained by heat-treating (sintering) the passivation material (a2-1) showed a certain degree of passivation performance and a negative fixed charge.
  • Reference Example 2-2 Similar to Reference Example 2-1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2 3 mass%] and a commercially available organometallic thin film coating type material [Vitamin Purity Laboratory, V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) can be obtained by heat treatment, Passivation materials (a2-2) to (a2-7) shown in Table 8 were prepared by mixing at different ratios.
  • each of the passivation materials (a2-2) to (a2-7) was applied to one side of a p-type silicon substrate and heat-treated (fired) to produce a passivation film.
  • the voltage dependence of the capacitance of the obtained passivation film was measured, and the fixed charge density was calculated therefrom.
  • the carrier lifetime was measured using a sample obtained by applying a passivation material to both sides of a p-type silicon substrate and performing heat treatment (firing).
  • the passivation materials (a2-2) to (a2-7) are all negative after the heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film. It was found that all the passivation films obtained from the passivation materials (a2-2) to (a2-7) stably show negative fixed charges and can be suitably used as a passivation for a p-type silicon substrate. .
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film by vapor deposition through a metal mask, and a capacitor having a MIS (metal-insulator-semiconductor) structure was fabricated.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) was shifted from the ideal value of ⁇ 0.81 V to +0.10 V. From this shift amount, it was found that the passivation film obtained from the passivation material (b2-1) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 6.2 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (b2-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (firing) the passivation material (b2-1) exhibits a certain degree of passivation performance and a negative fixed charge.
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film by vapor deposition through a metal mask, and a capacitor having a MIS (metal-insulator-semiconductor) structure was fabricated.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from the ideal value of ⁇ 0.81 V to +0.03 V. From this shift amount, it was found that the passivation film obtained from the passivation material (b2-2) showed a negative fixed charge with a fixed charge density (Nf) of ⁇ 2.0 ⁇ 10 11 cm ⁇ 2 .
  • the passivation material (b2-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere. A sample in which both surfaces of the substrate were covered with a passivation film was produced. The carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 170 ⁇ s. For comparison, the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by curing the passivation material (b2-2) exhibited a certain degree of passivation performance and a negative fixed charge.
  • Each of the passivation materials (c2-1) to (c2-6) is a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ) from which a natural oxide film has been removed in advance with hydrofluoric acid having a concentration of 0.49% by mass.
  • (Cm) was spin-coated on one side, placed on a hot plate, and pre-baked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and tantalum oxide. Using this passivation film, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • each of the passivation materials (c2-1) to (c2-6) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
  • the passivation materials (c2-1) to (c2-6) are all negative after heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film.
  • Al oxide (Al 2 O 3 ) As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d2-1) having a concentration of 5% by mass.
  • Al (OCH (CH 3 ) 2 ) 3 As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d2-1) having a concentration of 5% by mass.
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film by vapor deposition through a metal mask, and a capacitor having a MIS (metal-insulator-semiconductor) structure was fabricated.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) was shifted from an ideal value of ⁇ 0.81 V to ⁇ 0.30 V. From this shift amount, it was found that the passivation film obtained from the passivation material (d2-1) showed a negative fixed charge at a fixed charge density (Nf) of ⁇ 6.2 ⁇ 10 10 cm ⁇ 2 .
  • the passivation material (d2-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to a heat treatment (firing) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 610 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating the passivation material (d2-1) exhibited a certain degree of passivation performance and a negative fixed charge.
  • a plurality of aluminum electrodes having a diameter of 1 mm were formed on the above-described passivation film by vapor deposition through a metal mask, and a capacitor having a MIS (metal-insulator-semiconductor) structure was fabricated.
  • the voltage dependence (CV characteristics) of the capacitance of this capacitor was measured with a commercially available prober and LCR meter (HP, 4275A). As a result, it was found that the flat band voltage (Vfb) shifted from an ideal value of ⁇ 0.81 V to ⁇ 0.43 V. From this shift amount, it was found that the passivation film obtained from the passivation material (d-2) showed a negative fixed charge at a fixed charge density (Nf) of ⁇ 5.5 ⁇ 10 10 cm ⁇ 2 .
  • the passivation material (d2-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere. A sample in which both surfaces of the substrate were covered with a passivation film was produced. The carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 250 ⁇ s. For comparison, the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat treatment (firing) the passivation material (d2-2) exhibits a certain degree of passivation performance and a negative fixed charge.
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
  • aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing)
  • heat treatment (firing) Niobium oxide (Nb 2 O) by commercially available organometallic thin film coating type material (VCO, Ltd., high purity chemical research laboratory V-02, concentration 2 mass%) from which vanadium oxide (V 2 O 5 ) is obtained, and heat treatment (firing) 5 )
  • a commercially available organometallic thin film coating type material [Co-development High Purity Chemical Laboratory, Nb-05, concentration 5 mass%] obtained is mixed to obtain a passivation material (e2-2) which is a coating type material. Prepared (see Table 10).
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), heat treatment (firing) Niobium oxide (Nb) by commercially available organometallic thin film coating material [Tapurio Chemical Lab. Ta-10-P, concentration 10% by mass] from which tantalum oxide (Ta 2 O 5 ) can be obtained, and heat treatment (firing) 2 O 5 ), a commercially available organometallic thin film coating material [High Purity Chemical Laboratory Nb-05, concentration 5 mass%] is mixed to form a passivation material (e2-3) which is a coating material Was prepared (see Table 10).
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
  • aluminum oxide Al 2 O 3
  • heat treatment firing
  • Tantalum oxide Ti 2 O 5
  • heat treatment Niobium oxide
  • Nb 2 O 5 Niobium oxide
  • a commercially available organometallic thin film coating type material [High purity chemical research laboratory Nb-05, concentration 5 mass%] was mixed to prepare a passivation material (e2-4) as a coating type material (see Table 10).
  • Each of the passivation materials (e2-1) to (e2-4) was 725 ⁇ m thick and 8 inches thick with the natural oxide film removed beforehand with hydrofluoric acid having a concentration of 0.49% by mass, as in Reference Example 2-1. It was spin-coated on one side of a p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm), placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 650 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and two or more vanadium group element oxides.
  • each of the passivation materials (e2-1) to (e2-4) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
  • each of the passivation materials (f2-1) to (f2-9) was applied to one side of a p-type silicon substrate, and then heat treatment (firing) was performed to form a passivation film. This was used to measure the voltage dependence of the capacitance, and the fixed charge density was calculated therefrom.
  • a SiN film was formed on the light receiving surface side by plasma CVD as the light receiving surface antireflection film 103.
  • the passivation material (a2-1) prepared in Reference Example 2-1 was applied to the region excluding the contact region (opening OA) on the back surface side of the silicon substrate 101 by an inkjet method. Thereafter, heat treatment was performed to form a passivation film 107 having an opening OA.
  • a sample using the passivation material (c2-1) prepared in Reference Example 2-5 was separately prepared as the passivation film 107.
  • a paste mainly composed of silver was screen-printed in the shape of predetermined finger electrodes and bus bar electrodes.
  • a paste mainly composed of aluminum was screen-printed on the entire surface.
  • heat treatment fire-through
  • electrodes first electrode 105 and second electrode 106
  • aluminum is diffused into the opening OA on the back surface to form the BSF layer 104.
  • the fire-through process in which the SiN film is not perforated is described.
  • the opening OA is first formed in the SiN film by etching or the like, and then the silver electrode is formed. You can also
  • the passivation film 107 is not formed in the above manufacturing process, aluminum paste is printed on the entire back surface, and the p + layer 114 corresponding to the BSF layer 104 and the electrode 116 corresponding to the second electrode. was formed on the entire surface to form a solar cell element having the structure of FIG.
  • characteristic evaluation a short circuit current, an open circuit voltage, a fill factor, and conversion efficiency
  • the characteristic evaluation was performed according to JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005). The results are shown in Table 12.
  • the solar cell element having the passivation film 107 has both the short-circuit current and the open voltage increased as compared with the solar electronic element not having the passivation film 107, and the conversion efficiency (photoelectric conversion efficiency) is 0 at the maximum. It was found to improve by 6%.

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CN115581079A (zh) * 2022-11-03 2023-01-06 绍兴建元电力集团有限公司 一种吸光层钝化剂及其制备的钙钛矿太阳能电池

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CN112002771B (zh) * 2020-08-25 2022-04-29 东方日升（常州）新能源有限公司 一种掺镓背场的p型掺镓perc电池及其制备方法

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