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WO2013129002A1 - COMPOSITION POUR LA FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n, ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE - Google Patents

COMPOSITION POUR LA FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n, ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE Download PDF

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Publication number
WO2013129002A1
WO2013129002A1 PCT/JP2013/051798 JP2013051798W WO2013129002A1 WO 2013129002 A1 WO2013129002 A1 WO 2013129002A1 JP 2013051798 W JP2013051798 W JP 2013051798W WO 2013129002 A1 WO2013129002 A1 WO 2013129002A1
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WIPO (PCT)
Prior art keywords
diffusion layer
type diffusion
forming composition
compound
layer forming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/051798
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English (en)
Japanese (ja)
Inventor
鉄也 佐藤
吉田　誠人
野尻　剛
芦沢　寅之助
倉田　靖
洋一 町井
岩室　光則
明博 織田
麻理 清水
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to JP2014502076A priority Critical patent/JP5610100B2/ja
Publication of WO2013129002A1 publication Critical patent/WO2013129002A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H10P32/19—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H10P32/1408—
    • H10P32/171—
    • 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 n-type diffusion layer forming composition, a method for manufacturing an n-type diffusion layer, and a method for manufacturing a solar cell, and more specifically, a specific portion of a silicon substrate that is a semiconductor substrate.
  • the present invention relates to a technique that makes it possible to form an n-type diffusion layer.
  • a p-type semiconductor substrate having a texture structure formed on the light-receiving surface (surface) is prepared to promote the light confinement effect, and then a mixed gas of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen.
  • POCl 3 phosphorus oxychloride
  • the p-type semiconductor substrate is treated for several tens of minutes at 800 ° C. to 900 ° C. to uniformly form an n-type diffusion layer.
  • phosphorus is diffused into the p-type semiconductor substrate using a mixed gas, so that n-type diffusion layers are formed not only on the surface of the p-type semiconductor substrate but also on the side surfaces and the back surface.
  • a side etching step for removing the n-type diffusion layer formed on the side surface is necessary. Further, the n-type diffusion layer formed on the back surface needs to be converted into a p + -type diffusion layer. Therefore, after applying an aluminum paste containing aluminum as a group 13 element on the n-type diffusion layer on the back surface, a thermal diffusion treatment is performed to convert the n-type diffusion layer into a p + -type diffusion layer by aluminum diffusion. At the same time, I was getting ohmic contact.
  • a method of forming an n-type diffusion layer by applying a solution containing a phosphate such as ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) has been proposed (for example, Japanese Patent Laid-Open No. 2002-75894). reference).
  • a phosphate such as ammonium dihydrogen phosphate (NH 4 H 2 PO 4 )
  • NH 4 H 2 PO 4 ammonium dihydrogen phosphate
  • an n-type diffusion layer forming composition containing a glass powder containing a donor element and a dispersion medium is applied to a semiconductor substrate and subjected to thermal diffusion treatment, so that it is unnecessary on the side and back surfaces of the semiconductor substrate.
  • a method for manufacturing a solar cell element in which an n-type diffusion layer is formed in a specific region without forming an n-type diffusion layer has been proposed (see, for example, International Publication No. 11/090216 pamphlet).
  • the diffusion in the region other than directly under the electrode is compared with the diffusion concentration of the donor element in the region directly under the electrode (hereinafter also simply referred to as “diffusion concentration”).
  • diffusion concentration the diffusion concentration of the donor element in the region directly under the electrode
  • a selective emitter structure with a low concentration is known (see, for example, L. Debarge, M.Schott, JCMuller, R.Monna, Solar Energy Materials and Solar Cells 74 (2002) 71-75).
  • this region is also referred to as “selective emitter” is formed, so that the contact resistance between the electrode and silicon can be reduced.
  • the diffusion concentration is relatively low except in the region where the electrode is formed, the conversion efficiency of the solar cell element can be improved.
  • it is required to form an n-type diffusion layer in a thin line shape within a width of several hundred ⁇ m (about 50 ⁇ m to 200 ⁇ m).
  • the line width is expanded even if the n-type diffusion layer forming composition is applied in a thin line shape on a semiconductor substrate, There was a tendency that a desired thin line width could not be obtained.
  • the handling property of the n-type diffusion layer forming composition is improved. There was a tendency that application to the semiconductor substrate itself could not be performed.
  • the present invention has been made in view of the above-described conventional problems, and can be applied to a semiconductor substrate while suppressing an increase in the line width of a thin line pattern in a manufacturing process of a solar battery cell. Furthermore, an n-type diffusion layer forming composition capable of forming an n-type diffusion layer with a specific size in a desired specific region, a method for manufacturing the n-type diffusion layer, and a method for manufacturing a solar battery cell are provided. For the purpose.
  • the means for solving the above-mentioned problems are as follows.
  • the n-type diffusion layer forming composition part according to ⁇ 1>, which contains the gelling agent, and the gelling agent is an organic compound represented by the following structural formula (1).
  • R 1 and R 2 each independently represent H or CH 3 .
  • the content of the glass particles containing the gelling agent and containing the donor element is 1% by mass or more and 80% by mass or less, and the content of the gelling agent is 0.01% by mass or more and 5% or less.
  • ⁇ 4> The compound according to ⁇ 1>, wherein the compound having the ester bond or the compound having the urea group is contained, and the decomposition temperature of the compound having the ester bond or the compound having the urea group is 400 ° C. or lower. n-type diffusion layer forming composition.
  • a compound having an ester bond or a compound having a urea group, the content of glass particles containing the donor element being 1% by mass or more and 80% by mass or less, and the compound having the ester bond The composition for forming an n-type diffusion layer according to ⁇ 1> or ⁇ 4>, wherein the content of the compound having a urea group is 0.1% by mass or more and 10% by mass or less.
  • composition for forming an n-type diffusion layer according to ⁇ 1> which contains a compound having a urea group, and the compound having a urea group is a urea compound having a medium polar group at its terminal.
  • the glass particles containing the donor element include at least one donor element-containing material selected from P 2 O 3 , P 2 O 5 and Sb 2 O 3 , SiO 2 , K 2 O, and Na 2 O. And at least one glass component material selected from Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5 , SnO, ZrO 2 and MoO 3.
  • the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 6>.
  • n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 7>, further comprising at least one thickener selected from a cellulose derivative, an acrylic resin, and an alkyd resin.
  • n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 8>, further containing an inorganic filler.
  • composition for forming an n-type diffusion layer according to any one of ⁇ 1> to ⁇ 10>, wherein the glass particles containing the donor element have a volume average particle size of 0.1 ⁇ m or more and 10 ⁇ m or less. .
  • ⁇ 12> A step of applying the n-type diffusion layer forming composition according to any one of the above ⁇ 1> and ⁇ 11> on a semiconductor substrate; and heating the semiconductor substrate provided with the n-type diffusion layer forming composition. And a step of performing a diffusion treatment.
  • a step of applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 11> on the semiconductor substrate; and a semiconductor substrate provided with the n-type diffusion layer forming composition The manufacturing method of the photovoltaic cell which has the process of forming a n-type diffused layer by performing a thermal diffusion process, and the process of forming an electrode on the formed n-type diffused layer.
  • the present invention in the manufacturing process of a solar battery cell, it is possible to suppress the expansion of the line width of the fine line pattern on the semiconductor substrate, and further to a specific area in a specific size. It is possible to provide an n-type diffusion layer forming composition capable of forming an n-type diffusion layer, a method for producing an n-type diffusion layer using the composition, and a method for producing a solar battery cell.
  • the n-type diffusion layer forming composition of the present invention will be described, and then an n-type diffusion layer using the n-type diffusion layer forming composition and a method for producing a solar battery cell will be described.
  • the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended purpose of the process is achieved. included.
  • “to” indicates a range including the numerical values described before and after the minimum and maximum values, respectively.
  • “content rate” represents the mass% of a component with respect to 100 mass% of n type diffused layer formation compositions unless there is particular description.
  • the composition for forming an n-type diffusion layer of the present invention comprises glass particles containing at least a donor element (hereinafter sometimes simply referred to as “glass particles”), a gelling agent, a compound having an ester bond, and a compound having a urea group. And at least one selected from the group consisting of a dispersion medium. Furthermore, in consideration of applicability and the like, other additives may be contained as necessary.
  • the n-type diffusion layer forming composition contains glass particles containing a donor element, and after applying to the semiconductor substrate, the donor element is thermally diffused to form an n-type diffusion layer on the semiconductor substrate.
  • a material that can be used Since the donor element in the glass particles is difficult to volatilize even during the thermal diffusion treatment (firing), it is suppressed that the n-type diffusion layer is formed not only on the surface but also on the back surface and side surfaces due to the generation of the volatilizing gas. Therefore, by using an n-type diffusion layer forming composition containing a donor element in glass particles, an n-type diffusion layer is formed in a desired region in the semiconductor substrate, and unnecessary n-type diffusion layers are formed on the back surface and side surfaces. Not.
  • the composition for forming an n-type diffusion layer of the present invention is applied, the side etching step that is essential in the gas phase reaction method that has been widely employed is not required, and the process is simplified.
  • the step of converting the n-type diffusion layer formed on the back surface into the p + -type diffusion layer is not necessary. Therefore, the method for forming the p + -type diffusion layer on the back surface and the material, shape, and thickness of the back electrode are not limited, and the choice of manufacturing method, material, and shape to be applied is widened.
  • production of the internal stress in the semiconductor substrate resulting from the thickness of a back surface electrode is suppressed, and the curvature of a semiconductor substrate is also suppressed.
  • the glass particles contained in the n-type diffusion layer forming composition of the present invention are melted by a thermal diffusion treatment to form a glass layer on the n-type diffusion layer.
  • the glass layer is formed on the n-type diffusion layer also in the conventional gas phase reaction method and the method of applying a phosphate-containing solution or paste. Therefore, the glass layer produced
  • the semiconductor can be formed by suppressing an increase in line width when a thin line pattern is formed by the n-type diffusion layer forming composition. It can be applied on the substrate, and an n-type diffusion layer having a specific size can be formed in a desired specific region.
  • the fine line shape means a pattern shape having a set width of 200 ⁇ m or less.
  • the n-type diffusion layer forming composition when a compound having an ester bond or a compound having a urea group is contained in the n-type diffusion layer forming composition, thixotropic properties can be imparted. That is, the n-type diffusion layer forming composition containing a compound having an ester bond or a compound having a urea group exhibits a high viscosity when the shearing force is low, and exhibits a low viscosity when the shearing force is high. Exhibits sex.
  • the n-type diffusion layer forming composition when printing the n-type diffusion layer forming composition on a semiconductor substrate with a screen printer, when the stress is applied to the n-type diffusion layer forming composition in contact with the scraper or the squeegee by the operation of the scraper or the squeegee,
  • the n-type diffusion layer forming composition has low viscosity and fluidity, and passes through the mesh of the screen plate to form a print on the semiconductor substrate.
  • the n-type diffusion layer forming composition once formed as a printed material on the semiconductor substrate is in a state where the shape can be maintained without lowering the viscosity unless stress is applied.
  • the n-type diffusion layer forming composition of the present invention can form an n-type diffusion layer having a desired concentration in a desired portion of the semiconductor substrate. It is possible to form a selective region having a high (element) concentration.
  • a selective region having a high n-type dopant concentration (hereinafter, this region may be referred to as “selective emitter”) is formed immediately below the electrode. Te with n + -type diffusion layer or n ++ type diffusion layer, it is possible to reduce the contact resistance between the n-type diffusion layer and the electrode.
  • a vapor phase reaction method which is a general manufacturing method of an n-type diffusion layer, and a phosphate-containing solution are used. It is difficult to form by the method used.
  • the diffusion layer in the present invention includes not only the case where it is formed on the entire surface when the semiconductor substrate is observed as a plan view but also the case where it is formed on a part thereof.
  • a donor element is an element that can form an n-type diffusion layer by diffusing into a silicon substrate, which is a semiconductor substrate.
  • a Group 15 element can be used, and examples thereof include P (phosphorus), Sb (antimony), and As (arsenic). From the viewpoints of safety, ease of vitrification, etc., P or Sb is preferred.
  • Examples of the donor element-containing material used for introducing the donor element into the glass particles include P 2 O 3 , P 2 O 5 , Sb 2 O 3 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 5 , As 2. O 3 and As 2 O 5 may be mentioned, and it is preferable to use at least one selected from P 2 O 3 , P 2 O 5 and Sb 2 O 3 .
  • the glass particle containing a donor element can control a melting temperature, a softening point, a glass transition temperature, chemical durability, etc. by adjusting a component ratio as needed. Furthermore, it is preferable that the glass particle containing a donor element contains the glass component substance described below. Since P 2 O 5 forms the glass alone, the P 2 O 5 is not used in conjunction with the glass component material, it may be used in P 2 O 5 alone.
  • glass component materials include SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5 , SnO, ZrO 2 , WO 3 , MoO 3, MnO, La 2 O 3, Nb 2 O 5, Ta 2 O 5, Y 2 O 3, CsO 2, TiO 2, GeO 2, TeO 2 , and Lu 2 O 3 and the like, SiO 2, K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5, SnO, ZrO 2, MoO 3, GeO 2, Y 2 O 3, CsO 2 And at least one selected from TiO 2 , SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO It is more preferable to use at least one
  • the glass particles containing a donor element include a system containing both the donor element-containing material and the glass component material, and a P 2 O 5 -SiO 2 system (in order of donor element-containing material-glass component material). in described, the same applies hereinafter), P 2 O 5 -K 2 O based, P 2 O 5 -Na 2 O-based, P 2 O 5 -Li 2 O system, P 2 O 5 -BaO-based, P 2 O 5 - SrO-based, P 2 O 5 -CaO-based, P 2 O 5 -MgO-based, P 2 O 5 -BeO based, P 2 O 5 -ZnO-based, P 2 O 5 -CdO based, P 2 O 5 -PbO system , including P 2 O 5 -V 2 O 5 system, P 2 O 5 -SnO-based, P 2 O 5 -GeO 2 system, a P 2 O 5 as a donor element-containing material of P 2
  • glass particles containing two or more kinds of donor element-containing substances such as P 2 O 5 —Sb 2 O 3 series, P 2 O 5 —As 2 O 3 series, and the like may be used.
  • a composite glass containing two components is exemplified, but glass particles containing three or more components such as P 2 O 5 —SiO 2 —V 2 O 5 and P 2 O 5 —SiO 2 —CaO may be used.
  • the glass particles include at least one donor element-containing material selected from P 2 O 3 , P 2 O 5 and Sb 2 O 3 , SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5, SnO, ZrO 2, MoO 3, GeO 2, Y 2 O 3, at least one glass component is selected from CsO 2 and TiO 2 And at least one donor element-containing material selected from P 2 O 3 , P 2 O 5 and Sb 2 O 3 , and SiO 2 , K 2 O, Na 2 O, Li At least one glass component material selected from 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5 , SnO, ZrO 2 and MoO 3 ; A donor element-containing material that is P 2 O 5 and at least one glass component material selected from SiO 2 , ZnO, CaO,
  • Examples of the shape of the glass particles include a spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like, from the viewpoint of application property to a semiconductor substrate and a uniform diffusibility when it is an n-type diffusion layer forming composition, A spherical shape, a flat shape, or a plate shape is preferable.
  • the particle diameter of the glass particles is preferably 100 ⁇ m or less.
  • the particle diameter of the glass particles is more preferably 50 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the lower limit of the particle size of the glass particles is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the particle diameter of the glass particles represents a volume average particle diameter, and can be measured by a laser scattering diffraction method particle size distribution measuring apparatus or the like.
  • Glass particles containing a donor element are produced by the following procedure. First, raw materials, for example, the donor element-containing material and the glass component material are weighed and filled in a crucible.
  • the material for the crucible include platinum, platinum-rhodium, iridium, alumina, quartz, carbon, and the like, and are appropriately selected in consideration of the melting temperature, atmosphere, reactivity with the molten material, and the like.
  • the melt is poured onto a zirconia substrate or a carbon substrate to vitrify the melt. Finally, the glass is crushed into particles.
  • a known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
  • the content rate of the glass particle containing the donor element in the n-type diffusion layer forming composition is determined in consideration of the coating property, the diffusibility of the donor element, and the like.
  • the content of the glass particles in the n-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less, more preferably 1% by mass or more and 90% by mass or less. It is preferably 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 80% by mass or less, and particularly preferably 5% by mass or more and 20% by mass or less.
  • the n-type diffusion layer can be sufficiently formed on the semiconductor substrate.
  • the content is 95% by mass or less, the dispersibility of the glass particles in the n-type diffusion layer forming composition is improved, and the coating property of the n-type diffusion layer forming composition to the semiconductor substrate is improved.
  • the gelling agent as used in the field of this invention means the compound which can gelatinize and solidify a liquid. Generally, whether or not to solidify is greatly influenced by the ratio of the liquid and the gelling agent, but the gelling agent in the composition for forming an n-type diffusion layer of the present invention does not necessarily contain an amount of gelling agent to solidify. The thixotropy can be improved by including a small amount of the gelling agent.
  • the content of the gelling agent is preferably 0.01% by mass or more and 5% by mass or less, and preferably 0.1% by mass or more and 3% by mass or less in the n-type diffusion layer forming composition. Is more preferably 0.2% by mass or more and 2% by mass or less, particularly preferably 0.3% by mass or more and 1% by mass or less, 0.4% by mass or more, and 0.7% by mass or more. It is very preferable that the content is not more than mass%.
  • the content of the gelling agent is 0.01% by mass or more, a sufficient effect of improving printability can be obtained. Further, when the content of the gelling agent is 5% by mass or less, the viscosity or thixotropy does not become too high, and the screen printing workability is improved.
  • the gelling agent is not particularly limited and may be either a physical gelling agent or a chemical gelling agent, and it is preferable to use a physical gelling agent.
  • a physical gelling agent By using a physical gelling agent, the thixotropy tends to be easily adjusted.
  • physical gelling agents it is preferable to use an organic compound that gels by intermolecular hydrogen bonding.
  • Physical gelling agents include butyric acid (butyric acid), valeric acid (valeric acid), caproic acid, enanthic acid (heptylic acid), caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid
  • Carboxylic acids such as margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, octylic acid, oleic acid, ricinoleic acid, hydroxystearic acid, isostearic acid; Compound of the carboxylic acid and any one of sodium, potassium, lithium, calcium, barium, zinc, magnesium, aluminum and lead; sorbitol-based organic compound; fine particle silica such as Aerosil (manufactured by Nippon Aerosil Co., Ltd.) Dispalon 305 Hydrogen
  • the chemical gelling agent for example, a monomer, oligomer, polymer or the like having a polymerizable or crosslinkable functional group represented by an acryloyl group and an epoxy group can be used.
  • the chemical gelling agent is preferably a copolymer containing a cyano group.
  • a gelling agent may be used individually by 1 type, or may use 2 or more types together.
  • the gelling agent it is more preferable to use hydrogenated castor oil-based, fine-particle silica, or sorbitol-based organic compound, and it is more preferable to use a sorbitol-based organic compound.
  • the sorbitol-based organic compound has a hydroxyl group and an ether bond, and an appropriate thixotropy can be imparted to the n-type diffusion layer forming composition by hydrogen bonding between molecules due to the hydroxyl group and the ether bond.
  • sorbitol organic compound As the sorbitol organic compound, it is preferable to use a compound represented by the following structural formula (1).
  • R 1 and R 2 each independently represent H or CH 3 .
  • the gelling agent is preferably dissolved in the n-type diffusion layer forming composition. When the gelling agent is dissolved, the effects of the present invention can be expressed more effectively.
  • the decomposition temperature of the gelling agent is preferably 800 ° C. or lower, and more preferably 400 ° C. or lower.
  • production of a residue after a thermal diffusion process can be suppressed because the decomposition temperature of a gelatinizer is 800 degrees C or less. If the gelling agent, which is a polymer compound, remains on the semiconductor substrate as a residue, it causes a reduction in power generation performance of the solar cell.
  • the decomposition temperature of the gelling agent can be measured using differential thermal scanning calorimetry (DSC) or simultaneous differential thermal calorimetry (TG / DTA).
  • the n-type diffusion layer forming composition contains a compound having an ester bond or a compound having a urea group
  • the n-type diffusion layer forming composition can have an appropriate shear viscosity, and the printability is improved.
  • the n-type diffusion layer forming composition containing a compound having an ester bond or a compound having a urea group has high thixotropy, a thin line pattern is formed on the semiconductor substrate by the n-type diffusion layer forming composition.
  • the expansion of the line width is suppressed, and the generation of residues on the semiconductor substrate during the thermal diffusion process is suppressed.
  • the organic component is removed through drying and degreasing after applying the n-type diffusion layer forming composition to the semiconductor substrate.
  • inorganic materials may remain.
  • the inorganic material remains, the composition of the glass particles containing the donor element is changed by the inorganic material during the thermal diffusion treatment, and as a result, the doping of the donor element may be affected.
  • Examples of the compound having an ester bond include compounds such as hardened castor oil, beeswax and carnauba wax (ITOWAX CO-FA (castor oil fatty acid) from Ito Oil Co., Ltd .; DCO-FA (dehydrated castor oil fatty acid); E-210, E-230, E-250, E-270, E-70G (hydroxystearic acid ester wax); J-50, J-420, J-500, J-550S, J-530.J-630, J -700 (hydroxy fatty acid amide type)).
  • ITOWAX CO-FA castor oil fatty acid
  • DCO-FA dehydrated castor oil fatty acid
  • E-210, E-230, E-250, E-270, E-70G hydroxystearic acid ester wax
  • J-50, J-420, J-500, J-550S, J-530.J-630, J -700 hydroxy fatty acid amide type
  • the compound having a urea group for example, a compound having a medium polar group or a low polar group at its terminal (BIC Chemie Japan, trade name: BYK-410 (special modified urea), 411 (modified urea), 420 (modified) Urea), 425 (urea modified urethane), 428 (polyurethane), 430 (urea modified polyamide), 431 (urea modified polyamide), LPR20320 (special modified urea), P104, P105 and the like.
  • BIC Chemie Japan trade name: BYK-410 (special modified urea), 411 (modified urea), 420 (modified) Urea), 425 (urea modified urethane), 428 (polyurethane), 430 (urea modified polyamide), 431 (urea modified polyamide), LPR20320 (special modified urea), P104, P105 and the like.
  • a compound having a urea group among a compound having an ester bond and a compound having a urea group is preferable to use.
  • the reason is considered as follows.
  • the n-type diffusion layer forming composition contains a compound having a urea group, if no stress is applied to the n-type diffusion layer forming composition, a hydrogen bond is formed between the urea groups of individual molecules to form a network structure.
  • the compound having a urea group is preferably a urea compound having a medium polar group or a low polarity group at the terminal, and preferably a urea compound having a medium polar group at the terminal. More preferred. Examples of commercially available urea compounds having a medium polar group at the end include BYK-410.
  • the low polar group is a molecular chain having an alkyl group derived from fat or oil or an alkenyl group derived from fat or oil; a molecular chain having an alkyl group having 6 or more carbon atoms or an alkenyl group having 6 or more carbon atoms; a molecular unit having 4 or more carbon atoms
  • a molecular chain having a repeating unit; a molecular chain composed of a rosin skeleton or a hydrogenated rosin skeleton; and the like are preferable.
  • the low polarity group may be one kind of these groups or a combination of two or more kinds.
  • the alkyl group having 6 or more carbon atoms or the alkenyl group having 6 or more carbon atoms related to the low polar molecular chain may be linear, branched or cyclic.
  • the medium polar group is a group having a polar group in the low polar group or a group having a polar group in a nonpolar group.
  • the polar group include a heterocyclic group, a carboxyl group, a hydroxyl group, an amide group, an imide group, a nitro group, an amino group, an ammonium group, a sulfonyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, and a sulfide group.
  • An amide group is preferred.
  • Amide groups are preferred because they are less polar than carboxyl groups, hydroxyl groups and amino groups.
  • the polar group may be a single type of these groups or a combination of two or more types.
  • the nonpolar group include an alkyl group.
  • the nonpolar group may be a single type of these groups or a combination of two or more types.
  • a compound having a low-polar group at the end is defined as one that does not cause turbidity or separation when mixed with a low-polarity compound serving as an index.
  • a compound having a medium polar group at the end is defined as a compound that does not cause turbidity or separation even when mixed with a low-polarity compound serving as an index and a polar compound serving as an index.
  • an alkyd resin is a product obtained by modifying a condensate of a polybasic acid and a polyhydric alcohol with a fatty oil or a fatty acid, and is generally a low polarity compound.
  • a compound which is compatible with the alkyd resin, becomes turbid and does not separate is a compound having a medium polar group or a low polar group at the terminal.
  • Examples of the low polar compound that serves as an index include nonpolar solvents such as hexane, benzene, toluene, diethyl ether, ethyl acetate, chloroform, and methylene chloride.
  • Examples of polar compounds that serve as indicators include polar aprotic solvents such as tetrahydrofuran, acetone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide; acetic acid, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, formic acid, Polar proton solvents such as water; and the like.
  • the decomposition temperature of the compound having an ester bond or the compound having a urea group is preferably 400 ° C. or lower, more preferably 300 ° C. or lower, and further preferably 250 ° C. or lower.
  • the decomposition temperature of a compound having an ester bond or a compound having a urea group can be measured using a differential thermal scanning calorimetry (DSC) or a simultaneous differential calorific value calorimeter (TG / DTA).
  • the content of the compound having an ester bond or the compound having a urea group is preferably 0.1% by mass or more and 10% by mass or less with respect to 100 parts by mass of the n-type diffusion layer forming composition. More preferably, the content is from 5% by mass to 5% by mass, and further preferably from 1% by mass to 3% by mass.
  • the n-type diffusion layer forming composition of the present invention contains a dispersion medium.
  • the dispersion medium is a medium in which the glass particles are dispersed in the n-type diffusion layer forming composition.
  • the dispersion medium includes at least a solvent or water, and includes a thickener as necessary.
  • Solvents 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, dipropyl ketone, Ketone solvents such as diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, ⁇ -butyrolactone, ⁇ -valerolactone; diethyl ether, methyl ethyl ether, methyl- n-propyl ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane,
  • the solvent is preferably a terpene solvent, glycol monoether solvent or ester solvent, such as terpineol such as ⁇ -terpineol, diethylene glycol monoester.
  • terpineol such as ⁇ -terpineol
  • diethylene glycol monoester e.g., ethylene glycol monoester
  • -N-butyl ether (butyl carbitol) or diethylene glycol mono-n-butyl ether (butyl carbitol acetate) is more preferred
  • ⁇ -terpineol or diethylene glycol mono-n-butyl ether is more preferred
  • diethylene glycol mono-n-butyl ether acetate is particularly preferred preferable.
  • composition of the dispersion medium and the content of the dispersion medium in the n-type diffusion layer forming composition are determined in consideration of coating properties and donor concentration.
  • the content of the solvent can be 10% by mass to 95% by mass, and preferably 50% by mass to 90% by mass.
  • the n-type diffusion layer forming composition preferably contains a thickener.
  • Thickeners include polyvinyl alcohol, polyacrylamides, polyvinylamides, polyvinylpyrrolidone, polyethylene oxides, polysulfonic acid, acrylamide alkylsulfonic acid, cellulose ethers, cellulose derivatives, carboxymethylcellulose, hydroxyethylcellulose, ethylcellulose, gelatin, starch , Starch derivatives, sodium alginate, xanthan, guar, guar derivatives, scleroglucan, scleroglucan derivatives, tragacanth, tragacanth derivatives, dextrin, dextrin derivatives, acrylic resins [(meth) acrylic acid resins, (meth) acrylic acid esters Resin (for example, alkyl (meth) acrylate resin and dimethylaminoethyl (meth) acrylate resin), etc.], alkyd resin, Tajien resins,
  • the molecular weight of the thickener is not particularly limited, and it is desirable to adjust appropriately in view of the desired viscosity of the composition. Further, the constitution of the thickener and the content of the thickener in the n-type diffusion layer forming composition are determined in consideration of coating properties and a desired donor concentration in the semiconductor substrate.
  • the n-type diffusion layer forming composition of the present invention may contain an inorganic filler.
  • the inorganic filler include silica, clay, silicon carbide and the like. Among these, the inorganic filler preferably contains silica.
  • the n-type diffusion layer imparted on the semiconductor substrate in the drying process in which the dispersion medium, the gelling agent, etc. in the n-type diffusion layer formation composition are decomposed or volatilized because the n-type diffusion layer formation composition contains an inorganic filler. Thermal sagging of the layer forming composition can be suppressed. The cause of the thermal sag is considered to be that the viscosity of the dispersion medium, the gelling agent, etc.
  • the n-type diffusion layer forming composition contains an inorganic filler, it is considered that since the decrease in the viscosity of the n-type diffusion layer forming composition can be suppressed, thermal sag can be suppressed.
  • the BET specific surface area of the inorganic filler is preferably 50 m 2 / g to 500 m 2 / g, and more preferably 100 m 2 / g to 300 m 2 / g.
  • fumed silica can be exemplified.
  • fumed silica refers to ultrafine anhydrous silica, and is produced by hydrolyzing silanes such as silicon tetrachloride in a flame of oxygen and hydrogen. Since fumed silica is synthesized by a gas phase method, the primary particle size is small and the BET specific surface area is large.
  • the BET specific surface area of the inorganic filler can be calculated by measuring the amount of nitrogen adsorbed at 77K.
  • the fumed silica may be hydrophilic or hydrophobic. Hydrophobic fumed silica can be obtained by treating the surface of anhydrous silica with a silane coupling agent or the like.
  • the content of the inorganic filler in the n-type diffusion layer forming composition is preferably 0.01% by mass to 40% by mass, more preferably 0.1% by mass to 20% by mass, and 0.2% More preferably, the content is from 5% by mass to 5% by mass.
  • the n-type diffusion layer forming composition of the present invention may further contain alkoxysilane.
  • the n-type diffusion layer forming composition contains alkoxysilane, the viscosity of the n-type diffusion layer forming composition tends to be maintained in the drying step after the n-type diffusion layer forming composition is applied to the semiconductor substrate.
  • the alkoxy group constituting the alkoxysilane is preferably a linear or branched alkoxy group, and is a linear or branched alkoxy group having 1 to 24 carbon atoms or a straight chain or having 1 to 24 carbon atoms.
  • it is an alkoxy group having 1 to 10 carbon atoms and linear or 1 to 10 carbon atoms, and more preferably, linear or 1 to 4 carbon atoms or linear or 1 to 4 carbon atoms.
  • a branched alkoxy group is particularly preferred.
  • alkyl group of the alkoxy group examples include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, t-octyl group, decyl group.
  • the alkoxysilane it is preferable to use at least one selected from tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.
  • the content of alkoxysilane in the n-type diffusion layer forming composition is not particularly limited, and is preferably 30% by mass or less, and 20% by mass. % Or less is more preferable, and 10 mass% or less is still more preferable.
  • the n-type diffusion layer forming composition of the present invention may contain an organic filler.
  • Organic fillers include urea formalin resin, phenol resin, polycarbonate resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyurethane resin, polyolefin resin, acrylic resin, fluorine resin, polystyrene resin, cellulose, formaldehyde resin, A malon indene resin, lignin, petroleum resin, amino resin, polyester resin, polyether sulfone resin, butadiene resin, a copolymer thereof, and the like can be appropriately selected.
  • An organic filler is used individually by 1 type or in combination of 2 or more types.
  • the molecular weight of the resin used as the organic filler is not particularly limited, and it is desirable to adjust appropriately in view of the desired viscosity as the n-type diffusion layer forming composition.
  • Examples of the monomer constituting the acrylic resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, methacryl Pentyl acid, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acryl
  • the particle size (volume average particle size) of the organic filler is preferably 10 ⁇ m or less, and more preferably 0.1 ⁇ m or less.
  • the particle size of the organic filler is 10 ⁇ m or less, precipitation of the organic filler is easily suppressed in the n-type diffusion layer forming composition, and clogging is suppressed when printing the n-type diffusion layer forming composition. .
  • the composition for forming an n-type diffusion layer of the present invention preferably contains substantially no transition metal such as silver, copper, iron, zinc and the transition metal compound (for example, 5% by mass or less).
  • transition metals and transition metal compounds When these transition metals and transition metal compounds are dissolved in the semiconductor substrate, they act as carrier recombination centers in the semiconductor substrate, resulting in a problem of reduced conversion efficiency when the semiconductor substrate is applied to a solar cell. there's a possibility that.
  • the content rate of the transition metal and transition metal compound in an n type diffused layer formation composition it is more preferable that it is 0.5 mass% or less.
  • the viscosity of the n-type diffusion layer forming composition is not particularly limited.
  • the shear viscosity when the shear rate is 10 [1 s ⁇ 1 ] is preferably 1 Pa ⁇ s to 150 Pa ⁇ s (25 ° C.), It is more preferably 5 Pa ⁇ s to 100 Pa ⁇ s, and further preferably 7 Pa ⁇ s to 80 Pa ⁇ s.
  • the shear viscosity of the n-type diffusion layer forming composition when the shear rate is 10 [1 s ⁇ 1 ] is 1 Pa ⁇ s or more, the thickness of the coating film in screen printing tends to be uniform, and 150 Pa ⁇ s or less. If this is the case, clogging of the screen mask plate tends to be difficult to occur.
  • the thixotropy of the n-type diffusion layer forming composition is not particularly limited.
  • the logarithm of the shear viscosity ⁇ x when the shear rate is x [1 / sec] is expressed as log 10 ( ⁇ x ), and the thixotropy is expressed.
  • the TI value is preferably 0.3 to 2.5, and [log 10 ( ⁇ 0.01 ) ⁇ log 10 ( ⁇ 10 )] is preferably 1 to 2.2. More preferably, it is more preferably 1.5 to 2.0.
  • the TI value is 0.3 or more, the dripping of the n-type diffusion layer forming composition after screen printing on the semiconductor substrate is difficult to occur, and when it is 2.5 or less, the coating amount at the time of continuous printing is stable. Tend to. This tendency is the same in other coating methods such as an ink jet method.
  • the method for preparing the n-type diffusion layer forming composition of the present invention is not particularly limited.
  • a blender containing glass particles containing a donor element, a dispersion medium, a gelling agent, at least one selected from a compound having an ester bond and a compound having a urea group, and other additives as necessary.
  • the n-type diffusion layer forming composition of the present invention can be obtained by mixing using a mixer, a mortar or a rotor. Moreover, when mixing, you may heat as needed. When heating at the time of mixing, the temperature can be, for example, 30 ° C. to 100 ° C.
  • the gelling agent When the gelling agent is used, it is preferable to go through a step of once dissolving the gelling agent in the dispersion medium. Once dissolved, the n-type diffusion layer forming composition can be given more appropriate thixotropy. Once dissolved, the gelling agent may be in a dissolved state or in a precipitated state.
  • n-type diffusion layer forming composition Components contained in the n-type diffusion layer forming composition and the content of each component are confirmed using thermal analysis such as TG / DTA, NMR, HPLC, GPC, GC-MS, IR, MALDI-MS, etc. be able to.
  • the method for producing an n-type diffusion layer of the present invention includes a step of applying the n-type diffusion layer forming composition on a semiconductor substrate and a step of applying a thermal diffusion treatment to the semiconductor substrate to which the n-type diffusion layer forming composition is applied. And having.
  • the manufacturing method of the positive battery cell of this invention performs the process of providing the said n type diffused layer formation composition on a semiconductor substrate, and a thermal diffusion process to the semiconductor substrate which provided the n type diffused layer formation composition. Forming an n-type diffusion layer and forming an electrode on the formed n-type diffusion layer.
  • FIG. 1 is a schematic cross-sectional view conceptually showing an example of the manufacturing process of the solar battery cell of the present invention.
  • common constituent elements are denoted by the same reference numerals.
  • an alkaline solution is applied to a silicon substrate that is a p-type semiconductor substrate 10 to remove a damaged layer, and a texture structure is obtained on the surface of the p-type semiconductor substrate 10 by etching.
  • the damaged layer on the surface of the silicon substrate generated when slicing from the ingot is removed with 20% by mass caustic soda.
  • etching is performed with a mixed solution of 1% by mass caustic soda and 10% by mass isopropyl alcohol to form a texture structure (the description of the texture structure is omitted in the figure).
  • a texture structure on the light receiving surface (front surface) side, a light confinement effect is promoted and high efficiency is achieved.
  • the n-type diffusion layer forming composition layer 11 is formed by applying the n-type diffusion layer forming composition to the surface of the p-type semiconductor substrate 10, that is, the surface serving as the light receiving surface.
  • coating method of n type diffused layer formation composition For example, a printing method, a spin method, a brush coating method, a spray method, a doctor blade method, a roll coater method, and an inkjet method is mentioned.
  • the amount of the n-type diffusion layer forming composition applied is not particularly limited.
  • the amount of glass particles included in the n-type diffusion layer forming composition is set to 0.01 g / m 2 to 100 g / m 2 . It is preferably 0.1 g / m 2 to 10 g / m 2 .
  • the solvent contained in the n-type diffusion layer forming composition after being applied to the p-type semiconductor substrate 10 is volatilized, so that a drying step may be necessary.
  • drying is performed at a temperature of about 80 ° C. to 300 ° C. for about 1 minute to 10 minutes when using a hot plate and about 10 to 30 minutes when using a dryer.
  • the drying conditions depend on the solvent composition of the n-type diffusion layer forming composition, and are not particularly limited to the above conditions in the present invention.
  • the method for forming the p + -type diffusion layer (high-concentration electric field layer) 14 on the back surface is limited to a method by conversion from an n-type diffusion layer to a p-type diffusion layer using aluminum.
  • any conventionally known method can be adopted, and the choice of forming method is expanded. Therefore, for example, the high-concentration electric field layer 14 can be formed by applying the composition 13 containing a Group 13 element such as B (boron).
  • the p-type semiconductor substrate 10 on which the n-type diffusion layer forming composition layer 11 is formed is subjected to thermal diffusion treatment at 600 ° C. to 1200 ° C.
  • thermal diffusion treatment the donor element diffuses into the p-type semiconductor substrate 10 as shown in FIG.
  • a known continuous furnace, batch furnace, or the like can be applied to the thermal diffusion treatment.
  • the furnace atmosphere during the thermal diffusion treatment can be appropriately adjusted to air, oxygen, nitrogen or the like.
  • the time for the thermal diffusion treatment can be appropriately selected according to the content of the donor element contained in the n-type diffusion layer forming composition. For example, it can be 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes.
  • a glass layer such as phosphate glass is formed on the surface of the formed n-type diffusion layer 12, this phosphate glass is removed by etching.
  • etching a known method such as a method of immersing in an acid such as hydrofluoric acid or a method of immersing in an alkali such as caustic soda can be applied.
  • n-type diffusion layer 12 In the method for producing an n-type diffusion layer of the present invention, in which the n-type diffusion layer 12 is formed using the n-type diffusion layer forming composition of the present invention shown in FIGS.
  • the n-type diffusion layer 12 is formed in this part, and an unnecessary n-type diffusion layer is not formed on the back and side surfaces. Therefore, in the conventional method of forming an n-type diffusion layer by a gas phase reaction method, a side etching process for removing an unnecessary n-type diffusion layer formed on a side surface is essential. According to the manufacturing method of the invention, the side etching process is not required, and the process is simplified.
  • n-type diffusion layer formed on the back surface it is necessary to convert an unnecessary n-type diffusion layer formed on the back surface into a p-type diffusion layer.
  • a group 13 element is added to the n-type diffusion layer on the back surface.
  • a method is adopted in which a certain aluminum paste is applied and baked to diffuse aluminum into the n-type diffusion layer and convert it into a p-type diffusion layer.
  • conversion to the p-type diffusion layer is sufficient, and in order to form a high-concentration electric field layer of the p + -type diffusion layer, a certain amount of aluminum is required. There was a need to form.
  • the thermal expansion coefficient of aluminum is greatly different from the thermal expansion coefficient of silicon used as a semiconductor substrate.
  • n-type diffusion layer since an unnecessary n-type diffusion layer is not formed on the back surface, it is not necessary to perform conversion from the n-type diffusion layer to the p-type diffusion layer, and it is necessary to increase the thickness of the aluminum layer. Disappear. As a result, generation of internal stress in the semiconductor substrate and warpage of the semiconductor substrate can be suppressed. As a result, it is possible to suppress an increase in power loss and damage of the solar battery cell in the solar battery using this semiconductor substrate.
  • the manufacturing method of the p + -type diffusion layer (high concentration electric field layer) 14 on the back surface is limited to a method by conversion from an n-type diffusion layer to a p-type diffusion layer by aluminum.
  • either method can be adopted, and the choice of manufacturing method is expanded.
  • the material used for the front surface electrode (back surface electrode) 20 on the back surface is not limited to Group 13 aluminum, and Ag (silver), Cu (copper), etc. can be applied. It is possible to form a thinner thickness than the conventional one.
  • an antireflection film 16 is formed on the n-type diffusion layer 12.
  • the antireflection film 16 is formed by applying a known technique.
  • the antireflection film 16 is a silicon nitride film, it is formed by a plasma CVD method using a mixed gas of SiH 4 and NH 3 as a raw material.
  • hydrogen diffuses into the silicon crystal, which is a semiconductor substrate, and orbitals (ie, dangling bonds) that do not contribute to bonding of silicon atoms are combined with hydrogen to inactivate defects (hydrogen passivation) of the silicon crystal.
  • the mixed gas flow ratio NH 3 / SiH 4 is 0.05 to 1.0
  • the reaction chamber pressure is 13.3 Pa to 266.6 Pa (0.1 Torr to 2 Torr)
  • the silicon nitride film is formed under conditions where the temperature is 300 ° C. to 550 ° C. and the frequency for plasma discharge is 100 kHz or more.
  • a surface electrode metal paste is applied by screen printing on the antireflection film 16 on the surface (light receiving surface) and then dried to form the surface electrode 18.
  • the metal paste for a surface electrode includes (1) metal particles and (2) glass particles as essential components, and includes (3) a resin binder, (4) other additives, and the like as necessary.
  • the back electrode 20 is also formed on the high-concentration electric field layer 14 on the back surface.
  • the material and the forming method of the back electrode 20 are not particularly limited in the present invention.
  • the back electrode 20 may be formed by applying a metal paste for the back electrode including a metal such as aluminum, silver, or copper, and drying the paste. At this time, you may provide the silver paste for silver electrode formation in a part of back surface for the connection between the photovoltaic cells in a module process.
  • the electrode is fired to complete the solar cell.
  • the antireflection film 16 that is an insulating film is melted by the glass particles contained in the metal paste for the surface electrode on the surface side, and the surface of the p-type semiconductor substrate 10 is also one
  • the metal particles (for example, silver particles) in the paste form a contact portion with the p-type semiconductor substrate 10 and are solidified. Thereby, the formed surface electrode 18 and the p-type semiconductor substrate 10 are electrically connected. This is called fire-through.
  • FIG. 2A is a plan view of a solar cell in which the surface electrode 18 includes a bus bar electrode 30 and a finger electrode 32 intersecting with the bus bar electrode 30 as viewed from the light receiving surface (front surface).
  • FIG. 2B is an enlarged perspective view showing a part of FIG.
  • Such a surface electrode 18 can be formed, for example, by means such as screen printing of the above-described metal paste for surface electrode, plating of an electrode material, vapor deposition of an electrode material by electron beam heating in a high vacuum, or the like.
  • the surface electrode 18 composed of the bus bar electrode 30 and the finger electrode 32 is generally used as an electrode on the light receiving surface side and is well known, and it is possible to apply known forming means for the bus bar electrode and finger electrode on the light receiving surface side. it can.
  • the solar cell in which the n-type diffusion layer is formed on the front surface, the p + -type diffusion layer is formed on the back surface, and the front electrode and the back electrode are further provided on the respective diffusion layers has been described. If the diffusion layer forming composition is used, a back contact type solar battery cell can be produced.
  • the back contact type solar battery cell has all electrodes provided on the back surface to increase the area of the light receiving surface. That is, in the back contact solar cell, it is necessary to form both the n-type diffusion region and the p + -type diffusion region on the back surface to form a pn junction structure.
  • the composition for forming an n-type diffusion layer of the present invention can form an n-type diffusion site in a specific region of a p-type semiconductor substrate, and is therefore preferably applied to the production of a back-contact type solar cell. Can do.
  • FIG. 3 is a cross-sectional view conceptually showing an example of the manufacturing process of the back contact solar cell according to the present invention.
  • a p-type diffusion layer forming composition and an n-type diffusion layer forming composition are partially applied to the surface of one surface of the p-type semiconductor substrate 1, respectively, and subjected to thermal diffusion treatment, whereby a p + -type diffusion layer is formed.
  • the 3 and n type diffusion layers 6 can be formed in specific regions, respectively.
  • Examples of a method for applying the p-type diffusion layer forming composition and the n-type diffusion layer forming composition include an ink jet method or a pattern printing method.
  • the heat-treated material layer 2 of the p-type diffusion layer forming composition is formed on the p + -type diffusion layer 3 of the p-type semiconductor substrate 1.
  • a heat-treated product layer 5 of the n-type diffusion layer forming composition is formed thereon.
  • the p-type diffusion layer forming composition formed on the p + -type diffusion layer 3 was formed on the heat-treated product layer 2 and the n-type diffusion layer 6.
  • the heat-treated product layer 5 of the n-type diffusion layer forming composition is removed by etching or the like. Thereby, the p + -type diffusion layer 3 and the n-type diffusion layer 6 are selectively formed in the vicinity of the surface of the p-type semiconductor substrate 1.
  • an antireflection film or a surface protective film 7 is formed on the p-type semiconductor substrate 1 by a conventional method.
  • an antireflection film or a surface protection film 7 is partially formed so that at least a part of the p + type diffusion layer 3 and the n type diffusion layer 6 is exposed on the surface. May be.
  • an antireflection film or a surface protective film 7 may be formed so as to cover the p + type diffusion layer 3 and the n type diffusion layer 6.
  • the p + -type diffusion layer 3 and n The electrode 4 and the electrode 8 can be formed on the mold diffusion layer 6, respectively.
  • an antireflection film or a surface protective film 7 is formed so as to cover the p + type diffusion layer 3 and the n type diffusion layer 6 as shown in FIG.
  • the electrode 4 and the electrode 8 can be formed on the p + -type diffusion layer 3 and the n-type diffusion layer 6 as shown in FIG.
  • n-type diffusion layer forming composition 10 g of a solution containing glass particles and 20 g of a solution containing a gelling agent were mixed in a mortar to prepare an n-type diffusion layer forming composition (hereinafter also simply referred to as “paste”).
  • the obtained paste was applied by screen printing on the surface of a sliced p-type silicon substrate (hereinafter also referred to as “p-type slice silicon substrate”).
  • the squeegee speed and scraper speed during screen printing were both 300 mm / sec.
  • the printing pattern was printed with two types of masks: a solid pattern of 45 mm ⁇ 45 mm and a linear pattern with a width of 150 ⁇ m.
  • the paste on the p-type silicon substrate was dried on a hot plate at 150 ° C. for 5 minutes, and then air was supplied at 5 L / min. Thermal diffusion treatment was performed for 10 minutes in a 900 ° C.
  • the p-type silicon substrate is immersed in a 2.5 mass% HF aqueous solution for 6 minutes, and then washed with running water and ultrasonically. And drying was performed to obtain a p-type silicon substrate on which an n-type diffusion layer was formed. Further, a p-type mirror wafer having a p-type diffusion layer formed was obtained in the same manner except that a p-type mirror wafer was used instead of the p-type slice silicon substrate. Table 1 shows the evaluation results when using a p-type slice silicon substrate.
  • the n-type diffusion layer forming composition is applied to the surface of the p-type sliced silicon substrate in a 150 ⁇ m-wide linear pattern and dried at 150 ° C., and then the linear pattern width is measured with an optical microscope (Olympus Corporation, MX-51). Observed.
  • the linear pattern width after drying was 170 ⁇ m, and the print width increase rate with respect to the mask setting width of 150 ⁇ m was 113%.
  • the sheet resistance of the surface of the p-type slice silicon substrate on which the n-type diffusion layer was formed was measured by a four-probe method using a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition was applied was 40 ⁇ / ⁇ .
  • n-type diffusion layer forming composition was prepared so as to have the composition shown in Table 1, and evaluation was performed in the same manner as in Example 1 except that each n-type diffusion layer forming composition was used.
  • Table 1 the numerical value described in the column of composition indicates mass% with respect to the total amount of the n-type diffusion layer forming composition.
  • the evaluation results are shown in Table 1.
  • the used component is as follows.
  • Gelol MD manufactured by Shin Nippon Rika Co., Ltd., structural formula (3), 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol fumed silica; manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL 200 BET specific surface area: 200 m 2 / g
  • the printing width increase rate is close to 100%, and the expansion of the contact area of the pattern shape in the surface direction on the semiconductor substrate can be suppressed. it can.
  • Example 6 Glass particles (P 2 O 5 : 50%, SiO 2 : 43%, CaO: 7%) 10%, ethyl cellulose 5%, ⁇ -terpineol 83.5%, and urea compound solution BYK-410 (BIC Chemie Japan Co., Ltd.) 1.5% of a compound having a medium polar group at the end) was mixed into a paste to prepare an n-type diffusion layer forming composition 6.
  • Example 6 screen printing was performed with both the squeegee speed and the scraper speed being 300 mm / sec, and the surface of the p-type silicon substrate was 150 ⁇ m wide.
  • the linear pattern width after coating with a linear pattern and drying at 50 ° C. was measured with an optical microscope manufactured by Olympus Corporation.
  • the line width of the pattern was 180 ⁇ m, and the line thickness from the mask setting width of 150 ⁇ m was within 35 ⁇ m.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition 6 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance of the back surface to which the n-type diffusion layer forming composition 6 was not applied was 1000000 ⁇ / ⁇ or more, which was not measurable, and no n-type diffusion layer was formed.
  • Example 7 Glass particles (P 2 O 5 : 50%, SiO 2 : 43%, CaO: 7%) 10%, ethyl cellulose 5%, ⁇ -terpineol 80%, and urea compound solution BYK-410 (manufactured by Big Chemie Japan) 5 % was made into a paste to prepare an n-type diffusion layer forming composition 7.
  • the shear viscosity of the n-type diffusion layer forming composition 7 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 / s was 580 Pa ⁇ s (25 ° C.), while the shear rate was 30 / The shear viscosity at s was 1.36 Pa ⁇ s, the TI value was 2.63, and high thixotropic properties were obtained.
  • n-type diffusion layer forming composition 7 as in Example 6, screen printing was performed with both the squeegee speed and the scraper speed being 300 mm / sec, and a linear pattern with a width of 150 ⁇ m was formed on the surface of the p-type silicon substrate.
  • the linear pattern width after coating at 50 ° C. and measuring with an optical microscope manufactured by Olympus Corporation was 185 ⁇ m, the line thickness from the mask setting width of 150 ⁇ m was within 35 ⁇ m.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition 7 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance of the back surface to which the n-type diffusion layer forming composition 7 was not applied was 1000000 ⁇ / ⁇ or more, which was not measurable, and no n-type diffusion layer was formed.
  • Example 8 Glass particles (P 2 O 5 : 50%, SiO 2 : 43%, CaO: 7%) 10%, ethyl cellulose 5%, ⁇ -terpineol 80%, and urea compound solution BYK-411 (manufactured by Big Chemie Japan) 5 % was made into a paste to prepare an n-type diffusion layer forming composition 8.
  • the shear viscosity of the n-type diffusion layer forming composition 8 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 / s was 500 Pa ⁇ s (25 ° C.), while the shear rate was 30 / The shear viscosity at s was 10 Pa ⁇ s, the TI value was 1.70, and high thixotropy was obtained.
  • n-type diffusion layer forming composition 8 as in Example 6, screen printing with both the squeegee speed and scraper speed of 300 mm / sec was performed, and a 150 ⁇ m wide linear pattern was formed on the surface of the p-type silicon substrate.
  • the linear pattern width after coating at 50 ° C. and measured with an optical microscope manufactured by Olympus Corporation was 190 ⁇ m, and the line thickness from the mask setting width of 150 ⁇ m was within 40 ⁇ m.
  • the sheet resistance of the portion where the n-type diffusion layer forming composition 8 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance of the back surface to which the n-type diffusion layer forming composition 8 was not applied was 1000000 ⁇ / ⁇ or more, which was not measurable, and no n-type diffusion layer was formed.
  • the shear viscosity of the comparative n-type diffusion layer forming composition was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 / s was 176 Pa ⁇ s (25 ° C.), while the shear rate was 10 The shear viscosity at / s was 68 Pa ⁇ s, the TI value was 0.41, and sufficient thixotropy was not obtained.
  • Example 6 screen printing was performed with both the squeegee speed and scraper speed set to 300 mm / sec, and a 150 ⁇ m wide linear pattern was formed on the p-type silicon substrate surface. When it applied by the pattern, the comparative n type diffused layer formation composition was not printed in linear form, but the disconnection was seen in some places.
  • An n-type diffusion layer forming composition containing a compound containing a donor element of the present invention, a dispersion medium, a gelling agent, at least one selected from a compound having an ester bond and a compound having a urea group, It is possible to suppress the expansion of the line width of the fine line pattern on the semiconductor substrate and to form an n-type diffusion layer with a specific size in a desired specific region of the semiconductor substrate. .
  • a gelling agent, a compound having an ester bond, and a compound having a urea group an appropriate shear viscosity can be imparted to the n-type diffusion layer forming composition, Good printability can be provided.

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  • Paints Or Removers (AREA)

Abstract

Composition pour la formation d'une couche de diffusion de type n qui contient des particules de verre composées d'un élément donneur, d'un milieu de dispersion, d'un agent gélifiant, et d'au moins un composé choisi parmi des composés ayant une liaison ester et des composés ayant un groupe urée.
PCT/JP2013/051798 2012-02-29 2013-01-28 COMPOSITION POUR LA FORMATION D'UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n, ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE Ceased WO2013129002A1 (fr)

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JP2017143163A (ja) * 2016-02-09 2017-08-17 Koa株式会社 抵抗ペースト組成物およびそれを用いた厚膜チップ抵抗器

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