WO2013125254A1 - Composition de formation de couche de diffusion d'impureté, procédé de fabrication d'un substrat semi-conducteur doté d'une couche de diffusion d'impureté et procédé de fabrication d'un élément de cellule solaire - Google Patents

Composition de formation de couche de diffusion d'impureté, procédé de fabrication d'un substrat semi-conducteur doté d'une couche de diffusion d'impureté et procédé de fabrication d'un élément de cellule solaire Download PDF

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WO2013125254A1
WO2013125254A1 PCT/JP2013/050307 JP2013050307W WO2013125254A1 WO 2013125254 A1 WO2013125254 A1 WO 2013125254A1 JP 2013050307 W JP2013050307 W JP 2013050307W WO 2013125254 A1 WO2013125254 A1 WO 2013125254A1
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diffusion layer
forming composition
impurity diffusion
layer forming
group
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PCT/JP2013/050307
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Japanese (ja)
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岩室　光則
吉田　誠人
野尻　剛
洋一 町井
明博 織田
鉄也 佐藤
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日立化成株式会社
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Priority to JP2014500611A priority Critical patent/JP5655974B2/ja
Publication of WO2013125254A1 publication Critical patent/WO2013125254A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/2225—Diffusion sources
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • 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 an impurity diffusion layer forming composition, a method for manufacturing a semiconductor substrate with an impurity diffusion layer, and a method for manufacturing a solar cell element, and more specifically, forming an impurity diffusion layer in a specific part of a semiconductor substrate. It relates to technology that makes it possible.
  • n-type semiconductor substrate having a texture structure formed on the light-receiving surface side is prepared so as to promote the light confinement effect and increase the efficiency, and then in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen
  • An n-type impurity diffusion layer (n-type diffusion layer) is uniformly formed by performing several tens of minutes of heat treatment at 800 ° C. to 900 ° C. (gas phase reaction method).
  • 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.
  • 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, heat treatment is performed, and at the same time the n-type diffusion layer is converted to the p + -type diffusion layer by the diffusion of aluminum. , Got ohmic contact.
  • 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 a thermal diffusion treatment is performed, whereby an unnecessary impurity diffusion layer is formed on the side surface or the back surface 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 being formed has been proposed (see, for example, International Publication No. 2011/090216 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
  • the selective emitter structure since a region having a high diffusion concentration (hereinafter, this region is also referred to as “selective emitter”) is formed immediately below the electrode, the contact resistance between the electrode and the semiconductor substrate can be reduced. Furthermore, since 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. In order to construct such a selective emitter structure, it is required to form an impurity diffusion layer in a thin line shape within a width of several hundred ⁇ m (about 50 ⁇ m to 200 ⁇ m).
  • the back contact type solar cell element 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. It is required to form.
  • the n-type diffusion layer forming composition described in International Publication No. 2011/090216 pamphlet is used, for example, the n-type diffusion layer forming composition is applied to a semiconductor substrate in a thin line shape to form an n-type diffusion layer Even when the composition layer is formed, the line width of the n-type diffusion layer forming composition layer is widened, and there is a tendency that a desired thin line width cannot be obtained. In order to solve this problem, when the content of the dispersion medium is changed to increase the viscosity, the handling property is poor and the coating itself tends to be impossible.
  • the present invention has been made in view of the above-described problems of the prior art, and when an impurity diffusion layer forming composition layer is formed by being applied to a partial region on a semiconductor substrate, impurities are formed in the surface direction on the semiconductor substrate.
  • an impurity diffusion layer forming composition capable of suppressing an increase in the contact area of the diffusion layer forming composition layer, a method for manufacturing a semiconductor substrate with an impurity diffusion layer using the composition, and a method for manufacturing a solar cell element. For the purpose.
  • fatty acid amide contains at least one selected from the group consisting of compounds represented by the following general formulas (1), (2), (3) and (4) This is an impurity diffusion layer forming composition.
  • R 1 CONH 2 (1) R 1 CONH—R 2 —NHCOR 1 (2) R 1 NHCO—R 2 —CONHR 1 (3) R 1 CONH—R 2 —N (R 3 ) 2 ... (4)
  • R 1 and R 3 each independently represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and R 2 represents 1 to 10 carbon atoms.
  • the alkylene group is shown.
  • R 1 and R 3 may be the same or different.
  • fatty acid amide contains at least one selected from the group consisting of stearic acid amide, N, N′-methylenebisstearic acid amide, and stearic acid dimethylaminopropylamide.
  • ⁇ 4> The impurity diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 3>, wherein the decomposition temperature of the fatty acid amide is 400 ° C. or lower.
  • One or more donor element-containing materials selected from the group consisting of P 2 O 3 and P 2 O 5 , SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO. ⁇ 9> containing at least one glass component material selected from the group consisting of SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5 , SnO, ZrO 2 and MoO 3.
  • the content of P 2 O 3 and P 2 O 5 in the glass particles is 15% by mass or more, 80 It is an impurity diffusion layer forming composition as described in said ⁇ 10> which is the mass% or less.
  • ⁇ 12> The impurity diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 7>, wherein the compound containing the acceptor element contains B (boron) or Al (aluminum).
  • ⁇ 14> One or more acceptor element-containing substances selected from the group consisting of B 2 O 3 and Al 2 O 3 , and 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 TiO 2.
  • a step of forming the impurity diffusion layer forming composition layer by applying the impurity diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 20> to all or a part of the semiconductor substrate. And a step of heat-treating the semiconductor substrate on which the impurity diffusion layer-forming composition layer is formed to form an impurity diffusion layer, and a step of forming an electrode on the formed impurity diffusion layer. It is a manufacturing method of a battery element.
  • the contact area of the impurity diffusion layer forming composition layer is expanded in the surface direction on the semiconductor substrate. It is possible to provide a composition for forming an impurity diffusion layer capable of suppressing the above, a method for manufacturing a semiconductor substrate with an impurity diffusion layer using the composition, and a method for manufacturing a solar cell element.
  • FIG. 2A It is sectional drawing which shows notionally an example of the manufacturing process of the solar cell element of this invention. It is an example of the schematic plan view which looked at the solar cell element from the surface. It is a perspective view which expands and shows a part of FIG. 2A.
  • the impurity diffusion layer forming composition of the present invention will be described, and then a method for manufacturing a semiconductor substrate with an impurity diffusion layer and a solar cell element using the impurity diffusion layer forming composition 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 if the intended purpose of the process is achieved. included.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • content rate represents the mass% of a component with respect to 100 mass% of impurity diffusion layer forming compositions unless there is particular description.
  • the n-type impurity diffusion layer forming composition is referred to as an n-type diffusion layer forming composition.
  • the p-type impurity diffusion layer forming composition is referred to as a p-type diffusion layer forming composition.
  • the n-type impurity diffusion layer is referred to as an n-type diffusion layer.
  • the p-type impurity diffusion layer is referred to as a p-type diffusion layer.
  • the n-type diffusion layer forming composition and the p-type diffusion layer forming composition are collectively referred to as an impurity diffusion layer forming composition.
  • the n-type diffusion layer and the p-type diffusion layer are collectively referred to as an impurity diffusion layer.
  • the impurity diffusion layer forming composition of the present invention contains a compound containing a donor element or a compound containing an acceptor element, a dispersion medium, and a fatty acid amide. Furthermore, other additives may be contained as necessary in consideration of imparting properties and the like.
  • the impurity diffusion layer forming composition contains a compound containing a donor element or a compound containing an acceptor element, and is applied to a semiconductor substrate and then applied to the compound containing the donor element in the compound containing the donor element or the acceptor element.
  • the impurity diffusion layer forming composition of the present invention contains a fatty acid amide, when a stress is applied when printing on a semiconductor substrate with a screen printing machine, the viscosity is lowered and fluidity is exhibited, and the screen plate meshes through. Then, a patterned impurity diffusion layer forming composition layer corresponding to the screen pattern is formed on the semiconductor substrate as a printed material. On the other hand, the impurity diffusion layer forming composition layer once formed as a printed matter on the semiconductor substrate is in a state where its shape can be maintained without being reduced in viscosity unless stress is applied.
  • the impurity diffusion layer forming composition of the present invention when applied in a pattern on a semiconductor substrate to form a patterned impurity diffusion layer forming composition layer, the impurity diffusion layer forming composition layer causes dripping. Expansion of the contact area of the impurity diffusion layer forming composition layer in the surface direction on the semiconductor substrate is suppressed.
  • the impurity diffusion layer is formed in a region corresponding to the impurity diffusion layer forming composition layer in the semiconductor substrate. Is formed.
  • the compound containing the donor element or the compound containing the acceptor element is in the form of glass particles
  • the donor component or the acceptor component is difficult to volatilize even during heat treatment (firing), so that the generation of the volatilizing gas generates a region other than the desired specific region.
  • the formation of the impurity diffusion layer is more effectively suppressed. Therefore, when the compound containing a donor element or the compound containing an acceptor element is in the form of glass particles, an impurity diffusion layer having a higher impurity concentration than other regions can be formed in a specific region of the semiconductor substrate. .
  • the impurity diffusion layer forming composition of the present invention it is possible to easily form an impurity diffusion layer in a region corresponding to the electrode position in the production of a solar cell element having a selective emitter structure.
  • an impurity diffusion layer forming composition using a compound containing a donor element in the form of glass particles or a compound containing an acceptor element, impurity diffusion can be performed only at a desired site, unlike a conventional gas phase reaction method. A layer is formed, and the formation of an impurity diffusion layer in an unnecessary portion is suppressed. Therefore, when the impurity diffusion layer forming composition of the present invention is applied, the side etching step essential in the production of the solar cell element using the conventional gas phase reaction method becomes unnecessary, and the process is simplified.
  • an impurity diffusion layer forming composition using a compound containing a donor element in the form of glass particles, an n-type diffusion layer formed on the back surface is converted to a p + -type diffusion layer.
  • the process in (1) is also unnecessary. 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 options of the manufacturing method, material, and shape to be applied are expanded.
  • 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.
  • a donor element is an element that can form an n-type diffusion layer by diffusing into a semiconductor substrate.
  • a Group 15 element can be used, and examples thereof include P (phosphorus), Sb (antimony), and As (arsenic).
  • the compound containing a donor element preferably contains at least one of P and Sb, and more preferably P (phosphorus).
  • the oxide containing a donor element is mentioned.
  • an oxide containing a donor element an oxide of a donor element such as P 2 O 5 or P 2 O 3 ; a glass component substance as a constituent component in addition to a donor element-containing substance such as P 2 O 5 or P 2 O 3 Glass particles (glass particles containing a donor element); inorganic phosphorus compounds containing phosphorus such as phosphorus-containing silicon oxide compounds, phosphorus silicides, silicon particles doped with phosphorus, calcium phosphate, phosphoric acid, ammonium dihydrogen phosphate; Examples thereof include organic phosphorus compounds such as acid, phosphonous acid, phosphinic acid, phosphinic acid, phosphine, phosphine oxide, phosphate ester, and phosphite ester.
  • an oxide of a donor element such as P 2 O 3 or P 2 O 5 ; a glass particle containing a donor element; a phosphorus-containing silicon oxide compound; and a heat treatment temperature during thermal diffusion of the donor element to a semiconductor substrate (for example, , 800 ° C.
  • a compound that can be changed to a compound containing P 2 O 5 (ammonium dihydrogen phosphate, phosphoric acid, phosphonous acid, phosphinic acid, phosphinic acid, phosphine, phosphine oxide, phosphoric acid ester, phosphorus phosphite) It is preferable to use one or more selected from the group consisting of acid esters and the like, and among these, in the case of a compound that can change to a compound containing P 2 O 5 depending on the melting point (heat treatment temperature during thermal diffusion) It is more preferable to use a compound having a melting point of the compound containing P 2 O 5 of 1000 ° C. or lower.
  • glass particles containing a donor element or phosphorus-containing silicon oxide compounds are used as the compound containing a donor element from the viewpoint of keeping the impurity concentration low in a region other than the region where the impurity diffusion layer forming composition is applied. It is preferable to use glass particles containing a donor element.
  • the form of the particle may be a state where solid particles are dispersed in a dispersion medium or a state where the particles are partially dissolved in the dispersion medium.
  • the particle shape include a substantially spherical shape, a flat shape, a block shape, a plate shape, and a scale shape. From the viewpoint of imparting to the substrate and uniform diffusibility when the impurity diffusion layer forming composition is used, the particle shape is preferably substantially spherical, flat or plate-like.
  • the particle diameter is preferably 100 ⁇ m or less.
  • the particle size of the particles is more preferably 50 ⁇ m or less.
  • the lower limit of the particle size of the particles is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the particle size of the particles in the case where the compound containing the donor element is in the form of solid particles represents the volume average particle size, and can be measured by a laser scattering diffraction particle size distribution analyzer or the like.
  • the volume average particle diameter can be calculated based on the Mie scattering theory by detecting the relationship between the scattered light intensity and the angle of the laser light applied to the particles.
  • the dispersion medium which the particle
  • the compound containing a donor element may be in a state dissolved in a dispersion medium. In that case, the shape of the compound containing a donor element used for preparing the impurity diffusion layer forming composition is not particularly limited.
  • the compound containing a donor element is preferably a glass particle containing a donor element.
  • glass refers to a substance that has no irregular crystal structure in its X-ray diffraction spectrum, has an irregular network structure, and exhibits a glass transition phenomenon.
  • out-diffusion the diffusion of the donor element to a region other than the region to which the impurity diffusion layer forming composition is applied
  • out-diffusion the diffusion of the donor element to a region other than the region to which the impurity diffusion layer forming composition is applied
  • out-diffusion the diffusion of the donor element to a region other than the region to which the impurity diffusion layer forming composition is applied
  • formation of the n-type diffusion layer can be suppressed. That is, when the impurity diffusion layer forming composition of the present invention contains glass particles containing a donor element, an n-type diffusion layer can be formed in a more selective region.
  • the glass particles containing the donor element will be described in detail.
  • the glass particles contained in the impurity diffusion layer forming composition are melted at a heat treatment (firing) temperature (about 800 ° C. to 2000 ° C.) during thermal diffusion to form a glass layer on the n-type diffusion layer. . Therefore, out diffusion can be further suppressed.
  • the glass layer formed on the n-type diffusion layer can be removed by etching (for example, a hydrofluoric acid aqueous solution).
  • the glass particles containing a donor element can be formed including, for example, a donor element-containing material and a glass component material.
  • the donor element-containing material used for introducing the donor element into the glass particles is preferably a compound containing at least one of P (phosphorus) and Sb (antimony), and is a compound containing P (phosphorus). It is more preferable that it is at least one selected from the group consisting of P 2 O 3 and P 2 O 5, and particularly preferable is P 2 O 5 .
  • the content of the donor element-containing substance in the glass particles containing the donor element is not particularly limited.
  • the content is preferably 0.5% by mass or more and 100% by mass or less, and more preferably 2% by mass or more and 80% by mass or less.
  • the glass particle containing the donor element contains 0.5% by mass or more of at least one selected from the group consisting of P 2 O 3 and P 2 O 5 as a donor element-containing substance from the viewpoint of diffusibility of the donor element.
  • the content is preferably 100% by mass or less, more preferably 5% by mass or more and 99% by mass or less, and particularly preferably 15% by mass or more and 80% by mass or less.
  • the glass particles containing a donor element can control the melting temperature, the softening temperature, the glass transition temperature, the chemical durability, etc. by adjusting the component ratio as necessary. It is preferable that the glass particle containing a donor element contains 1 or more types of the glass component substance described below.
  • 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 ,
  • glass component materials include 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 .
  • PbO, CdO, V 2 O 5 , SnO, ZrO 2 and MoO 3 It is more preferable to use one or more selected from the group consisting of PbO, CdO, V 2 O 5 , SnO, ZrO 2 and MoO 3 .
  • the glass particles containing a donor element include a system containing both the donor element-containing substance and the glass component substance.
  • P 2 O 5 —SiO 2 system in the order of donor element-containing material—glass component material, the same applies hereinafter
  • P 2 O 5 —K 2 O system P 2 O 5 —Na 2 O system , P 2 O 5 —Li 2 O system, P 2 O 5 —BaO system, P 2 O 5 —SrO system, P 2 O 5 —CaO system, P 2 O 5 —MgO system, P 2 O 5 —BeO system , P 2 O 5 —ZnO, P 2 O 5 —CdO, P 2 O 5 —PbO, P 2 O 5 —V 2 O 5 , P 2 O 5 —SnO, P 2 O 5 —GeO 2 system, the glass particles of the system containing P 2 O 5 as a donor element-containing substance such as P 2 O 5 -TeO 2 system
  • 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 the group consisting of 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 , CsO 2 and TiO 2.
  • P 2 O 3 , P 2 O 5 and Sb 2 O 3 SiO 2 , K 2 O, Na 2 O, Li 2 O.
  • the content ratio of the specific glass component material in the glass particles is the melting temperature, It is desirable to set appropriately considering the softening temperature, glass transition temperature, and chemical durability.
  • the specific glass component substance is preferably 0.01% by mass or more and 80% by mass or less, more preferably 0.1% by mass or more and 50% by mass or less in 100% by mass of the glass particles. .
  • An n-type diffused layer can be efficiently formed as it is 0.01 mass% or more. Moreover, formation of the n-type diffusion layer in the part which has not provided the impurity diffusion layer forming composition as it is 80 mass% or less can be suppressed more effectively.
  • the glass particles may contain at least one of a network modification oxide (for example, an alkali oxide or an alkaline earth oxide) and an intermediate oxide that does not vitrify alone.
  • a network modification oxide for example, an alkali oxide or an alkaline earth oxide
  • an intermediate oxide that does not vitrify alone.
  • the content ratio of CaO that is a network modification oxide is preferably 1% by mass or more and 30% by mass or less. % Or more and 20% by mass or less is more preferable.
  • the softening point of the glass particles is preferably 200 ° C. to 1000 ° C., and more preferably 300 ° C. to 900 ° C., from the viewpoints of diffusibility during the diffusion treatment and dripping.
  • the softening point of the glass particles can be obtained from a differential heat (DTA) curve using a differential heat / thermogravimetric simultaneous measurement apparatus. Specifically, the value of the third peak from the low temperature of the DTA curve can be set as the softening point.
  • Glass particles containing a donor element are produced by the following procedure.
  • 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, which are appropriately selected in consideration of the melting temperature, atmosphere, reactivity with the molten material, and the like.
  • it heats with the temperature according to a glass composition with an electric furnace, and is set as a melt. At this time, it is desirable to stir the melt uniformly.
  • the obtained melt is poured onto a zirconia substrate, a carbon substrate, or the like to vitrify the melt.
  • the glass is crushed into powder.
  • a known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
  • the compound containing a donor element may be a phosphorus-containing silicon oxide compound.
  • the phosphorus-containing silicon oxide compound will be described in detail.
  • Phosphorus-containing silicon oxide compound means a compound synthesized based on a sol-gel reaction using a phosphorus compound and a silicon oxide precursor as starting materials, and contains phosphorus so that it can be distinguished from the above glass particles in the synthesis method. It will be described as a silicon oxide compound.
  • the sol-gel reaction here refers to the hydrolysis of silicate, a silicon oxide precursor, and the condensation reaction of silanol groups, resulting in the formation of a three-dimensionally crosslinked silica gel matrix with silicon-oxygen bonds as structural units. It is.
  • the phosphorus-containing silicon oxide compound obtained by reacting the silicon oxide precursor with the phosphorus compound has a structure in which the phosphorus compound is dispersed in the network of silicon oxide (siloxane), so that the properties of the phosphorus compound alone are greatly different. For example, since the volatility of the phosphorus compound is suppressed, out diffusion is suppressed at a high temperature at which an n-type diffusion layer is formed on a semiconductor substrate such as a silicon substrate.
  • the phosphorus compound not included in the silicon oxide (siloxane) network may be removed by washing with water before the phosphorus-containing silicon oxide compound is added to the n-type diffusion layer forming composition. By doing in this way, out diffusion can further be suppressed.
  • a silicon alkoxide as a silicon oxide precursor, a phosphorus compound, a solvent used in a sol-gel reaction, water, and an acid or alkali catalyst are mixed, and a predetermined temperature is set.
  • a silicon oxide compound containing a phosphorus compound in a siloxane network can be synthesized.
  • hygroscopicity can also be suppressed, reaction with a dispersion medium and reaction with moisture are suppressed, and chemical stability in the impurity diffusion layer forming composition can be improved.
  • silicon alkoxide examples include silicon methoxide, silicon ethoxide, silicon propoxide, silicon butoxide and the like, and at least one selected from the group consisting of silicon methoxide and silicon ethoxide is available because of availability. It is preferable to use it.
  • the solvent used in the sol-gel reaction is not particularly limited as long as it dissolves the silicon oxide precursor polymer; alcohols such as ethanol and isopropanol; acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzo Nitrile compounds such as nitriles; cyclic ethers such as dioxane and tetrahydrofuran; and the like are preferably used. These solvents may be used alone or in combination of two or more.
  • the amount of the solvent is preferably 100 equivalents or less with respect to the silicon oxide precursor, more preferably 1 equivalent to 10 equivalents. When the amount of the solvent is too large, the sol-gel reaction of the silicon oxide precursor tends to be slow.
  • an acid or an alkali as a catalyst for controlling hydrolysis and dehydration condensation polymerization.
  • alkali catalyst alkali metal hydroxide such as sodium hydroxide, ammonia, tetramethylammonium hydroxide and the like are generally used.
  • An inorganic protonic acid or an organic protonic acid can be used as the acid catalyst. Examples of the inorganic protonic acid include hydrochloric acid, sulfuric acid, boric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid and the like.
  • the organic protonic acid examples include acetic acid, oxalic acid, methanesulfonic acid and the like. Since the solubility of the sol in the solvent varies depending on the amount of the catalyst, the amount of the catalyst used may be adjusted so that the solubility of the sol is soluble. Specifically, the catalyst is 0 with respect to the silicon oxide precursor. It is preferably used in an amount of 0.0001 equivalent to 1 equivalent.
  • a solution containing a metal nitrate, ammonium salt, chloride salt, sulfate or the like is added to the sol solution of the silicon oxide precursor, and then the sol-gel reaction is allowed to proceed to thereby convert the phosphorus-containing silicon oxide compound.
  • the salt is not particularly limited, and examples thereof include aluminum nitrate, iron nitrate, zirconium oxynitrate, titanium chloride, aluminum chloride, zirconium oxychloride, zirconium oxynitrate, titanium sulfate, and aluminum sulfate.
  • the solvent is not particularly limited as long as it dissolves a salt.
  • Carbonate compounds such as ethylene carbonate and propylene carbonate; heterocyclic compounds such as 3-methyl-2-oxazolidinone and N-methylpyrrolidone; dioxane, tetrahydrofuran and the like Cyclic ether compounds; chain ether compounds such as diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether; methanol, ethanol, isopropanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether , Polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.
  • Alcohol compounds such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; Nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile; Carboxylic acid esters and phosphoric acid esters Ester compounds such as phosphonic acid esters; aprotic polar substances such as dimethyl sulfoxide, sulfolane, dimethylformamide and dimethylacetamide; low polar solvents such as toluene and xylene; chlorinated solvents such as methylene chloride and ethylene chloride; be able to
  • Phosphorus compounds used in the sol-gel reaction include phosphoric acid, ammonium hydrogen phosphate, diphosphorus pentoxide, diphosphorus trioxide, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, phosphine, phosphate ester and It is preferable to use at least one selected from phosphites. Among these, it is preferable to use phosphate ester or phosphite ester. By using an ester compound, when the sol-gel reaction proceeds in a state of being mixed with silicon alkoxide, P—O—Si bonds are likely to be formed, and outdiffusion tends to be suppressed.
  • Examples of the phosphate ester include compounds represented by general formula (I), and examples of the phosphite ester include compounds represented by general formula (II).
  • R 1 to R 6 are each independently a monovalent organic group having 1 to 12 carbon atoms.
  • the monovalent organic group represented by R 1 to R 6 in general formula (I) and general formula (II) is not particularly limited, and each independently represents an alkyl group, an organic group having a functional group, or a hetero atom. And an organic group having an unsaturated bond.
  • the alkyl group represented by R 1 to R 6 may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkyl group represented by R 1 to R 6 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. Further preferred.
  • Specific examples of the alkyl group represented by R 1 to R 6 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Can be mentioned.
  • examples of the functional group include a chloro group, a bromo group, and a fluoro group.
  • the organic group having a functional group represented by R 1 to R 6 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. More preferably.
  • Specific examples of the organic group having the functional group represented by R 1 to R 6 include chloroethyl group, fluoroethyl group, chloropropyl group, dichloropropyl group, fluoropropyl group, difluoropropyl group, chlorophenyl group, fluoro A phenyl group etc. are mentioned.
  • examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the organic group having a hetero atom represented by R 1 to R 6 preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. More preferably.
  • Specific examples of the organic group having a hetero atom represented by R 1 to R 6 include a dimethylamino group, a diethylamino group, a diphenylamino group, a methyl sulfoxide group, an ethyl sulfoxide group, and a phenyl sulfoxide group.
  • the organic group having an unsaturated bond represented by R 1 to R 6 preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and 2 to 4 carbon atoms. More preferably it is.
  • Specific examples of the organic group having an unsaturated bond represented by R 1 to R 6 include an ethylenyl group, an ethynyl group, a propenyl group, a propynyl group, a butenyl group, a butynyl group, and a phenyl group.
  • the monovalent organic group of R 1 to R 6 is preferably an alkyl group, and more preferably an alkyl group having 1 to 10 carbon atoms.
  • the phosphorus compound used in the sol-gel reaction it is preferable to use at least one selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate, and tributyl phosphate.
  • the content of the phosphorus compound in the phosphorus-containing silicon oxide compound is not particularly limited.
  • it is preferably 0.5% by mass or more and 99% by mass or less, and more preferably 5% by mass or more and 95% by mass or less.
  • An acceptor element is an element that can form a p-type diffusion layer by diffusing into a semiconductor substrate.
  • a Group 13 element can be used, and from the viewpoint of safety and the like, it is preferable to contain at least one of B (boron) and Al (aluminum).
  • B boron
  • Al aluminum
  • an oxide of a single acceptor element such as B 2 O 3 or Al 2 O 3 ; a glass component substance is formed in addition to an acceptor element-containing substance such as B 2 O 3 or Al 2 O 3
  • Glass particles as components glass particles containing an acceptor element
  • the compound containing an acceptor element is preferably BN particles, glass particles containing an acceptor element or boron-containing silicon oxide compound particles, and more preferably glass particles containing a BN particle or an acceptor element.
  • glass particles or BN particles containing an acceptor element the out-diffusion tends to be more effectively suppressed, and an unnecessary p-type diffusion layer is formed in addition to the region to which the p-type diffusion layer forming composition is applied. Can be suppressed. That is, a p-type diffusion layer can be formed in a more selective region by including glass particles or BN particles containing an acceptor element.
  • the glass particles containing an acceptor element can be formed including, for example, an acceptor element-containing substance and a glass component substance.
  • the acceptor element-containing material used for introducing the acceptor element into the glass particles is preferably a compound containing at least one selected from the group consisting of B 2 O 3 and Al 2 O 3 .
  • the content of the acceptor element-containing substance in the glass particles containing the acceptor element is not particularly limited.
  • it is preferably 0.5% by mass or more and 100% by mass or less, and more preferably 2% by mass or more and 80% by mass or less.
  • 0.5% by mass or more of at least one selected from the group consisting of B 2 O 3 and Al 2 O 3 as the acceptor element-containing substance is contained in the impurity diffusion layer forming composition. It is preferably contained at 100% by mass or less, more preferably 5% by mass or more and 99% by mass or less, further preferably 15% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 80% by mass or less. It is particularly preferable to include it.
  • the 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 , Y 2 O 3 , CsO 2 , TiO 2 , TeO 2 , La 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , GeO 2 , Lu 2 O 3 and it is preferable to use at least one selected from the group consisting of MnO, SiO 2, K 2 O , Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5, SnO, the use of the ZrO 2, MoO 3, GeO 2 , Y 2 O 3, CsO 2 and at least one selected from the group consisting of TiO 2 , K 2 O, Na 2 O, Li 2 O
  • the glass particles include glass particles containing both the acceptor element-containing substance and the glass component substance, and are described in the order of B 2 O 3 —SiO 2 (acceptor element-containing substance-glass component substance, hereinafter The same), B 2 O 3 —ZnO system, B 2 O 3 —PbO system, B 2 O 3 single system and the like containing B 2 O 3 as the acceptor element-containing substance, Al 2 O 3 —SiO 2 system, etc.
  • the acceptor element-containing substance include glass particles such as a system containing Al 2 O 3 .
  • glass particles containing one component or two components are exemplified, but glass particles containing three or more components such as B 2 O 3 —SiO 2 —CaO may be used. Further, glass particles containing two or more kinds of acceptor element-containing substances such as Al 2 O 3 —B 2 O 3 system may be used.
  • the acceptor element-containing glass particles include at least one acceptor element-containing substance selected from the group consisting of B 2 O 3 and Al 2 O 3 , and 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 , Y 2 O 3 , At least one glass component material selected from the group consisting of CsO 2 , TiO 2 , TeO 2 , La 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , GeO 2 , Lu 2 O 3 and MnO.
  • At least one acceptor element-containing material selected from the group consisting of B 2 O 3 and Al 2 O 3 , SiO 2 , K 2 O, Na From 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 TiO 2
  • It is more preferable to contain at least one glass component material selected from the group consisting of: at least one acceptor element-containing material selected from the group consisting of B 2 O 3 and Al 2 O 3 ; and SiO 2 2 at least selected from the group consisting of K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, V 2 O 5 , SnO, ZrO 2 and MoO 3.
  • the glass particles include Al 2 O 3 as the acceptor element-containing material, and at least one selected from the group consisting of SiO 2 , ZnO, CaO, Na 2 O, Li 2 O, and BaO as the glass component material. It is preferable to include.
  • B 2 O 3 which is an acceptor element-containing substance is used alone, the sheet resistance of the formed impurity diffusion layer is lower, and the out diffusion is further suppressed. It becomes possible.
  • the form and volume average particle diameter of the particle may be the same as the glass particle containing the donor element.
  • the compound containing an acceptor element may be in a state dissolved in a dispersion medium.
  • the shape of the glass particles is not particularly limited.
  • the glass particles containing the acceptor element are produced in the same procedure as the glass particles containing the donor element, except that the donor element-containing substance is replaced with the acceptor element-containing substance.
  • the crystal form of BN may be any of hexagonal, cubic, rhombohedral, Hexagonal crystals are preferred because they can be easily controlled.
  • the method for preparing BN is not particularly limited, and can be prepared by a usual method. Specifically, a method in which boron powder is heated to 1500 ° C.
  • a method in which molten boric acid and nitrogen or ammonia are reacted in the presence of calcium phosphate, boric acid or an alkali boride, urea, guanidine Illustrates a method of reacting an organic nitrogen compound such as melamine in a high temperature nitrogen-ammonia atmosphere, a method of reacting molten sodium borate and ammonium chloride in an ammonia atmosphere, a method of reacting boron trichloride and ammonia at a high temperature, etc. be able to. There is no problem even in manufacturing methods other than the above. Among the above production methods, it is preferable to use a method in which boron trichloride and ammonia are reacted at a high temperature because high-purity BN can be obtained.
  • the compound containing an acceptor element may be a boron-containing silicon oxide compound.
  • the boron-containing silicon oxide compound will be described in detail.
  • the boron-containing silicon oxide compound means a compound synthesized by reacting a boron compound and a silicon oxide precursor based on a sol-gel reaction, and the boron particles can be distinguished from the glass particles so that the synthesis method is different. It will be described as a contained silicon oxide compound.
  • the boron-containing silicon oxide compound obtained by reacting a silicon oxide precursor with a boron compound has a structure in which the boron compound is dispersed in a silicon oxide (siloxane) network, so that the volatility of the boron compound is suppressed, and silicon Outdiffusion is suppressed at a high temperature at which a p-type diffusion layer is formed on a semiconductor substrate such as a substrate.
  • the boron-containing silicon oxide compound may be washed with water before being added to the p-type diffusion layer forming composition to remove boron compounds not included in the silicon oxide (siloxane) network. By doing in this way, out diffusion can be controlled more effectively.
  • Examples of the method for synthesizing the boron-containing silicon oxide compound include the same method as the method for synthesizing the phosphorus-containing silicon oxide compound described above except that the phosphorus compound is replaced with a boron compound.
  • Examples of the silicon alkoxide, the solvent used for the sol-gel reaction, and the acid and alkali used as a catalyst for controlling hydrolysis and dehydration condensation polymerization are the same as those mentioned in the method for synthesizing the phosphorus-containing silicon oxide compound. It is done.
  • a solution containing a metal nitrate, ammonium salt, chloride salt, sulfate salt or the like is added to the silicon oxide precursor sol solution, and then the sol-gel reaction is allowed to proceed to thereby form a boron-containing silicon oxide compound. It may be prepared.
  • the metal nitrate, ammonium salt, chloride salt, sulfate, and salt solvent that can be used here are the same as those mentioned in the method for synthesizing the phosphorus-containing silicon oxide compound.
  • boron compound used for the sol-gel reaction examples include boron oxide and boric acid.
  • Boron oxide is a compound represented by B2O3, which may be a crystallized product or a glassy material.
  • Boric acid is a compound represented by H 3 BO 3 or B (OH) 3 . These compounds are dissolved in water and exist in the state of H 3 BO 3 .
  • any compound that can be dissolved in water to form H 3 BO 3 is not limited to the type of boron compound used as an auxiliary material.
  • Examples of the compound that dissolves in water to become H 3 BO 3 include boric acid esters.
  • Examples of the boric acid ester include compounds represented by the following general formula (III).
  • R 7 to R 9 in the general formula (III) are each independently an organic group having 1 to 12 carbon atoms or a hydrogen atom, and at least one of R 7 to R 9 is an organic group.
  • the organic group represented by R 7 to R 9 in the general formula (III) is not particularly limited, and each independently represents an alkyl group, an organic group having a functional group, an organic group having a hetero atom, and an unsaturated bond.
  • the alkyl group represented by R 7 to R 9 may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkyl group represented by R 7 to R 9 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. Further preferred.
  • Specific examples of the alkyl group represented by R 7 to R 9 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. It is done.
  • examples of the functional group include a chloro group, a bromo group, and a fluoro group.
  • the organic group having a functional group represented by R 7 to R 9 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 10 carbon atoms. More preferably, it is 3.
  • Specific examples of the organic group having a functional group represented by R 7 to R 9 include chloroethyl group, fluoroethyl group, chloropropyl group, dichloropropyl group, fluoropropyl group, difluoropropyl group, chlorophenyl group, fluoro A phenyl group etc. are mentioned.
  • examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the organic group having a hetero atom represented by R 7 to R 9 preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. More preferably.
  • Specific examples of the organic group having a hetero atom represented by R 7 to R 9 include a dimethylamino group, a diethylamino group, a diphenylamino group, a methyl sulfoxide group, an ethyl sulfoxide group, and a phenyl sulfoxide group.
  • the organic group having an unsaturated bond represented by R 7 to R 9 preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and 2 to 4 carbon atoms. More preferably it is.
  • Specific examples of the organic group having an unsaturated bond represented by R 7 to R 9 include an ethylenyl group, an ethynyl group, a propenyl group, a propynyl group, a butenyl group, a butynyl group, and a phenyl group.
  • the monovalent organic group of R 7 to R 9 is preferably an alkyl group, and more preferably an alkyl group having 1 to 10 carbon atoms.
  • the borate ester used in the sol-gel reaction it is preferable to use at least one selected from the group consisting of trimethyl borate, triethyl borate, tripropyl borate, and tributyl borate.
  • the content of the compound containing the donor element or the compound containing the acceptor element in the impurity diffusion layer forming composition is determined in consideration of the coating property, the diffusibility of the compound containing the donor element or the compound containing the acceptor element, and the like.
  • the content of the compound containing a donor element or the compound containing an acceptor element in the impurity diffusion layer forming composition is 0.1% by mass or more and 95% by mass or less in the impurity diffusion layer forming composition. It is preferably 1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 80% by mass or less, particularly preferably 2% by mass or more and 50% by mass or less, and 5% by mass. It is very preferable that it is 20% by mass or less.
  • the impurity diffusion layer can be sufficiently formed, and is 95% by mass or less.
  • the dispersibility of the compound containing the donor element or the compound containing the acceptor element in the impurity diffusion layer forming composition is improved, and the coating property to the semiconductor substrate is improved.
  • the impurity diffusion layer forming composition of the present invention contains a dispersion medium.
  • the dispersion medium is a medium in which the compound containing the donor element or the compound containing the acceptor element and the fatty acid amide are dispersed or dissolved in the composition.
  • the dispersion medium preferably contains at least a solvent or water.
  • a dispersion medium in addition to a solvent or water, you may contain the organic binder mentioned later.
  • 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 diisobutylketone, 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
  • acetone is the ketone solvent
  • diethylene glycol di-n-butyl ether is the ether solvent
  • 2- (2-butoxyethoxy) ethyl acetate is the ester solvent
  • N- is the aprotic polar solvent.
  • terpineol (terpineol) is preferably ⁇ -terpineol ( ⁇ -terpineol) or dihydroterpineol (dihydroterpineol)
  • terpene solvent is preferably ⁇ -terpinene or ⁇ -pinene.
  • the content of the dispersion medium in the impurity diffusion layer forming composition is determined in consideration of the coating property and the concentration of the donor element or the acceptor element.
  • the content of the dispersion medium is preferably 5% by mass to 99% by mass, more preferably 20% by mass to 95% by mass, and 40% by mass to 90% by mass. More preferably, it is at most mass%.
  • the impurity diffusion layer forming composition of the present invention contains a fatty acid amide.
  • Fatty acid amide imparts thixotropic properties to the impurity diffusion layer forming composition, and becomes a sol form when stress is applied at a constant temperature, and gives a property of returning to a gel form when left standing.
  • the impurity diffusion layer formation is performed.
  • the composition is reduced in viscosity and exhibits fluidity, and passes through the screen plate mesh to form a printed material on the object.
  • the impurity diffusion layer forming composition once formed as a printed matter on the object maintains its shape without decreasing the viscosity unless stress is applied.
  • a fatty acid amide By using a fatty acid amide, an appropriate diffusion viscosity can be imparted to the impurity diffusion layer forming composition, and good impartability can be imparted. Specifically, the value of thixotropic characteristics (thixotropic properties) described later can be adjusted appropriately.
  • the impurity diffusion layer forming composition when the impurity diffusion layer forming composition layer is formed by being applied to a partial region on the semiconductor substrate, the impurity diffusion layer is formed in the surface direction on the semiconductor substrate. Expansion of the contact area of the forming composition layer is suppressed. In addition, an impurity diffusion layer having an impurity concentration higher than that of other regions can be formed at a specific portion of the semiconductor substrate.
  • fatty acid amide can suppress the generation of residues during heat treatment. This is presumably because the fatty acid amide has good thermal decomposability (decomposes at about 400 ° C. or lower) and hardly generates fatty acid amide-derived residues.
  • an inorganic material when used to suppress the spread of the contact area of the impurity diffusion layer forming composition layer in the surface direction on the semiconductor substrate, it remains after removing organic components through drying and degreasing, The composition of the compound containing the donor element or the acceptor element may be changed during the diffusion treatment, and as a result, the doping of the donor element or the acceptor element may be affected.
  • fatty acid amides include fatty acid monoamides represented by general formula (1), N-substituted fatty acid amides represented by general formula (2) or (3), and N-substituted fatty acid amide amines represented by general formula (4). It is done.
  • R 1 CONH 2 (1) R 1 CONH—R 2 —NHCOR 1 (2) R 1 NHCO—R 2 —CONHR 1 (3) R 1 CONH—R 2 —N (R 3 ) 2 ... (4)
  • R 1 and R 3 each independently represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and R 2 represents 1 to 10 carbon atoms.
  • the alkylene group is shown.
  • R 1 and R 3 may be the same or different.
  • the alkyl group and alkenyl group represented by R 1 and R 3 each independently have 1 to 30 carbon atoms.
  • the alkyl group and alkenyl group represented by R 1 each independently preferably has 5 to 25 carbon atoms, more preferably 10 to 20 carbon atoms, and further preferably 15 to 18 carbon atoms. preferable.
  • the alkyl group and alkenyl group represented by R 3 each independently preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms. preferable.
  • R 3 is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1 Particularly preferred are ⁇ 3 alkyl groups.
  • the alkyl group and alkenyl group having 1 to 30 carbon atoms represented by R 1 and R 3 may each independently be linear, branched or cyclic, and are linear or branched. It is preferable.
  • Examples of the alkyl group and alkenyl group having 1 to 30 carbon atoms represented by R 1 and R 3 include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, decyl group, dodecyl group, octadecyl group, Examples include a hexadecenyl group and a hencicosenyl group.
  • the alkyl group and alkenyl group having 1 to 30 carbon atoms represented by R 1 and R 3 may be unsubstituted or may have a substituent.
  • Examples of such a substituent include a hydroxyl group, a chloro group, a bromo group, a fluoro group, an aldehyde group, an acyl group, an nitro group, an amino group, a sulfonic acid group, an alkoxy group, and an acyloxy group.
  • each alkylene group represented by R 2 independently has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, It is more preferably 1 to 6 and still more preferably 1 to 4 carbon atoms.
  • Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R 2 include an ethylene group, a propylene group, a butylene group, and an octylene group.
  • fatty acid monoamide represented by the general formula (1) examples include lauric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide and the like.
  • N-substituted fatty acid amide represented by the general formula (2) examples include N, N′-ethylenebislauric acid amide, N, N′-methylenebisstearic acid amide, N, N′-ethylenebisamide.
  • Examples thereof include amide, N, N′-hexamethylenebisstearic acid amide, N, N′-hexamethylenebisoleic acid amide, N, N′-xylylene bisstearic acid amide, and the like.
  • N-substituted fatty acid amide represented by the general formula (3) examples include N, N′-dioleyl adipate amide, N, N′-distearyl adipate amide, N, N′-dioleyl.
  • Examples include sebacic acid amide, N, N′-distearyl sebacic acid amide, N, N′-distearyl terephthalic acid amide, N, N′-distearyl isophthalic acid amide, and the like.
  • N-substituted fatty acid amidoamine represented by the general formula (4) include stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid.
  • fatty acid amides at least one selected from the group consisting of stearic acid amide, N, N′-methylenebisstearic acid amide, and stearic acid dimethylaminopropylamide from the viewpoint of solubility in a dispersion medium. It is preferable to use at least one selected from stearamide and N, N′-methylenebisstearic acid amide.
  • the fatty acid amide is preferably evaporated or decomposed at 400 ° C. or lower, more preferably evaporated or decomposed at 300 ° C. or lower, and further preferably evaporated or decomposed at 250 ° C. or lower.
  • the transpiration or decomposition of the fatty acid amide is preferably 80 ° C. or higher.
  • the temperature is more preferably 100 ° C. or higher, and further preferably 150 ° C. or higher.
  • the transpiration or decomposition temperature of the fatty acid amide is measured by examining the temperature at which the weight retention is 20% or less using a thermogravimetric analyzer.
  • Fatty acid amides may be used alone or in combination of two or more.
  • the content of the fatty acid amide is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, with respect to 100% by mass of the impurity diffusion layer forming composition. More preferably, it is at least 20% by mass.
  • the compound containing a donor element or the compound containing an acceptor element has a softening point of 450 ° C. to 900 ° C.
  • the fatty acid amide is 40 ° C.
  • the compound containing the donor element or the acceptor element has a softening point of 500 ° C. to 800 ° C.
  • the fatty acid amide is 150 ° C. to 350 ° C. It has a transpiration or decomposition temperature of 0C.
  • the impurity diffusion layer forming composition of the present invention includes an organic binder, a surfactant, an inorganic powder (inorganic filler) as necessary. ), An alkoxysilane, a silicone resin, a reducing compound, and the like.
  • the impurity diffusion layer forming composition of the present invention may further contain one or more organic binders.
  • the organic binder By including the organic binder, the viscosity as the impurity diffusion layer forming composition can be adjusted, or thixotropy can be imparted, and the impartability to the semiconductor substrate is further improved.
  • the organic binder examples include an alkyd resin; a polyvinyl butyral resin; a polyvinyl alcohol resin; a polyacrylamide resin; a polyvinyl amide resin; a polyvinyl pyrrolidone resin; a polyethylene oxide resin; a polysulfone resin; Cellulose derivatives such as ethyl cellulose; gelatin, gelatin derivatives; starch, starch derivatives; sodium alginate, sodium alginate derivatives; xanthan, xanthan derivatives; gua, gua derivatives; Dextrin derivative; (meth) acrylic resin; alkyl (meth) acrylate Resin, (meth) acrylic acid esters such as dimethyl aminoethyl (meth) acrylate resin resin; butadiene resin; a styrene resin; and may appropriately select these copolymers.
  • an organic binder it is preferable to use a cellulose derivative, a (meth) acrylic acid resin, a (meth) acrylic acid ester resin or a polyethylene oxide resin from the viewpoint of degradability and easy handling.
  • the molecular weight of the organic binder is not particularly limited, and is preferably adjusted appropriately in view of the desired viscosity as the composition.
  • content in the case of containing an organic binder is preferably 0.5% by mass or more and 30% by mass or less, and preferably 3% by mass or more and 25% by mass or less in the impurity diffusion layer forming composition. More preferably, it is 3 mass% or more and 20 mass% or less.
  • the impurity diffusion layer forming composition of the present invention may further contain one or more surfactants.
  • the surfactant include a nonionic surfactant, a cationic surfactant, and an anionic surfactant.
  • nonionic surfactants or cationic surfactants are preferable because impurities such as heavy metals are not brought into the semiconductor substrate.
  • nonionic surfactants include silicon surfactants, fluorine surfactants, hydrocarbon surfactants, and the like. Of these, hydrocarbon surfactants are preferred because they are quickly removed during heating such as diffusion.
  • hydrocarbon surfactants include ethylene oxide-propylene oxide block copolymers, acetylene glycol compounds, and the like. From the viewpoint of further reducing variation in the sheet resistance value of the semiconductor substrate, an acetylene glycol compound is preferred.
  • the impurity diffusion layer forming composition of the present invention may further contain one or more inorganic fillers.
  • the inorganic filler include silica (silicon oxide), clay, silicon carbide, silicon nitride and the like. 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.
  • an inorganic filler By adding an inorganic filler, it is more effective to expand the contact area of the pattern on the semiconductor substrate due to bleeding and dripping of the impurity diffusion layer forming composition layer in the process of applying and drying the impurity diffusion layer forming composition. Can be suppressed.
  • bleeding that occurs during coating it is considered that the dispersion medium and the inorganic filler interact to suppress the bleeding of the dispersion medium.
  • bleeding and heat dripping at the time of drying occur at a temperature of about 100 ° C. to 500 ° C. at which the dispersion medium is decomposed and volatilized, for example, because a reducing compound such as polyethylene glycol described later melts. It is considered that the bleeding and heat dripping are suppressed by the interaction between the melted polyethylene glycol and the inorganic filler.
  • the BET specific surface area of the inorganic filler is preferably 1 m 2 / g to 300 m 2 / g, and more preferably 10 m 2 / g to 200 m 2 / g.
  • fumed silica refers to anhydrous silica in the form of ultrafine particles (BET specific surface area of 30 m 2 / g to 500 m 2 / g), and hydrolyzes silanes such as silicon tetrachloride in a flame of oxygen and hydrogen. Manufactured. Since it is synthesized by the gas phase method, the primary particle size is small and the BET specific surface area is large.
  • the viscosity of the composition for forming an impurity diffusion layer is reduced by the interaction with the dispersion medium (solvent) whose viscosity has been lowered in the drying process due to physical and van der Waals forces. Tends to be suppressed.
  • the BET specific surface area can be calculated from an adsorption isotherm of nitrogen at ⁇ 196 ° C. For example, it can be measured using BELSORP (manufactured by Nippon Bell Co., Ltd.).
  • the fumed silica may be either hydrophilic or hydrophobic, but it is preferable to use fumed silica made hydrophobic by a hydrophobizing treatment.
  • Hydrophobic silica particles can be treated with a silane coupling agent having an organic functional group such as methyl, ethyl, propyl, butyl, or phenyl with a surface treatment by dipping or spraying. The method of doing can be mentioned.
  • the fumed silica is hydrophobic if the methanol concentration at which the floating amount becomes 0% is 30% in the degree of hydrophobicity determined by the method of measuring the floating ratio of particles with respect to the solution by changing the water-methanol ratio. This refers to the case where the volume is at least%.
  • the content of the inorganic filler in the impurity diffusion layer forming composition is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass. Preferably, it is 0.5 to 3% by mass.
  • the coating characteristics (fine wire formability) of the impurity diffusion layer forming composition it is possible to more effectively ensure suppression of bleeding during printing and suppression of dripping during heat drying.
  • the ratio (mass basis) between the fatty acid amide and the inorganic filler is preferably 10:90 to 99: 1, and more preferably 30:70 to 95: 5.
  • the inorganic filler is preferably dispersed in the impurity diffusion layer forming composition.
  • distribution method of an inorganic filler When an inorganic filler melt
  • the inorganic filler does not dissolve in the dispersion medium, it is preferable to disperse using an ultrasonic dispersion, a bead mill, a ball mill, a homogenizer, a sand mill, a roll, a kneader, a dissolver, and a stirring blade.
  • the impurity diffusion layer forming composition of the present invention may further contain one or more alkoxysilanes.
  • the alkoxy group constituting the alkoxysilane is preferably a linear or branched alkoxy group, more preferably a linear or branched alkoxy group having 1 to 24 carbon atoms, still more preferably Is a linear or branched alkoxy group having 1 to 10 carbon atoms, particularly preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • alkyl group in 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 content of alkoxysilane is not particularly limited and is preferably 0.1% by mass to 30% by mass, and preferably 1% by mass to 20% by mass. More preferably, it is more preferably 2% by mass to 10% by mass.
  • the impurity diffusion layer forming composition of the present invention may further contain one or more silicone resins.
  • silicone resin By including the silicone resin, the film thickness uniformity of the printed matter of the impurity diffusion layer forming composition tends to be improved.
  • silicone resin include organopolysiloxane and modified silicone resin.
  • the impurity diffusion layer forming composition may further contain one or more reducing compounds.
  • the reducing compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and terminal alkylated products of polyalkylene glycols; monosaccharides such as glucose, fructose and galactose, and derivatives of monosaccharides; disaccharides and disaccharides such as sucrose and maltose And polysaccharides and polysaccharide derivatives; and the like.
  • polyalkylene glycol is preferable, and polypropylene glycol is more preferable.
  • the impurity diffusion layer forming composition of the present invention is distinguished from the electrode forming composition, the metal as a conductive material is not a main component, and the metal content is less than 50% by mass and 30% by mass or less. Preferably, it is 10 mass% or less, more preferably 5 mass% or less. And it is preferable that the impurity diffusion layer forming composition of this invention does not contain a metal substantially (0.5 mass% or less) other than in a donor element containing compound and an acceptor element containing compound, and does not contain a metal. (0% by mass) is more preferable.
  • the method for producing the impurity diffusion layer forming composition of the present invention is not particularly limited. For example, it can be obtained by mixing a compound containing a donor element or a compound containing an acceptor element, a fatty acid amide, a dispersion medium and components added as necessary using a blender, a mixer, a mortar, a rotor or the like. Moreover, when mixing, you may add a heat
  • the components contained in the impurity 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. can do.
  • the viscoelasticity of the impurity diffusion layer forming composition of the present invention is not particularly limited, but considering the impartability, the shear viscosity (25 ° C.) at a shear rate of 0.01 s ⁇ 1 is 50 Pa ⁇ s or more and 10,000 Pa. It is preferably s or less, and more preferably 100 Pa ⁇ s or more and 6000 Pa ⁇ s or less.
  • the shear viscosity (25 ° C.) at a shear rate of 0.01 s ⁇ 1 is 50 Pa ⁇ s or more, the thickness of the coating film in screen printing tends to be uniform, and if it is 10000 Pa ⁇ s or less, a screen mask There is a tendency that clogging of the plate is less likely to occur.
  • Thixotropic properties of the impurity diffusion layer forming composition is not particularly limited, the logarithm of the shear viscosity eta x at a shear rate of at 25 ° C. is x [s -1] log 10 ( denoted as eta x), the TI value indicating the thixotropy when the [log 10 ( ⁇ 0.01) -log 10 ( ⁇ 10)], TI value of 0.5 or more, is 6.0 or less It is preferably 0.5 or more and 4.0 or less, more preferably 0.5 or more and 3.0 or less.
  • the TI value is 0.5 or more, dripping of the impurity diffusion layer forming composition layer after screen printing hardly occurs, and when it is 6.0 or less, the application amount during continuous printing tends to be stable. In addition, the same effect can be obtained in other application methods such as an ink jet method. Further, the shear viscosity can be measured using a viscoelasticity measuring apparatus (Rheometer MCR301 manufactured by Anton Paar).
  • the method for producing a semiconductor substrate with an impurity diffusion layer of the present invention includes a step of forming the impurity diffusion layer forming composition layer by applying the impurity diffusion layer forming composition of the present invention to all or part of the semiconductor substrate; Heat-treating the semiconductor substrate on which the impurity diffusion layer forming composition layer is formed.
  • the method for producing a solar cell element of the present invention includes a step of forming the impurity diffusion layer forming composition layer by applying the impurity diffusion layer forming composition of the present invention to all or part of the semiconductor substrate,
  • the semiconductor substrate on which the impurity diffusion layer forming composition layer is formed includes a step of performing a heat treatment to form an impurity diffusion layer, and a step of forming an electrode on the formed impurity diffusion layer.
  • the method for producing a semiconductor substrate with an impurity diffusion layer and the method for producing a solar cell element of the present invention may further include other steps as necessary.
  • FIG. 1 is a schematic cross-sectional view conceptually showing an example of a method for producing a solar cell element of the present invention.
  • common constituent elements are denoted by the same reference numerals.
  • size of each component is an example, and does not restrict
  • an alkaline solution is applied to a silicon substrate which is a p-type semiconductor substrate 10 to remove a damaged layer, and a texture structure is obtained 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 on the light receiving surface (surface) side (the description of the texture structure is omitted in the figure).
  • a texture structure on the light receiving surface (surface) side the description of the texture structure is omitted in the figure.
  • 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.
  • the application method is not limited, and examples thereof include a printing method such as screen printing, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
  • the coating amount of the n-type diffusion layer forming composition is not particularly limited.
  • the amount of the compound containing a donor element or the compound containing an acceptor element should be 0.01 g / m 2 to 100 g / m 2. Is preferable, and more preferably 0.1 g / m 2 to 10 g / m 2 .
  • the ratio of the line thickness to the design value of the line width is preferably within 200%, and within 180%. Is more preferably 150% or less, and particularly preferably 120% or less.
  • a drying step for decomposing or volatilizing the solvent contained in the impurity diffusion layer forming composition may be necessary after coating.
  • drying is performed at a temperature of about 80 ° C. to 300 ° C. for about 1 to 10 minutes when using a hot plate, and about 10 to 30 minutes when using a dryer or the like.
  • the drying conditions depend on the solvent composition of the impurity diffusion layer forming composition and are not particularly limited to the above conditions in the present invention.
  • the semiconductor substrate 10 coated with the n-type diffusion layer forming composition 11 is heat-treated (thermal diffusion treatment).
  • the temperature of the heat treatment is not particularly limited, but is preferably 600 ° C. to 1200 ° C., more preferably 750 ° C. to 1050 ° C.
  • the time for the heat treatment is not particularly limited, but it is preferably 1 to 30 minutes.
  • the donor element diffuses into the semiconductor substrate, and the n-type diffusion layer 12 is formed.
  • a known continuous furnace, batch furnace, or the like can be applied to the heat treatment.
  • the furnace atmosphere at the time of heat processing can also be suitably adjusted to air, oxygen, nitrogen, etc.
  • a glass layer such as phosphate glass is formed on the surface of the 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.
  • an n-type diffusion layer 12 is formed at the electrode position, and the other light-receiving surface regions are formed more than the n-type diffusion layer 12.
  • An n-type diffusion layer 13 having a low donor element diffusion concentration is formed.
  • the method for forming the n-type diffusion layer 13 is not particularly limited, and examples thereof include a method using an impurity diffusion layer forming composition having a low donor element content and a gas phase reaction method using phosphorus oxychloride.
  • the semiconductor with an impurity diffusion layer (n-type diffusion layer) of the present invention which is shown in FIGS. 1 (2) and (3) and forms the n-type diffusion layer 12 using the n-type diffusion layer forming composition layer 11 of the present invention.
  • the n-type diffusion layer 12 is formed only in a desired portion, and unnecessary n-type diffusion layers are formed in the region other than the region where the n-type diffusion layer forming composition layer is formed, the back surface, and the side surface.
  • a side etch 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 etch process is not required, and the process is simplified.
  • a side etching process is required.
  • an antireflection film 14 is formed on the n-type diffusion layer 12.
  • the antireflection film 14 is formed by applying a known technique.
  • the antireflection film 14 is a silicon nitride film, it is formed by a plasma CVD method using a mixed gas of SiH4 and NH3 as a raw material. At this time, hydrogen diffuses into the crystal, and orbits that do not contribute to the bonding of silicon atoms, that is, dangling bonds and hydrogen are combined to inactivate defects (hydrogen passivation).
  • the mixed gas flow ratio NH 3 / SiH 4 is 0.05 to 1.0
  • the reaction chamber pressure is 13.3 Pa (0.1 Torr) to 266.6 Pa (2 Torr)
  • the thickness of the antireflection film is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm.
  • a surface electrode metal paste is printed on the antireflection film 14 on the surface (light receiving surface) by screen printing and dried to form a surface electrode metal paste layer 15 '.
  • 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 high-concentration electric field layer 16 and the back surface electrode 17 on the back surface are formed.
  • a back electrode metal paste layer containing aluminum is used to form a back electrode metal paste layer, which is fired to form the back electrode 17 and at the same time a p + -type diffusion layer (high concentration on the back surface).
  • Electric field layer) 16 is formed.
  • a silver paste for forming a silver electrode may be partially applied to the back surface for connection between solar cell elements in the module process.
  • the warp easily causes the cell to be damaged when the solar cell element is transported in the module process or when it is connected to a copper wire called a tab wire.
  • the thickness of the semiconductor substrate is being reduced due to the improvement of the slice processing technique, and the solar cell element tends to be easily broken.
  • the n-type diffusion layer forming composition of the present invention if used, an unnecessary n-type diffusion layer is not formed on the back surface. It is not necessary to convert the diffusion layer to the p-type diffusion layer, and the necessity of increasing the thickness of the aluminum layer is eliminated. As a result, generation of internal stress in the semiconductor substrate and warpage of the semiconductor substrate can be suppressed. As a result, an increase in power loss can be suppressed and damage to the solar cell element can be suppressed.
  • the manufacturing method of the p + type diffused layer (high concentration electric field layer) 16 of a back surface is not limited to the method by the metal paste for back surface electrodes containing aluminum. Any of the conventionally known methods can be adopted, and the options for the manufacturing method are expanded.
  • a p-type diffusion layer forming composition containing a Group 13 element such as B (boron) can be applied to form the p + -type diffusion layer (high concentration electric field layer) 16.
  • the p-type diffusion layer forming composition of the present invention can be used as this p-type diffusion layer forming composition.
  • the material used for the back electrode 17 is not limited to Group 13 aluminum, and Ag (silver), Cu (copper), or the like can be applied. In addition, it can be formed thinner than the conventional one.
  • the material and forming method of the back electrode 17 are not particularly limited.
  • the back electrode 17 may be formed by applying and drying a back electrode paste containing a metal such as aluminum, silver, or copper.
  • the electrode is fired to complete the solar cell element. Firing can be performed in the range of 600 ° C. to 900 ° C. for several seconds to several minutes.
  • the antireflection film 14 which is an insulating film is melted by the glass particles contained in the electrode metal paste, and the surface of the semiconductor substrate 10 is also partially melted, so that the metal particles in the electrode metal paste (for example, Silver particles) form contact portions with the semiconductor substrate 10 and solidify. Thereby, the formed surface electrode 15 and the semiconductor substrate 10 are electrically connected. This is called fire-through.
  • FIG. 2A is a plan view of a solar cell element in which the surface electrode 15 includes a bus bar electrode 30 and a finger electrode 32 intersecting with the bus bar electrode 30 as viewed from the surface.
  • FIG. 2B is an enlarged perspective view illustrating a part of FIG.
  • Such a surface electrode 15 can be formed, for example, by applying a metal paste by screen printing or the like as described above and baking the metal paste. Further, it can be formed by means such as plating of electrode material, vapor deposition of electrode material by electron beam heating in high vacuum.
  • the surface electrode 15 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 element 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 surface electrode and the back surface electrode are provided on the respective layers has been described. If the forming composition is used, a back contact type solar cell element can be produced.
  • the back contact type solar cell element has all electrodes provided on the back surface to increase the area of the light receiving surface. That is, in the back contact type solar cell element, 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 impurity diffusion layer forming composition of the present invention can form an impurity diffusion site only at a specific site, and therefore can be suitably applied to the production of a back contact type solar cell element.
  • a back contact type solar cell element there is no restriction
  • the solar cell element manufactured by the manufacturing method is used for manufacturing a solar cell.
  • the solar cell includes at least one type of solar cell element manufactured by the manufacturing method, and is configured by arranging a wiring material 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 particular limitation on the shape and size of the solar cell, but it is preferably 0.5 m 2 to 3 m 2 .
  • Examples of the present invention will be described more specifically below, but the present invention is not limited to these examples. Unless otherwise stated, all chemicals used reagents. “%” Means “% by mass” unless otherwise specified. Moreover, the component of the dopant source compound used by each Example and the comparative example is put together in Table 1, and is shown. In Examples, a compound containing a donor element or a compound containing an acceptor element is referred to as a dopant source compound.
  • the impurity diffusion layer forming composition 1 has a shear viscosity of room temperature (25) within a shear rate of 0.01 s ⁇ 1 to 10 s ⁇ 1 using a viscoelasticity measuring device (Rheometer MCR301 manufactured by Anton Paar). C.) was measured. The shear viscosity is measured at a temperature of 25 ° C. using a rotary shear viscometer equipped with a cone plate (diameter 50 mm, cone angle 1 °). The impurity diffusion layer forming composition 1 has a shear viscosity of 378 Pa.s at a shear rate of 0.01 s ⁇ 1 . On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 23 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.22.
  • TI value logarithmic value difference
  • the impurity diffusion layer forming composition 1 described above was applied to the surface of the p-type silicon wafer in a fine line shape by screen printing and dried on a hot plate at 150 ° C. for 1 minute.
  • the impurity diffusion layer forming composition 1 was applied in an amount of 3 mg / cm 2 after drying.
  • the screen printing plate used was designed to obtain a thin line with a width of 150 ⁇ m, and the squeegee speed and scraper speed were both 200 mm / sec. When the thickness of the thin line was measured with an optical microscope manufactured by Olympus Corporation, it was 180 ⁇ m, and the line thickness from the design value was within 35 ⁇ m.
  • the impurity diffusion layer forming composition 1 described above was applied to the surface of the p-type silicon wafer in a solid form, dried on a hot plate at 150 ° C. for 1 minute, and then air was supplied at 5 L / min. Heat treatment (thermal diffusion treatment) was performed for 10 minutes in a 900 ° C.
  • tunnel furnace horizontal tube diffusion furnace ACCURON CQ-1200, manufactured by Kokusai Electric Co., Ltd.
  • the substrate is immersed in a 2.5% by mass HF aqueous solution for 5 minutes, and then washed with running water, ultrasonically washed, and dried to obtain n-type.
  • a p-type silicon substrate on which a diffusion layer was formed was obtained.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 1 was applied in a solid form was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • the sheet resistance was measured by a four-probe method using a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation.
  • Example 2 1 g of ethyl cellulose and 10 g of stearamide were added to 55.7 g of terpineol and dissolved at 160 ° C. over 30 minutes. Next, after the temperature was lowered to 100 ° C., 33.3 g of the 30% glass particle-dispersed terpineol solution obtained in Synthesis Example 1 was added to this solution, stirred for 30 minutes, cooled to room temperature, and pasted to form an impurity diffusion layer. Composition 2 was prepared.
  • the shear viscosity (25 ° C.) of the impurity diffusion layer forming composition 2 was examined by the same method as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 50 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 1.36 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.57.
  • the impurity diffusion layer forming composition 2 described above was applied to the surface of the p-type silicon wafer by screen printing in a thin line shape and dried on a hot plate at 150 ° C. for 1 minute.
  • the screen printing plate used was designed to obtain a thin line with a width of 150 ⁇ m, and the squeegee speed and scraper speed were both 300 mm / sec.
  • the thickness of the thin line was measured with an optical microscope manufactured by Olympus Corporation, it was 185 ⁇ m, and the line thickness from the design value was within 35 ⁇ m.
  • the impurity diffusion layer forming composition 2 described above was applied to the surface of the p-type silicon wafer in a solid form, dried on a hot plate at 150 ° C. for 1 minute, and then air was supplied at 5 L / min.
  • Heat treatment was carried out for 10 minutes in a tunnel furnace (horizontal tube diffusion furnace ACCURON CQ-1200, manufactured by Kokusai Electric Co., Ltd.) at 900 ° C.
  • the substrate is immersed in an aqueous 2.5% by mass HF solution for 5 minutes, and then washed with running water, ultrasonically washed, and dried, thereby performing n-type diffusion.
  • a p-type silicon substrate having a layer formed thereon was obtained.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 2 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Example 3 An impurity diffusion layer forming composition 3 was obtained in the same manner as in Example 1 except that stearic acid amide in Example 1 was replaced with N, N′-methylenebisstearic acid amide.
  • the shear viscosity of the impurity diffusion layer forming composition 3 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 390 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 27 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.16.
  • the impurity diffusion layer forming composition 3 described above was applied to the surface of the p-type silicon wafer by screen printing in a thin line shape and dried on a hot plate at 150 ° C. for 1 minute.
  • the screen printing plate used was designed to obtain a thin line with a width of 150 ⁇ m, and the squeegee speed and scraper speed were both 300 mm / sec.
  • the thickness of the thin line was measured with an optical microscope manufactured by Olympus Corporation, it was 175 ⁇ m, and the line thickness from the design value was within 35 ⁇ m.
  • the impurity diffusion layer forming composition 3 described above was applied to the surface of the p-type silicon wafer in a solid form, dried on a hot plate at 150 ° C. for 1 minute, and then air was supplied at 5 L / min.
  • Heat treatment was carried out for 10 minutes in a tunnel furnace (horizontal tube diffusion furnace ACCURON CQ-1200, manufactured by Kokusai Electric Co., Ltd.) at 900 ° C.
  • the substrate is immersed in a 2.5% by mass HF aqueous solution for 5 minutes, and then washed with running water, ultrasonically washed, and dried to obtain n-type.
  • a p-type silicon substrate on which a diffusion layer was formed was obtained.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 3 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Example 4 An impurity diffusion layer forming composition 4 was obtained in the same manner as in Example 1 except that stearic acid amide in Example 1 was replaced with dimethylaminopropylamide stearate (Croda).
  • the shear viscosity of the impurity diffusion layer forming composition 4 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 280 Pa ⁇ s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 25 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.05.
  • Example 2 In the same manner as in Example 1, except that the thickness of the fine line was measured instead of the impurity diffusion layer forming composition 4, it was 170 ⁇ m, and the line thickness from the design value was within 35 ⁇ m. .
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 4.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 4 was applied was 40 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Example 5 In the same manner as in Example 1, except that terpineol was replaced with dihydroterpineol, a 30% glass particle-dispersed dihydroterpineol solution was prepared. 3.0 g of ethyl cellulose and 10 g of stearamide were added to 53.7 g of dihydrodoterpineol (manufactured by Nippon Terpene Chemical Co., Ltd.) and dissolved at 160 ° C. over 30 minutes.
  • the shear viscosity of the impurity diffusion layer forming composition 5 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 378 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 30 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.10.
  • Example 2 In the same manner as in Example 1, except that the thickness of the thin line was measured instead of the impurity diffusion layer forming composition 5, it was 170 ⁇ m, and the line thickness from the design value was within 35 ⁇ m. .
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, but in place of the impurity diffusion layer forming composition 5.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 5 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Example 6 3.0 g of ethyl cellulose, 10 g of stearamide, and 1 g of Aerosil 200 (fumed silica, manufactured by Nippon Aerosil Co., Ltd.) were added to 52.7 g of dihydroterpineol and stirred at 160 ° C. for 30 minutes. Next, after the temperature was lowered to 100 ° C., 33.3 g of the 30% glass particle-dispersed dihydroterpineol solution obtained in Synthesis Example 1 was added to this solution, stirred for 30 minutes, and then cooled to room temperature to form a paste. Forming composition 6 was prepared.
  • the shear viscosity of the impurity diffusion layer forming composition 6 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 380 Pa ⁇ s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 18 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.32.
  • the thickness of the thin wire was measured in the same manner as in Example 1 except that it was replaced with the impurity diffusion layer forming composition 6, it was 175 ⁇ m, and the thickness from the design value was within 35 ⁇ m. .
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 6.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 6 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Impurity diffusion layer forming composition 7 was prepared in the same manner as in Example 6 except that Aerosil 90G (fumed silica, manufactured by Nippon Aerosil Co., Ltd.) was used instead of Aerosil 200.
  • Aerosil 90G fumed silica, manufactured by Nippon Aerosil Co., Ltd.
  • the shear viscosity of the impurity 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 ⁇ 1 was 350 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 25 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.15.
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 7.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 7 was applied was 40 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Impurity diffusion layer forming composition 8 was prepared in the same manner as in Example 6 except that Aerosil RY200 (fumed silica, manufactured by Nippon Aerosil Co., Ltd.) was used instead of Aerosil 200.
  • Aerosil RY200 fumed silica, manufactured by Nippon Aerosil Co., Ltd.
  • the shear viscosity of the impurity 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 ⁇ 1 was 405 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 22 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.27.
  • the thickness of the fine line was measured instead of the impurity diffusion layer forming composition 8, it was 170 ⁇ m, and the line thickness from the design value was within 35 ⁇ m. .
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 8.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 8 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Example 9 A 40% glass particle-dispersed terpineol solution was prepared in the same manner as in Synthesis Example 1, except that the concentration of glass particles was 40%. Next, 3.0 g of ethyl cellulose and 10 g of stearamide were added to 37.0 g of terpineol and dissolved at 160 ° C. over 30 minutes. Next, after the temperature was lowered to 100 ° C., 50.0 g of 40% glass particle-dispersed terpineol solution was added to this solution, stirred for 30 minutes, and then cooled to room temperature to form a paste, thereby preparing an impurity diffusion layer forming composition 9.
  • the shear viscosity of the impurity diffusion layer forming composition 9 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 430 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 25 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.23.
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, but in place of the impurity diffusion layer forming composition 9.
  • the sheet resistance on the surface on which the impurity diffusion layer forming composition 9 was applied was 40 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 1000 ⁇ / ⁇ or more, which was not measurable, and the n-type diffusion layer was not formed.
  • Example 10 ⁇ Synthesis Example 2> (Synthesis of dopant source compound 2) 10 g of tetraethoxysilane (manufactured by Wako Pure Chemical Industries) was dissolved in 40 g of ethanol. To this, 10 g of a 10% nitric acid aqueous solution was added. Subsequently, 7.0 g of triethyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25 ° C. for 1 hour. Subsequently, it evaporated to dryness at 60 degreeC. Subsequently, it dried at 100 degreeC for 1 hour. The obtained powder was pulverized in an agate mortar to obtain a dopant source compound 2. The average secondary particle diameter measured by the laser diffraction method was 6 ⁇ m.
  • Impurity diffusion layer forming composition 10 was obtained in the same manner as in Example 1 except that dopant source compound 2 was used instead of dopant source compound 1.
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 10.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 10 was applied was 45 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 450 ⁇ / ⁇ .
  • Example 11 As the dopant source compound 3, ammonium dihydrogen phosphate (manufactured by Wako Pure Chemical Industries) was used as it was. Aerosil (RY200, manufactured by Nippon Aerosil) and terpineol were mixed to a concentration of 5% by mass, pulverized with 3 mm yttria-stabilized zirconia beads using a planetary ball mill, and a 5% aerosil / terpineol dispersion was obtained. Prepared. Impurity diffusion layer forming composition 11 was prepared in the same manner as in Example 1 except that dopant source compound 3 was used instead of dopant source compound 1.
  • the shear viscosity of the impurity diffusion layer forming composition 11 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 282 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 25 Pa ⁇ s, and the logarithmic value difference (TI value) of the shear viscosity was 1.05.
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that the impurity diffusion layer-forming composition 11 was used.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 11 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 300 ⁇ / ⁇ .
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 12.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 12 was applied was 40 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 800 ⁇ / ⁇ .
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 13.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 13 was applied was 40 ⁇ / ⁇ , and P (phosphorus) diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 200 ⁇ / ⁇ .
  • Example 14 Boron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the dopant source compound 6 as it was.
  • Impurity diffusion layer forming composition 14 was prepared in the same manner as in Example 1 except that dopant source compound 6 was used instead of dopant source compound 1.
  • Dopant source compound 6 / stearic acid amide / ethyl cellulose / terpineol / tetraethoxysilane / aerosil 200 15/6/2/74/2/1 (mass ratio) and mixed in a mortar to form an impurity diffusion layer forming composition Article 14 was prepared.
  • the shear viscosity of the impurity diffusion layer forming composition 14 was examined in the same manner as in Example 1, the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 385 Pa.s. On the other hand, the shear viscosity at a shear rate of 10 s ⁇ 1 was 18 Pa ⁇ s, the logarithmic value difference (TI value) of the shear viscosity was 1.33, and high thixotropy was obtained.
  • a p-type silicon substrate on which an n-type diffusion layer was formed was obtained in the same manner as in Example 1, except that instead of the impurity diffusion layer forming composition 14.
  • the sheet resistance of the surface on which the impurity diffusion layer forming composition 14 was applied was 45 ⁇ / ⁇ , and P (phosphorus) was diffused to form an n-type diffusion layer.
  • the sheet resistance on the back surface was 150 ⁇ / ⁇ .
  • composition 1 ′ containing no fatty acid amide was prepared.
  • the impurity diffusion layer forming composition 1 ′ was examined for shear viscosity in the same manner as in Example 1.
  • the shear viscosity at a shear rate of 0.01 s ⁇ 1 was 176 Pa.s.
  • the shear viscosity at a shear rate of 10 s ⁇ 1 was 68 Pa ⁇ s
  • the difference in logarithmic value (TI value) of the shear viscosity was 0.41, and sufficient thixotropy was not obtained.
  • the impurity diffusion layer has a thin line pattern.
  • the forming composition is applied onto a semiconductor substrate, it is possible to suppress line thickening, and it is possible to form an impurity diffusion layer with a specific size in a desired specific region.
  • the fatty acid amide an appropriate diffusion viscosity can be imparted to the impurity diffusion layer forming composition, good printability can be imparted, and the impurity diffusion layer is formed in a desired specific region. be able to.
  • Example 15 An n-type diffusion layer was formed in the same manner as in Example 1 except that the p-type silicon substrate (5 cm ⁇ 5 cm) was coated on the half surface instead of the entire surface.
  • the sheet resistance of the surface of the portion where the impurity diffusion layer forming composition 1 was applied was 38 ⁇ / ⁇ , and P was diffused to form an n-type diffusion layer.
  • the sheet resistance of the surface of the portion where the impurity diffusion layer forming composition 1 is not applied cannot be measured, the n-type diffusion layer is not formed, and is selected as the portion where the n-type diffusion layer forming composition is applied.
  • an n-type diffusion layer was formed. Further, the sheet resistance on the back surface was not measurable, and it was determined that the n-type diffusion layer was not substantially formed.
  • Example 16 In the same manner as in Example 15, except that the impurity diffusion layer forming composition 10 of Example 10 was used instead of the impurity diffusion layer forming composition 1, an n-type diffusion layer was formed.
  • the sheet resistance of the surface of the portion where the impurity diffusion layer forming composition 1 was applied was 45 ⁇ / ⁇ , and P was diffused to form an n-type diffusion layer.
  • the sheet resistance of the surface where the impurity diffusion layer forming composition 1 was not applied was 450 ⁇ / ⁇ .

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Abstract

La présente invention a trait à une composition de formation de couche de diffusion d'impureté qui contient un composé contenant un élément donneur ou un élément accepteur, un milieu de dispersion et un amide d'acide gras. La présente invention a également trait à un procédé permettant de fabriquer un substrat semi-conducteur doté d'une couche de diffusion d'impureté, lequel procédé comprend une étape consistant à appliquer la composition de formation de couche de diffusion d'impureté de manière à former une couche de composition de formation de couche de diffusion d'impureté sur l'ensemble ou une partie d'un substrat semi-conducteur, et une étape consistant à effectuer un traitement thermique sur le substrat semi-conducteur sur lequel la couche de composition de formation de couche de diffusion d'impureté a été formée.
PCT/JP2013/050307 2012-02-23 2013-01-10 Composition de formation de couche de diffusion d'impureté, procédé de fabrication d'un substrat semi-conducteur doté d'une couche de diffusion d'impureté et procédé de fabrication d'un élément de cellule solaire WO2013125254A1 (fr)

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JPWO2016121641A1 (ja) * 2015-01-30 2017-11-09 東レ株式会社 不純物拡散組成物、それを用いた半導体素子の製造方法および太陽電池
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WO2015088029A1 (fr) * 2013-12-12 2015-06-18 日立化成株式会社 Procédé de production de substrat semi-conducteur, substrat semi-conducteur, procédé de production d'élément de cellule solaire et élément de cellule solaire
JP2015115487A (ja) * 2013-12-12 2015-06-22 日立化成株式会社 半導体基板の製造方法、半導体基板、太陽電池素子の製造方法及び太陽電池素子
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TWI658500B (zh) * 2013-12-12 2019-05-01 日立化成股份有限公司 半導體基板的製造方法、半導體基板、太陽電池元件的製造方法及太陽電池元件
WO2015093608A1 (fr) * 2013-12-20 2015-06-25 日立化成株式会社 Procédé de fabrication d'un substrat semiconducteur, substrat semiconducteur, procédé de fabrication d'un élément de cellule solaire, et élément de cellule solaire
CN105830200A (zh) * 2013-12-20 2016-08-03 日立化成株式会社 半导体基板的制造方法、半导体基板、太阳能电池元件的制造方法及太阳能电池元件
JPWO2015093608A1 (ja) * 2013-12-20 2017-03-23 日立化成株式会社 半導体基板の製造方法、半導体基板、太陽電池素子の製造方法及び太陽電池素子
JPWO2016121641A1 (ja) * 2015-01-30 2017-11-09 東レ株式会社 不純物拡散組成物、それを用いた半導体素子の製造方法および太陽電池
EP3608368A4 (fr) * 2017-04-07 2020-09-23 Harima Chemicals, Inc. Dispersion de particules inorganiques
CN115559000A (zh) * 2022-09-27 2023-01-03 北京化学试剂研究所有限责任公司 一种硼扩散源组合物、硼扩散源及其制备方法和应用
CN115573038A (zh) * 2022-10-13 2023-01-06 北京化学试剂研究所有限责任公司 一种磷扩散源及其制备方法
CN115573038B (zh) * 2022-10-13 2024-10-15 北京化学试剂研究所有限责任公司 一种磷扩散源及其制备方法

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