WO2013105602A1 - COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, ENSEMBLE DE COMPOSITIONS DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION DESTINÉ À UN SUBSTRAT SEMI-CONDUCTEUR DOTÉ D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION DESTINÉ À UN ÉLÉMENT DE CELLULE SOLAIRE - Google Patents

COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, ENSEMBLE DE COMPOSITIONS DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION DESTINÉ À UN SUBSTRAT SEMI-CONDUCTEUR DOTÉ D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION DESTINÉ À UN ÉLÉMENT DE CELLULE SOLAIRE Download PDF

Info

Publication number
WO2013105602A1
WO2013105602A1 PCT/JP2013/050303 JP2013050303W WO2013105602A1 WO 2013105602 A1 WO2013105602 A1 WO 2013105602A1 JP 2013050303 W JP2013050303 W JP 2013050303W WO 2013105602 A1 WO2013105602 A1 WO 2013105602A1
Authority
WO
WIPO (PCT)
Prior art keywords
type diffusion
diffusion layer
forming composition
composition
layer forming
Prior art date
Application number
PCT/JP2013/050303
Other languages
English (en)
Japanese (ja)
Inventor
明博 織田
吉田　誠人
野尻　剛
倉田　靖
洋一 町井
岩室　光則
麻理 清水
鉄也 佐藤
芦沢　寅之助
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN201380005051.7A priority Critical patent/CN104081499A/zh
Priority to JP2013553307A priority patent/JP5892178B2/ja
Publication of WO2013105602A1 publication Critical patent/WO2013105602A1/fr

Links

Images

Classifications

    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • 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 at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier 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
    • H01L31/04—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 at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier 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
    • H01L31/0682—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 at least one potential-jump barrier or surface barrier 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 back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction 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 System
    • 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 n-type diffusion layer forming composition, an n-type diffusion layer forming composition set, a method for manufacturing a semiconductor substrate with an n-type diffusion layer, and a method for manufacturing a solar cell element.
  • a p-type silicon substrate having a textured structure formed on the light receiving surface is prepared so as to promote the light confinement effect, and then in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen.
  • An n-type diffusion layer is uniformly formed by performing several tens of minutes at 800 ° C. to 900 ° C.
  • n-type diffusion layers are formed not only on the surface but also on the side surface and the back surface. Therefore, a side etching process for removing the side n-type diffusion layer is necessary.
  • the n-type diffusion layer 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 subjected to thermal diffusion treatment, so that it is unnecessary on the side surface or 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 forming an n-type diffusion layer 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
  • a selective emitter structure with a low concentration is known (see, for example, L. Debarge, M. Schott, JCMuller, R.Monna, Solar Energy Materials and Solar Cells 74 (2002) 71-75).
  • this region is also referred to as “selective emitter” is formed, so that the contact resistance between the electrode and silicon can be reduced.
  • the diffusion concentration is relatively low except in the region where the electrode is formed, the conversion efficiency of the solar cell element can be improved.
  • the present invention has been made in view of the above-described conventional problems, and an n-type diffusion layer can be formed in a specific region, and the diffusion concentration of a donor element in the formed n-type diffusion layer can be easily achieved. It is an object of the present invention to provide an n-type diffusion layer forming composition that can be adjusted to the above, a method for manufacturing a semiconductor substrate with an n-type diffusion layer using the composition, and a method for manufacturing a solar cell element.
  • a compound containing a donor element is different from the compound containing a donor element, and a metal compound containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal, and a dispersion And an n-type diffusion layer forming composition containing the medium.
  • the compound containing the donor element is the n-type diffusion layer forming composition according to ⁇ 1>, which is a compound containing P (phosphorus).
  • the metal compound is a compound containing at least one metal element selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and radium ⁇ 1 > Or ⁇ 2>.
  • the n-type diffusion layer forming composition is a compound containing at least one metal element selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and radium ⁇ 1 > Or ⁇ 2>.
  • n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the metal compound is 0.01% by mass or more and 50% by mass or less.
  • the metal compound is a solid particle at normal temperature, and the volume average particle diameter of the particle is 0.01 ⁇ m or more and 30 ⁇ m or less. This is a mold diffusion layer forming composition.
  • ⁇ 6> The compound according to any one of ⁇ 1> to ⁇ 5>, wherein the compound containing the donor element is a compound containing at least one selected from the group consisting of P 2 O 3 and P 2 O 5.
  • the n-type diffusion layer forming composition is a compound containing at least one selected from the group consisting of P 2 O 3 and P 2 O 5.
  • the compound containing a donor element is the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 6>, which is in the form of glass particles.
  • At least one donor element-containing material 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.
  • 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 Is an n-type diffusion layer forming composition.
  • n-type diffusion layer forming composition according to ⁇ 7> or ⁇ 8> wherein the glass particle content is 1% by mass or more and 80% by mass or less.
  • ⁇ 10> The content according to any one of ⁇ 7> to ⁇ 9>, wherein the total content of P 2 O 3 and P 2 O 5 in the glass particles is 0.01% by mass or more and 10% by mass or less. It is an n-type diffusion layer forming composition.
  • n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 10>, further including an organic binder.
  • ⁇ 12> A step of forming a composition layer by applying the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 11> to the entire surface or a part of a semiconductor substrate; And a step of performing a heat treatment on the semiconductor substrate on which the composition layer is formed.
  • a step of forming a first composition layer by applying a first n-type diffusion layer forming composition containing a compound containing a donor element and a dispersion medium to a partial region on a semiconductor substrate. And the step of forming the n-type diffusion layer forming composition layer is on the same surface as the surface on which the first composition layer is formed on the semiconductor substrate, and the first composition layer
  • the first n-type diffusion layer forming composition has a content of a metal compound containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal in a region different from the region where the first n-type diffusion layer is formed. It is a manufacturing method of the semiconductor substrate with an n-type diffused layer as described in said ⁇ 12> which is a process of providing the said n-type diffused layer formation composition larger than this.
  • ⁇ 14> forming a first composition layer by applying a first n-type diffusion layer forming composition containing a compound containing a donor element and a dispersion medium to a partial region on a semiconductor substrate; ⁇ 1> to ⁇ 11 in a region different from a region where the first composition layer is formed on the same surface as the surface on which the first composition layer is formed on the semiconductor substrate.
  • the n-type diffusion layer forming composition according to any one of the above, wherein the content of the metal compound containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal is the first Applying a second n-type diffusion layer forming composition larger than the n-type diffusion layer forming composition to form a second composition layer, and the first composition layer and the second composition
  • the semiconductor substrate on which the layer is formed is subjected to a thermal diffusion treatment, and the second on the semiconductor substrate
  • the n + -type diffusion layer in a region where the composition layer is formed of, n ++ type diffusion layer having the n + -type diffusion small surface sheet resistance than layer on the first composition layer is formed regions Are respectively formed, and a step of forming an electrode on the n ++ type diffusion layer.
  • the content of the metal compound containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal in the first n-type diffusion layer forming composition is 10% by mass or less.
  • the content of the metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals in the second n-type diffusion layer forming composition is 0.01% by mass or more and 50% by mass.
  • % Is the method for producing a solar cell element according to ⁇ 14>.
  • ⁇ 16> Forming a composition layer on a semiconductor substrate by applying at least one of the n-type diffusion layer forming composition according to any one of ⁇ 1> to ⁇ 11>, and the composition
  • This is a method for manufacturing a solar cell element, which includes a step of forming a n-type diffusion layer by subjecting a semiconductor substrate on which a physical layer is formed to a thermal diffusion treatment and a step of forming an electrode on the n-type diffusion layer.
  • An n-type diffusion layer forming composition set comprising a layer forming composition.
  • an n-type diffusion layer can be formed in a specific region, and the diffusion concentration of the donor element in the formed n-type diffusion layer can be easily adjusted.
  • a forming composition, a method for producing a semiconductor substrate with an n-type diffusion layer using the composition, and a method for producing a solar cell element can be provided.
  • an n-type diffusion layer forming composition of the present invention will be described, and then a method for manufacturing a semiconductor substrate with an n-type diffusion layer and a solar cell element using the n-type 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 the component with respect to 100 mass% of n type diffused layer formation compositions, unless there is particular description.
  • the n-type diffusion layer forming composition of the present invention is a compound (A) containing a donor element and a compound different from the compound containing a donor element (at least selected from the group consisting of alkaline earth metals and alkali metals). It contains a metal compound (B) containing one kind of metal element and a dispersion medium (C), and may contain other additives as required in consideration of coating properties and the like.
  • the n-type diffusion layer forming composition of the present invention comprises a metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals (hereinafter referred to as “specific”) in addition to the compound containing a donor element.
  • the diffusibility of the donor element into the semiconductor substrate can be suppressed as compared with the case of using the n-type diffusion layer forming composition not containing the specific compound. Therefore, for example, in the semiconductor substrate, the n-type diffusion layer forming composition of the present invention is applied to a region where the diffusion concentration of the donor element is desired to be adjusted to be lower than other regions, and the n-type diffusion layer formation containing no specific compound is performed in the other regions.
  • the thermal diffusion treatment with the composition the diffusion concentration of the donor element in a desired region can be easily adjusted to be low. That is, it is possible to easily form a region where the diffusion concentration of the donor element is selectively different in the same plane of the semiconductor substrate. The reason for this can be considered as follows.
  • P 2 O 5 (or a material that changes to a compound containing P 2 O 5 at 800 ° C. or higher) and P 2 O 3 that are preferably used as a compound containing a donor element are both acidic oxides. These are believed to diffuse into the semiconductor substrate as P 2 O 5 or P 2 O 3 .
  • the specific compound is contained in the n-type diffusion layer forming composition, the reactivity between the compound containing the donor element and the specific compound is higher than the reactivity between the compound containing the donor element and the semiconductor substrate. It is considered that the diffusibility of the donor element into the semiconductor substrate can be suppressed.
  • the specific compound is a basic compound
  • an acid-base reaction occurs between the specific compound and the compound containing the donor element, and the acid-base reaction is highly reactive, so the semiconductor substrate of the donor element is more effective. It is thought that diffusion into the inside can be suppressed.
  • the specific compound is stable even at a high temperature (for example, 500 ° C. or higher), so that the effect of the present invention can be sufficiently exerted when the donor element is diffused into the semiconductor substrate. Furthermore, even when the specific compound is dissolved in the semiconductor substrate, it does not act as a carrier recombination center in the semiconductor substrate, so that it is possible to suppress the occurrence of a problem that the conversion efficiency is lowered when the semiconductor substrate is applied to a solar cell. .
  • the diffusion concentration of the donor element into the semiconductor substrate can be adjusted more precisely. Furthermore, by including the specific compound, out diffusion can be suppressed even if the compound containing the donor element is a highly volatile compound. This is considered to be because, for example, the volatility of the compound containing the donor element is suppressed by the chemical interaction of the specific compound with the compound containing the donor element.
  • the present invention provides a selective emitter structure that has conventionally required a complicated manufacturing process combining a plurality of thermal diffusion processes and partial etching by masking, etc., with a simple manufacturing process, for example, a single thermal diffusion process. It has the effect of making it possible to form.
  • a donor element is an element capable of forming an n-type diffusion layer by thermal diffusion in a semiconductor substrate.
  • the donor element a Group 15 element can be used, and P (phosphorus) is preferable from the viewpoint of safety and the like.
  • P phosphorus
  • a metal oxide containing a donor element a single metal oxide such as P 2 O 5 or P 2 O 3 ; phosphorous silicide, silicon particles doped with phosphorus, calcium phosphate, phosphoric acid, phosphorus-containing glass particles, etc.
  • the organic phosphorus compound is a compound that can be changed to a compound containing P 2 O 5 at a high temperature (for example, 800 ° C. or higher) at which the donor element thermally diffuses into the semiconductor substrate.
  • a compound for example, ammonium dihydrogen phosphate
  • a compound containing P 2 O 5 at a high temperature for example, 800 ° C. or more
  • P 2 O 3 , P 2 O 5 and a donor element are thermally diffused into a semiconductor substrate.
  • the melting point is 1000. It is more preferable to use a compound having a temperature of 0 ° C. or lower.
  • the donor element can be uniformly thermally diffused to the semiconductor substrate. Even if the compound has a melting point of more than 1000 ° C., a compound having a melting point of less than 1000 ° C. is further added to the semiconductor substrate from the compound containing the donor element to the semiconductor substrate through the compound having a melting point of less than 1000 ° C. The element may be thermally diffused.
  • the compound containing the donor element in the n-type diffusion layer forming composition is in the form of particles at normal temperature (25 ° C.), the shape in the case of particles is approximately spherical, flat, block, plate, scale, etc. Is mentioned. From the viewpoint of the coating property to the substrate and the uniform diffusibility when the n-type diffusion layer forming composition is used, the composition is preferably substantially spherical, flat or plate-like.
  • the particle diameter of the particles is preferably 100 ⁇ m or less. When particles having a particle size of 100 ⁇ m or less are used, a smooth composition layer is easily obtained.
  • the particle diameter of the particles is more preferably 50 ⁇ m or less.
  • grains in case the compound containing a donor element is a solid particle form represents a volume average particle diameter, and can be measured with a laser scattering diffraction method particle size distribution measuring apparatus. 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 the donor element may be in a state dissolved in the dispersion medium, and in that case, the shape and particle size of the compound containing the donor element used for preparing the n-type diffusion layer forming composition are not particularly limited.
  • the content rate of the compound containing the donor element in the n-type diffusion layer forming composition is determined in consideration of the coating property, the diffusibility of the donor element, and the like.
  • the content of the compound containing a donor element in the n-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less in the n-type diffusion layer forming composition. % To 90% by mass, more preferably 1% to 80% by mass, further preferably 2% to 80% by mass, and more preferably 5% to 20% by mass. It is particularly preferred that When the content of the compound containing a donor element is 0.1% by mass or more, the n-type diffusion layer can be sufficiently formed. When the content is 95% by mass or less, the dispersibility of the compound containing the donor element in the n-type diffusion layer forming composition is improved, and the coating property to the semiconductor substrate is improved.
  • 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 n-type diffusion layer forming composition is applied
  • out-diffusion the diffusion of the donor element to a region other than the region to which the n-type diffusion layer forming composition is applied
  • the formation of an unnecessary n-type diffusion layer can be suppressed. That is, an n-type diffusion layer can be formed more selectively by including glass particles containing a donor element.
  • the glass particles containing the donor element will be described in detail.
  • the glass particles contained in the n-type diffusion layer forming composition of the present invention are melted at a firing temperature (about 800 ° C. to 2000 ° C.) during thermal diffusion to form a glass layer on the n-type diffusion layer. To do. Therefore, out diffusion can be further suppressed.
  • the glass layer formed on the n-type diffusion layer can be removed by etching (hydrofluoric acid aqueous solution or the like).
  • 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 P (phosphorus), and at least one selected from the group consisting of P 2 O 3 and P 2 O 5 More preferably.
  • the content of the donor element-containing substance in the glass particles containing the donor element is not particularly limited. For example, from the viewpoint of the diffusibility of the donor element, 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. It is preferably contained in an amount of not more than mass%, more preferably not less than 2 mass% and not more than 80 mass%.
  • the glass particle containing a donor element can control a melting temperature, a softening point, a glass transition point, chemical durability, etc. by adjusting the component ratio as needed. Furthermore, it is preferable to contain at least 1 sort (s) of the glass component material described below.
  • the glass component materials include SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, V 2 O 5 , SnO, and WO 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 shall apply hereinafter
  • 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 and P 2 O 5 , SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, At least one glass selected from the group consisting of 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 donor element-containing material selected from the group consisting of P 2 O 3 and P 2 O 5 , 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, at least one glass selected from the group consisting of ZrO 2 and MoO 3 More preferably containing a minute substance, a donor element-containing material is a P 2 O 5, SiO 2, ZnO, CaO, Na 2 O, at least one selected from the group consisting of Li 2 O and BaO It is more preferable to contain these glass component substances. Thereby, the sheet resistance of the n-type diffusion layer to be formed can be further reduced.
  • the content ratio of the glass component material selected from the group consisting of SiO 2 and GeO 2 in the glass particles is the melting temperature, softening point, glass transition point, chemical durability. It is preferable to set appropriately considering the above.
  • the specific glass component substance is preferably 0.01% by mass or more and 80% by mass or less, and 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 n-type diffusion layer formation composition as it is 80 mass% or less can be suppressed more effectively.
  • the glass particles may contain a network-modified oxide (for example, alkali oxide or alkaline earth oxide) or an intermediate oxide that does not vitrify alone.
  • a network-modified oxide for example, alkali oxide or alkaline earth oxide
  • the content ratio of CaO that is a network modification oxide is preferably 1% by mass to 30% by mass, and preferably 5% by mass. More preferably, it is 20 mass% or less.
  • the softening point of the glass particles is preferably 200 ° C. to 1000 ° C., more preferably 300 ° C. to 900 ° C., from the viewpoints of diffusibility and dripping during the diffusion treatment.
  • 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, and 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, stirring is preferably performed so that the melt becomes uniform.
  • the obtained melt is poured onto a zirconia substrate, a carbon substrate, or the like to vitrify the melt.
  • the glass is pulverized into powder.
  • a known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
  • the content of the donor element in the glass particles is 0.01% by mass or more and 40% by mass or less in the glass particles from the viewpoint of diffusion performance. Preferably, it is 0.1 to 35% by mass, more preferably 1 to 30% by mass.
  • the content rate of the glass particle in an n type diffused layer formation composition is in an n type diffused layer formation composition from a viewpoint of the uniformity of diffusion. It is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 10% by mass or more and 40% by mass or less.
  • the n-type diffusion layer forming composition of the present invention is a compound different from the compound containing the donor element. And at least one metal compound (specific compound) containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals. Thereby, the diffusion concentration of the donor element to the semiconductor substrate can be easily controlled.
  • an n-type diffusion layer forming composition containing a metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals is used.
  • the diffusion concentration of the donor element is higher than when the n-type diffusion layer forming composition not containing a metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals is used.
  • An n-type diffusion layer having a low thickness can be formed.
  • the specific compound (B) is a compound different from the compound (A) containing the donor element, for example, the compound (A) containing the donor element is a glass particle, and the glass component constituting the glass particle Even when an alkaline earth metal or a compound containing an alkali metal is contained as a substance, the n-type diffusion layer forming composition of the present invention is independent of the compound (A) containing the specific compound (B) and the donor element. Is meant to be contained.
  • the metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals may be a liquid at room temperature (about 20 ° C.) or a solid. Since the thermal diffusion temperature of the donor element is high, it is preferably a solid compound at a high temperature (for example, 500 ° C. or higher) at which thermal diffusion treatment is performed.
  • the metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals is at least one type selected from the group consisting of alkaline earth metals and alkali metals.
  • metal salts containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals are examples of metal salts containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals.
  • a metal compound (specific compound) containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal changes to a basic compound at a high temperature of 700 ° C. or higher at which a donor element is thermally diffused.
  • a compound is preferred.
  • the specific compound is at least one metal element selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and radium as the metal element. It is preferable to contain at least one metal element selected from the group consisting of magnesium, calcium, potassium and barium, and at least one selected from the group consisting of magnesium, calcium and potassium It is more preferable to contain these metal elements.
  • the specific compound is selected from metal oxides, metal carbonates, metal nitrates, metal sulfates and metal hydroxides containing at least one selected from the group consisting of these metal elements. It is preferably at least one selected from the group consisting of, and particularly preferably at least one selected from the group consisting of metal oxides, metal carbonates, and metal hydroxides.
  • Specific compounds include metal oxides such as sodium oxide, potassium oxide, lithium oxide, calcium oxide, magnesium oxide, rubidium oxide, cesium oxide, beryllium oxide, strontium oxide, barium oxide, radium oxide, and complex oxides thereof.
  • Metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide
  • Metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, strontium carbonate, barium carbonate, radium carbonate; sodium nitrate, potassium nitrate, lithium nitrate Metal nitrates such as sodium, calcium sulfate, magnesium nitrate, rubidium nitrate, cesium nitrate, beryllium n
  • the specific compounds are sodium carbonate, sodium oxide, potassium carbonate, potassium oxide, calcium carbonate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium sulfate from the viewpoint of low toxicity and availability.
  • at least one selected from the group consisting of calcium sulfate, magnesium nitrate, calcium nitrate and magnesium oxide is used, and potassium carbonate, potassium oxide, magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium sulfate, sulfuric acid
  • at least one selected from the group consisting of lucium, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium oxide and magnesium hydroxide is used, and potassium oxide, calcium carbonate, calcium oxide, calcium hydroxide and magnesium carbonate are more preferable. It is particularly preferable to use at least one selected from the group consisting of
  • the particle diameter of the particles is preferably 0.01 ⁇ m or more and 30 ⁇ m or less, more preferably 0.02 ⁇ m or more and 10 ⁇ m or less, and 0.03 ⁇ m or more and 5 ⁇ m or less. More preferably.
  • the particle diameter is 30 ⁇ m or less, the donor element can be uniformly diffused (doped) by the application region of the n-type diffusion layer forming composition on the semiconductor substrate. Moreover, it exists in the tendency which can disperse
  • the specific compound may be dissolved in the dispersion medium.
  • the particle diameter represents a volume average particle diameter, and can be measured with a laser scattering diffraction particle size distribution measuring apparatus or the like.
  • the method for obtaining solid particles of a specific compound having a particle diameter in a desired range for example, 0.01 ⁇ m to 30 ⁇ m.
  • it can be obtained by pulverization.
  • a grinding method a dry grinding method and a wet grinding method can be employed.
  • a jet mill, a vibration mill, a ball mill, or the like can be employed.
  • a wet pulverization method a bead mill, a ball mill or the like can be employed.
  • the lifetime of carriers in the semiconductor substrate may be reduced. It is preferable to select a material with less influence. Specifically, partially stabilized zirconia or the like can be used.
  • a desired specific compound can be obtained by using a gas phase oxidation method, a hydrolysis method, or the like.
  • the shape of the specific compound is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a scale shape, a block shape, an oval shape, a plate shape, and a rod shape.
  • the shape of a specific compound can be determined by observing using a scanning electron microscope.
  • the specific compound may be reacted in advance with a compound containing a donor element.
  • a material obtained by immersing calcium oxide in a phosphoric acid aqueous solution to fix the phosphorus compound on the surface of the calcium oxide and then separating the calcium oxide to which the phosphorus compound is fixed by filtration includes a donor element. You may use as a compound and a specific compound.
  • the content of the specific compound in the n-type diffusion layer forming composition is determined in consideration of the coating property, the diffusion concentration of the donor element into the semiconductor substrate, and the like.
  • the content of the specific compound in the n-type diffusion layer forming composition is preferably 0.01% by mass or more and 50% by mass or less in the n-type diffusion layer forming composition, and is 0.02% by mass. It is more preferably 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and particularly preferably 0.1% by mass or more and 5% by mass or less.
  • the content of the specific compound is 0.01% by mass or more, thermal diffusion of the donor element contained in the compound containing the donor element to the semiconductor substrate can be appropriately suppressed. Moreover, it exists in the tendency which does not inhibit the thermal diffusion to the semiconductor substrate of the donor element contained in the compound containing a donor element too much that it is 50 mass% or less.
  • the content ratio of the specific compound with respect to the compound containing a donor element in the n-type diffusion layer forming composition is not particularly limited. From the viewpoint of uniformity of diffusion of the donor element into the semiconductor substrate, it is preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 8% by mass with respect to 100% by mass of the compound containing the donor element. % Or less, more preferably 0.5% by mass or more and 6% by mass or less.
  • the n-type diffusion layer forming composition of the present invention contains a dispersion medium.
  • the dispersion medium is a medium in which a compound containing the donor element and a metal compound containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal 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 ketone solvents; ether solvents; ester solvents such as 2- (2-butoxyethoxy) ethyl acetate; aprotic polar solvents; alcohol solvents; glycol monoether solvents such as diethylene glycol mono-n-butyl ether; ⁇ -terpinene Terpinene such as ⁇ -terpineol, pinene such as ⁇ -pinene and ⁇ -pinene, terpene solvents such as myrcene, alloocimene, limonene, dipentene, carvone, osimene, and ferrandrene.
  • the solvent those described in JP2012-084830A may be used.
  • n-type diffusion layer forming composition at least one selected from the group consisting of a terpene solvent, a glycol monoether solvent and an ester solvent is preferable from the viewpoint of applicability to the substrate.
  • a terpene solvent a glycol monoether solvent
  • an ester solvent is preferable from the viewpoint of applicability to the substrate.
  • Terpineol, diethylene glycol mono-n-butyl ether Or 2- (2-butoxyethoxy) ethyl acetate is preferred.
  • the content of the dispersion medium in the n-type diffusion layer forming composition is determined in consideration of the coating property and the concentration of the donor element.
  • it is preferably 5% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 95% by mass or less, and 40% by mass or more and 90% by mass or less. More preferably it is.
  • the n-type diffusion layer forming composition of the present invention in addition to a compound containing a donor element, a metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals, and a dispersion medium, If necessary, an organic binder, a surfactant, an inorganic powder, a resin containing a silicon atom, a reducing additive, a thixotropic agent, and the like can be contained.
  • the n-type diffusion layer forming composition may further contain at least one organic binder.
  • the organic binder By including the organic binder, it is possible to adjust the viscosity and impart thixotropy as the n-type diffusion layer forming composition, thereby further improving the impartability to the semiconductor substrate.
  • organic binder examples include polyvinyl alcohol; polyacrylamide resin; polyvinyl amide resin; polyvinyl pyrrolidone resin; polyethylene oxide resin; polysulfone resin; acrylamide alkyl sulfone resin; cellulose derivatives such as cellulose ether, carboxymethyl cellulose, hydroxyethyl cellulose, and ethyl cellulose; Starch and starch derivatives; sodium alginate and sodium alginate derivatives; xanthan and xanthan derivatives; gua and guar derivatives; scleroglucan and scleroglucan derivatives; tragacanth and tragacanth derivatives; Resin; alkyl (meth) acrylate resin, dimethylaminoethyl Meth) acrylates such as resin (meth) acrylic acid ester resin; butadiene resin; a styrene resin; and can select these copolymers as appropriate. These are used singly or in combination of two or more. When using
  • 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 0.5 mass% or more and 30 mass% or less in n type diffused layer formation composition, and is 3 mass% or more and 25 mass% or less. Is more preferable, and more preferably 3% by mass or more and 20% by mass or less.
  • the surfactant examples 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 rapidly fired 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 inorganic powder is preferably a substance that can function as a filler.
  • examples of the inorganic powder include silicon oxide, titanium oxide, silicon nitride, and silicon carbide powder.
  • the n-type diffusion layer forming composition may contain a reducing compound.
  • reducing compounds include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, 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 n-type diffusion layer forming composition may contain a thixotropic agent containing a solid content.
  • thixotropy can be easily controlled, and an n-type diffusion layer forming composition for screen printing having a viscosity suitable for printing can be constituted.
  • thixotropy is controlled, bleeding or sagging from the print pattern of the n-type diffusion layer forming composition during printing can be suppressed.
  • the method for producing the n-type diffusion layer forming composition of the present invention is not particularly limited.
  • a compound containing a donor element, a metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals, a dispersion medium, and components to be added as needed are blender, mixer, mortar, rotor It can obtain by mixing using etc.
  • the temperature can be, for example, 30 ° C. to 100 ° C.
  • the components contained in the n-type diffusion layer forming composition, and the content of each component are thermal analysis such as TG / DTA, spectral analysis such as NMR, IR, MALDI-MS, GC-MS, HPLC, GPC It can be confirmed using chromatographic analysis.
  • the total of the compound containing the donor element, the metal compound containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals, and the dispersion medium is preferably 1% by mass or more, more preferably 5% by mass or more in the n-type diffusion layer forming composition.
  • Preferred embodiments of the composition for forming an n-type diffusion layer of the present invention are as follows, for example. (1) A compound containing at least one selected from the group consisting of P 2 O 5 and P 2 O 3 as a donor element, magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and radium An n-type diffusion layer forming composition containing a metal compound containing at least one metal element selected from the group consisting of and a dispersion medium.
  • An n-type diffusion layer-forming composition containing a compound and a dispersion medium.
  • An n-type diffusion layer forming composition comprising at least one selected from the group consisting of metal compound particles having a particle size of 0.01 ⁇ m or more and 30 ⁇ m or less, and a dispersion medium.
  • At least one selected from the group consisting of P 2 O 5 and P 2 O 3 is included as a donor element, the particle diameter is 0.01 ⁇ m or more and 100 ⁇ m or less, and the content is 0.1% by mass or more and 95 Metal oxide containing glass particles having a mass% or less and at least one metal element selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and radium , At least one selected from the group consisting of metal carbonates, metal nitrates, metal sulfates and metal hydroxides, having a particle size of 0.01 ⁇ m or more and 30 ⁇ m or less, and a content of 0.01% by mass An n-type diffusion layer forming composition containing metal compound particles in an amount of 50% by mass or less and a dispersion medium.
  • Glass particles containing as a donor element at least one selected from the group consisting of P 2 O 5 and P 2 O 3 , magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium and A metal that contains at least one metal element selected from the group consisting of radium and is at least one selected from the group consisting of metal oxides, metal carbonates, metal nitrates, metal sulfates, and metal hydroxides It is an n-type diffusion layer forming composition containing a compound and a dispersion medium, wherein the content ratio of the metal compound to the glass particles containing the donor element is 0.01% by mass or more and 10% by mass or less.
  • the n-type diffusion layer forming composition of the present invention contains substantially no other metal other than the metal contained in the compound containing the donor element and the metal contained in the specific compound (0.5% by mass or less). Is preferable, and it is more preferable not to contain a metal (0 mass%).
  • the n-type diffusion layer forming composition set of the present invention includes a first n-type diffusion layer forming composition containing a compound containing a donor element and a dispersion medium, a compound containing a donor element, an alkaline earth metal, and an alkali metal.
  • a second n-type diffusion layer forming composition is containing a compound containing a donor element and a dispersion medium, a compound containing a donor element, an alkaline earth metal, and an alkali metal.
  • the n-type diffusion layer forming composition set is a combination (set) of the first n-type diffusion layer forming composition and the second n-type diffusion layer forming composition.
  • the composition can be suitably used for manufacturing a semiconductor substrate having regions having different diffusion concentrations of donor elements.
  • the details of the second n-type diffusion layer forming composition are as described above.
  • the specific compound content in the first n-type diffusion layer forming composition is not particularly limited as long as it is lower than the specific compound content in the second n-type diffusion layer forming composition.
  • the content rate of the specific compound can be, for example, 10% by mass or less in the first n-type diffusion layer forming composition, preferably 1% by mass or less, and substantially free of the specific compound. More preferred.
  • that the specific compound is not substantially contained means that the inevitable mixing of the specific compound is not prevented.
  • the ratio of the specific compound content in the second n-type diffusion layer forming composition to the specific compound content in the first n-type diffusion layer forming composition is preferably 5 or more, and preferably 10 or more. More preferably.
  • the method for producing a semiconductor substrate with an n-type diffusion layer according to the present invention comprises a step of forming a composition layer by applying the composition for forming an n-type diffusion layer according to the present invention on a semiconductor substrate, and the composition layer is formed. And subjecting the semiconductor substrate to a heat treatment.
  • the method for manufacturing a semiconductor substrate with an n-type diffusion layer may further include other steps as necessary.
  • the semiconductor substrate can be appropriately selected from commonly used semiconductor substrates according to the purpose. Of these, a silicon substrate is preferable.
  • the semiconductor substrate may be a p-type semiconductor substrate or an n-type semiconductor substrate.
  • the method for applying the n-type diffusion layer forming composition of the present invention on a semiconductor substrate is not particularly limited, and can be appropriately selected from commonly used coating methods.
  • Examples of the application method include a printing method, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
  • the application amount of the n-type diffusion layer forming composition is not particularly limited.
  • the amount of the compound containing a donor element is preferably 0.01 g / m 2 to 100 g / m 2, and more preferably 0.1 g / m 2 to 10 g / m 2 .
  • the drying can be performed at a temperature of about 80 ° C. to 300 ° C.
  • the drying time can be, for example, about 1 to 10 minutes when using a hot plate, and about 10 to 30 minutes when using a dryer.
  • the drying conditions can be appropriately selected according to the solvent composition of the n-type diffusion layer forming composition, and are not particularly limited to the above conditions in the present invention.
  • the semiconductor substrate on which the composition layer is formed is heat treated.
  • the temperature of the heat treatment can be set to 600 ° C. to 1200 ° C., for example.
  • the donor element is thermally diffused into the semiconductor substrate, and an n-type diffusion layer 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.
  • the heat treatment time can be appropriately selected according to the content of the donor element contained in the n-type diffusion layer forming composition.
  • the heat treatment time is preferably 1 minute to 60 minutes, and more preferably 2 minutes to 30 minutes.
  • a glass layer such as phosphate glass derived from a compound containing a donor element may be formed on the surface of the formed n-type diffusion layer. In that case, it is preferable to remove the glass layer by etching.
  • etching method 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.
  • a first n-type diffusion layer forming composition containing a compound containing a donor element and a dispersion medium is applied to a partial region on the semiconductor substrate. And forming the n-type diffusion layer forming composition layer on the same surface as the surface on which the first composition layer is formed on the semiconductor substrate.
  • a metal compound (specific compound) containing at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal in a region different from the region where the first composition layer is formed It is preferable that it is a process of providing the said n type diffused layer formation composition whose content rate is larger than said 1st n type diffused layer formation composition.
  • a first n-type diffusion layer forming composition containing a compound containing a donor element and a dispersion medium is applied to a partial region on the semiconductor substrate.
  • the content ratio of the metal compound containing the at least one metal element selected from the group consisting of an alkaline earth metal and an alkali metal in the n-type diffusion layer forming composition of the present invention in different regions is the first n.
  • a step of forming a second composition layer by applying a second n-type diffusion layer forming composition larger than the mold diffusion layer forming composition, and the first composition layer and the second composition layer include: With an n-type diffusion layer having a step of heat-treating the formed semiconductor substrate It is preferably a method for producing a conductive substrate. Thereby, a semiconductor substrate in which two or more n-type diffusion layer regions having different donor element diffusion concentrations are formed on the same surface can be produced by a simple method. Specifically, it is formed in the region where the second composition layer is formed, rather than the diffusion concentration of donor atoms in the n + -type diffusion layer formed in the region where the first composition layer is formed. The diffusion concentration of donor atoms in the n ++ type diffusion layer can be increased.
  • the second composition layer may be further formed on the first composition layer in addition to a region different from the region where the first composition layer is formed.
  • the 1st aspect in the manufacturing method of the solar cell element of this invention contains the compound and dispersion medium containing a donor element, and contains the at least 1 sort (s) of metallic element chosen from the group which consists of an alkaline-earth metal and an alkali metal.
  • the method includes forming two or more regions having different donor element diffusion concentrations on a semiconductor substrate using two or more types of n-type diffusion layer forming compositions having different metal compound contents.
  • a step of forming a first composition layer by applying a first n-type diffusion layer forming composition containing a compound containing a donor element and a dispersion medium to a partial region on a semiconductor substrate And an alkaline earth metal and a region different from a region where the first composition layer is formed on the same surface as the surface on which the first composition layer is formed on the semiconductor substrate.
  • Second n-type diffusion layer forming composition in which the content of the metal compound (specific compound) containing at least one metal element selected from the group consisting of alkali metals is larger than that of the first n-type diffusion layer forming composition
  • An n + -type diffusion layer is formed in the region where the second composition layer is formed, Forming n ++ type diffusion layer having a small surface sheet resistance than the n + -type diffusion layer formed product layer formed regions respectively, the n ++ type diffusion layer, forming an electrode
  • the manufacturing method of the solar cell element which has these.
  • the content ratio of the specific compound in the first n-type diffusion layer forming composition and the second n-type diffusion layer forming composition is higher in the first n-type diffusion layer forming composition than in the first n. As long as it is larger than in the mold diffusion layer forming composition, it is not particularly limited.
  • the content of the specific compound in the first n-type diffusion layer forming composition is 10% by mass or less, and the content of the specific compound in the second n-type diffusion layer forming composition is 0.01% by mass.
  • the content rate of the specific compound in said 1st n type diffused layer formation composition is 1 mass% or less, and in said 2nd n type diffused layer formation composition More preferably, the content of the specific compound is 0.01% by mass or more and 50% by mass or less, and the content of the specific compound in the first n-type diffusion layer forming composition is 0.1% by mass or less. More preferably, the content of the specific compound in the second n-type diffusion layer forming composition is 0.5% by mass or more and 30% by mass or less.
  • the diffusion concentration of the donor element in the n ++ type diffusion layer and the n + type diffusion layer formed by the manufacturing method is not particularly limited, and can be appropriately selected according to the purpose. For example, 80 [Omega / ⁇ or less the sheet resistance of 10 [Omega / ⁇ or more in the surface of the n ++ type diffusion layer, than the sheet resistance value at the surface of the sheet resistance n ++ type diffusion layer in the surface of the n + -type diffusion layer.
  • the sheet resistance value on the surface of the n ++ type diffusion layer is 10 ⁇ / ⁇ or more and less than 70 ⁇ / ⁇ , and it is preferably on the surface of the n + type diffusion layer.
  • the sheet resistance value is 70 ⁇ / ⁇ or more and 150 ⁇ / ⁇ or less
  • the sheet resistance value on the surface of the n ++ type diffusion layer is 30 ⁇ / ⁇ or more and 60 ⁇ / ⁇ or less
  • the sheet resistance value is 80 ⁇ / ⁇ or more and 120 ⁇ / ⁇ or less.
  • the sheet resistance value on the surface of the semiconductor substrate is measured by a commonly used four-point probe method. The four-probe method can be performed using, for example, a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation.
  • the shapes of the first and second composition layers formed by applying the first and second n-type diffusion layer forming compositions on the semiconductor substrate are not particularly limited and are appropriately selected according to the purpose. Is done.
  • the first composition layer is formed in a region corresponding to the region where the electrode is formed, and the second composition layer is formed at least in a region other than the region where the electrode is formed.
  • the second composition layer is formed on the entire surface of the semiconductor substrate including the region where the first composition layer is formed. It may be formed.
  • the solar cell element which has a selective emitter structure can be efficiently manufactured by forming the 1st and 2nd composition layer.
  • an electrode is formed on the n ++ type diffusion layer formed by thermal diffusion treatment.
  • the electrode formation method is not particularly limited, and can be appropriately selected from commonly used electrode formation methods. For example, an electrode forming method using a commercially available silver paste can be applied.
  • the method for manufacturing the solar cell element further includes a step of forming an electrode on the p-type diffusion layer on the semiconductor substrate.
  • the method for forming the electrode on the p-type diffusion layer is not particularly limited, and can be appropriately selected from commonly used electrode forming methods. For example, an electrode forming method using a commercially available aluminum paste can be applied.
  • the second aspect of the method for producing a solar cell element of the present invention is a metal containing at least one metal element selected from the group consisting of a compound containing a donor element, an alkaline earth metal, and an alkali metal on a semiconductor substrate.
  • a step of forming an n-type diffusion layer forming composition layer by applying at least one kind of an n-type diffusion layer forming composition containing a compound and a dispersion medium, and the n-type diffusion layer forming composition layer was formed
  • a method for manufacturing a solar cell element comprising: a step of forming a n-type diffusion layer by performing a heat treatment on a semiconductor substrate; and a step of forming an electrode on the formed n-type diffusion layer.
  • the manufacturing method of the second aspect includes an acceptor element on the same surface as the surface on which the n-type diffusion layer forming composition layer is formed on the semiconductor substrate before the step of forming the n-type diffusion layer. It is preferable to further include a step of forming a p-type diffusion layer forming composition layer by applying a p-type diffusion layer forming composition containing a compound and a dispersion medium. Thereby, for example, a back contact type solar cell element can be efficiently manufactured.
  • the solar cell element manufactured by the method for manufacturing a solar cell element is used for manufacturing a solar cell.
  • the solar cell includes at least one type of solar cell element manufactured by the above manufacturing method, and is configured by arranging a wiring material (such as a tab wire) on the electrode of the solar cell element.
  • 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. For example, it is preferably 0.5 m 2 to 3 m 2 .
  • FIG. 1 is a schematic cross-sectional view conceptually showing an example of the manufacturing process of the solar cell element according to the present embodiment.
  • common constituent elements are denoted by the same reference numerals.
  • the size of each component shown in the drawings is an example, and does not limit the relative size relationship between the components.
  • an alkaline solution is applied to a crystalline silicon substrate which is a p-type semiconductor substrate 10 to remove a damaged layer, and a texture structure (the description of the texture structure is omitted in the figure) is obtained by etching.
  • a texture structure (the description of the texture structure is omitted in the figure) is obtained by etching.
  • the damaged layer on the silicon surface 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.
  • front surface the light confinement effect is promoted and high efficiency is achieved.
  • the first composition layer 11 is formed by applying the first n-type diffusion layer forming composition to the surface that becomes the light receiving surface of the p-type semiconductor substrate 10.
  • the application method include a printing method, a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
  • the amount of glass powder is preferably 0.01 g / m 2 to 100 g / m 2, and more preferably 0.1 g / m 2 to 10 g / m 2 .
  • drying can be performed at a temperature of about 80 ° C. to 300 ° C.
  • the drying time can be about 1 to 10 minutes when using a hot plate or the like, and about 10 to 30 minutes when using a dryer or the like.
  • the drying conditions depend on the solvent composition of the n-type diffusion layer forming composition, and are not particularly limited to the above conditions in the present invention.
  • a second n-type diffusion layer forming composition is applied to the entire light receiving surface including the first composition layer 11 to form the second composition layer 12.
  • the concentration of the metal compound (specific compound) containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals contained in the second n-type diffusion layer forming composition is It is relatively higher than the concentration of the specific compound contained in one n-type diffusion layer forming composition.
  • the first n-type diffusion layer forming composition containing 10% by mass or less, preferably not containing the specific compound is applied.
  • a second n-type diffusion layer forming composition containing 0.01% to 50% by weight of the specific compound on the entire light-receiving surface and having a higher concentration of the specific compound than the first n-type diffusion layer forming composition It is preferable to give.
  • the second composition layer 12 is formed in the region of the light receiving surface other than the first composition layer. May be.
  • the semiconductor substrate 10 on which the first composition layer 11 and the second composition layer 12 are formed is heat-treated.
  • 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 heat treatment time is not particularly limited. For example, it is preferably performed for 1 to 30 minutes.
  • the donor element diffuses into the semiconductor substrate as shown in FIG. 1 (3), and an n ++ type diffusion layer 13 and an n + type diffusion layer 14 are 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.
  • the heat treatment time can be appropriately selected according to the content of the donor element contained in the first and second n-type diffusion layer forming compositions. For example, it can be 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes.
  • the n + -type diffusion layer 14 formed by the second n-type diffusion layer forming composition containing a large amount of a metal compound containing at least a metal element selected from the group consisting of alkaline earth metals and alkali metals.
  • n ++ type diffusion layer 13 and the n + type diffusion layer 14 are formed using the first and second n-type diffusion layer forming compositions, as described above, two or more kinds having different diffusion concentrations of the donor element are used. Since the n-type diffusion layer is selectively formed in a desired region by a simple method, a solar cell element having a selective emitter structure can be manufactured efficiently.
  • the heat-treated product layer 11A of the first n-type diffusion layer forming composition is formed on the surface of the n ++ -type diffusion layer 13 formed by the heat treatment, and the second n-type diffusion layer is formed on the surface of the n + -type diffusion layer 14.
  • a heat treatment product layer 12A of the composition is formed. Since a glass layer such as phosphate glass is formed in these heat-treated layers, the phosphate glass is removed by an etching process.
  • 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.
  • etching two types of n-type diffusion layers, n ++ -type diffusion layer 13 and n + -type diffusion layer 14 having different donor element diffusion concentrations, can be easily formed as shown in FIG.
  • the first and second n-type diffusion layer forming compositions two types of n-type diffusion layers having different donor element diffusion concentrations can be easily formed by a single heat treatment.
  • two types of n-type diffusion layers with different donor element diffusion concentrations were formed.
  • three or more types of n-type diffusion layer forming compositions with different specific compound contents were prepared and selected. In particular, by providing the desired region, it is possible to easily form three or more types of n-type diffusion layers having different donor element diffusion concentrations.
  • the antireflection film 15 is formed by applying a known technique.
  • the antireflection film 15 is a silicon nitride film, it is formed by a plasma CVD method using a mixed gas of SiH 4 and NH 3 as a raw material. 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 flow rate ratio NH 3 / SiH 4 of the mixed gas is 0.05 to 1.0
  • the pressure in the reaction chamber is 0.1 Torr (13.3 Pa) to 2 Torr (266.6 Pa)
  • the film is formed under the conditions of a temperature of 300 ° C. to 550 ° C. and a frequency for plasma discharge of 100 kHz or more.
  • the thickness of the antireflection film is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm.
  • a surface electrode metal paste is applied by screen printing or the like on the antireflection film 15 formed on the n ++ type diffusion layer 13 region of the light receiving surface and dried. Then, the surface electrode metal paste layer 16A is formed.
  • 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.
  • a back electrode metal paste layer 17A is formed on the back side.
  • the material and forming method of the back electrode 17 are not particularly limited.
  • the back electrode metal paste layer 17 ⁇ / b> A may be formed by applying a metal paste for the back electrode including a metal such as aluminum, silver, or copper and drying the paste.
  • a back electrode metal paste layer 17A is formed using a back electrode metal paste containing aluminum, and this is fired to form the back electrode 17, and at the same time, a p + -type diffusion layer (high Concentration electric field layer) 18 is formed.
  • a silver electrode forming silver paste may be provided on a part of the rear surface for connection between solar cell elements in the module process.
  • the manufacturing method of the p + -type diffusion layer (high concentration electric field layer) 18 on the back surface is not limited to the method using the metal paste for the back electrode containing aluminum, and any conventionally known method is used. Can be adopted, and the choice of manufacturing method is expanded.
  • the p + -type diffusion layer 18 can be formed by applying a p-type diffusion layer forming composition containing a Group 13 element such as B (boron).
  • the thickness of the front surface electrode 17 on the back surface can be made thinner than the conventional one.
  • the semiconductor substrate on which the front electrode metal paste layer 16A and the back electrode metal paste layer 17A are formed is baked to form the front electrode 16 and the back electrode 17 as shown in FIG. To complete.
  • the baking treatment can be performed in the range of 600 ° C. to 900 ° C. for several seconds to several minutes.
  • the antireflection film 15 that is an insulating film is melted by the glass particles contained in the metal paste layer 16A for the surface electrode, and the surface of the p-type semiconductor substrate 10 is also partially melted, so that the metal particles ( For example, silver particles) form a contact portion with the n ++ type diffusion layer 13 of the p-type semiconductor substrate 10 and solidify.
  • the surface electrode 16 and the p-type semiconductor substrate 10 are electrically connected. This is called fire-through.
  • the back electrode metal paste layer 17A containing aluminum is formed on the back surface side, when the back electrode 17 is formed, a p + type diffusion layer 18 in which aluminum diffuses into the p type semiconductor substrate 10 is formed.
  • the back surface field effect called Back Surface Field appears and contributes to high efficiency.
  • FIGS. 2A and 2B the surface electrode 16 includes a bus bar electrode 30 and finger electrodes 32 intersecting with the bus bar electrode 30.
  • FIG. 2A is a plan view of a solar cell element in which the surface electrode 16 includes a bus bar electrode 30 and a finger electrode 32 intersecting the bus bar electrode 30 as viewed from the light receiving surface (front surface).
  • FIG. 2B is an enlarged perspective view showing a part of FIG.
  • Such a surface electrode 16 can be formed, for example, by applying a metal paste by screen printing or the like as described above and baking it. 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 16 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 known forming means for the bus bar electrode and finger electrode on the light receiving surface side can be applied. it can.
  • the n ++ type diffusion layer 13 and the n + type diffusion layer 14 are formed on the front surface
  • the p + type diffusion layer 18 is formed on the back surface
  • the surface is further formed on the n ++ type diffusion layer 13 and the p + type diffusion layer 18, respectively.
  • the solar cell element provided with the electrode 16 and the back electrode 17 has been described.
  • a back contact solar cell element can be easily 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.
  • n-type diffusion layer forming composition of the present invention can form an n + -type diffusion layer portion only at a specific portion, and thus can be suitably applied to the production of a back contact type solar cell element. .
  • an n type diffusion layer forming composition containing a donor element such as phosphorus and a p type diffusion layer forming composition containing an acceptor element such as boron An n + -type diffusion layer region and a p + -type diffusion layer region can be formed by applying an object to each desired region and performing heat treatment.
  • the n-type diffusion layer forming composition of the present invention can adjust the diffusibility of the donor element by containing the specific compound, the diffusion concentration of the n-type diffusion layer forming composition into the semiconductor substrate can be adjusted. it can. Thereby, the n + -type diffusion layer portion and the p + -type diffusion layer portion can be formed at the same time, and the process time can be shortened.
  • a back contact solar cell element can be manufactured by a manufacturing method including a manufacturing process as schematically shown in FIG.
  • a texture structure (the description of the texture structure is omitted in FIG. 3) is formed on the light receiving surface (front surface) of the n-type semiconductor substrate 10A, and the back surface is a low defect structure such as a mirror shape.
  • the n-type semiconductor substrate is immersed in a mixed acid containing nitric acid, hydrofluoric acid, acetic acid, and the like to remove defects.
  • a texture structure is formed only on the light receiving surface by a technique such as alkali etching or plasma etching.
  • a technique such as alkali etching or plasma etching.
  • the n-type diffusion layer forming composition and the p-type diffusion layer forming composition of the present invention are partially applied to the back surface of the n-type semiconductor substrate 10A and dried, as shown in FIG.
  • the n-type diffusion layer forming composition layer 12 and the p-type diffusion layer forming composition layer 19 are formed respectively.
  • the p-type diffusion layer forming composition include a composition containing a compound (preferably in the form of glass particles) containing a Group 13 element such as B (boron) and a dispersion medium.
  • B boron
  • a printing method there are a spin method, a brush coating, a spray method, a doctor blade method, a roll coater method, and an ink jet method.
  • a drying method there is no restriction
  • the p + -type diffusion layer 18 and the n + -type diffusion layer 14 become as shown in FIG. As shown in (3), each is formed in a specific region.
  • heat treatment is preferably performed so that the surface sheet resistance value of the p + -type diffusion layer is 30 ⁇ / ⁇ to 140 ⁇ / ⁇ , and the surface sheet resistance value of the n + -type diffusion layer is 30 ⁇ / ⁇ to 100 ⁇ / ⁇ .
  • the n-type diffusion layer forming composition contains a specific compound and the diffusion capacity of the donor element is controlled, the p + -type diffusion layer and the n + -type diffusion layer can be formed at the same time, thus simplifying the manufacturing process. it can.
  • the atmosphere in the furnace during the heat treatment can be appropriately adjusted to air, oxygen, nitrogen, or the like.
  • a glass layer such as a phosphate glass layer is formed on the formed n + -type diffusion layer as the heat-treated product layer 12A of the n-type diffusion layer forming composition.
  • a glass layer such as a borosilicate glass layer is formed as the heat-treated product layer 19A of the p-type diffusion layer forming composition.
  • an antireflection film 15 is formed on the light receiving surface, and a passivation film 20 is formed on the back surface.
  • the antireflection film 15 is formed by applying a known technique.
  • the antireflection film 15 is a silicon nitride film, it is formed by a plasma CVD method using a mixed gas of SiH 4 and NH 3 as a raw material. 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 flow rate ratio NH 3 / SiH 4 of the mixed gas is 0.05 to 1.0
  • the pressure in the reaction chamber is 0.1 Torr (13.3 Pa) to 2 Torr (266.6 Pa)
  • the film is formed under the conditions of a temperature of 300 ° C. to 550 ° C. and a frequency for plasma discharge of 100 kHz or more.
  • the passivation film on the back surface may be a silicon nitride film as in the case of the light receiving surface, but a silicon oxide (SiO 2 ) film, an amorphous silicon film, or the like may be formed by a CVD method or the like.
  • the antireflection film and the passivation film may each have a two-layer structure made of a silicon oxide (SiO 2 ) film, a silicon nitride film, or the like.
  • an electrode is formed on each of the n + type diffusion layer and the p + type diffusion layer formed on the semiconductor substrate.
  • the electrode is formed, for example, by forming an electrode forming metal paste layer 17A containing glass powder having fire-through properties on the passivation film 20. Next, by baking this, a back electrode 17 penetrating the passivation film 20 can be formed as shown in FIG.
  • the composition of the electrode forming metal paste is not particularly limited. What contains metals, such as aluminum, silver, copper, and the glass powder which has fire through property, can be used.
  • Example 1> (Preparation of n-type diffusion layer forming composition) A solution of terpineol (manufactured by Nippon Terpene Chemical Co., Ltd., Terpineol-LW) containing 3.8% by mass of ethyl cellulose (manufactured by Dow Chemical Co., Ltd., Etcelle “STD200”) was prepared. 9 g of this solution and 1 g of diphosphorus pentoxide as a compound containing a donor element were mixed in a mortar to obtain a paste.
  • terpineol manufactured by Nippon Terpene Chemical Co., Ltd., Terpineol-LW
  • ethyl cellulose manufactured by Dow Chemical Co., Ltd., Etcelle “STD200”
  • 0.1 g of magnesium oxide (manufactured by Wako Pure Chemical Industries, volume average particle size 0.2 ⁇ m, substantially spherical) is added to 10 g of this paste and mixed in a mortar to obtain n as a second n-type diffusion layer forming composition.
  • a mold diffusion layer forming composition was prepared.
  • n ++ type diffusion layer forming composition ⁇ for evaluation
  • a solution of terpineol (manufactured by Nippon Terpene Chemical Co., Ltd., Terpineol-LW) containing 3.8% of ethyl cellulose (manufactured by Dow Chemical Co., Ltd., Etcelle “STD200”) was prepared.
  • 9 g of this solution and 1 g of diphosphorus pentoxide (manufactured by High-Purity Chemical Laboratory) as a compound containing a donor element are mixed in a mortar to form an n ++- type diffusion layer as a first n-type diffusion layer forming composition.
  • Composition ⁇ was prepared.
  • an n ++ -type diffusion layer forming composition ⁇ is partially applied by screen printing on a hot plate at 150 ° C. And dried for 1 minute to form a first composition layer. Subsequently, the n-type diffusion layer forming composition obtained by the preparation of the n-type diffusion layer forming composition is applied to the entire surface including the first composition layer on the surface of the p-type silicon substrate, and a hot plate at 150 ° C. A second composition layer was formed by drying for 1 minute. Air is 5 L / min.
  • Thermal diffusion treatment was performed for 10 minutes in a tunnel furnace (horizontal tube diffusion furnace ACCURON CQ-1200, manufactured by Kokusai Electric) at 950 ° C., which was flowed in Thereafter, in order to remove the glass layer formed on the surface of the p-type silicon substrate, 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, and n ++ A p-type silicon substrate on which a type diffusion layer and an n + type diffusion layer were formed was obtained.
  • a tunnel furnace horizontal tube diffusion furnace ACCURON CQ-1200, manufactured by Kokusai Electric
  • n + -type diffusion layer and the n ++ type diffusion layer is formed on the p-type silicon substrate
  • Ag electrode paste at the top of the region n ++ diffusion layer is formed of a light-receiving surface of the imparted by screen printing, including Ag
  • An electrode forming composition layer was formed.
  • An Al electrode paste was screen-printed on the entire back surface to form an electrode-forming composition layer containing Al.
  • firing was performed at a first zone: 400 ° C., a second zone: 850 ° C., and a third zone: 650 ° C. with a tact time of 10 seconds, and then the edge was cut to obtain a solar cell element.
  • the obtained solar cell element was evaluated for IV characteristics using a solar cell evaluation system (NF circuit design block, As-510-PV), the conversion efficiency was 9.2%.
  • the powder X-ray diffraction (XRD) pattern of the obtained glass particles was measured with an X-ray diffractometer (RINT-2000, manufactured by Rigaku Corp.) using Cu—K ⁇ ray using a Ni filter, it was amorphous. It was confirmed that there was.
  • the particle diameter of the obtained glass particles was substantially spherical, and the volume average particle diameter was measured by a laser diffraction particle size distribution measuring device to be 8 ⁇ m.
  • the volume average particle diameter was 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.
  • a sample obtained by dispersing 0.1 g of a sample in 10 g of terpineol as a dispersion medium was used as a measurement sample.
  • the wavelength of the laser beam was 750 nm.
  • the glass particle shape was determined by observation using a TM-1000 scanning electron microscope manufactured by Hitachi High-Technologies Corporation.
  • a terpineol solution containing 3.8% ethyl cellulose was prepared. 9 g of this solution and 1 g of the glass particles obtained above as a compound containing a donor element were mixed in a mortar to obtain a paste. Next, 0.1 g of magnesium oxide (manufactured by Wako Pure Chemical Industries, volume average particle size 0.2 ⁇ m, substantially spherical) is added to 10 g of this paste and mixed, and the n-type diffusion layer forming composition of Example 2 is used as an n-type. A diffusion layer forming composition was prepared.
  • n ++ type diffusion layer forming composition ⁇ A terpineol solution containing 3.8% ethylcellulose was prepared. 9 g of this solution and 1 g of the glass powder obtained above as a compound containing a donor element were mixed in a mortar to prepare an n ++ type diffusion layer forming composition ⁇ as a first n type diffusion layer forming composition. .
  • Example 2 I evaluated n-type diffusion layer-forming composition of Example 2 I did it.
  • Examples 3 to 10 Comparative Examples 1 to 3> (Preparation of n-type diffusion layer forming composition)
  • the n-type diffusion layers of Examples 3 to 10 and Comparative Examples 1 to 3 were the same as Example 2 except that the materials used for the preparation of the n-type diffusion layer forming composition were changed as shown in Table 1.
  • a forming composition was prepared.
  • the numerical values in Table 1 indicate the blending amount (g), and “-” indicates that the blending is not performed.
  • an n-type diffusion layer could be formed in a specific region. Further, by using the n-type diffusion layer forming compositions of Examples 1 to 10 and the n ++ type diffusion layer forming composition ⁇ or ⁇ , diffusion layers having different diffusion concentrations can be formed by a single thermal diffusion treatment. did it. Further, the sheet resistance value of Example 4 in which the compounding amount of calcium hydroxide is 1 g is 95 ⁇ , the sheet resistance value of Example 4 in which the compounding amount of calcium hydroxide is 0.5 g is 85 ⁇ , and the compounding amount of calcium hydroxide. The sheet resistance value of Example 4 in which is 0.01 g was 40 ⁇ .
  • the n-type diffusion layer forming composition of the present invention adjusts the blending amount of the metal compound (specific compound) containing at least one metal element selected from the group consisting of alkaline earth metals and alkali metals. This shows that the diffusion concentration can be easily adjusted. In addition, the conversion efficiency of the solar cell elements prepared using the n-type diffusion layer forming compositions of Examples 1 to 10 was good.
  • the region to which the first n-type diffusion layer forming composition is applied and the second n-type diffusion layer forming composition A clear difference was not recognized in the surface sheet resistance value of the region to which the product was applied. That is, it can be seen that the n-type diffusion layer forming composition not containing an alkaline earth metal or a metal compound having an alkali metal does not have an effect of adjusting the diffusion concentration. Further, the conversion efficiency of the solar cell elements prepared using the n-type diffusion layers of Comparative Examples 1 to 3 was low.
  • Comparative Example 2 it is considered that the effect of adjusting the diffusion concentration could not be obtained because polyethyleneimine was decomposed at a high temperature (in this case, 950 ° C.) subjected to thermal diffusion treatment.
  • Comparative Example 3 it is considered that the iron element diffused in the substrate becomes a recombination center of carriers (electrons and holes) in the semiconductor substrate, and the conversion efficiency is lowered because the lifetime of the carriers is shortened.
  • an n-type diffusion layer can be formed in a specific region, and the diffusion concentration of the donor element in the formed n-type diffusion layer can be easily achieved. It can be seen that it is possible to adjust to.

Abstract

La présente invention a trait à une composition de formation de couche de diffusion de type n qui contient : un composé qui inclut un élément donneur; un composé métallique qui est un composé différent du composé qui inclut l'élément donneur et qui contient au moins un type d'élément métallique choisi dans le groupe constitué par un métal alcalino-terreux et un métal alcalin; et un milieu de dispersion. La présente invention a également trait à un procédé de production destiné à un substrat semi-conducteur doté d'une couche de diffusion de type n, permettant d'appliquer la composition de formation de couche de diffusion de type n sur le substrat semi-conducteur et de former une couche de composition et de traiter thermiquement le substrat semi-conducteur doté de la couche de composition qui est formée sur celui-ci.
PCT/JP2013/050303 2012-01-10 2013-01-10 COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, ENSEMBLE DE COMPOSITIONS DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION DESTINÉ À UN SUBSTRAT SEMI-CONDUCTEUR DOTÉ D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION DESTINÉ À UN ÉLÉMENT DE CELLULE SOLAIRE WO2013105602A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201380005051.7A CN104081499A (zh) 2012-01-10 2013-01-10 n型扩散层形成用组合物、n型扩散层形成用组合物套剂、带n型扩散层的半导体基板的制造方法、以及太阳能电池元件的制造方法
JP2013553307A JP5892178B2 (ja) 2012-01-10 2013-01-10 ｎ型拡散層形成組成物セット、ｎ型拡散層付き半導体基板の製造方法、及び太陽電池素子の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012002632 2012-01-10
JP2012-002632 2012-01-10

Publications (1)

Publication Number Publication Date
WO2013105602A1 true WO2013105602A1 (fr) 2013-07-18

Family

ID=48781546

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/050303 WO2013105602A1 (fr) 2012-01-10 2013-01-10 COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, ENSEMBLE DE COMPOSITIONS DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION DESTINÉ À UN SUBSTRAT SEMI-CONDUCTEUR DOTÉ D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION DESTINÉ À UN ÉLÉMENT DE CELLULE SOLAIRE

Country Status (4)

Country Link
JP (2) JP5892178B2 (fr)
CN (1) CN104081499A (fr)
TW (1) TW201331991A (fr)
WO (1) WO2013105602A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015130406A (ja) * 2014-01-07 2015-07-16 三菱電機株式会社 光起電力装置およびその製造方法、光起電力モジュール

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201331991A (zh) * 2012-01-10 2013-08-01 Hitachi Chemical Co Ltd ｎ型擴散層形成組成物、ｎ型擴散層形成組成物套組、帶有ｎ型擴散層的半導體基板的製造方法以及太陽電池元件的製造方法
CN113782423B (zh) * 2021-08-25 2022-08-23 中国科学院宁波材料技术与工程研究所 杂质扩散方法和太阳能电池制造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004221149A (ja) * 2003-01-10 2004-08-05 Hitachi Ltd 太陽電池の製造方法
JP2006310373A (ja) * 2005-04-26 2006-11-09 Shin Etsu Handotai Co Ltd 太陽電池の製造方法及び太陽電池並びに半導体装置の製造方法
JP2009091548A (ja) * 2007-09-21 2009-04-30 Ricoh Co Ltd ペースト組成物、絶縁膜、多層配線構造、プリント基板、画像表示装置、及びペースト組成物の製造方法
JP2010062334A (ja) * 2008-09-03 2010-03-18 Japan Vam & Poval Co Ltd リン拡散用塗布液
WO2011090216A1 (fr) * 2010-01-25 2011-07-28 日立化成工業株式会社 COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE FABRICATION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE
WO2011132777A1 (fr) * 2010-04-23 2011-10-27 日立化成工業株式会社 COMPOSITION FORMANT UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION D'UN ÉLÉMENT DE CELLULE SOLAIRE
JP2012500502A (ja) * 2008-08-20 2012-01-05 ハネウェル・インターナショナル・インコーポレーテッド リン含有ドーパント、及びリン含有ドーパントを用いて半導体基材中にリンがドープされた領域を形成する方法
WO2012005253A1 (fr) * 2010-07-07 2012-01-12 日立化成工業株式会社 Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL207969A (fr) * 1955-06-28
TW201331991A (zh) * 2012-01-10 2013-08-01 Hitachi Chemical Co Ltd ｎ型擴散層形成組成物、ｎ型擴散層形成組成物套組、帶有ｎ型擴散層的半導體基板的製造方法以及太陽電池元件的製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004221149A (ja) * 2003-01-10 2004-08-05 Hitachi Ltd 太陽電池の製造方法
JP2006310373A (ja) * 2005-04-26 2006-11-09 Shin Etsu Handotai Co Ltd 太陽電池の製造方法及び太陽電池並びに半導体装置の製造方法
JP2009091548A (ja) * 2007-09-21 2009-04-30 Ricoh Co Ltd ペースト組成物、絶縁膜、多層配線構造、プリント基板、画像表示装置、及びペースト組成物の製造方法
JP2012500502A (ja) * 2008-08-20 2012-01-05 ハネウェル・インターナショナル・インコーポレーテッド リン含有ドーパント、及びリン含有ドーパントを用いて半導体基材中にリンがドープされた領域を形成する方法
JP2010062334A (ja) * 2008-09-03 2010-03-18 Japan Vam & Poval Co Ltd リン拡散用塗布液
WO2011090216A1 (fr) * 2010-01-25 2011-07-28 日立化成工業株式会社 COMPOSITION DE FORMATION DE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE FABRICATION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE FABRICATION D'UNE CELLULE SOLAIRE
WO2011132777A1 (fr) * 2010-04-23 2011-10-27 日立化成工業株式会社 COMPOSITION FORMANT UNE COUCHE DE DIFFUSION DE TYPE n, PROCÉDÉ DE PRODUCTION D'UNE COUCHE DE DIFFUSION DE TYPE n ET PROCÉDÉ DE PRODUCTION D'UN ÉLÉMENT DE CELLULE SOLAIRE
WO2012005253A1 (fr) * 2010-07-07 2012-01-12 日立化成工業株式会社 Composition et procédé de formation d'une couche de diffusion d'impuretés, procédé de fabrication d'une couches de diffusion d'impuretés, et procédé de fabrication d'un élément de cellule photovoltaïque

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015130406A (ja) * 2014-01-07 2015-07-16 三菱電機株式会社 光起電力装置およびその製造方法、光起電力モジュール

Also Published As

Publication number Publication date
CN104081499A (zh) 2014-10-01
JPWO2013105602A1 (ja) 2015-05-11
TW201331991A (zh) 2013-08-01
JP5892178B2 (ja) 2016-03-23
JP2016021588A (ja) 2016-02-04

Similar Documents

Publication Publication Date Title
KR20170086001A (ko) ｎ 형 확산층 형성 조성물, ｎ 형 확산층의 제조 방법, 및 태양 전지 셀의 제조 방법
JP2010524257A (ja) 厚膜伝導性組成物、および半導体デバイスの製造における使用方法
JP2011523492A (ja) 導電性組成物、および半導体デバイスの製造における使用方法
JP2011517117A (ja) 伝導性組成物、および半導体デバイスの製造における使用方法
KR20100080616A (ko) 반도체 소자의 제조에 사용하기 위한 전도성 조성물 및 공정
JP2011502330A (ja) 鉛フリーの伝導性組成物、および半導体デバイスの製造における使用方法：Ｍｇ含有添加剤
JP2011501866A (ja) 鉛フリーの伝導性組成物、および半導体デバイスの製造における使用方法：フラックス材料
JP2011502345A (ja) 伝導性組成物、および半導体デバイスの製造における使用方法：複数の母線
KR20110090780A (ko) ｐ 형 확산층 형성 조성물, ｐ 형 확산층의 제조 방법, 및 태양 전지 셀의 제조 방법
JP5958485B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
TWI485875B (zh) 形成不純物擴散層的組成物、形成ｎ型擴散層的組成物、ｎ型擴散層的製造方法、形成ｐ型擴散層的組成物、ｐ型擴散層的製造方法及太陽能電池的製造方法
JP5892178B2 (ja) ｎ型拡散層形成組成物セット、ｎ型拡散層付き半導体基板の製造方法、及び太陽電池素子の製造方法
JP6460055B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層を有する半導体基板の製造方法、及び太陽電池素子の製造方法
KR101541660B1 (ko) n 형 확산층 형성 조성물, n 형 확산층의 제조 방법, 및 태양 전지 소자의 제조 방법
KR20130086146A (ko) 불순물 확산층 형성 조성물, 불순물 확산층의 제조 방법, 및 태양 전지 소자의 제조 방법
JP5935254B2 (ja) 不純物拡散層形成組成物、不純物拡散層の製造方法、太陽電池素子の製造方法および太陽電池の製造方法
JP5541138B2 (ja) ｐ型拡散層形成組成物、ｐ型拡散層の製造方法及び太陽電池セルの製造方法
KR101384874B1 (ko) n 형 확산층 형성 조성물, n 형 확산층의 제조 방법 및 태양 전지 소자의 제조 방법
TWI482302B (zh) 形成ｎ型擴散層的組成物、ｎ型擴散層的製造方法及太陽電池元件的製造方法
JP5541139B2 (ja) ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池セルの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13735904

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013553307

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13735904

Country of ref document: EP

Kind code of ref document: A1