WO2018021121A1 - Composition de diffusion d'impuretés et procédé de production d'éléments semi-conducteurs utilisant la composition de diffusion d'impuretés - Google Patents

Composition de diffusion d'impuretés et procédé de production d'éléments semi-conducteurs utilisant la composition de diffusion d'impuretés Download PDF

Info

Publication number
WO2018021121A1
WO2018021121A1 PCT/JP2017/026150 JP2017026150W WO2018021121A1 WO 2018021121 A1 WO2018021121 A1 WO 2018021121A1 JP 2017026150 W JP2017026150 W JP 2017026150W WO 2018021121 A1 WO2018021121 A1 WO 2018021121A1
Authority
WO
WIPO (PCT)
Prior art keywords
impurity diffusion
group
diffusion composition
carbon atoms
film
Prior art date
Application number
PCT/JP2017/026150
Other languages
English (en)
Japanese (ja)
Inventor
剛 北田
由洋 池上
新井　名奈
Original Assignee
東レ株式会社
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 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2017538732A priority Critical patent/JPWO2018021121A1/ja
Publication of WO2018021121A1 publication Critical patent/WO2018021121A1/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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an impurity diffusion composition for diffusing an impurity diffusion component in a semiconductor substrate, and a method for manufacturing a semiconductor element using the same.
  • an impurity diffusion source is formed on the semiconductor substrate, and thermal diffusion is performed in the semiconductor substrate.
  • a method of diffusing impurity diffusion components is employed.
  • the impurity diffusion source is formed by a CVD method or a solution coating method of a liquid impurity diffusion composition.
  • a thermal oxide film is first formed on the surface of the semiconductor substrate, and then a resist having a predetermined pattern is laminated on the thermal oxide film by photolithography. Then, using the resist as a mask, the portion of the thermal oxide film not masked with the resist is etched with acid or alkali, and then the resist is removed to form a mask with the thermal oxide film. Subsequently, an n-type or p-type impurity diffusion composition is applied, and the impurity diffusion composition is adhered to the portion where the mask is opened. Thereafter, the impurity diffusion component in the composition is thermally diffused into the semiconductor substrate at 600 ° C. to 1250 ° C. to form an n-type or p-type impurity diffusion layer.
  • the conventional impurity diffusion composition is not irradiated with laser light when the impurity diffusion component is locally diffused from the impurity diffusion composition film into the semiconductor substrate using laser light or the like.
  • the “dry film of the impurity diffusion composition” is a portion of the impurity diffusion composition film formed by coating on a semiconductor substrate that is not irradiated with laser light, that is, a portion not irradiated with laser.
  • the present invention has been made in view of the above circumstances, and has an excellent impurity diffusibility to a semiconductor substrate and cleans a dry film (a laser-irradiated portion) of the impurity diffusion composition remaining on the semiconductor substrate.
  • An object of the present invention is to provide an impurity diffusion composition having excellent properties and a method for producing a semiconductor device using the same.
  • the impurity diffusion composition according to the present invention contains polysiloxane (A) and an impurity diffusion component (B), and the polysiloxane (A) It contains at least one of a carboxyl group and a dicarboxylic anhydride structure.
  • the impurity diffusion composition according to the present invention is characterized in that, in the above invention, the polysiloxane (A) is a polysiloxane represented by the following general formula (1).
  • R 1 represents a substituent containing at least one of a carboxyl group and a dicarboxylic anhydride structure, and a plurality of R 1 may be the same or different from each other.
  • R 1 in the general formula (1) includes a group represented by any one of the following general formulas (2) to (6). It is characterized by.
  • R 5 , R 7 , R 8 and R 9 represent a divalent organic group having 1 to 20 carbon atoms.
  • R 6 represents a hydrogen atom or 1 to Represents an alkyl group of 3.
  • R 10 , R 11 and R 12 each represents a single bond, a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, or a carbon number Represents a 2-6 alkylcarbonyloxy group, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group having 6 to 16 carbon atoms, or a divalent group having any one of these.
  • the atom is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a hydroxy group, an amino group, a carboxyl group, or Optionally substituted with a thiol group, h, j, k and And l represents an integer of 0 to 3.
  • the impurity diffusion composition according to the present invention is characterized in that, in the above invention, the content of the impurity diffusion component (B) is from 0.1% by mass to 20% by mass.
  • the impurity diffusion component (B) is phosphoric acid, diphosphorus pentoxide, polyphosphoric acid, phosphoric acid ester, boron oxide, boric acid, boric acid ester. 1 or more types selected from boronic acid and boronic acid ester.
  • the impurity diffusion component (B) contains one or more selected from boric acid, boronic acid, boric acid ester, and boronic acid ester, And water and a water-soluble binder.
  • the impurity diffusion composition according to the present invention is characterized in that, in the above invention, the water-soluble binder is polyvinyl alcohol.
  • a method for manufacturing a semiconductor device includes a film forming step of forming an impurity diffusion composition film by applying the impurity diffusion composition according to any of the above inventions on a semiconductor substrate, and the impurity And a layer forming step of diffusing an impurity diffusion component from the diffusion composition film into the semiconductor substrate to form an impurity diffusion layer.
  • a method for manufacturing a semiconductor device includes a film forming step of forming an impurity diffusion composition film by applying the impurity diffusion composition according to any of the above inventions on a semiconductor substrate, and the impurity And a layer forming step of irradiating the diffusion composition film with laser light to diffuse an impurity diffusion component from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer.
  • a method for manufacturing a semiconductor device includes a film forming step of forming an impurity diffusion composition film by applying the impurity diffusion composition according to any of the above inventions on a semiconductor substrate, and the impurity A layer forming step of irradiating a part of the diffusion composition film with laser light to diffuse an impurity diffusion component from the part of the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer; and the impurity diffusion composition And a removal step of removing, by an acid or an alkali, an unirradiated portion of the material film that has not been irradiated with the laser beam.
  • the impurity diffusion composition which has the outstanding impurity diffusivity to a semiconductor substrate, and was excellent in the cleaning property of the dry film of the impurity diffusion composition which remain
  • the production method can be provided.
  • FIG. 1A is a diagram illustrating an example of a method for manufacturing a semiconductor device according to an embodiment of the present invention.
  • FIG. 1B is a diagram showing an example of a method for manufacturing a solar cell using a semiconductor element according to an embodiment of the present invention.
  • the impurity diffusion composition according to the present invention is a composition for forming an impurity diffusion layer of a desired conductivity type (n-type, p-type) on a semiconductor substrate when manufacturing a semiconductor element such as a solar cell, Polysiloxane (A) and an impurity diffusion component (B) are contained.
  • polysiloxane (A) contains at least one of a carboxyl group and a dicarboxylic anhydride structure.
  • the polysiloxane (A) in the present invention is a polysiloxane containing at least one of a carboxyl group and a dicarboxylic anhydride structure.
  • the polysiloxane (A) can impart excellent impurity diffusibility to the semiconductor substrate when contained in the impurity diffusion composition.
  • the polysiloxane (A) can improve the detergency of the dry film of the impurity diffusion composition remaining on the semiconductor substrate after the diffusion of the impurity diffusion component into the semiconductor substrate with an acid or alkali.
  • the polysiloxane (A) contains at least one of a carboxyl group and a dicarboxylic acid anhydride structure, so that at least one of the carboxyl group and the dicarboxylic acid anhydride structure in the polysiloxane (A) is acidic or alkaline. Affinity with the cleaning solution is improved. That is, when the dry film of the impurity diffusion composition containing the polysiloxane (A) in the present invention is cleaned, the solubility of the dry film in the cleaning liquid is improved by the polysiloxane (A). The detergency of the dry film can be improved.
  • the polysiloxane (A) containing at least one of a carboxyl group and a dicarboxylic anhydride structure is preferably a polysiloxane represented by the following general formula (1).
  • R 1 represents a substituent containing at least one of a carboxyl group and a dicarboxylic anhydride structure.
  • the plurality of R 1 may be the same or different.
  • R 2 , R 3 and R 4 are a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or a carbon number Represents any of 6 to 15 aryl groups;
  • a plurality of R 2 , R 3 and R 4 may be the same or different.
  • the polysiloxane (A) represented by the general formula (1) may be a block copolymer or a random copolymer.
  • the content of the carboxyl group in the polysiloxane (A) is measured, for example, by measuring the 29 Si-NMR spectrum of the polysiloxane (A), and the peak area of the Si atom to which the carboxyl group is bonded and the carboxyl group is not bonded. It can obtain
  • the content of the dicarboxylic acid anhydride structure in the polysiloxane (A) can be determined by, for example, measuring the 29 Si-NMR spectrum of the polysiloxane (A), the peak area of the Si atom bonded with the dicarboxylic acid anhydride structure, and the dicarboxylic acid anhydride structure. It can be determined from the ratio to the peak area of Si atoms to which the acid anhydride structure is not bonded. In addition, when the Si atom and the dicarboxylic acid anhydride structure are not directly bonded, the integral ratio between the peak derived from the dicarboxylic acid anhydride structure and the other peaks excluding the silanol group is determined using the 1 H-NMR spectrum.
  • the content of dicarboxylic acid anhydride structure in the whole polysiloxane (A) is calculated, and the result of this calculation and the result of the 29 Si-NMR spectrum described above are combined to obtain the dicarboxylic acid indirectly bonded to the Si atom.
  • the content of the acid anhydride structure can be calculated.
  • R 1 in the general formula (1) preferably contains a group represented by any one of the following general formulas (2) to (6).
  • R 5 , R 7 , R 8 and R 9 represent a divalent organic group having 1 to 20 carbon atoms.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 10 , R 11 and R 12 are each a single bond, a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, or an alkylcarbonyloxy group having 2 to 6 carbon atoms.
  • the hydrogen atoms of these groups are alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 16 carbon atoms, alkylcarbonyloxy groups having 2 to 6 carbon atoms, hydroxy groups, amino groups It may be substituted with a group, a carboxyl group or a thiol group.
  • h, j, k, and l represent an integer of 0 to 3.
  • This organosilane compound is a raw material of polysiloxane (A) containing at least one of a carboxyl group and a dicarboxylic anhydride structure.
  • the polysiloxane (A) represented by the general formula (1) can be obtained by appropriately selecting and hydrolyzing and condensing an organosilane compound described below.
  • organosilane compound having a carboxyl group examples include a urea group-containing organosilane compound represented by the following general formula (7) or a urethane group-containing organosilane compound represented by the following general formula (8). Can be mentioned. As the organosilane compound having a carboxyl group, two or more of these may be used.
  • R 13 , R 15 and R 19 represent a divalent organic group having 1 to 20 carbon atoms.
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 16 , R 17 and R 18 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, Represents any of 15 aryl groups.
  • R 16 , R 17 and R 18 may be the same or different. However, at least one of R 16 , R 17 and R 18 is an alkoxy group having 1 to 6 carbon atoms.
  • R 13 and R 19 in the general formulas (7) and (8) include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a phenylene group, —CH 2 —C 6 H 4 —CH.
  • examples thereof include hydrocarbon groups such as 2 — and —CH 2 —C 6 H 4 —.
  • carbon atoms having an aromatic ring such as a phenylene group, —CH 2 —C 6 H 4 —CH 2 —, —CH 2 —C 6 H 4 — as R 13 and R 19
  • a hydrogen group is preferred.
  • R 14 in the general formula (7) is preferably hydrogen or a methyl group from the viewpoint of reactivity.
  • R 15 in the general formulas (7) and (8) include hydrocarbon groups such as a methylene group, an ethylene group, an n-propylene group, an n-butylene group and an n-pentylene group, and an oxymethylene group. Oxyethylene group, oxy n-propylene group, oxy n-butylene group, oxy n-pentylene group and the like.
  • R 15 represents methylene group, ethylene group, n-propylene group, n-butylene group, oxymethylene group, oxyethylene group, oxy n-propylene group, oxy n-butylene. Groups are preferred.
  • R 16 , R 17 and R 18 in the general formulas (7) and (8) specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Among these, a methyl group or an ethyl group is preferable as the alkyl group for R 16 , R 17 and R 18 from the viewpoint of ease of synthesis.
  • specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.
  • a methoxy group or an ethoxy group is preferable as the alkoxy group for R 16 , R 17, and R 18 from the viewpoint of ease of synthesis.
  • substituent of the substituent of R 16 , R 17 and R 18 include a methoxy group and an ethoxy group. Specific examples include a 1-methoxypropyl group and a methoxyethoxy group.
  • the urea group-containing organosilane compound represented by the general formula (7) includes an aminocarboxylic acid compound represented by the following general formula (9) and an isocyanate group-containing organosilane represented by the following general formula (11). It can be obtained from a compound by a known urea formation reaction.
  • the urethane group-containing organosilane compound represented by the general formula (8) includes a hydroxycarboxylic acid compound represented by the following general formula (10) and an isocyanate group-containing compound represented by the following general formula (11). It can be obtained from an organosilane compound by a known urethanization reaction.
  • R 13 , R 15 and R 19 represent a divalent organic group having 1 to 20 carbon atoms.
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 16 , R 17 and R 18 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, Represents any of 15 aryl groups.
  • Preferred examples of these R 13 ⁇ R 19 of the general formula (7) is as described above for R 13 ⁇ R 19 in (8).
  • organosilane compound having a carboxyl group examples include a compound represented by the general formula (12).
  • R 20 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 carbon atoms. Represents any of ⁇ 15 aryl groups.
  • the plurality of R 20 may be the same or different.
  • q represents an integer of 1 to 3.
  • r represents an integer of 2 to 20.
  • organosilane compound having a dicarboxylic acid anhydride structure examples include organosilane compounds represented by any one of the following general formulas (13) to (15).
  • organosilane compound having a dicarboxylic acid anhydride structure two or more of these may be used.
  • R 22 , R 23 and R 24 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It represents either an acyl group having 2 to 6 or an aryl group having 6 to 15 carbon atoms. However, at least one of R 22 , R 23 and R 24 is an alkoxy group having 1 to 6 carbon atoms.
  • R 21 , R 25 and R 26 are each a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, or an alkylcarbonyloxy group having 2 to 6 carbon atoms.
  • the hydrogen atoms of these groups are alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 16 carbon atoms, alkylcarbonyloxy groups having 2 to 6 carbon atoms, hydroxy groups, amino groups It may be substituted with a group, a carboxyl group or a thiol group.
  • h, j, k, and l represent an integer of 0 to 3.
  • R 21 , R 25 and R 26 include —C 2 H 4 —, —C 3 H 6 —, —C 4 H 8 —, —O—, —C 3 H 6 OCH 2 CH (OH). Examples thereof include CH 2 O 2 C—, —CO—, —CO 2 —, —CONH—, and organic groups listed below.
  • organosilane compound represented by the general formula (13) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride.
  • Etc Specific examples of the organosilane compound represented by the general formula (14) include 3-trimethoxysilylsilylpropylcyclohexyl dicarboxylic acid anhydride.
  • organosilane compound represented by the general formula (15) include 3-trimethoxysilylsilylpropylphthalic anhydride.
  • an organosilane compound other than an organosilane compound containing at least one of a carboxyl group and a dicarboxylic anhydride structure is used in combination. It is also possible.
  • organosilane compounds include tetrafunctional silane, trifunctional silane, bifunctional silane, and monofunctional silane.
  • examples of the tetrafunctional silane include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane.
  • examples of trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxy.
  • Examples of the bifunctional silane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidide) And xylpropyl) methyldiethoxysilane, di (1-naphthyl) dimethoxysilane, and di (1-naphthyl) diethoxysilane.
  • Examples of monofunctional silanes include trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, and (3-glycidoxypropyl) dimethylethoxysilane. Two or more of these organosilanes may be used.
  • the production method of polysiloxane (A) containing at least one of a carboxyl group and a dicarboxylic anhydride structure is not particularly limited, and a known method such as partial condensation of an organosilane compound can be used.
  • Examples of this production method include a method of adding a reaction solvent, water and, if necessary, a catalyst to an organosilane mixture and heating and stirring at 50 to 150 ° C. for about 0.5 to 100 hours.
  • hydrolysis by-products alcohols such as methanol
  • condensation by-products water
  • the partial condensation means that Si—OH remains in a part of the resulting polysiloxane (A) rather than condensing all of the hydrolyzed Si—OH.
  • Si—OH is generally partially left, and in the present invention, the amount of Si—OH to be left is not limited.
  • the reaction solvent is not particularly limited, but usually the same solvent as described below can be used.
  • the addition amount of such a reaction solvent is preferably 10 parts by weight or more and 1500 parts by weight or less with respect to 100 parts by weight of a monomer such as organosilane.
  • the addition amount of the water used for a hydrolysis reaction is 0.5 mol or more and 5 mol or less with respect to 1 mol of a hydrolysable group.
  • the catalyst added as necessary is not particularly limited, but an acid catalyst is preferably used.
  • the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin.
  • the addition amount of such a catalyst is preferably 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of a monomer such as organosilane.
  • the catalyst can be removed from the polysiloxane solution after hydrolysis and partial condensation as necessary.
  • the water washing is a method of diluting a polysiloxane solution with a suitable hydrophobic solvent and then concentrating the organic layer obtained by washing several times with water with an evaporator or the like.
  • the treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with an appropriate ion exchange resin.
  • the content of the polysiloxane (A) containing at least one of a carboxyl group and a dicarboxylic anhydride structure in the impurity diffusion composition in the present invention is 0.1% by mass or more and 90% by mass in the impurity diffusion composition. % Or less, more preferably 0.1% by mass or more and 50% by mass or less.
  • the content of the polysiloxane (A) is within the above range, excellent impurity diffusibility and cleanability of the impurity diffusion composition can be obtained.
  • carbon number represents the total number of carbon atoms including a group further substituted on the group.
  • an alkyl group having 1 to 10 carbon atoms means that the total number of carbon atoms in the alkyl group (including the substituent, if any) is 1 or more and 10 or less.
  • the impurity diffusion component (B) is a component for forming an impurity diffusion layer of a desired conductivity type (n-type or p-type) in the semiconductor substrate.
  • the impurity diffusion component (B) is preferably a compound containing a Group 13 or Group 15 element.
  • group 13 element boron, aluminum and gallium are preferable, and boron is particularly preferable.
  • group 15 element phosphorus, arsenic, antimony and bismuth are preferable, and phosphorus is particularly preferable.
  • Examples of phosphorus compounds include phosphate esters and phosphites.
  • Examples of phosphate esters include diphosphorus pentoxide, phosphoric acid, polyphosphoric acid, methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, propyl phosphate, and dipropyl phosphate. , Tripropyl phosphate, butyl phosphate, dibutyl phosphate, tributyl phosphate, phenyl phosphate, diphenyl phosphate, triphenyl phosphate, and the like.
  • Examples of the phosphite ester include methyl phosphite, dimethyl phosphite, trimethyl phosphite, ethyl phosphite, diethyl phosphite, triethyl phosphite, propyl phosphite, dipropyl phosphite, Examples include tripropyl phosphate, butyl phosphite, dibutyl phosphite, tributyl phosphite, phenyl phosphite, diphenyl phosphite, triphenyl phosphite and the like. Of these, phosphoric acid, diphosphorus pentoxide or polyphosphoric acid is preferable from the viewpoint of doping.
  • Examples of the boron compound include boric acids, borates, halides, boronic acids, boric acid esters, and boronic acid esters.
  • examples of boric acids include boric acid and boron oxide.
  • examples of borates include ammonium borate.
  • Examples of the halide include boron trifluoride, boron trichloride, boron tribromide, boron triiodide and the like.
  • Examples of boronic acids include methyl boronic acid and phenyl boronic acid.
  • Examples of borate esters include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trioctyl borate, triphenyl borate, and the like.
  • boronic acid esters examples include 2-phenyl-1,3,2-dioxaborinane and diisopropylmethylborane.
  • boric acids, boronic acids, boric acid esters, and boronic acid esters are preferable.
  • the content of the impurity diffusion component (B) in the impurity diffusion composition according to the present invention can be arbitrarily determined according to the resistance value required for the semiconductor substrate, and is 0.01% by mass or more and 50% by mass or less. Is preferable, and it is more preferable that it is 0.1 mass% or more and 20 mass% or less. When the content of the impurity diffusion component (B) is within the above range, sufficient diffusibility of the impurity diffusion component (B) with respect to the semiconductor substrate can be obtained.
  • the impurity diffusion component (B) preferably contains a binder resin.
  • the impurity diffusion component (B) preferably contains at least one selected from boric acid, boronic acid, boric acid ester and boronic acid ester, and further contains water and a water-soluble binder.
  • the water-soluble binder refers to a binder having a solubility of 10% by weight or more with respect to water at 25 ° C.
  • examples of the binder resin such as the above water-soluble binder include the following.
  • the binder resin in the impurity diffusion component (B) is not limited to these.
  • the above “(meth) acrylic acid” means “acrylic acid
  • the binder resin can be used alone or in combination of two or more.
  • the binder resin has a 1,2-diol structure or 1,3-diol from the viewpoint of the formation of a complex with the boron compound and the stability of the formed complex.
  • Those having a structure are preferable, and polyvinyl alcohol is particularly preferable.
  • the polymerization degree of the binder resin in the impurity diffusion component (B) is not particularly limited, but a preferable polymerization degree range is 1000 or less, and particularly preferably 800 or less. As a result, excellent solubility of a hydroxyl group-containing polymer such as polyvinyl alcohol in an organic solvent is exhibited.
  • the lower limit of the degree of polymerization is not particularly limited, but is preferably 100 or more from the viewpoint of easy handling of the binder resin.
  • the degree of polymerization of the binder resin is determined as the number average degree of polymerization in terms of polystyrene in GPC (gel permeation chromatography) analysis.
  • the impurity diffusion composition according to the present invention preferably contains a solvent.
  • This solvent can be used without particular limitation, but is appropriately selected depending on a coating method such as a spin coating method, an ink jet method, a screen printing method or a roll coating printing method.
  • solvents include ketone solvents, ether solvents, ester solvents, ether acetate solvents, aprotic polar solvents, alcohol solvents, glycol monoether solvents, terpene solvents, water, and the like. . One of these may be used alone, or two or more of these may be used in combination.
  • ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, and methyl-n-hexyl.
  • Ketone diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, ⁇ -butyrolactone, ⁇ -valerolactone, etc. It is done.
  • ether solvents include diethyl ether, methyl ethyl ether, methyl-n-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di- n-Butyl Ete , Diethylene glycol methyl-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tri
  • ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, and acetic acid.
  • ether acetate solvents include ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol-n. -Butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate and the like.
  • aprotic polar solvent examples include acetonitrile, N-methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-dimethylsulfoxide and the like.
  • alcohol solvents examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methylbutanol.
  • glycol monoether solvent examples include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, Examples include ethoxy triglycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether.
  • terpene solvent examples include ⁇ -terpinene, ⁇ -terpineol, myrcene, alloocimene, limonene, dipentene, ⁇ -pinene, ⁇ -pinene, terpineol, carvone, osymene, and ferrandolene.
  • the content of the solvent in the impurity diffusion composition according to the present invention can be arbitrarily determined according to the viscosity of the impurity diffusion composition, but is preferably in the range of 1% by mass to 90% by mass.
  • the impurity diffusion composition according to the present invention may contain a surfactant.
  • a surfactant When the impurity diffusion composition contains a surfactant, uneven coating when the impurity diffusion composition is applied to the semiconductor substrate is improved, and as a result, a uniform coating film of the impurity diffusion composition film is obtained.
  • a fluorine-based surfactant or a silicone-based surfactant is preferably used.
  • the fluorosurfactant include a fluorosurfactant composed of a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain.
  • a fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl.
  • silicone surfactants examples include, for example, SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone), BYK067A, BYK310, BYK322, BYK331, BYK333, BYK355 (BIC Chemie Japan) Etc.).
  • the content of the surfactant in the impurity diffusion composition is preferably 0.0001 mass% or more and 1 mass% or less.
  • the impurity diffusion composition according to the present invention may contain a thickener for viscosity adjustment.
  • the thickener include organic type and inorganic type.
  • organic thickeners include cellulose, cellulose derivatives, starch, starch derivatives, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, polystyrene.
  • polyester resin synthetic rubber, natural rubber, polyacrylic acid, various acrylic resins, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, silicone oil, sodium alginate, xanthan gum polysaccharide, gellan gum polysaccharide, guar gum Polysaccharides, carrageenan polysaccharides, locust bean gum polysaccharides, carboxyvinyl polymers, hydrogenated castor oil, hydrogenated castor oil and fatty acid flax
  • a mixture with a wax, a special fatty acid, a polyethylene oxide, a mixture of a polyethylene oxide and an amide, a fatty acid polyvalent carboxylic acid, a phosphate ester surfactant, a salt of a long-chain polyaminoamide and phosphoric acid, Specially modified polyamide system is exemplified.
  • Inorganic thickeners include, for example, bentonite, montmorillonite, magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, beidellite, aluminiderite, sapphire, aluminian support stone, laponite, Examples thereof include aluminum silicate, aluminum magnesium silicate, organic hectorite, fine particle silicon oxide, colloidal alumina, and calcium carbonate. You may use these in combination of multiple types.
  • thixotropic agents that impart thixotropic properties include cellulose, cellulose derivatives, sodium alginate, xanthan gum polysaccharides, gellan gum polysaccharides, guar gum polysaccharides, carrageenan polysaccharides, locust beans.
  • a cellulose thickener there exist 11110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 2200, 2260, 2280, 2450, etc. by Daicel Finechem.
  • Commercially available polysaccharide thickeners include Viscalin PC209, Viscarin PC389, SeaKemXP8012, manufactured by FM Chemicals, CAM-H, GJ-182, SV-300, LS-20, LS-30, manufactured by Mitsubishi Corporation.
  • Hydroated castor oil thickener Commercially available products of hydrogenated castor oil thickener include Disparon 308 and NAMLONT-206 manufactured by Enomoto Kasei Co., Ltd., and T-20SF and T-75F manufactured by Ito Oil Co., Ltd.
  • commercially available products of polyethylene oxide thickeners include D-10A, D-120, D-120-10, D-1100, DS-525, DS-313 manufactured by Ito Oil Co., Ltd., and Disparon 4200 manufactured by Enomoto Kasei Co., Ltd.
  • amide type thickeners include T-250F, T-550F, T-850F, T-1700, T-1800, T-2000 manufactured by Ito Oil Co., Ltd., Dispalon 6500, 6300 manufactured by Enomoto Kasei Co., Ltd.
  • bentonite-based thickener Commercially available products of bentonite-based thickener include Hojun's Bengel, Bengel HV, HVP, F, FW, Bright 11, A, W-100, W-100U, W-300U. SH, Multiven, Esben, Esben C, E, W, P, WX, Organite, Organite D, and the like.
  • fine particle silicon oxide-based thickeners Nippon Aerosil Co., Ltd.
  • AEROSILR972, R974, NY50 RY200S, RY200, RX50, NAX50, RX200, RX300, VPNKC130, R805, R104, R711, OX50, 50, 90G, 130, 200, 300, 380, WACKER HDK S13, V15, N20, N20P, T30, T40, manufactured by Asahi Kasei Corporation H15, H18, H20, H30, etc.
  • polyethylene glycol polyethylene oxide, polypropylene glycol, polypropylene oxide, and various acrylic ester resins are preferable from the viewpoint of degradability.
  • polyethylene oxide, polypropylene oxide, or acrylic ester resin is more preferable, and polyethylene oxide is particularly preferable.
  • acrylic ester resins include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, Examples thereof include polyacrylic acid esters such as polyhydroxyethyl methacrylate, polybenzyl methacrylate, and polyglycidyl methacrylate, and copolymers thereof.
  • the acrylic ester resin is a copolymer
  • the acrylic ester component may be 60 mol% or more as a polymerization ratio, and other copolymerizable components such as polyacrylic acid and polystyrene can be polymerized with vinyl.
  • the components may be copolymerized.
  • polyethylene oxide and polypropylene oxide these two types of copolymers are also preferred. Any of acrylic ester resins, polyethylene oxide, and polypropylene oxide having a weight average molecular weight of 100,000 or more is preferable because the thickening effect is high.
  • the content of the thickener in the impurity diffusion composition is preferably in the range of 1% by mass to 20% by mass.
  • the viscosity of the impurity diffusion composition according to the present invention is not particularly limited, and can be appropriately changed according to the application method or film thickness of the impurity diffusion composition.
  • the viscosity of the impurity diffusion composition is preferably 100 [mPa ⁇ s] or less.
  • the viscosity of an impurity diffusion composition is 5,000 [mPa * s] or more and 100,000 [mPa * s] or less.
  • the viscosity when the viscosity is less than 1,000 [mPa ⁇ s], it is a value measured at a rotation speed of 20 rpm using an E-type digital viscometer based on JIS Z8803 (1991) “Solution Viscosity—Measurement Method”.
  • the viscosity is 1,000 [mPa ⁇ s] or more, the viscosity is a value measured at a rotational speed of 20 rpm using a B-type digital viscometer based on JIS Z8803 (1991) “Solution Viscosity—Measurement Method”.
  • the solid content concentration of the impurity diffusion composition according to the present invention is not particularly limited, but is preferably 1% by mass or more and 90% by mass or less. When the solid content concentration of the impurity diffusion composition is in the above range, the diffusibility and storage stability of the impurity diffusion composition are good.
  • a method for manufacturing a semiconductor device using the impurity diffusion composition according to the present invention uses a method for forming an impurity diffusion layer using an impurity diffusion composition containing polysiloxane (A) and an impurity diffusion component (B). is there.
  • a manufacturing method of such a semiconductor element includes a film forming step of forming the impurity diffusion composition film on the semiconductor substrate by applying the impurity diffusion composition described above, and the impurity diffusion composition film into the semiconductor substrate. And a layer forming step of diffusing the impurity diffusion component (B) to form an impurity diffusion layer.
  • a semiconductor device manufacturing method includes the above-described film formation step, and the impurity diffusion composition film on the semiconductor substrate is irradiated with laser light, and the impurity diffusion composition film is used. And a layer forming step of diffusing the impurity diffusion component (B) in the semiconductor substrate to form an impurity diffusion layer.
  • a part of the impurity diffusion composition film is formed by irradiating a part of the impurity diffusion composition film formed on the semiconductor substrate with the above film formation step.
  • FIG. 1A is a diagram showing an example of a method for manufacturing a semiconductor element according to an embodiment of the present invention.
  • the manufacturing method applied when manufacturing the semiconductor element for back junction type solar cells is illustrated.
  • a semiconductor element for a back junction solar cell a p-type impurity diffusion layer and an n-type impurity diffusion layer are formed on the back surface that is the surface opposite to the light receiving surface of the solar cell.
  • a first film forming step (step ST101) is performed.
  • the first conductivity type impurity diffusion composition in the present invention is applied onto a predetermined surface of the semiconductor substrate 1 (the back surface in the solar cell).
  • the impurity diffusion composition film 2 is formed on the predetermined surface of the semiconductor substrate 1.
  • the impurity diffusion composition film 2 is a first conductivity type impurity diffusion composition film having a predetermined conductivity type (n-type or p-type).
  • the first conductivity type impurity diffusion composition is an impurity diffusion composition containing the above-described polysiloxane (A) and the first conductivity type impurity diffusion component (B-1).
  • the first conductivity type impurity diffusion component (B-1) is an embodiment of the impurity diffusion component (B) described above (for example, a compound containing a group 13 element or a group 15 element), and the second conductivity type impurity described later. It has a conductivity type different from that of the diffusion component (B-2).
  • the semiconductor substrate 1 for example, n-type single crystal silicon having an impurity concentration of 10 15 to 10 16 [atoms / cm 3 ], polycrystalline silicon, and other elements such as germanium and carbon are mixed.
  • An example is a crystalline silicon substrate.
  • p-type crystalline silicon or a semiconductor substrate other than silicon can be used.
  • the semiconductor substrate 1 preferably has a thickness of 50 [ ⁇ m] to 300 [ ⁇ m] and an outer shape of a substantially square shape with sides of 100 [ ⁇ m] to 250 [ ⁇ m]. Further, in order to remove slice damage and natural oxide film on each surface of the semiconductor substrate 1, it is preferable to etch each surface of the semiconductor substrate 1 with a hydrofluoric acid solution or an alkaline solution.
  • a protective film may be formed on the light receiving surface of the semiconductor substrate 1 (the surface opposite to the surface on which the impurity diffusion composition film 2 is formed).
  • This protective film can be formed by a technique such as CVD (chemical vapor deposition) or spin-on-glass (SOG).
  • CVD chemical vapor deposition
  • SOG spin-on-glass
  • a known protective film such as silicon oxide or silicon nitride can be applied as the protective film.
  • the coating method of the first conductivity type impurity diffusion composition applied to the step ST101 examples include spin coating, screen printing, ink jet printing, slit coating, letterpress printing, and intaglio printing.
  • the impurity diffusion composition film 2 is in the range of 50 ° C. to 200 ° C. with a hot plate, oven, IR heater or the like. It is preferable to dry for 1 second to 30 minutes.
  • the film thickness of the impurity diffusion composition film 2 after drying is preferably 200 [nm] or more and 5 [ ⁇ m] or less in consideration of the diffusibility of the impurity diffusion component (B-1) into the semiconductor substrate 1. .
  • a first layer forming step (step ST102) is performed as shown in FIG. 1A.
  • the impurity diffusion component (B-1) is diffused from the impurity diffusion composition film 2 into the semiconductor substrate 1, thereby forming the impurity diffusion layer 3 in the semiconductor substrate 1.
  • the impurity diffusion layer 3 is a first conductivity type impurity diffusion layer having the same conductivity type as the impurity diffusion composition film 2.
  • the impurity diffusion composition film 2 is irradiated with the laser beam 10 to diffuse the impurity diffusion component (B-1) from the impurity diffusion composition film 2 into the semiconductor substrate 1.
  • a target portion for example, a portion forming a desired pattern
  • the impurity diffusion component (B-1) in the impurity diffusion composition film 2 is partially diffused (in a desired pattern) into the semiconductor substrate 1 by heating by the irradiation of the laser beam 10 (hereinafter referred to as “laser heating”).
  • laser heating the impurity diffusion layer 3 is formed in a desired pattern in the semiconductor substrate 1.
  • the portion where the impurity diffusion layer 3 is formed by laser heating may be lost by ablation or remains without being lost. May be.
  • the laser beam 10 used for the laser heating is not particularly limited, and a known one can be used.
  • a fundamental wave (1064 [nm]), a second harmonic (532 [nm]), a third harmonic (355 [nm]), or a XeCl excimer of an Nd: YAG laser or an Nd: YVO 4 laser is used.
  • Laser light such as laser (308 [nm]), KrF excimer laser (248 [nm]), ArF excimer laser (198 [nm]) can be used.
  • the energy density of the laser beam 10 is preferably 0.25 [J / cm 2 ] or more and 25 [J / cm 2 ] or less.
  • the diffusion time of the impurity diffusion component (impurity diffusion component (B-1) in step ST102) by laser heating is appropriately set so as to obtain desired diffusion characteristics such as the concentration and diffusion depth of the target impurity diffusion component. be able to.
  • the concentration of the impurity diffusion component on the semiconductor substrate surface is preferably such that an impurity diffusion layer of 10 19 to 10 21 [atoms / cm 3 ] can be formed.
  • the diffusion atmosphere of the impurity diffusion component by laser heating is not particularly limited and may be the same atmosphere as the atmosphere, or an atmosphere in which the amount of oxygen in the atmosphere is appropriately controlled using an inert gas such as nitrogen or argon It may be.
  • a first removal step (step ST103) is performed as shown in FIG. 1A.
  • the impurity diffusion composition film 2 remaining on the semiconductor substrate 1 is removed using a cleaning liquid.
  • a portion of the impurity diffusion composition film 2 that has not been irradiated with the laser beam 10 remains on the semiconductor substrate 1.
  • a cleaning liquid for example, a known acid or alkali cleaning solution such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, TMAH or KOH can be used.
  • an alkaline cleaning liquid such as TMAH or KOH.
  • step ST104 a second film formation step is performed as shown in FIG. 1A.
  • the second conductivity type impurity diffusion composition according to the present invention is applied onto a predetermined surface of the semiconductor substrate 1.
  • the impurity diffusion composition film 4 is formed on the predetermined surface of the semiconductor substrate 1.
  • the application method of the second conductivity type impurity diffusion composition is not particularly limited, and a known application method similar to the method of applying the first conductivity type impurity diffusion composition in step ST101 described above may be used. it can.
  • the impurity diffusion composition film 4 is a second conductivity type impurity diffusion composition film having a conductivity type different from the conductivity type (first conductivity type) of the impurity diffusion composition film 2 described above.
  • the second conductivity type impurity diffusion composition is an impurity diffusion composition containing the above-described polysiloxane (A) and the second conductivity type impurity diffusion component (B-2).
  • the second conductivity type impurity diffusion component (B-2) is an embodiment of the impurity diffusion component (B) described above (for example, a compound containing a group 13 element or a group 15 element). It has a conductivity type different from that of the diffusion component (B-1).
  • the impurity diffusion composition film 4 after forming the impurity diffusion composition film 4 as in the above-described step ST101.
  • the film thickness of the impurity diffusion composition film 4 after drying is set in consideration of, for example, the diffusibility of the impurity diffusion component (B-2) into the semiconductor substrate 1.
  • a second layer forming step (step ST105) is performed as shown in FIG. 1A.
  • the impurity diffusion component (B-2) is diffused from the impurity diffusion composition film 4 into the semiconductor substrate 1, thereby forming the impurity diffusion layer 5 in the semiconductor substrate 1.
  • the impurity diffusion layer 5 is a second conductivity type impurity diffusion layer having the same conductivity type as the impurity diffusion composition film 4. That is, the conductivity type (second conductivity type) of the impurity diffusion layer 5 is different from the conductivity type (first conductivity type) of the impurity diffusion layer 3 already formed.
  • the impurity diffusion composition film 4 is irradiated with laser light 10 to diffuse the impurity diffusion component (B-2) from the impurity diffusion composition film 4 into the semiconductor substrate 1.
  • a target portion of the impurity diffusion composition film 4 (for example, a portion other than the impurity diffusion layer 3 and forming a desired pattern) is irradiated with the laser beam 10, and the target portion is Heat with laser.
  • the impurity diffusion component (B-2) in the impurity diffusion composition film 4 is partially diffused (in a desired pattern) into the semiconductor substrate 1.
  • the impurity diffusion layer 5 is formed in a desired pattern in the semiconductor substrate 1.
  • the portion where the impurity diffusion layer 5 is formed by laser heating may be lost by ablation or remains without being lost. May be.
  • the laser beam 10 used for the laser heating is not particularly limited, and is a known method similar to the method of laser heating the first conductivity type impurity diffusion composition (impurity diffusion composition film 2) in the above-described step ST102. Things can be used.
  • the diffusion time of the impurity diffusion component by laser heating is appropriately set so as to obtain desired diffusion characteristics such as the concentration and diffusion depth of the target impurity diffusion component. be able to.
  • the concentration of the impurity diffusion component on the semiconductor substrate surface is preferably such that an impurity diffusion layer of 10 19 to 10 21 [atoms / cm 3 ] can be formed.
  • the diffusion atmosphere of the impurity diffusion component by laser heating is not particularly limited and may be the same atmosphere as the atmosphere, or an atmosphere in which the amount of oxygen in the atmosphere is appropriately controlled using an inert gas such as nitrogen or argon It may be.
  • a second removal step is performed as shown in FIG. 1A.
  • the impurity diffusion composition film 4 remaining on the semiconductor substrate 1 is removed using a cleaning liquid.
  • the laser non-irradiated portion of the impurity diffusion composition film 4 remains on the semiconductor substrate 1.
  • a cleaning liquid for example, a known acid or alkali cleaning solution such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, TMAH or KOH can be used.
  • an alkaline cleaning liquid such as TMAH or KOH.
  • the semiconductor element 15 according to this embodiment is manufactured by sequentially performing the above-described steps ST101 to ST106.
  • the semiconductor element 15 is suitable as a semiconductor element for a back junction solar cell.
  • FIG. 1B is a diagram showing an example of a method for manufacturing a solar cell using a semiconductor element according to an embodiment of the present invention.
  • FIG. 1B illustrates a process after the manufacture of the semiconductor element 15 (see FIG. 1A) used for manufacturing the solar cell according to the present embodiment.
  • the method for manufacturing a solar cell according to this embodiment includes the method for manufacturing the semiconductor element 15 shown in FIG. 1A. That is, after manufacturing the semiconductor element 15 as described above, the solar cell (back junction solar cell) in the present embodiment can be manufactured using a known method.
  • a protective film forming step is performed as shown in FIG. 1B following the manufacturing step of the semiconductor element 15 shown in FIG. 1A.
  • the protective film 6 is formed on the back surface of the semiconductor substrate 1.
  • the back surface of the semiconductor substrate 1 is the surface opposite to the light receiving surface of the semiconductor element 15 (the lower surface in FIG. 1B), and is the surface on which the impurity diffusion layers 3 and 5 having different conductivity types are formed. It is.
  • the protective film 6 is formed on the entire back surface of the semiconductor substrate 1.
  • the protective film 6 include a laminate of a thermal oxide layer, an aluminum oxide layer, a SiNx layer, and an amorphous silicon layer.
  • vapor deposition methods such as a plasma CVD method and ALD (atomic layer deposition) method, or the apply
  • step ST202 a pattern processing step is performed as shown in FIG. 1B.
  • the protective film 6 on the back surface of the semiconductor substrate 1 is processed into a desired pattern (pattern processing) by an etching method or the like.
  • a plurality of openings 6 a are formed in the protective film 6.
  • Each of the plurality of openings 6 a is for exposing the impurity diffusion layers 3 and 5 formed in the semiconductor substrate 1 in a discrete manner.
  • step ST203 an electrode formation step (step ST203) is performed as shown in FIG. 1B.
  • an electrode paste is applied in a pattern to each region including the opening 6a of the protective film 6 on the back surface of the semiconductor substrate 1 by a method such as a stripe coating method or a screen printing method, and the applied electrode paste is applied. Bake.
  • contact electrodes 7 and 8 are formed in the respective regions of the semiconductor substrate 1.
  • one contact electrode 7 is a first conductivity type contact electrode connected to the first conductivity type impurity diffusion layer 3.
  • the other contact electrode 8 is a second conductivity type contact electrode connected to the second conductivity type impurity diffusion layer 5.
  • first conductivity type and “second conductivity type” are different conductivity types, one representing p-type and the other representing n-type.
  • first conductivity type is p-type
  • second conductivity type is n-type.
  • the impurity diffusion composition according to the present invention and the method for manufacturing a semiconductor device using the same are not limited to the above-described embodiments, and various modifications such as design changes may be added based on the knowledge of those skilled in the art. An embodiment to which such a modification is possible is also included in the scope of the present invention.
  • the impurity diffusion composition according to the present invention is a photovoltaic device such as a solar cell, or a semiconductor device in which an impurity diffusion layer is patterned on the surface of a semiconductor substrate, such as a transistor array, a diode array, a photodiode array, or a transducer. Etc.
  • the sheet resistance value evaluation is for evaluating the sheet resistance value (also referred to as surface resistivity) of the impurity diffusion layer in the semiconductor substrate.
  • the semiconductor substrate for evaluation was an n-type silicon wafer (Ferrotech Silicon Co., Ltd., surface resistivity 410 [ ⁇ / ⁇ ]) cut to 3 cm ⁇ 3 cm. This silicon wafer was immersed in a 1% hydrofluoric acid aqueous solution for 5 minutes, washed with water, air blown, and then heat treated at 100 ° C. for 5 minutes with a hot plate.
  • the impurity diffusion composition to be measured is applied to a silicon wafer for evaluation by a known spin coating method so that the prebaked film thickness is about 400 nm, and the impurity diffusion to be measured is spread on the silicon wafer surface.
  • a coating film of the composition (that is, an impurity diffusion composition film) was formed.
  • this silicon wafer was pre-baked at 140 ° C. for 3 minutes.
  • the pre-baked film thickness (film thickness after pre-baking) of the impurity diffusion composition film on the silicon wafer surface was measured with a surface shape measuring device (Surfcom 1400, manufactured by Tokyo Seimitsu Co., Ltd.).
  • each silicon wafer on which the impurity diffusion composition film is formed by the above-described method is irradiated with a predetermined laser beam in a range of 1 cm ⁇ 1 cm to diffuse the impurities in the impurity diffusion composition film into each silicon wafer.
  • Component (B) was thermally diffused.
  • the laser beam was an Nd: YVO 4 laser.
  • the wavelength was 355 [nm]
  • the pulse width was 25 [ns]
  • the frequency was 20 [kHz].
  • the laser output was 1 [W].
  • the spot shape was a rectangle of 40 [ ⁇ m].
  • the scan speed was 3000 [mm / s].
  • each silicon wafer was immersed in a 1% by mass TMAH aqueous solution at 23 ° C. for 10 minutes. Thereby, the impurity diffusion composition film (diffusion agent) cured by the laser beam irradiation was peeled off.
  • Each silicon wafer after the film is peeled is subjected to p / n determination using a p / n determiner, and the surface resistance of the diffusion portion of the impurity diffusion component (B) in each silicon wafer is determined by four probes.
  • a sheet resistance value was measured using a type surface resistance measuring device (RT-70V, manufactured by Napson Corporation). The sheet resistance value is an index of the diffusibility of the impurity diffusion component (B) in the semiconductor substrate.
  • a smaller sheet resistance value means a larger diffusion amount of the impurity diffusion component (B).
  • Detergent evaluation of the dry film evaluates the detergency of the impurity diffusion composition film (dry film) remaining in a dry state on the semiconductor substrate surface after the thermal diffusion of the impurity diffusion component (B) by laser light irradiation. It is.
  • the semiconductor substrate for evaluation was an n-type silicon wafer (Ferrotech Silicon Co., Ltd., surface resistivity 410 [ ⁇ / ⁇ ]) cut to 3 cm ⁇ 3 cm. This silicon wafer was immersed in a 1% hydrofluoric acid aqueous solution for 5 minutes, washed with water, air blown, and then heat treated at 100 ° C. for 5 minutes with a hot plate.
  • the impurity diffusion composition to be measured is applied to a silicon wafer for evaluation by a known spin coating method so that the prebaked film thickness is about 400 nm, and the impurity diffusion to be measured is spread on the silicon wafer surface. A composition film was formed. Subsequently, this silicon wafer was pre-baked at 140 ° C. for 3 minutes. Thereby, the impurity diffusion composition film to be measured was used as the dry film (pre-baked film). Thereafter, the silicon wafer was immersed in a cleaning solution, and the time until the prebaked film on the silicon wafer surface was dissolved was measured.
  • Example 1 the polysiloxane (A) was synthesized as follows, and the impurity diffusion composition containing the obtained polysiloxane (A) was evaluated for sheet resistance and dry film detergency. .
  • polysiloxane (A) of Example 1 15.73 g (0.06 mol) of 3-trimethoxysilylpropyl succinic acid and 155.29 g (1.14 mol) of methyltrimethoxy were added to a 500 mL three-necked flask. Silane and 192.29 g of propylene glycol monomethyl ether were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.5 g of formic acid in 64.0 g of water was added over 30 minutes while stirring at 40 ° C. After completion of dropping, the resulting solution was stirred at 40 ° C. for 1 hour, then heated to 70 ° C. and stirred for 30 minutes.
  • the temperature of the oil bath was raised to 115 ° C.
  • the internal temperature of this solution reached 100 ° C., and from this time, this solution was heated and stirred (internal temperature was 100 ° C. to 110 ° C.).
  • the solution thus obtained was cooled in an ice bath to obtain a polysiloxane solution.
  • the obtained polysiloxane solution had a solid content concentration of 42.0% by mass. From this polysiloxane solution, the polysiloxane (A) of Example 1 was obtained.
  • the impurity diffusion composition of Example 1 was adjusted with the composition ratio, molar ratio, and content of each composition described in Table 1 described later. Evaluation of the sheet resistance value of Example 1 and evaluation of the cleaning property of the dry film were performed on the impurity diffusion composition of Example 1. As a result, as shown in Table 2 described later, a good value (that is, good diffusibility of the impurity diffusion component (B) (hereinafter referred to as “impurity diffusibility”)) is obtained in the sheet resistance value evaluation, and the detergency evaluation It was excellent.
  • impurity diffusibility good diffusibility of the impurity diffusion component
  • Example 2 to 8 In Examples 2 to 8, as in Example 1 described above, polysiloxane (A) was synthesized at the ratio of the organosilane compound described in Table 1, and the composition ratio, molar ratio, and ratio of each composition described in Table 1 were synthesized.
  • the impurity diffusion compositions of Examples 2 to 8 were adjusted according to the content.
  • sheet resistance value evaluation and dry film detergency evaluation were performed. As a result, as shown in Table 2, in each of Examples 2 to 8, both the sheet resistance value (impurity diffusibility) and the cleaning property evaluation were good.
  • the content ratio (molar ratio) of the organosilane having at least one of a carboxyl group and a dicarboxylic anhydride structure in the polysiloxane (A) is a Si atom mole of the entire polysiloxane (A) derived from the organosilane.
  • the impurity diffusibility was good and the detergency evaluation was excellent.
  • Example 9 In Example 9, “X-22-3701E” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the polysiloxane (A) having a carboxyl group. The polysiloxane (A) (8 g), phosphoric acid (6 g), BYK333 (0.03 g), and propylene glycol monomethyl ether (85.97 g) were mixed to obtain the impurity diffusion composition of Example 9. It was adjusted. In Example 9, with respect to the impurity diffusion composition thus obtained, sheet resistance evaluation and dry film detergency evaluation were performed. As a result, as shown in Table 2, a good value (good impurity diffusibility) was obtained in the sheet resistance value evaluation, and the detergency evaluation was good.
  • the content ratio of the component derived from the organosilane having a carboxyl group in the polysiloxane “X-22-3701E” of Example 9 is the entire polysiloxane derived from the organosilane.
  • the Si atom mole ratio relative to the number of moles of Si atoms is less than 5 mol%.
  • Comparative Example 1 In Comparative Example 1, in the same manner as in Example 1 described above, polysiloxane was synthesized at the ratio of the organosilane compound described in Table 1, and the composition ratio, molar ratio, and content of each composition described in Table 1 were compared. 1 impurity diffusion composition was prepared. The sheet resistance value evaluation of Comparative Example 1 and the cleaning property evaluation of the dried film were performed on the impurity diffusion composition of Comparative Example 1 obtained as described above. As a result, as shown in Table 2, the sheet resistance value (impurity diffusibility) was good, but the detergency evaluation was bad.
  • the impurity diffusion composition according to the present invention and the method for manufacturing a semiconductor device using the same are as follows. Impurity diffusibility with respect to a semiconductor substrate and cleaning performance of an impurity diffusion composition film remaining on the semiconductor substrate after impurity diffusion. It is suitable for improving both.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La composition de diffusion d'impuretés selon un mode de réalisation est destinée à diffuser un composant de diffusion d'impuretés conductrices désiré dans un substrat semi-conducteur. La composition de diffusion d'impuretés contient un polysiloxane (A) et un composant de diffusion d'impuretés (B). Le polysiloxane (A) contient un groupe carboxyle et/ou une structure d'anhydride d'acide dicarboxylique. La composition de diffusion d'impuretés est destinée à être utilisée dans un procédé de production d'éléments semi-conducteurs et est particulièrement appropriée pour être utilisée dans la production de cellules solaires.
PCT/JP2017/026150 2016-07-29 2017-07-19 Composition de diffusion d'impuretés et procédé de production d'éléments semi-conducteurs utilisant la composition de diffusion d'impuretés WO2018021121A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017538732A JPWO2018021121A1 (ja) 2016-07-29 2017-07-19 不純物拡散組成物およびこれを用いた半導体素子の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-149356 2016-07-29
JP2016149356 2016-07-29

Publications (1)

Publication Number Publication Date
WO2018021121A1 true WO2018021121A1 (fr) 2018-02-01

Family

ID=61016188

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/026150 WO2018021121A1 (fr) 2016-07-29 2017-07-19 Composition de diffusion d'impuretés et procédé de production d'éléments semi-conducteurs utilisant la composition de diffusion d'impuretés

Country Status (3)

Country Link
JP (1) JPWO2018021121A1 (fr)
TW (1) TW201829625A (fr)
WO (1) WO2018021121A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002539615A (ja) * 1999-03-11 2002-11-19 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング 半導体にｐ、ｐ＋およびｎ、ｎ＋領域を形成するためのドーパント・ペースト
JP2009238824A (ja) * 2008-03-26 2009-10-15 Tokyo Ohka Kogyo Co Ltd 半導体用電極の製造方法及びこれを用いた太陽電池
JP2014168026A (ja) * 2012-03-07 2014-09-11 Toray Ind Inc マスクペースト組成物、これを用いて得られる半導体素子および半導体素子の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002539615A (ja) * 1999-03-11 2002-11-19 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング 半導体にｐ、ｐ＋およびｎ、ｎ＋領域を形成するためのドーパント・ペースト
JP2009238824A (ja) * 2008-03-26 2009-10-15 Tokyo Ohka Kogyo Co Ltd 半導体用電極の製造方法及びこれを用いた太陽電池
JP2014168026A (ja) * 2012-03-07 2014-09-11 Toray Ind Inc マスクペースト組成物、これを用いて得られる半導体素子および半導体素子の製造方法

Also Published As

Publication number Publication date
JPWO2018021121A1 (ja) 2019-05-16
TW201829625A (zh) 2018-08-16

Similar Documents

Publication Publication Date Title
JP3821165B2 (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
KR100698391B1 (ko) 방사선 경화성 조성물, 그 보존방법, 경화막 형성방법,패턴 형성방법, 패턴 사용방법, 전자부품 및 광도파로
JP6361505B2 (ja) 不純物拡散組成物および半導体素子の製造方法
JP7459511B2 (ja) 半導体素子の製造方法、および、太陽電池の製造方法
JP2016195203A (ja) ｐ型不純物拡散組成物、それを用いた半導体素子の製造方法および太陽電池。
JP2017103379A (ja) 不純物拡散組成物、およびそれを用いた半導体素子の製造方法
WO2018021121A1 (fr) Composition de diffusion d'impuretés et procédé de production d'éléments semi-conducteurs utilisant la composition de diffusion d'impuretés
WO2016121641A1 (fr) Composition de diffusion d'impuretés, procédé de fabrication d'élément à semi-conducteur la mettant en œuvre, et cellule solaire
JP6772836B2 (ja) ｐ型不純物拡散組成物、それを用いた半導体素子の製造方法および太陽電池の製造方法
JP4600090B2 (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP3818307B2 (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP3801192B2 (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
WO2018021117A1 (fr) Procédé de production d'éléments semi-conducteurs et procédé de production de cellules solaires
JP2006091906A (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP3781049B2 (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP4655633B2 (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP2006091806A (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP2006257437A (ja) 放射線硬化性組成物及びその硬化膜、並びに、電子部品及び光導波路
JP2006091827A (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP2012242483A (ja) シリカ系感光性樹脂組成物、パターンを有するシリカ系絶縁被膜の形成方法及びそれを備える電子部品
JP2006091805A (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP2012222104A (ja) シリカ系被膜の形成方法及び電子部品
JP2006091818A (ja) 硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP2006195175A (ja) 放射線硬化性組成物、その保存方法、硬化膜形成方法、パターン形成方法、パターン使用方法、電子部品及び光導波路
JP2012159739A (ja) 感光性樹脂組成物、シリカ系被膜の形成方法及び電子部品

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2017538732

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 17834129

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17834129

Country of ref document: EP

Kind code of ref document: A1