JP5955545B2 - Mask material composition and method for forming impurity diffusion layer - Google Patents

Description

  The present invention relates to a mask material composition, a method for forming an impurity diffusion layer, and a solar cell.

  Conventionally, in the manufacture of solar cells, for example, when an N-type or P-type impurity diffusion layer is formed in a semiconductor substrate, a diffusing agent containing an N-type or P-type impurity diffusion component is patterned on the surface of the semiconductor substrate. The impurity diffusion component is diffused from the patterned diffusing agent to form an N-type or P-type impurity diffusion layer. Specifically, first, a thermal oxide film is 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 that is not masked with acid or alkali is etched, and the resist is removed to form a mask of the thermal oxide film. Subsequently, a diffusing agent containing an N-type or P-type impurity diffusing component is applied to form an impurity diffusing agent layer in a portion where the mask is opened. Thereafter, an impurity diffusion component in the impurity diffusing agent layer is diffused at a high temperature to form an N-type or P-type impurity diffusion layer.

  Regarding the manufacture of such a solar cell, Patent Document 1 discloses a masking paste used as a diffusion control mask. By using such a masking paste, fine patterning of the impurity diffusion region can be easily performed without using a complicated photolithography technique or the like, and a low-cost solar cell can be manufactured.

  In addition, semiconductor substrates used for solar cells are often not mirror-finished on the surface. Alternatively, a semiconductor substrate used for a solar cell is often provided with a textured portion having a fine concavo-convex structure on the surface in order to prevent reflection of light on the surface of the semiconductor substrate. For this reason, when a mask is formed on the surface of such a semiconductor substrate, the mask material may accumulate in the recesses, and the thickness of the mask in the recesses may increase. In that case, in the mask material of patent document 1, the crack generate | occur | produced in the part where the film thickness became large, and there existed a possibility that the diffusion protection performance of a mask material might be impaired by this. Moreover, in the mask material of patent document 1, the molecular weight of resin which comprises a mask material may increase with a time-dependent change. When the molecular weight of the resin increases, the properties such as the viscosity of the mask material change, and the coating stability may be reduced.

  On the other hand, the present inventors have proposed a mask material composition having high crack resistance and high coating stability in Patent Document 2. This mask material composition contains a siloxane resin having a bulky aryl group, and the aryl group imparts flexibility to the mask and suppresses an increase in the molecular weight of the siloxane resin due to changes over time. To improve resistance and application stability.

JP 2007-49079 A JP 2011-116953 A

  The above-described mask material composition is required to have less bleeding and spreading when selectively applied onto a semiconductor substrate in order to realize highly accurate patterning or finer patterning. On the other hand, as a result of intensive studies, the present inventors have recognized that there is room for improvement in the conventional mask material composition with respect to suppression of bleeding and spreading of the mask material composition applied on the semiconductor substrate. It reached.

  The present invention has been made based on such recognition by the inventor, and an object of the present invention is to provide a mask material that can be suitably used for a mask formed for diffusion protection when an impurity diffusion component is diffused into a semiconductor substrate. The object is to provide a composition, a method for forming an impurity diffusion layer using the mask material composition, and a solar cell.

［一般式（ａ１）中、Ｒ_１は単結合又は炭素数１〜５のアルキレン基であり、Ｒ_２は炭素数６〜２０のアリール基である。］

In order to solve the above problems, an aspect of the present invention is a mask material composition. This mask material composition is a mask material composition used for diffusion protection of impurity diffusion components to a semiconductor substrate, and includes a siloxane resin (A1) containing a structural unit (a1) represented by the general formula (a1); A surfactant (B) having a dimethylsiloxane structural unit (b1) represented by the general formula (b1) and an alkylene oxide structural unit (b2), and a solvent (C), and a surfactant ( B) is characterized by having a content of 5000 ppm or less and an abundance ratio of the dimethylsiloxane structural unit (b1) to the alkylene oxide structural unit (b2) being 35:65 to 99: 1.

[In General Formula (a1), R ₁ is a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₂ is an aryl group having 6 to 20 carbon atoms. ]

  According to this aspect, it is possible to provide a mask material composition that can be suitably used for a mask formed for diffusion protection when an impurity diffusion component is diffused into a semiconductor substrate.

  Another embodiment of the present invention is a method for forming an impurity diffusion layer. The method for forming an impurity diffusion layer includes a step of selectively applying the mask material composition of the above aspect to a semiconductor substrate, and using the mask material composition applied to the semiconductor substrate as a mask, an impurity diffusion component on the semiconductor substrate. And a diffusion step of selectively applying and diffusing.

  According to this aspect, the impurity diffusion layer can be formed with higher accuracy.

  Yet another embodiment of the present invention is a solar cell. This solar cell includes a semiconductor substrate having an impurity diffusion layer formed by the impurity diffusion layer forming method of the above aspect.

  According to this aspect, a more reliable solar cell can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the mask material composition which can be employ | adopted suitably for the mask formed for diffusion protection in the case of the diffusion of the impurity diffusion component to a semiconductor substrate, and formation of the impurity diffusion layer using the said mask material composition Methods and solar cells can be provided.

1A to 1F are process cross-sectional views for describing a method for manufacturing a solar cell including a method for forming an impurity diffusion layer according to an embodiment.

  Hereinafter, the present invention will be described based on preferred embodiments. The embodiments do not limit the invention but are exemplifications, and all features and combinations described in the embodiments are not necessarily essential to the invention.

  The mask material composition according to the present embodiment is a mask material composition used for diffusion protection of impurity diffusion components to a semiconductor substrate, and includes a siloxane resin (A), a surfactant (B), a solvent ( And C). Hereinafter, each component will be described in detail.

<Siloxane resin (A)>
Siloxane resin (A) is resin which comprises a mask material main body. The mask material composition according to the present embodiment includes, as the siloxane resin (A), a siloxane containing a structural unit represented by the following general formula (a1) (hereinafter, this structural unit is appropriately referred to as a structural unit (a1)). Resin (A1) is contained.

［一般式（ａ１）中、Ｒ_１は単結合又は炭素数１〜５のアルキレン基であり、Ｒ_２は炭素数６〜２０のアリール基である。］

[In General Formula (a1), R ₁ is a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₂ is an aryl group having 6 to 20 carbon atoms. ]

  Here, the “structural unit” means a monomer unit (monomer unit, unit) constituting a polymer compound (polymer, copolymer).

In general formula (a1), as the alkylene group having 1 to 5 carbon atoms of R ₁ , a linear alkylene group such as a methylene group, an ethylene group, an n-propylene group, and an n-butylene group, an isopropylene group, Examples include branched alkylene groups such as a t-butylene group. R ₁ is preferably a methylene group or an ethylene group.

In the general formula (a1), examples of the aryl group having 6 to 20 carbon atoms of R ₂ include a phenyl group, a naphthyl group, and an anthracenyl group. The aryl group may have a substituent such as an alkoxy group, a hydroxy group, a carboxy group, an imino group, and an amino group. R ₂ is preferably a phenyl group or a naphthyl group.

  Structural unit (as a specific example of a1, for example, a structural unit represented by the following formula (a1-1) (hereinafter, this structural unit will be referred to as the structural unit (a1-1) as appropriate), a formula (a1-2) ) (Hereinafter, this structural unit is referred to as a structural unit (a1-2) as appropriate), a structural unit represented by the following formula (a1-3) (hereinafter, this structural unit is appropriately referred to as a structural unit ( and a structural unit represented by the following formula (a1-4) (hereinafter, this structural unit is appropriately referred to as a structural unit (a1-4)), and the like.

  Further, the siloxane resin (A1) may include a structural unit represented by the following general formula (a2) (hereinafter, this structural unit is appropriately referred to as a structural unit (a2)).

［一般式（ａ２）中、Ｒ_３は、炭素数１〜２０の脂肪族炭化水素基である。］

[In General Formula (a2), R ₃ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]

In General Formula (a2), the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ₃ may have a substituent such as an alkoxy group, a hydroxy group, a carboxy group, an imino group, or an amino group. Further, the aliphatic hydrocarbon group may be either saturated or unsaturated. Examples of the saturated hydrocarbon group include a linear alkyl group such as a methyl group, an ethyl group, an n-butyl group, a hexyl group, an octyldecyl group, a dodecyl group, and an octadecyl group, an isopropyl group, and a t-butyl group. Examples thereof include a cyclic alkyl group such as a branched alkyl group, a cyclopentyl group, a cyclohexyl group, and a norbornyl group. Examples of the unsaturated hydrocarbon group include a propenyl group (allyl group), a butynyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group.

Specific examples of the structural unit (a2), methyl silsesquioxane monomer R ₃ is a methyl group, ethyl silsesquioxane monomer R ₃ is an ethyl group, a propyl silsesquioxane R ₃ is a propyl group Oki A sun monomer etc. are mentioned. Specific examples of the silsesquioxane resin that is a copolymer of the structural unit (a1) and the structural unit (a2) include those represented by the following formula (A1-1).

［式（Ａ１−１）中、ｊ：ｋは、１：９９〜９９：１の範囲である。］

[In the formula (A1-1), j: k is in the range of 1:99 to 99: 1. ]

  The copolymer of the structural unit (a1) and the structural unit (a2) has a copolymerization ratio of the structural unit (a1) of 50% or more, that is, j: k is 50:50 to 1:99. Moreover, it is more preferable that the copolymerization ratio of the structural unit (a1) is 70% or more, that is, j: k is 30:70 to 1:99.

  Further, the siloxane resin (A1) may include a structural unit represented by the following general formula (a3) (hereinafter, this structural unit is appropriately referred to as a structural unit (a3)).

［一般式（ａ３）中、Ｒ_４及びＲ_５は、炭素数６〜２０のアリール基、又は炭素数１〜２０の脂肪族炭化水素基である。］

[In General Formula (a3), R ₄ and R ₅ are an aryl group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]

In the general formula (a3), specific examples of the aryl group having 6 to 20 carbon atoms of R ₄ and R ₅ and the aliphatic hydrocarbon group having 1 to 20 carbon atoms include an aryl group having 6 to 20 carbon atoms of R ₂ And R _{3 is} the same as the aliphatic hydrocarbon group having 1 to 20 carbon atoms. In the structural unit (a3), R ₄ and R ₅ are preferably aryl groups having 6 to 20 carbon atoms.

  The mask material composition according to the present embodiment contains a siloxane resin (A1) containing the structural unit (a1). The aryl group contained in the structural unit (a1) has a bulky structure. Therefore, due to steric hindrance caused by the aryl group, bonding between adjacent structural units or adjacent polymers can be moderately suppressed. Further, when the mask is formed on the surface of the semiconductor substrate, the bulky aryl group is burned away by the thermosetting of the mask material composition, and a porous is formed in the mask. And, by this porous, volume shrinkage due to the bond between adjacent structural units or adjacent polymers (silanol dehydration condensation) is moderately suppressed. Therefore, the mask can be flexible by including the structural unit (a1). Thereby, even when the film thickness of the mask becomes large at the concave portion on the surface of the semiconductor substrate, it is possible to suppress the occurrence of cracks at the location. That is, the crack resistance of the mask can be improved.

  The structural unit (a1) has a structure in which a bulky aryl group is bonded to one of four bonds of silicon (Si). Therefore, for example, when compared with conventional spin-on-glass (SOG), the siloxane resin (A) constituting the mask is poor in reactivity, and therefore the change in molecular weight is small. Therefore, it can suppress that the molecular weight of a siloxane resin (A) increases with a time-dependent change. Thereby, it can suppress that characteristics, such as a viscosity of a mask material, change, can improve the crack tolerance of a mask, and can maintain favorable application | coating stability.

  The siloxane resin (A1) is preferably a silsesquioxane resin containing the structural unit (a1). Moreover, the silsesquioxane resin containing a structural unit (a1) and a structural unit (a2) may be sufficient. Since the silsesquioxane resin has a three-dimensional structure such as a cage structure, it is easy to form a three-dimensional network structure. Therefore, when the siloxane resin (A1) is a silsesquioxane resin, the crack resistance of the mask can be further enhanced as compared with other siloxane resins.

  Furthermore, the siloxane resin (A1) is preferably a silsesquioxane resin composed only of the structural unit (a1). In this case, since the ratio of the aryl group contained in the mask can be increased, the crack resistance of the mask can be improved, and the effect of improving the crack resistance by the silsesquioxane resin can also be obtained. As such a silsesquioxane resin, what is represented by the following general formula (A1-2) is mentioned, for example.

［一般式（Ａ１−２）中、Ｒ_６、Ｒ_８は単結合又は炭素数１〜５のアルキレン基であり、Ｒ_７、Ｒ_９はアリール基であり、Ｒ_６とＲ_７からなる有機基と、Ｒ_８とＲ_９とからなる有機基とは互いに同じでも異なってもよく、異なる場合、ｍ：ｎは１：９９〜９９：１の範囲である。］

[In General Formula (A1-2), R ₆ and R ₈ are a single bond or an alkylene group having 1 to 5 carbon atoms, R ₇ and R ₉ are aryl groups, and an organic group composed of R ₆ and R _7. And the organic group consisting of R ₈ and R ₉ may be the same as or different from each other, and if different, m: n is in the range of 1:99 to 99: 1. ]

  Specific examples of the silsesquioxane resin represented by the general formula (A1-2) include those represented by the following formula (A1-2a) (hereinafter, silsesquioxane resin (A1-2a) as appropriate) And those represented by the following formula (A1-2b) (hereinafter referred to as silsesquioxane resin (A1-2b) as appropriate).

  The mass average molecular weight of the siloxane resin (A1) is preferably 1000 to 30000, and more preferably 1500 to 10000. By setting the mass average molecular weight in such a range, good coating stability can be obtained.

  In addition, a mask material composition may contain the siloxane resin (A2) which does not contain a structural unit (a1) as a siloxane resin (A). Examples of the siloxane resin (A2) include a silsesquioxane resin composed only of the structural unit (a2), a siloxane resin composed only of the structural unit (a3), or a siloxane resin composed of the structural unit (a2) and the structural unit (a3). Etc.

  The resin concentration of the mask material composition is preferably 1 to 50%, and more preferably 5 to 40%. By setting the resin concentration within such a range, good coating stability can be obtained.

<Surfactant (B)>
The surfactant (B) has a dimethylsiloxane structural unit (b1) represented by the following general formula (b1).

  Moreover, surfactant (B) has an alkylene oxide structural unit (b2). The alkylene oxide structural unit (b2) includes at least one of an ethylene oxide (EO) structural unit and a propylene oxide (PO) structural unit. When the alkylene oxide structural unit (b2) includes an EO structural unit and a PO structural unit, the abundance ratio between the EO structural unit and the PO structural unit can be 1:99 to 99: 1.

  The abundance ratio of the dimethylsiloxane structural unit (b1) to the alkylene oxide structural unit (b2) in the surfactant (B) is 35:65 to 99: 1, and preferably 40:60 to 99: 1. By setting the abundance ratio of the dimethylsiloxane structural unit (b1) to 35 or more, bleeding and spreading of the mask material composition on the substrate can be suppressed.

  The surfactant is usually oriented at the gas-liquid interface and the solid-liquid interface of the mask material composition. The surfactant (B) in the present embodiment includes a dimethylsiloxane structural unit (b1) in the main skeleton (main chain). Therefore, when the surfactant (B) is applied on the silicon substrate, the dimethylsiloxane structural unit (b1) appears at the interface between the silicon substrate and the surfactant (B). As a result, the spread and spread of the mask material composition on the silicon substrate is suppressed.

  The mask material composition may contain other surfactant. Examples of other surfactants include anionic, cationic, and nonionic compounds, and nonionic surfactants are preferred from the viewpoint of reducing the risk of contamination with metal impurities.

  The content of the surfactant (B) in the mask material composition is 5000 ppm or less, preferably 50 to 5000 ppm, more preferably 500 to 5000 ppm. By setting the content of the surfactant (B) to 5000 ppm or less, the repelling and shrinkage of the mask material composition on the substrate can be suppressed.

<Solvent (C)>
The solvent (C) may be any solvent that can dissolve the siloxane resin (A) and the surfactant (B). Specific examples of the solvent (C) include alcohols such as methanol, ethanol, isopropyl alcohol and butanol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol dipropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, triethylene glycol mono Chill ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol monopropyl ether, propylene glycol dipropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, Glycol derivatives such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 3-pentanone, cyclohexa Non-ketones such as methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, octyl acetate, 2-ethylhexyl acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Esters such as monobutyl ether acetate, polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, ethylene carbonate, propylene carbonate, and aromatic hydrocarbons such as benzene, toluene, xylene And aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane. These may be used alone or in combination of two or more.

  Moreover, it is preferable that a solvent (C) contains the organic solvent (C1) whose boiling point is 100 degreeC or more. By containing the organic solvent (C1), drying of the mask material composition can be suppressed. Therefore, when the ink jet printing method is adopted for forming the mask pattern, it is possible to prevent clogging of the ink jet nozzle caused by drying of the mask material composition. Further, when the screen printing method is adopted for forming the mask pattern, it is possible to avoid the mask material composition from being dried and fixed on the printing plate. Therefore, a high-precision mask pattern can be formed on the semiconductor substrate by containing the organic solvent (C1) in the solvent (C). When the organic solvent (C1) is contained in the solvent (C), the organic solvent (C1) is preferably contained so as to be 10% by mass or more based on the total mass of the solvent (C).

  Specific examples of the organic solvent (C1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol. Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl- 3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, propyl propionate, isopropyl propionate, methyl-3-methoxypropionate Ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propyl Poxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, butyl acetate, isoamyl acetate, methyl acetoacetate, methyl lactate, ethyl lactate, benzyl methyl ether, benzyl ethyl ether, benzene, toluene Xylene, butanol, isobutanol, 3-methyl-3-methoxybutanol, hexanol, cyclohexanol and the like. These may be used alone or in combination of two or more.

  Moreover, it is preferable that a solvent (C) contains the organic solvent (C2) whose boiling point is 180 degreeC or more. By containing the organic solvent (C2), the drying of the mask material composition can be further suppressed. Therefore, when the inkjet printing method is adopted for forming the mask pattern, it is possible to more reliably prevent the clogging of the inkjet nozzle caused by the drying of the mask material composition. Further, when the screen printing method is adopted for forming the mask pattern, it is possible to more reliably avoid the mask material composition from being dried and fixed on the printing plate. Therefore, a highly accurate mask pattern can be formed with a semiconductor substrate by making the solvent (C) contain the organic solvent (C2). When the organic solvent (C2) is contained in the solvent (C), the organic solvent (C2) is preferably 1 to 60%, and preferably 5 to 50% with respect to the total mass of the mask material composition. Is more preferable, and it is further more preferable that it is 10 to 40%. By setting it in such a range, good coating stability can be obtained.

  Specific examples of the organic solvent (C2) include ethylene glycol, propylene glycol, hexylene glycol, propylene glycol diacetate, 1,3-butylene glycol diacetate, diethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, glycerin, benzyl alcohol, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3- Methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl Acetate, 4-methyl-4-methoxypentyl acetate, ethyl acetoacetate, butyl lactate, ethyl lactate Hexyl, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, .gamma.-butyrolactone, etc. terpineol and the like. These may be used alone or in combination of two or more.

<Others>
The concentration of the metal impurity contained in the mask material composition is preferably about 500 ppb or less, and more preferably about 100 ppb or less. Moreover, a mask material composition may contain a general thickener etc. as another additive.

<Method for forming impurity diffusion layer and method for producing solar cell>
With reference to FIGS. 1A to 1F, an example of a method for forming an impurity diffusion layer and a method for manufacturing a solar cell including a semiconductor substrate on which an impurity diffusion layer is formed by the method will be described. 1A to 1F are process cross-sectional views for describing a method for forming an impurity diffusion layer and a method for manufacturing a solar cell according to an embodiment.

  First, as shown in FIG. 1A, a mask material composition M according to the present embodiment is selectively applied onto an N-type semiconductor substrate 1 such as a silicon substrate. The mask material composition M is selectively applied to the surface of the semiconductor substrate 1 by an ink jet method to form a pattern. That is, patterning is performed by discharging the mask material composition M to a predetermined region of the semiconductor substrate 1 from an inkjet nozzle of a known inkjet discharge machine. As an inkjet discharger, a piezo-type discharger using a piezoelectric element (piezoelectric element) that deforms when a voltage is applied is used. Note that a thermal-type dispenser using bubbles generated by heating may be used. After forming the mask pattern, the mask material composition M is dried by baking.

  Next, as shown in FIG. 1B, with the mask material composition M applied onto the semiconductor substrate 1 as a mask, a diffusing agent composition 2 containing a P-type impurity diffusion component, and an N-type impurity A diffusing agent composition 3 containing a diffusing component is selectively applied onto the semiconductor substrate 1. The diffusing agent composition 2 and the diffusing agent composition 3 are prepared by a known method.

  Next, as shown in FIG. 1 (C), the semiconductor substrate 1 on which the diffusing agent composition 2 and the diffusing agent composition 3 are patterned is placed in a diffusion furnace such as an electric furnace, fired, and diffused. The P-type impurity diffusion component in the agent composition 2 and the N-type impurity diffusion component in the diffusing agent composition 3 are diffused from the surface of the semiconductor substrate 1 into the semiconductor substrate 1. Instead of the diffusion furnace, the semiconductor substrate 1 may be heated by conventional laser irradiation. In this way, the P-type impurity diffusion component diffuses into the semiconductor substrate 1 to form the P-type impurity diffusion layer 4, and the N-type impurity diffusion component diffuses into the semiconductor substrate 1, and N A type impurity diffusion layer 5 is formed.

  Next, as shown in FIG. 1D, the mask material composition M, the diffusing agent composition 2, and the diffusing agent composition 3 are removed using a release agent such as hydrofluoric acid.

  Next, as shown in FIG. 1E, a passivation layer 6 is formed on the surface of the semiconductor substrate 1 on which the P-type impurity diffusion layer 4 and the N-type impurity diffusion layer 5 are formed by thermal oxidation or the like. . Further, a textured portion having a fine concavo-convex structure is formed on the surface opposite to the surface on which the passivation layer 6 of the semiconductor substrate 1 is formed by a known method such as a wet etching method, and the reflection of sunlight is prevented thereon. A silicon nitride film 7 having an effect is formed.

  Next, as shown in FIG. 1F, the passivation layer 6 is selectively removed by a known photolithography method and etching method, and predetermined regions of the P-type impurity diffusion layer 4 and the N-type impurity diffusion layer 5 are obtained. A contact hole 6a is formed so that is exposed. Then, the contact hole 6a provided on the P-type impurity diffusion layer 4 is filled with a desired metal by, for example, an electrolytic plating method and an electroless plating method, and is electrically connected to the P-type impurity diffusion layer 4 8 is formed. Similarly, an electrode 9 electrically connected to the N-type impurity diffusion layer 5 is formed in the contact hole 6 a provided on the N-type impurity diffusion layer 5. Through the above steps, solar cell 10 according to the present embodiment can be manufactured.

  As described above, the mask agent composition according to the present embodiment has a siloxane resin (A1) containing the structural unit (a1), a dimethylsiloxane structural unit (b1), and an alkylene oxide structural unit (B2). A surfactant (B) and a solvent (C) are contained. And surfactant (B) content is 5000 ppm or less, and the abundance ratio of a dimethylsiloxane structural unit (b1) and an alkylene oxide structural unit (b2) is 35: 65-99: 1. Therefore, the inclusion of the dimethylsiloxane structural unit (b1) suppresses the spread and spread of the mask material composition while improving the crack resistance of the mask and maintaining good coating stability by including the structural unit (a1). can do. Therefore, the mask material composition according to the present embodiment can be suitably used for a mask formed at the time of diffusion protection of an impurity diffusion component to a semiconductor substrate.

  Further, when the impurity diffusion layer is formed using the mask material composition according to the present embodiment, the impurity diffusion layer can be formed with higher accuracy. When a semiconductor substrate on which an impurity diffusion layer is formed by such a method for forming an impurity diffusion layer is used for a solar cell, a more reliable solar cell can be obtained.

  The present invention is not limited to the above-described embodiments, and various modifications such as design changes can be added based on the knowledge of those skilled in the art, and the embodiments to which such modifications are added. Are also included in the scope of the present invention. A new embodiment generated by the combination of the above-described embodiment and the following modified example has the effects of the combined embodiment and modified example.

  For example, in the above-described embodiment, the mask material composition M is selectively applied to the semiconductor substrate 1 by the ink jet printing method. However, the spin coating method, the spray printing method, the roll coating printing method, the screen printing method, and the relief printing method are used. Other printing methods such as an intaglio printing method and an offset printing method may be employed.

  In the above-described embodiment, the mask material composition is used for manufacturing a solar cell. However, the present invention is not particularly limited thereto, and can be used for manufacturing various semiconductor devices on which semiconductor elements are mounted.

  Examples of the present invention will be described below. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

(Creation of mask material composition)
Examples 1 to 5, Comparative Examples 3 and 4: Siloxane resin (A) (product name “TOS-174H”, manufactured by Toray Fine Chemical Co., Ltd., silsesquioxane resin (A1-2b) as the main resin, and mass average (Molecular weight 4500) 25.0% by mass, alkylene oxide-modified polydimethylsiloxane 0.1% by mass (1000 ppm) as surfactant (B), and propylene glycol monomethyl ether (PGME) 36.9 as solvent (C) Mask material composition by mixing 37.5% by mass and 37.5% by mass of dipropylene glycol monomethyl ether (DPGME) (product name “MFDG”, manufactured by Nippon Emulsifier Co., Ltd.) and 0.5% of adhesive as an additive A product was made. Examples 1 to 5 are mask material compositions to which the surfactant (B) of the present embodiment is added. Comparative Examples 3 and 4 are different from the Examples in that the surfactant (B) in which the abundance ratio of the dimethylsiloxane structural unit (b1) and the alkylene oxide structural unit (b2) is out of the present embodiment is added. It is a composition.

  Comparative Example 1: 25.0% by mass of siloxane resin (A), 37.0% by mass of PGME as a solvent (C) and 37.5% by mass of DPGME, and 0.5% of an adhesive as an additive were mixed. A mask material composition was prepared. Comparative Example 1 is a mask material composition different from the Examples in that the surfactant (B) is not added.

  Comparative Example 2: Siloxane resin (A) 25.0% by mass, polyoxylene glycol alkyl ether 0.1% by mass (1000 ppm) as non-silicone surfactant as surfactant (B), solvent (C ) PGME 36.9% by mass and DPGME 37.5% by mass and an adhesive 0.5% as an additive were mixed to prepare a mask material composition. Comparative Example 2 is a mask material composition that is different from the Examples in that a non-silicon surfactant is added.

  Table 1 shows the abundance ratio of the dimethylsiloxane structural unit (b1) and the alkylene oxide structural unit (b2) in the surfactant (B) in each Example and each Comparative Example.

  In the alkylene oxide structural unit (b2), in Embodiment 1, the abundance ratio between the EO structural unit and the PO structural unit was 38: 0. In the second embodiment, the abundance ratio between the EO structural unit and the PO structural unit is set to 26: 0. In Embodiment 3, the abundance ratio between the EO structural unit and the PO structural unit is 20:20. In the fourth embodiment, the abundance ratio between the EO structural unit and the PO structural unit is 50:12. In the fifth embodiment, the abundance ratio between the EO structural unit and the PO structural unit is 40: 6. In Comparative Example 3, the abundance ratio between the EO structural unit and the PO structural unit was 43:43. In Comparative Example 4, the abundance ratio between the EO structural unit and the PO structural unit was 36:30.

(Printing of mask material composition)
The mask material composition of each Example and each Comparative Example was discharged onto a silicon wafer using an inkjet discharge machine (product name “MID-500C”, manufactured by Musashi Engineering Co., Ltd.), and a line-shaped mask was printed. The injection frequency was 8500 Hz, and the mask material composition was discharged from 7 nozzles of the inkjet discharger (bitmap 7 pixels). The set value of the line width was 420 μm. After forming the line mask, each silicon wafer was placed on a hot plate and dried at 200 ° C. for 1 minute.

(Measurement of line width)
Using an optical microscope, the line width (μm) before and after drying in the line-shaped mask of each example and each comparative example was measured. The term “before drying” refers to the time after the formation of the line-shaped mask and before placement on the hot plate. The line width was an average value of values measured at five locations on the line mask. Further, the error of the line width after drying with respect to the set value (420 μm) was calculated. The results of each example and each comparative example are shown in Table 1.

(Evaluation of addition amount of surfactant (B))
Mask material compositions of Examples 3-1 to 3-7 and Comparative Examples 5 and 6 in which the amount of addition of the surfactant (B) in the mask material composition of Example 3 described above was varied as shown in Table 2. A product was made. Note that Example 3-4 corresponds to Example 3 described above. A line-shaped mask having a line width set value of 420 μm was formed from the prepared mask material composition by the same method as described above. Then, using an optical microscope, the line width (μm) before and after drying in the line masks of Examples 3-1 to 3-7 and Comparative Examples 5 and 6 was measured, and the line after drying with respect to the set value (420 μm) The width error was calculated. The results of Examples 3-1 to 3-7 and Comparative Examples 5 and 6 are shown in Table 2.

  As shown in Table 1, in Examples 1 to 5, the error of the line width with respect to the set value was small as compared with Comparative Examples 1 to 4. From this, it was found that according to the mask material compositions of Examples 1 to 5 in which the abundance ratio of the dimethylsiloxane structural unit (b1) is 35 or more, bleeding and spreading when printed on a silicon wafer can be suppressed. . Therefore, the mask material composition of each example can be suitably employed in the ink jet printing method. In addition, Examples 1 to 3 and 5 had smaller errors than Example 4. From this, it was found that bleeding and spreading can be further suppressed when the abundance ratio of the dimethylsiloxane structural unit (b1) is 40 or more.

  Moreover, the board | substrate normally used for a solar cell has many unevenness | corrugations on the surface. For this reason, a mask material composition that shows repelling or shrinking on the substrate has a low follow-up property with respect to the unevenness, and there is a high possibility that the line shape of the mask cannot be maintained. Therefore, the mask material composition is required to have less bleeding and spreading on the substrate, and more than that, there is no need to repel or shrink on the substrate. On the other hand, in Examples 1 to 5, there was no difference in line width before and after drying. From this, it turned out that according to the mask material composition of Examples 1-5, the repelling and shrinkage | contraction of a mask on a board | substrate can be suppressed.

  Moreover, as shown in Table 2, Examples 3-1 to 3-7 had no difference in line width before and after drying, whereas Comparative Examples 5 and 6 had reduced line width after drying. This indicates that repelling and shrinking of the mask material composition did not occur in Examples 3-1 to 3-7, whereas repelling and shrinkage of the mask material composition occurred in Comparative Examples 5 and 6. From this, it was found that the repelling and shrinkage of the mask material composition can be suppressed when the content of the surfactant (B) is 5000 ppm or less. Further, in Examples 3-3 to 3-7, the error was smaller than in Examples 3-1 and 3-2. From this, it was found that bleeding and spreading can be further suppressed when the content of the surfactant (B) is 500 ppm or more.

  M mask material composition, 1 semiconductor substrate, 2, 3 diffusing agent composition, 4 P-type impurity diffusion layer, 5 N-type impurity diffusion layer, 6 passivation layer, 6a contact hole, 7 silicon nitride film, 8, 9 electrode, 10 Solar cell.

Claims (7)

A mask material composition used for diffusion protection of impurity diffusion components to a semiconductor substrate,
A siloxane resin (A1) containing the structural unit (a1) represented by the general formula (a1);
A surfactant (B) having a dimethylsiloxane structural unit (b1) represented by the general formula (b1) and an alkylene oxide structural unit (b2);
A solvent (C),
The surfactant (B) has a content of 5000 ppm or less, and the abundance ratio of the dimethylsiloxane structural unit (b1) to the alkylene oxide structural unit (b2) is 35:65 to 99: 1. A mask material composition.

[In General Formula (a1), R ₁ is a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₂ is an aryl group having 6 to 20 carbon atoms. ]

  The mask material composition according to claim 1, wherein the alkylene oxide structural unit (b2) includes at least one of an ethylene oxide structural unit and a propylene oxide structural unit.   The mask material composition according to claim 1 or 2, wherein the siloxane resin (A1) is a silsesquioxane resin composed only of the structural unit represented by the general formula (a1). The said silsesquioxane resin is a mask material composition of Claim 3 represented by general formula (A1-2).

[In General Formula (A1-2), R ₆ and R ₈ are a single bond or an alkylene group having 1 to 5 carbon atoms, R ₇ and R ₉ are aryl groups, and an organic group composed of R ₆ and R _7. And the organic group consisting of R ₈ and R ₉ may be the same as or different from each other, and if different, m: n is in the range of 1:99 to 99: 1. ]   The mask material composition according to any one of claims 1 to 4, wherein the solvent (C) contains an organic solvent (C1) having a boiling point of 100 ° C or higher.   The mask material composition according to any one of claims 1 to 5, wherein the solvent (C) contains an organic solvent (C2) having a boiling point of 180 ° C or higher. A step of selectively applying the mask material composition according to any one of claims 1 to 6 to a semiconductor substrate;
Using the mask material composition applied to the semiconductor substrate as a mask, a diffusion step of selectively applying and diffusing an impurity diffusion component to the semiconductor substrate; and
A method for forming an impurity diffusion layer, comprising:

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