TW201506086A - Mask paste composition, semiconductor element obtained using the same and method for producing semiconductor element - Google Patents

Abstract

The invention provides a mask paste composition excellent in preservation stability of a solution before curing, a patterning property when coating, a masking property in an impurity diffusion step after coating, and crack-resistance. A characteristic of the mask paste composition is: containing (a) a specific polysiloxane, (b) silica particles of an average particle diameter of 150 nm or less, and (c) a solvent of a boiling point of 130DEG C or higher. A weight-average molecular weight of (a) the polysiloxane is 1000 or more. The silica particles in a solid constituent of the composition range from 20 wt% to 70 wt%. A concentration of P, B, and Al in the entire composition is 20 ppm or less respectively.

Description

Mask slurry composition, semiconductor device obtained using the same, and method for manufacturing semiconductor device

The present invention relates to a mask paste composition for masking a non-doped region in a semiconductor substrate while diffusing a dopant. Further, there is a semiconductor element such as a cured film formed of a mask paste composition and a photoelectric conversion element in which impurities are patterned.

At present, in the manufacture of a solar cell, when an N-type or P-type doped layer is formed in a semiconductor substrate, solution coating of N-type or P is performed by a chemical vapor deposition (CVD) method or a doped paste. The dopant component is then diffused into the semiconductor substrate by thermal diffusion to form a doped layer. For example, when a doping paste is used, a thermal oxide film is first formed on the surface of the semiconductor substrate, and then a resist having a specific pattern is laminated on the thermal oxide film by photolithography. Next, the resist is used as a mask, and the thermal oxide film which is not covered by the resist is partially etched by an acid or a base, and the resist is peeled off to form a mask of the thermal oxide film. Next, an N-type or P-type doping paste is applied to adhere the slurry to the portion of the opening of the mask. Of course Thereafter, the doping component in the slurry is thermally diffused at 700 ° C to 1100 ° C to form an N-type or P-type doped layer.

In the production of such a solar cell, in recent years, it has been studied to form a fine patterning of the mask layer region by printing or the like without using the conventional photolithography technique as described in Patent Document 1. Solar cells are manufactured at low cost.

On the other hand, many semiconductor substrates used in solar cells do not have a mirror surface finish on their surfaces. When a mask is formed on the surface of such a semiconductor substrate, the mask material stays in the concave portion, and the thickness of the mask of the concave portion becomes large, and the cover of the convex portion is enlarged. The film thickness becomes smaller. Therefore, the thickness of the mask layer after coating becomes uneven, and as the mask paste, a material having a large film thickness range which is a difference between the upper limit of the film thickness and the lower limit of the film thickness which can be used is required. In particular, in the boundary portion of the mask layer region, the film thickness tends to be thin. Therefore, in terms of the fine pattern processability of the mask, it is required to have a film thickness of about 0.1 μm to 0.2 μm. Cover the curtain.

Patent Document 1 and Patent Document 2 propose a decane-based mask slurry. In addition, in the case of the patent document 3, it is proposed that the structure after baking is loosened by the functional group which disappears after baking, and the structure after baking is loose, and it is excellent in the crack-resistant property at the time of thick film formation.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-49079

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-194306

Patent Document 3: Japanese Patent Laid-Open No. 2011-116953

However, the mask slurry described in Patent Document 1 to Patent Document 2 exhibits a masking property in a film thickness of about 0.2 μm, but has poor crack resistance and poor film thickness. When the film is thickened, when the mask layer treated at a high temperature is cured or the dopant component is thermally diffused, there is a problem that the film is cracked and the mask property is lost.

Further, the mask slurry described in Patent Document 3 must be thickened in order to obtain the masking property, and the masking property cannot be obtained in the low film thickness region. In addition, there is a problem that crack resistance is not sufficient.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a mask slurry which is excellent in crack resistance and excellent in curtain covering properties. Specifically, it is an object of the present invention to provide a film thickness which is less likely to be cracked during calcination and thermal diffusion of a doping component in the case of thick film formation, and which is excellent in masking properties when filming is performed, and is practically applicable. Wide cover curtain.

In order to solve the above problems, the present invention has the following configuration. In other words, the composition of the mask slurry contains (a) a polysiloxane produced by reacting one or more kinds of organodecane represented by the formula (1), and (b) an average particle diameter of 150 nm. The following cerium oxide particles and (c) a solvent having a boiling point of 130 ° C or higher, wherein (a) the polyoxymethane has an average weight molecular weight of 1,000 or more, and the cerium oxide particles in the solid content of the composition are 20% by weight or more. 70% by weight or less, the concentration of P, B, and Al in all the compositions is 20 ppm or less: (R ¹ ) _n Si(OR ² ) _4-n (1)

(wherein R ¹ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms; and a plurality of R ^{1 's} may be the same R ² represents any of hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{2 's} may be the same or may be the same. Different; n means an integer from 0 to 3.)

The mask paste composition of the present invention has excellent crack resistance in a high-temperature process such as hardening and calcination, in the case of thermal diffusion of a dopant, and the cured film has excellent masking properties against a dopant. Therefore, the mask slurry has a feature that is resistant to a practical wide range of film thicknesses. In addition, the pattern precision at the time of pattern coating is also excellent, and the change of the characteristics at the time of long-term storage of the slurry is extremely small.

10‧‧‧Semiconductor substrate

12‧‧‧ mask pattern

14‧‧‧P type doping pattern

16‧‧‧N type doping pattern

18‧‧‧ Passivation film

20‧‧‧ nitride film

22‧‧‧Electrode

24‧‧‧P type impurity diffusion layer

26‧‧‧N type impurity diffusion layer

30‧‧‧Striped coating device

31‧‧‧Semiconductor substrate

32‧‧‧ platform

33‧‧‧Linear drive (X direction)

34‧‧‧Linear drive (Y direction)

35‧‧‧ bracket

36‧‧‧CCD camera

37‧‧‧ Height sensor

38‧‧‧Nozzles

40‧‧‧Semiconductor substrate

41‧‧‧Nozzles

42‧‧‧Spray outlet

43‧‧·Pulp

44‧‧‧Liquid beads

45‧‧‧Management

46‧‧‧pressure port

47‧‧‧Pulp supply port

1(1) to 1(6) are process diagrams showing an example of a method of manufacturing a semiconductor device using the mask paste composition of the present invention.

Fig. 2 is a perspective view showing a slit coating device used in the embodiment.

3 is a cross-sectional view showing a state in which a slurry is applied in a stripe shape by a slit coating device.

The mask slurry composition of the present invention contains (a) a polysiloxane produced by reacting one or more kinds of organodecane represented by the formula (1), and (b) an average particle diameter. It is a ceria particle of 150 nm or less, and (c) a solvent whose boiling point is 130 degreeC or more.

(R ¹ ) _n Si(OR ² ) _4-n (1)

In the formula, R ¹ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{1 's} may be the same or different different. R ² represents any of hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{2 's} may be the same or different. n represents an integer from 0 to 3.

By using polyoxyalkylene as a main component, it is also possible to suppress the disappearance of the mask layer due to oxidative decomposition during a high-temperature process such as thermal diffusion of the dopant. Further, by coexisting the cerium oxide particles, the masking property and the crack resistance of the dopant can be improved. Since the cerium oxide particles have a high crosslinking density, the masking property of the mask layer can be improved. Further, in the polyoxyalkylene component, a terminal which can carry out a crosslinking reaction accompanied by hydrolysis, such as a stanol group or an unreacted alkoxy group, is carried out, and a crosslinking reaction is carried out in a high-temperature process. At this time, deformation occurs due to volume shrinkage, and cracks occur when the deformation is large. On the other hand, the cross-linking density of cerium oxide particles is itself high, and it is difficult to cause volume shrinkage in a high-temperature process. Therefore, by coexisting the ceria particles, the aggregation of the deformation of the mask layer can be alleviated, and the crack resistance can be improved.

Further, the present invention must also contain a solvent having a boiling point of 130 ° C or higher. This is due to the following reasons. The polymerization catalyst of the polyoxyalkylene of the present invention preferably has a hydrocarbon acid as a catalyst. In this case, in order to prevent the catalyst component having an adverse effect on storage stability from remaining in the polyoxane, Must be removed by evaporation. Therefore, it must be in the aggregation The polymerization system is controlled to be higher than the boiling point of the catalyst during the process.

The reason why the hydrocarbon acid is preferably used as a catalyst is that the catalyst such as phosphoric acid or a metal salt thereof may be an ion source that hinders masking properties. Further, the slurry of the present application is applied to a substrate by using various coating devices, but it is also necessary to contain a solvent having a boiling point of 130 ° C or more in terms of suppressing precipitation of the slurry onto a nozzle, a plate, a pipe, a roll, or the like. . When only a solvent having a boiling point of less than 130 ° C is contained, the solid component of the portion of the slurry in the environment is precipitated in a short time, so that it is not dissolved by supplying a new slurry, and becomes a nozzle clogging, device contamination, and substrate. The cause of pollution.

The concentration of P, B and Al in the composition of the present invention must be 20 ppm or less, more preferably 1 ppm or less, and even more preferably 0.5 ppm or less. The lower the concentration, the higher the masking property, and the masking property is good even with a thin film thickness. P, B, and Al are common dopant components. If these components are present in a high concentration in the mask paste composition, these dopant components will thermally diffuse to the substrate side during thermal diffusion, which should be hidden. Part of the pollution, so it can not function as a mask layer.

In the present invention, the contents of P, B and Al are values measured by the following methods. P is a value measured by an inductively coupled plasma (ICP) mass spectrometry after decomposing an organic component of a sample by a known wet decomposition method; and B is a well-known oxygen by B The value measured by ICP emission spectrometry after decomposing the organic component of the sample by the flask combustion method, and the value measured by combustion ion chromatography for Al.

The cover slurry composition of the present invention preferably has an aryl group concentration of 6 to 15 in a solid content of 15% by weight or more. The reason is believed to be: in polyoxyalkylene The fluffy aryl group is introduced in advance to impart steric hindrance, and the cross-linking density of the polyoxyalkylene skeletons is reduced to a loose structure to further suppress cracking.

Here, the loose structure is a structure in which the crosslinking density is small and the degrees of freedom of the skeletons are high. The fluffy functional group may be an alkyl group, an alkenyl group or an alicyclic functional group in addition to a phenyl group, and an aromatic functional group is preferred in view of heat resistance. On the other hand, if the crosslink density of the polyoxyalkylene skeletons is small, there is a concern that the masking property is impaired, but the problem can be solved by introducing the cerium oxide particles as described above. In other words, in the present invention, by containing a specific amount of an aryl group in the polysiloxane, it is possible to suppress the occurrence of cracks in a high-temperature process, and to compensate for the inclusion by containing cerium oxide particles having excellent masking properties. The loosening of the structure by the phenyl group is accompanied by a reduction in the masking property, and at the same time, it satisfies excellent crack resistance and masking properties.

The upper limit of the concentration of the aryl group having a carbon number of 6 to 15 in the solid content is preferably 60% by weight or less, more preferably 50% by weight or less. Here, the aryl concentration refers to the concentration of the aryl body. For example, when 1-(p-hydroxyphenyl)ethyltrimethoxydecane is used as the monomer unit of the decane, the phenyl moiety (disubstituted) is represented. The concentration of the molecular weight is 76).

The aryl group concentration can be adjusted by the kind of the organic decane represented by the formula (1) and the amount of the reaction input thereof. Further, the aryl concentration of the mask paste composition obtains structural information about which functional group is contained in the composition by, for example, Si-NMR, H-NMR, infra-red (IR), or the like, and is utilized. The amount of each functional group is quantified by C-NMR or Raman spectroscopy, and can be estimated. High performance liquid chromatography (HPLC) by combination The aliquoting process is divided to improve the quantitativeness.

The alkyl group, the alkenyl group, and the aryl group in R ¹ of the formula (1) may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, and 3,3,3. -trifluoropropyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, [(3-ethyl-3-oxetanyl)methoxy]propane Base, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatopropyl. Specific examples of the alkenyl group include a vinyl group, a 3-propenyloxypropyl group, and a 3-methylpropenyloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a p-styryl group, a p-methoxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, and a 2-(p-hydroxyphenyl group). Ethyl, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl, naphthyl.

The alkyl group, the fluorenyl group and the aryl group in R ² of the formula (1) may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the mercapto group include an ethyl group. Specific examples of the aryl group include a phenyl group.

n of the formula (1) represents an integer of 0 to 3. When n=0, it is a tetrafunctional decane, when n=1, it is a trifunctional decane, when n=2, it is a difunctional decane, and when n=3, it is a monofunctional decane.

Specific examples of the organic decane represented by the formula (1) include tetrafunctional decane such as tetramethoxy decane, tetraethoxy decane, tetraethoxy decane, and tetraphenoxy decane, and methyl group. Trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl Triethoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-butyl trimethoxy decane, positive Butyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methyl propylene醯oxypropyltrimethoxydecane, 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, phenyltrimethoxydecane, phenyltriethyl Oxydecane, p-hydroxyphenyltrimethoxydecane, 1-(p-hydroxyphenyl)ethyltrimethoxynonane, 2-(p-hydroxyphenyl)ethyltrimethoxynonane, 4-hydroxy-5-( p-Hydroxyphenylcarbonyloxy)pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3 -Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxy Alkane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, [(3-ethyl-3- Oxecyclobutyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxydecane, 3-mercaptopropyltrimethyl a trifunctional decane such as oxydecane or 3-trimethoxydecyl propyl succinic acid, dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl diethoxy decane, and n-Butyldimethoxydecane, diphenyldimethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)methyldiethyl a difunctional decane such as oxydecane, trimethyl methoxy decane, tri-n-butyl ethoxy decane, (3-glycidoxypropyl) dimethyl methoxy decane, (3-glycidyloxy) A monofunctional decane such as propyl)dimethyl methoxy decane. In addition, these organic decane can be single It can be used alone or in combination of two or more. Among these organic decanes, trifunctional decane is preferably used in terms of crack resistance and hardening speed of the cured film.

Further, the polyoxyalkylene used in the present invention preferably contains an aryl group having 6 to 15 carbon atoms.

As the decane compound having an aryl group having 6 to 15 carbon atoms, phenyltrimethoxydecane, phenyltriethoxydecane, p-hydroxyphenyltrimethoxydecane, p-tolyltrimethoxy can be preferably used. Baseline, p-styryltrimethoxydecane, p-methoxyphenyltrimethoxydecane, 1-(p-hydroxyphenyl)ethyltrimethoxynonane, 2-(p-hydroxyphenyl)ethyltrimethoxy Baseline, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxydecane, diphenyldimethoxydecane, 1-naphthyltrimethoxydecane, 2-naphthyltrimethoxy Decane, 1-naphthyltriethoxydecane, 2-naphthyltriethoxydecane, decyltrimethoxydecane. Among these, in terms of cost, it is preferably a phenyl group as compared with a polycyclic ring system such as a naphthalene type or an anthracene type.

From the viewpoint of heat resistance and crack resistance, it is preferable that the composition of the mask slurry is a constituent component of polyoxyalkylene other than particles, which is only a decane compound containing an aryl group. The content of the aryl group in the solid content of the mask paste composition is more preferably 20% by weight or more, and most preferably 25% by weight or more. When the aryl group content is less than the amount, the crack-resistant film thickness in the high-temperature process becomes low.

Further, in terms of the side of the environment, in order to discharge the decomposition product derived from the aromatic ring compound such as benzene at the time of calcination, it is suppressed to a low level as much as possible, and the use of only the aryl group having no carbon number of 6 to 15 is used. Polyoxyalkylene is also a preferred embodiment. That is, R ¹ in the formula (1) is preferably any of hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.

Specific examples of the organic decane in this case include tetrafunctional decane such as tetramethoxy decane, tetraethoxy decane, and tetraethoxy decane, methyltrimethoxydecane, and methyltriethoxy group. Decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy Baseline, n-propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxy Decane, decyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltri Ethoxy decane, 3-propenyloxypropyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxy Decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy Baseline, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-oxetanyl)methoxy]propyl Trifunctional decane such as triethoxy decane, 3-mercaptopropyltrimethoxydecane, 3-trimethoxydecylpropyl succinic acid, dimethyldimethoxydecane, dimethyldiethoxydecane , dimethyldiethoxydecane, di-n-butyldimethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl) A Difunctional decane such as bis-ethoxy decane, trimethyl methoxy decane, tri-n-butyl ethoxy decane, (3-glycidoxypropyl) dimethyl methoxy decane, (3- Monofunctional decane such as glycidoxypropyl) dimethyl ethoxy decane. Further, these organic decane may be used singly or in combination of two or more. Among these organic decanes, trifunctional decane is preferably used in terms of crack resistance and hardening speed of the cured film.

In addition, the weight average molecular weight (Mw) of the polyoxyalkylene used in the present invention is required to be 1,000 or more in terms of a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). When Mw is less than 1,000, the reactive terminal group of the decane which is a main component increases, and storage stability deteriorates. Further, since the debonding group at the time of firing is increased, the calcination deformation is large and the crack resistance is also deteriorated. The larger the Mw, the better the storage stability, and therefore it is preferable. However, if the Mw is too large, the filter permeability in the coating process is deteriorated, and the solubility in the peeling liquid may be deteriorated in the peeling step of the mask layer. Therefore, the upper limit of Mw is preferably less than 100,000, more preferably less than 50,000, and most preferably less than 20,000.

The present invention is characterized in that it is different from a low molecular weight such as tetraethene decane, and the molecular weight of the polyoxyalkylene component is high, and it is important that the polyoxyalkylene has a weight average molecular weight of 1,000 or more. Here, the weight average molecular weight of the polyoxyalkylene is a weight average molecular weight of the copolymer when the polysiloxane is combined with the cerium oxide particles.

The mask slurry composition of the present invention contains cerium oxide particles having an average particle diameter of 150 nm or less. Here, the average particle diameter in the present invention means a number average particle diameter. The lower limit of the number average particle diameter of the cerium oxide particles is preferably 2 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and the upper limit is preferably 125 nm or less, more preferably 100. Below nm. When the number average particle diameter of the cerium oxide particles is more than 150 nm, the film thickness uniformity and the masking property of the film of the cured film are lowered. Further, when the number average particle diameter of the cerium oxide particles is 2 nm or more, the effect of improving the crack resistance is further enhanced. Regarding the number average particle diameter of the cerium oxide particles, when the particles can be separated from the composition, the cerium oxide particles are dried, calcined, and the specific surface area of the obtained particles is measured, and then the particles are assumed to be spherical. The specific surface area was determined by the specific surface area, and the average particle diameter was determined by number-averaging. The apparatus to be used is not particularly limited, and ASAP 2020 (manufactured by Micromeritics Co., Ltd.) or the like can be used. Further, when it is difficult to separate the cured film or the like, a scanning electron microscope (SEM) photograph of the film cross section or the film surface is taken in the cured film, and 50 particles can be arbitrarily selected to measure the particle diameter, and The number average particle size is obtained.

Further, by containing the cerium oxide particles in the slurry composition, the diffusion of the solution on the substrate when applied to the substrate is suppressed, and excellent coating patterning accuracy can be obtained.

Specific examples of the cerium oxide particles include IPA-ST having a particle diameter of 12 nm using isopropyl alcohol as a dispersion medium, and MIBK-ST having a particle diameter of 12 nm using methyl isobutyl ketone as a dispersion medium. Isopropyl alcohol is a dispersion medium of IPA-ST-L having a particle diameter of 45 nm, IPA-ST-ZL having a particle diameter of 85 nm, and PGM-ST having a particle diameter of 15 nm using propylene glycol monomethyl ether as a dispersion medium (the above is a commercial product). Name, Nissan Chemical Industry Co., Ltd.), OSCAL 101 with a particle size of 12 nm with γ-butyrolactone as a dispersion medium, and Cataloid-S with a particle size of 5 nm to 80 nm with water as a dispersion (the above are trade names, Catalyst Chemical Industry Co., Ltd.), with propylene glycol monomethyl ether as the dispersion medium, the particle size is Quartron PL-2L-PGME with 16 nm, Quartron PL-2L-BL with particle size of 17 nm with γ-butyrolactone as dispersion medium, and Quartron PL-2L-DAA with particle size of 17 nm with diacetone alcohol as dispersion medium The dispersion solution is Quartron PL-2L with water particle size of 18 nm to 20 nm, Quartron PL-1 with particle diameter of 15 nm, Quartron PL-3 with particle diameter of 35 nm, Quartron PL-7 with particle diameter of 75 nm, and particle size. 18 nm GP-2L (product name, manufactured by Fuso Chemical Industry Co., Ltd.), REOLOSIL (trade name, manufactured by Tokuyama Co., Ltd.) having a particle diameter of 5 nm to 50 nm, and a particle size of 7 nm to 40 nm. Aerosil (trade name, manufactured by Aerosil (Japan)), etc. Further, these cerium oxide particles may be used singly or in combination of two or more.

The content of the cerium oxide particles in the mask slurry composition of the present invention is 20% by weight or more, more preferably 30% by weight or more, and most preferably 40% by weight or more, based on the solid content. The upper limit is 70% by weight or less. When the amount of the cerium oxide particles is less than 20% by weight, the effect of improving the masking property, the crack resistance, and the coating patterning property is insufficient. When the amount is more than 70% by weight, the void ratio of the particles becomes large, so that the mask is covered. Reduced sex.

In the mask slurry composition of the present invention, the cerium oxide particles may be a mixed component which does not form a bonding bond with the polysiloxane, or may be bonded to the polyoxyalkylene.

The method for forming a bond between the cerium oxide particles and the polysiloxane is not particularly limited, and can be preferably applied: coexisting cerium oxide particles in a condensation reaction step of polyoxyalkylene, and polymerization reaction with a condensation reaction A method in which a reaction is carried out in parallel; or a method in which a polysiloxane and a cerium oxide particle after polymerization are allowed to coexist, and a terminal stanol group is subjected to a condensation reaction with each other by heating.

The polyoxyalkylene of the present invention can be obtained by subjecting the hydrolyzate to a condensation reaction in the presence of a solvent or in a solvent without hydrolyzing the organodecane compound.

The various conditions of the hydrolysis reaction, such as the acid concentration, the reaction temperature, the reaction time, and the like, may be appropriately set in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. For example, it is preferred to carry out the organic decane compound in a solvent for 1 minute to 180 minutes. After adding the acid catalyst and water in a minute, the reaction is carried out at room temperature to 110 ° C for 1 minute to 180 minutes. By carrying out the hydrolysis reaction under such conditions, the impatient reaction can be suppressed. The reaction temperature is more preferably from 30 ° C to 130 ° C.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. Examples of the acid catalyst include hydrogen halide-based inorganic acids such as hydrochloric acid, hydrobromic acid, and hydroiodic acid, and other inorganic chemicals such as sulfuric acid, nitric acid, phosphoric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, boric acid, tetrafluoroboric acid, and chromic acid. Acid, sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid, pyruvic acid, citric acid, A carboxylic acid such as succinic acid, fumaric acid or malic acid. From the viewpoint of masking properties, the acid catalyst of the present invention preferably contains no atoms other than hydrazine, hydrogen, carbon, oxygen, nitrogen or sulfur as much as possible, and it is preferred to use a carboxylic acid or sulfonic acid system. Acid catalyst. Among them, in terms of the removability, it is more preferably a low boiling point such as formic acid or acetic acid having a boiling point of 120 ° C or lower.

In terms of storage stability of the composition, it is also preferred to use a low-boiling acid catalyst to control the system to a boiling point or higher of the acid catalyst after the hydrolysis reaction, and to partially or completely the acid component. Remove.

The content of the acid catalyst is preferably from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of all the organic decane compound used in the hydrolysis reaction. By setting the amount of the acid catalyst to the above range, it is possible to easily control the hydrolysis reaction in a necessary and sufficient manner.

After the stanol compound is obtained by the hydrolysis reaction of the organic decane compound, the reaction solution is preferably heated at a temperature of 50 ° C or higher and a boiling point of the solvent or lower for 1 hour to 100 hours to carry out a condensation reaction. Further, in order to increase the degree of polymerization of the polyoxyalkylene, the alkali catalyst may be heated or added again.

The solvent used for the hydrolysis reaction of the organic decane compound and the condensation reaction of the hydrolyzate is not particularly limited, and may be appropriately selected in consideration of stability, coatability, volatility, and the like of the resin composition. Further, two or more kinds of solvents may be combined, and the reaction may be carried out without a solvent. Specific examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, 1-methoxy-2-propanol, pentanol, and 4-methyl. Alcohols such as 2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-tert-butoxy-2-propanol, diacetone alcohol Glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol tert-butyl ether, propylene glycol n-butyl ether, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, diethylene glycol methyl ether, dipropylene glycol n-butyl ether, dipropylene glycol monomethyl ether, diisopropyl ether, two positive Ethers such as dibutyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether; methyl ethyl ketone, acetamidine acetone, methyl propyl ketone, Methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone, diisobutyl ketone, cyclohexanone, cycloheptanone, etc. Ketones; decylamines such as dimethylformamide and dimethylacetamide; isopropyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, acetic acid Butyl ester, isobutyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl diglycol acetate, 1,3-butylene glycol diacetate, ethyl diethylene glycol Acetate, dipropylene glycol methyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, triethyl decyl glycerol, etc.; toluene, xylene, hexane, cyclohexane, ethyl benzoate An aromatic or aliphatic hydrocarbon such as naphthalene or 1,2,3,4-tetrahydronaphthalene; γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylimidazolidinone, and dimethyl Kea, propyl carbonate and the like.

In the hydrolysis reaction of the organic siloxane in the present invention, the acid catalyst is heated to a boiling point or higher and removed, and is preferably one of the preferred embodiments, preferably a solvent having a boiling point of 130 ° C or higher. In terms of solubility, coatability, and the like, diethylene glycol methyl ether (bp 176 ° C), ethylene glycol monoethyl ether acetate (bp 156.4 ° C), and ethylene glycol monomethyl are preferably exemplified. Ether acetate (bp 145 ° C), methyl lactate (bp 145 ° C), ethyl lactate (bp 155 ° C), diacetone alcohol (bp 169 ° C), propylene glycol monomethyl ether acetate (bp 145 ° C), 3-methoxy-3-methyl-1-butanol (bp 174 ° C), dipropylene glycol monomethyl ether (bp 188 ° C), dipropylene glycol n-butyl ether (bp 229 ° C), γ-butyrolactone (bp 204 ° C), diethylene glycol monoethyl ether acetate (bp 217 ° C), butyl diglycol acetate (bp 246 ° C), ethyl acetate (bp 181 ° C), N-methyl-2 -pyrrolidone (bp 204 ° C), N,N-dimethylimidazolidinone (bp 226 ° C), dipropylene glycol methyl ether acetate (bp 213 ° C), 1,3-butanediol diacetate (bp 232 ° C), diisobutyl ketone (bp 168 ° C), propylene glycol tert-butyl ether (bp 151 ° C), propylene glycol n-butyl ether (bp 170 ° C).

When a solvent is formed by a hydrolysis reaction, hydrolysis can also be carried out without a solvent. It is also preferred to adjust the solvent to an appropriate concentration as a resin composition by further adding a solvent after completion of the reaction. Further, after the hydrolysis, the produced alcohol or the like may be distilled and removed in an appropriate amount under heating and/or reduced pressure, and then a preferred solvent is added.

The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the total of the organic decane compound. By setting the amount of the solvent to the above range, it is possible to easily control the hydrolysis reaction in a necessary and sufficient manner.

Further, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be arbitrarily selected, and is preferably used in the range of 1.0 mol to 4.0 mol with respect to 1 mol of Si atom.

Further, the mask slurry composition of the present invention may contain a solvent other than the solvent used in the hydrolysis and condensation reaction as long as the effects of the present invention are not impaired. The mixed solvent is preferably selected from the above solvents, and may be a single solvent system or a combination of two or more solvents. For example, a solvent having a boiling point of 130 ° C or higher is used as a solvent used in the hydrolysis and condensation reaction, and a composition used as a mask slurry is mixed with a low boiling point solvent having a boiling point of 100 ° C or less to impart coating dryness. Good implementation.

The mask slurry composition of the present invention preferably contains a sulfonic acid or a salt thereof, or a carboxylic acid Or its salt.

Examples of the carboxylic acid or a salt thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, and pearlic acid. (margaric acid), stearic acid, trifluoroacetic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid ), eicosapentaenoic acid, lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid ), various carboxylic acids such as mellitic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pyruvic acid, and the like, and The metal salt or acid anhydride of these carboxylic acids is not limited to these. Hereinafter, the carboxylic acid or a salt thereof is collectively referred to as a carboxylic acid compound.

Examples of the sulfonic acid or a salt thereof include various sulfonic acids such as sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, fluorosulfonic acid, 10 camphorsulfonic acid, and taurine, and metal salts of these sulfonic acids. Other commonly referred to as thermal acid generators are: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI -110L, SI-145L, SI-150L, SI-160L, SI-180L, SI-200 (all are sulfonium sulfonate salts manufactured by Sanxin Chemical Industry Co., Ltd.); 4-hydroxyphenyldimethyl phthalate Fluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-ethylhydrazine Oxyphenyl dimethyl fluorene trifluoromethanesulfonate, 4-ethenyloxyphenylbenzylmethyl fluorene triflate, 4-methoxycarbonyloxy phenyl dimethyl sulfonate Fluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate Acid salts, etc., but are not limited to these. Hereinafter, the sulfonic acid or its salt is collectively referred to as a sulfonic acid compound

For example, when the solid content concentration is high and the particles are contained in the slurry at a high concentration, although depending on the stability or motility of the particles, under high-temperature hardening conditions, aggregation of the particles occurs during prebaking or calcination. Happening. When the aggregation of the particles is caused, not only the film surface is rough, the film thickness is not fixed, and the curtain performance is remarkably lowered. The reason for this is that the fluidity of the oxoxane composition becomes high at a high temperature. Therefore, in the present invention, by containing these carboxylic acid compounds and sulfonic acid compounds, the stanol groups and polyfluorenes of the cerium oxide particles are promoted at a timing in which the fluidity of the oxoxane composition becomes high under high-temperature hardening conditions. The cross-linking reaction of oxane suppresses the flow of particles and suppresses aggregation.

The amount of the carboxylic acid compound or the sulfonic acid compound added is preferably 0.1% by weight or more based on the solid content. If the amount added is less than 0.1% by weight, the hardening is insufficient. The upper limit is not particularly limited. When the amount is more than 5% by weight, the crosslinking is carried out at room temperature, and the storage stability is lowered, which is not preferable. Further, these carboxylic acid compounds and sulfonic acid compounds may be used singly or in combination of two or more. In this case, it is preferable that the total content is 0.1% by weight or more.

Further, the mask slurry composition of the present invention may further contain: a decane coupling agent, a crosslinking agent, a sensitizer, a thermal radical generator, a dissolution promoter, a dissolution inhibitor, within a range not impairing the effects of the present invention. Various additives such as surfactants, tackifiers, stabilizers, antifoaming agents, and metal compound particles other than cerium oxide particles.

Specific examples of the decane coupling agent include dimethyl dimethoxy fluorene. Alkane, dimethyldiethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 3-methylpropene oxime Oxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropene oxime Propyl methyl diethoxy decane, 3-propenyl methoxy propyl trimethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, 3-three Ethoxy decyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxydecane, [( 3-ethyl-3-oxetanyl)methoxy]propyltriethoxydecane, 3-mercaptopropyltrimethoxydecane , 3-mercaptopropylmethyldimethoxydecane, 3-ureidopropyltriethoxydecane, 3-isocyanatopropyltriethoxydecane, 3-trimethoxydecylpropyl succinic acid N-tert-butyl-3-(3-trimethoxydecylpropyl) succinimide, tris-(3-trimethoxydecylpropyl)isocyanate, and the like.

Among them, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and 3-aminopropyltrimethyl can be preferably used in terms of substrate adhesion or storage stability of the composition. Oxydecane, 3-aminopropyltriethoxydecane, 3-isocyanatopropyltriethoxydecane, N-tert-butyl-3-(3-trimethoxydecylpropyl) Amber succinimide, tris-(3-trimethoxydecylpropyl) iso-cyanate.

The amount of the decane coupling agent to be added is not particularly limited, and when it is used, it is preferably It is in the range of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the polysiloxane or the solid content of the particles. When the amount is less than 0.1 part by weight, the effect of improving the adhesion is insufficient. When the amount is more than 10 parts by weight, the decane coupling agents are subjected to a condensation reaction during storage to cause gelation.

The mask paste composition of the present invention may contain a surfactant. By containing a surfactant, coating unevenness is improved and a uniform coating film can be obtained. A fluorine-based surfactant or an anthrone-based surfactant can be preferably used.

Specific examples of the fluorine-based surfactant include a fluorine-based surfactant having a compound having a fluoroalkyl group or a fluoroalkyl group at at least any of a terminal, a main chain, and a side chain: 1, 1, 2 , 2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2, 2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl) Ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9 ,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(perfluorooctanesulfonamide)propyl]-N,N'- Dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine, phosphoric acid double (N - perfluorooctylsulfonyl-N-ethylaminoethyl) ester, monoperfluoroalkylethyl phosphate, and the like. In addition, commercially available products include: MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183, MEGAFAC F444, MEGAFAC F475, MEGAFAC F477 (above manufactured by Dainippon Ink and Chemicals), Eftop EF301, Eftop EF303, Eftop EF352 (manufactured by New Akita Chemicals Co., Ltd.), Fluorad FC-430, Fluorad FC-431 (Sumitomo 3M (share) manufacturing), AsahiGuard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (Asahi Glass) Manufactured by BM-1000, BM-1100 (manufactured by Yusei Co., Ltd.), NBX-15, FTX-218, DFX-218 (manufactured by NEOS).

Examples of commercial products of an anthrone-based surfactant include SH28PA, SH7PA, SH21PA, SH30PA, and ST94PA (all manufactured by Dow Corning Toray Silicone Co., Ltd.), BYK067A, BYK310, and BYK322. BYK331, BYK333, BYK355 (made by BYK-Chemie Japan Co., Ltd.), etc.

In the mask slurry composition, the content of the surfactant is usually set to 0.0001% by weight to 1% by weight.

In the mask slurry composition of the present invention, the solid content concentration is not particularly limited, but is preferably in the range of 2% by weight to 50% by weight. When the solid content concentration is less than the concentration range, the coating film thickness becomes too thin to obtain desired masking properties, and if it is higher than the concentration range, the storage stability is lowered.

The mask paste composition of the present invention is a non-photosensitive composition which is formed by a full-surface coating or a pattern coating by various coating methods and is cured by heat to form a mask layer.

The coating method can be applied by a known coating method such as a spin coating method, a roll coating method, a spray printing method, a relief printing method, a gravure printing method, a screen printing method, an inkjet printing method, or a slit printing method. It is placed on a base substrate such as a ruthenium substrate. When coating Various types of nozzles and nozzles can be preferably used, for example, in the slit coating method: a method in which a slit nozzle is divided into a plurality of nozzles, and a plurality of lines are applied in a stripe shape.

The preferred coating patterning method of the mask slurry composition of the present invention is not particularly limited, and a screen printing method is exemplified in terms of the degree of freedom in pattern design and the ease of nozzle maintenance.

When adapted to the screen printing method, it is preferred that the viscosity of the mask paste composition is 3000 mPa. s above. With a paste viscosity of 3000mPa. s or more, and it is easy to control the amount of the coating liquid permeation of the coating or the screen portion of the screen plate on the screen plate, and since the coating liquid is difficult to diffuse after it contacts the coated substrate, the pattern accuracy is improved. The viscosity is more preferably 5000mPa. Above s, the best is 10000mPa. s or above is appropriate. The upper limit is not particularly limited, and from the viewpoint of the operation of the solution, it is preferably less than 100,000 mPa. s. Here, the viscosity is a value measured by a B-type digital viscometer according to JIS Z8803 (1991) "Solid viscosity-measurement method".

In order to adjust the viscosity to the range, it is preferred to contain various tackifiers. As the tackifier, various cellulose compounds such as polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate, methyl cellulose, ethyl cellulose, and nitrocellulose can be exemplified, and polymethacrylic acid is exemplified. An acrylate resin such as a methyl ester, polyethylene oxide or polypropylene oxide.

Among these, one or more types of tackifiers selected from the group consisting of acrylate resins, polyethylene oxide, and polypropylene oxide are particularly preferred. The reason is that there is no calcination residue when the siloxane is hardened, and the crack resistance and the masking property are not lowered.

The reason for the above situation is that these tackifiers are compared with other tackifiers. The temperature of complete thermal decomposition is low and it is easy to thermally decompose. If there is a residue derived from the undecomposed substance of the tackifier after calcination, there is contamination in the calcining furnace, or contamination of the peeling step due to incomplete peeling in the peeling step of the subsequent step, or deterioration of substrate performance. And thus poor. Further, regarding the crack resistance, the condensation hardening of the decane is continued from the temperature rise to about 600 ° C at the time of firing, and the deformation due to the volume shrinkage is a cause of cracking. When the tackifier is used in combination, the deformation due to the disappearance of the decomposition of the tackifier becomes a major cause of the crack. Here, even in the stage where the hardening and contraction of the siloxane is progressing, the thermal decomposition of the usual tackifier is caused, and cracking is likely to occur. On the other hand, in the above-mentioned preferred tackifier, since the tackifier is decomposed in the early stage of the hardening shrinkage of the siloxane, the deformation in the mask layer due to the decomposition of the tackifier is affected by it. After the hardening shrinkage absorption of the decane. Therefore, it is considered that a mask layer which does not have reduced crack resistance, is finally dense, and the curtain performance is not lowered can be obtained. Moreover, as for these preferable tackifiers, in terms of calcination residue, crack resistance, and curtain properties, it is also preferred to increase the viscosity by a small amount.

Examples of the acrylate-based resin include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, and polyacrylic acid acrylate. Polyacrylates such as esters, polybutyl acrylate, polyhydroxyethyl methacrylate, polybenzyl methacrylate, polyglycidyl methacrylate, and copolymers of these. In the case of a copolymer, the acrylate component may be 60 mol% or more in terms of a polymerization ratio, and a vinyl polymerizable component such as polyacrylic acid or polystyrene which is another copolymer component may be copolymerized.

In addition, as for polyethylene oxide and polypropylene oxide, these two are also preferable. Copolymer.

The acrylate resin, polyethylene oxide, and polypropylene oxide are each preferably having a weight average molecular weight of 100,000 or more, and have a high viscosity-increasing effect. These can be used in combination.

In terms of the viscosity-increasing effect, the content of the tackifier in the composition is preferably 1% by weight or more, and more preferably in terms of suppression of the calcination residue, crack resistance, and curtain performance. 10% by weight or less.

A method of forming a cured film using the mask paste composition of the present invention will be described. After coating by the various coating methods described above, the coated substrate is pre-baked by a heating device such as a hot plate or an oven. The prebaking is preferably carried out in the range of 50 ° C or more and 150 ° C or less for 30 seconds to 30 minutes, and the film thickness after prebaking is set to 0.05 μm to 10 μm. After the prebaking, the mask layer is formed by curing in a range of 400 ° C or more and 1200 ° C or less in a heating apparatus such as a hot plate or an oven for 30 minutes to 2 hours. It is also preferred to carry out middle bake for about 10 minutes to 2 hours in the range of 200 ° C or more and 250 ° C or less between prebaking and curing. These prebaking, intermediate baking, and curing can be carried out under well-known conditions such as N ₂ , O ₂ , N ₂ /O ₂ , and air.

Here, in the present invention, it is preferable that the curing step includes a step of heating in a temperature range of 400 ° C or higher and 900 ° C or lower for 5 minutes or more in an environment having an oxygen concentration of 5% or more. More preferably, it is a step of heating in a temperature range of 500 ° C or more and 800 ° C or less in an environment having an oxygen concentration of 5% or more for 5 minutes or more. By this step, the thermal decomposition of the polyoxyalkylene or the tackifier component is promoted, Therefore, the peeling residue can be lowered in the step of removing the cured film. Further preferably, in the curing step, even in a non-constant temperature state, the oxygen concentration and the temperature range are satisfied in the temperature rising process and the temperature decreasing process for more than 5 minutes; and preferably: controlling in the curing step. Before and after this condition, the control is outside the range of the oxygen concentration such as the nitrogen condition or outside the temperature range.

Preferably, the mask paste composition of the present invention is applied to the entire surface of the substrate, and is preferably formed by selectively forming a mask pattern by a screen printing method, an inkjet printing method, or the like. After the entire surface coating is performed on the substrate by a spin coating method or the like, the photosensitive mask paste is recoated on the upper layer, and the doped region corresponding to the doped region is selectively removed by, for example, a well-known photolithography method and an etching method. Part of the formation of the mask pattern. It is also preferred that after the mask layer of the present invention is formed, the mask layer is not peeled off and is directly used as a protective film.

Further preferably, after the mask slurry is selectively applied to the substrate, the substrate is pre-baked or calcined by a superheating device such as a hot plate or an oven, and then the doping paste is selectively applied to the entire surface. Or, in a region where the mask slurry is not applied, the substrate is subjected to calcination and thermal diffusion, and impurities are selectively diffused in the semiconductor substrate. Further, it is also a preferred embodiment that the mask layer and the hardened layer of the paste are removed by a release agent such as hydrofluoric acid to form a semiconductor element in which the doped region is patterned. By setting this process, it is possible to reduce not only the loss of the mask paste composition but also the mask slurry at the same time as the prior method in which the mask paste is applied over the entire surface and hardened and calcined. Hardening calcination and hardening calcination and thermal diffusion of the doped pulp can reduce the number of calcination and simplify the process.

The semiconductor device can be manufactured by the steps of: forming a mask pattern on the semiconductor substrate using the mask paste composition of the present invention; and using the mask pattern formed on the semiconductor substrate as a mask to diffuse impurities The step to the above semiconductor substrate. In the following, a method of forming an impurity diffusion layer using the mask paste and a method of manufacturing a semiconductor device using the same will be described by taking a method of manufacturing a solar cell as one type of photoelectric conversion element.

First, as shown in Fig. 1 (1), a mask paste composition is selectively applied onto the N-type semiconductor substrate 10 to form a stripe mask pattern 12. The coating method includes a method of applying a mask slurry by a slit coating method including a plurality of nozzles, an inkjet printing method, a screen printing method, a letterpress printing method, a gravure printing method, a roll coating method, or a spray. Printing method, etc. After coating, calcination is performed to harden the mask slurry to form the mask pattern 12. The calcination preferably includes a step of heating in a temperature range of 400 ° C or higher and 900 ° C or lower for 5 minutes or more in an environment having an oxygen concentration of 5% or more.

Next, as shown in FIG. 1 (2), a P-type doping pattern 14 and an N-type doping pattern 16 are selectively formed between the mask patterns 12 on the semiconductor substrate 10. The formation method can be exemplified by the same method as the mask pattern.

Next, as shown in FIG. 1 (3), the semiconductor substrate 10 is fired to diffuse each doping component into the semiconductor substrate 10. The P-type impurity diffusion layer 24 and the N-type impurity diffusion layer 26 are formed in this manner.

Next, as shown in FIG. 1 (4), the mask pattern 12, the P-type doping pattern 14, and the N-type doping pattern 16 are peeled off by using a release agent such as hydrofluoric acid.

Next, as shown in FIG. 1 (5), the semiconductor substrate is thermally oxidized or the like. A passivation film 18 is provided on the surface of 10. Further, on the surface on the opposite side to the side on which the passivation film is formed, a tantalum nitride film 20 having an antireflection effect of sunlight is formed by a well-known method.

Next, as shown in FIG. 1 (6), the passivation film 18 is selectively removed, and a specific region of the P-type impurity diffusion layer 24 and the N-type impurity diffusion layer 26 is exposed to form a contact hole. Next, a desired metal is filled in the contact hole by, for example, electrolytic plating or electroless plating, and an electrode 22 electrically connected to the P-type impurity diffusion layer 24 and the N-type impurity diffusion layer 26 is formed. By the above steps, the solar cell of the present embodiment can be manufactured.

The present invention is not limited to the above-described embodiments, and various modifications such as design changes may be added to the knowledge of the manufacturer, and embodiments in which such modifications are added are also included in the scope of the present invention.

The mask paste composition of the present invention may be extended to a semiconductor element such as a transistor array or a diode which forms a p-type and/or n-type region on a semiconductor surface in addition to a photovoltaic semiconductor such as a solar cell. Arrays, photodiode arrays, converters, etc.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the following indicates the use of abbreviations in the compounds used.

GBL: γ-butyrolactone (bp 205 ° C)

IPA: isopropanol (bp 82 ° C)

MMB: 3-methoxy-3-methyl-1-butanol (bp 174 ° C)

1,3BGDA: 1,3-butanediol diacetate (bp 232 ° C)

EDM: diethylene glycol methyl ether (bp 176 ° C)

PGME: 1-methoxy-2-propanol (bp 118 ° C)

PGMEA: propylene glycol monomethyl ether acetate (bp 145 ° C)

PTB: propylene glycol tert-butyl ether (bp 151 ° C)

PEO: polyethylene oxide

PMMA: Polymethyl methacrylate

PPO: polypropylene oxide

PVP: polyvinylpyrrolidone.

(1) Determination of solid content concentration

1 g of the solution to be measured was weighed in an aluminum cup, and the solution components were evaporated by heating at 250 ° C for 30 minutes using a hot plate. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the solution.

(2) Determination of weight average molecular weight

The weight average molecular weight of polyoxyalkylene was filtered by a membrane filter having a pore size of 0.45 μm, and then subjected to gel permeation chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Co., Ltd.). Solvent: tetrahydrofuran, development speed: 0.4 ml/min), which was determined by polystyrene conversion.

(3) Determination of P, B and Al in solution

For P, the sample is hydrolyzed using sulfuric acid, nitric acid, hydrofluoric acid, and perchloric acid, and concentrated until the white sulfuric acid is produced, by ICP mass spectrometry (Agilent Agilent 4500 (manufactured by Agilent Technology) was used to determine the content in the composition.

Regarding B, the sample was weighed into a platinum crucible, and after adding ethanol, it was burned in a sealed container made of stainless steel filled with oxygen, and the sodium hydroxide aqueous solution was absorbed to generate a gas, and nitric acid was added thereto for neutralization and constant volume. For the constant volume solution, quantitative analysis of B was performed by ICP emission spectrometry (SPS3000 manufactured by SII NanoTechnology Co., Ltd.).

Regarding Al, the content in the composition was determined by combustion ion chromatography (AQF-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

(4) Determination of solution viscosity

Using a B-type digital viscometer (DV-II+Pro manufactured by Yinghong Seiki Co., Ltd.), the chamber was kept at 23 ° C, and the value after 5 minutes from the start of rotation of the rotor was read, and the solution viscosity was calculated.

(5) Slit coating confirmation

The mask paste composition was patterned into stripes by a slit nozzle, and the stripe width accuracy was confirmed.

As the substrate, a semiconductor substrate including n-type single crystal germanium having a side of 100 mm was prepared, and both surfaces were subjected to alkali etching in order to remove chip damage or natural oxide. At this time, innumerable irregularities having a typical width of 40 μm to 100 μm and a depth of about 3 μm to 4 μm are formed on both surfaces of the semiconductor substrate, and this is used as a coated substrate.

Fig. 2 is a schematic view showing a stripe coating apparatus used in the present embodiment. The mask slurry is applied in a strip shape by moving the nozzle 38 in the Y direction with respect to the semiconductor substrate 31 adsorbed on the stage 32 by vacuum. As shown in FIG. 3, the plurality of discharge ports 42 formed in the lower portion of the nozzle 41 eject the slurry 43 containing the composition of the mask slurry, and the nozzles are formed in a state in which the liquid droplets 44 are formed between the semiconductor substrate 40 and the discharge port 42. 41 Moves vertically in the paper direction.

After the mask slurry was applied in stripes, the substrate was heated at 100 ° C for 5 minutes in air and then heated at 230 ° C for 30 minutes to form a thickness of about 1.0 μm, a width of 240 μm, a pitch of 600 μm, and a length. It is an 8cm mask pattern.

Here, the line width is measured at 10 points at an equal interval for any one of the lines, and the standard deviation σ of the coating width is determined to be good within 10 μm, and the standard deviation σ of the coating width is determined to be less than 10 μm. .

(6) Screen printing confirmation

The mask paste composition was patterned into stripes by screen printing, and the stripe width accuracy was confirmed.

As the substrate, a semiconductor substrate including n-type single crystal germanium having a side of 100 mm was prepared, and both surfaces were subjected to alkali etching in order to remove chip damage or natural oxide. At this time, innumerable irregularities having a typical width of 40 μm to 100 μm and a depth of about 3 μm to 4 μm are formed on both surfaces of the semiconductor substrate, and this is used as a coated substrate.

As the coated substrate, an n-type single crystal including one side of 100 mm is used. A non-polished semiconductor substrate. On the coated surface, a typical number of irregularities having a width of 40 μm to 100 μm and a depth of 3 μm to 4 μm are formed.

Using a screen printing machine (TM-750 type of Microtek Co., Ltd.), 50 openings having a width of 200 μm and a length of 6 cm were formed using a pitch of 600 μm (SUS, 400 mesh, wire diameter) It is 23 μm) as a screen mask to form a striped mask pattern.

After the mask paste was screen-printed, the substrate was heated at 100 ° C for 5 minutes in air and then heated at 230 ° C for 30 minutes, thereby forming a thickness of about 1.5 μm, a width of 210 μm, a pitch of 600 μm, and a length of 6cm mask pattern.

In the center line, the line width is measured at 10 points at equal intervals, and the standard deviation of the coating width is judged to be good within 15 μm, and the standard deviation of the coating width is determined to be less than 15 μm.

(7) Determination of crack film thickness

A P-type germanium wafer (manufactured by E&M, surface resistivity: 0.291 Ω/□, ground) cut into 3 cm × 3 cm was immersed in a 1% hydrofluoric acid aqueous solution for 5 minutes, and then washed with water, and heated by a hot plate. The treatment was carried out at 100 ° C for 5 minutes.

A mask slurry is applied to the tantalum wafer by a known spin coating method. The sample was prepared to change the rotational speed, and after calcination, the film thickness was changed by changing the film thickness by 0.1 μm each time. In the film area, it is suitably used to dilute with the same solvent composition as the mask slurry. After coating, each of the tantalum wafers was prebaked at 100 ° C for 5 minutes. Then, the pre-baked film thickness was measured by a surface shape measuring device (Surfcom 1400, manufactured by Tokyo Seiko Co., Ltd.).

Next, unless otherwise specified, each of the tantalum wafers was placed in an electric furnace, and the temperature was raised from 20 ° C at 10 ° C / min in an air atmosphere, and then heated at 800 ° C for 60 minutes to calcine the mask paste composition. Then, the film thickness after calcination was measured. The surface of the sample having the largest thickness of the mask layer in which no crack was observed was observed as a cracked film thickness by observing the surface with an optical microscope to which a 5× lens was attached.

(8) Evaluation of peeling residue and measurement of film thickness of curtain

For the cracked film thickness observation sample, an impurity diffusion liquid containing phosphorus (polytetraethylene decane was 5.9% by weight and phosphorus pentoxide was 5.0% by weight) was applied onto the mask by a known spin coating method. After the application of the diffusing agent, each of the tantalum wafers was prebaked at 140 ° C for 5 minutes. Next, the impurity-diffusing component was thermally diffused by heating at 1000 ° C for 90 minutes in an N ₂ atmosphere.

Each of the heat-diffused wafers was immersed in a 10% by weight aqueous solution of hydrofluoric acid at 23 ° C for 10 minutes to peel off the diffusing agent and the mask. After the peeling, the crucible wafer was immersed in pure water for cleaning, and the presence or absence of the residue was visually observed by the surface. After immersing for 10 minutes, the surface adhering matter was visually confirmed, and it was not possible to remove it by Dipping with a rag to set it as D (with peeling residue); after immersing for 10 minutes, the surface adhering matter was confirmed by visual observation, but by crushing The cloth was wiped and removed, and it was set to C. The immersion was carried out for more than 5 minutes and within 10 minutes, and it was not possible to visually confirm the surface adhering matter, B (no peeling residue); the immersion was performed within 5 minutes, and the surface adhering matter could not be visually confirmed. Is A (no stripping residue). The surface resistance of the tantalum wafer after peeling was measured using a four-probe surface resistance measuring device (RT-70V, manufactured by Nippon Nippon).

Here, the germanium wafer used for the measurement (blank, impurity-free thermal diffusion) The surface resistivity of the tantalum wafer which was thermally diffused by the phosphorus-containing impurity diffusion liquid as a reference example without a mask layer was measured and found to be 0.291 Ω/□ (P/N was judged as P). Ω/□ (P/N is judged as P), and high resistance is achieved by thermal diffusion of impurities. Here, for the tantalum wafer after peeling, it is judged that the surface resistivity is 0.32 Ω/□ (P/N is judged to be P) or more, and there is no masking property, and the mask having the masking mask layer thickness is minimized. The film thickness after calcination is used as a mask film thickness.

Further, the difference between the crack film thickness and the mask film thickness means a range which can be used as a mask material, and the wider the range, the wider the applicable range and the more excellent.

(9) P/N decision

The P/N determination was performed using the P/N determiner on the surface of the tantalum wafer after the peeling.

(10) preservation stability

The mask slurry was placed in a sealed container, and after storage at 23 ° C for 30 days, the viscosity change rate was less than 10%, which was particularly good (A), and the viscosity change rate was 10% or more and less than 15%. Good (B), the viscosity change rate is higher than the above (C).

Synthesis Example 1

198.29 g (1.0 mol) of phenyltrimethoxydecane and 239.63 g of MMB were placed in a 500 mL three-necked flask, and 3.80 g of formic acid was dissolved in the hydrolysis of the monomer, which was necessary for 30 minutes, while stirring at room temperature. Aqueous formic acid in water (54.00 g). Then, the flask was immersed in an oil bath of 70 ° C and stirred for 1 hour, and then the oil bath was heated to 150 ° C over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100 ° C, and heating and stirring were started for 30 minutes (the internal temperature was 100 ° C). ~130°C). In the reaction, 72.8 g of methanol, water and formic acid as a by-product were distilled off.

In the MMB solution of the obtained polyoxyalkylene, MMB was added so that the solid content concentration of the polyoxyalkylene was 40% by weight to obtain a polyoxyalkylene solution (A-1). The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 1,500.

Synthesis Example 1-2

The polysiloxane solution (A-2) was obtained in the same manner as in Synthesis Example 1-1 except that the reaction time after the internal temperature was 100 ° C was changed to 3 hours. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,000.

Synthesis Example 1-3

A polysiloxane solution (A-3) was obtained in the same manner as in Synthesis Example 1-1 except that the solvent was changed to 1,3BGDA instead of MMB. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 1,500.

Synthesis Example 1-4

A polysiloxane solution (A- was obtained in the same manner as in Synthesis Example 1-1 except that the solvent was changed to 1,3 BGDA in place of MMB, and the reaction time after the internal temperature reached 100 ° C was set to 3 hours. 4). The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,500.

Synthesis Example 1-5

A polysiloxane solution (A-5) was obtained in the same manner as in Synthesis Example 1-1 except that the solvent was set to EDM instead of MMB, and the reaction time after the internal temperature reached 100 ° C was set to 3 hours. . The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 3,500.

Synthesis Example 1-6

A polysiloxane solution (A-6) was obtained in the same manner as in Synthesis Example 1-1 except that the solvent was set to GBL instead of MMB, and the reaction time after the internal temperature reached 100 ° C was set to 3 hours. . The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 3,500.

Synthesis Example 1-7

A polyoxane solution (A-7) was obtained in the same manner as in Synthesis Example 1-1 except that the solvent was changed to PMBEA instead of MMB, and the reaction time after the internal temperature reached 100 ° C was set to 3 hours. . The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 6,000.

Synthesis Example 1-8

The reaction was carried out in the same manner as in Synthesis Example 1-1 except that 0.82 g of phosphoric acid was used in place of the formic acid, and the reaction time after the internal temperature reached 100 ° C was changed to 3 hours, to obtain a polyoxane solution (A- 8). The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,500.

Synthesis Example 1-9

A polyoxoxane solution (A-9) was obtained in the same manner as in Synthesis Example 1-1 except that 16.00 g of boric acid was used instead of formic acid, and the reaction time after the internal temperature of 100 ° C was reached. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 3,000.

Synthesis Example 1-10

The solvent was used as PGME instead of MMB, and the reaction time after the internal temperature reached 100 ° C was set to 3 hours, except that the same procedure as in Synthesis Example 1-1 was obtained. Polyoxane solution (A-10). The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,500.

Synthesis Example 1-11

A polyoxane solution (A-11) was obtained in the same manner as in Synthesis Example 1-1 except that the amount of the formic acid added was changed to 0.5 g, and the reaction time after the internal temperature reached 100 ° C was 10 minutes. ). The obtained polyoxyalkylene has a weight average molecular weight (Mw) of 500 or less.

Synthesis Example 1-12

A polysiloxane solution (A-12) was obtained in the same manner as in Synthesis Example 1-1 except that the reaction time after the internal temperature reached 100 ° C was changed to 5 hours. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 7,500.

Synthesis Example 2-1

In a 500 mL three-necked flask, 59.49 g (0.30 mol) of phenyltrimethoxydecane, PL-2L-IPA (colloidal cerium oxide manufactured by Fuso Chemical Industry Co., Ltd.), IPA dispersion, and an average particle size of cerium oxide were added. 17 nm, cerium oxide concentration: 25.4% by weight) 165.57 g (0.70 mol, in terms of SiO ₂ ), and 133.07 g of MMB, while stirring at room temperature, a solution of 3.04 g of formic acid dissolved in a monomer was added over 30 minutes. An aqueous solution of formic acid obtained from the necessary water (16.20 g). Then, the flask was immersed in an oil bath of 70 ° C and stirred for 1 hour, and then the oil bath was heated to 150 ° C over 30 minutes. One hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C, and heating and stirring were started for 3 hours (the internal temperature was 100 ° C to 138 ° C). In the reaction, 147.3 g of methanol, IPA, water and formic acid as a by-product were distilled off.

In the MMB solution of the obtained polyoxyalkylene, MMB was added so that the solid content concentration of the polyoxyalkylene was 40% by weight to obtain a polyoxyalkylene solution (B-1). The obtained polyoxyalkylene oxide was a copolymer bonded to cerium oxide particles, and the weight average molecular weight (Mw) of the copolymer was 1,500.

Synthesis Example 2-2

The input amount of the monomer and the solvent was changed to: phenyltrimethoxydecane 49.57 g (0.25 mol), 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane 12.32 g (0.05 mol), In the same manner as in Synthesis Example 2-1 except that phenyl dimethoxy decane was 24.44 g (0.10 mol), 142.92 g (0.60 mol, in terms of SiO ₂ ), PL-2L-IPA, and 155.86 g of MMB. A polyoxane solution (B-2) was obtained. The obtained polyoxyalkylene oxide was a copolymer bonded to cerium oxide particles, and the weight average molecular weight (Mw) of the copolymer was 2,300.

Synthesis Example 2-3

In addition, the amount of the monomer and the solvent to be charged is phenyltrimethoxydecane 109.06 g (0.55 m01), 106.44 g (0.45 mol, in terms of SiO ₂ ), PL-2L-IPA, and 168.87 g of GBL. A polysiloxane solution (B-3) was obtained in the same manner as in Synthesis Example 2-1. The obtained polyoxyalkylene oxide was a copolymer bonded to cerium oxide particles, and the weight average molecular weight (Mw) as a copolymer was 2,100.

Synthesis Example 3

The amount of the monomer and the solvent to be charged was set to: 123.93 g (0.625 mol) of phenyltrimethoxydecane, 30.80 g (0.125 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and Phenyldimethoxydecane 61.09 g (0.25 mol), 270.74 g of MMB, A polyoxyalkylene solution C was obtained in the same manner as in Synthesis Example 1, except that the reaction time after the internal temperature reached 100 ° C was changed to 3 hours. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 5,500.

Synthesis Example 4

A polysiloxane solution D was obtained in the same manner as in Synthesis Example 1, except that the amount of the monomer and the solvent was changed to 241.30 g (1.0 mol) of p-styryltrimethoxydecane and 278.64 g of MMB. . The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,000.

Synthesis Example 5

A polyoxoxane solution E was obtained in the same manner as in Synthesis Example 1, except that the amount of the monomer and the solvent was changed to 212.30 g (1.0 mol) of p-tolyltrimethoxydecane and 254.32 g of MMB. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,000.

Synthesis Example 6

Polyoxyl oxide was obtained in the same manner as in Synthesis Example 1, except that the amount of the monomer and the solvent to be charged was 228.32 g (1.0 mol) of 4-methoxyphenyltrimethoxydecane and 284.68 g of MMB. Alkane solution F. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,000.

Synthesis Example 7

A polysiloxane solution G was obtained in the same manner as in Synthesis Example 1, except that the amount of the monomer and the solvent was 248.35 g (1.0 mol) of 1-naphthyltrimethoxydecane and 308.38 g of MMB. . Weight average molecular weight of the obtained polyoxyalkylene (Mw) is 4500.

Synthesis Example 8

The amount of the monomer and the solvent to be charged was 90.80 g (0.67 mol) of methyltrimethoxydecane, 66.09 g (0.33 mol) of phenyltrimethoxydecane, and MNB of 171.20 g, and the synthesis example was used. 1 A polyoxane solution H was obtained in the same manner. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,000.

Synthesis Example 9

A polyoxyalkylene solution I was obtained in the same manner as in Synthesis Example 1, except that the amount of the monomer and the solvent was 164.22 g (1.0 mol) of propyltrimethoxydecane and 98.52 g of GBL. The obtained polyoxyalkylene had a weight average molecular weight (Mw) of 4,500.

Synthesis example of solvent replacement product of particle dispersion

200 g of PL-2L-IPA and 150 g of MMB were added to the eggplant type flask under reduced pressure, and after about 150 g of distillate was obtained in a trap under reduced pressure in a 40 ° C water bath by an evaporator. , return to normal pressure, then add 150g of MMB. The pressure was further reduced in a bath to obtain PL-2L (MMB replacement) having the same solid concentration as PL-2L-IPA and the solvent was replaced by MMB.

By the same method as described above, other solvents, instead of MMB, were used to obtain PL-2L 1,3BGDA replacement product, EDM replacement product, GBL replacement product, PGMEA replacement product, and PTB replacement product.

By the same method, PL-3-IPA (a colloidal ceria, IPA dispersion, and ceria having a mean particle size of 35 nm, two manufactured by Fuso Chemical Industry Co., Ltd.) was obtained. 1,3BGDA replacement product having a cerium oxide concentration of 17.0% by weight, PL-7 (colloidal cerium oxide manufactured by Fuso Chemical Industry Co., Ltd., water dispersion, average particle diameter of 75 nm, and cerium oxide concentration of 23.0% by weight) MMB replacement product, MLB replacement product of PL-20 (colloidal ceria produced by Fuso Chemical Industry Co., Ltd., water dispersion, average particle diameter of 220 nm, and cerium oxide concentration of 20.0% by weight).

Example 1

In the polyaluminoxane solution A-1, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was Add MMB for 25%. Here, the monomer molar ratio of PL-2L of the cerium oxide particles is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. The obtained composition was subjected to slit coating property, P, B, and Al contents in the solution, peel residue evaluation, crack film thickness measurement, mask thickness measurement, P/N determination, and storage stability. Evaluation (hereinafter referred to as "each measurement and evaluation"). The evaluation results are shown in Table 3.

Example 2

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each measurement and evaluation of the obtained composition was performed. The evaluation results are shown in Table 3.

Example 3

In the polyoxane solution A-3, PL-3 (1,3BGDA replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and was solid. 1,3BGDA was added in such a manner that the concentration of the component was 25% by weight. Here, the monomer molar ratio of PL-3 is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 4

In the polyoxane solution B-1, MMB was added so that the solid content concentration was 25% by weight, and San-Aid SI-200 (manufactured by Sanshin Chemical Industry Co., Ltd.) was added so as to be 0.5% by weight based on the solid content. And mixed and dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 5

In the polyoxane solution A-4, PL-2L (1,3BGDA replacement) was mixed in a mixing ratio of a monomer molar ratio of 20 mol%/PL-2L of 80 mol%, and was solid. 1,3BGDA was added in such a manner that the concentration of the component was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 6

In the polyoxane solution A-4, PL-2L (1,3BGDA replacement) was mixed in a manner that the monomer molar ratio was a mixture ratio of polyoxylane 60 mol%/PL-2L 40 mol%, and was solid. 1,3BGDA was added in such a manner that the concentration of the component was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 7

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 40 mol%/PL-2L 60 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, MEGAFAC F444 (perfluoroalkyl ethylene oxide adduct manufactured by DIC) was added in an amount of 500 ppm based on the total amount of the composition, and mixed and dissolved. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 8

In the polyoxane solution A-5, PL-2L-PGME (manufactured by Fuso Chemical Industry Co., Ltd.) is mixed in such a manner that the monomer molar ratio is a mixture ratio of polyoxylane 40 mol%/PL-2L 60 mol%. PGME and EDM were added so that the solvent composition of the composition was PGME70/EDM30 (weight ratio) and the solid content concentration was 25% by weight, and the colloidal cerium oxide and the PGME dispersion were 17 nm. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 9

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in a mixing ratio of a monomer molar ratio of 40 mol%/PL-2L 60 mol%, and the solid concentration was Add GBL for 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, polypropylene glycol PPG4000 (molecular weight: 4000, glycol type) was added so as to be 500 ppm with respect to the entire composition, and mixed and dissolved. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 10

In the polyoxane solution A-4, PL-2L (1,3BGDA replacement) was mixed in a mixing ratio of a monomer molar ratio of 40 mol%/PL-2L of 60 mol%, and was solid. 1,3BGDA was added in such a manner that the concentration of the component was 25% by weight. then, BYK333 (Biak Chemical (poly) polyether modified polydimethyl siloxane) was added in a manner of 500 ppm with respect to the total composition and mixed and dissolved. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 11

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 40 mol%/PL-2L 60 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, BYK355 (acrylic leveling agent manufactured by BYK Chemical Co., Ltd.) was added in an amount of 500 ppm based on the total amount of the composition, and mixed and dissolved. Next, SI-200 was added so as to be 0.1% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 12

In the polyoxane solution A-7, PL-2L (PTB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 40 mol%/PL-2L 60 mol%, and the composition was PTB and PGMEA were added so that the solvent composition was PTB60/PGMEA40 (weight ratio) and the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 1% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 13

In the polyoxane solution C, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 40 mol%/PL-2L 60 mol%, and the solid concentration was 25 MMB is added in a weight % manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 14

In the polyoxyalkylene solution B-2, MMB was added so that the solid content concentration was 25% by weight. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 15

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, 10-camphorsulfonic acid (CSA) was added so as to be 0.2% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 16

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, citric acid was added so as to be 0.2% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 17

In the case where the solid content ratio is A-2 (99.5% by weight) / A-8 (0.5% by weight), the monomer molar ratio is 30 mol%/PL-2L 70 mol% of polysiloxane. The PL-2L (MMB replacement) was mixed in a mixing ratio, and MMB was added so that the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Add SI-200 and mix and dissolve. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 18

In the case where the solid content ratio is A-2 (95% by weight) / A-8 (5% by weight), the monomer molar ratio is 30 mol%/PL-2L 70 mol% of polysiloxane. The PL-2L (MMB replacement) was mixed in a mixing ratio, and MMB was added so that the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Add SI-200 and mix and dissolve. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 19

In the polyoxane solution D, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was 25 MMB is added in a weight % manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 20

In the polyoxane solution E, PL-2L (MMB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxyalkylene 30 mol%/PL-2L 70 mol%, and the solid concentration was 25 MMB is added in a weight % manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 21

In the polyoxane solution F, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a 25 wt% manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 22

In the polyaluminoxane solution G, PL-2L (MMB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxyalkylene 30 mol%/PL-2L 70 mol%, and the solid concentration was 25 MMB is added in a weight % manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 23

In the polyoxane solution A-5, PL-7 (MMB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 40 mol%/PL-7 60 mol%, and the composition was MMB and EDM were added so that the solvent composition was MMB70/EDM30 (weight ratio) and the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-7 is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 24

In the case where the solid content ratio is A-2 (99.6% by weight) / A-9 (0.4% by weight), the monomer molar ratio is 30 mol%/PL-2L 70 mol% of polysiloxane. The PL-2L (MMB replacement) was mixed in a mixing ratio, and MMB was added so that the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Add SI-200 and mix and dissolve. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 25

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Then, SI-200 (manufactured by Sanshin Chemical Industry Co., Ltd.) was added in an amount of 0.5% by weight based on the solid content, and aluminum acetate was added so as to have an aluminum content of 20 ppm in the solution, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 26

In the polyoxane solution H, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was 25 MMB is added in a weight % manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the cover slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm, and each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Example 27

In the polyoxane solution I, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 35 mol%/PL-2L 65 mol%, and the solid concentration was 25 MMB is added in a weight % manner. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3.

Comparative example 1

In the polyoxane solution A-10, PL-2L-PGME was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L 70 mol%, and the solid concentration was 25 weight. % of the way to add PGME. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. In the polymerization, only a solvent having a boiling point of less than 130 ° C was used, and since the temperature rise was insufficient, the formic acid component remained without being removed by distillation, and the storage stability was poor. Further, since the composition contains only a solvent having a boiling point of less than 130 ° C, precipitates of oxoxane are deposited around the slit nozzle every time the number of coatings is repeated.

Comparative example 2

In the polyoxane solution A-11, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. Polyoxymethane has a low molecular weight and poor storage stability. In addition, the crack film thickness is also small. Further, in terms of slit coating properties, there is also a large amount of bleed, and the line width unevenness becomes large.

Comparative example 3

In the polyoxane solution A-5, PL-20-PGME was mixed in a mixing ratio of a monomer molar ratio of 40 mol%/PL-20 60 mol%, and the solid concentration was 25 weight. % of the way to add EDM. Here, the monomer molar ratio of PL-20 is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. Since the particle size of the cerium oxide particles is too large, the thickness of the mask film is large and the storage stability is also poor.

Comparative example 4

In the case where the solid content ratio is A-2 (90% by weight) / A-8 (10% by weight), the monomer molar ratio is 30 mol%/PL-2L 70 mol% of polysiloxane. The PL-2L (MMB replacement) was mixed in a mixing ratio, and MMB was added so that the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Add SI-200 and mix and dissolve. Then, the cover slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm, and each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. Since the phosphorus content is large, the film thickness of the mask becomes large.

Comparative Example 5

In the case where the solid content ratio is A-2 (99.2% by weight) / A-9 (0.8% by weight), the monomer molar ratio is 30 mol%/PL-2L 70 mol% of polysiloxane. The PL-2L (MMB replacement) was mixed in a mixing ratio, and MMB was added so that the solid content concentration was 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Add SI-200 and mix and dissolve. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. In the mask property evaluation, the surface resistivity of the tantalum wafer after peeling off the mask layer in a part of the sample was inversely reduced as compared with the blank before the mask slurry coating. It is considered that boron as an impurity in the slurry is doped into the germanium wafer to cause contamination. The film thickness of the mask cannot be calculated due to the influence of boron.

Comparative Example 6

In a tetraethoxy decane (TEOS), PL-2L-PGME was mixed in a mixing ratio of monomeric molar ratio of tetramethyl decane 30 mol%/PL-2L 70 mol%, and the solid concentration was 25 The solvent was added in such a manner that the weight % and the solvent ratio were PGME 70% by weight/MMB 30% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. The weight average molecular weight of the decane is as low as 300 or less, and the storage stability is poor. In addition, the crack film thickness is also small. Further, in terms of slit coating properties, there is also a large amount of bleed, and the line width unevenness becomes large.

Comparative Example 7

In the polyaluminoxane solution A-2, PL-2L (MMB replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxyalkylene 70 mol%/PL-2L 30 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. Since the particle content is small, the crack film thickness is small, and the mask film thickness is increased.

Comparative Example 8

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 15 mol%/PL-2L 85 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. Since the particle content is excessive, the film thickness of the mask becomes large.

Comparative Example 9

MMA was added to the polyoxane solution A-12 so that the solid content concentration was 25% by weight, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. Since the particles are not contained, the thickness of the cracked film is small, and the thickness of the mask is increased. Further, in terms of slit coating properties, there is also a large amount of bleed, and the line width unevenness becomes large.

Comparative Example 10

In the polyoxane solution A-2, PL-2L (MMB replacement) was mixed in a mixing ratio of a monomer molar ratio of 30 mol%/PL-2L of 70 mol%, and the solid concentration was MMB was added in a manner of 25% by weight. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Next, SI-200 was added so as to be 0.5% by weight based on the solid content, and aluminum acetate was added so as to have an aluminum content of 40 ppm in the solution, and the mixture was dissolved. Then, the mask slurry composition was obtained by filtration through a filter having a pore size of 0.45 μm. Each of the obtained compositions was subjected to measurement and evaluation. The evaluation results are shown in Table 3. In the mask property evaluation, the surface resistivity of the tantalum wafer after peeling off the mask layer in a part of the sample was inversely reduced as compared with the blank before the mask slurry coating. It is considered that aluminum as an impurity in the slurry is doped into the germanium wafer to cause contamination. The film thickness of the mask cannot be calculated due to the influence of aluminum.

Examples of the case where the slurry composition of the present invention is applied to screen printing applications are listed below.

Example 28

In the polyoxane solution A-3, PL-2L (1,3BGDA replacement) was mixed with a monomer molar ratio of 30 mol%/PL-2L 70 mol% of the polyoxane, and 1 was added. , 3BGDA. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering by a filter having a pore size of 0.45 μm, a polyglycolic acid methyl ester (hereinafter referred to as PMMA, weight average molecular weight: 996,000) was added to the composition in an amount of 8 wt% in the composition. The mixture was dissolved by stirring to obtain a mask slurry composition (solid content concentration: 33% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 29

The polyaluminoxane solution B-3 was dissolved in GBL, filtered through a filter having a pore size of 0.45 μm, and then PMMA (weight average molecular weight: 996,000) was added in an amount of 5% by weight in the composition. The mixture was dissolved by stirring to obtain a mask slurry composition (solid content concentration: 30% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 30

In the polyaluminoxane solution I, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxyalkylene 35 mol%/PL-2L 65 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering by a filter having a pore size of 0.45 μm, PMMA (weight average molecular weight: 996,000) of a tackifier was added in an amount of 8 wt% in the composition, and the mixture was stirred and dissolved to obtain a mask slurry composition. (The solid content concentration was 33% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 31

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 30 mol%/PL-2L 70 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering by a filter having a pore size of 0.45 μm, a tackifier-containing polyethylene oxide (hereinafter referred to as PEO, weight average molecular weight of 850,000) was added thereto in an amount of 7 wt% in the composition, followed by stirring. The composition of the mask slurry (solid content concentration: 32% by weight) was obtained by dissolution. The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 32

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 30 mol%/PL-2L 70 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering by a filter having a pore size of 0.45 μm, polyethylene oxide (hereinafter referred to as PEO, weight average molecular weight: 850,000) of a tackifier was added in an amount of 4% by weight in the composition, followed by stirring. The composition of the mask slurry (solid content concentration: 29% by weight) was obtained by dissolution. The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 33

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 30 mol%/PL-2L 70 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering through a filter having a pore size of 0.45 μm, then a tackifier PEO (weight average molecular weight of 850,000) was added in an amount of 2% by weight in the composition to be 0.5% by weight in the composition. In the manner of adding polypropylene oxide (hereinafter, PPO, weight average molecular weight: 228,000), the mixture was stirred and dissolved to obtain a mask slurry composition (solid content concentration: 27.5% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 34

In the polyoxane solution A-6, Aerosil 300 (a powder manufactured by Japan Aerotech Co., Ltd.) is added in such a manner that the monomer molar ratio is a mixture ratio of 40 mol% of polysiloxane and 60 mol% of ceria particles. The cerium oxide particles have an average particle diameter of cerium oxide of 7 nm. Here, the monomer molar ratio of Aerosil 300 is calculated by using SiO ₂ as a monomer unit. Then, PMMA (weight average molecular weight: 996,000) of GBL and a tackifier was added to the composition in an amount of 5% by weight, and the mixture was stirred and dissolved to obtain a mask slurry composition (solid content concentration: 30% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5.

Example 35

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 30 mol%/PL-2L 70 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering by a filter having a pore size of 0.45 μm, polyvinylpyrrolidone (hereinafter, PVP, weight average molecular weight: 90,000) of a tackifier was added in an amount of 15% by weight in the composition, and the mixture was stirred and dissolved. A mask slurry composition (solid content concentration of 40% by weight) was obtained. The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5. When the hydrofluoric acid after the calcination is peeled off, there is an undissolved residue which is considered to be derived from the tackifier, and the crack resistance and the curtain performance are both low.

Example 36

In the polyoxane solution A-4, PL-2L (1,3BGDA replacement) was mixed with a monomer molar ratio of 30 mol%/PL-2L 70 mol% of the polyoxane, and 1 was added. , 3BGDA. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. Ethylcellulose (Wako Pure Chemicals Co., Ltd.) ethylcellulose 100,49 was added to the composition by filtration through a filter having a pore size of 0.45 μm, followed by addition of a viscous agent in an amount of 3% by weight in the composition. % ethoxy group), which was stirred and dissolved to obtain a mask slurry composition (solid content concentration: 28% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5. When the hydrofluoric acid after the calcination is peeled off, there is an undissolved residue which is considered to be derived from the tackifier, and the crack resistance and the curtain performance are both low.

Example 37

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 30 mol%/PL-2L 70 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering through a filter having a pore diameter of 0.45 μm, a polyvinyl butyral (hereinafter referred to as PVB and a molecular weight of 66,000) of a tackifier added thereto in an amount of 10% by weight in the composition was obtained by stirring and dissolving. The curtain slurry composition (solid content concentration: 35 wt%). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5. When the hydrofluoric acid after the calcination is peeled off, there is an undissolved residue which is considered to be derived from the tackifier, and the crack resistance and the curtain performance are both low. Further, since the viscosity is low, in the screen printing, the amount of bleeding is large, and the line width is not σ = 20 μm and is slightly increased.

Example 38

In the polyoxane solution A-6, PL-2L (GBL replacement) was mixed in such a manner that the monomer molar ratio was a mixture ratio of polyoxylane 30 mol%/PL-2L 70 mol%, and GBL was added. Here, the monomer molar ratio of PL-2L is calculated by using SiO ₂ as a monomer unit. After filtering by a filter having a pore diameter of 0.45 μm, a polyvinyl butyral (hereinafter referred to as PVB, molecular weight: 66,000) of a tackifier was added in an amount of 7 wt% in the composition, followed by stirring and dissolving. The curtain slurry composition (solid content concentration: 32% by weight). The obtained composition was subjected to screen printing property confirmation, viscosity measurement, and each measurement and evaluation. The evaluation results are shown in Table 5. When the hydrofluoric acid after the calcination is peeled off, there is an undissolved residue which is considered to be derived from the tackifier, and the crack resistance and the curtain performance are both low. Further, since the viscosity is low, in the screen printing, the amount of bleeding is large, and the line width is not σ = 35 μm and becomes large.

Example 39 to Example 44 (calcination conditions)

The cover slurry composition obtained in Example 28 was changed to the calcination conditions shown in Table 6 after prebaking (the temperature was raised from 20 ° C at 10 ° C/min to the temperature shown in Table 6 to Table 6). The temperature was maintained and the calcination was carried out while maintaining the time indicated in Table 6. In Example 42, after calcination at 300 ° C for 60 minutes, the temperature was raised from 20 ° C to 800 ° C at 10 ° C / min under a nitrogen atmosphere (0%), and the mixture was further calcined for 60 minutes. The evaluation results are shown in Table 6. The results of Example 28 are again disclosed in Table 6. By performing a high-temperature calcination process in the presence of a certain amount of oxygen or more, a mask layer having no peeling residue and excellent crack resistance and mask performance can be obtained.

The respective synthesis examples, examples, and comparative examples are summarized in Tables 1 to 6.

10‧‧‧Semiconductor substrate

18‧‧‧ Passivation film

20‧‧‧ nitride film

22‧‧‧Electrode

24‧‧‧P type impurity diffusion layer

26‧‧‧N type impurity diffusion layer

Claims (13)

A masking slurry composition comprising (a) a polysiloxane produced by reacting one or more kinds of organodecane represented by the formula (1), and (b) an average particle diameter of 150 nm or less (2) a solvent having a boiling point of 130 ° C or higher, and (a) a polyoxymethane having a weight average molecular weight of 1,000 or more, and a ceria component in a solid content of the composition of 20% by weight or more 70% by weight or less, the P, B, and Al concentrations in all the compositions are each 20 ppm or less: (R ¹ ) _n Si(OR ² ) _4-n (1) (wherein R ¹ represents hydrogen and the carbon number is Any of 1 to 10 alkyl groups, 2 to 10 carbon atoms, or 6 to 15 carbon atoms, and a plurality of R ^{1 's} may be the same or different; R ² represents hydrogen and the carbon number is 1 Any of an alkyl group of ~6, a fluorenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{2 's} may be the same or different; n is an integer of 0 to 3). The mask slurry composition according to claim 1, wherein an aryl group having a carbon number of 6 to 15 in the solid content of the composition is 15% by weight or more. For example, the mask paste composition described in claim 1 or 2 has a viscosity of 3000 mPa. s above. The mask slurry composition according to any one of claims 1 to 3, which contains at least one selected from the group consisting of an acrylate resin, polyethylene oxide, and polypropylene oxide. The mask slurry composition according to claim 4, wherein the content of any one or more of the acrylate resin, the polyethylene oxide, and the polypropylene oxide selected from the composition is 1% by weight or more, 10% by weight or less. The mask slurry composition according to any one of claims 1 to 5, which contains a sulfonic acid or a salt thereof, or a carboxylic acid or a salt thereof. The mask slurry composition according to any one of claims 1 to 6, which contains a sulfonium sulfonate salt as a sulfonic acid. A mask layer obtained by hardening a mask paste composition according to any one of claims 1 to 7. A semiconductor element formed by forming a mask layer as described in claim 8 of the patent application. A semiconductor element obtained by diffusing impurities by using a mask layer as described in claim 9 of the patent application. The semiconductor element according to claim 9 or 10, wherein the semiconductor element is a photoelectric conversion element. A method of manufacturing a semiconductor device, comprising: forming a mask pattern on a semiconductor substrate using a mask paste composition according to any one of claims 1 to 7; The mask pattern formed on the semiconductor substrate is used as a mask to diffuse impurities to the semiconductor substrate. The method of manufacturing a semiconductor device according to claim 12, wherein the step of forming the mask pattern comprises: using the semiconductor substrate as described in any one of claims 1 to 7 Cover curtain composition a step of applying a pattern; and heating the pattern in an atmosphere having an oxygen concentration of 5% or more in a temperature range of 400 ° C or higher and 900 ° C or lower for 5 minutes or longer.