Composition for forming protective film for manufacturing semiconductor chip, semiconductor substrate, semiconductor chip, and method for manufacturing semiconductor chip

Abstract

The purpose of the present invention is to provide, by a simpler method, a semiconductor chip with a protective film capable of protecting a semiconductor chip from damage associated with conveyance when the semiconductor chip is conveyed, said semiconductor chip being obtained by dicing a semiconductor substrate. Provided is a composition for forming a protective film for semiconductor chip production, said composition being capable of easily forming a protective film for semiconductor chip production, said protective film being arranged on a semiconductor chip. A composition for forming a protective film for manufacturing a semiconductor chip, which is used for preventing damage to the circuit surface or the back surface of a semiconductor substrate or a semiconductor chip, and which contains a polymer and a solvent, the polymer is selected from the group consisting of a phenolic hydroxyl group-containing polymer and a carboxyl group-containing polymer.

Description

Technical Field

[0001] The present invention relates to a composition for forming a protective film for semiconductor chip manufacturing, which is used to form a protective film disposed on a semiconductor chip, a semiconductor substrate and a semiconductor chip having the protective film for semiconductor chip manufacturing, and a method for manufacturing a semiconductor chip. Background Art

[0002] In the manufacture of semiconductor devices, particularly in the so-called post-process, a semiconductor substrate (eg, a wafer) with circuits formed thereon is attached to a support sheet (eg, a dicing tape), and then the semiconductor substrate is diced to obtain semiconductor chips.

[0003] The semiconductor chips are then transported to and placed on a support sheet or printed circuit board in order to be reattached to another support sheet or mounted on a printed circuit board. During this transport, it is required that the semiconductor chips are not damaged or broken.

[0004] In addition, Patent Document 1 discloses a process of obtaining a semiconductor device with a protective film (equivalent to the so-called semiconductor chip in the present invention) by cutting a semiconductor substrate and a protective film, and picking up the semiconductor device with a protective film (semiconductor chip) from a supporting sheet (see paragraph

[0012] of Patent Document 1, etc.), and in an embodiment of Patent Document 1, it is disclosed that even if a semiconductor wafer with a protective film is transported using a robot arm, the film for forming a protective film adhered to the semiconductor wafer does not deform (see paragraph

[0160] of Patent Document 1, etc.).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2021 / 166991 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] In Patent Document 1, a protective film-forming film is temporarily produced, and the protective film-forming film produced in a sheet form is attached to a semiconductor substrate to obtain a semiconductor wafer with a protective film.

[0010] In order to prevent damage during transportation when transporting individual semiconductor chips obtained by cutting a semiconductor substrate, it is effective to provide semiconductor chips with a protective film, as described in Patent Document 1. However, from the perspective of simplifying the device structure and operating steps for manufacturing semiconductor chips with a protective film, the manufacturing method described in the above Patent Document 1 cannot be said to be sufficient and there is room for improvement.

[0011] It is desirable to provide a semiconductor chip with a protective film that can be produced by a simpler method.

[0012] Therefore, the present invention aims to provide a semiconductor chip with a protective film that can protect the semiconductor chip from damage associated with transportation when transporting individual semiconductor chips obtained by cutting a semiconductor substrate through a simpler method, and to provide a composition for forming a protective film for semiconductor chip manufacturing that can easily form a protective film for semiconductor chip manufacturing to be arranged on the semiconductor chip.

[0013] In addition, the present invention aims to provide a composition for forming a protective film for semiconductor chip manufacturing that can form a protective film for semiconductor chip manufacturing, so that the protective film formed by the composition for forming a protective film for semiconductor chip manufacturing can be easily dissolved in a removing liquid such as an alkaline removing liquid and can be easily removed from the semiconductor chip.

[0014] Furthermore, the present invention aims to provide a protective film for semiconductor chip manufacturing formed from the protective film-forming composition for semiconductor chip manufacturing, a semiconductor substrate or a semiconductor chip having the protective film for semiconductor chip manufacturing, and a method for manufacturing the semiconductor chip.

[0015] Means for solving problems

[0016] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, thereby completing the present invention having the following gist.

[0017] That is, the present invention includes the following aspects.

[0018] [1] A composition for forming a protective film for use in semiconductor chip manufacturing, which is used to prevent damage to the circuit surface or back surface of a semiconductor substrate or a semiconductor chip. The protective film-forming composition for semiconductor chip manufacturing comprises a polymer and a solvent. The polymer is selected from any one of a polymer containing a phenolic hydroxyl group, a polymer containing a carboxyl group, and a polymer containing a blocked carboxyl group.

[0019] [2] The protective film-forming composition for semiconductor chip manufacturing according to [1], wherein the protective film-forming composition for semiconductor chip manufacturing forms a protective film that is soluble in an alkaline removing liquid, an acidic removing liquid, a neutral removing liquid, or an organic solvent.

[0020] [3] The protective film forming composition for semiconductor chip manufacturing according to [1] or [2], wherein the protective film forming composition for semiconductor chip manufacturing contains 50% by mass or more of the polymer relative to the total solid content in the composition.

[0021] [4] The composition for forming a protective film for semiconductor chip manufacturing according to any one of [1] to [3], wherein the protective film for semiconductor chip manufacturing is arranged on the semiconductor substrate in order to protect the semiconductor chips from damage during transportation of the individual semiconductor chips obtained by dicing the semiconductor substrate.

[0022] [5] The composition for forming a protective film for semiconductor chip manufacturing according to any one of [1] to [4], wherein the polymer containing a phenolic hydroxyl group is selected from any one of phenol novolac, naphthol novolac, polyhydroxystyrenes, polyhydroxyphenyl (meth)acrylates and poly(N-hydroxyphenyl (meth)acrylamides).

[0023] [6] The composition for forming a protective film for semiconductor chip manufacturing according to any one of [1] to [5], wherein the carboxyl group-containing polymer is selected from any one of (meth)acrylic resins, polyvinyl benzoic acid, carboxymethyl cellulose, and polyamic acid.

[0024] [7] The composition for forming a protective film for semiconductor chip manufacturing according to [6], wherein the polyamic acid is a polyamic acid having structural units derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group.

[0025] [8] The composition for forming a protective film for manufacturing a semiconductor chip according to any one of [1] to [7], wherein the composition for forming a protective film for manufacturing a semiconductor chip contains at least one of a crosslinking agent, an acid catalyst, and an additive.

[0026] [9] The composition for forming a protective film for semiconductor chip manufacturing according to [8], wherein the crosslinking agent is selected from any one of an aminoplast crosslinking agent, a phenolic plastic crosslinking agent, and a crosslinking agent containing an epoxy group.

[0027]

[10] A protective film for semiconductor chip manufacturing, which is a fired product of a coating film formed from the protective film-forming composition for semiconductor chip manufacturing according to any one of [1] to [9].

[0028]

[11] The protective film for semiconductor chip manufacturing according to

[10] , wherein the film thickness of the protective film for semiconductor chip manufacturing is 1 to 10 μm.

[0029]

[12] A semiconductor substrate having the protective film for semiconductor chip manufacturing described in

[10] or

[11] .

[0030]

[13] A semiconductor chip having the protective film for semiconductor chip manufacturing described in

[10] or

[11] .

[0031]

[14] A method for manufacturing a semiconductor chip, comprising the following steps: a step of applying the composition for forming a protective film for manufacturing a semiconductor chip described in any one of [1] to [9] on a semiconductor substrate and firing the composition to form a protective film for manufacturing a semiconductor chip; a step of cutting the semiconductor substrate provided with the protective film for manufacturing a semiconductor chip to obtain a semiconductor chip with the protective film for manufacturing a semiconductor chip; and a step of transporting the semiconductor chip.

[0032]

[15] The method for manufacturing a semiconductor chip according to

[14] further comprises the step of removing the protective film for manufacturing the semiconductor chip from the semiconductor chip by cleaning it with an alkaline removing solution, an acidic removing solution, a neutral removing solution or an organic solvent.

[0033] Effects of the Invention

[0034] Through the present invention, in order to provide a semiconductor chip with a protective film that can protect the semiconductor chip from damage associated with transportation when transporting individual semiconductor chips obtained by cutting a semiconductor substrate through a simpler method, a composition for forming a protective film for semiconductor chip manufacturing can be provided that can easily form a protective film for semiconductor chip manufacturing to be arranged on the semiconductor chip.

[0035] In addition, the present invention can provide a composition for forming a protective film for semiconductor chip manufacturing that can form a protective film for semiconductor chip manufacturing, which can be easily dissolved in a removing liquid such as an alkaline removing liquid and can be easily removed from the semiconductor chip.

[0036] Furthermore, the present invention can provide a protective film for semiconductor chip manufacturing formed from the protective film-forming composition for semiconductor chip manufacturing, a semiconductor substrate or a semiconductor chip having the protective film for semiconductor chip manufacturing, and a method for manufacturing the semiconductor chip. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic cross-sectional view showing an example of a semiconductor substrate.

[0038] Figure 2A This is a schematic cross-sectional view showing an example of a semiconductor substrate having a coating film of the protective film-forming composition for semiconductor chip manufacturing.

[0039] Figure 2B This is a schematic cross-sectional view showing an example of a semiconductor substrate having a protective film for semiconductor chip manufacturing.

[0040] Figure 3 This is a schematic cross-sectional view showing another example of a semiconductor substrate having a protective film for semiconductor chip manufacturing.

[0041] Figure 4 This is a schematic cross-sectional view for explaining an example of a method for manufacturing a semiconductor chip according to the present invention.

[0042] Figure 5A This is a schematic cross-sectional view for explaining an example of a method for manufacturing a semiconductor chip according to the present invention.

[0043] Figure 5B This is a schematic cross-sectional view for explaining an example of a method for manufacturing a semiconductor chip according to the present invention.

[0044] Figure 6 This is a schematic cross-sectional view for explaining an example of a method for manufacturing a semiconductor chip according to the present invention.

[0045] Figure 7A This is a schematic cross-sectional view for explaining another example of the method for manufacturing a semiconductor chip according to the present invention.

[0046] Figure 7B This is a schematic cross-sectional view for explaining another example of the method for manufacturing a semiconductor chip according to the present invention. DETAILED DESCRIPTION

[0047] (Protective film-forming composition for semiconductor chip manufacturing)

[0048] The protective film-forming composition for semiconductor chip manufacturing of the present invention is a composition for forming a protective film for semiconductor chip manufacturing to be placed on a semiconductor chip.

[0049] The protective film-forming composition for semiconductor chip production of the present invention is used to prevent damage to the circuit surface or back surface of a semiconductor substrate or a semiconductor chip.

[0050] The protective film-forming composition for semiconductor chip production contains a polymer and a solvent.

[0051] The polymer is selected from a polymer containing a phenolic hydroxyl group and a polymer containing a carboxyl group. These polymers are soluble in removing solutions such as alkaline removing solutions. Therefore, the protective film for manufacturing semiconductor chips of the present invention formed by the protective film-forming composition for manufacturing semiconductor chips of the present invention is easily dissolved in removing solutions such as alkaline removing solutions (in this specification, "removing solutions such as alkaline removing solutions" are also referred to as "removing solutions" or "developing solution") and can be easily removed from the semiconductor chip.

[0052] The protective film for semiconductor chip manufacturing of the present invention is disposed on a semiconductor chip and can effectively protect the semiconductor chip from damage during transportation of individual semiconductor chips obtained by dicing a semiconductor substrate as described above.

[0053] The phenolic hydroxyl group-containing polymer is preferably selected from phenol novolacs, naphthol novolacs, polyhydroxystyrenes, polyhydroxyphenyl (meth)acrylates, and poly(N-hydroxyphenyl (meth)acrylamides).

[0054] The carboxyl group-containing polymer is preferably selected from any one of (meth)acrylic resins, polyvinyl benzoic acid, carboxymethyl cellulose, and polyamic acid.

[0055] Furthermore, the composition for forming a protective film for semiconductor chip manufacturing preferably contains 50% by mass or more of the polymer relative to the total solid content in the composition, more preferably 60% by mass or more, further preferably 70% by mass or more, further more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0056] <Phenol novolac / naphthol novolac>

[0057] As the phenol novolac or naphthol novolac (novolac resin), those conventionally used in positive photosensitive materials can be used without limitation, and examples thereof include resins obtained by polymerizing phenols (including naphthol) and aldehydes in the presence of an acid catalyst.

[0058] Examples of the phenols include phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, and Alkylphenols such as phenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkylpolyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (the alkyl group has 1 to 4 carbon atoms); α-naphthol, β-naphthol, hydroxybiphenyl, bisphenol A, etc. These phenols may be used alone or in combination of two or more.

[0059] Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

[0060] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and p-toluenesulfonic acid; and metal salts such as zinc acetate.

[0061] In the present application, a naphthol-cresol novolac in which α-naphthol and / or β-naphthol are polymerized may also be used.

[0062] <Polyhydroxystyrenes>

[0063] The polyhydroxystyrenes include polyhydroxystyrene and polyhydroxystyrene derivatives.

[0064] Examples of polyhydroxystyrene or polyhydroxystyrene derivatives include poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxystyrene, poly-α-methyl-m-hydroxystyrene, and poly-α-methyl-p-hydroxystyrene.

[0065] The polyhydroxystyrene or polyhydroxystyrene derivative may be a homopolymer of hydroxystyrene which may have a substituent, or a copolymer obtained by copolymerizing hydroxystyrene which may have a substituent with another compound. Examples of the other compound include (meth)acrylic acid, (meth)acrylic acid derivatives, acrylonitrile, methacrylonitrile, styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, and p-chlorostyrene.

[0066] The polyhydroxystyrenes according to the present application can be obtained by polymerizing hydroxystyrenes which may have a substituent, and preferably have the following unit structure, for example.

[0067]

[0068] (In formula (1), R represents a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, or an alkoxy group having 1 to 9 carbon atoms. n represents an integer of 0 to 4. When n is 2 or more, n R groups may be the same or different.)

[0069] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0070] Examples of the alkoxy group having 1 to 9 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl -n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, n-heptyloxy, n-octyloxy and n-nonyloxy.

[0071] <Polyhydroxyphenyl (meth)acrylates>

[0072] The polyhydroxyphenyl (meth)acrylates include polyhydroxyphenyl (meth)acrylate and polyhydroxyphenyl (meth)acrylate derivatives.

[0073] The polyhydroxyphenyl (meth)acrylate or the polyhydroxyphenyl (meth)acrylate derivative may be a homopolymer of hydroxyphenyl (meth)acrylate which may have a substituent, or a copolymer obtained by copolymerizing hydroxyphenyl (meth)acrylate which may have a substituent and other compounds as described above.

[0074] The polyhydroxyphenyl (meth)acrylates according to the present application can be obtained by polymerizing hydroxyphenyl (meth)acrylate which may have a substituent, and preferably has the following unit structure, for example.

[0075]

[0076] (In formula (2), R1 represents a hydrogen atom or a methyl group. R represents a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, or an alkoxy group having 1 to 9 carbon atoms. n represents an integer from 0 to 4. When n is 2 or more, the n R groups may be the same or different.)

[0077] Poly(N-hydroxyphenyl(meth)acrylamide)

[0078] The poly(N-hydroxyphenyl(meth)acrylamide)s include poly(N-hydroxyphenyl(meth)acrylamide) and poly(N-hydroxyphenyl(meth)acrylamide) derivatives.

[0079] The poly(N-hydroxyphenyl(meth)acrylamide) or poly(N-hydroxyphenyl(meth)acrylamide) derivative may be a homopolymer of N-hydroxyphenyl(meth)acrylamide which may have a substituent, or a copolymer obtained by copolymerizing N-hydroxyphenyl(meth)acrylamide which may have a substituent and other compounds as described above.

[0080] The poly(N-hydroxyphenyl(meth)acrylamide)s according to the present application can be obtained by polymerizing N-hydroxyphenyl(meth)acrylamide which may have a substituent, and preferably have the following unit structure, for example.

[0081]

[0082] (In formula (3), R1 represents a hydrogen atom or a methyl group. R represents a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, or an alkoxy group having 1 to 9 carbon atoms. n represents an integer from 0 to 4. When n is 2 or more, the n R groups may be the same or different.)

[0083] <(Meth)acrylic resin>

[0084] The (meth)acrylic resin according to the present application is a (meth)acrylic resin having a carboxyl group.

[0085] The (meth)acrylic resin used in the present application may be any resin conventionally used in positive photosensitive materials without limitation, and examples thereof include resins obtained by polymerizing a polymerizable monomer having a (meth)acryloyl group in the presence of a radical polymerization initiator.

[0086] The carboxyl group may be a blocked carboxyl group. Examples of blocked carboxyl groups include carboxyl groups protected by vinyl ether.

[0087] The (meth)acrylic resin having a carboxyl group may be, for example, a homopolymer of a polymerizable monomer (I) having a carboxyl group and a (meth)acryloyl group, or a copolymer obtained by copolymerizing a polymerizable monomer (I) having a carboxyl group and a (meth)acryloyl group with a polymerizable monomer (II) having a (meth)acryloyl group as shown below.

[0088] Examples of the polymerizable monomer (I) having a carboxyl group and a (meth)acryloyl group include (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid.

[0089] Examples of the polymerizable monomer (II) having a (meth)acryloyl group include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, trifluoroethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; acrylamides such as diacetone acrylamide; tetrahydrofurfuryl (meth)acrylate, dialkylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate.

[0090] The polymerizable monomer (I) or the polymerizable monomer (II) used in combination with the polymerizable monomer (I) may be used in combination of two or more types.

[0091] Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, dicumyl peroxide, and dibutyl peroxide; and azobis compounds such as azobisisobutyronitrile and azobisvaleronitrile.

[0092] Furthermore, the (meth)acrylic resin according to the present application may be a copolymer obtained by copolymerizing other compounds in addition to the polymerizable monomer (I) or the polymerizable monomer (I) and the polymerizable monomer (II).

[0093] For example, it can be a copolymer obtained by adding polymerizable monomers (I), or polymerizable monomers (I) and polymerizable monomers (II) to polymerizable monomers (I) or to polymerizable monomers (I) and polymerizable monomers (II) a polymerizable styrene derivative substituted at the α-position or on the aromatic ring, such as styrene, vinyltoluene, α-methylstyrene, etc.; esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; or one or more polymerizable monomers such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid.

[0094] In addition, in this specification, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid".

[0095] Polyvinylbenzoic acid

[0096] The polyvinylbenzoic acid of the present application can be obtained by, for example, polymerizing the following 4-vinylbenzoic acid by a known method.

[0097]

[0098] <Carboxymethyl cellulose>

[0099] The carboxymethylcellulose of the present application has the structure shown below.

[0100]

[0101] R=H or CH2CO2H

[0102] (where n represents the number of repeating units)

[0103] <Polyamic acid>

[0104] The protective film forming composition for semiconductor chip manufacturing of the present invention may include a carboxyl-containing polymer of a polyamic acid having a structural unit derived from a diamine compound having at least one carboxyl group as described in International Publication No. 2018 / 159665. The above-mentioned polymer may also be a polyamic acid having a structural unit derived from a diamine compound having at least one carboxyl group (a) a tetracarboxylic dianhydride compound and (b), and a structural unit derived from a diamine compound having at least one carboxyl group (a) a tetracarboxylic dianhydride compound and (c) a diamine compound different from (b).

[0105] The (c) diamine compound may be a diamine compound not having a carboxyl group.

[0106] Examples of the polyamic acid contained in the protective film-forming composition for semiconductor chip manufacturing of the present invention include the following polyamic acids (29) to (41) (wherein p1, p2, p3, and p4 represent the ratio of each structure in the polyamic acid). Here, (29) to (36) are polyamic acids produced from one tetracarboxylic dianhydride compound and two diamine compounds, (37) and (38) are polyamic acids produced from two tetracarboxylic dianhydride compounds and one diamine compound, (39) is a polyamic acid produced from two tetracarboxylic dianhydride compounds and two diamine compounds, and further, (40) and (41) are polyamic acids produced from one tetracarboxylic dianhydride compound and one diamine compound.

[0107]

[0108] It should be noted that the contents of International Publication No. 2018 / 159665 are incorporated into this specification to the same extent as if all were expressly stated.

[0109] The weight average molecular weight of the polymer involved in the present application, as measured by gel permeation chromatography (GPC), is, for example, 1,000 to 100,000, or 1,000 to 50,000, preferably 2,000 to 50,000, in terms of polystyrene. A weight average molecular weight of 1,000 or greater improves coating properties, while a weight average molecular weight of 100,000 or less ensures sufficient solubility of the resulting protective film for semiconductor chip manufacturing in an alkaline stripping solution.

[0110] Solvents

[0111] The protective film forming composition for semiconductor chip production of the present invention can be easily prepared by uniformly mixing the above-mentioned components, and can be used in a solution state by being dissolved in an appropriate solvent. Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. Furthermore, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate may be mixed and used.

[0112] The protective film forming composition solution prepared in this way is preferably filtered using a filter with a pore size of about 0.2 μm before use. The protective film forming composition solution prepared in this way also has excellent long-term storage stability at room temperature.

[0113] The solid content ratio in the protective film-forming composition for semiconductor chip manufacturing of the present invention is not particularly limited as long as the components are uniformly dissolved, and is, for example, 0.5 to 50% by mass, and another example is 1 to 30% by mass. The solid content herein refers to the content after removing the solvent component from all the components of the protective film-forming composition for semiconductor chip manufacturing.

[0114] Furthermore, the protective film-forming composition for semiconductor chip production of the present invention preferably contains at least one of a cross-linking agent, an acid catalyst, and an additive.

[0115] Cross-linking agent

[0116] The crosslinking agent is preferably any one of an aminoplast-based crosslinking agent, a phenoplast-based crosslinking agent, and an epoxy group-containing crosslinking agent.

[0117] <<Aminoplast crosslinking agent>>

[0118] Aminoplast crosslinking agents are addition condensation products of compounds having amino groups, such as melamine and guanamine, with formaldehyde.

[0119] <<Phenolic plastic crosslinking agent>>

[0120] The so-called phenolic plastic crosslinking agent is an addition condensation product of a compound having a phenolic hydroxyl group and formaldehyde.

[0121] <<Crosslinking agent containing epoxy group>>

[0122] The cross-linking agent containing an epoxy group may also contain a compound having at least two epoxy groups. As such a compound, there is no particular limitation as long as it is a compound having an epoxy group. For example, tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropyloxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc. can be mentioned.

[0123] Examples of compounds having at least two epoxy groups and epoxy resins having amino groups include YH-434 and YH434L (trade names of Nippon Steel Chemical & Materials Co., Ltd.); examples of epoxy resins having a cyclohexene oxide structure include Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celoxide 2021, and Celoxide 3000 (trade names of Daicel Chemical Co., Ltd.); and examples of bisphenol A epoxy resins include Epicotate 1001, Epicotate 1002, Epicotate 1003, Epicotate 1004, Epicotate 1007, Epicotate 1009, Epicotate 1010, and Epicotate 828 (trade names of Yuka Shell). Examples of the bisphenol F type epoxy resin include Epicote 807 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.); examples of the phenol novolac type epoxy resin include Epicote 152 and Epicote 154 (trade names, manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN 201 and EPPN 202 (trade names, manufactured by Nippon Kayaku Co., Ltd.); examples of the cresol novolac type epoxy resin include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (trade names, manufactured by Nippon Kayaku Co., Ltd.), and Epicote 180S75 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.); examples of the alicyclic epoxy resin include Denacol EX-252 (Nagase As aliphatic polyglycidyl ethers, there are CY175, CY177, CY179 (above, manufactured by CIBA-GEIGY AG, trade names), Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by CIBA-GEIGY AG, trade names), Epicron 200, Epicron 400 (above, manufactured by Dainippon Ink Industries, Ltd., trade names), Epicote 871, Epicote 872 (above, manufactured by Yuka Shell Epoxy Co., Ltd., trade names), ED-5661, ED-5662 (above, manufactured by Celanese Coating Co., Ltd., trade names), etc.Examples include Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, and Denacol EX-321 (trade names manufactured by Nagase ChemteX Co., Ltd.).

[0124] The content of the crosslinking agent is, for example, 5 to 70 parts by mass, or 10 to 60 parts by mass, preferably 10 to 30 parts by mass, relative to 100 parts by mass of the polymer. If the content of the crosslinking agent is less than 5 parts by mass, the degree of hardening of the protective film for semiconductor chip manufacturing may be insufficient. If the content exceeds 70 parts by mass, sufficient solubility in a stripping solution such as an alkaline stripping solution may not be achieved.

[0125] Preferred embodiments of the cross-linking agent include, for example, compounds having two or more of the following structures.

[0126]

[0127] (In the structure, R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.)

[0128] The bonding bond is, for example, to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0129] As R 101 , preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure.

[0130]

[0131] (In the structure, R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.)

[0132] As the crosslinking agent, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group are preferred, and these may be used alone or in combination of two or more.

[0133] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or mixtures thereof.

[0134] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are methoxymethylated, or mixtures thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are acyloxymethylated, or mixtures thereof.

[0135] Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are methoxymethylated, or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated, or mixtures thereof.

[0136] Furthermore, the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E).

[0137]

[0138] (In formula (1E), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0139] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0140]

[0141] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0142]

[0143] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0144] (In formula (3d), R1 represents a methyl group or an ethyl group.)

[0145] Examples of the glycoluril derivatives represented by formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4). Further examples of the compounds represented by formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0146]

[0147] Examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated, or a mixture thereof, and tetramethoxyethylurea.

[0148] Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (G-1) or formula (G-2).

[0149]

[0150] (In formula (G-1) and formula (G-2), Q 1 It represents a single bond or an m1-valent organic group.

[0151] R 1 and R 4 Each represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms.

[0152] R 2 and R 5 Each represents a hydrogen atom or a methyl group.

[0153] R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0154] n1 represents an integer of 1≤n1≤3, n2 represents an integer of 2≤n2≤5, n3 represents an integer of 0≤n3≤3, n4 represents an integer of 0≤n4≤3, and n1, n2, n3, n4 represent integers of 3≤(n1+n2+n3+n4)≤6.

[0155] n5 represents an integer of 1≤n5≤3, n6 represents an integer of 1≤n6≤4, n7 represents an integer of 0≤n7≤3, n8 represents an integer of 0≤n8≤3, and n5, n6, n7, n8 represent integers of 2≤(n5+n6+n7+n8)≤5.

[0156] m1 represents an integer from 2 to 10.)

[0157] Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (G-3) or formula (G-4).

[0158] The compound represented by formula (G-1) or formula (G-2) can be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0159]

[0160] (In formula (G-3) and formula (G-4), Q 2 Represents a single bond or an m2-valent organic group.

[0161] R 8 、R 9 、R 11 and R 12 Each represents a hydrogen atom or a methyl group.

[0162] R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0163] n9 represents an integer of 1≤n9≤3, n 10 Indicates 2≤n 10 Integer ≤ 5, n 11 Indicates 0≤n 11 Integer ≤ 3, n 12 Indicates 0≤n 12 An integer ≤3, and n9, n 10 、n 11 、n 12 It means 3≤(n9+n 10 +n 11 +n 12 )≤6.

[0164] n 13 Indicates 1≤n 13 Integer ≤ 3, n 14 Indicates 1≤n 14 Integer ≤ 4, n 15 Indicates 0≤n 15 Integer ≤ 3, n 16 Indicates 0≤n 16 An integer ≤3, and n 13 、n 14 、n 15 、n 16 means 2≤(n 13 +n 14 +n 15 +n 16 )≤5.

[0165] m2 represents an integer from 2 to 10.)

[0166] As Q 2 Examples of the m2-valent organic group include an m2-valent organic group having 1 to 4 carbon atoms.

[0167] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds.

[0168]

[0169] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds.

[0170]

[0171] The above compounds can be obtained as products of Asahi Organic Chemicals Industries, Ltd. and Honshu Chemical Industry Co., Ltd. As an example of the product, there is TMOM-BP, a trade name of Asahi Organic Chemicals Industries, Ltd.

[0172] Among them, glycoluril compounds are preferred, specifically, tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated, or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated, or mixtures thereof, and tetramethoxymethyl glycoluril is more preferred.

[0173] <Acid Catalyst>

[0174] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and p-toluenesulfonic acid; and metal salts such as zinc acetate.

[0175] The content of the acid catalyst is, for example, preferably (0.01) to (10) parts by mass, more preferably (0.1) to (5) parts by mass, and even more preferably (0.5) to (3) parts by mass, relative to 100 parts by mass of the polymer.

[0176] Furthermore, as the acid catalyst, a hardening catalyst may be used.

[0177] <Curing catalyst>

[0178] As the curing catalyst contained as an optional component in the resist underlayer film-forming composition, either a thermal acid generator or a photoacid generator may be used, but a thermal acid generator is preferably used.

[0179] Examples of the thermal acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine -p-Toluenesulfonate (pyridine -p-toluenesulfonic acid), pyridine Phenolsulfonic acid, pyridine -p-Hydroxybenzenesulfonic acid (pyridinium phenolsulfonate salt), pyridine - Sulfonic acid compounds and carboxylic acid compounds such as trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0180] Examples of the photoacid generator include: Salt compounds, sulfonimide compounds and disulfonyldiazomethane compounds, etc.

[0181] As Salt compounds, for example, diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyl iodide Nonafluorobutanesulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate and bis(4-tert-butylphenyl)iodide trifluoromethanesulfonate and other iodine Sulfonium salt compounds and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0182] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0183] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0184] The curing catalyst may be used alone or in combination of two or more.

[0185] When a curing catalyst is used, the content ratio of the curing catalyst relative to the cross-linking agent is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.

[0186] <Additives>

[0187] The protective film-forming composition for semiconductor chip production of the present invention may contain a light-absorbing compound, a surfactant, an adhesion promoter, and a rheology modifier as additives.

[0188] <<Light-absorbing compounds>>

[0189] The light-absorbing compound is not particularly limited as long as it absorbs at the exposure wavelength used. Compounds having aromatic ring structures such as anthracene, naphthalene, benzene, quinoline, and triazine rings are preferably used. Furthermore, compounds having phenolic hydroxyl groups, carboxyl groups, or sulfonic acid groups are preferably used to maintain the solubility of the protective film for semiconductor chip manufacturing in alkaline strippers and other removal solutions.

[0190] Examples of the light-absorbing compound having a large absorption for light of a wavelength of 248 nm include 1-naphthoic acid, 2-naphthoic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2-hydroxynaphthalene, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid ... 8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-hydroxy-1-naphthalene dicarboxylic acid, 1-hydroxy-2-naphthalene dicarboxylic acid, 3-hydroxy-2-naphthalene dicarboxylic acid, 6-hydroxy-2-naphthalene dicarboxylic acid, 1-bromo- 2-Hydroxy-3-naphthoic acid, 1-bromo-4-hydroxy-3-naphthoic acid, 1,6-dibromo-2-hydroxy-3-naphthoic acid, 3-hydroxy-7-methoxy-2-naphthoic acid, 1-amino-2-naphthol, 1,5-dimercaptonaphthalene, 1,4,5,8-naphthalenetetracarboxylic acid, 3,5-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2,6-dichloro-1-naphthol, methyl 2-hydroxy-3-naphthoate, 6-hydroxy- Methyl 2-naphthoate, methyl 3-hydroxy-7-methoxy-2-naphthoate, methyl 3,7-dihydroxy-2-naphthoate, 2,4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphtholthiophenol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphthoic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthalene, 1-acetyl-2-naphthol, 9-anthracenecarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, 1,8,9-trihydroxyanthracene, etc.

[0191] In addition, examples of light-absorbing compounds having a large absorption capacity for light of 193 nm in wavelength include benzoic acid, 4-methylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-methoxybenzoic acid, isophthalic acid, terephthalic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-acetoxybenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, trimesic acid, 1,4-benzenedicarboxylic acid, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 1,4-dihydroxybenzoic acid. Formic acid, 3,5-dihydroxybenzoic acid, 4-acetylbenzoic acid, pyromellitic acid, trimesic anhydride, 2-[bis-(4-hydroxyphenyl)-methyl]benzoic acid, 3,4,5-trihydroxybenzoic acid, 2-benzophenonecarboxylic acid, m-phenylbenzoic acid, 3-(4'-hydroxyphenoxy)benzoic acid, 3-phenoxybenzoic acid, phenol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 2-methylphenol, 3-methylphenol, 4-methylphenol, 1,3,5-trihydroxybenzene, 2,2-bis-4-hydroxyphenylpropane, 2-hydroxybiphenyl, 2-aminophenol, 3-aminophenol, 4-aminophenol and 4-benzyloxyphenol, etc.

[0192] Furthermore, in order to suppress sublimation during firing for forming a protective film for semiconductor chip production, these absorbing compounds may be reacted with a polymer and / or a compound having one or more reactive groups.

[0193] For example, in the case of a light-absorbing compound having a carboxyl group and / or a phenolic hydroxyl group, tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris(p-(2,3-epoxypropyloxy)phenyl)propane ...1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl)cyclohexane, 1,2-epoxy-4-(oxiranyl) Compounds obtained by reacting a multifunctional epoxy compound such as 2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether, and / or a polymer containing a structure having an epoxy group such as glycidyl methacrylate. Examples include polymers having unit structures represented by the following (42), (43), and (44), and a compound represented by (45). In formula (45), Ar represents a benzene ring, a naphthalene ring or anthracene ring which may be substituted by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a thioalkyl group having 1 to 5 carbon atoms, a carboxyl group, a phenoxy group, an acetyl group, an alkoxycarbonyl group having 1 to 5 carbon atoms or a vinyl group.

[0194]

[0195] The above-mentioned absorbing compounds can be used alone or in combination of two or more. When using a light-absorbing compound, its content is, for example, 1 to 300 parts by mass, or 1 to 200 parts by mass, or 1 to 100 parts by mass, or 5 to 100 parts by mass, relative to 100 parts by mass of the polymer. If the amount of the absorbing compound exceeds 300 parts by mass, the solubility of the protective film for semiconductor chip manufacturing in a removal solution such as an alkaline remover may be reduced.

[0196] The protective film forming composition for semiconductor chip manufacturing of the present invention may contain an acid generator. Examples of the acid generator include thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienonone, benzoin tosylate, 2-nitrobenzyl tosylate, other organic sulfonic acid alkyl esters, bis(4-tert-butylphenyl)iodide, Photoacid generators such as trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin tosylate, and N-hydroxysuccinimide trifluoromethanesulfonate are used. The amount of the acid generator to be added is 10% by mass or less, preferably 3% by mass or less, based on the solid content of the protective film-forming composition for semiconductor chip manufacturing, as needed.

[0197] In the composition for forming a protective film for semiconductor chip manufacturing of the present invention, a polyphenol compound or a compound containing a carboxyl group may be added for the purpose of accelerating the dissolution rate in a removing solution such as an alkaline removing solution. Such compounds are not particularly limited, and examples thereof include tris-hydroxyphenylethane, bisphenol-A, bisphenol-S, 4,4'-isopropylidene-di-o-cresol, 5-tert-butylpyrogallol, hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5',6,6'-tetrol, 4,4'-(9-fluorenylene)biphenol, bisphenol-AP, bisphenol- P, 5-α,α-dimethyl-4-hydroxybenzyl salicylic acid, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 5,5'-di-tert-butyl-2,2',4,4'-tetrahydroxybenzophenone and other polyphenols, pyromellitic acid, phthalic acid, trimellitic acid, 4-sulfophthalic acid, mellitic acid, 2,3-naphthalene dicarboxylic acid, 4-hydroxyphthalic acid dicarboxylic acid, 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3'-, 4,4'-biphenyltetracarboxylic acid, 3,3'-, 4,4'-benzophenonetetracarboxylic acid, 3,3'-, 4,4'-diphenylethertetracarboxylic acid, 3,3'-, 4,4'-diphenylsulfonetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3, Polycarboxylic acids such as 4-cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclohexanetetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, and polymers containing carboxylic acids or carboxylic anhydrides such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. The above compounds may be added in an amount of 20% by mass or less, preferably 10% by mass or less, based on the solid content of the protective film-forming composition for semiconductor chip manufacturing, as needed.

[0198] In the composition for forming a protective film for semiconductor chip manufacturing of the present invention, in addition, for the purpose of adjusting the dissolution rate in a removing solution such as an alkaline removing solution, a compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid, such as a tert-butyl group, a tetrahydropyranyl group, a 1-ethoxyethyl group and a trimethylsilyl group, can be added.

[0199] Examples of such compounds include di-tert-butyl malonate, tert-butyl acetate, tert-butyl propionate, tert-butyl acetoacetate, tert-amyl acetate, tert-butyl benzoate, and tert-butyl pivalate. Furthermore, compounds of formulae (46) to (54) are also included.

[0200]

[0201] These compounds can easily generate carboxyl groups or phenolic hydroxyl groups in the presence of an acid, thereby obtaining compounds having improved solubility in a removing liquid such as an alkaline removing liquid.

[0202] Therefore, these compounds are preferably added to the composition for forming a protective film for semiconductor chip manufacturing together with a photoacid generator. That is, in the protective film for semiconductor chip manufacturing formed by the composition for forming a protective film for semiconductor chip manufacturing comprising a compound having a carboxyl group or phenolic hydroxyl group protected by the above-mentioned group that is easily decomposed in the presence of an acid and a photoacid generator, the acid generated from the photoacid generator by exposure to the exposed portion regenerates the carboxyl group or phenolic hydroxyl group of the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid. As a result, the solubility of the protective film for semiconductor chip manufacturing in the exposed portion in the stripping solution is improved. In contrast, the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid does not change in the unexposed portion, and the solubility of the protective film for semiconductor chip manufacturing in the stripping solution of this portion is not improved. Therefore, by using a compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid together with a photoacid generator, a difference in solubility in the removing solution between the exposed portion and the non-exposed portion of the protective film for semiconductor chip manufacturing after exposure can be created, thereby facilitating pattern formation by development.

[0203] When using the above-mentioned compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid, the content thereof is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or 20 to 10 parts by mass, relative to 100 parts by mass of the polymer. When using a photoacid generator together with the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid, the content thereof is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or 1 to 10 parts by mass, relative to 100 parts by mass of the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid.

[0204] <<Surfactants>>

[0205] The protective film-forming composition for semiconductor chip production of the present invention may contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Fluorochemical surfactants such as EF301, EF303, and EF352 (trade names of Tochem Products), Megafax F171 and F173 (trade names of Dainippon Ink and Chemicals), Fluorad FC430 and FC431 (trade names of Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names of Asahi Glass), and organosiloxane polymer KP341 (trade name of Shin-Etsu Chemical Co., Ltd.) are used. The amount of these surfactants blended in the composition for forming a protective film for semiconductor chip manufacturing of the present invention is usually 0.2% by mass or less, preferably 0.1% by mass or less. These surfactants may be added alone or in combination of two or more.

[0206] (Protective film for semiconductor chip manufacturing)

[0207] The protective film for semiconductor chip manufacturing of the present invention is formed using the protective film-forming composition for semiconductor chip manufacturing of the present invention, and is a fired product of a coating film formed from the protective film-forming composition for semiconductor chip manufacturing.

[0208] The protective film for semiconductor chip manufacturing is formed by applying the composition for forming a protective film for semiconductor chip manufacturing of the present invention to a semiconductor substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, etc.) by a suitable coating method such as spin coating (spin coating), cast coating, or roll coating, and then firing. The firing conditions are appropriately selected from a firing temperature of 80° C. to 300° C. and a firing time of 0.3 to 60 minutes.

[0209] By heating (baking) or heating under reduced pressure, the coating film is partially or completely freed of the solvent, thereby promoting the solidification and / or hardening of the solid components contained in the coating film. "Curing" refers to solidification, and "hardening" refers to the increase in molecular weight by connecting molecules to each other (e.g., cross-linking, polymerization, etc.). This operation forms a protective film for semiconductor chip manufacturing.

[0210] When the protective film-forming composition for semiconductor chip manufacturing of the present invention is used, a coating film can be formed using, for example, the aforementioned coating methods such as spin coating (spin coating), cast coating, and roll coating. That is, when the protective film-forming composition for semiconductor chip manufacturing of the present invention is used, a coating film can be quickly and uniformly formed on a semiconductor substrate using a simple method.

[0211] Thus, by using the protective film-forming composition for semiconductor chip manufacturing of the present invention, a protective film for semiconductor chip manufacturing can be formed on a semiconductor substrate by a simple method, and a semiconductor substrate with a protective film for semiconductor chip manufacturing can be easily produced.

[0212] The protective film for semiconductor chip production of the present invention has a thickness of usually 1 to 10 μm, preferably 1 to 3 μm.

[0213] The dissolution rate of the formed protective film for semiconductor chip manufacturing in the photoresist developer is 0.1 nm to 50 nm per second, preferably 0.2 nm to 40 nm per second, and more preferably 0.3 to 20 nm per second. If the dissolution rate is lower than this, the time required to remove the protective film for semiconductor chip manufacturing becomes longer, resulting in reduced productivity.

[0214] The dissolution rate of the protective film for semiconductor chips formed from the protective film-forming composition for semiconductor chips of the present invention in the removal solution can be controlled by varying the firing conditions during formation. Given a given firing time, a higher firing temperature results in a protective film for semiconductor chips that dissolves less rapidly in the removal solution.

[0215] The protective film for semiconductor chip manufacturing of the present invention can be exposed after the film is formed. Exposure can be performed on the entire surface of the wafer or through a mask with a predetermined pattern. For exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), etc. can be used. Post-exposure baking (PEB) can also be performed after exposure as needed.

[0216] Next, the protective film for semiconductor chip manufacturing is removed using a removing liquid.

[0217] The protective film for semiconductor chip manufacturing is formed on a semiconductor substrate or a semiconductor chip as described below, for example. Removal in this case means removal from the semiconductor substrate or the semiconductor chip.

[0218] <Removal liquid>

[0219] The removing liquid may be any liquid capable of removing the protective film for semiconductor chip production from the semiconductor substrate or the semiconductor chip, and examples thereof include alkaline removing liquids, acidic removing liquids, neutral removing liquids, and organic solvents.

[0220] The removing liquid may contain water or an organic solvent.

[0221] The removing liquid may contain 50% by mass or more of an organic solvent.

[0222] Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0223] Examples of the removing liquid include an alkaline removing liquid, an acidic removing liquid, and a neutral removing liquid.

[0224] Among these, an alkaline removing liquid or an acidic removing liquid is preferred, and an alkaline removing liquid is more preferred, because the protective film for semiconductor chip production can be effectively dissolved and removed.

[0225] The alkaline removing liquid contains a base. Examples of the base include ammonia, inorganic alkaline compounds, quaternary ammonium hydroxide, amines, and hydrazine.

[0226] The alkaline remover may be a developer or cleaning solution used in semiconductor manufacturing processes and exhibits alkalinity. For example, NMD-3 (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd.) may be used as a developer.

[0227] Examples of the inorganic base compound include potassium hydroxide, sodium hydroxide, lithium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate and the like.

[0228] Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and choline.

[0229] Examples of the amine include ethanolamine, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, and ethylenediamine.

[0230] Examples of hydrazine include hydrazine monohydrate and the like.

[0231] In addition, the alkaline removal liquid may be SC-1 (ammonia-hydrogen peroxide solution).

[0232] The acidic removing liquid contains an acid. Examples of the acid include inorganic acids and organic acids. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and hydrofluoric acid.

[0233] The acidic removing liquid is, for example, an aqueous solution containing dilute hydrofluoric acid.

[0234] The acidic removing liquid may be, for example, an aqueous solution containing sulfuric acid and hydrogen peroxide, or an aqueous solution containing acetic acid or a chelating agent. Examples of the chelating agent include organic acids, organic acid salts, amino acids, and amino acid derivatives.

[0235] The so-called dissolution of the protective film for semiconductor chip manufacturing of the present invention by a removing liquid means that if the removing liquid is used for immersion, cleaning, etc., the protective film dissolves in the removing liquid and disappears from the semiconductor substrate and the semiconductor chip. The so-called dissolution in the present invention means that, for example, the protective film formed on the semiconductor substrate is removed from the initially formed film thickness by at least 90% (i.e., the thickness of the residual film is less than 10% of the initial film thickness) or by at least 95% (i.e., the thickness of the residual film is less than 5% of the initial film thickness) or by at least 99% (i.e., the thickness of the residual film is less than 1% of the initial film thickness), and most preferably by 100% (i.e., the thickness of the residual film is 0% of the initial film thickness (no residual film)).

[0236] (Semiconductor substrate)

[0237] The semiconductor substrate of the present invention has thereon a protective film for semiconductor chip production obtained using the protective film-forming composition for semiconductor chip production of the present invention.

[0238] The main material constituting the entire semiconductor substrate is not particularly limited as long as it is a material used for such applications, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0239] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc-shaped semiconductor substrate. It should be noted that a disc-shaped semiconductor substrate does not necessarily require a completely circular surface. For example, the outer periphery of the semiconductor substrate may have a straight portion known as an orientation flat, or may have a notch known as a notch.

[0240] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate. For example, it is 500 to 1,000 μm.

[0241] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate. For example, it is 100 to 1,000 mm.

[0242] The semiconductor substrate may have bumps. A bump is a protruding terminal.

[0243] In a semiconductor substrate, bumps are typically formed on the surface where the circuit is formed. The circuit can be single-layer or multi-layer, and there are no particular restrictions on the shape of the circuit.

[0244] In the semiconductor substrate, the surface (back surface) opposite to the surface (front surface) having the bumps is the surface to be processed.

[0245] The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited.

[0246] Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps.

[0247] Generally, the bump height, radius, and pitch are appropriately determined based on the following conditions: a bump height of approximately 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm.

[0248] Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy platings primarily containing Sn.

[0249] Furthermore, the bump may have a stacked-layer structure including a metal layer formed of at least one of these components.

[0250] An example of a semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0251] A schematic cross-sectional view showing an example of a semiconductor substrate having a protective film for semiconductor chip manufacturing of the present invention is shown in FIG. Figure 2B In. Figure 2B 1 shows a semiconductor substrate 100 with a protective film, in which a protective film 2 for semiconductor chip manufacturing is formed on a surface A side of a semiconductor substrate 1 on which a circuit is formed.

[0252] exist Figure 2B The semiconductor wafer 100 with a protective film shown in FIG. 1 can be obtained as follows.

[0253] like Figure 1 As shown, there is a semiconductor substrate 1 on which a circuit is formed. For example, the surface on which the circuit is formed is referred to as a front surface A, and the surface opposite to the surface on which the circuit is formed is referred to as a back surface B.

[0254] A coating film 2a ( Figure 2A By firing the coating film 2a, the protective film 2 for semiconductor chip manufacturing can be formed on the semiconductor substrate 1. Thus, a semiconductor substrate 100 with a protective film can be obtained ( Figure 2B ).

[0255] It should be noted that, in the present invention, the purpose is to protect the semiconductor chip from damage during transportation. It is sufficient to configure the semiconductor chip with a protective film for semiconductor chip manufacturing. Therefore, the protective film for semiconductor chip manufacturing can be configured on the surface of the semiconductor chip or on the back. That is, the protective film for semiconductor chip manufacturing can be configured on the surface A side of the semiconductor substrate or on the back B side. Therefore, the protective film 2 for semiconductor chip manufacturing can be configured not only on the surface A side of the semiconductor substrate 1 (refer to Figure 2B ), and can also be Figure 3 As shown, it is arranged on the back surface B side of the semiconductor substrate 1.

[0256] (Semiconductor Chip)

[0257] The semiconductor chip of the present invention has thereon a protective film for semiconductor chip production obtained by using the protective film-forming composition for semiconductor chip production of the present invention.

[0258] The semiconductor chip with a protective film for manufacturing a semiconductor chip of the present invention can be obtained by dicing a semiconductor substrate with a protective film for manufacturing a semiconductor chip having the protective film for manufacturing a semiconductor chip formed on the semiconductor substrate.

[0259] It should be noted that the semiconductor chip of the present invention may be mounted on an electronic component and used as a part of the electronic component.

[0260] Examples of the electronic component include an IC (Integrated Circuit) chip and a semiconductor element including an IC chip.

[0261] Examples of semiconductor devices including an IC chip include BGA (Ball Grid Array), CSP (Chip-Scale Package), PGA (Pin Grid Array), and LGA (Line Grid Array).

[0262] (Method for Manufacturing Semiconductor Chip)

[0263] The method for manufacturing a semiconductor chip of the present invention includes a first step, a second step, and a third step, and may further include a fourth step.

[0264] The first step is a step of applying the protective film-forming composition for semiconductor chip manufacturing of the present invention onto a semiconductor substrate and firing the composition to form a protective film for semiconductor chip manufacturing.

[0265] The second step is a step of dicing the semiconductor substrate on which the protective film for semiconductor chip manufacturing is provided to obtain semiconductor chips with the protective film for semiconductor chip manufacturing.

[0266] The third step is a step of conveying semiconductor chips.

[0267] The fourth step is a step of cleaning the protective film for semiconductor chip production with an alkaline removal solution to remove it from the semiconductor chip.

[0268] <Step 1>

[0269] The first step is a step of applying the protective film-forming composition for semiconductor chip manufacturing of the present invention onto a semiconductor substrate and firing the composition to form a protective film for semiconductor chip manufacturing.

[0270] Regarding the first step, use Figure 2A and Figure 2B As described above, a coating film 2a ( Figure 2A ), the coating film 2a is fired, thereby obtaining a semiconductor substrate 100 with a protective film in which a protective film 2 for semiconductor chip manufacturing is arranged on a semiconductor substrate 1 ( Figure 2B ).

[0271] <Step 2>

[0272] The second step is a step of dicing the semiconductor substrate on which the protective film for semiconductor chip manufacturing is provided to obtain semiconductor chips with the protective film for semiconductor chip manufacturing.

[0273] If it will pass Figure 2B The obtained semiconductor substrate 100 with a protective film is placed on a support sheet (dicing tape) 3 (see Figure 4 ) is provided to the dicing process, a semiconductor chip with a protective film for semiconductor chip manufacturing can be obtained (refer to Figure 5A ).

[0274] <Step 3>

[0275] The third step is a step of conveying semiconductor chips.

[0276] exist Figure 5A The semiconductor chips with protective films for semiconductor chip manufacturing obtained in the process are transported to various electronic components such as support sheets and printed circuit boards using a transport mechanism such as a robot arm and placed thereon (see Figure 5B ).

[0277] Since the protective film for semiconductor chip manufacturing is arranged on the semiconductor chip, it is possible to effectively prevent damage or breakage of the semiconductor chip due to physical contact that may occur during the transportation of the semiconductor chip.

[0278] <Step 4>

[0279] The fourth step is a step of cleaning the protective film for semiconductor chip manufacturing with a removing liquid to remove it from the semiconductor chip.

[0280] If Figure 5B The semiconductor chip 11 with the protective film 12 for semiconductor chip manufacturing is placed on another support sheet 4 and subjected to a cleaning step. The protective film 12 for semiconductor chip manufacturing is dissolved by the removal liquid 5 as a cleaning liquid, and the protective film 12 for semiconductor chip manufacturing is removed from the semiconductor chip 11 (see Figure 6 ).

[0281] Examples of the removing liquid used in the cleaning step include the removing liquids listed in the description section regarding the protective film for semiconductor chip manufacturing.

[0282] The cleaning method is not particularly limited, and examples thereof include a method of immersing the semiconductor substrate with the protective film for semiconductor chip manufacturing in an alkaline removing solution and a method of spraying the alkaline removing solution onto the semiconductor substrate with the protective film for semiconductor chip manufacturing.

[0283] The cleaning conditions are not particularly limited, but for example, the temperature of the cleaning liquid is 5° C. to 50° C. The cleaning time is appropriately selected from 2 to 500 seconds or 3 to 400 seconds.

[0284] For example, the protective film for semiconductor chip production can be easily peeled off at room temperature (eg, 25° C.) using a commonly used 2.38% by mass tetramethylammonium hydroxide aqueous solution.

[0285] In the above <1st step>, the case where the coating film 2a of the protective film-forming composition for semiconductor chip manufacturing is formed on the surface A side of the semiconductor substrate 1 is explained as an example. In the case where the coating film 2a of the protective film-forming composition for semiconductor chip manufacturing is formed on the back surface B side of the semiconductor substrate 1, the above <2nd step> and the above <3rd step> are as follows. Figure 7A and Figure 7B As shown.

[0286] If you will pass Figure 3 The obtained semiconductor substrate 100 with a protective film is placed on a support sheet (dicing tape) and then subjected to a dicing step, thereby obtaining a semiconductor chip with a protective film for semiconductor chip manufacturing (see Figure 7A ).

[0287] exist Figure 7A The semiconductor chips with protective films for semiconductor chip manufacturing obtained in the process are transported to various electronic components such as support sheets and printed circuit boards using a transport mechanism such as a robot arm and placed thereon (see Figure 7B ).

[0288] Since the protective film for semiconductor chip manufacturing is arranged on the semiconductor chip, it is possible to effectively prevent damage or breakage of the semiconductor chip due to physical contact that may occur during the transportation of the semiconductor chip.

[0289] The method for manufacturing a semiconductor chip of the present invention is specified to include the above-mentioned steps 1 to 3 (preferably also including step 4), but may also include other steps. For example, it may include various processing steps such as polishing the semiconductor substrate, forming a through-electrode, etc., which are performed during post-processing of the semiconductor substrate on which the circuit is formed.

[0290] For example, the protective film for semiconductor chip manufacturing is formed by applying the protective film-forming composition for semiconductor chip manufacturing of the present invention to the surface of a semiconductor substrate having a circuit formed thereon and firing the composition.

[0291] Next, the semiconductor substrate with the protective film for semiconductor chip manufacturing is placed so that the protective film for semiconductor chip manufacturing faces the support tape 1 (background tape), and the semiconductor substrate with the protective film for semiconductor chip manufacturing is temporarily bonded to the support tape 1 .

[0292] The back surface of the semiconductor substrate is ground to make it thinner.

[0293] Then, the protective film for semiconductor chip manufacturing and the support tape 1 are peeled off.

[0294] Next, the semiconductor substrate with the protective film for semiconductor chip manufacturing is placed with its back surface facing the support tape 2 (dicing tape), and the semiconductor substrate with the protective film for semiconductor chip manufacturing is attached to the support tape 2 .

[0295] The semiconductor substrate provided with the protective film for semiconductor chip manufacturing is diced to obtain semiconductor chips with the protective film for semiconductor chip manufacturing.

[0296] The semiconductor chip with the protective film for semiconductor chip manufacturing is conveyed by a conveying mechanism to be placed on another supporting sheet 3 or various electronic components such as a printed circuit board.

[0297] Example

[0298] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0299] (Example 1)

[0300] (Preparation of a protective film-forming composition for semiconductor chip manufacturing)

[0301] A solution was prepared by adding 0.04 g of a surfactant (product name: Megafax R-40, manufactured by DIC Corporation), 75.15 g of propylene glycol monomethyl ether, and 8.35 g of propylene glycol monomethyl ether acetate to 16.45 g of polyhydroxystyrene (product name: VP-8000, manufactured by Nippon Soda Co., Ltd.). This solution was filtered through a polyethylene filter with a pore size of 0.03 μm to prepare a composition for forming a protective film for semiconductor chip manufacturing.

[0302] (Evaluation of a protective film-forming composition for semiconductor chip manufacturing)

[0303] The solution of the protective film-forming composition for semiconductor chip manufacturing was applied (spin-coated) to a silicon wafer using a spin coater. The coated silicon wafer was heated on a hot plate at 200° C. for 1 minute to form a film (protective film for semiconductor chip manufacturing) having a thickness of 1500 nm.

[0304] Using a T-3000-PRO die bonder (Dr. Tresky, chuck diameter 1 mm) with suction holes, the wafer with the protective film was held for 1 minute under a 4 kg load. The die bonder was then stopped and the resulting wafer was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 2 minutes.

[0305] It was confirmed that the film obtained from the protective film-forming composition for semiconductor chip manufacturing prepared in Example 1 was completely dissolved in NMD-3.

[0306] The upper surface of the wafer after the NMD-3 treatment was observed with an optical microscope and evaluated based on the following criteria.

[0307] 0; No traces of adsorption can be seen at all

[0308] ×; Adsorption traces can be seen

[0309] The wafer with a protective film for semiconductor chip production obtained in Example 1 was evaluated according to the above-mentioned criteria, and the results are shown in Table 1 below.

[0310] (Comparative Example 1)

[0311] On the other hand, as Comparative Example 1, a silicon wafer on which a film of the composition for forming a protective film for semiconductor chip manufacturing was not formed was used. As in Example 1, the silicon wafer was adsorbed and maintained for 1 minute using a crystal bonding machine T-3000-PRO with adsorption holes under a load of 4 kg during adsorption. Then, after being treated with NMD-3, the upper surface of the wafer was confirmed using an optical microscope.

[0312] The silicon wafer obtained in Comparative Example 1 was evaluated based on the above criteria, and the results are shown in Table 1 below.

[0313] [Table 1]

[0314] No adsorption traces were observed in Example 1 having the protective film for semiconductor chip manufacturing of the present invention. On the other hand, adsorption traces were observed in Comparative Example 1 not having the protective film for semiconductor chip manufacturing of the present invention.

[0315] Explanation of symbols

[0316] 1. Semiconductor substrate

[0317] A Surface

[0318] B Back

[0319] 2a Coating film

[0320] 2 Protective film for semiconductor chip manufacturing

[0321] 100 Semiconductor substrate with protective film for semiconductor chip manufacturing

[0322] 3 Support sheet (cutting tape)

[0323] 4 Other supporting films

[0324] 5 Alkaline removal solution

[0325] 11. Semiconductor Chips

[0326] 12 Protective film for semiconductor chip manufacturing.

Claims

1. A composition for forming a protective film for semiconductor chip manufacturing, which is used to prevent damage to the circuit surface or back surface of a semiconductor substrate or a semiconductor chip. The protective film-forming composition for semiconductor chip manufacturing comprises a polymer and a solvent. The polymer is selected from any one of a polymer containing a phenolic hydroxyl group, a polymer containing a carboxyl group, and a polymer containing a blocked carboxyl group. 2 . The protective film-forming composition for semiconductor chip manufacturing according to claim 1 , which forms a protective film soluble in an alkaline removing liquid, an acidic removing liquid, a neutral removing liquid, or an organic solvent. 3 . The protective film-forming composition for semiconductor chip manufacturing according to claim 1 , comprising 50% by mass or more of the polymer relative to the total solid content in the composition. 4 . The protective film-forming composition for semiconductor chip manufacturing according to claim 1 , wherein the protective film for semiconductor chip manufacturing is disposed on the semiconductor substrate in order to protect the semiconductor chips from damage during transportation of individual semiconductor chips obtained by dicing the semiconductor substrate.

5. The composition for forming a protective film for semiconductor chip manufacturing according to claim 1, wherein the polymer containing a phenolic hydroxyl group is selected from any one of phenol novolacs, naphthol novolacs, polyhydroxystyrenes, polyhydroxyphenyl (meth)acrylates, and poly(N-hydroxyphenyl (meth)acrylamides). The protective film-forming composition for semiconductor chip manufacturing according to claim 1 , wherein the carboxyl group-containing polymer is selected from any one of (meth)acrylic resins, polyvinyl benzoic acid, carboxymethyl cellulose, and polyamic acid. 7 . The protective film-forming composition for semiconductor chip manufacturing according to claim 6 , wherein the polyamic acid is a polyamic acid having structural units derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group. 8 . The protective film-forming composition for semiconductor chip manufacturing according to claim 1 , comprising at least one of a cross-linking agent, an acid catalyst, and an additive. 9 . The composition for forming a protective film for semiconductor chip manufacturing according to claim 8 , wherein the crosslinking agent is selected from the group consisting of an aminoplast crosslinking agent, a phenoplast crosslinking agent, and an epoxy group-containing crosslinking agent. 10 . A protective film for producing a semiconductor chip, which is a fired product of a coating film formed from the protective film-forming composition for producing a semiconductor chip according to claim 1 . 11 . The protective film for semiconductor chip manufacturing according to claim 10 , wherein the protective film has a thickness of 1 to 10 μm. 12 . A semiconductor substrate comprising the protective film for semiconductor chip production according to claim 10 . 13 . A semiconductor chip comprising the protective film for semiconductor chip production according to claim 10 .

14. A method for manufacturing a semiconductor chip, comprising the following steps: a step of applying the composition for forming a protective film for manufacturing a semiconductor chip according to any one of claims 1 to 9 onto a semiconductor substrate and firing the composition to form a protective film for manufacturing a semiconductor chip; a step of cutting the semiconductor substrate provided with the protective film for manufacturing a semiconductor chip to obtain a semiconductor chip with the protective film for manufacturing a semiconductor chip; and a step of transporting the semiconductor chip. 15 . The method for manufacturing a semiconductor chip according to claim 14 , further comprising the step of removing the protective film for semiconductor chip manufacturing from the semiconductor chip by cleaning with an alkaline removing liquid, an acidic removing liquid, a neutral removing liquid, or an organic solvent.

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