Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/04—Epoxynovolacs
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
  • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/60—Wet etching
  • H10P50/64—Wet etching of semiconductor materials
  • H10P50/642—Chemical etching
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
  • H10P50/692—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their composition, e.g. multilayer masks or materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
  • H10P50/693—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their size, orientation, disposition, behaviour or shape, in horizontal or vertical plane
  • H10P50/695—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their size, orientation, disposition, behaviour or shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture

Definitions

• the present invention relates to a composition for forming a protective film having excellent resistance to a wet etching solution for semiconductors in a lithography process in semiconductor manufacturing.
• the present invention also relates to a method for manufacturing a substrate with a resist pattern to which the protective film is applied, and a method for manufacturing a semiconductor device.
• Patent Documents 1 and 2 disclose a protective film-forming composition for an aqueous hydrogen peroxide solution containing a specific compound.
• the resist underlayer film When the resist underlayer film is used as an etching mask and the underlying substrate is processed by wet etching, the resist underlayer film has a good masking function against the wet etching solution during the underlayer substrate processing (that is, the masked portion can protect the substrate. ) Is required. In such a case, the resist underlayer film will be used as a protective film for the substrate.
• SC-1 ammonia-hydrogen peroxide solution
• a low molecular weight compound for example, gallic acid
• the present invention includes the following.
• the following formula (1-1) (In the formula (1-1), Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and R 1 is a hydroxy group, a mercapto group which may be protected by a methyl group, or an amino which may be protected by a methyl group.
• L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms
• E represents an epoxy group
• a polymer having a unit structure represented by an alkylene group having 1 to 10 carbon atoms which may be interrupted by a bond, and T 1 representing a nitrogen atom or an amide bond when n2 2), thermal polymerization.
• a protective film-forming composition for a wet etching solution for semiconductors which comprises an initiator and a solvent.
• L 1 is the following formula (1-2):
• R 2 and R 3 are independent of each other, hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-. It represents a butyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group, and R 2 and R 3 may be bonded to each other to form a ring having 3 to 6 carbon atoms).
• a protective film-forming composition for a wet etching solution for semiconductors is the following formula (1-2):
• a protective film against a wet etching solution for semiconductors which is a fired product of a coating film composed of the protective film forming composition according to any one of [1] to [5].
• a method for manufacturing a substrate with a resist pattern which comprises a step of forming a resist pattern by exposure and development, and then using the resist pattern for manufacturing a semiconductor.
• a protective film is formed on a semiconductor substrate on which an inorganic film may be formed on the surface using the protective film forming composition according to any one of [1] to [5], and the protective film is formed on the protective film.
• a resist pattern is formed, the protective film is dry-etched using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and a wet etching solution for semiconductor is used using the protective film after dry etching as a mask.
• a method for manufacturing a semiconductor device which comprises a step of wet etching and / or cleaning the inorganic film or the semiconductor substrate.
• the protective film forming composition of the present invention has a good masking function against the wet etching solution at the time of processing the base substrate in the lithography process in semiconductor manufacturing, so that the semiconductor substrate can be easily finely processed.
• the protective film forming composition of the present application has the following formula (1-1):
• Ar represents a benzene ring, a naphthalene ring or an anthracene ring
• R 1 is protected by a hydroxy group or a methyl group as a substituent of a hydrogen atom contained in the benzene ring, a naphthalene ring or an anthracene ring.
• the number of carbon atoms may be 1 to 10 which may be substituted with a mercapto group, an amino group which may be protected with a methyl group, a halogeno group, or a hetero atom and which may be interrupted or substituted with a hydroxy group.
• N1 represents an integer of 0 to 3
• n2 represents 1 or 2
• L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms
• E represents an epoxy group
• it is a protective film-forming composition for a wet etching solution for semiconductors, which contains a polymer having a unit structure represented by (or an amide bond), a thermal polymerization initiator and a solvent.
• the R 1 may be an alkoxy group having 1 to 10 carbon atoms.
• alkoxy group having 1 to 10 carbon atoms examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and an n-.
• Pentoxy group 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy Group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3- Methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group , 2,2-Dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group Group, 1,1,2-trimethyl-n-propoxy group
• the unit structure represented by the above formula (1-1) may be one type or a combination of two or more types.
• it may be a copolymer having a plurality of unit structures in which Ar is the same type, and the types of Ar are different, for example, Ar has a unit structure containing a benzene ring and a unit structure having a naphthalene ring.
• Copolymers having a plurality of unit structures are not excluded from the technical scope of the present application.
• any carbon-carbon atom in the alkylene group is a heteroatom (that is, in the case of oxygen, an ether bond or sulfur).
• it means that it is interrupted by a sulfide bond), an ester bond or an amide bond. It means having a bond, a sulfide bond in the case of sulfur), an ester bond or an amide bond.
• the alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom is a hetero atom (preferably a halogeno group) in which one or more hydrogen atoms contained in the alkyl group having 1 to 10 carbon atoms are present. It means that it has been replaced.
• alkyl group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, and t-.
• alkylene group having 1 to 10 carbon atoms examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, and a t-butylene group.
• Cyclobutylene group 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene Group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1- Methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-Ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-
• L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and the following formula (1-2):
• R 2 and R 3 are independent of each other, hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-. It represents a butyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group, and R 2 and R 3 may be bonded to each other to form a ring having 3 to 6 carbon atoms). .. Among these, it is preferable that both R 2 and R 3 are hydrogen atoms (that is,-(CR 2 R 3 )-is a methylene group).
• the halogeno group refers to halogen-X (F, Cl, Br, I) substituted with hydrogen.
• the polymer is not particularly limited as long as it satisfies the unit structure of the above formula (1). It may be manufactured by a method known per se. Commercially available products may be used. Commercially available products include heat-resistant epoxy novolac resin EOCN (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.) and epoxy novolac resin D.I. E. Examples include the N (registered trademark) series (manufactured by Dow Chemical Japan Co., Ltd.).
• the weight average molecular weight of the polymer is 100 or more, 500 to 200,000, 600 to 50,000, and 700 to 10,000.
• Examples of the polymer of the present application include those having the following unit structure.
• the thermal polymerization initiator of the present application refers to a compound in which an acid is predominantly generated by heating (for example, 50 ° C. to 300 ° C.) as compared with the case of light irradiation.
• the thermal polymerization initiator of the present application is preferably a thermal cationic polymerization initiator.
• sulfonic acid compounds such as 5-sulfosalicylic acid, chlorobenzenesulfonic acid, methyl 4-phenolsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, citric acid, benzoic acid, carboxylic acid compounds, and quaternary ammonium salts of trifluoromethanesulfonic acid.
• Certain K-PURE® TAG2689, TAG2690, TAG2678, CXC-1614, etc. (all manufactured by King Industries, Ltd.), 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2- Nitrobenzyltosylate, an aromatic sulfonium salt, San-Aid (registered trademark) SI series (for example, SI-45, SI-60, SI-80, SI-100, SI-110, SI-150, etc.) (Sanshin Kagaku Kogyo) (Manufactured by Co., Ltd.), and other organic sulfonic acid alkyl esters and the like can be mentioned.
• an onium salt compound is preferable, a quaternary ammonium salt-containing compound is preferable, and a quaternary ammonium salt of trifluoromethanesulfonic acid is preferable.
• thermal polymerization initiators may be contained alone or in combination of two or more.
• the content of the thermal acid generator in the protective film-forming composition is 0.0001 to 20% by weight, preferably 0.01 to 15% by weight, more preferably, based on the total solid content of the protective film-forming composition. Is 0.1 to 10% by mass.
• the protective film-forming composition of the present invention can be prepared by dissolving each of the above components in a solvent, preferably an organic solvent, and is used in a uniform solution state.
• the solvent of the protective film-forming composition according to the present invention can be used without particular limitation as long as it is a solvent that can dissolve solid components at room temperature contained in the protective film-forming composition of the present application.
• the protective film forming composition according to the present invention is used in a uniform solution state, it is recommended to use a solvent generally used in the lithography process in combination in consideration of its coating performance.
• organic solvent examples 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, and propylene glycol monoethyl ether.
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone and the like are preferable.
• propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.
• the protective film-forming composition of the present invention can contain a cross-linking agent component.
• the cross-linking agent include melamine-based, substituted urea-based, and polymers thereof.
• it is a cross-linking agent having at least two cross-linking substituents, methoxymethylated glycol uryl, butoxymethylated glycol uryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, It is a compound such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Further, a condensate of these compounds can also be used.
• a cross-linking agent having high heat resistance can be used.
• a compound containing a cross-linking substituent having an aromatic ring for example, a benzene ring or a naphthalene ring
• an aromatic ring for example, a benzene ring or a naphthalene ring
• this compound examples include a compound having a partial structure of the following formula (2-1) and a polymer or oligomer having a repeating unit of the following formula (2-2).
• R 18 , R 19 , R 20 and R 21 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and these alkyl groups can use the above-mentioned examples.
• n 3 is 1 ⁇ n 3 ⁇ 6 ⁇ n 4
• n 4 is 1 ⁇ n 4 ⁇ 5
• n 5 is 1 ⁇ n 5 ⁇ 4-n 6
• n 6 is 1 ⁇ n 6 ⁇ 3.
• the compound represented by the formula (2-1) is exemplified by the following formulas (2-3) to (2-19).
• the above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd.
• the compound of the formula (2-15) can be obtained under the trade name TMOM-BP of Asahi Organic Materials Industry Co., Ltd.
• the amount of the cross-linking agent added varies depending on the coating solvent used, the underlying substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 0.001 with respect to the total solid content of the protective film forming composition. It is 80% by weight, preferably 0.01 to 50% by weight, and more preferably 0.1 to 40% by weight.
• These cross-linking agents may cause a cross-linking reaction by self-condensation, but if cross-linking substituents are present in the above-mentioned polymer of the present invention, they can cause a cross-linking reaction with those cross-linking substituents.
• the protective film-forming composition of the present invention may contain a surfactant as an optional component in order to improve the coatability on the semiconductor substrate.
• a surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene.
• Polyoxyethylene alkylaryl ethers such as nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitantry Polyoxyethylene fatty acid esters such as stearates, polyoxyethylene sorbitan monolaurates, polyoxyethylene sorbitan monopalmitates, polyoxyethylene sorbitan monostearates, polyoxyethylene sorbitan trioleates, polyoxyethylene sorbitan tristearates, etc.
• Nonionic surfactants such as oxyethylene sorbitan fatty acid esters, Ftop [registered trademarks] EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck [registered trademarks] F171, F173, R -30, R-40, R-40-LM (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard [registered trademark] AG710, Surfron [registered trademark] S-382 , SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorosurfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
• the protective film-forming composition contains a surfactant, the content thereof is 0.0001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total solid content of the protective film-forming composition. be.
• the solid content of the protective film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass.
• the solid content is the content ratio of all the components excluding the solvent from the protective film forming composition.
• the proportion of the polymer in the solid content is preferably 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass in this order.
• etching solution for semiconductors a general chemical solution for etching a wafer for semiconductors can be used, and for example, a substance showing acidity and a substance showing basicity can be used.
• Examples of the substance showing acidity include hydrogen peroxide, phosphoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogenfluoride, buffered ammonium fluoride, hydrochloric acid, nitrate, sulfuric acid, phosphoric acid or a mixture thereof. ..
• organic amines such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and triethanolamine are mixed with hydrogen peroxide solution to make the pH basic.
• a hydrogen hydrogen solution can be mentioned. Specific examples include SC-1 (ammonia-hydrogen peroxide solution).
• SC-1 ammonia-hydrogen peroxide solution
• those that can make the pH basic for example, those that mix urea and hydrogen hydrogen solution and cause thermal decomposition of urea by heating to generate ammonia, and finally make the pH basic.
• These chemicals may contain additives such as surfactants.
• the operating temperature of the wet etching solution for semiconductors is preferably 25 ° C to 90 ° C, and more preferably 40 ° C to 80 ° C.
• the wet etching time is preferably 0.5 minutes to 30 minutes, and more preferably 1 minute to 20 minutes.
• the substrate with a resist pattern according to the present invention can be produced by applying the above-mentioned protective film forming composition on a semiconductor substrate and firing it.
• Examples of the semiconductor substrate to which the protective film forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. ..
• the inorganic film can be, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum deposition. It is formed by the method, spin coating method (spin-on-glass: SOG).
• ALD atomic layer deposition
• CVD chemical vapor deposition
• reactive sputtering method reactive sputtering method
• ion plating method vacuum deposition. It is formed by the method, spin coating method (spin-on-glass: SOG).
• the inorganic film examples include a polysilicon film, a silicon oxide film, a silicon nitride film, a silicon nitride film, a BPSG (Boro-Phospho Silicone Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten nitride film, and a gallium arsenide film. , And a gallium arsenide film.
• the protective film forming composition of the present invention is applied onto such a semiconductor substrate by an appropriate coating method such as a spinner or a coater. Then, a protective film is formed by baking using a heating means such as a hot plate.
• the baking conditions are appropriately selected from a baking temperature of 100 ° C. to 400 ° C. and a baking time of 0.3 minutes to 60 minutes.
• the baking temperature is preferably 120 ° C. to 350 ° C. and the baking time is 0.5 minutes to 30 minutes, and more preferably the baking temperature is 150 ° C. to 300 ° C. and the baking time is 0.8 minutes to 10 minutes.
• the resist pattern is formed through a mask (reticle) for forming a predetermined pattern, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) exposure or EB (electron beam) drawing.
• a mask for forming a predetermined pattern
• An alkaline developer is used for development, and the development temperature is appropriately selected from 5 ° C. to 50 ° C. and the development time is 10 seconds to 300 seconds.
• the alkaline developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like.
• Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like.
• An aqueous solution of an alkali such as a quaternary ammonium salt, cyclic amines such as pyrrole and piperidine can be used.
• an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous solution of the alkali to be used.
• the preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.
• a surfactant or the like can be added to these developers.
• a method of developing with an organic solvent such as butyl acetate to develop a portion of the photoresist in which the alkali dissolution rate has not been improved can also be used.
• the protective film is dry-etched using the formed resist pattern as a mask. At that time, when the inorganic film is formed on the surface of the used semiconductor substrate, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the used semiconductor substrate, the semiconductor substrate is exposed. Expose the surface.
• Epoxy novolac resin EOCN-104S (Nippon Kayaku Co., Ltd. product, equivalent to formula (1)) 2.00 g (50 mass% PGMEA solution, weight average molecular weight 3100) as a thermoacid generator K-PURE [registered trademark] ] TAG-2689 (King Industries product) 2.08 g (0.5 mass% PGME solution), and 19.23 g of PGMEA and 6.62 g of PGME as solvents were mixed to prepare a 3.5 mass% solution. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 ⁇ m to prepare a protective film-forming composition.
• K-PURE [registered trademark] as a thermoacid generator in 2.08 g (50 mass% PGME solution, weight average molecular weight 900) of epoxy novolak resin DEN438 (Dow Chemical Japan Co., Ltd. product, equivalent to formula (2)) 2.08 g (0.5 mass% PGME solution) of TAG-2689 (a product of King Industries) and 20.27 g of PGMEA and 5.58 g of PGME as solvents were mixed to prepare a 3.5 mass% solution. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 ⁇ m to prepare a protective film-forming composition.
• Epoxynovolak resin EOCN-104S (Nippon Kayaku Co., Ltd. product, equivalent to formula (1)) 2.00 g (50 mass% PGMEA solution, weight average molecular weight 3100) as a photoacid generator triphenylsulfonium trifluoromethanesulfonate 0.05 g (manufactured by Midori Chemical Co., Ltd., trade name TPS105) and 19.27 g of PGMEA and 8.69 g of PGMEA as solvents were mixed to prepare a 3.5 mass% solution. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 ⁇ m to prepare a protective film-forming composition.
• the protective film forming composition prepared in Example 1, Example 2, and Comparative Example 1 was applied onto a silicon substrate by a spinner. Then, the obtained coating film was baked on a hot plate at a temperature of 250 ° C. for 1 minute to form a protective film (film thickness 90 nm). Further, the protective film forming composition prepared in Comparative Example 2 and Comparative Example 3 was applied onto a silicon substrate by a spinner. Then, the obtained coating film was baked on a hot plate at a temperature of 100 ° C.
• the protective film-forming compositions prepared in Example 1, Example 2, and Comparative Example 1 were applied by a spinner onto a silicon substrate on which a titanium nitride film was formed on the surface. Then, the obtained coating film was baked on a hot plate at a temperature of 250 ° C. for 1 minute to form a protective film (film thickness 90 nm). Further, the protective film forming composition prepared in Comparative Example 2 and Comparative Example 3 was applied by a spinner on a silicon substrate on which a titanium nitride film was formed on the surface. Then, the obtained coating film was baked on a hot plate at a temperature of 100 ° C.
• the protective film formed on the silicon substrate is immersed in a basic hydrogen peroxide aqueous solution (abbreviated as APM in Table 1 below) having the composition shown in Table 2 below at the temperature shown in the same table.
• APM in Table 1 a basic hydrogen peroxide aqueous solution
• Table 2 a basic hydrogen peroxide aqueous solution
• the time until the protective film was peeled off from the silicon substrate was measured, and the APM resistance was evaluated.
• the results are shown in Table 1.
• Table 1 “ ⁇ ” indicates a state in which peeling of the resist underlayer film was not observed when immersed for 10 minutes
• "x” indicates a state in which peeling was observed in a part or all of the resist underlayer film when immersed for 10 minutes. Represents.
• the protective film prepared using the protective film forming composition prepared in Example 1, Example 2, and Comparative Example 1 showed solvent resistance to the resist solvent only by thermosetting. ..
• the protective film prepared by using the protective film forming composition prepared in Comparative Example 2 and Comparative Example 3 showed solvent resistance to the resist solvent only by photocuring.
• the resin used in the protective film-forming composition of the present invention resulted in superior APM resistance as compared with the protective film-forming compositions prepared in Comparative Example 2 and Comparative Example 3.
• the resin used in the protective film-forming composition of the present invention resulted in superior storage stability as compared with the protective film-forming composition prepared in Comparative Example 1. It is considered that the protective film-forming composition prepared in Comparative Example 1 had poor storage stability, cross-linking did not proceed sufficiently, and APM resistance did not develop.
• the protective film forming composition according to the present invention provides a protective film having excellent resistance when a wet etching solution is applied to substrate processing.

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