CN106502052B - Etching-resistant phenolic aldehyde positive photoresist - Google Patents
Etching-resistant phenolic aldehyde positive photoresist Download PDFInfo
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- CN106502052B CN106502052B CN201611198717.7A CN201611198717A CN106502052B CN 106502052 B CN106502052 B CN 106502052B CN 201611198717 A CN201611198717 A CN 201611198717A CN 106502052 B CN106502052 B CN 106502052B
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- 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
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Abstract
The invention discloses an etching-resistant phenolic positive photoresist which mainly comprises phenolic resin, a photosensitive compound and a solvent and is characterized in that the phenolic positive photoresist also contains 0.5-30 wt% of a metal compound which can be dissolved in the solvent. In the dry etching process after photoetching of the photoresist, the plasma carries out physical bombardment and chemical reaction dual-action etching on the glue film graph, volatile reactants formed by carbon and oxygen components in the glue layer are removed, metal components are slowly deposited, and a new metal protective layer is formed on the surface of the glue film, so that the aim of improving the etching resistance of the photoresist is fulfilled. The photoresist can be widely applied to the field of production of microelectronic components requiring dry etching.
Description
Technical Field
The invention belongs to the field of photoresist, and particularly relates to an etching-resistant phenolic positive photoresist.
Background
The photoresist is the most critical basic material for the development of microelectronic technology, and is also called photoresist, which is an etch-resistant thin film material with the solubility changed by the irradiation or radiation of exposure sources such as ultraviolet light, electron beams, ion beams, excimer laser beams, X-rays and the like. After the photoresist film is exposed and developed to form a photoresist pattern, dry etching or wet etching is performed. The part of the substrate material which is not covered by the adhesive film is directly etched, and the substrate surface which is covered by the adhesive film is protected by the photoresist film and is not etched. The etching resistance is an important evaluation index of the photoresist, the excellent etching resistance can ensure that the photoresist can protect the surface of the substrate from being damaged in the etching process, the etching process is effectively simplified, and the yield of the etched finished product is greatly improved.
The phenolic positive photoresist has the obvious advantages of high light sensitivity, high yield, high process tolerance, easy photoresist stripping and the like, and is widely applied to photoetching processes of MEMS, LED, IC, LCD and the like. However, the existing phenolic positive photoresist has a very common performance in terms of etching resistance, and in the deep etching process, the increase of the thickness of the photoresist film and the increase of the film hardening temperature of the photoresist before etching are usually adopted to improve the etching resistance, but the effect is not ideal, and the temperature resistance requirement of the photoresist at high temperature is higher. In addition, there is another report of applying an inorganic or organic layer with high etching resistance, i.e., a "resist underlayer" or a "hard mask", between a photoresist pattern and an etched substrate to achieve the purpose of etching resistance, such as CN103906740A and CN105612459A, but the solution has disadvantages of complex operation of two-layer or multi-layer film process, low efficiency, high manufacturing cost, and is not used in the conventional dry etching process in China.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides the phenolic aldehyde positive photoresist with high etching resistance, avoids a multilayer film process in deep etching, effectively reduces the thickness of the photoresist film, increases the process tolerance of film hardening temperature, and simplifies the process flow.
In order to solve the technical problems, the invention provides the following technical scheme:
the etching-resistant phenolic positive photoresist is mainly composed of phenolic resin, a photosensitive compound and a solvent, and is characterized in that the phenolic positive photoresist contains 0.5-30 wt% of a metal compound which can be dissolved in the solvent. Preferably, the phenolic positive photoresist contains 1 to 20wt% of a metal compound soluble in the solvent. More preferably, the phenolic positive-working photoresist contains 2 to 10wt% of a metal compound soluble in the solvent.
Preferably, the metal compound is a complex or salt formed by at least one selected from the group consisting of magnesium, calcium, barium, titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, cadmium, indium, tin, and antimony, and at least one selected from the group consisting of alkyl, alkenyl, alkoxy, acyloxy, β -diketone ligand, C ≡ O, halogen, nitro, and nitrate.
The alkyl group may be a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 3, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1, 2-dimethyl-cyclopropyl, 2, 3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-methyl-cyclopropyl, 2-ethyl-cyclopropyl, 2-methyl-cyclopropyl, 1-ethyl-cyclopropyl, 1-methyl-n-propyl, 1-ethyl-cyclopropyl, 1-methyl, Cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2, 2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2, 4-dimethyl-cyclobutyl, 3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2, 2-trimethyl-cyclopropyl, 1,2, 3-trimethyl-cyclopropyl, 2, 3-methyl-cyclopropyl, 2-methyl-cyclobutyl, 2-methyl-cyclopentyl, 2, 3-methyl-cyclobutyl, 2-dimethyl-cyclobutyl, 2,3, 2,2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, and the like.
The alkenyl group can be a linear, branched or cyclic alkenyl group with 2-10 carbon atoms, such as: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 1-methyl-3-butenyl, 2-methyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-1-propenyl, 2-, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1-isopropylvinyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 3-isopropylvinyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-pentenyl, 3-cyclopentenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, methyl-2-pentenyl, 4-methyl-4-pentenyl, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s-butylvinyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 1-isobutylvinyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl-1-butenyl, 2-dimethyl-3-butenyl, 1-isobutyl-ethyl-2-propenyl, 2-methyl-3-butenyl, 2-dimethyl-1-butenyl, 2-dimethyl-3-butenyl, 2-dimethyl-1-butenyl, 2,2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3-dimethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 2-methyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 2-tert-butylvinyl, 2-methyl-1-ethyl-2-propenyl, 2-, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-isopropyl-1-propenyl group, 1-isopropyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, methyl-2-propenyl group, methyl-1-cyclopentenyl group, methyl-2-propenyl group, methyl-2-cyclopentenyl group, methyl-2-, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1-methyl-2, 4-cyclopentadiene, etc.
The alkoxy is C1-10 alkoxy, such as: 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-dimethyl-n-propoxy, 1, 2-dimethyl-n-propoxy, 2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy, 1-dimethyl-n-butoxy, 1, 2-dimethyl-n-butoxy, 1, 3-dimethyl-n-butoxy, sec-butoxy, tert-, 2, 2-dimethyl-n-butoxy group, 2, 3-dimethyl-n-butoxy group, 3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1, 2-trimethyl-n-propoxy group, 1,2, 2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group and the like.
The acyloxy is an acyloxy group having 1 to 10 carbon atoms, for example: formyloxy, acetoxy, n-propylcarbonyloxy, isopropylcarbonyloxy, cyclopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, s-butylcarbonyloxy, t-butylcarbonyloxy, cyclobutylcarbonyloxy, 1-methyl-cyclopropylcarbonyloxy, 2-methyl-cyclopropylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1-dimethyl-n-propylcarbonyloxy, 1, 2-dimethyl-n-propylcarbonyloxy, 2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, cyclopentylcarbonyloxy, 1-methyl-cyclobutylcarbonyloxy, cyclopropylcarbonyloxy, cyclopentylcarbonyloxy, n-butylcarbonyloxy, n-butylcarbonyl, 2-methyl-cyclobutylcarbonyloxy, 3-methyl-cyclobutylcarbonyloxy, 1, 2-dimethyl-cyclopropylcarbonyloxy, 2, 3-dimethyl-cyclopropylcarbonyloxy, 1-ethyl-cyclopropylcarbonyloxy, 2-ethyl-cyclopropylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1-dimethyl-n-butylcarbonyloxy, 1, 2-dimethyl-n-butylcarbonyloxy, 1, 3-dimethyl-n-butylcarbonyloxy, 2-dimethyl-n-butylcarbonyloxy, 2-methyl-cyclopropylcarbonyloxy, 2-dimethyl-, 2, 3-dimethyl-n-butylcarbonyloxy, 3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1, 2-trimethyl-n-propylcarbonyloxy, 1,2, 2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, cyclohexylcarbonyloxy, 1-methyl-cyclopentylcarbonyloxy, 2-methyl-cyclopentylcarbonyloxy, 3-methyl-cyclopentylcarbonyloxy, 1-ethyl-cyclobutylcarbonyloxy, 2-ethyl-cyclobutylcarbonyloxy, n-butylcarbonyloxy, 3-ethyl-cyclobutylcarbonyloxy, 1, 2-dimethyl-cyclobutylcarbonyloxy, 1, 3-dimethyl-cyclobutylcarbonyloxy, 2, 2-dimethyl-cyclobutylcarbonyloxy, 2, 3-dimethyl-cyclobutylcarbonyloxy, 2, 4-dimethyl-cyclobutylcarbonyloxy, 3-dimethyl-cyclobutylcarbonyloxy, 1-n-propyl-cyclopropylcarbonyloxy, 2-n-propyl-cyclopropylcarbonyloxy, 1-isopropyl-cyclopropylcarbonyloxy, 2-isopropyl-cyclopropylcarbonyloxy, 1,2, 2-trimethyl-cyclopropylcarbonyloxy, 1,2, 3-trimethyl-cyclopropylcarbonyloxy, 2, 3-trimethyl-cyclopropylcarbonyloxy, 1-ethyl-2-methyl-cyclopropylcarbonyloxy, 2-ethyl-1-methyl-cyclopropylcarbonyloxy, 2-ethyl-2-methyl-cyclopropylcarbonyloxy and 2-ethyl-3-methyl-cyclopropylcarbonyloxy.
The beta-diketone ligand has the following structural formula:
The above halogens may be exemplified by: fluorine, chlorine, bromine, iodine.
The phenol resin according to the present invention is a resinous polymer obtained by polycondensation of one or more phenols such as phenol, o-cresol, m-cresol, p-cresol, xylenol, trimethylphenol, t-butylphenol, ethylphenol, 2-naphthol, and 1, 3-dihydroxynaphthol, with an aldehyde in the presence of an acidic or basic catalyst. Specifically, a known phenol resin used for a conventional phenol-formaldehyde based positive type resist can be used.
The photosensitive compound of the present invention may be a known photosensitive compound used in conventional phenolic positive-working photoresists, and includes at least one of diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, arsonium salts, oxonium salts, halogenated organic compounds, quinonediazide compounds, bis (sulfonyl) diazomethane compounds, sulfone compounds, organic acid ester compounds, and organic acid imide compounds.
The photosensitive compounds may be specifically listed as follows: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2, 4-dimethylphenylsulfonyl) diazomethane, 2,1, 4-diazonaphthoquinone sulfonate, 2,1, 5-diazonaphthoquinone sulfonate, 2,3, 4-trihydroxybenzophenone, 1, 2-benzoquinone diazide-4-sulfonic acid, 1, 2-naphthoquinone diazide-5-sulfonic acid, and the like.
The solvent used in the present invention may be any solvent capable of dissolving the photoresist composition of the present invention to produce a homogeneous solution, and may be one or a combination of solvents among known solvents that have been used as solvents for conventional phenolic positive-working photoresists. The solvents mentioned may be mentioned by way of example: diethyl carbonate, methyl acetate, ethyl acetate, N-propyl acetate, isopropyl acetate, N-butyl acetate, isobutyl acetate, methylcyclohexyl acetate, N-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol phenyl ether acetate, ethylene glycol diacetate, ethyl propionate, N-butyl propionate, isoamyl propionate, methyl lactate, ethyl lactate, N-butyl lactate, N-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, N-methylformamide, N-dimethylformamide, N-diethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, N-methylpropionamide, isopropyl acetate, N-butyl acetate, isobutyl acetate, methylcyclohexyl acetate, N-nonyl acetate, methyl propionate, methyl lactate, ethyl lactate, N-pentyl lactate, diethyl malonate, dimethyl phthalate, n-methylpyrrolidone, dimethylsulfide, diethylsulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, 1, 3-propanesultone, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, N-pentane, isopentane, N-hexane, isohexane, N-heptane, isoheptane, benzene, toluene, xylene, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, diethyl ether, ethylene glycol ethyl ether, and the like.
Preferably, the phenolic positive-working photoresist comprises:
10-70 wt% of phenolic resin;
0.5 to 20wt% of a photosensitive compound;
0.5 to 30wt% of a metal compound soluble in the solvent;
10 to 80wt% of a solvent.
Preferably, the phenolic positive photoresist further contains 0.05 to 10wt% of an adhesion promoter, a surfactant, a solvent inhibitor, a plasticizer and/or an antihalation agent.
A method of photolithography, comprising: (1) coating phenolic positive photoresist on a substrate, (2) exposing and developing, and (3) etching, wherein 0.5-30 wt% of metal compound is dissolved in the phenolic positive photoresist.
Preferably, the metal compound is a complex or salt formed by at least one selected from the group consisting of magnesium, calcium, barium, titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, cadmium, indium, tin, and antimony, and at least one selected from the group consisting of alkyl, alkenyl, alkoxy, acyloxy, β -diketone ligand, C ≡ O, halogen, nitro, and nitrate.
In the photoresist composition, the metal compound is completely dissolved in the traditional phenolic positive photoresist, in the photoetching process, after the photoresist is coated, dried and formed into a film, the metal compound is uniformly distributed in a glue film, and is exposed and developed, the metal compound of an exposed reaction part and the glue film are dissolved in a developing solution during development, and the glue film of an unexposed reaction part and the metal compound are remained on the surface of a substrate together to form a photoetching pattern. In the subsequent dry etching, the plasma carries out the dual-action etching of physical bombardment and chemical reaction on the photoresist film containing the metal compound, wherein the carbon-oxygen component forms a volatile reactant to be removed, the metal component is slowly deposited, and a new protective layer is formed on the surface of the photoresist film to play a role in obstructing the etching, thereby achieving the purpose of improving the etching resistance of the photoresist.
Compared with the existing method for improving the etching resistance by increasing the thickness of the photoresist and improving the film hardening temperature and the method for improving the etching resistance of the photoresist by coating the 'lower resist layer' or the 'hard mask', the photoresist can omit the coating of the 'lower resist layer' or the 'hard mask', the operation flow is simpler, the excellent etching resistance can effectively simplify the etching process, the yield of finished products is increased, and the use cost of the photoresist is reduced. The photoresist can be widely applied to the field of production of microelectronic components requiring dry etching.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
43g of linear phenolic resin, 10g of 2,1, 4-diazonaphthoquinone sulfonate, 16g of 2-methylcyclopentadienyl manganese tricarbonyl, 1g of gamma-aminopropyltriethoxysilane and 100g of propylene glycol monomethyl ether acetate are mixed, fully dissolved and filtered by a filter membrane with the aperture of 0.02 micrometer, so that the photoresist 1 is obtained.
The structure of the novolac resin in this example is as follows:
Example 2
43g of linear phenolic resin, 10g of 2,1, 5-diazonaphthoquinone sulfonate, 16g of zirconium propionate, 1g N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 100g of propylene glycol monomethyl ether acetate are mixed, fully dissolved and filtered by a filter membrane with the aperture of 0.02 micron to obtain the photoresist 2.
The structure of the novolac resin in this example is as follows:
Example 3
65g of linear phenolic resin, 15g of 1, 2-benzoquinone diazide-4-sulfonic acid, 8g of ferric trifluoroacetylacetonate (CAS: 14526-22-8), 2g of gamma-aminopropyltriethoxysilane, 40g of benzene and 80g of propylene glycol monomethyl ether acetate are mixed, fully dissolved and filtered by a filter membrane with the aperture of 0.02 micron to obtain the photoresist 3.
The structure of the novolac resin in this example is as follows:
wherein R is methyl and n = 50.
Example 4
65g of linear phenolic resin, 10g of 1, 2-naphthoquinone diazide-5-sulfonic acid, 8g of chromium acetylacetonate (CAS:21679-31-2), 2g N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 40g of ethanol and 80g of propylene glycol monomethyl ether acetate are mixed, fully dissolved and filtered by a filter membrane with the aperture of 0.02 micron to obtain the photoresist 4.
The structure of the novolac resin in this example is as follows:
Comparative example 1
43g of linear phenolic resin, 10g of 2,1, 4-diazonaphthoquinone sulfonate, 1g N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 100g of propylene glycol monomethyl ether acetate are mixed, fully dissolved and filtered by a filter membrane with the aperture of 0.02 micrometer, thus obtaining the contrast photoresist.
The structure of the phenolic novolac resin in this comparative example is as follows:
And (3) testing:
spin-coating photoresist on a cleaned gallium nitride substrate, adjusting the rotating speed to make the thickness of the photoresist film about 8 μm, pre-baking (PAB) with a hot plate at 100 ℃/180s, exposing through an i-line, soaking and developing with 2.38wt% TMAH for 180s, cleaning with deionized water, baking with an oven, and curing at 120 ℃/120 s. Dry etching was performed for 60min in an etching gas atmosphere of boron trichloride and chlorine, the film thickness loss of the photoresist and the etching depth of the substrate were measured, and the etching ratio was calculated from the loss of the film thickness/the etching depth of the substrate, and the results are shown in the following table.
According to the test results, the phenolic aldehyde positive photoresist can obviously improve the etching resistance of the photoresist.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. An etching-resistant phenolic positive photoresist mainly comprises phenolic resin, a photosensitive compound and a solvent, and is characterized in that the phenolic positive photoresist contains 0.5-30 wt% of a metal compound which can be dissolved in the solvent;
the metal compound is a complex or salt formed by at least one of magnesium, calcium, barium, titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, cadmium, indium, tin and antimony and at least one of alkyl, alkenyl, alkoxy, acyloxy, beta-diketone ligand, C.ident.O, halogen, nitro and nitrate.
2. The phenolic positive-working photoresist of claim 1, wherein the phenolic positive-working photoresist contains 1 to 20wt% of the metal compound soluble in the solvent.
3. The phenolic positive-working photoresist of claim 2, wherein the phenolic positive-working photoresist contains 2 to 10wt% of the metal compound soluble in the solvent.
4. The phenolic positive-working photoresist according to claim 1, wherein the phenolic resin is a resin polymer obtained by polycondensation of at least one of phenol, o-cresol, m-cresol, p-cresol, xylenol, trimethylphenol, t-butylphenol, ethylphenol, 2-naphthol, and 1, 3-dihydroxynaphthol with an aldehyde in the presence of an acidic or basic catalyst.
5. The phenolic positive-working photoresist according to claim 1, wherein the photosensitive compound comprises at least one of a diazonium salt, an ammonium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, an arsonium salt, an oxonium salt, a halogenated organic compound, a quinonediazide compound, a bis (sulfonyl) diazomethane compound, a sulfone compound, an organic acid ester compound, and an organic acid imide compound.
6. The phenolic positive-working photoresist of claim 1, wherein the phenolic positive-working photoresist comprises:
10-70 wt% of phenolic resin;
0.5 to 20wt% of a photosensitive compound;
0.5 to 30wt% of a metal compound soluble in the solvent;
10 to 80wt% of a solvent.
7. The phenolic positive-working photoresist of claim 6, further comprising 0.05 to 10wt% of an adhesion promoter, a surfactant, a solvent blocker, a plasticizer and/or an antihalation agent.
8. A method of photolithography, comprising: (1) coating phenolic positive photoresist on a substrate, (2) exposing and developing, and (3) etching, wherein 0.5-30 wt% of metal compound is dissolved in the phenolic positive photoresist;
the metal compound is a complex or salt formed by at least one of magnesium, calcium, barium, titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, cadmium, indium, tin and antimony and at least one of alkyl, alkenyl, alkoxy, acyloxy, beta-diketone ligand, C.ident.O, halogen, nitro and nitrate.
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| CN201611198717.7A CN106502052B (en) | 2016-12-22 | 2016-12-22 | Etching-resistant phenolic aldehyde positive photoresist |
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