JPH0736187A - Negative chemically sensitized resist composition - Google Patents

Abstract

PURPOSE:To obtain good balance in sensitivity, film remaining rate, and resolution and to obtain excellent durability against dry etching by incorporating a resin soluble with an alkali aq. soln., crosslinking agent, photoacid producing agent, and compd. having an azide group. CONSTITUTION:This resist compsn. contains (1) resin soluble with an alkali aq. soln., (2) crosslinking agent which causes crosslinking reaction with an acid catalyst, (3) photoacid producing agent which produces an acid catalyst by radioactive rays, and (4) compd. having an azide group. The compd. having an azide group (4) is an aromatic azide compd. The weight average mol.wt. (Mw) of the resin soluble with an alkali aq. soln. (1) is 1000-30000 and the resin (1) is a novolac resin or polyvinylphenol. The crosslinking agent (2) which causes crosslinking reaction with an acid catalyst is alkoxymethylated melamine resin, etc. Thereby, the obtd. compsn. is highly sensitive to radioactive rays and has extremely excellent resolution in a transferred pattern without swelling, excellent durability for dry etching, and excellent heat resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron rays, ion rays and X-rays, and particularly IC
The present invention relates to a negative chemically amplified resist composition suitable for producing semiconductor integrated circuits such as those described above and photomasks.

[0002]

2. Description of the Related Art Conventionally, in the fabrication of semiconductor integrated circuits, photomasks, etc., a fine resin pattern is formed by applying a resist on a substrate such as a silicon wafer or a chromium vapor deposition plate, irradiating it with radiation, and further developing it. Is formed, and then the substrate portion other than the pattern portion is etched. In recent years, in order to improve the performance and reliability of integrated circuits, there is an increasing demand for higher density of elements.

A composition using a cyclized rubber and a bisazide compound has been used as a negative resist composition. However, since this system uses an organic solvent for development, swelling occurs, and the resolution is limited to 2 to 3 μm. Further, in order to enhance the dry etching resistance required for processing after development, it is advantageous to use a resin having an aromatic ring, but this system does not have an aromatic ring and the resistance is not sufficient.

On the other hand, chloromethylated polystyrene and chlorinated polymethylstyrene resin compositions containing polystyrene as a trunk polymer are known. These compositions have high sensitivity and are excellent in dry etching resistance because they have an aromatic ring, but since they require development treatment with an organic solvent, the transfer pattern is distorted due to the effect of swelling, and the resolution is poor due to peeling of the film. It has drawbacks.

JP-A-63-191142 discloses an example of a composition using an alkali-soluble resin and a bisazide compound. These compositions can be developed with an aqueous alkaline solution, do not swell, and have improved resolution. However, since the azide compound forms a reaction product such as an azo compound upon irradiation with ultraviolet rays, there is a problem that absorption near the irradiation light increases and light does not reach the lower part of the resist layer sufficiently, resulting in an inverted trapezoidal pattern. is there. Furthermore, this compound
It has the drawback of not having sufficient sensitivity to radiation such as electron beams, ion beams and X-rays.

A resist composition (Japanese Patent Laid-Open No. 164045/1987) comprising an alkali-soluble thermosetting resin and a halogen compound as a photoacid generator is known. This composition, the acid generated from the photoacid generator by radiation,
Since the resin is catalytically crosslinked by the heat treatment in the next step, it is characterized by high sensitivity and is generally called a chemically amplified resist. However, in this resist composition, the trace amount of impurities contained in the composition or the presence of impurities and active sites on the substrate also function as a catalyst, the crosslinking reaction proceeds even in unnecessary portions, and the obtained transfer pattern is an image. It has a drawback that the contrast is low, the cross-sectional shape is easily drawn, and adjacent patterns are joined together, or it is difficult to obtain a high-resolution pattern such as many residual defects.

Further, a novolac resin as an alkali-soluble resin, an alkoxymethylated melamine resin which is polymerized with an acid, a halogenated triazine compound as an acid generator, and naphthoquinone diazide (chemical name: diazonaphthoquinone-5 (4) -sulfonic acid) as an additive. Resist composition comprising a benzophenone ester compound of
217855) is known. However, this resist composition is not practical because it requires a long development time to obtain a high-resolution pattern.

[0008]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention Sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron rays, ion rays and X-rays, and having a good balance of sensitivity, residual film rate and resolution, heat resistance and dry etching resistance. There is a demand for the development of a negative chemically amplified resist composition which is excellent in fine processing and capable of being alkali-developed for fine processing.

[0009]

Means for Solving the Problems The inventors of the present invention have achieved the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes (i) (1) an aqueous alkali solution-soluble resin, (2) a cross-linking agent that causes a cross-linking reaction with an acid catalyst, (3) a photo-acid generator that generates an acid catalyst by radiation, and (4) an azide group. A negative chemically amplified resist composition containing a compound having: (ii) a composition having (i) an azido group-containing compound is an aromatic azide compound,
(Iii) The composition of (i) in which the weight average molecular weight (Mw) of the alkaline aqueous solution-soluble resin of (1) is 1,000 to 30,000, (iv) the alkaline aqueous solution-soluble resin is a novolac resin or A composition of (i) which is polyvinylphenol and the crosslinking agent which causes a crosslinking reaction by the acid catalyst of (2) is an alkoxymethylated melamine resin or an alkoxymethylated benzoguanamine resin,
(V) When the content of each component is 100 parts by weight based on the total solid content, 60 to 95 parts by weight of the alkaline aqueous solution soluble resin of (1) and the crosslinking agent which causes a crosslinking reaction by the acid catalyst of (2) 5 to 30 parts by weight, 0.5 to 15 parts by weight of the photo-acid generator which generates an acid catalyst by the radiation of (3),
It relates to the composition of (i), wherein the compound having an azido group of (4) is 0.1 to 10 parts by weight.

The negative chemically amplified resist composition of the present invention will be described in detail below. The alkali-soluble resin (1) used in the negative chemically amplified resist composition of the present invention is not particularly limited as long as it has good coatability and is compatible with other components. For example, phenol novolac. Resin, novolak resin such as cresol novolac resin, polyvinylphenol resin, methyl (meth) acrylate- (meth) acrylic acid copolymer, styrene-
Examples thereof include maleic acid copolymers, but novolak resins and polyvinylphenol resins are particularly preferably used.

Novolak resins include phenol, o
-Cresol, m-cresol, p-cresol, bisphenol-A, bisphenol-F, resorcinol, pyrogallol, 2,6-xylenol, 2,4-xylenol, 2,5-xylenol, 3,5-xylenol, 2,4 , 6-trimethylphenol, 2,3,5
-Formaldehyde, paraformaldehyde, trioxane, benzaldehyde, o-nitrobenzaldehyde, p-nitrobenzaldehyde, or a combination of two or more phenols such as trimethylphenol.
It can be obtained by polycondensation with aldehydes such as o-methylbenzaldehyde and p-methylbenzaldehyde in the presence of an acidic catalyst. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, oxalic acid, acetic acid and the like.

As a polyvinylphenol resin, 4-vinylphenol, 3-vinylphenol, 2-vinylphenol, 2-methyl-4-vinylphenol, 2,6-
It can be obtained by radical polymerization using vinylphenols such as dimethyl-4-vinylphenol alone or in combination of two or more, using a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide. Vinylphenols and polyvinylphenols are described in detail in "Vinylphenol Basics and Applications" (published by the Education Publishing Center), edited by Maruzen Petrochemical Co., Ltd.

An alkali-soluble resin is used in order to increase the solubility difference in the alkali developing solution between the irradiated portion and the non-irradiated portion of the radiation, improve the image contrast, and improve the adhesiveness to the silicon substrate or the chromium substrate. Has a weight average molecular weight (Mw) of 1,000 to 30,
000, preferably 2,000 to 25,000.

The cross-linking agent capable of cross-linking with an acid catalyst (2) used in the negative chemically amplified resist composition of the present invention is not particularly limited as long as it shows a cross-linking property with an acid catalyst, and examples thereof include alkoxy. Methylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated acetoguanamine resin, alkoxymethylated urea resin, alkoxymethylated glycoluril resin, resole resin, etc. are mentioned, but alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin Is preferably used.

The alkoxymethylated melamine resin is prepared by subjecting melamine to N-methylol conversion with aldehydes such as formaldehyde, paraformaldehyde and trioxane in a basic aqueous solution such as sodium hydroxide and potassium hydroxide, and then hydrochloric acid, It can be obtained by reacting a lower alcohol such as methanol, ethanol, propanol or butanol under an acid catalyst such as sulfuric acid or acetic acid. These resins are commercially available from Mitsui Cyanamid Co., Ltd. as Cymel 200 series, Cymel 300 series, and Cymel 500 series.

The alkoxymethylated benzoguanamine resin is obtained by subjecting benzoguanamine to N-methylol conversion with aldehydes such as formaldehyde, paraformaldehyde and trioxane in a basic aqueous solution such as sodium hydroxide and potassium hydroxide, and then hydrochloric acid, It can be obtained by reacting a lower alcohol such as methanol, ethanol, propanol or butanol in the presence of an acid catalyst such as sulfuric acid or acetic acid. These resins are commercially available from Mitsui Cyanamid Co., Ltd. as Cymel 1100 series and the like. Regarding these alkoxymethylated melamine resins and alkoxymethylated benzoguanamine resins, colorants, Vol. 63, No. 1, 19
Pp. 28-28 "Amino resins for paints".

The acid generator (3) used in the negative chemically amplified resist composition of the present invention to generate an acid upon irradiation with radiation includes a large number of compounds and mixtures thereof. This includes onium salts such as iodonium salts, sulfonium salts, phosphonium salts, selenonium salts and arsonium salts, complex compounds such as metallocenes, o-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, p-nitrobenzyl-9. , 10-alkoxyanthracene sulfonates and other sulfonic acid esters, 2,4
-Bistrichloromethyl-6-phenyl-s-triazine, 2,4-bistrichloromethyl-6-phenyl-
(4'-Methoxyphenyl) -s-triazine, 2,4
-Bistrichloromethyl-6-naphthyl-s-triazine, 2,4,6-tristrichloromethyl-s-triazine, tribromomethylphenyl sulfone, tetrabromobisphenol-A, tetrabromobisphenol-
Examples thereof include halides such as S and DDT. Details of specific examples of these compounds can be found in the Journal of Photopolymer Scie
nce and Technology, 2 (2), (1989) pages 283-28
Although it is described as a photo-acid generator over page 4,
Any compound capable of generating an acid upon irradiation with radiation can be used without limitation.

The compound (4) having an azide group (hereinafter simply referred to as an azide group compound) used in the negative chemically amplified resist composition of the present invention is not particularly limited.
Aromatic azide compounds are preferred. Specific examples of the aromatic azide compound include, for example, 4,4′-diazidodiphenylsulfone, 3,3′-diazidodiphenylsulfone,
Azidophenyl sulfones such as 3,4′-diazidodiphenyl sulfone, azidostilbenes such as 4,4′-diazidostilbene, 1,3-bis- (4′-azidobenzal) -acetone, 1,3-bis -(4'-azidocinnamylidene) -2-propanone, 4,4'-diazidochalcone, 2,6-bis- (4'-azidobenzal) -cyclohexanone, 2,6-bis- (4'-azidobenzal) ) -4-Methylcyclohexanone, 2,6-bis-
(4'-azidobenzal) -4-tert-butylcyclohexanone, 4-azidoacetophenone, 4-azidobenzalacetophenone, 4-azidobenzalacetone and other azidophenyl-ketones, 4-azidobenzaldehyde and other azidophenylaldehydes , 4-azidobenzoic acid, and other azidophenylcarboxylic acids. Further, the aromatic azide compounds described in JP-A-63-191142 can also be used.

In the present invention, the content ratio of each component is 10 based on the total solid content in consideration of properties such as sensitivity, pattern shape, resolution, alkali solubility and dry etching resistance.
When the amount is 0 parts by weight, the alkali-soluble resin is 60 to 9
5 parts by weight, preferably 65 to 90 parts by weight, 5 to 30 parts by weight, preferably 1
0 to 25 parts by weight, 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, for a photoacid generator that generates an acid by radiation, and 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight for an azide compound. It is desirable to contain 3 to 8 parts by weight.

The negative chemically amplified resist composition of the present invention is usually used in the form of a photosensitive solution by dissolving the above components in an organic solvent. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, cellosolves such as butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cellosolve acetate such as butyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Propylene glycol acetate such as propylene glycol butyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, propionate such as ethyl ethoxypropionate, lactate such as methyl lactate, ethyl lactate, butyl lactate , Diethylene glycol monomethyl ether, diethylene glycol mono Examples include diethylene glycols such as chill ether, acetic acid esters such as methyl acetate, ethyl acetate, butyl acetate and amyl acetate, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone. However, propylene glycol acetic acid esters, propionic acid esters, and lactic acid esters, which have a strong dissolving power for the composition of the present invention, are excellent in coating properties, and have low toxicity, are particularly useful. These may be used alone or in combination of two or more.

Next, a method for forming a fine pattern using the composition thus obtained will be described. The total solid content of the prepared composition is dissolved in the solvent as described above to a concentration of 1 to 60%, preferably 5 to 40%, and if necessary, a plasticizer, a photochromic agent, a dye, After addition of additives such as an adhesion improver and a surfactant, insoluble matter is removed by filtration with a membrane filter or the like, if necessary, to obtain a photosensitive solution. This photosensitive solution is first applied onto a substrate such as a silicon wafer or a chromium vapor deposition plate by a spinner or the like to obtain a uniform film, which is then subjected to a solvent at a temperature of 70 to 140 ° C, preferably 80 to 130 ° C. Heat treatment is performed for the purpose of removing and improving the adhesion. At this time, a part of the azide compound causes thermal decomposition,
It is considered that the compound changes to a compound having an amino group and an imino group and suppresses an unnecessary crosslinking reaction, but the details are unknown.

Next, radiation such as ultraviolet rays, far ultraviolet rays, electron beams, ion beams, and X-rays is applied. At this time, a part of the acid generated by irradiation is captured by the thermally decomposed azide compound, but the decrease in sensitivity is slight due to the large amount of acid generated. However, since a small amount of acid generated in an undesired portion due to backscattering, proximity effect, etc. is almost completely captured, the portion to be crosslinked in the subsequent heating step is only the irradiated portion.

The heat treatment after irradiation with radiation is a treatment for sensitizing the sensitivity of the negative chemically amplified resist composition, and is essential for achieving the object of the present invention. This processing temperature is 90 to 160 ° C., preferably 100 to 150 ° C., in consideration of the sensitivity and the ease of joining the transfer patterns. The substrate that has been heat-treated after irradiation with radiation can be transferred to a fine resin pattern on the substrate by being developed with an alkaline aqueous solution having an appropriate concentration.

Examples of the alkaline aqueous solution used in the negative chemically amplified resist composition of the present invention include tetraalkylammonium such as tetramethylammonium hydroxide, trialkylamine such as triethylamine, and trialkanolamine such as triethanolamine. Although an alkaline aqueous solution, an inorganic alkaline aqueous solution such as an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, an alkali metal carbonate such as sodium carbonate and potassium carbonate can be used, in the integrated circuit manufacturing process,
It is desirable to use an organic alkaline aqueous solution.

The negative chemically amplified resist composition of the present invention has high sensitivity to radiation, and the transferred pattern has no swelling and is extremely excellent in resolution, and is also extremely excellent in dry etching resistance and heat resistance.

[0026]

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Example 1 71.45 parts by weight of polyvinylphenol having a weight average molecular weight of 5,200 (trade name: Marca Linker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.), an alkoxymethylated benzoguanamine resin (trade name: Cymel 1123 Mitsui Cyanamid ( 21.44 parts by weight, tribromomethylphenyl sulfone 3.57 parts by weight and 3,3′-
3.54 parts by weight of diazidodiphenyl sulfone was dissolved in ethyl lactate so that the solid content concentration became 15%, and the obtained solution was pressure-filtered using a membrane filter having a pore size of 0.1 μm to obtain a solution of the present invention. A photosensitive solution in which the composition was dissolved was obtained.

Next, this photosensitive solution was spin-coated at 2,000 rpm on a chromium vapor-deposited substrate surface-treated by a known method, and heated for 5 minutes on a hot plate having a surface temperature of 100 ° C. to give a film thickness of 0. A resist layer having a thickness of 0.7 μm was obtained.
Then, an accelerating voltage of 2 is applied to the resist layer by using an electron beam drawing apparatus (ELS-3300 type manufactured by Elionix Co., Ltd.).
An irradiation dose of 1 to 5 μC / cm ² was applied at 0 kV, and a line and space pattern of 1 μm was drawn. After drawing, a heat sensitization reaction was performed for 10 minutes on a hot plate having a surface temperature of 130 ° C., and immersed in an aqueous solution of tetramethylammonium hydroxide (hereinafter, abbreviated as “TMAH”) having a concentration of 2.38% for 60 seconds, and an electron beam was not applied. The irradiated part was dissolved and removed to obtain a resin pattern. When this transfer pattern was observed, the proper irradiation amount was 1.4 μC / cm ² , a residual film rate of 90% or more was shown, the cross-sectional shape was rectangular, and no biting phenomenon at the substrate interface was observed. Further, although the transferred pattern became thicker as the irradiation amount increased, joining of adjacent patterns, skirting, whiskers, residues and the like were not observed at all.

Example 2 Polyvinylphenol having a weight average molecular weight of 5,200 (trade name: Marca Linker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.) 68.96 parts by weight, alkoxymethylated benzoguanamine resin (trade name: Cymel 1123) 20.69 parts by weight of Mitsui Cyanamid Co., Ltd., 3.45 parts by weight of tribromomethylphenyl sulfone and 3,3'-
6.90 parts by weight of diazidodiphenyl sulfone was dissolved in ethyl lactate so that the solid content concentration was 15%, and the resulting solution was filtered under pressure using a membrane filter having a pore size of 0.1 μm to obtain a solution of the present invention. A photosensitive solution in which the composition was dissolved was obtained.

Next, this photosensitive solution is put on a chromium vapor-deposited substrate 2,
Spin coating at 000 rpm and heat on a hot plate with a surface temperature of 100 ° C for 5 minutes to obtain a film thickness of 0.7μ
m resist layer was obtained. Then, the same electron beam drawing apparatus as in Example 1 was used to apply a dose of ² to 8 μC / cm ^{2 to} the resist layer at an accelerating voltage of 20 kV to draw a line and space pattern of 1 μm. Surface temperature after drawing 1
A heat sensitization reaction is performed on a hot plate at 30 ° C. for 10 minutes, and immersed in a TMAH solution having a concentration of 2.38% for 60 seconds,
The electron beam non-irradiated portion was dissolved and removed to obtain a resin pattern. When this transfer pattern was observed, the proper irradiation amount was 3.0.
It was μC / cm ² , showed a residual film rate of 90% or more, had a rectangular cross-sectional shape, and the phenomenon of biting at the substrate interface was not observed. Also, although the transfer pattern increases in irradiation dose and becomes thicker, it is possible to join adjacent patterns together.
No hemming, whiskers, residues, etc. were observed.

Example 3 72.01 parts by weight of polyvinylphenol having a weight average molecular weight of 5,200 (trade name: Marca Linker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.), an alkoxymethylated benzoguanamine resin (trade name: Cymel 1123) Mitsui Cyanamid Co., Ltd.) 19.95 parts by weight, tribromomethylphenyl sulfone 7.27 parts by weight and 3,3′-
0.78 parts by weight of diazidodiphenyl sulfone was dissolved in ethyl lactate so that the solid content concentration was 9.5%,
The resulting solution was pressure-filtered using a membrane filter having a pore size of 0.1 μm to obtain a photosensitive solution in which the composition of the present invention was dissolved.

Next, this photosensitive solution was deposited on a chromium vapor deposition substrate to
Spin coating at 000 rpm and heat on a hot plate with a surface temperature of 100 ° C for 5 minutes to give a film thickness of 0.3μ
m resist layer was obtained. Then, using the same electron beam drawing apparatus as in Example 1, a dose of 5 to 12 μC / cm ² was applied to the resist layer at an accelerating voltage of 20 kV to draw a line and space pattern of 1 μm. After drawing, a heat sensitization reaction was carried out for 10 minutes on a hot plate having a surface temperature of 105 ° C., and it was immersed in a TMAH solution having a concentration of 2.38% for 60 seconds to dissolve and remove the electron beam non-irradiated portion to obtain a resin pattern. . When this transfer pattern was observed, the proper irradiation amount was 6.4 μC / cm ² , the residual film rate was 90% or more, the cross-sectional shape was rectangular, and the biting phenomenon at the substrate interface was not observed. Further, although the transferred pattern became thicker as the irradiation amount increased, joining of adjacent patterns, skirting, whiskers, residues and the like were not observed at all.

Example 4 71.49 parts by weight of polyvinylphenol having a weight average molecular weight of 5,200 (trade name: Marca Linker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.), an alkoxymethylated benzoguanamine resin (trade name: Cymel 1123) Mitsui Cyanamid Co., Ltd.) 19.63 parts by weight, tribromomethylphenyl sulfone 7.11 parts by weight and 3,3′-
1.76 parts by weight of diazidodiphenyl sulfone was dissolved in ethyl lactate so that the solid content concentration was 9.5%,
The resulting solution was pressure-filtered using a membrane filter having a pore size of 0.1 μm to obtain a photosensitive solution in which the composition of the present invention was dissolved.

Next, this photosensitive solution was deposited on a chromium vapor deposition substrate.
Spin coating at 000 rpm and heat on a hot plate with a surface temperature of 100 ° C for 5 minutes to give a film thickness of 0.3μ
m resist layer was obtained. Then, using the same electron beam drawing apparatus as in Example 1, a dose of 5 to 12 μC / cm ² was applied to the resist layer at an accelerating voltage of 20 kV to draw a line and space pattern of 1 μm. After drawing, a heat sensitization reaction was carried out for 10 minutes on a hot plate having a surface temperature of 105 ° C., and it was immersed in a TMAH solution having a concentration of 2.38% for 60 seconds to dissolve and remove the electron beam non-irradiated portion to obtain a resin pattern. . When this transfer pattern was observed, the proper irradiation amount was 6.4 μC / cm ² , the residual film rate was 90% or more, the cross-sectional shape was rectangular, and the biting phenomenon at the substrate interface was not observed. Further, although the transferred pattern became thicker as the irradiation amount increased, joining of adjacent patterns, skirting, whiskers, residues and the like were not observed at all.

Example 5 77.03 parts by weight of polyvinylphenol having a weight average molecular weight of 5,200 (trade name: Markerlinker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.), an alkoxymethylated benzoguanamine resin (trade name: Cymel 1123) 21.05 parts by weight of Mitsui Cyanamid Co., Ltd., 1.52 parts by weight of tribromomethylphenyl sulfone and 3,3′-
0.40 parts by weight of diazidodiphenyl sulfone was dissolved in ethyl lactate so that the solid content concentration was 9.5%,
The resulting solution was pressure-filtered using a membrane filter having a pore size of 0.1 μm to obtain a photosensitive solution in which the composition of the present invention was dissolved.

Next, this photosensitive solution was deposited on a chromium vapor deposition substrate.
Spin coating at 000 rpm and heat on a hot plate with a surface temperature of 100 ° C for 5 minutes to give a film thickness of 0.3μ
m resist layer was obtained. Then, using the same electron beam drawing apparatus as in Example 1, an irradiation amount of 8 to 18 μC / cm ² was applied to the resist layer at an accelerating voltage of 20 kV to draw a line and space pattern of 1 μm. After drawing, a heat sensitization reaction was carried out for 10 minutes on a hot plate having a surface temperature of 110 ° C., and it was immersed in a TMAH solution having a concentration of 2.38% for 60 seconds to dissolve and remove an electron beam non-irradiated portion to obtain a resin pattern. . When this transfer pattern was observed, the proper irradiation amount was 10.0 μC / cm ² , a residual film rate of 90% or more was shown, and the cross-sectional shape was rectangular, and no biting phenomenon at the substrate interface was observed. Further, although the transferred pattern became thicker as the irradiation amount increased, joining of adjacent patterns, skirting, whiskers, residues and the like were not observed at all.

Example 6 72.96 parts by weight of polyvinylphenol having a weight average molecular weight of 24,500 (trade name: Marca Linker MH-2P manufactured by Maruzen Petrochemical Co., Ltd.), an alkoxymethylated melamine resin (trade name: Cymel 303) 21.91 parts by weight of Mitsui Cyanamid Co., Ltd., 3.66 parts by weight of 2,4,6-tristrichloromethyl-s-triazine and 2,6-bis- (4'-azidobenzal) -4-tert-butyl. 1.48 parts by weight of cyclohexanone having a solid content of 1
Dissolve it in propylene glycol monomethyl ether acetate so that the concentration of the solution becomes 5%.
A photosensitive solution in which the composition of the present invention was dissolved was obtained by pressure filtration using a membrane filter of m.

Next, this photosensitive solution is put on a chromium vapor deposition substrate for 2,
Spin coating at 000 rpm and heat for 5 minutes on a hot plate with a surface temperature of 100 ° C to obtain a film thickness of 0.5μ.
m resist layer was obtained. Then, using the same electron beam drawing apparatus as in Example 1, an irradiation amount of 1 to 8 μC / cm ² was applied to the resist layer at an accelerating voltage of 20 kV to draw a line and space pattern of 1 μm. Surface temperature after drawing 1
A heat sensitization reaction is performed for 10 minutes on a hot plate at 05 ° C., and it is immersed in a TMAH solution of 2.38% concentration for 60 seconds,
The electron beam non-irradiated portion was dissolved and removed to obtain a resin pattern. When this transfer pattern was observed, the proper irradiation amount was 2.0.
It was μC / cm ² , showed a residual film rate of 90% or more, had a rectangular cross-sectional shape, and the phenomenon of biting at the substrate interface was not observed. Also, although the transfer pattern increases in irradiation dose and becomes thicker, it is possible to join adjacent patterns together.
No hemming, whiskers, residues, etc. were observed.

Example 7 72.73 parts by weight of m, p-cresol novolac resin having a weight average molecular weight of 6,000, 18.18 parts by weight of alkoxymethylated melamine resin (trade name: Cymel 303, manufactured by Mitsui Cyanamid Co., Ltd.), 7.27 parts by weight of 2,4-bistrichloromethyl-6-phenyl-s-triazine and 1.82 parts by weight of 4,4′-diazidochalcone were added to propylene glycol monomethyl so that the solid content concentration became 18%. The solution was dissolved in ether acetate, and the resulting solution was pressure-filtered using a membrane filter having a pore size of 0.1 μm to obtain a photosensitive solution in which the composition of the present invention was dissolved.

Next, this photosensitive solution is put on a chromium vapor deposition substrate for 2,
Spin coating at 000 rpm and heat for 5 minutes on a hot plate with a surface temperature of 100 ° C to give a film thickness of 0.9μ
m resist layer was obtained. Then, the same electron beam drawing apparatus as in Example 1 was used to apply a dose of 0.5 to ⁵ μC / cm ^{2 to} the resist layer at an accelerating voltage of 20 kV to draw a line and space pattern of 1 μm. After drawing, a heat sensitization reaction was carried out for 10 minutes on a hot plate having a surface temperature of 100 ° C., and it was immersed in a TMAH solution having a concentration of 2.38% for 60 seconds to dissolve and remove an electron beam non-irradiated portion to obtain a resin pattern. . When this transfer pattern was observed, the proper irradiation amount was 1.0 μC / cm ² , a residual film rate of 90% or more was shown, the cross-sectional shape was rectangular, and no biting phenomenon at the substrate interface was observed. Further, although the transferred pattern became thicker as the irradiation amount increased, joining of adjacent patterns, skirting, whiskers, residues and the like were not observed at all.

Example 8 72.96 parts by weight of polyvinylphenol having a weight average molecular weight of 2,300 (trade name: Marcalinker MS-1P manufactured by Maruzen Petrochemical Co., Ltd.), an alkoxymethylated benzoguanamine resin (trade name: Cymel 1123) 21.91 parts by weight of Mitsui Cyanamid Co., Ltd., 3.66 parts by weight of tribromomethylphenyl sulfone, and 1.48 parts by weight of 3,3′-diazidodiphenylsulfone were added to ethyl so that the solid content concentration became 16%. It was dissolved in lactate, and 1.5 parts by weight of Antage STDP-N (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was added as a sensitizer. The resulting solution was pressure filtered using a membrane filter having a pore size of 0.1 μm to obtain a photosensitive solution in which the composition of the present invention was dissolved.

Next, this photosensitive solution was spin-coated on a silicon wafer at 2,000 rpm for 30 seconds to obtain a surface temperature of 10
By heating on a 0 ° C hot plate for 5 minutes,
A resist layer having a film thickness of 0.7 μm was obtained. Next, a V-42, UVD-35 filter manufactured by Toshiba Glass was attached to the ultra-high pressure mercury lamp, and ultraviolet rays of 365 nm which had passed through were used to obtain a value of 0.
Irradiation was performed at 30 to 100 mJ / cm ² through a mask on which a 5 μm line-and-space pattern was drawn.
Next, a heat sensitization reaction is performed for 10 minutes on a hot plate having a surface temperature of 110 ° C., and by immersing in a TMAH solution having a concentration of 2.38% by weight for 60 seconds, the UV-irradiated portion is dissolved and removed to obtain a resin pattern. It was When the transfer pattern was observed, the proper irradiation amount was 50 mJ / cm ² ,
The residual film ratio was not less than%, the sectional shape was rectangular, and no biting phenomenon at the substrate interface was observed. Further, although the transferred pattern became thicker as the irradiation amount increased, joining of adjacent patterns, skirting, beard and residue were not observed at all.

[0042]

Comparative Example 1 A photosensitive solution was prepared in the same manner as in Example 1 except that 3,3′-diazidodiphenyl sulfone was omitted.
In the subsequent operation, the transfer pattern was evaluated according to Example 1. However, as the irradiation amount of the transfer pattern increased, the number of residue defects increased, such as the occurrence of joining of adjacent patterns, skirting, and whiskers.

[0043]

Comparative Example 2 A sensitizing solution was prepared in the same manner as in Example 7 except that 4,4′-diazidochalcone was omitted, and thereafter the processing was carried out according to Example 4. When the transferred pattern was observed, there was no particular problem with the proper irradiation amount, but when the irradiation amount increased by about 15% from the proper value, the tailing was observed at the interface between the pattern and the substrate, and when the irradiation amount increased by 30%, the adjacent pattern was increased. Was observed.

[0044]

INDUSTRIAL APPLICABILITY The negative chemically amplified resist composition of the present invention has a high sensitivity to radiation, the pattern transferred to the substrate does not swell, the sensitivity and resolution are extremely excellent, and there is no peeling and the pattern. It is extremely useful in the manufacture of semiconductor integrated circuits because it has a very wide tolerance until residues such as joining, tailing, and beard are generated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03F 7/028 H01L 21/027

Claims (5)

[Claims] 1. An alkali aqueous solution-soluble resin, (2)
Negative-type chemically amplified resist composition containing a crosslinking agent that causes a crosslinking reaction with an acid catalyst, (3) a photoacid generator that generates an acid catalyst with radiation, and (4) a compound having an azide group. 2. The composition according to claim 1, wherein the compound (4) having an azide group is an aromatic azide compound. 3. The composition according to claim 1, wherein (1) the weight average molecular weight (Mw) of the aqueous alkaline solution resin is 1,000 to 30,000. 4. The (1) alkaline aqueous solution-soluble resin is a novolac resin or polyvinylphenol, and (2) the crosslinking agent which causes a crosslinking reaction with an acid catalyst is an alkoxymethylated melamine resin or an alkoxymethylated benzoguanamine resin. Composition of 5. When the content of each component is 100 parts by weight based on the total solid content, 60 to 95 parts by weight of the alkali aqueous solution soluble resin of (1), and (2) crosslinking which causes a crosslinking reaction by an acid catalyst. 5 to 30 parts by weight of the agent, 0.5 to 15 parts by weight of (3) a photo-acid generator that generates an acid catalyst by radiation, and 0.1 to 10 of the compound of (4) having an azide group.
The composition of claim 1 in parts by weight.