JPS6236663A - Naphthoquinonediazide type compound and positive type photoresist composition containing it - Google Patents

Abstract

PURPOSE:To obtain a positive type photosensitive composition high in sensitivity and resolution and pattern form by forming a positive type photosensitive composition composed of a specified naphthoquinone diazide derivative or containing it. CONSTITUTION:The positive type photoresist composition is made of or contains the naphthoquinone derivative represented by general formula I in which R<1> is H or nitro; R<2> is H, COOH, or CCOR<3>; R<3> is an optionally substituted hydrocarbon group; l is 1 or 2; m is 0, 1, or 2; n is 2 or 3; 2<=m+n<=3; and Q is a group represented by one of formulae II. A mixture of this compound with an alkali-soluble resin such as, a vinylphenol resin or novolak resin, in an amount of 5-50wt% of the resin is used as a resist composition. A substrate is coated with a solution of this mixture dissolved in a solvent high in polarity, exposed to a light in a prescribed pattern, and developed to obtain a good resist.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention generally relates to a radiation-sensitive sootquinonediazide compound and a positive photosensitive resin composition containing the compound.

[Conventional technology]

The degree of integration of integrated circuits has been increasing at an accelerating rate year by year, and we are now moving into the era of so-called ultra-LSIs with higher integration density.As a result, the requirements for photolithography technology are becoming stricter year by year.

In the recent phosphorography process, in order to improve resolution, a process has been introduced in which a reduced projection is performed using monochromatic light with low intensity, and a single sheet of wafer is divided and exposed many times. Furthermore, as the degree of integration increases, the figures to be drawn are becoming more and more complex, and the number of exposures is also increasing, meaning that the proportion of exposure time in the overall process is increasing. Therefore, improving the sensitivity of the resist will greatly improve the throughput of VLSI manufacturing, and will also greatly contribute to cost performance as it will improve the throughput of processes that use extremely expensive machines such as reduced projection exposure machines. . Under these circumstances, there has been a strong desire for the emergence of a positive resist that maintains the high resolution characteristic of positive resists and has improved sensitivity.

Tokukai Akira! ; r-/7//K publication discloses a novolac resin with a softening point of 10 to 1 tts°C obtained by condensing a mixture of ortho-, meta-, and para-cresol with formaldehyde, and a toquinonediazide-based sensitizer. Positive-acting photoresist compositions are described.

[Structure of the invention]

As a result of intensive studies, the present inventors discovered a new naphthoquino/diazide-based compound that provides a positive photoresist composition with excellent sensitivity, resolution, and pattern shape, and were able to complete the present invention.

That is, the gist of the present invention is represented by the general formula [I] CR1: a hydrogen atom, a halogen atom, or a nitro group.

R8: hydrogen atom, -000H group or pe0OR1 group (H
m represents a hydrocarbon group which may have a substituent. l
A naphthoquinone diazide compound represented by @, where is/or co, m is o, i or con is co or 3, and co≦m≦n≦3, and a positive photoresist composition containing the compound. Exists.

The naphthoquinone diazide compound in the present invention has the general formula [11] [wherein R1, R1, l s m and n have the same meanings as in the above general formula (I). ] is obtained by reacting a benzophenone compound represented by the general formula [1] Q-cz... (1) with a 7-toquinonediazide sulfonyl chloride according to a conventional method. I can do it. General formula [l
Specific examples of R1 in D include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a nitro group;
Specific examples of 8 include -000H group or Be00R1 group. Examples of the -00OR'' group include alkyl esters such as methyl, ethyl and propyl groups, substituted aryl esters such as methoxyethyl and ethoxyethoxyethyl groups, and aryl esters such as phenyl ester.

In the present invention, the sootquinone diazide compound represented by the general formula [1] is mixed with an alkali-soluble resin such as a novolak resin or a vinylphenol resin and used as a resist composition. -5m-1p-cresol, co, 3-1
2.5-1J, 1I-13,5-xylenol or α
It is obtained by condensing a compound having a heptenolic OR group such as -1β-naphthol with an aldehyde such as formaldehyde, acetaldehyde, or benzaldehyde. In addition, the vinylphenol 7-toquinone diazide compound of the present invention has S
~50 Jugetsu' are mixed and used.

These are usually dissolved in an appropriate solvent before use.

The solvent is not particularly limited as long as it does not react with the photosensitizer or alkali-soluble resin, has sufficient solubility, and provides good coating properties, but examples include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, Cellosolve solvents such as ethyl cellosolve acetate, ester solvents such as butyl acetate and amyl acetate, highly polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide, or mixed solvents thereof, or aromatic hydrocarbons. Examples include those added.

A good resist can be obtained by coating the resist composition on a substrate by a known method, exposing it to light in a predetermined pattern, and developing it.

The developing solution for the positive photoresist composition of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, etc. Tertiary amines, tertiary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, quaternary amines such as dimethylammonium hydroxide, trimethylhydroxyethylammonium hydroxyoxide, etc. An aqueous solution of amine or the like, or a solution to which alcohol, surfactant, etc. are added can be used.

The positive photosensitive resin composition of the present invention is useful not only for VLSIs, but also for general engineering C manufacturing, mask manufacturing, and offset printing.

The resist composition of the present invention may contain additives such as dyes, plasticizers, adhesion promoters, development accelerators, and surfactants.

〔Example〕

The present invention will be explained in more detail below with reference to specific examples.
However, the present invention is not limited in any way by the embodiments as long as the gist thereof is not exceeded.

Example 1 Cobenzoylco/, 3/141/) IJ hydroxyazobenzene 8 to 11 (Da, EX10-”mol)
Approximately 0/, ! -S7 Toquinone--Diazido 3-
Sulfonyl chloride, il<1. ;, yxtθ- snow mole) t is dissolved in dioxane jO-, triethylamine/, fl is added with stirring, and the reaction is continued at da time -j~JO°C. After cooling, t00rnl of water is added to precipitate the reactant and P is separated. Finally, it was washed by suspension in /00ytl of ethanol, separated by f, and dried to produce an orange powder (decomposition point l).
Cobenzoylco/, 31, Q
/ ) Lyhydroxyazobenzenetris (8-1 naphthoquinone-diazide-5-sulfone)),
? , λI was obtained. The product obtained is λmaX=,74c
jH was 0 Example 1 - Pennzoilder Krollo! ,! , q′-trihydroxyazobenzene J , p (t,p x io-”
Mo/L/) and l, Corner 7 Toquinone--Diazido! -Sulfonyl chloride da, da, F (/, 6 da x
70-" mol) in dioxane!Oml and reacted in the same manner as in Example 1 to form a brown powder (decomposition point /lj~/20°C
)'s Kobenzoilder Kuroroko'1.7/, q/
) lyhydroxyazobenzene tris(ll corner 7-toquinone-codiazido!-sulfonate) 4',
/, F was obtained. The product obtained is λmax=J! It was rO Tomo.

Examples 3 to 9 Naphthoquinone diazide compounds shown in Table 7K below were synthesized in the same manner as in Example.

7・'/〆' Table-1 Example 10 So-7-toquinonediazide compound synthesized in Example/0.
．． 2-I, m-cresol Jot amount, p-cresol 0ttht, λ,! -Xylenol, 777ti
[And to the novolak resin synthesized from formalin]
ethyl cellosolve acetate),? , / # dissolved in 0. A positive resist coating solution was prepared by filtration through a -μ Millipore filter.

This was spin-coated on a silicon wafer with an oxide film (81,0 snow) of 5oooX and 0'C.
j Prebaked for 0 minutes to obtain a coating film of 80 μm. Sensitivity (expressed as the reciprocal of the minimum exposure time that gives the residual film rate Q) was determined using a step tablet manufactured by Kodak ■ and a mask aligner MA-10 manufactured by Mikasa. Development was carried out at 10°C/minute using Tokyo Ohka ■nNMD-,7. The resolution test was carried out using the above-mentioned mask aligner using the resolution test pattern of Toppan Printing ■.

In addition, it is defined as the remaining film rate as a percentage of the film thickness after development relative to the film thickness before development in the unexposed area, and is used as a measure of the degree of film loss after development in the unexposed area.

Furthermore, the cross-sectional shape of the pattern was observed using an electron microscope.

Furthermore, the 7-toquinone diazide compounds synthesized in Examples A, 3, D, and J were evaluated in the same manner as above, and Table 1c is also summarized.

In addition, the amount of m-cresol JOIt used above, p-
Cresol san〇weight excellent, Ko! The method for synthesizing the novolak resin using 30% r-xylenol and formalin is as follows.

m-cresol l hirokosry (/, Jcomol), p
-Cresol t9011 (/, 74 mol), J, j-
Xylenol/4/I (8-2 mol), 37 thiformin 273.21 (J, 39 mol) and oxalic acid dihydrate 1
0I is reacted for 5 hours with stirring at t9-93°C.

Thereafter, the mixture was cooled to room temperature, reduced to JOM, Hj/, and gradually heated again to expel moisture and residual residual moisture.

Finally, it was heated to 176°C and molded for 3 hours.

The remaining resin was poured into a stainless steel vat and cooled.

Yield: 1IJ7j, p.

It was 6/θ.

Table 1 [Effects of the Invention] According to the compounds and compositions of the present invention, a positive photoresist with excellent sensitivity, resolution, and pattern shape can be obtained, and it is very effective when used for precision processing in VLSI etc. be.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (7 others)

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
I] [R^1: represents a hydrogen atom, a halogen atom, or a nitro group. R^2: Hydrogen atom, -COOH group or -COOR^3
represents a group (R^3 is a hydrocarbon group which may have a substituent). l represents 1 or 2, m represents 0, 1 or 2, n represents 2 or 3, and represents 2≦m+n≦3. In the formula, Q is ▲a mathematical formula, chemical formula, table, etc.▼or▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ Shows. ] A naphthoquinone diazide compound represented by (2) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
I] [R^1: represents a hydrogen atom, a halogen atom, or a nitro group. R^2: Hydrogen atom, -COOH group or -COOR^3
represents a group (R^3 is a hydrocarbon group which may have a substituent). l represents 1 or 2, m represents 0, 1 or 2, n represents 2 or 3, and represents 2≦m+n≦3. In the formula, Q is ▲a mathematical formula, chemical formula, table, etc.▼or▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ Shows. ] A positive photoresist composition characterized by containing a naphthoquinone diazide compound represented by: