JPS5848045A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition superior in developing performance, adhesion, and resolution, by using a reaction product of a specified silicone compd. and a quinonediazide compd., or a mixture of the 2 compds. as an active component. CONSTITUTION:A photosensitive composition having superior developability, adhesion, and resolution is obtained by adding a silicone compd. having general formulaI, such as formula II, and a quinone diazide compd., such as formula III, etc. In formulaI, A is a residue of an optionally substd. phenolic compd. or an alcohol compd. freed from a phenolic or alcoholic hydroxyl group; R<1> is 1-12C divalent hydrocarbon group; R<2> is a 1-12C optionally substd. monovalent hydrocarbon group; Y is O or S; Z is OH or a hydrolyzable group; (a) is 0-3; l is 0-30; m is 0-20; n is 0 or 1; and p is 1-30. In formula II, Me is methyl, and p and p' are each a positive integer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive composition, and more particularly to a positive photosensitive composition containing a quinone azide group.

Conventionally, as photosensitive compositions for photolithography, IC, L, and ElI, negative photosensitive compositions consisting of a combination of polyvinyl cinnamate or cyclized rubber and a bisazide compound, or phenol novolac resins and 1. Positive-working photosensitive compositions formed in combination with 2-quinonediazide compounds are widely known and are in practical use.

In general, the above-mentioned negative-tone photosensitive compositions exhibit good adhesion to the support, but have the disadvantage of poor resolution, while positive-tone compositions exhibit extremely high resolution. However, the range of use thereof is limited because the film obtained from this film has disadvantages of poor readability and brittleness, and poor adhesion when applied to a support as a photosensitive film.

Recently, there has been a strong demand for ultra-fine processing in the electronics industry, especially in the IC% LSI manufacturing industry, and in particular the development of photosensitive compositions that have high sensitivity for patterning silicon wafers and also strongly adhere to the support wafer. It is strongly requested.

However, at present, no composition has been found that satisfies the above requirements. Therefore, for the purpose of realizing the above-mentioned requests even to a small extent,
When applying a high-sensitivity positive-working photosensitive composition to a silicon wafer, the wafer is treated with silazane (for example, hexamethylsilazane, etc.) to make the SIO layer on the wafer oleophilic, and then a positive-working photosensitive composition is applied. It has been proposed that a chemical composition be applied, followed by exposure, development, and etching treatments.

However, this method has problems, such as being economically disadvantageous due to the use of expensive silazane, and various difficulties involved in processing, making it difficult to perform reproducible processing.

Therefore, there has been a long-awaited positive-working photosensitive composition that has excellent adhesive properties and high resolution even without silazane treatment.

The present inventors have conducted extensive research in order to eliminate the disadvantages and drawbacks of conventional photosensitive compositions as described above, and to develop a photosensitive composition that has excellent developability, adhesion, and resolution. The present invention has now been completed.

That is, the present invention relates to the general formula (wherein A is a residue obtained by removing a phenolic hydroxyl group or an alcoholic hydroxyl group from a substituted or unsubstituted phenol compound or alcohol compound, and R1 is a residue obtained by removing a phenolic hydroxyl group or an alcoholic hydroxyl group from a substituted or unsubstituted phenol compound or alcohol compound;
divalent hydrocarbon group %R8 is a substituted or unsubstituted monovalent hydrocarbon group of C1 to cts, Y is an oxygen atom or a sulfur atom,
2 is a hydroxyl group or a hydrolyzable group, 1 is an integer of 0 to O, t is an integer of θ to 30, m is an integer of 0 to 20, n is 0 or 1bP is an integer of 1 to 60) A reaction product of a silicone compound and a quinonediazide compound and/or
The present invention relates to a photosensitive composition containing a mixture thereof as an active ingredient.

According to the present invention, conventional phenolic novolak resin and 1.
While maintaining the high resolution possessed by the 2-quinonediazide compound, it is possible to significantly improve the brittleness due to the rigidity of phenol novolak resins and poor adhesion to the support, which have been considered drawbacks to date. Further, as additional effects, significant effects such as improved heat resistance and plasma resistance are provided.

The reason for this effect is not clear, but this is because the silicone compound used in the present invention is extremely heat resistant and flexible compared to the phenol novolac resin, and the introduction of silicone makes the chemical imparting inorganic properties similar to those of the support;
Furthermore, since the modified end is a polar group such as a hydroxyl group or a hydrolyzable group, it is presumed that the adhesion to the support is greatly improved.

In addition, the reason why high resolution can be maintained is mainly due to the inherent characteristics of the quinonediazide compound and the fact that the photosensitive film uses a silicone: gtW compound, which improves flexibility and reduces film chipping during development. This seems to be due to the following.

Hereinafter, the photosensitive composition according to the present invention will be explained in detail.

First, the main ingredient in the present invention is a reaction product of the silicone compound represented by the general formula (1) described above and a quinonediazide compound, and/or a mixture thereof.

In the formula, A is a residue obtained by removing a 7-enolic hydroxyl group or an alcoholic hydroxyl group from a substituted or unsubstituted phenol compound or alcohol compound, and includes, for example, phenol, aminophenol, allylphenol,
Phenol compounds such as cresol, catechol, hydroquinone, urushiol, cardanol, etc. or their derivatives; phenol novolak resins and resol-type phenol resins synthesized from the above-mentioned phenol compounds and formaldehyde; and oligomers of polyvinylphenol and isopropenylphenol. Or these halogen-substituted products, trihydroxybenzophenone, alkyl gallate, bisphenol A, 4.4'-
Phenol compounds such as dihydroxybiphenyl or allyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, cyclopentane-1,
Examples include groups obtained by removing a phenolic hydroxyl group or an alcoholic hydroxyl group from an alcohol compound such as 2-diol, partially saponified polyvinyl alcohol, or completely saponified polyvinyl alcohol.

In the present invention, among the above-mentioned residues, groups derived from substituted or unsubstituted phenol novolac resins are used as phenol thread residues from the viewpoint of economy and reactivity, and alcohol thread residues are also used. Among the groups, polyvinyl alcohol residues are preferred.

The divalent hydrocarbon group of Ct-co represented by R1 includes alkylene groups such as methylene group, ethylene group and propylene group, arylene group such as phenylene group, 1,4-xylylene group, 7-eneethylene group, and The substituted or unsubstituted monovalent hydrocarbon group of Cl-C1m includes a methyl group,
Lower alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, lower alkenyl group such as vinyl group, allyl group, 1-propenyl group, phenyl group, xylyl group, tolyl group, naphthyl group Alternatively, mononuclear and dinuclear aryl groups such as a benzyl group, cycloalkyl groups such as a cyclobutyl group, cycloheptyl group, and cyclohexyl group, cyano group-substituted lower alkyl groups such as a cyanoethyl group, a siarabrubyl group, and a cyanobutyl group, a chloromethyl group, Salt-substituted alkyl groups such as tetrapropyl group and chlorophenyl group, aryl group-substituted alkyl group such as aryl group and phenylethyl group, (CF)sCFOCHICH
,CH,-1(CF3)ICF(CFs)ICOCHg
Examples include double-atom substituted alkyl groups such as CH-1CF30H, CH, and the like.

Y represents an oxygen atom or a sulfur atom. Furthermore, 2 represents a hydroxyl group or a hydrolyzable group, and examples of this hydrolyzable group include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, acyloxy groups such as acetoxy groups, and alkenyl groups such as propenoxy groups. Examples include oxy groups.

a, t, m, n and p in the formula are each as described above.

Specific examples of such silicone compounds include those shown below (however, in the following description, M. represents a methyl group, Et represents an ethyl group, and 1-
Pr represents an isopropyl group, ph represents a phenyl group, and vl represents a vinyl group).

Among the silicone compounds mentioned above, compounds obtained by modifying phenolic compounds with organosilicon compounds are preferred from the viewpoint of resolution and ease of development processing. Those modified with silicon compounds are particularly suitable in the present invention.

The silicone compound used in the present invention can be synthesized by various methods. For example, a compound capable of forming the above-mentioned residue (phenol compound or alcohol compound) is pre-mixed with a predetermined amount of alkali. A method of reacting with all class compounds to form a metal phenoxide or alkoxide, and reacting this with a halogenosilane or halogenosiloxane, or a method of reacting a phenol compound or alcohol compound with a halogenosilane or halogenosiloxane in a polar solvent in the presence of an alkali. or a method in which a phenol compound having an aliphatic unsaturated bond is subjected to an addition reaction with a silane or siloxane containing a 3st-H bond.

The reaction formula for the synthesis is shown below.

(In the formula, X represents a halogen atom, and all others have the same meanings as above).

Among the silicone compounds obtained as described above, those whose terminal group is a hydrolyzable group can be hydrolyzed by a known method to convert the terminal group into a hydroxyl group.

Examples of the halogenosilane or halogenosiloxane that can be used in the synthesis include the compounds shown below.

M@ M・M@
M・M・Me
01111 C1CHs-81-01Pr CtcH2-8
i-OCM*I M e M e
Me Ms Mel
1 1 CLCH@81 0C=CH2Ct 81 0Me
1 M e M e
H3 ■ CLCHs Si(OMe)2, CI CHg
S i (OMe included, 6 Cl-CH2Cf (11CH2S 10MeMe Me CICHB CHg CH2S l (OMe)
, M・O I 11 CLCHBCH2CH2-81-OCMe- 1 CLCH281OMe etcH2-8t-O
Me1 Ph EtVi
Mel1 CICHB-81-0M@B r CHl -8i -
OMe1 M e M e Me
0 11 B r CHz CH Snow CHg 81 0 CM e
M・ Me Me 1 CtCHII St O810Me 1 Me Me Me Mg2 1 CtCHICHI-81-0-81-0M@I Me Me Me M・ 0 111 CjcHl -8l -0-81-OCM・1 Ma Me 1 Next The present invention Examples of the quinonediazide compound used in the above include the following compounds.

C twist H.

CHl Q Among the various quinonediazide compounds mentioned above, 1
．． A 2-naphthoquinonediazide sulfonic acid compound is suitable from the viewpoint of chemical stability and sensitivity when used as a photosensitive composition.

One of the active ingredients in the photosensitive composition of the present invention is a reaction product of the silicone compound represented by the general formula (1) described above and a quinonediazide compound. It can be obtained by synthesizing the silicone compound represented by formula (1) and then reacting it with a halide such as quinonediazide sulfonic acid chloride.

There is no particular restriction on the reaction molar ratio of the two in this reaction, but the molar ratio is such that the final product has at least one group represented by the formula % (n is the same meaning as above). The best way is to perform the reaction.

These reactions can also be carried out using basic substances, such as inorganic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., in suitable organic solvents, such as polar solvents such as dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, and methyl ethyl ketone. This can be carried out in the presence of an alkali compound or an organic alkali compound such as pyridine or pyrrolidone.

The reaction temperature is not particularly limited, but in consideration of the stability of the product, it is preferably in the range of 50 to 15oC.

An example of the product obtained as described above is shown below.

Φ″ Me 〒03 0HO-CHl -81-OMe O′ Me
(Y CH, CHI CH.

＼Such a reaction product can be obtained in high yield by extraction according to a conventional method after the completion of the reaction as described above, followed by washing with water, drying, and stripping.

In addition, the active ingredient in the photosensitive composition of the present invention includes a mixture of the silicone compound represented by the general formula (i) described above and a quinonediazide compound, and in this case, the proportion of the two used is It can be appropriately selected from a wide range depending on the type of compound, purpose of use, etc., and is not particularly limited.

Furthermore, in the present invention, a mixture of the reaction product and a silicone compound and/or a quinone diazide compound represented by the above general formula can also be used, and as for the silicone compound, a silicone-modified phenol compound and a silicone-modified alcohol compound are used in combination. There is no problem, and all of these are included within the technical scope of the present invention.

There is no need to add and blend various other additives that are added to ordinary photosensitive compositions, such as film forming agents, photosensitizers, heat stabilizers, surfactants, pigments, dyes, and organic solvents. There are no restrictions.

Supports that can be used for the application of the composition of the present invention include, for example, silicon, aluminum, copper,
Examples include metals such as zinc and chromium, oxides thereof, semiconductor compounds such as gallium-phosphorus compounds and gallium-arsenide compounds, and glass.

In addition, alkaline aqueous solutions such as sodium metasilicate and trisodium phosphate are preferred as the developing solution used when applying the composition, but these are merely examples and are not limiting. Instead, various types can be used.

The silicone compound used in the present invention, unlike conventional phenol novolac resins and their modified compounds with quinonediazide compounds, has extremely excellent flexibility and has extremely good adhesion to the support. Whether the product is used as the active ingredient alone or added to a conventional positive-working photosensitive composition, there is no loss or cracking of the image after alkaline development, and the product has a high Images with high resolution and reproducibility can be stably obtained.

On the other hand, the above-described features can also be obtained by using a mixture of the silicone compound represented by the general formula (1) and a quinonediazide compound (particularly a quinonediazide sulfonic acid ester compound).

The object can also be achieved by adding a reaction product of a silicone compound and a quinonediazide compound to this mixture.

The composition according to the present invention is said to be useful for printing plates, printed circuit boards, etc., and is particularly suitable as a positive photoresist for ICs and LSIs.

Examples of the present invention will be given below, but these are not intended to limit the present invention in any way.

Example 1 After dissolving phenol novolak resin 9002 with a molecular weight of 900 and a hydroxyl equivalent of 100 in a mixed solvent consisting of 1000 r of toluene and 1000 r of dimethyl sulfoxide,
An aqueous solution containing 120f of sodium hydroxide dissolved in 151:IK of water was added thereto, and the mixture was reacted at reflux temperature for 2 hours, while water in the reaction system was completely removed by azeotropic dehydration. The reaction temperature was maintained at reflux temperature, and the mixture was gradually added dropwise over 30 minutes using a dropping funnel. After the reaction was carried out at the same temperature for 10 hours, extraction treatment was performed with methyl isobutyl ketone and water. When the solvent was distilled off from the methyl isobutyl ketone layer at 150° C. under a reduced pressure of 20 mmHg, 10,529 brown products were obtained.

This product was confirmed by IR analysis to be a silicone-modified phenol compound represented by the following formula.

Next, add 1 of the silicone-modified phenol compound obtained above.
Hydrolysis was performed with a 0% acetic acid aqueous solution to obtain a silicone-modified phenol compound represented by the following formula.

Next, 127t of the silicone-modified phenol compound (represented by formula (1)) obtained above and 81F of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride were dissolved in 500v of methyl ethyl ketone at room temperature.
The temperature of this mixed solution was raised to 70° C. while stirring, and then 170 v of a 10% aqueous solution of sodium carbonate was gradually added dropwise to carry out a reaction for about 5 hours. After the reaction was completed, 300v of methyl imbutyl ketone was added, and the organic layer was washed with water to remove the organic layer.
The reaction product was distilled off under reduced pressure of 20#Hg at 150°C.

15 t of this reaction product was dissolved in 100 f of ethylene glycol hetanoether and filtered through a millibore filter of Q, 5 μm.

The filtrate was transferred to a 3-inch silicon wafer (thickness: 60orm,
3500 to 600 using a K spinner (evaporate aluminum to a thickness of 1.2 μm on 12 m of 810W layer)
After spin coating at a speed of 0 r, p, -m, 70~
It was baked at 80°C for 10 minutes.

The photosensitive copying layer thus obtained was exposed to UvII light under the resolution test original, then developed with a 5-thiol aqueous solution of metasilicic acid, and etched with an etching solution for aluminum according to a conventional method. , an image identical to the original image with a resolution of 1.5 μm was obtained without any image deletions or pinholes.

Example 2゜Silicone-modified phenol compound obtained in Example 1 (formula (
2)) 1oor, alkali-soluble phenol novolac resin 50F, 1,2-benzoquinone-2-
Diazide-4-sulfonic acid methyl ester 50v1 After dissolving hydroquinone o, ir as a heat stabilizer in 300t of ethylene glycol moptyl ether, this was used and subjected to photolithography, development, and etching treatment in the same manner as in Example 1 above. Ta.

The image thus obtained also had no defects or pinholes, and the resolution was 2.5~.

For comparison, an image obtained by performing the same processing as above without using any silicone-modified phenol compound had a part of the image missing during development and a significantly low resolution.

Example 3 Polyvinyl alcohol with a degree of polymerization of 500 (degree of saponification 98.
5 or more) 50v methanol 150? After dissolving in a mixed solvent of and dimethylformamide 150f, 40v of sodium methylate was added and the reaction was carried out at 80°C for 2 hours. After the reaction was carried out for 5 hours, the reaction product was extracted with methyl ethyl ketone and water. The organic layer was heated at 170°C and 20mmH.
The solvent was distilled off under reduced pressure of H to obtain a reaction product.

This product was confirmed to be a silicone-modified alcohol compound represented by the following formula by IR analysis (yield: 95f
).

50 vol of silicone-modified alcohol compound obtained above, 100 t of alkali-soluble phenol novolac resin and 50 t of 1,2-naphthoquinone-2-diazide-4-sulfonic acid ethyl ester were dissolved in 1 t of dioxane.
It was filtered using a standard millibore filter.

Next, apply the filtrate obtained above to a flat glass surface with a thickness of 1 μm.
The coating was spin-coated on a substrate with a thick chrome plating layer at 5800 r, p, m using a spinner, and then baked at 85° C. for 15 minutes.

The photosensitive film thus obtained was exposed to UV light under the original for resolution verification, and then triethanolamine 30
When I developed it using Lucerosol 170f and 500t of water and etched it with a chromium etching solution according to the method, it was an extremely sharp image with no pinholes or missing images, and the resolution was an original image of 5μm.
I was able to get

Example 4 A silicone-modified phenol compound as shown below was synthesized in the same manner as the synthesis of the silicone-modified phenol compound in Example 1.

100f of the silicone-modified phenol compound obtained above and 30t of 1,2-naphthoquinone-2-diazide-5-sulfonic acid methyl ester were dissolved in dioxane to give a 10%
A solution was prepared.

Using this solution, apply, expose, develop, and perform the same steps as in Example 1.
Etching was performed.

The resulting image had no defects or pinholes, and had a resolution of 6.5μ.

Patent applicant: Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula (wherein A is a residue obtained by removing the phenolic hydroxyl group or alcoholic hydroxyl group from a substituted or unsubstituted phenol compound or alcohol compound; R1 is C1 to aSS
Bm is a substituted or unsubstituted monovalent hydrocarbon group of 01 to C1g, Y is an oxygen atom or a sulfur atom,
2 is a hydroxyl group or a hydrolyzable group, a is an integer of 0 to 3, t is an integer of 0 to 60, m is an integer of 0 to 20, n is 0 or 1S P is an integer of 1 to '50) Photosensitive composition 2 comprising a reaction product of a silicone compound and a quinonediazide compound represented by and/or a mixture of both as an active ingredient, A in the above formula in the silicone compound is derived from a substituted or unsubstituted phenol novolak resin The photosensitive composition according to claim 1, wherein the quinonediazide compound is a 1,2-naphthoquinonediazide sulfonic acid compound. photosensitive composition