JPS61295549A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having a high sensitivity and an excellent film forming property, and an anti printing and a heat-resisting properties. CONSTITUTION:The titled composition is composed of a photosensitive compd. having a substd. or an unsubstd. benzophenone structure and a o-quinone diazide group in a molecule. The prescribed positive type photosensitive composition has the high sensitivity and the excellent fine working property, and is suitable to be used as the super-fine working resist material in a manufacture of IC and LSI elements, and also as the photosensitive material in a manufacture of a lithographic plate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photosensitive material used as a resist for ultrafine processing used in the production of elements such as IC-LSI, and in the production of lithographic printing plates. This invention relates to a positive-working photosensitive composition that has high sensitivity and excellent microprocessability.

[Conventional technology]

The conventional di-type photosensitive compositions include (1) a mixture of a polymer soluble in an alkaline aqueous solution and a low-molecular 0-quinonediazide compound, and (2) an 0-quinonediacid sulfone in the side chain of the alkali-soluble poly ff-. It can be broadly classified into condensed acids. Polymers soluble in alkaline aqueous solutions used in the former (1) include phenol, phenol resins synthesized from cresol, etc., and formaldehyde, polyhydroxystyrene, etc., and 0-quinone noanodo compounds include those by J. Koser. Light 5ensit
lves 5yst@ms”339-352, (1
965), John Wllley & 5onsTn
c, (New York) and W, S, DsFors
Written by st” Photo-r+pslst 50+
(1975), MeGrow-Hlll Inc.

(New York). Mention may be made of 0-quinonenoanodo compounds.

On the other hand, those belonging to the latter (2) are U.S. Patent No. 3
0-quinonediazide sulfonic acid ester of phenol formaldehyde resin or cresol formaldehyde resin described in No. 046120 and Japanese Patent Publication No. 4
O-quinonediazide sulfonic acid ester of polyhydroxyphenyl obtained by condensation polymerization of acetone and pyrogallol, described in Japanese Patent Publication No. 3-28403, 1973
4-liaminostyrene and 0-quinone diat sulfonic acid ester described in JP-A No. 9-34681, JP-A-1987-
These include polyhydroxystyrene and 0-quinonediazide sulfonic acid ester described in No. 113305.

Comparing the former (1) and the latter (2), in (1) 0-
It is possible to control the development conditions of the photosensitive composition by changing the amount of the quinonediazide compound added (2)
In this method, since the polymer is reacted with an 0-quinonediazide compound in advance, it is difficult to control the development conditions compared to (1).

In addition, since the 0-quinonediazide compound (1) is a low-molecular compound, it has poor film-forming properties and reduces heat resistance (pattern flow) when used in positive photorenost, making it difficult to use in lithographic printing plates. In this case, the printing durability will be reduced. On the other hand, in type (2), there is no deterioration in coating film performance due to the low molecular weight O-quinonediazide compound, but type (2) has low sensitivity. This is because the type (2) has a high molecular weight, so it dissolves slowly into the alkaline aqueous developer solution due to molecular entanglement, and has lower sensitivity than the type (1).

[Problem that the invention seeks to solve]

An object of the present invention is to provide a photosensitive composition that is highly sensitive, has excellent film-forming properties, and has excellent printing durability and heat resistance.

[Means for solving problems]

The present invention relates to a photosensitive composition comprising a photosensitive compound having a substituted or unsubstituted benzophenone structure and an o-Q nondiazide group in one molecule.

The above-mentioned substituted or unsubstituted benzophenone structure is, for example, the general formula % (wherein X and Y are each independently a hydroxyl group, an alkoxyl group having 1 to 5 carbon atoms, or a C 1 to 5 alkoxyl group). Represents an alkyl group, a carboxyl group, an amide group, an amine group, and a nitro group, n is an integer of O to 4, m is an integer of O to 4, k is an integer of O to 5, and t is an integer of O to 3. Examples include compounds having the structure represented by:

The photosensitive compound of the present invention can be obtained from, for example, (1) an epoxy compound, (b) a polyhydroquine benzophenone derivative, and (c) a -quinonediazide compound.

As a method for producing the photosensitive compound of the present invention from (IL) an epoxy compound, (b) a #hydroxybenzophenone derivative, and (c) an O-quinonediazide compound, for example, first, the epoxy compound and the polyhydroxybenzophenone derivative are A hydroxyl group-containing photosensitive compound precursor is synthesized by reacting with a catalyst or in the presence of a ring-opening catalyst (e.g., tertiary amines, alkali metal compounds, phosphorous acid compounds, etc.), and subsequently, A method of reacting the precursor with an 0-quinonediazide compound can be mentioned.

As an epoxy compound, for example, one synthesized from bisphenol A and epichlorohydrin with a number average molecular weight of 30
Knob 2 with a number average molecular weight of 300 to 2000 synthesized from an epoxy resin of 0 to 3000, phenol tumerac and/or cresol novolak and epichlorohydrin
Epoxy resins such as Tsuku-type epoxy resins; vinyl 7-chlorohexene dioxide, synclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclo to'#bunkalzne-), 314-x
Alicyclic molding such as 6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexylene cargonate/a resin synthesized from polyhydric alcohol and epichlorohydrin f! Low-molecular epoxy resins such as +7 resin; polymers containing glycidyl groups in the side chains made of polymerizable monomers containing glycidyl groups such as glycidyl acrylate and glycidyl methacrylate; various epoxy compounds and polycargenic acids described above; Epoxy group-containing ester compounds obtained by reacting the above-mentioned various epoxy compounds and aromatic polyhydroxy 7 compounds, and the like, and one or two of these epoxy compounds. A mixture of two or more species can be used.

For producing the photosensitive compound used in the present invention, it is preferable to use an epoxy resin having a number average epoxy resin of 1000 or less.

The polyhydroxybenzophenone derivative used in the present invention has the general formula (where x, y, z and W each independently represent a hydroxyl group,
Flucoxyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
alkyl group, carboxyl group, amide group, amine group,
and represents a nitro group, n is an integer of 0 to 4, m is O to 4
k represents an integer of 0 to 5, and t represents an integer of θ to 3. ) can be mentioned.

Examples of the polyhydroxybenzophenone derivatives used in the present invention include 2,4-dihydroxybenzophenone, 21314-) IJ hydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, and 3,415-dipenzophenone in trihydro. , 2,3.4-)rihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'
-dimethquine penzophenone, 2,3,4.4'-tetrahydroxybenzophenone, 2.2',3,4.4
Examples include dibenzophenone in '-pentahydro, and one or more of these can be used in combination.

When synthesizing a hydroxyl group-containing photosensitive compound, ?
It is desirable to select the total blending ratio so that the hydroxyl group of the 84 units of rehydroquipenzophenone is 1 equivalent or more, preferably 1.1 to 5.0 equivalents.

In addition, in order to obtain sufficient heat sensitivity, the hydroxyl group-containing photosensitive compound precursor obtained as described above preferably has a number average molecular weight of 300 to 5,000, and a number average molecular weight of 400 to 2,000. In addition, it is more suitable that
The number of equivalents of hydroxyl groups is preferably 500 or less.

The o=quinonediazide compound used in the production of the photosensitive compound of the present invention includes O
-quinonediazide group.

Examples of such 0-quinonediat compounds include:
O-quinonenoacytosulfonic acids such as pe/fuquinone-1,2-diazide-4-sulfonic acid, naphthoquinone-1,2-diazide-(2)-5-sulfonic acid; benzoquinone-1,2-diazide-4- Examples include halodanides of O-quinonediazide sulfonic acid such as sulfonyl chloride and naphthoquinone-1,2-diazide-(2)-5-sulfonyl chloride, and various other known compounds such as "Light Sensitive" by Noei Kosar. Systems'' (John Wiley & Joms Co., Ltd. 1965)
Examples include compounds described in detail on pages 339 to 353 (published in 2010).

The reaction ratio between the hydroxyl group-containing photosensitive compound precursor and the o-quinonediazide compound is such that the number of groups capable of reacting with the hydroxyl group of the 0-quinonenoasite compound is 0.2 to 1. 2 current view, preferably 0.3
It is desirable to select a range of 1.0 to 1.0 equivalents.

In order to obtain sufficient photosensitivity, the photosensitive compound thus produced preferably has 0.4 to 3.4 moles of 0-quinonediazide group in 1000.9 of the photosensitive compound, and 1.0 It is more preferable that the amount is 3.0 mol.

The photosensitive composition of the present invention is generally used by mixing the photosensitive compound and an alkali-soluble resin.

The mixing ratio at that time is the photosensitive compound and the alkali-soluble resin i.
It is preferable to adjust the ratio to be in the range of 1:0.5 to 1:10.

Examples of such alkali oJ soluble VIJ resins include phenol-formaldehyde resin, cresol-formaldehyde resin, polyhydro #7 styrene resin, styrene-maleic acid resin, shellac, phenol-bresol-formaldehyde copolymer, and bisphenol-formaldehyde resin.
Examples include those generally used in photosensitive compositions such as formaldehyde copolymers.

The photosensitive resin composition of the present invention may further be used as a heat stabilizer, a filler, a dye, etc. for various photoresists, as necessary.
Adjustments are made by adding additives used in printing plate materials.

The composition of the present invention is usually used after being dissolved in a suitable organic solvent, and examples of such solvents include 1, ethyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate, ethylene glycol dimethyl ether, and soethylene glycol dimethyl ether. ethers such as; aliphatic esters such as butyl acetate; acetone,
These include aliphatic ketones such as methyl isobutyl ketone; and cyclic ethers such as diocypne. The above solvents can be used alone or in combination of two or more.

The photosensitive composition of the present invention is coated on a suitable support after being dissolved in the above-mentioned solvent.

The photosensitive composition of the present invention is applied to a support by a well-known coating method such as whirler coating, dip coating, curtain coating, roll coating, spray coating, air knife coating, doctor knife coating, or spinner coating.

Specific examples of the support include aluminum plates, zinc plates, copper plates, stainless steel plates, and metal plates; paper coated with synthetic resin such as polyethylene terephthalate, polycarbonate, and cellulose derivatives, or coated with synthetic resin melting; Composite materials in which a metal layer is provided on a resin by techniques such as vacuum deposition and lamination; examples include silicone urethane.

As a support for the printing plate, a metal plate made of aluminum, copper, zinc, etc. whose surface has been roughened mechanically, chemically, or by air-chemically is used.

The photosensitive layer of the photosensitive image-forming material thus obtained is subjected to imagewise exposure using a positive image, and is developed with a developer to dissolve and remove the exposed portion, thereby forming a corresponding image on the support.

At that time, the developing solution mainly contains water, including organic ammoniums, amines, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, and dibasic sodium phosphate. , tertiary ammonium phosphate, ammonium diphosphate, sodium bicarbonate, sodium hydrogen phosphate, sodium metasilicate, and other alkaline agents, and in some cases, further contains additives such as organic solvents and surfactants. Things can be used.

Suitable light sources used for exposure include carmen arc lamps, mercury lamps, xenon lamps, metal halide lamps, lasers, and the like.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Actual death example]

Add the compound and (b) the solvent listed in Table 1 of the polyhydroxybenzophenone derivative and heat at 150°C while stirring.
The reaction was carried out for 2 hours (3 hours for [■]) to synthesize a hydroxyl group-containing photosensitive compound precursor.

Diobun was added to this precursor in the composition shown in Table 1, and the temperature of the reaction solution was cooled to 40°C or less, and (c)
Naphthoquinone-1,2-diazide-(2)-5-sulfonyl chloride listed in Table 1 was added as an o-quinonediazide compound, and while stirring, a weak alkali listed in Table 1 was added dropwise while maintaining the temperature at 40°C. Add, then continue,
The reaction was carried out under the reaction conditions listed in Table 1.

In the case of (1), (II), C■] and [IX), the photosensitive compound is obtained by dispersing the reaction solution in total pure water 21 with stirring, distributing it from house to house, and drying the obtained product F. I got it. Also, (13, [] , [V) , C
(2) In the case of 1 and [2], the photosensitive compound precursor is obtained by filtering the reaction solution and drying the solution by a conventional method.

With the formulation shown in the table, the photosensitive compound and the alkali-soluble resin were metacresol-noblack resin [softening point 145
°C: A photosensitive composition was prepared by dissolving Dainippon Ink ■ [Bryofen] in ethyl cellosolve.

The composition prepared in 2 above was applied onto a silicone wafer using a spinner and dried on a hot grate heated to 90° C. to prepare a photosensitive image forming material. The thickness of the photosensitive film of the image forming material after drying was 1.2 μm.

3-2. Photosensitivity measurement conditions A contact type mask aligner equipped with an ultra-high pressure mercury lamp was applied to the photosensitive image forming material obtained in 3-1 above.
Exposure was carried out using "pLA-soOJ" manufactured by 7M Co., Ltd., and setting the intensity of the photoresist film surface to be 33 mW/cm2.

Next, an exposure method using a contact a mask aligner will be explained. As shown in FIGS. 1 and 2, the photoresist film 2 formed on the silicon wafer 1 is tl, t2 . t3. t
4. Crossing the dividing lines at t5 and t6, SO, SL, S2.
S3,84. The exposed photoresist film is divided into seven sections, S5° and SO, and is first positioned at the dividing line at the left end ft6 of the hard mask 3 in the figure to expose the SO section and shield the other sections with the hard mask 3. was exposed to light for 1 second. Next, the hard mask 3 was moved to the right in the drawing, its left end was positioned at the dividing line t5, and exposure was performed again for 1 second. Similarly, the left end of the hard mask 3 was positioned at each dividing line of t 4 t t 3 pt 2-tl, and exposure was performed for 1 second at each position.

This operation results in SO, Sl, 82, 83. S4゜S5
,86. Each section was exposed to light for 5.6 seconds at 0, 1, 2, 3, and 4 degrees, respectively. The thus obtained photosensitive image forming material 4 with different UV exposure levels was placed in a developer (25° C.) for 1 minute at 1S! After shaking the crushed mixture lightly, it was taken out, washed with water, and dried. The photosensitivity was expressed by the exposure time of the section with the shortest exposure time among the developed sections.

(The shorter the exposure time, the higher the sensitivity.)
The developer used was a 1.3-thimetasilicate aqueous solution.

Using a photosensitive image forming material prepared in the same manner as in 3-1 above, a 2 micron fine IiI! Each photoresist film is exposed with the pattern mask in close contact with the sensitivity (exposure seconds) measured in 3-2 above, and developed in the same manner as 3-2 above to form a 2-micron fine line pattern. did. All of the photoresist films of Examples showed high resolution. Seven wafers with fine line patterns were prepared for each of the examples. 120℃, 125℃, 13
0℃.

During the heating open set at 135C, 140°C, 1145°C, and 150°C, one wafer from each example was placed in the open set at each set temperature and heated for 30 minutes, and the fine line pattern of 2 microns was deformed using an electron microscope. I checked to see if it was. Evaluate heat resistance based on the highest temperature at which no deformation occurs.

For comparison, two types of photosensitive compositions that have been conventionally used as positive-working photosensitive compositions were prepared, photosensitive image forming materials were prepared in the same manner as in the examples, and photosensitive compositions were prepared in the same manner as in the examples. Sensitivity was measured and heat resistance was evaluated.

The contents and results of each side above are summarized in Tables 1 and 2.

[Brief explanation of drawings]

FIG. 1 shows a top view of a photosensitive image forming material 4 and a hard mask 3 during exposure in a contact type mask aligner. t1 to t6 in the figure represent division lines. FIG. 2 shows a side view of the photosensitive image forming material 4 and hard mask 3 during exposure in a contact type mask aligner. 81 to S6 in the figure are t1 in FIG.
The sections are divided by dividing lines from t6 to t6, with 1 representing a silicon wafer and 2 representing a photoresist film. Agent Patent Attorney Katsutoshi Takahashi vJ1 Figure zffJ

Claims (1)

[Scope of Claims] A photosensitive composition comprising a photosensitive compound having a substituted or unsubstituted benzophenone structure and an o-quinone diazide group in one molecule. 2. Substituted or unsubstituted benzophenone structure has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X, Y, Z and W are each independently a hydroxyl group,
Alkoxyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
represents an alkyl group, a carboxyl group, an amide group, an amino group and a nitro group, n is an integer of 0 to 4, m is an integer of 0 to 4, k is an integer of 0 to 5, and l is an integer of 0 to 3. represent. ) The photosensitive composition according to claim 1, which has a structure represented by: 3. Photosensitivity according to claim 1 or 2, wherein the photosensitive compound is obtained from (a) an epoxy compound, (b) a polyhydroxybenzophenone derivative, and (c) an o-quinonediazide compound. Composition. 4. The photosensitive composition according to claim 3, wherein the epoxy compound is an epoxy resin. 5. The photosensitive composition according to claim 3, wherein the epoxy compound is a low molecular weight epoxy resin. 6. The photosensitive composition according to claim 3, wherein the epoxy compound is a polymer containing a glycidyl group in its side chain. 7. The photosensitive composition according to claim 4, wherein the epoxy resin is an aromatic epoxy resin or an aliphatic epoxy resin.