JPH0259753A - Resist composition - Google Patents

Abstract

PURPOSE:To provide the resist compsn. which can form resist patterns having high sensitivity and high definition by combining silylated polyorganosylcesoxane and compd. which are respectively specified at specific ratios, thereby constituting the resist compsn. CONSTITUTION:The resist compsn. is constituted by compounding 1 to 50pts.wt. halogen compd. expressed by formula III with 100pts.wt. silylated polyorganosylcesoxane in which at least 20% of the hydrogen atom of the silano group (-Si-OH) existing in the silicone compd. expressed by formula I is substd. with the group expressed by formula II. In formulas I to III, R<1> denotes the phenyl substd. with deriv. of 1 to 4C alkyl, etc.; (p) denotes 10 to 10,000 positive integer; (q) denotes 4 to 10,000 positive integer; R<3> to R<4> independently denote the phenyl substd. with deriv. of 1 to 4C alkyl, etc.; R<5> denotes H, the phenyl substd. with deriv. of 1 to 4C alkyl, etc. or heterocyclic group; X denotes a halogen element; (m) and (n) independently denote 0 or 1 to 3 integer. The formation of the X-ray resist patterns having the excellent sensitivity and definition is possible in this way.

Description

[Detailed Description of the Invention] [Summary] Resist material used for pattern formation of semiconductor devices, etc.
The purpose of the present invention is to provide a resist composition that is particularly suitable for use as an X-ray resist material for the upper layer of a two-layer resist, and that enables the formation of an X-ray resist pattern with excellent sensitivity and resolution. (i) Formula (I): (S101.SR')+1(0°,,11)q ・
...(I) (wherein R1 is C5-C4 alkyl, halogenated CI"" Ca alkyl, 02-C4 alkenyl,
represents phenyl or phenyl substituted with 01-C4 alkyl, 02-C4 alkenyl, carbonyl, amino, hydroxy, halogen, cyano or a derivative thereof, and each of p R1s may be the same or different, p is a positive integer from 10 to 10,000, and q is 4
(a positive integer of ~10,000) at least 20% of the hydrogen atoms of the silanol group (-3i-OH) present in the silicone compound represented by the formula (II) -5i-R'...(II) (
In the formula, R2, Rff and R4 are independently 01-C4 alkyl, halogenated 01-C4 alkyl, Ct-C4 alkenyl, phenyl or C, -C4 alkyl, 02-C, alkenyl, carbonyl, amine, hydroxy, cyano or A silylated polyorganosilsesquioxane substituted with a group represented by the following phenyl substituted with a derivative thereof, (I1) formula (II): [Industrial Field of Application] The present invention relates to a pattern of a semiconductor device. The present invention relates to a resist composition used for forming a resist material, particularly as an X-ray resist material for the upper layer of a two-layer resist.

(In the formula, R5 is H, Cl1zX, CHXz, C
X3, C+ ~Ca alkyl group, halogenated CZ
~C4 alkyl, cz~C, alkenyl, phenyl or phenyl substituted with 01~C4 alkyl, 02~C4 alkenyl, carbonyl, amine, hydroxy, cyano or a derivative thereof, or a heterocyclic group, and X is a halogen element and m and n independently represent 0 or a positive integer of 1 to 3) is blended in an amount of 1 to 50 parts by weight per 100 parts by weight of the silylated polyorganosilsesquioxane. constitute a resist composition.

[Conventional technology]

It is well known that in recent years, thin film formation technology and photolithography technology have been frequently used in the formation of semiconductor integrated circuits. With the progress of these technologies, semiconductor unit elements are becoming increasingly finer, and large-capacity elements such as LSIVLSI are being put into practical use.

That is, regarding the wiring pattern, a resist is coated on a thin film made of a wiring forming material formed on a substrate to be processed, and then selectively exposed to ultraviolet light through a mask, and then developed to form a resist pattern. A method is used in which a fine wiring pattern is formed by etching the wiring pattern.

However, in the case of ultraviolet exposure, there is a limit to the miniaturization of resist patterns because pattern deformation and distortion occur due to light scattering, reflection, and the influence of standing waves. Therefore, research on exposure techniques and resist materials for forming finer patterns is being actively conducted. In particular, exposure technology using X-rays, which is virtually free from the effects of diffraction and interference and has excellent properties for forming fine patterns in principle, is attracting attention as a technology that enables finer patterns.

Since the X-ray resist is based on the action of secondary electrons generated by X-ray irradiation, its photosensitive mechanism is similar to that using an electron beam, and there is an advantage that the electron beam resist can be used as is.

[Problem to be solved by the invention]

However, when an electron beam resist is used as an X-ray resist, the X-ray absorption characteristics of the electron beam resist are low.
There is a problem that sufficient sensitivity cannot be obtained and exposure takes a long time. Therefore, X-ray resists that have high sensitivity by introducing halogens with high X-ray absorptivity into electron beam resists have been developed, but sufficient effects have not been obtained. SUMMARY OF THE INVENTION An object of the present invention is to provide a resist composition that solves the problems of the prior art and makes it possible to form an X-ray resist pattern with excellent sensitivity and resolution.

[Means to solve the problem]

According to the present invention, the above problem can be solved by (i) Formula (I): (Sift, SR')9(00,5H)Q ・(I
) (wherein, R1 is C1-C4 alkyl, halogenated C3
~C4 alkyl, 02~C4 alkenyl, phenyl or phenyl substituted with C, ~C4 alkyl, 02~C4 alkenyl, carbonyl, amino, hydroxy, halogen, cyano or a derivative thereof, p R1
may be the same or different, and p is 1
A positive integer from 0 to 10,000, and q is from 4 to 10,000.
20%, preferably 50 to 100%, of the hydrogen atoms of the silanol groups (-Si-OH) present in the silicone compound represented by formula (II), which is a positive integer of (II) (wherein RZ, R3 and R4 are independently C, -C.

Alkyl, halogenated C1-c4 al-Ji-)Lt,
c.

~C4 alkenyl, phenyl or C8-c4 alkyl,
(ii) Formula (■): (In the formula, R5 is H, CHzX, CHXz, CX3
, C+ ~C4 alkyl group, halogenated 02~C
4 alkyl, C2-C4 alkenyl, phenyl or 01
~C4 alkyl, C2-C4 alkenyl, carbonyl,
represents a phenyl or heterocyclic group substituted with amino, hydroxy, cyano or a derivative thereof, X represents a halogen element, m and n independently represent 0 or a positive integer from 1 to 3) This is achieved by a resist composition comprising 1 to 50 parts by weight of a compound according to 100 parts by weight of the silylated polyorganosilsesquioxane.

According to the present invention, a resist composition is prepared by blending 1 to 50 parts by weight, preferably 3 to 20 parts by weight, of the compound of general formula (II[) with respect to 100 parts by weight of the silylated polyorganosilsesquioxane. For example, by using this resist composition as an upper layer resist of a general two-layer structure resist, high sensitivity and high resolution can be obtained by performing X-ray exposure as shown in the following example. A resist pattern can be formed.

The silylated polyorganosilsesquioxane, which is one of the essential components constituting the resist composition of the present invention, is a compound of the general formula (I) and the formula Y-Si-R3... (IV
) R4 (wherein R2, R: l and R4 are as defined above, and Y represents halogen or lower alkoxy) without a catalyst or in the presence of an organic base, at room temperature or under heated conditions. By this, the desired compound can be easily produced by substituting the silanol group of compound (I) with the group of general formula (II). The preferred molecular weight of the silylated polyorganosilsesquioxane synthesized in this way is a weight average molecular weight of 5,000 to 100,000,
Mw/Mn is 1.0 to 2.0.

On the other hand, the general formula (I[
Examples of the halogen compound in [) include dichloromethylpiperazine, trichloromethylpiperazine, and tridichloromethylpiperazine. The resist composition according to the present invention is generally prepared by dissolving these components in a suitable solvent, applying the solution onto a substrate in a conventional manner, particularly on the upper layer of a two-layer resist, and heating at a temperature of 80 to 120°C for 5 to 50 minutes.
A pre-laked resist film can be created for 20 minutes, irradiated with X-rays, and developed.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail according to examples, but it goes without saying that the scope of the present invention is not limited to the following examples.

Kinsoufuto Methyl Isophyl Ketone (Mon IBK) 100ml
Pyridine 18- was added to the mixture, and the mixture was cooled to -60°C. To this, 30 g of vinyltrichlorosilane and then 18 ml of ion-exchanged water were sequentially added dropwise, and the temperature of the reaction solution was gradually raised. Furthermore, while bubbling with nitrogen gas,
The condensation polymerization reaction was carried out at ℃ for 5 hours. After the reaction is completed, the solution is
It was washed with water ~6 times, and the 1'11BK layer was separated.

Next, 30 m of trimethylchlorosilane and 30 m of pyridine
ff was added and heated at 60° C. for 3 hours to silylate unreacted hydroxyl groups. Next, the reaction solution was washed with water 10 times, and f
After filtration, the mixture was poured into acetonitrile to precipitate and collect silylated polyvinylsilsesquioxane. The obtained resin was dissolved in 50% of benzene and freeze-dried.

The silylated polyvinylsilsesquioxane obtained in this synthesis example had an average molecular weight M w = 5. Q
0', Mw/Mn=1.8.

"Tsuage" ■ - 1 g of silylated polyvinyl silsesquioxane obtained in Synthesis Example 1 was dissolved in 9 g of MIBK, and 0.05 g of dichloromethylbiperazine was added as a halogen compound to prepare a resist solution.

After spin-coding MP-1350 resist (manufactured by Shisopra) on a silicon substrate to a film thickness of 2 tm,
It was cured by heating at 200° C. for 1 hour.

After spin-coding the resist previously prepared on this film to a film thickness of 0.2 μm, blebbing was performed at 80° C. for 20 minutes. After irradiating the film with PdLα rays through a mask, it was developed with MIBK and subsequently rinsed with isopropyl alcohol. Next, the substrate to be processed was placed in a parallel plate type dry etching apparatus, and the upper layer pattern was transferred to the lower layer using oxygen plasma. As a result, this resist was able to resolve a 0.5 μm line and space pattern at an exposure dose of 50 mJ/c++I.

Silylated polyvinylsilsesquioxide was prepared in the same manner as in Synthesis Example 1, except that the compound shown in Table 1 was used in the indicated amount in place of 30 g of vinyltrichlorosilane as the compound of general formula (I). Synthesized Sun.

Average molecular weight MI M w and weight average molecular weight/number average molecular weight ratio of the obtained silylated polyvinylsilsesquioxane? Lw/Mn was as shown in Table 1.

Part"-Table No."LTable 2 7lyltrichlorosilane (32)
4.2 X 10'3 Methyltrichlorosilane (28) 9. OX 10'4
Ethyltrik Lucilashi (30)
5.2 X 10'5 Phenyltrichlorosilane (39) 4.6 X 10'
6 Rion Mechi 11 Triku B Shin 5 (34)
3.2XlO' Compound of Synthesis Example 2〃 3 〃 4 〃 〃 5 〃 In Example 1, silylated polyorganosilsesquioxane synthesized in Synthesis Examples 2 to 6 was used instead of silylated polyvinylsilsesquioxane. Except for this, X-ray irradiation was carried out in the same manner as in Example 1, and an exposure amount capable of resolving a 0.5 μm line-and-space pattern was determined. On the other hand, as a comparative example, chloromethylated polystyrene, which is a highly sensitive electron beam resist, was tested.

〔Effect of the invention〕

According to the present invention, as described above, it is possible to provide an upper layer X-ray resist for a two-layer structure that meets the needs of the times and has superior sensitivity and resolution compared to conventional resists.

Claims (1)

[Claims] 1. (i) Formula (I): (SiO_1_._5R^1_p(O_0_._5H)
_q...(I) (wherein, R^1 is C_1-C_4 alkyl, halogenated C_1-C_4 alkyl, C_2-C_4 alkenyl,
Phenyl or C_1-C_4 alkyl, C_2-C_4
Indicates phenyl substituted with alkenyl, carbonyl, amino, hydroxy, halogen, cyano, or a derivative thereof, p R^1s may be the same or different, and p is a positive number of 10 to 10,000. is an integer, and q is a positive integer from 4 to 10,000).
Formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R^2, R^3 and R^4 are independently C_1 ~C
_4 alkyl, halogenated C_1 to C_4 alkyl, C
_2-C_4 alkenyl, phenyl or C_1-C_4
Silylated polyorganosolsesquioxane substituted with a group represented by alkyl, C_2-C_4 alkenyl, carbonyl, amino, hydroxy, phenyl substituted with cyano or derivatives thereof), (ii) formula (I
II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, R^5 is H, CH_2X, CHX_2, CX_
3, C_1-C_4 alkyl group, halogenated C_2-C
_4 alkyl, C_2-C_4 alkenyl, phenyl or phenyl substituted with C_1-C_4 alkyl, C_2-C_4 alkenyl, carbonyl, amino, hydroxy, cyano or a derivative thereof, or a heterocyclic group; X represents a halogen element; , m and n independently represent 0 or a positive integer of 1 to 3), the silylated polyorganosilsesquioxane 10
1. A resist composition comprising 1 to 50 parts by weight per 0 parts by weight. 2. A method for forming a resist pattern, comprising using the resist composition according to claim 1 as an upper layer resist of a two-layer resist. 3. The resist pattern forming method according to claim 2, wherein X-rays are used as the exposure light source.