JPS59219313A - Triallylsilane polymer - Google Patents

Abstract

PURPOSE:The titled polymer having excellent resistance to oxygen plasma, obtained by radical-polymerizing a triallylsilane monomer. CONSTITUTION:A triallylsilane monomer of formula I (wherein R is H, a lower alkyl such as methyl, ethyl or propyl, or phenyl) is radical-polymerized in the presence of a radical initiator, e.g., benzoyl peroxide. Before gelation, methanol is added to the system to stop the reaction and to precipitate a triallylsilane polymer having structural units of formulas II-IV. EFFECT:This polymer is soluble in organic solvents such as benzene, toluene, acetone, and chloroform, has a high transition point and can be readily formed into a film. USE:Resist material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel triallylsilane polymer having a silicon atom, and more particularly to a polymer having extremely high resistance to oxygen plasma.

In recent years, in the manufacture of integrated circuits, bubble memory devices, etc., as patterns have become finer, dry etching using gas plasma has replaced conventional wet etching in order to accurately transfer resist patterns onto substrates. . For this reason, there is a need for resist materials that are highly resistant to drying and etching. In addition, in recent years, for the purpose of obtaining high resolution, three-layer structure resists (from the bottom, the first layer is a thick organic film, the second layer is a silicon film, silicon oxide film, or silicon nitride film, and the third layer is an organic resist film) ) has been proposed.

(J.M. Moran, Journal Ofno<ki,-
Science and Technology, 16, 1920
．． 1979) (J, M, Moran, J, Va
Cuum Sci, and Tech, , 16
However, the disadvantage of this method is that the process is complicated and long. If there is a resist material that is resistant to drying and etching caused by 02 plasma, it can serve as both the second and third layers, making it possible to use a two-layer structure, which greatly simplifies the process. . Therefore, there is an increasing demand for resist materials that have excellent resistance to dry etching.

To date, several organic resist materials have been developed, such as polychloromethylstyrene, polymethylmethacrylate, polydiallyl di7talate, etc., but they are clearly insufficient for the above purpose.

Polydimethylsiloxane is 0. It is well known that it is extremely superior to plasma, and its eratin gray I is almost zero (G.N. Taylor, T.M. Wolff and J.M. Moran, Journal of Vacuum Reliance and Technology, 19 (4).
), 872.1981)' (G, N, Taylor.

T+M, Wolf and J, M, Moran
, J. Vacuum Sci.

and Tech, 19(4), 872.19
81) However, since this polymer is liquid at room temperature, it is not suitable as a resist material because it has drawbacks such as easy dust adhesion and difficulty in obtaining high resolution due to its fluidity.

The object of the present invention is to provide a novel triallylsilane polymer that does not have these drawbacks and has excellent properties as a resist material.

In the present invention, the polymer can be produced using a radical initiator commonly employed in triallysilane compounds, such as peroxides such as benzoyl peroxide, α,α-azobistoptyronitrile, and azide compounds. If the reaction goes too far in this production, gelation will occur, so before gelation, the polymer is poured into methanol to precipitate the polymer and at the same time stop the reaction. Furthermore, the polymer can be easily fractionated and purified by dropping methanol into a methyl ethyl ketone (MEK) solution of the polymer and adding a small amount of methanol after the solution becomes cloudy. The reaction formula for this production is shown below.

(1) The compound of the present invention is soluble in common organic solvents such as benzene, toluene, acetone, chloroform, etc., has a high glass transition point, and can easily form a film, thereby eliminating the above-mentioned drawbacks.

The resistance of the compounds of the present invention to oxygen plasma can be compared with commonly used resist materials such as Nopola, resin (trade name AZ-1350J, commercially available from Silapray).
(4) When compared with 1.5 μm etching of novolak resin (1.5 μm etching of novolac resin, 200× etching is not etched, and 250 AL etching is not etched. It was confirmed that the compound of the present invention has strong resistance to O, plasma. resist for forming battens and (7
However, in the case of a two-layer resist, the first layer organic film is usually coated to a thickness of 2.0 to 2.571 m, and it is appropriate to coat the upper layer resist to a thickness of about 2000×. . It has been found that the polymers of the invention have sufficient resistance to 02 plasma for the above-mentioned purposes.

Next, the production of monomers and polymers of the present invention will be explained using Examples.

Example 1 The monomer H-8i (OH2-OH=OH,) was manufactured by the following method. 1" In a flask, charge 36.5 jj (1,5 atoms) of Grignard metal magnesium and 100 ml of ethyl ether, and add ant bromide #1 at room temperature.
5111.2 mol) (dissolved in 200 mt of ethyl ether) was added dropwise at a rate that did not cause severe reflux. After the addition was completed, 150 g (0.37 mol) of trichlorosilane (dissolved in ethyl ade/I/300 mt) was added dropwise at a rate that would not cause rapid reflux again. The entire mixture solidified during the process, but the dropping was continued and made uniform with a mechanical stirrer. After being left at room temperature for 10 hours, it was poured into water and extracted with ethyl ether. After drying the ether layer with sodium sulfate, the ether was distilled off, and the residual liquid was distilled under reduced pressure. Shuan is 3.3
p (58%). The boiling point of the product is 49°C/10 fl block.

The analytical values of the product are as follows.

Infrared absorption spectrum (Iyn-”): 2120
(Si-H), 1630 (OH, -CH-), 900 (
St-H).

860 (Si-OH,) Nuclear magnetic resonance absorption spectrum (!J) ppm: 1.
70-1.85 (6H, m, OH, 8i), 3
．． 8-4.0 (IH.

H8i), 4.8~5.3 (6H,m, 0H2
=OH-).

5.7-6.3 (3H, m, 0H2=0dan-) Elemental analysis: Calculated value 0; 71.10. H; 10.53°Si; 1
8.42o actual value 0; 71.23. ! (; 10
．． 10°8fold; 18.28 Example 2 The monomer 0H, -8i (OH, -0R=OH,) was produced by the following method.

36.5 g (1,5 atoms) of Grignard metal magnesium and 100 mt of ethyl ether were placed in an IL three-bottle flask equipped with a nitrogen blowing tube, reflux condenser, and dropping flow If, and 151 g of allyl bromide was added at room temperature.
/ethyl ether at 200 mA was added dropwise at a rate that did not cause severe reflux. After dropping, add 50 g (0.33 mol) of trichloromethylsilane/300 m of ethyl ether.
1 was added dropwise at a rate that did not cause violent reflux again. The entire mixture solidified during the process, but the dripping was continued and the mixture was made uniform with a mechanical stirrer. After being left at room temperature for 10 hours, it was poured into water and extracted with ethyl ether. After drying the ether layer with sodium sulfate, the ether was distilled off, and the residual liquid was distilled under reduced pressure. Yield: 23g (42%).

The boiling point of the product is 58°C/12 van Hg.

The analytical values of the product are as follows.

Infrared absorption spectrum (cn7”): lG30
(Akyl group), 900. 860 (Si-C nuclear magnetic resonance absorption spectrum (δ) ppm: 0.2 (3
H.

8,0H3), 1.8 (6H,-0f-1,,
-), 4.9-5.3 (6H.

m, OH2=OH-), 5.7-6.3 (3n
, m, ci-i2=light-) Elemental analysis: Calculated value 0; 72.29. H; 10
．． 84°8i; 16.87 Actual ho 1j value 0; 71.
97, H; 10.77°St; 16.54 Example 3 Ph-8i (0H2-OH=OH,)s monomer was produced by the following method.

Grignard metal magnesium 2911.2 atom) and ethyl ether l Q
Q mt was prepared, and 121 g of allyl bromide/20 (l ITI)2 of ethyl bromide was added dropwise at room temperature at a rate that would not cause violent reflux. After the completion of the dropwise addition, 50 g (0.24 mol) of t+)chlorophenylsilane/ethyl ether 3
Q Q ml was added dropwise at a rate that would not cause violent reflux. The entire mixture solidified during the process, but the dripping was continued and a mechanical stirrer was used to make it uniform. The ether layer was left to stand at room temperature for 10 hours and then extracted with ethyl ether. After drying with sodium sulfate, the ether was distilled off and the residual liquid was distilled under reduced pressure. Yield: 36.9 (67%).

The boiling point of the product is 80°G/0.4 mHg.

The analytical values of the product are as follows.

Infrared absorption spectrum (cm-'): 1630 (
allyl group), 1430 (vinyl group), 11.10.9
00 (5i-ph), 700 (), nyl group) nuclear magnetic resonance absorption spectrum ψ) ppm: L85 (6i (, d
, -OH,-), 4.7-5.1 (6H,m,
OH,=CH-), 5.4-6.2 (3i-I
, m, 0H2=(with a man).

7.2-7.5 (5H, m, Ph).

Elemental analysis: Calculated value 0: 78.95. H; 877°S r ; 12-78 Actual value 0; 78.88. H
; 8.53°Si; 12.50 Example 4 11 Si ((M(,-(EH=CI(,),) Polymer was produced in the following manner.

7.6 g (0.05 mol) of triallylsilane in the polymerization tube
.

7.5 ml of benzene was charged, the tube was attached to a rubber tube with a rubber tube, and the solution was degassed using liquid nitrogen to solidify it. This operation was repeated 5 times to complete degassing. This solution was poured into a 100 ml tube equipped with a nitrogen blowing tube and a reflux condenser.
Three ml of the mixture was added to a 1" flask and heated to reflux. Benzoyl peroxide (BPU) 0.12. ! i'(1,
Omolti) was added every hour, and when it was added six times, the viscosity had increased considerably, so the reaction was continued for an additional 30 minutes, and then the polymerization solution was poured into methanol. Polymer 1 sank to the bottom layer and the resulting solution was decanted. The polymer was dissolved in 100 rnl of benzene and poured into a large amount of methanol. The above operation was repeated three times, and the resulting powdered polymer was passed through the mouth and dried under reduced pressure. The yield and analytical values of the product are as follows.

Infrared absorption spectrum (cm-”): 2]50(
Sj -H), 1630 (A group), 920 (Si
t().

Nuclear magnetic resonance spectrum (δ) ppm: to 05-2,3(
10H, br alkane), 3.7~4.3 (10
, br, H-8i).

4, 3-6.2 (3PI, br, CH2=OH-
) Elemental analysis: Calculated value 0; 71.10. H; 10
．． 53°Si; l 8.42. , actual value 0; 7
1.40. J-I; 10.20.

Si;1&07 Example 5 A polymer of 0H, -8i (OH2-OH=OH2)s was produced by the following method.

A polymerization tube was charged with 8=:l (0.05 mol) of triallylmethylsilane and 8.3 mt of benzene, which was attached to a rubber tube with a cock, and the solution was solidified using liquid nitrogen and degassed. Repeat this operation 5 times to completely degas frO. Blow this solution into a nitrogen tube.

The mixture was charged into a 100 mt three-necked flask equipped with a reflux condenser and heated until reflux. 1.2 g (1 molty) of BPOo was added every hour, and when the 10th addition was made, the viscosity had increased considerably, and after heating for an additional hour, the polymerization solution was poured into methanol.

The polymer settled to the bottom layer and the solution was decanted. The polymer was dissolved in 100 tons of benzene and poured into a large amount of methanol. The above operation was repeated three times, and the obtained powdered polymer was dried under reduced pressure after four filtration. Yield is 3.3g (40%) Mw = 130.00
(,1, Mn = 19,000 + MwlM, n
=8 The analytical value of the product is as follows.

Infrared absorption spectrum (ffi'): 1630 (allyl group), 1260.820 (St-0) Nuclear magnetic resonance spectrum (δ) ppm: 0.0-2.3 (13H, br
, alkanes and C! H, Si), 4.0-6
．． 3 (3H, br, 0H2=OH) Elemental analysis: Calculated value 0; 72.29, H; 10
．． 84.

Si; l 6.870 Actual value 0; 72.02
, H; 10.55°8i; 16.32°Example 6 A Ph-Si (0H2-014=OH2) polymer was produced in the following manner.

10g triallylphenylsilane (0,044
mol) and 10 mt of benzene were charged and attached to a rubber tube with a stopcock.The solution was solidified using liquid nitrogen and degassed.This operation was repeated 5 times to complete deaeration. This solution was poured into a 10
Add 1 g (1 mole) of ○BPOO, which was charged into a 0 ml three-necked flask and heated until reflux, every hour.
The viscosity increased after the second addition, and after refluxing for an additional hour, the polymerization solution was poured into a large amount of methanol.

The polymer sank to the bottom layer and the solution was decanted. The polymer was dissolved in 100 ml of benzene and poured into a large amount of methanol. The above operation was repeated three times to obtain a powdered polymer, which was then passed through the mouth and dried under reduced pressure. Yield is 4.2g (42%) o Mw=4. OO+0
00. M, 1 = 38,000. MW, 7Mn=1
0.5. 3.5g of polymer to 350ml of methyl ethyl ketone
While stirring, methanol was added dropwise. When did you add 50mt of methanol? Shu Shisara 2 Q
mA was added and the mixture was gently warmed to become transparent. - After standing for days and nights, the polymer sank to the bottom of F, and the upper layer liquid was decanted to separate it from the polymer.

The polymer was dissolved in 5 Q mA of benzene and poured into a large amount of methanol to obtain the first fraction of polymer (@
Combined yield 0.8 g) o M-w=700,000.

Mn =540.000, Mw week n := 1゜3
．． 20 mt of methanol was added to the decanded liquid to obtain a second fraction of polymer in the same manner (polymer yield: 0).
．． 7g) 1Mw=340,000, Mn=26
4,000, Mw/Mn=1.3, and further 20
ml of methanol was added to the third fraction of polymer e.
ipu ot (polymer number 1nO-9, !9) o Mw=13
6,000, Mn = 103,000.

MW/Mn=1. a.

The analytical values before fractional purification are as follows.

Infrared absorption spectrum (, cm'): 1280°8
90(8i-C3), 990. 700 (vinyl group).

1620, 780 (phenyl group) Nuclear magnetic resonance spectrum ψ) ppm: 0.2-2.3 (1
2H, br, alkane), 4.5-6.3 (3f
4゜br, 0H2-OH-), 7.0~7.8
(51 (, br, Ph) elemental analysis: calculated value 0; 7
8.95, I-I; 8.77°Si; 12.7
8

Claims (1)

[Claims] 几<;hi2-cu=ci-i2 (m) (-OH, -OH→ "CH. R-8i-OH2-OH=OH2 0H, ~-C!H=OH2 (R is Represents a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, ], a nyl group)