JPH04251851A - Photosensitive resin and photosensitive resin composition using the same - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin sensitively responding to the light of 200-400nm wave length and having high O2-RIE resistance and excellent resolution. CONSTITUTION:The photosensitive resin is constituted of a copolymer of 2,000-100,000 wt. av. molecular weight consisting of a polysiloxan derivative part expressed by the formula I having R<2>, which is one kind or above of group selected from group consisting of unsaturated group, alkyl group and alkylhalide, and polysilylene derivative part expressed by the formula II (in the formula II, RA is alkyl group or phenyl group).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photosensitive resin suitable as a resist material used in the manufacture of semiconductor devices, etc., and a photosensitive resin composition using the same.

0002

2. Description of the Related Art Substrate processing in the manufacture of semiconductor devices, for example, the formation of metal wiring patterns in ICs, involves forming a wiring metal film over the entire surface of the substrate to be processed, forming a resist film on this, and exposing and developing it. A resist pattern is obtained, a metal film is etched using this resist pattern as a mask, and then this resist pattern is removed.

However, as ICs become more highly integrated and faster,
Ultra-fine wiring patterns and the adoption of multilayer wiring are being carried out, and with this ultra-fine miniaturization, the pattern aspect ratio tends to be increased in order to lower the wiring resistance, so the steps on the processed substrate are becoming larger and larger. Become. For this reason, when forming a resist pattern on a substrate to be processed, the following problems arise. That is, since the step may become larger than the depth of focus of the reduced projection exposure apparatus, it becomes difficult to form a resist pattern with a desired size using the reduced projection exposure apparatus. In particular, when patterning in the submicron region, a reduction projection exposure system equipped with a lens with a large numerical aperture is used, so the depth of focus becomes increasingly shallow, so the problem of the step difference becomes even more pronounced, and the conventional There is a possibility that pattern formation may not be possible with only one layer of resist such as this.

[0004] Therefore, as a technique for solving the above-mentioned problems, for example, the literature (Journal of El
electrochemical society:SO
LID-STATE SCIENCE AND
TECHNOLOGY (Journal of Electrochemical Society: Solid State
Science and Technology) Vol. 1
32, No. 5 (1985.5) pp. 1178-11
82) was known. This technology is
In addition to a resist pattern forming technique called the two-layer resist method, a positive type resist sensitive to the far ultraviolet region (200 to 300 nm) was used.

[0005] Here, the two-layer resist method is as explained below.

[0006] First, a thick thermosetting resin is formed on a substrate to be processed having steps, and the resin is thermally cured to flatten the substrate. A very thin photosensitive resin layer having high resistance to etching by oxygen plasma is formed on this, and then this photosensitive resin layer is exposed and developed to form a pattern. Next, using this pattern as a mask, the thermosetting resin layer is etched by reactive ion etching (O2-RIE) using oxygen gas to obtain a two-layer resist pattern with a high aspect ratio. Furthermore, the base metal layer on the substrate to be processed is etched using this two-layer resist pattern as a mask.

The advantage of the two-layer resist method is that the pattern of the photosensitive resin layer is formed on the thick planarization layer without being affected by the underlying substrate, and therefore without dimensional variation. The ability to form patterns.

[0008] Resists used for such photosensitive resin layers include those containing silicon, and according to the above-mentioned literature, poly(trimethylsilylmethyl methacrylate)
3-oximino-2-butanone methacrylate) copolymers are disclosed. This resist uses deep ultraviolet (De)
It had a sensitivity capable of resolving a 1 μm line-and-space pattern at a dose of 250 mJ/cm 2 using UV (ep-UV), and had a minimum resolving power of 0.75 μm.

[0009]

[Problems to be Solved by the Invention] However, since the above-mentioned conventional resist has a silicon layer content as low as 9.6% by weight, the etching rate by O2-RIE is only 15nm.
It is fast at m/min. That is, there was a problem that O2-RIE resistance was low. Further, there was a problem that the resolution and sensitivity were not sufficient.

[0010] This application has been filed in view of the above-mentioned points, and therefore, the purpose of the first invention of this application is to solve the above-mentioned problems and provide a photosensitive resin with excellent film quality and processing accuracy. It is in.

[0011] A second object of the present invention is to provide a photosensitive resin composition with even higher sensitivity using the photosensitive resin of the first invention.

0012

[Means and effects for solving the problems] In order to achieve the object of the first invention, the photosensitive resin of the first invention of this application is selected from the group consisting of unsaturated groups, alkyl groups and halogenated alkyl groups. The present invention is characterized in that it is composed of a copolymer consisting of a polysiloxane derivative portion having one or more types of groups, and a polysilylene derivative portion.

In this configuration, by changing the structure of the polysilylene derivative portion (for example, the presence or absence of branching ((3
), (see formula (4))), and by changing the number of silicon atoms and types of substituents in the polysilylene derivative part, this polysilylene derivative part can be made to absorb light of any wavelength in the wavelength range of 200 to 400 nm. When exposed to light of that wavelength, active species such as silyl radicals and silylene are generated. Therefore, when the polysiloxane derivative portion in the photosensitive resin has an unsaturated group, the active species adds to this unsaturated group to initiate polymerization. Further, when the polysiloxane derivative portion has an alkyl group and/or a halogenated alkyl group, the active species abstracts hydrogen from the alkyl group and halogen from the halogenated alkyl group, so that polymerization is initiated. Since the polymerized portion of the polysiloxane derivative portion becomes insoluble in organic solvents, a desired resist pattern can be obtained by selectively irradiating the photosensitive resin with light. Furthermore, since the polysilylene derivative moieties are randomly present in the photosensitive resin composition, it is thought that polymerization is efficiently initiated.

Furthermore, since both the polysiloxane derivative part and the polysilylene derivative part have a high silicon content, the silicon content of the photosensitive resin is at least 10% by weight, and as a result, the photosensitive resin has excellent O2-RIE resistance. can get.

Here, specific examples of the polymer constituting the photosensitive resin of the first invention include a polysiloxane derivative portion represented by the following formula (1) and a polysilylene derivative portion represented by the following formula (3). A copolymer consisting of the following (1)
A copolymer consisting of a polysiloxane derivative part represented by the formula and a polysilylene derivative part represented by the following formula (4), a copolymer consisting of a polysiloxane derivative part represented by the following formula (2) and the following (
3) A copolymer consisting of a polysilylene derivative moiety represented by the following formula, a copolymer consisting of a polysiloxane derivative moiety represented by the following formula (2) and a polysilylene derivative moiety represented by the following formula (4), and a copolymer thereof Copolymers of two or more types of polymers can be mentioned. In addition, from the viewpoint of storage stability of these exemplary copolymers, it is common knowledge that the OH groups in these copolymers are protected with an inert group such as a trimethylsilyl group, and it is preferable to do so in this invention as well. be.

[0016]

[C4]

[0017]

[0018]

[C5]

[0019]

The above-mentioned exemplary copolymers can be synthesized by a method similar to the method for synthesizing polysiloxane derivatives proposed in JP-A-63-210839 filed by the applicant of this application. In that case, the compound shown in (1a) below is used as a raw material for synthesis of the polysiloxane derivative part (1), and the compound shown in (2a) below is used as a raw material for synthesis of polysiloxane derivative part (2). As a synthetic raw material for the polysilylene derivative portion in 3), the compound shown in (3a) below can be used, and as a synthetic raw material for the polysilylene derivative portion in (3), a compound shown in the following (4a) can be used.

[0021]

[C6]

[0022]

[0023] However, the above (1) to (4), (1a) to (
4a) In the formula, R2, R3, R5, R6 and R are groups selected from the group consisting of unsaturated groups, alkyl groups and halogenated alkyl groups, and may be the same or different. Moreover, m and n are positive integers. Moreover, X is a halogen or an alkoxy group. Also, RA, RB, R
C, RD, RE, RF, RG, RH, RI, RJ and R
' is a group selected from the group consisting of (a) to (g) below, and may be the same or different.

(a): A chain, branched or cyclic alkyl group having 10 or less carbon atoms.

(b): Phenyl group having no substituent.

(c): Naphthyl group having no substituents.

(d): A phenyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group.

(e): A naphthyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group.

(f): A biphenyl group having no substituents.

(g): A biphenyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group.

Further, the silicon number l in formula (3) is an integer satisfying 2≦l≦10. (4) Silicon number i in formula
, j, and k are integers satisfying 0≦i≦7, 1≦j≦8, 1≦k≦8, and i+j+k≦9. ).

[0032] The above-mentioned unsaturated group is, for example, a vinyl group (CH2=CH-), an allyl group (CH2=CH-C
H2-), isopropenyl group (CH2=C(CH3)-
) and 2-butenyl group (CH2=CH-CH2-CH2
−).

Further, the above-mentioned alkyl group includes, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tert-butyl group (however, all the substituents of the polysiloxane derivative part) ) is a tert-butyl group.

Further, the halogenated alkyl group includes, for example, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group,
Bromopropyl group, bromobutyl group, iodomethyl group,
These are an iodoethyl group, an iodopropyl group, and an iodobutyl group (however, the number of halogens in each halogenated alkyl group may be any number within the range of 1 or more and the maximum number that can be taken by the group).

A synthetic raw material for the polysiloxane derivative portion shown in (1a) or (2a) and (3a) or (
The raw materials for the synthesis of the polysilylene derivative portion shown in 4a) are appropriately selected and mixed. Then, this mixture is hydrolyzed at -100°C to room temperature in the presence of a catalyst, and then heated to reflux temperature to cause polycondensation, to obtain the desired copolymer (details are explained in the Examples section). .)
.

[0036] The temperature during the above hydrolysis is preferably -40°C or lower from the viewpoint of ease of control of the reaction temperature.

Further, the above hydrolysis and polycondensation are carried out in the presence of a solvent. The solvent used for this is not specified as long as it can be used within the range of -100°C to room temperature. For example, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, toluene, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, etc. can be used. Further, the catalyst used is not specified as long as it is a basic catalyst. For example, triethylamine, tri-
n-butylamine, pyridine, lutidine, γ-collidine, imidazole, potassium carbonate, etc. can be used.

In such a synthesis method, by changing the polymerization conditions, the weight average molecular weight can be increased from 2,000 to 10.
0,000 of the polymer according to the present invention can be obtained with good controllability. When trying to synthesize a compound having a weight average molecular weight of 100,000 or more, gelation tends to occur during the synthesis stage. In addition, since this polymer constitutes a photosensitive resin, from that point of view, if the weight average molecular weight is less than 2,000, it will not crystallize, so a resist film cannot be formed and the exposure amount required for patterning will be reduced. Indicates a problem such as an extremely large number of cases. From these points, it is preferable that the weight average molecular weight of the polymer according to the present invention is 2,000 to 100,000.

[0039] When synthesizing these polymers, it is preferable that the amount of the synthetic material for the polysilylene derivative portion be within the range of 0.5 to 10 mol% relative to the synthetic material for the polysiloxane derivative portion. . If the amount of the synthetic material for the polysilylene derivative portion is 0.5 mol% or less, the proportion of the polysilylene derivative portion (portion exhibiting photosensitive function) in the photosensitive resin will be small, resulting in extremely low sensitivity; If it is 10 mol % or more, the proportion of the polysilylene derivative portion becomes too large, and the portion of the photosensitive resin that decomposes when exposed to light becomes too large, which causes a decrease in sensitivity. Furthermore, if the charging amount is 10 mol% or more, the proportion of the polysiloxane derivative moiety in the photosensitive resin decreases, and the silicon content of the resin may decrease to such an extent that the O2-RIE resistance of the resin may be impaired. It is from.

Further, the photosensitive resin composition of the second invention of this application is characterized in that it contains the photosensitive resin of the first invention and a sensitizer.

Various sensitizers can be used, but it is particularly preferable to use a hydrosilane compound which has the property of trapping silylene emitted when the polysilylene derivative portion is decomposed by light. This hydrosilane compound has 1
It is desirable to have a Si--H bond in the molecule and to be liquid or solid from the viewpoint of use as a resist. Specifically, it is preferable to use a hydrosilane compound selected from among the hydrosilane compounds represented by the following formulas (5) to (9).

(R)rSi(H)s...(5)(
R)tSi2(H)u...(6)

[C7]

[0043]

[0044] However, R in formulas (5) and (6), (7)
R' in the formula is an alkyl group, a phenyl group without a substituent, a phenyl group with a substituent, a naphthyl group without a substituent, a naphthyl group with a substituent,
It is a group selected from a biphenyl group without a substituent and a biphenyl group having a substituent. Also (7)
~(9) In the formula, R is at least one hydrogen and the others are hydrogen, an alkyl group, or a phenyl group having no substituent,
phenyl group having a substituent, naphthyl group not having a substituent, naphthyl group having a substituent, biphenyl group not having a substituent, biphenyl group having a substituent. This is a group selected from among these. Furthermore, (5) to (
9) In the formula, r, s, t, u, v, w are r+s=4, r
≧1, s≧1, t+u=6, u≧1, 1≦v≦5, 1≦
It is a positive integer satisfying w≦6. ).

Further, in this photosensitive resin composition, the addition rate of the sensitizer to the photosensitive resin of the first invention is 0.1 to
A value within the range of 30% by weight (wt) is preferred. The sensitizing effect is small below 0.1 wt%, and 30 wt%
This is because problems arise in the film-forming properties of the resist film.

[0046]

EXAMPLES Examples of the photosensitive resin composition of the present invention will be described below. In addition, in the following examples, specific conditions will be exemplified and explained in order to facilitate understanding of the present invention. However, it should be understood that the invention is not limited only to these examples. Further, among the chemicals used in the following examples, although the sources may be omitted, all were chemically sufficiently pure and easily available. 1. Description of the first invention <Example 1> 1-1. Synthesis of Photosensitive Resin of Example 1 First, the photosensitive resin of Example 1 is synthesized as follows.

First, 176 g (1 mol) of allyltrichlorosilane, which is a type of compound represented by the above formula (2a),
) and 22.3 g (0.053 mol) of permethylhexasilylenyl dichloride represented by the following formula (10), which is a type of compound represented by the above formula (3a), in -4
The mixture was added to 500 ml of methyl isobutyl ketone cooled to 0° C., stirred and dissolved, and then 139 ml (1 mol) of triethylamine was added dropwise to this solution over 45 minutes. Note that Me in formula (10) is a methyl group. The same applies to each formula below.

[0048]

[Chemical formula 8]

[0049]

Next, after stirring this solution for 15 minutes, 160 ml of water was added dropwise to it over 2 hours, and then this solution was cooled for 1 hour while stirring.

The solution is then left with stirring until the temperature of the solution reaches room temperature and for at least 3 hours, after which it is heated slowly to reflux temperature in 1 hour. This solution is then stirred for 1 hour while being kept at reflux temperature.

Next, after cooling this solution to room temperature, 100 ml of hydrochloric acid was added to it to stop the reaction.

Next, 1 liter (liter) of toluene was added to this solution to dilute it, and then the aqueous layer was removed using a separatory funnel.
The organic layer is then washed with water until neutral.

Next, the solvent was distilled off from this organic layer under reduced pressure to obtain an oily substance (photosensitive resin of Example 1).

The weight average molecular weight (MW) of this oil is 2
3,000, and the dispersion (MW/Mn) was 4.3. Moreover, no gel was formed in this oily substance.

1-2. Patterning experiment of the photosensitive resin of Example 1 (Part 1) Next, 100 g of the photosensitive resin of Example 1 synthesized as described above was dissolved in 900 g of xylene,
Thereafter, this solution is filtered through a membrane filter having pores of 0.2 μm in diameter to prepare a coating solution of the photosensitive resin of Example 1.

Next, in order to form a lower resist layer on the silicon substrate, a photoresist (in this example, MP240 manufactured by Shipley) was applied to the silicon substrate by a spin coating method.
0) under predetermined conditions, and then the sample was placed in an oven at a temperature of 200° C. for 1 hour to harden the photoresist. As a result, a lower resist layer having a thickness of 1.5 μm is formed.

Next, the photosensitive resin of Example 1 was coated on this lower resist layer by a spin coating method to a film thickness of 0.2 μm, and then this sample was heated at a temperature of 60° C. using a hot plate. Pre-bake for 1 minute.

Next, this sample has a minimum line width of 0.5 μm.
An exposure device (in this example, a PLA501 aligner manufactured by Canon Inc.) is equipped with a mask having various line-and-space test patterns, and is equipped with an Xe-Hg lamp and a CM250 cold mirror. Exposure is performed while changing the exposure amount.

Next, the exposed sample was treated with 1:1 of methyl isobutyl ketone and isopropyl alcohol (IPA).
1 immersed in a mixed solution (volume ratio) for 45 seconds and developed.
Thereafter, it is immersed in IPA for 30 seconds for rinsing, and then baked at a temperature of 60° C. for 1 minute using a hot plate.

When the developed sample was observed, the initial film thickness (in this example, the film thickness after spin coating was 0.2 μm).
) The exposure amount (Dn0.5) at which the residual film rate is 50%
is 1.2.8 counts (here, 1 count (ct)
=39mJ/cm2. Same below. ). Furthermore, when the obtained resist pattern was observed with a scanning electron microscope (SEM), the minimum resolution dimension was 0.5 μm line and space (L/S), which is the same as the minimum dimension of the mask used. I found out. Note that the minimum line width of the test pattern used in this experiment was 0.
5 μm, it was only possible to confirm that a resolving power of 0.5 μm was secured, but it should be understood that the photosensitive resin of Example 1 has an even higher resolving power (see each example below). The same applies to patterning experiments.)

1-3. Patterning experiment of the photosensitive resin of Example 1 (Part 2) The same patterning experiment as described above (Part 1) was carried out except that the photosensitive resin of Example 1 was used and the light source used for exposure was a KrF excimer laser. Perform patterning experiments in steps.

Note that the laser oscillator used is one manufactured by Lambda Physics. This laser oscillator can obtain an irradiation amount of 0.50 mJ/cm2 per pulse, and the exposure amount can be controlled by the number of pulses.

As a result, the sensitivity (Dn0.5) was 580m
It was found to be J/cm2. It was also found that a line and space pattern of 0.5 μm can be resolved.

1-4. Patterning experiment of the photosensitive resin of Example 1 (Part 3) A patterning experiment using the two-layer resist method using the photosensitive resin of Example 1 as an upper layer resist was also conducted as described below.

First, a lower resist layer (MP2400 layer) was formed using the same procedure as in the patterning experiment (Part 1).
Furthermore, a pattern of the photosensitive resin of Example 1 is formed on this lower resist layer. However, in this patterning experiment, the thickness of the lower resist layer was 2 μm, and the amount of exposure of the photosensitive resin of Example 1 by the Xe-Hg lamp was 20 counts.

Next, the sample whose upper layer has been patterned is placed in a parallel plate type dry etching apparatus (in this example, DEM451 manufactured by Nichiden Anelva Co., Ltd.). and,
O2 gas pressure 1.0Pa, O2 gas flow rate 20SCC
The lower resist layer is etched under the conditions that the RF power density is 0.12 W/cm 2 and the etching time is 35 minutes.

When the cross section of the two-layer resist pattern obtained after this etching was observed using an SEM, it was found that 0.
It was found that although the line and space pattern was 5 μm in diameter and had an aspect ratio of 4, a rectangular line and space pattern was formed.

1.5. O2-R of photosensitive resin of Example 1
IE Resistance Investigation Results Next, the O2-RIE resistance of the photosensitive resin of Example 1 was investigated as follows.

First, the photosensitive resin of Example 1 was coated on a silicon substrate to a thickness of 0.2 μm by spin coating, and then this sample was baked at 60° C. for 1 minute using a hot plate.

Next, this sample was placed in a DEM451 dry etching apparatus and etched under the same dry etching conditions as in the patterning experiment (Part 3). However, the etching time was 20 minutes.

Next, the film thickness of the photosensitive resin film of Example 1 after completion of etching was measured using a film thickness meter (in this case, Talystep manufactured by Taylor Hobson) to calculate the amount of film loss due to etching. When it was determined, it was found to be 4.7 nm. Even though the etching conditions in this example were more severe than in the conventional literature, only 4.7 nm was etched in 20 minutes, indicating that the photosensitive resin of Example 1 has better O2-RIE resistance than the conventional one. I can understand something.

<Example 2> Next, 35.6 g of penta(phenylmethylsilylenyl) dichloride represented by the following formula (11), which is a type of compound represented by the above formula (3a), was used as a material for synthesizing a polysilylene derivative. (0.053mol
) The photosensitive resin of Example 2 was synthesized in the same manner as in Example 1, except for the following. As a result, 127 g of an oily substance (photosensitive resin of Example 2) was obtained. In addition, (11
) where Ph is phenyl. The same applies to each formula below.

[0074]

[Chemical formula 9]

[0075]

The weight average molecular weight (MW) of this oil is 2
5,000, and the dispersion (MW/Mn) was 4.5.

Next, using the photosensitive resin of Example 2, a coating solution thereof is prepared in the same manner as in Example 1. after that,
A patterning experiment was conducted using the same procedure as in the patterning experiment (part 1) of Example 1 (experiment using Xe-Hg as a light source), and the sensitivity (Dn
0.5) and resolution, respectively.

As a result, the sensitivity of the photosensitive resin of Example 2 (
Dn0.5) was found to be 1.2 ct. Also,
It was found that a 0.5 μm line and space pattern was resolved.

A patterning experiment was also conducted on the photosensitive resin of Example 2 in the same manner as in the patterning experiment (part 2) of Example 1 (experiment using a KrF excimer laser light source). The sensitivity (Dn 0.5) and resolution of the photosensitive resin No. 2 to KrF excimer laser will be investigated.

As a result, the KrF of the photosensitive resin of Example 2
Sensitivity to excimer laser (Dn0.5) is 80mJ
/cm2. It was also found that a 0.5 μm line and space pattern was resolved.

<Example 3> Next, 26.2 g of tetraphenyltetramethyltetrasilylenyl dichloride represented by the following formula (12), which is a type of compound represented by the above formula (3a), was used as a material for synthesizing a polysilylene derivative. (0.05
The photosensitive resin of Example 3 was synthesized in the same manner as in Example 1, except that the amount was changed to 3 mol). As a result, 121 g of an oily substance (photosensitive resin of Example 3) was obtained.

[0082]

[Chemical formula 10]

[0083]

The weight average molecular weight (MW) of this oil is 2
3,000, and the dispersion (MW/Mn) was 4.2.

Next, using the photosensitive resin of Example 3, a coating solution thereof is prepared in the same manner as in Example 1. after that,
A patterning experiment was conducted using the same procedure as in the patterning experiment (Part 2) of Example 1 (experiment using KrF excimer laser as a light source), and the sensitivity of the photosensitive resin of Example 3 to KrF excimer laser (Dn0. 5) and resolution, respectively.

As a result, the KrF of the photosensitive resin of Example 3
Sensitivity to excimer laser (Dn0.5) is 120m
It was found to be J/cm2. It was also found that a 0.5 μm line and space pattern was resolved.

<Example 4> Next, 29.0 g of triphenylheptamethylpentasilylenyl dichloride represented by the following formula (13), which is a type of compound represented by the above formula (3a), was used as a material for synthesizing a polysilylene derivative. (0.053
The photosensitive resin of Example 3 was synthesized in the same manner as in Example 1, except that the mol) was changed. As a result, 130 g of an oily substance (photosensitive resin of Example 4) was obtained.

[0088]

[Chemical formula 11]

[0089]

The weight average molecular weight (MW) of this oil is 2
7,000, and the dispersion (MW/Mn) was 3.9.

Next, using the photosensitive resin of Example 4, a coating solution thereof is prepared in the same manner as in Example 1. after that,
A patterning experiment was conducted using the same procedure as in the patterning experiment (part 2) of Example 1 (experiment using KrF excimer laser as a light source), and the sensitivity of the photosensitive resin of Example 4 to KrF excimer laser (Dn0. 5) and resolution, respectively.

As a result, the KrF of the photosensitive resin of Example 4
Sensitivity to excimer laser (Dn0.5) is 240m
It was found to be J/cm2. It was also found that a 0.5 μm line and space pattern was resolved.

<Example 5> Next, the procedure was the same as in Example 1 except that chloromethyltrichlorosilane, which is a type of compound represented by the above formula (2a), was used as the synthetic raw material for the polysiloxane derivative part. The photosensitive resin of Example 5 is synthesized. As a result, an oily substance (photosensitive resin of Example 5)
89g was obtained.

The weight average molecular weight (MW) of this oil is 3
0,000, and the dispersion (MW/Mn) was 4.8.

Next, using the photosensitive resin of Example 5, a coating solution thereof is prepared in the same manner as in Example 1. after that,
A patterning experiment was conducted using the same procedure as in the patterning experiment (Part 2) of Example 1 (experiment using KrF excimer laser as a light source), and the sensitivity of the photosensitive resin of Example 5 to KrF excimer laser (Dn0. 5) and resolution, respectively.

As a result, the KrF of the photosensitive resin of Example 3
Sensitivity to excimer laser (Dn0.5) is 670m
It was found to be J/cm2. It was also found that a 0.5 μm line and space pattern was resolved.

<Example 6> Next, dimethyldichlorosilane, which is a type of compound represented by the above formula (1a), was used as the synthetic raw material for the polysiloxane derivative portion, and the synthetic material for the polysilylene derivative was used as the synthetic material for the polysilylene derivative used in Example 1. Methylhexasilylenyl dichloride However, the amount charged is 13.0g (0.
The photosensitive resin of Example 6 was synthesized in the same manner as in Example 1, except that the amount was changed to 0.31 mol). As a result,
115 g of oil (photosensitive resin of Example 6) was obtained.

The weight average molecular weight (MW) of this oily substance is 5.
6,000, and the dispersion (MW/Mn) was 6.0.

Next, using the photosensitive resin of Example 6, a coating solution thereof is prepared in the same manner as in Example 1. after that,
A patterning experiment was conducted using the same procedure as in the patterning experiment (part 2) of Example 1 (experiment using KrF excimer laser as a light source), and the sensitivity of the photosensitive resin of Example 6 to KrF excimer laser (Dn0. 5) and resolution, respectively.

As a result, the KrF of the photosensitive resin of Example 6
Sensitivity to excimer laser (Dn0.5) is 1200
It was found to be mJ/cm2. It was also found that a 0.5 μm line and space pattern was resolved.

Composition of the photosensitive resin of each example of the first invention
In order to clarify the difference in sensitivity, the composition and sensitivity of each photosensitive resin are summarized in Table 1. However, in the sensitivity section in Table 1, the sensitivity shown in ct is the sensitivity when using the Xe-Hg lamp and cold mirror, and the one shown in mJ/cm2 is the sensitivity when using the KrF excimer laser. .

[0102]

[Table 1]

[0103]

[0104]2. Description of the second invention Next, 100 g of the photosensitive resin of Example 2 of the first invention and 10 g of dimethylphenylsilane represented by the following formula (15) as a sensitizer were dissolved in 900 g of xylene. A coating solution of the photosensitive resin composition of Example of the second invention is prepared.

Next, a patterning experiment was conducted in the same manner as in the patterning experiment (part 2) of Example 1 of the first invention (experiment using a KrF excimer laser as a light source), and this photosensitive resin composition was The sensitivity (Dn 0.5) and resolution to the KrF excimer laser will be investigated.

As a result, KrF of this photosensitive resin composition
Sensitivity to excimer laser (Dn0.5) is 50mJ
/cm2. It was also found that a 0.5 μm line and space pattern was resolved.

[0107] The sensitivity to KrF excimer laser using only the photosensitive resin of Example 2 of the first invention was 80 mJ/cm2.
Considering that, it can be understood that the sensitivity is improved by 30 mJ/cm2 by adding a sensitizer.

[0108]

Effects of the Invention As is clear from the above explanation, the photosensitive resin of the first invention of this application is a polysiloxane derivative part known to have high O2-RIE resistance, and contains unsaturated groups and alkyl groups. A copolymer consisting of a polysiloxane derivative portion having one or more functional groups selected from and halogenated alkyl groups, and a polysilylene derivative portion that efficiently generates silyl radicals highly reactive with this functional group. Since it is composed of a combination, it has high sensitivity, high resolution, and high O
2-Shows RIE resistance.

[0109] Therefore, a photosensitive resin with excellent film quality and processing accuracy can be provided.

Further, according to the photosensitive resin of the present invention, by appropriately selecting the structure (for example, presence or absence of branching) and substituents of the polysilylene derivative portion, wavelengths of 200 to 400 nm can be obtained.
The optical absorption wavelength can be changed over a wide range of m, so it is suitable for i-line,
For XeCl excimer laser, for rF excimer laser, A
It becomes possible to construct a resist for rF excimer laser.

The photosensitive resin of the second invention, which is composed of the photosensitive resin of the first invention mixed with a sensitizer, has the feature of high sensitivity in addition to the characteristics of the photosensitive resin of the first invention.

Claims (12)

[Claims] Claim 1: Comprised of a copolymer consisting of a polysiloxane derivative portion having one or more groups selected from the group consisting of an unsaturated group, an alkyl group, and a halogenated alkyl group, and a polysilylene derivative portion. Characteristic photosensitive resin. 2. In the photosensitive resin according to claim 1, the polysiloxane derivative portion is represented by the following formula (1), the following formula (2), or a copolymer thereof. A photosensitive resin characterized by the following characteristics (however,
R2, R3, R5 and R6 are groups selected from the group consisting of unsaturated groups, alkyl groups and halogenated alkyl groups, and may be the same or different. Also, m, n
is a positive integer. ). [Chemical formula 1] 3. In the photosensitive resin according to claim 1 or 2, the unsaturated group is a vinyl group (CH2=CH-
), an allyl group (CH2=CH-CH2-), an isopropenyl group (CH2=C(CH3)-), and a 2-butenyl group (CH2=CH-CH2-CH2-). . 4. In the photosensitive resin according to claim 1 or 2, the alkyl group is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, or a tertiary butyl group. A photosensitive resin characterized by the following (provided that the case where all the substituents in the polysiloxane derivative part are tert-butyl groups is excluded). 5. In the photosensitive resin according to claim 1 or 2, the halogenated alkyl group is a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group, a bromopropyl group, or a bromobutyl group. A photosensitive resin characterized by having a group, an iodomethyl group, an iodoethyl group, an iodopropyl group, and an iodobutyl group (provided that the number of halogens in each of the halogenated alkyl groups is 1 or more and less than or equal to the maximum number possible in the group). Any number within the range is fine.) 6. The photosensitive resin according to claim 1, wherein the polysilylene derivative portion is represented by the following formula (3) or the following formula (4). (However, RA, RB, RC, RD,
RE, RF, RG, RH, RI and RJ are as follows (a
) to (g), and may be the same or different. (a): A chain, branched or cyclic alkyl group having 10 or less carbon atoms. (b): Phenyl group having no substituent. (c): Naphthyl group having no substituent. (d): A phenyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group. (e): A naphthyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group. (f): A biphenyl group having no substituents. (g): A biphenyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group. Further, the silicon number l in formula (3) is an integer satisfying 2≦l≦10. (4) The silicon numbers i, j, and k in formula (4) are 0≦i≦
7, an integer satisfying 1≦j≦8, 1≦k≦8, and i+j+k≦9. ). [Chemical 2] 7. The photosensitive resin according to claim 1, wherein the charged amount of the raw material for the polysilylene derivative portion is 0.0.
A photosensitive resin characterized in that the amount thereof is within the range of 5 to 10 mol%. 8. The photosensitive resin according to claim 1, wherein the copolymer has a weight average molecular weight of 2,000 or more and 10
A photosensitive resin characterized in that it has a molecular weight of 0,000 or less. 9. A photosensitive resin composition comprising the photosensitive resin according to claim 1 and a sensitizer. 10. The photosensitive resin composition according to claim 9, wherein the sensitizer is a hydrosilane compound. 11. In the photosensitive resin composition according to claim 10, the hydrosilane compound is one of the following (5) to (
9) A photosensitive resin composition selected from hydrosilane compounds represented by the formula (however,
R in formulas (5) and (6) and R' in formula (7) are an alkyl group, a phenyl group without a substituent, a phenyl group with a substituent, or a phenyl group with a substituent. The group is selected from a naphthyl group without a substituent, a naphthyl group with a substituent, a biphenyl group without a substituent, and a biphenyl group with a substituent. In addition, at least one of R in formulas (7) to (9) is hydrogen, and the others are hydrogen, an alkyl group,
A phenyl group without a substituent, a phenyl group with a substituent, a naphthyl group without a substituent, a naphthyl group with a substituent, a biphenyl group without a substituent, A group selected from biphenyl groups having substituents. Furthermore, in formulas (5) to (9), r, s,
t, u, v, w are r+s=4, r≧1, s≧1, t+
It is a positive integer that satisfies u=6, u≧1, 1≦v≦5, and 1≦w≦6. ). (R)rSi(H)s...(5)(R)tSi2
(H) u ... (6) [Chemical formula 3] 12. The photosensitive resin composition according to claim 9, wherein the sensitizer is added in an amount of 0.1 to 30% by weight based on the photosensitive resin. A photosensitive resin composition characterized in that: