JP2938199B2 - Negative photosensitive resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin suitable as a resist material used for manufacturing semiconductor devices and the like.

[0002]

2. Description of the Related Art In processing a substrate in the manufacture of a semiconductor device, for example, forming a metal wiring pattern in an IC, a metal film for wiring is formed on the entire surface of a substrate to be processed, a resist film is formed thereon, and this is exposed and developed. In this procedure, a resist pattern is obtained, a metal film is etched using the resist pattern as a mask, and then the resist pattern is removed.

[0003] However, with the increasing integration and speed of ICs,
The use of ultra-miniaturized wiring patterns and the adoption of multilayer wiring has led to the trend toward higher pattern aspect ratios in order to reduce wiring resistance. . Therefore, when a resist pattern is formed on a substrate to be processed, the following problems occur. That is, a step may become larger than the depth of focus of the reduced projection exposure apparatus, so that it is difficult to form a resist pattern of a target size using the reduced projection exposure apparatus. In particular, when performing patterning in the submicron region, the depth of focus becomes increasingly shallow because a reduced projection exposure apparatus equipped with a lens having a large numerical aperture is used. There is a possibility that a pattern cannot be formed only with such a single-layer resist.

Therefore, as a conventional technique for solving the above-mentioned problems, for example, a document (Journal Of E)
Electrochemical Society: SO
LID-STATE SCIENCE AND TEC
HNOLOGY ((Journal of Electrochemical Society: Solid State Science and Technology) V01.132, No. 5 (19
85.5) pp. 1178-1182). This technique uses a positive resist having sensitivity in the far ultraviolet region (200 to 300 (nm)) in addition to a resist pattern forming technique called a two-layer resist method.

Here, the two-layer resist method is as described below.

First, a thick thermosetting resin is formed on a substrate having a step, and the thermosetting resin is thermoset to flatten the substrate. An extremely thin photosensitive resin layer having high resistance to etching by oxygen plasma is formed thereon, and then the photosensitive resin layer is exposed and developed to form a pattern thereof. Next, using this pattern as a mask, the thermosetting resin layer is etched by reactive ion etching (O ₂ -RIE) using oxygen gas to obtain a two-layer resist pattern having a high aspect ratio. Further, the underlying metal layer on the substrate to be processed is etched using the two-layer resist pattern as a mask.

[0007] The advantage of the two-layer resist method is that the pattern of the photosensitive resin layer is formed on the thick planarizing layer, so that it is not affected by the underlying substrate, and therefore has a high aspect ratio without dimensional fluctuation. That is, a pattern can be formed.

As a resist used for such a photosensitive resin layer, there is a resist containing silicon, and the above-mentioned literature discloses poly (trimethylsilylmethyl methacrylate-3).
-Oximino-2-butanone methacrylate) copolymer is disclosed. This resist is made of deep ultraviolet (Dee)
(p-UV), the sensitivity was such that a 1 μm line and space pattern could be resolved at a dose of 250 mJ / cm ² , and the minimum resolution was 0.75 μm.

[0009]

However, the conventional resist described above has a low silicon layer content of 9.6% by weight, so that the etching rate by O ₂ -RIE is 15 n.
Fast as m / min. That is, there is a problem that O ₂ -RIE resistance is low. Further, there is a problem that the resolution and the sensitivity are not sufficient.

[0010] The present invention has been made in view of the above points, and an object of the present invention is to solve the above-mentioned problems and to provide a photosensitive resin having excellent film quality and processing accuracy.

[0011]

In order to achieve this object, the negative photosensitive resin of the present invention comprises at least one kind selected from the group consisting of unsaturated groups, alkyl groups and alkyl halide groups. Wherein the main chain contains a polysilylene derivative part that generates an active species by receiving light within a wavelength range of 200 to 400 nm.

With this configuration, a polysiloxane derivative in which the polysiloxane is bridged by the polysilylene derivative portion is obtained. The structure of the polysilylene derivative can be changed (for example, whether or not there is a branch ((3), (4)
Formula)) and / or by changing the number of silicon and the type of the substituent in the polysilylene derivative part, the wavelength 200
It absorbs over a wide range of 400 nm and receives light of that wavelength to generate active species such as silyl radicals and silylenes. Therefore, when the polysiloxane derivative has an unsaturated group, the active species is added to the unsaturated group to initiate polymerization. When the polysiloxane derivative has an alkyl group and / or a halogenated alkyl group, polymerization starts because the active species abstracts hydrogen from the alkyl group and abstracts halogen from the halogenated alkyl group. The polymerized portion of the polysiloxane derivative becomes insoluble in the organic solvent (ie,
It becomes a negative type. ). Therefore, a desired negative resist pattern can be obtained by selectively irradiating the photosensitive resin composition with light. Preferably, the amount of the starting material for obtaining the polysilylene derivative part is 1 to 30 with respect to the starting material for obtaining the polysiloxane derivative.
The amount is in the range of mol%. When the charged amount of polysilylene is 1 mol% or less, the ratio of the polysilylene derivative portion in the photosensitive resin is reduced, so that the sensitivity of the photosensitive resin does not become a desired value. When the charged amount of polysilylene is 30 mol% or more, the ratio of the polysilylene derivative portion is large. It becomes too much, and the portion of the photosensitive resin that decomposes when receiving light becomes too large. This causes a reduction in sensitivity, that is, a loss of function as a negative resist.

Since the polysiloxane derivative has a high silicon content, the photosensitive resin has a silicon content of at least 10% by weight, and as a result, O ₂ -RIE
A photosensitive resin having excellent resistance can be obtained.

Here, the above-mentioned polysiloxane derivative, which is a constituent component of the photosensitive resin, has a basic skeleton represented by, for example, the following formula (1) or the following formula (2). Is preferred. Of course, these may be mixed.

[0015]

Embedded image

[0016]

However, in formulas (1) and (2), R ² , R ³ ,
R ⁵ and R ⁶ are groups selected from the group consisting of unsaturated groups, alkyl groups and halogenated alkyl groups, and may be the same or different. Further, R ¹¹ , R ¹² , R ⁴¹ , R
⁴² , R ⁴³ and R ₄₄ are polysilylene derivative portions, which may be the same or different. M and n are positive integers.

The polysilylene derivative portion contained in the main chain of the polysiloxane derivative is preferably, for example, one represented by the following formula (3) or one represented by the following formula (4). .

[0019]

Embedded image

[0020]

However, R in the formulas (3) and (4) is selected from the group consisting of the following (a) to (h) and may be the same or different. However, at least two or more of R are those shown in the following (a).

(A) A polysiloxane derivative having at least one group selected from the group consisting of an unsaturated group, an alkyl group and a halogenated alkyl group.

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

(C) a phenyl group having no substituent.

(D) a naphthyl group having no substituent.

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

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

(G) a biphenyl group having no substituent.

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

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

The polysiloxane derivative having a basic skeleton represented by the formula (1) can be obtained, for example, by adding a polysiloxane having a bifunctional or higher functionality to a linear polysiloxane derivative having a terminal hydroxyl group represented by the following formula (5). It is obtained by reacting in the presence of a catalyst. In addition, polysiloxane derivatives having a basic skeleton represented by the formula (2) can also be obtained, for example, by adding a polysilylene having a bifunctional or higher functionality to a polysilsesquioxane derivative having a terminal hydroxyl group represented by the following formula (6) in the presence of a basic catalyst. By reacting with That is, the photosensitive resin of the present invention can be synthesized by bridging a polysiloxane derivative having a terminal hydroxyl group with a bifunctional or higher polysilylene. Of course, polysilylene may be allowed to act on a mixture of the formula (5) and the formula (6). According to such a synthesis method, a photosensitive resin having a molecular weight larger than the weight average molecular weight of the polysiloxane used as a raw material can be easily obtained. When a plurality of polysiloxanes having different substituents are used as a starting material, a photosensitive resin composed of a block copolymer can be obtained.

[0032]

Embedded image

[0033]

However, R ² , R ³ , and R ² in the formulas (5) and (6)
R ⁵ and R ⁶ are groups selected from the group consisting of unsaturated groups, alkyl groups and halogenated alkyl groups, and may be the same or different. M and n are positive integers.

One of polysilsesquioxane derivatives having a terminal hydroxyl group represented by the formula (6) used in the synthesis:
R ² , R ³ , R ⁵ and R ⁶ are, for example, alkenyl groups selected from vinyl group, allyl group, isopropenyl group and 2-butenyl group, or substituted with one or more chlorine, bromine or iodine. Examples of the alkyl group having 4 or less carbon atoms include those described in, for example,
No. 10839 and easily available.
Further, those in which R ⁵ and R ⁶ are alkyl groups can be easily obtained because they can be synthesized by a method according to the synthesis method disclosed in the publication. Further, the linear polysiloxane derivative having a terminal hydroxyl group represented by the formula (5) can be easily obtained by using trichlorosilane as dichlorosilane in the synthesis method disclosed in JP-A-63-210839. And a resin represented by the formula (5):
Any of the resins represented by the formula (6) has a weight average molecular weight of 2,000 to 100,000 by changing the synthesis conditions.
It can be obtained with good controllability up to a degree. Also, oligomers smaller than that can be easily obtained with good controllability.

However, when the photosensitive resin of the present invention synthesized from these starting materials is used as a resist material, the starting material used has a weight average molecular weight of 500 to 10
It is better to be in the range of 000. If the weight average molecular weight of the polysiloxane derivative as the starting material is 500 or less, the molecular weight increases due to crosslinking with polysilylene, but the resulting photosensitive resin does not become crystalline because the molecular weight is too low and the resist film is not formed. This is because it is difficult and the amount of exposure required for patterning becomes extremely large. If the weight average molecular weight of the starting polysiloxane derivative is 100,000 or more, the molecular weight of the photosensitive resin becomes too high due to the increase in molecular weight due to the crosslinking of polysilylene, and this resin is dissolved in a solvent for adjusting the coating solution. This is because there is a possibility that it will not be performed. Of course, as long as it is within the above preferred range, a plurality of types of polysiloxanes having different molecular weights may be mixed and used as a starting material.

The polysilylene having two or more functionalities, which is the other material used for the synthesis, is a material capable of making the polysiloxane derivative in the polysilylene derivative represented by the formulas (3) and (4) a functional group. If so, various known ones can be used.

The amount of polysilylene charged during the synthesis may be any number as long as the number of functional groups of the polysilylene is equal to or larger than the number of OH groups of the polysiloxane derivative having a terminal hydroxyl group. Although it depends on the number of groups, the amount is preferably in the range of 1 to 30 mol% based on the polysiloxane derivative. When the charged amount of polysilylene is 1 mol% or less, the ratio of the polysilylene derivative portion in the photosensitive resin becomes small, so that the sensitivity of the photosensitive resin does not become a desired value. This is because the number of portions that decompose when receiving the light of the photosensitive resin becomes too large, which causes a decrease in sensitivity.

As the basic catalyst used in the synthesis, for example, triethylamine, tri-n-butylamine, pyridine, lutidine, γ-collidine, imidazole and the like can be used. Of course, it is not limited to these. Here, the amount of the basic catalyst used may be in the range of from equimolar amount to 10-fold molar amount with respect to the functional group of polysilylene.

The solvent used for dissolving the starting materials in the synthesis includes, for example, dimethylformamide, tetrahydrofuran, dimethylsulfoxide,
Examples thereof include 4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, and toluene.

The photosensitive resin of the present invention can be used together with a sensitizer to form a photosensitive resin composition in order to further increase the sensitivity.

Various sensitizers can be used. In particular, it is preferable to use a hydrosilane compound having a property of capturing silylene. The hydrosilane compound preferably has a Si-H bond in one molecule, and is preferably a liquid or solid from the viewpoint of use as a resist. Specifically, for example, it is preferable to be selected from the compounds represented by the following formulas (7) to (11). However, (7) and (8)
R in the formula, R ′ in the formula (9) represents an alkyl group, a phenyl group having no substituent, a phenyl group having a substituent, a naphthyl group having no substituent, a substituent A naphthyl group, a biphenyl group having no substituent,
This is a group selected from biphenyl groups having a substituent. In the formulas (9) to (11), R represents at least one hydrogen and the other hydrogen, an alkyl group, a phenyl group having no substituent, a phenyl group having a substituent, or a substituent. It is a group selected from a naphthyl group having no substituent, a naphthyl group having a substituent, a biphenyl group having no substituent, and a biphenyl group having a substituent. Further, in the equations (7) to (11), r, s, t, u, v, w
Are r + s = 4, r ≧ 1, s ≧ 1, t + u = 6, u ≧
It is a positive integer satisfying 1, 1 ≦ v ≦ 5, 1 ≦ w ≦ 6.

(R) _r Si (H) _s (7) (R) _t Si ₂ (H) _u (8)

Embedded image

[0044]

It is preferable that the addition ratio of the sensitizer to the photosensitive resin is in the range of 0.1 to 30% by weight. If it is less than 0.1% by weight, the sensitizing effect is small,
If the content is more than 0% by weight, there is a problem in film-forming properties.

[0046]

EXAMPLES Examples of the photosensitive resin of the present invention will be described below. In the following examples, specific conditions will be described by way of example in order to facilitate understanding of the present invention.
It should be understood that the present invention is not limited to only these examples. In addition, among the chemicals used in the following examples, the source may be omitted, but all of them are chemically pure and easily available. <Example 1> 1-1. Description of Synthesis of Photosensitive Resin of Example 1 First, a polysiloxane derivative constituting the photosensitive resin of Example 1 is synthesized as follows.

In this embodiment, the starting material is polyallylsilsesquioxane having an OH terminal (R ³ and R ⁴ in the above formula (6) are allyl groups) and have a number average molecular weight M _n = 6,500, weight average molecular weight M _w = 1
6,000 polyallylsilsesquioxanes are used.

The polyallylsilsesquioxane 93.
2 g (1 mol) and 1,5-dichloro-1,2,2,2 represented by the following formula (12) as polysilylene in this case:
20.8 g (0.0309 mol) of 3,4,5-pentaphenylpentamethylpentasilane are dissolved in 1.2 l of toluene as a solvent, and the solution is stirred in an ice bath. In the formula (12), Me is a methyl group,
Ph is a phenyl group. The same applies hereinafter.

[0049]

Embedded image

[0050]

Next, in an ice bath, 3.1 g (0.0309 mol) of triethylamine was added to this solution as a basic catalyst.
Is added dropwise with stirring, after which stirring is continued for 15 minutes.

Next, the solution is removed from the ice bath and stirred at room temperature for 3 hours.

Next, this solution is diluted with a solvent (in this case, toluene) and the insoluble matter is filtered. Next, the solvent used for dilution is distilled off. Thereafter, dilution with a solvent, filtration of the insoluble matter, and distillation of the solvent are repeated until no insoluble matter is generated.

When this operation is completed, an oily substance (Example 1)
69.2 g of a photosensitive resin). The weight-average molecular weight M _W of this oil was 38,000 and the dispersion (M _W / M
_n ) was 4.3.

1-2. Next, 100 g of the oily substance synthesized as described above is dissolved in 730 g of xylene. Next, this solution was filtered through a membrane filter having pores having a diameter of 0.2 μm to prepare a coating solution of the photosensitive resin composition of Example 1.

Next, a patterning experiment is performed according to the following procedure using a Xe-Hg lamp as a light source for exposure.

First, in order to form a lower resist layer on the silicon substrate, a photoresist (MP24 manufactured by Shipley Co., Ltd. in this embodiment) was formed on the silicon substrate by spin coating.
00) is applied under predetermined conditions, and then the sample is placed in an oven at a temperature of 200 ° C. for 1 hour to cure the photoresist. Thus, a lower resist layer having a thickness of 1.5 μm is formed.

Next, the photosensitive resin of Example 1 was applied on the lower resist layer so as to have a thickness of 0.2 μm by a spin coating method, and then the sample was heated to 60 ° C. using a hot plate. And bake for 1 minute.

Next, this sample has a minimum line width of 0.5 μm.
Exposure apparatus equipped with a Xe-Hg lamp and a CM250 cold mirror (in this embodiment, a PLA501 aligner manufactured by Canon Inc.) with masks having various line and space test patterns adhered thereto. Is performed while changing the exposure amount.

Next, the exposed sample is immersed in a 1: 1 mixture (volume ratio) of methyl isobutyl ketone and isopropyl alcohol (IPA) for 45 seconds to perform development, and then in IPA for 30 seconds. It is immersed and rinsed, and then baked at a temperature of 60 ° C. for 1 minute using a hot plate.

When the sample after development was observed, the initial film thickness (in this example, 0.2 μm, which is the film thickness after spin coating).
Exposure amount (D _n ^0.5 ) at which the residual film ratio with respect to m) becomes 50%
Is 1.5 counts (where 1 count (ct) = 3
9 mJ / cm ² . The same applies hereinafter. ). When the obtained resist pattern was observed with a scanning electron microscope (SEM), the minimum resolution was 0.5 μm line and space (L / S), which is the same as the minimum dimension of the mask used. I understood that.

Since the minimum line width of the test pattern used in this experiment was 0.5 μm, it was only confirmed that a resolution of 0.5 μm was secured.
It is to be understood that the photosensitive resin has higher resolving power (the same applies to the patterning experiments of the following examples).

1-3. Patterning experiment of the photosensitive resin composition of Example 1 (Part 2)
A patterning experiment is performed in the same procedure as the above-described patterning experiment (No. 1) except that an rF excimer laser is used.

Incidentally, a laser oscillator manufactured by Lambda Physics Co., Ltd. is used. This laser oscillator can provide an irradiation amount of 0.50 mJ / cm ² per pulse, and can control the exposure amount by the number of pulses.

As a result, the sensitivity (D _n ^0.5 ) was 182 mJ /
cm ² . It was also found that a 0.5 μm line and space pattern could be resolved.

1-4. Patterning Experiment of Photosensitive Resin of Example 1 (Part 3) A patterning experiment by a two-layer resist method using the photosensitive resin of Example 1 as an upper layer resist is performed as described below.

First, formation of a lower resist layer (MP2400 layer) and patterning of the photosensitive resin of the first embodiment are performed in the same procedure as in the patterning experiment (part 1). However, the exposure amount by the Xe-Hg lamp is set to 2.4 counts.

Next, this sample was subjected to a parallel plate type dry etching apparatus (DEM manufactured by Nidec Anelva Co., Ltd. in this embodiment).
451). Then, the O ₂ gas pressure is set at 1.0
a, The lower resist layer is etched under the conditions that the O ₂ gas flow rate is 20 SCCM, 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 SEM,
It was found that a rectangular line-and-space pattern having a line-and-space pattern of 5 μm and an aspect ratio of 4 was formed.

As is clear from the results of the above-described patterning experiments, it can be understood that the photosensitive resin of Example 1 is superior in both sensitivity and resolution to the conventional photosensitive resin.

1-5. O ₂ -R of the photosensitive resin of Example 1
Investigation Results of IE Resistance Next, the O ₂ -RIE resistance of the photosensitive resin of Example 1 is investigated as follows.

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

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

After completion of the etching, the thickness of the photosensitive resin film of Example 1 was measured using a film thickness meter (Talistep manufactured by Taylor Hobson), and the film thickness was reduced by etching for 20 minutes. The etching rate was found to be 4.2 nm / min.

The conventional photosensitive resin etching rate is 15
Considering that the etching condition at this time is lower than that of this embodiment, it can be understood that the photosensitive resin of Example 1 has better O ₂ -RIE resistance than the conventional one. <Example 2> Next, 15.3 g of 1,5-dichloro-1,1,2,2-tetraphenyltetramethyltetrasilane represented by the following formula (13) was used as the polysilylene used for the synthesis of the photosensitive resin. A polysiloxane derivative (the photosensitive resin of Example 2) is synthesized in the same procedure as in Example 1 except that the amount is 0.0309 mol). The yield is 63.
It was 5 g. The weight average molecular weight M _W of the polysiloxane derivative is 43,000, dispersion (M _W / M _n) was 4.6.

[0076]

Embedded image

[0077]

Next, the sensitivity (D _n ^0.5 ) and the resolving power of the photosensitive resin of Example 2 are examined by the same procedure as that of the patterning experiment (No. 1) of Example 1.

As a result, it was found that the sensitivity of the photosensitive resin of Example 2 was 1.9 counts. Also, 0.5 μm
It was found that the line and space pattern was resolved. <Example 3> Next, 13.0 g of 1,6-dichloropermethylhexasilane (0.0309 mol) represented by the following formula (14) was used as the polysilylene used for the synthesis of the photosensitive resin.
A polysiloxane derivative (the photosensitive resin of Example 3) is synthesized in the same procedure as in Example 1 except that l) is used. The yield was 68.3 g. The weight average molecular weight M _W of this polysiloxane derivative was 38,000, and the dispersion (M _W / M _n ) was 3.9.

[0080]

Embedded image

[0081]

Next, the sensitivity (D _n ^0.5 ) and the resolving power of the photosensitive resin of Example 3 are examined by the same procedure as that of the patterning experiment (No. 1) of Example 1.

As a result, it was found that the sensitivity of the photosensitive resin of Example 3 was 9.8 counts. Also, 0.5 μm
It was found that the line and space pattern was resolved. <Example 4> Next, polysilylene used for the synthesis of a photosensitive resin was converted to 1,1, -dichloro-2,2,2, -tristrimethylsilyldisilane 1 represented by the following formula (15).
A polysiloxane derivative (the photosensitive resin of Example 4) is synthesized in the same procedure as in Example 1 except that the amount is 1.2 g (0.0309 mol). The yield was 70.0 g. Weight average molecular weight M _{W of} this polysiloxane derivative
Was 40,000 and the variance ( _MW / _Mn ) was 4.1.

[0084]

Embedded image

[0085]

Next, the sensitivity (D _n ^0.5 ) and the resolving power of the photosensitive resin of Example 4 are examined by the same procedure as that of the patterning experiment (No. 1) of Example 1.

As a result, it was found that the sensitivity of the photosensitive resin of Example 4 was 28.0 counts. Also, 0.5μ
It was found that m line and space patterns were resolved. <Example 5> Next, M _W = 33,000 polysiloxane used for the synthesis of the photosensitive resin (6) A poly-chloromethyl-silsesquioxane is a kind of type, M _n = 10,
A polysiloxane derivative (the photosensitive resin of Example 5) is synthesized in the same procedure as in Example 1 except that the amount is 101.6 g (1 mol). The yield is 66.0.
g. The weight average molecular weight M _W of the polysiloxane derivative is 70,000, dispersion (M _W / M _n) is 9.
It was 7.

Next, the sensitivity (D _n ^0.5 ) and the resolving power of the photosensitive resin of Example 5 are examined by the same procedure as that of the patterning experiment (No. 1) of Example 1.

As a result, it was found that the sensitivity of the photosensitive resin of Example 5 was 1.8 counts. Also, 0.5 μm
It was found that the line and space pattern was resolved. <Example 6> Next, M _W = 42,000 polysiloxane used for the synthesis of the photosensitive resin (5) a polyvinyl siloxane is a kind of type, those of M _n = 12,000 9
A polysiloxane derivative (the photosensitive resin of Example 6) is synthesized in the same procedure as in Example 1 except that the amount is 8.26 g (1 mol). The yield was 56.7 g. The weight average molecular weight M _W of the polysiloxane derivative 92,
000 and the variance ( _MW / _Mn ) was 10.5.

Next, the sensitivity (D _n ^0.5 ) and the resolving power of the photosensitive resin of Example 6 are examined by the same procedure as that of the patterning experiment (No. 1) of Example 1.

As a result, it was found that the sensitivity of the photosensitive resin of Example 6 was 2.3 counts. Also, 0.5 μm
It was found that the line and space pattern was resolved.

As is apparent from the results of the experiment of patterning the photosensitive resins of Examples 2 to 4, it can be understood that each of these photosensitive resins has a higher sensitivity and resolution than the conventional photosensitive resin.

Table 1 summarizes the differences in the constitution and characteristics of the photosensitive resin in each of the examples. However, in the sensitivity section in Table 1, the unit in mJ / cm ² is K
This is the sensitivity when an rF excimer laser is used, and the unit indicated by ct is the sensitivity when an Xe-Hg lamp and a cold mirror are used.

[0094]

[Table 1]

[0095]

[0096]

As is clear from the above description, the photosensitive resin of the present invention has at least one functional group selected from an unsaturated group, an alkyl group and a halogenated alkyl group. A polysiloxane derivative known to have a high _2- RIE resistance, comprising a polysiloxane derivative having a polysilylene derivative part which efficiently generates a silyl radical having a high reactivity with the functional group in the main chain thereof. Therefore, it shows high sensitivity, high resolution, and high O ₂ -RIE resistance.

Accordingly, a photosensitive resin having excellent film quality and processing accuracy can be provided.

The photosensitive resin can be used together with a sensitizer to form a photosensitive resin. Then, this photosensitive resin composition can constitute a resist having higher sensitivity than the case where the photosensitive resin is used alone.

Further, according to the photosensitive resin of the present invention, the wavelength of the polysilylene derivative portion can be adjusted to 200-200 by appropriately selecting the structure of the polysilylene derivative portion (for example, presence or absence of branching), the number of silicons contained in the polysilylene derivative portion and the type of the substituent. Since the light absorption wavelength can be changed over a wide range of 400 nm, for X-rays, Xe
For Cl excimer laser, KrF excimer laser, AF
It becomes possible to form a resist for an excimer laser.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/075 C08G 77/48 G03F 7/038 G03F 7/26 511

Claims (6)

(57) [Claims] 1. A polysiloxane derivative having at least one group selected from the group consisting of an unsaturated group, an alkyl group and a halogenated alkyl group, wherein the polysiloxane derivative has a wavelength of 20% in its main chain.
A polysiloxane derivative containing a polysilylene derivative part that generates an active species by receiving light in the range of 0 to 400 nm, wherein the basic skeleton of the polysiloxane derivative is represented by the following formula (1) or (2) ), Or
These copolymers (provided that R ¹¹ , R ¹² , R ⁴¹ ,
R ⁴² , R ⁴³ and R ⁴⁴ are a polysilylene derivative part,
They may be the same or different. Also, R ² , R
³ , R ⁵ and R ⁶ are groups selected from the group consisting of unsaturated groups, alkyl groups and halogenated alkyl groups, and may be the same or different. M and n are positive integers. A negative type photosensitive resin wherein the amount of the starting material for obtaining the polysilylene derivative portion is in the range of 1 to 30 mol% based on the starting material for obtaining the polysiloxane derivative. . Embedded image 2. The negative photosensitive resin according to claim 1, wherein the unsaturated group is a vinyl group (CH ₂ ＣＨCH—), an allyl group (CH ₂ ＣＨCH—CH ₂ —), or an isopropenyl group. (C
_{H 2 = C (CH 3)} -) and 2-butenyl group (CH ₂ =
CH-CH ₂ -CH _2- ). 3. The negative photosensitive resin according to claim 1, wherein the alkyl group is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group. A negative photosensitive resin (excluding a case where all the substituents of the polysiloxane derivative are tertiary butyl groups). 4. The negative photosensitive resin according to claim 1, wherein the halogenated alkyl group is chloromethyl, chloroethyl, chloropropyl, chlorobutyl, bromomethyl, bromoethyl, bromopropyl, bromobutyl. Group, iodomethyl group, iodoethyl group, iodopropyl group and iodobutyl group, wherein the number of halogens in each of the halogenated alkyl groups is at least 1 Any number within the following range may be used.) 5. The negative photosensitive resin according to claim 1, wherein the polysilylene derivative portion is represented by the following formula (3) or the following formula (4). Negative-type photosensitive resin (where R is the following (a) to
(H) and may be the same or different. However, in each of the formulas (3) and (4), at least two or more of R are represented by the following (a). ). (A) A polysiloxane derivative having at least one group selected from the group consisting of an unsaturated group, an alkyl group and a halogenated alkyl group. (B) A chain, branched or cyclic alkyl group having 10 or less carbon atoms. (C) a phenyl group having no substituent. (D) a naphthyl group having no substituent. (E) A phenyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group. (F) a naphthyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group. (G) a biphenyl group having no substituent. (H) a biphenyl group having a group selected from a nitro group, an alkoxy group having 5 or less carbon atoms, and a halogen group. The number of silicon 1 (L) in the formula (3) is 2 ≦ l ≦ 10
An integer that satisfies. Further, the silicon numbers i, j,
k is 0 ≦ i ≦ 7, 1 ≦ j ≦ 8, 1 ≦ k ≦ 8 and i +
It is an integer satisfying j + k ≦ 9. Embedded image 6. The negative photosensitive resin according to claim 1, wherein a starting material for obtaining the polysiloxane derivative is a linear polysiloxane derivative having a terminal hydroxyl group having a weight average molecular weight of 500 to 100,000. Or a weight average molecular weight of 5
A negative-type photosensitive resin comprising a polysilsesquioxane derivative having a terminal hydroxyl group of from 00 to 100,000.