JPH02149848A - Photosensitive material and photosensitive composition using the same - Google Patents

Abstract

PURPOSE:To obtain a resist pattern having high sensitivity to far ultraviolet rays having <=310nm wavelength by constituting the resist pattern of a specified alpha-halo-tau-butyrolactone deriv. CONSTITUTION:The resist pattern is constituted of an alpha-halo-tau-butyrolactone deriv. expressed by the formula I, wherein one of X1 and X2 is a halogen atom such as Cl atom, and another is an H atom; each R1 and R2 is a group selected from an alkyl group, aralkyl group, aryl group, haloalkyl group or H atom; one of R3 and R4 is a haloalkyl group and another is a group selected from an alkyl group, aralkyl group, aryl group, haloalkyl group or H atom. Thus, a resist can be obtained a negative type or a positive type, and a high sensitivity to far ultraviolet rays having <=310nm wavelength is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive material whose polarity changes significantly with deep ultraviolet light having a wavelength of 310 nm or less, and a photosensitive composition using the same, which is described above. The present invention relates to a photosensitive composition that is sensitive to far ultraviolet rays such as XeC9 excimer laser beams (wavelength 308 nm), KrF excimer laser beams (wavelength 248 nm), ArF excimer laser beams (wavelength 193 nm), electron beams, X-rays, etc. .

(Prior Art) As semiconductor devices become more highly integrated and operate at higher speeds, requirements for microfabrication techniques used in the manufacture of semiconductor devices are becoming increasingly strict. Among these microfabrication techniques, resist process technology in particular is a fundamental technology for manufacturing semiconductor devices, and therefore a technology that can obtain a desired resist pattern is desired.

The pattern-forming photosensitive compositions (hereinafter sometimes referred to as resists) used in such resist processes have traditionally been available in a variety of types, or are based on novolac resins because of their high resolution. A positive resist consisting of a resin and a nutoquinone cyacyto-based photosensitive material added thereto was often used. According to this positive resist, 9 lines of ultra-high pressure mercury lamp (wavelength 436n)
The resolution line width is 0.8 using a reduction projection type exposure system using
It is now possible to form a resist pattern with a size of approximately 100 um.

By the way, if the resolution line width is R, the numerical aperture of the reduction projection lens provided in the exposure device is NA, and the wavelength of the light used for exposure is λ, then this resolution line width R is expressed as R=in/NA. (k
is determined by a constant determined by the process). Therefore, if the resolution is to be increased in the future, it is necessary to reduce λ or increase NA.

However, increasing the numerical aperture has the disadvantage that the depth of focus becomes shallower. In addition, in order to achieve the desired depth of focus and ensure a constant field size, it is necessary to use a lens with a large diameter, or it is often technically difficult to create such a large lens. , therefore,
It is not desirable to increase the numerical aperture.

On the other hand, reducing the wavelength of the light source, that is, shortening the wavelength of the light source, is currently being done by using a Xe-Hg lamp.
48 nm) has become available as a light source for link graphing. Therefore, by using these light sources and resists compatible with these light sources, it is possible to form a roughly fine resist pattern.

Therefore, when considering a resist for such short wavelength light,
Conventionally, the following was known.

As a positive type resist, there was a resist called MP-2400 sold by Silaplay, which was a combination of a cresol novolac resin and a quinone diazide photosensitive material. This MP-2400 could not be said to have sufficient transparency against far ultraviolet rays, but it could provide a certain degree of resolution.

On the other hand, as a negative type, for example, the literature (IEEE
TRANSACTIONS ON ELECTRON
DEVICES (IEE Transaction on Electron Devices) ED-28 (
II) Nov, (1981) P.

There was a resist for deep ultraviolet rays that was a combination of poly(vinylphenol) and bisazide, as disclosed in No. 306). According to this resist, when contact exposure is performed using a XeH9 lamp and a cold mirror CM290 u, a line pattern with a width of 0.4 um is %1.2.
It is said that it is possible to resolve images at intervals of um.

(Problem to be Solved by the Invention) However, in the case of quinonediazide-based photosensitive materials, when irradiated with light, it becomes a five-membered ring derivative containing carboxylic acid, which only becomes alkali-soluble. This only acted as a crosslinking agent by generating nitrene radicals upon irradiation with light. Therefore, even if the base resin of a resist containing these photosensitive materials is changed to one with or without a crosslinking site,
As a result, this resist could not be changed into a negative type/positive type.

This invention has been made in view of these points, and therefore, the purpose of the first invention of this application is to improve dissolution inhibiting ability (i.e., polarity) before and after irradiation with deep ultraviolet light of 310 nm or less.
It is a photosensitive material that changes significantly, and when used in a resist, the photosensitivity can be changed into either a negative resist or a positive resist depending on the presence or absence of a crosslinking site in the base resin of the resist. The purpose is to provide materials.

A second object of the present invention is to provide a photosensitive composition using the above-mentioned photosensitive material.

(Means for Solving the Problem) In order to achieve the object of the first invention of this application, the inventor of this application has conducted extensive research on various compounds. It is a compound that is generally used as a solvent for plastic production, etc., and is made by bonding a halogen to γ-butyrolactone, which itself is highly polar, to make it less polar.Currently, it is used as a reagent in organic chemistry. This invention has been completed by focusing on a compound that has been developed to a certain degree.

Therefore, the photosensitive material of the first invention of this application is characterized by comprising an α-halo-γ-butyrolactone derivative represented by the following general formula (I) (provided that in formula (I),
, and ×2 have at least one halogen atom and R
5 and B2 are mutually the same or different groups selected from an alkyl group, an aralkyl group, an aryl group, an aryl group having a substituent, a haloalkyl group, and hydrogen, and these B1 and R2 together form a ring. Further, at least one of R3 and R4 is a haloalkyl group, and the other is an alkyl group, an aralkyl group, an aryl group, an aryl group having a substituent, a haloalkyl group, and hydrogen. selected groups, and the R3 and R4
Even if one of R1 and R2 is integrated with one of R1 and R2 to form a ring, specific examples of the α-halo-γ-butyrolactoxy derivatives mentioned here include the following (1) to (1).
7) Can list things that are shown in the formula.

However, it is not limited to these.

CH.

O Nitriles such as tonitrile and propionitrile are specifically preferred.

Among the above-mentioned compounds, formulas (1) to (9) and (15) to
The compounds represented by (17) can be synthesized from appropriate starting materials by an intramolecular cyclization method using cuprous chloride as a catalyst, as shown in the following formula (+1).

In order to prevent intermolecular reactions, it is preferable that the amount of the catalyst used in this synthesis be as large as possible (for example, 10 to 30 mo1%). In addition, the solvent used for the synthesis is acetic acid or the formula (1
Each of the compounds represented by 0) to (13) is commercially available.

Further, according to the photosensitive composition of the second invention of this application, in the photosensitive composition containing a solvent, a base resin, and a photosensitive material, the photosensitive material is represented by the above-mentioned general formula (I). It is characterized by containing at least one kind of the α-octarow γ-butyrolactone derivatives shown below.

Here, the base resin should be one that does not absorb in the wavelength region of 310 nm or less, or one that does not absorb at a wavelength of 310 nm or less, or one that does not absorb at a wavelength of 310 nm or less, or one that does not absorb at a wavelength of 24 nm or less
Examples of such base resins, which are preferably transparent (with an absorption window) to 8 nm), include p-cresol novolak, polyvinylphenol, polyvinylpyrrolidone, polyvinyl alcohol, poly-α-methylhydroxystyrene, and polyvinyl Examples include phenol/methyl methacrylate copolymer. However, the base material is not limited to those mentioned above, and other suitable materials may of course be used.

In addition, in constituting the photosensitive composition, α-halo-γ
- If the content of the butyrolactone derivative in the base resin is less than 5% by weight or more than 50% by weight, the sensitivity and film forming properties will decrease and the resist will no longer be usable, so the content should be 5 to 50% by weight. A value within the range of % by weight is preferred.

(Function) The photosensitive material of the first invention of this application is sensitive to light, especially at wavelengths of 3.
When exposed to deep ultraviolet light of 10 nm or less, it releases halogen through a photoreaction. For example, when X and x2 in the formula (CI) are both halogens (for example, chlorine), the halogen is released by photoreaction as shown in the formula (I[I) below.

Therefore, if there is active hydrogen in a system containing this photosensitive material, this Cq radical is considered to be a radical that extracts hydrogen, and if no olefin is present, it is thought that the Cq radical will extract hydrogen from the system.

In addition, the removal of chlorine by photoreaction of monohalides may be easier than that of the dihalides mentioned above, and the change also releases halogen.

Accordingly, the polarity of the photosensitive material increases as the halogen is released, and as a result, the solubility in water increases and the solubility in organic solvents of relatively low polarity decreases.

Therefore, when the photosensitive material of the first invention is used together with an alkali-soluble base resin to form a photosensitive composition (resist), the irradiated portions of this material become more polar and become soluble in the developer. Therefore, it can be used as a positive resist.

On the other hand, when the photosensitive material of the first invention is used together with a base resin having a crosslinking site to form a photosensitive composition (resist), the irradiated portion of the photosensitive material is released from the photosensitive material. Since crosslinking occurs using radical generation due to hydrogen abstraction from the radicals, it becomes insoluble in the developer, so it can be used as a negative resist.

(Example) Examples of the photosensitive material of the present invention and a photosensitive composition using the same will be described below. However, the numerical conditions, bags used, chemicals used, etc. described in the following examples are merely illustrative, and therefore, the present invention is limited only to the numerical conditions, packaging used, and chemicals described below. Please understand that this is not the case.

Description of the photosensitive material First, we will explain some examples of the photosensitive material that is the first invention of this application, the synthesis method of the starting material of each photosensitive material, and the synthesis of the photosensitive material from this starting material. law, and
This will be explained using material data.

<Example 1> As Example 1, 2,2-dichloro-3-chloromethyl-γ-butyrolactone represented by the above-mentioned formula (1) will be explained.

■Synthesis of starting materials.

As a starting material for the photosensitive material of Example 1, alcohol trichloroacetate is used. This allyl trichloroacetate was synthesized as described below.

To a mixture of 163.49 (1,00 mol) of trichloroacid W and a catalytic amount of para-toluenesulfonic acid, 135 ml (2,00 mol) of allyl alcohol was added dropwise over 10 minutes.Next, the reaction mixture obtained thereby was added. 2
The mixture was heated under reflux for 0 hours. The water generated during this heating and refluxing process was removed by the heating method in a funnel filled with a Type-3A molecular sieve.Next, after cooling the reaction mixture that had been heated and refluxed, 150ml of water was added to it. Water was added and the mixture was extracted with methylene chloride (400 ml). This extract was washed with an aqueous sodium bicarbonate solution and a saturated saline solution, and then dried over magnesium sulfate. This dried product was subjected to J-line temperature distillation using an evaporator to obtain allyl trichloroacetate (+86.89%, yield 94.1%) as a starting material. When we investigated the material data of this starting material, we found the following.

■...R 4 (a is 0.
It was 68.

Note that RfJlm was measured as follows. As starting material solvents, hexane, ethyl ether and %1
A liquid mixed at a ratio of :1 (volume ratio) was used. Also R
For the measurement of t'+a, a C plate commercially available from Aldrich was used. Color development was performed by spraying an ethanol solution of toluidine and then irradiating it with UV light (the same applies below).

■-H'NMR (60MHz, CC0j4): 4
．． 78 (dd, 2H, J=5.2, 1.8Hz, 0CQ
2), 5.17-6.35 (m, 3H, olefin proton).

■-IR spectrum (neat): 1770.16
50.1230°990.940.755cm- ■・B, P, (boiling point above reduced pressure): 76.5-77.5
°C, / l 7mmH9°■...Synthesis of the photosensitive material of Example 1.

Next, from allyl trichloroacetate synthesized as described above,
The photosensitive material of Example 1, 2,2-dichloro-3-
Chloromethyl-γ-butyrolactone was synthesized as described below.

In an autoclave, cuprous chloride 19 (10 mmol
) and allyl trichloroacetate 20.5q (100mmo
l) and 500ml of dry acetonitrile (Type-3
After pre-drying with a molecular sieve (pre-dried from phosphorus pentoxide) and heating at a temperature of 140°C for 3 hours with vigorous stirring, the solvent was removed from the crude product. Column chromatography using silica gel revealed white crystals of 2,2-dichloro-3.
-Chloromethyl-γ-butyrolactone was isolated (+5.
79, yield 77%), starting material 1.49 (7%)
was recovered. When the substance data of the photosensitive material in Example] was investigated, the following was found.

■...Rf (a: 0.38 (hexane ethyl ether=1=1 (volume ratio)).

■-H'NMR (90MHz, CDC(+3):
3.36 (m, IH, C3!:ri, 3.73 (dd 1
ike t, IH,, b8.8. IO, OHz, Csl
:ri, 3.97(dd,lH,J□5.0.IO,
OHz, CJ), 4.21 (dd 1iket, IH
1=8.0, 9.3Hz, CJj), 4.65(d
d, IH, J = 7.3.9.3Hz.

C4H).

■・”CNMR (25MHz, CDCu3): C
,=167,1, C2=78.7, C3=53.
4, C4=68.7. Cs=39.7° Note that C8 to C5 in each of the above NMR data correspond to carbon in the structural formula below (the same applies to Examples 2 to 4 below).

■・IR spectrum (CDC(13): 1810.
cm-' (CJ group).

■...Elemental analysis C3H502C (j3' total jl(a
(C=29.528=2.48. Cu=52.28
%), analysis value (C=29.47.8=2.3609・
52.29%).

■...Melting point: 71.6-72.0°C.

The elemental analysis and melting point were measured using a sample recrystallized from hexane (the same applies hereinafter).

■-H'NMR (60MHz, CC1J, ):
4.89 (d, 2H1=5.8Hz, OC!lh)
, 5.9-7.0 (m, 2H, olefin proton), 7.30 (br s, 5H, aromatic proton).

■-IR spec'7/L, (neat): 1760
．． ! 650.1600゜1250.965.690
680cl'■-B, P,: 90.5-107.5
°C/6.6 x 10-2 mmHq.

Example 2> As Example 2, 2,2-dichloro-3-(1-chloro-1-phenylmethyl)-γ-butyrolactone represented by the above formula (2) will be explained.

Cinnamyl trichloroacetate was used as a starting material for the photosensitive material of Example 2. The synthesis was carried out in accordance with the method described in Example]. The substance data of the obtained starting material were as follows.

■...Rf (6: 0.57 (hexane: ethyl ether 1:] (volume ratio)).

■...Synthesis of the photosensitive material of Example 2.

Next, from the above-mentioned cinnamyl trichloroacetate, Example 2
2,2-dichloro-3-(1-chloro-1-phenylmethyl)-γ-butyrolactone, which is a photosensitive material, was synthesized by a method similar to the method for synthesizing the photosensitive material of Example 1. The substance data of the photosensitive injection material of Example 2 were as follows.

■...Rda: 0.3+ (hexane:ethyl ether 1.1 (volume ratio)).

(b, l...H'NMR (90MH2, CDCQ,
) 2 3.40-3.80 (ddd.

1ike dt, IH, J=7.2. ! 0. O,IO,
OH2, CC (hCH), 4.29 (dd 1ike
t, IH, J=IO, 0, IO, OHz, OCH),
4.77 (dd.

IH1=7.2. IO, OHz, 0CH), 5.25
(d, IH, J=IO, OHz, C(LCjj),
7.45 (br s, 5H, aromatic proton).

■・IR spectrum (CDC!L3): 1795,
1810 cm-' (C・0 group).

■...Elemental analysis C++Hs02C (13: Total "W value (
C=47.26°H=3.25. CQ=38.05%
), analysis value (C・47.8+, H・3.05.Cu=
38.29%).

■...Melting point: 90.4-91.2°C.

Incidentally, when synthesizing the photosensitive material of Example 2, cinnamyl chloride was obtained as a by-product.

Example 3> As Example 3, 2,2-dichloro-3-(1-chloroethyl)-γ-butyrolactone represented by the above formula (3) will be explained.

As the starting material for the photosensitive material of Example 3, crotyl trichloroacetate was used. The synthesis was carried out according to the method of Example 1. The material data of the obtained starting material was as follows.

■...Rt value: 0.63 (hexane, ethyl ether = 1.1 (volume ratio)).

■-H'NMR (60MHz, CCL): 1.
78 (d, 3H1=5.882, CH3), 4.7
6 (d, 2H, J□5.8Hz, CH2), 5.
35-6.35 (m, 2H, olefin proton).

■・IR spectrum (neat): I 760.1
675. , 1230°960.750,690cm-■-B,P,: 49.5~53.0°C/5 m
mHq.

■ Synthesis of photosensitive material of Example 3.

Next, 2,2-dichloro-3-(1chloroethyl)-γ-butyrolactone, which is the photosensitive material of Example 3, is synthesized from the above-mentioned crotyl 1,1 chloroacetate using the method for synthesizing the photosensitive material of Example 1. It was synthesized by the same method. As a result,
The photosensitive material of Example 3 was obtained as a diastereomer mixture. In addition, to the diastereomer: diastereomer B=1O:3. The material data for each substance is as follows).

It was something like that.

(Diastereomer A) ■...RftI: 0.44 (hexane:ethyl ether=1:] (volume ratio)).

■-H'NMR (90Mllz, CDCQ3): 1
．． 85 (d, 3H, J□6.3Hz, C!1lj3)
, 3.20 (ddd, IH, J"?, 5, 9.5. I
O, OH2, C9□-CCjj), 4.20 (dd,
IH, J=9.5. IO, OHz, 0CH), 4.4
3 (dq, IH, J=6.8, 9.5Hz, CQCj
j), 4.73 (dd, lH, J=7.5°9.5
Hz, OCH).

■・IR spectrum (neat): 1805cm
-' (C=0 group) (diastereomer=8) ■...Rf value: 0.16 (hexane:ethyl ether=1=1 (volume ratio)).

■...Total NMR (90MH2, CDC(13):
1.56 (d, 3H, J□6.8H2, CH3), 3
．． 1~4.4 (m, IH, C112CC, 4.0~
4.8 (m, 3H,0CH2 and C1IC1j).

■-IR spectrum (C0CQ 3): 1810c
m-'(C.

<Example 4> As Example 4, 2-chloro- shown by the above formula (4)
3-chloromethyl-T-butyrolactone will be explained.

Allyl dichloroacetate was used as the starting material for the photosensitive material of Example 4. The synthesis was carried out in accordance with the method of Example 1. The substance data of the obtained starting material were as follows.

■...Rt'+a: 0.68 (hexane:ethyl ether=1:] (volume ratio)).

■-H'NMR (60MHz, CC9,):
4.32 (d, 2H, J = 5.OH2,0CH2),
5.2-6.5 (m, 3H, olefin proton)
, 6.00 (s, I) 1. HCCQ2)-@-JR spectrum (neat): 1750.1645.12
50゜985.940cm (d')-B, P,: 71.0~71.5℃/18m
mH9゜■...Synthesis of the photosensitive material of Example 4.

Next, 2-chloro-3-chloromethyl-γ-butyrolactone, which is the photosensitive material of Example 4, was synthesized from the above-mentioned allyl dichloroacetate. This synthesis was carried out in accordance with the method for synthesizing the photosensitive material of Example 1, except that bipyridyl in an amount equivalent to cuprous chloride was added to the reaction system, and the reaction time was increased to 21 hours. The photosensitive material of Example 4 was obtained as a diastereomer mixture. The substance data of the mixture were as follows.

■...R, value: O, I3 (hexane: ethyl ether = 1:1 (volume ratio)).

■-H'NMR (90MHz, CDC(h): 2
．． 85-3.40 (m, 2H.

CuCH and OH), 3.50-4.00 and 4.15
~4.80 (m, 4H, 0C) i2 and C (LCH2
).

■・IR spectrum (neat): 1795cm
-' (C=0 group).

<Example 5> As Example 5, 22-dichloro-3-chloromethyl-4-methyl-γ-butyrolactone represented by the above formula (5) will be explained.

■Synthesis of starting materials.

Trichlorovine vinegar # as a starting material for the photosensitive material of Example 5
I-methylallyl is used. This 1-methylallyl trichloroacetate was synthesized as described below.

43 ml of 1-buten-3-ol cooled and stirred to O″C
(500 mmol) and 49 ml (600 mmol) of dry pyridine distilled from garlic leaves were dissolved in 400 ml of dry diethyl ether distilled from Na, and 67 ml (600 mmol) of trichloroacetic acid chloride and 20 ml of dry diethyl ether (200 ml) were dissolved. It was added dropwise over a period of minutes. This results in a white suspension property of 3.5
After stirring for an hour, the mixture was poured into a dilute aqueous sulfuric acid solution (250 ml).The resulting organic layer was separated and the aqueous layer was extracted with diethyl ether. The extract and the organic layer were washed with an aqueous sodium bicarbonate solution and saturated brine, and then dried over magnesium sulfate. The dried product was distilled after removing the solvent using a rotary evaporator to obtain 1-methylallyl trichloroacetate (97.29, yield 89.4%) as a starting material. When we investigated the material data of this starting material, we found the following.

■...Rf (a.0.72 (hexane: ethyl ether = 1:1 (volume ratio)).

■-H'NMR (60MHz, CIJj4):
1.45 (d, 3H, J = 6.0H2, CH3),
5.0-6.2 (m, 4H, 0Cjj and olefin protons).

■-IR spectrum (neat): 1760.16
50.1245°990.920cm ■・B, P,: 82.5~85.5℃/21mmt
b+.

■--Synthesis of the photosensitive material of Example 5.

Next, from 1-methylallyl trichloroacetate synthesized as described above, 2,2-dichloro-3-chloromethyl-4-methyl-γ-butyrolactone, which is the photosensitive material of Example 5, was added to the photosensitive material of Example 1. It was synthesized using the same method as the material. The photosensitive material of Example 5 was obtained as a mixture of cis and trans forms (diastereomer mixture). Note that diastereomer 〇 and diastereomer D = 87:13. The data for each substance was as follows.

(Diastereomer C) ■...R, value: 0.42 (hexane:ethyl ether=1=1 (volume ratio)).

■-H'NMR (100MHz, CDC(13)
: 1.65 (d, 3H, J=6.4 H2, (:s)
l! 3), 2.90 (ddd, IH, J=5.4,7
．． 5,9. IHz.

C3)j), 3.74(dd, IH, J□7.5.I
2. IH2,C5H), 4.02(dd, IH,
J:5.4.12. lHz, C5H), 4.50 (d
q, IH, J=6.4゜9, IH2, C4)j)
.

■・= I3CNMR (25MHz, CDC(j3)
: C+ = 166.3, C280,1, C3=
60.0,C,・78.6,C5=38.8,C6
・19.4°C9 to C6 in each of the above NMR data
corresponds to carbon in the following structural formula (the same applies to diastereomer D below).

77.9, C3=54.8, C,=76.7, C5=
38.5, C6=+4.7°■-IR spectrum (CD
Cf13): 1800 (C=0 group), 1220m ■-IR spectrum (neat): 1800 (C
= O group), +220m ■... Elemental analysis C6H702C (13: Total N value (C
・３３． +3H・3.24. Cσ・48.91%)
, Analysis @(C・33.52.H・3.32.C(1
・48.07%).

(Diastereomer D) ■...R, @: 0.42 (hexane:ethyl ether=1=1 (volume ratio)).

■・-H'NMR (100MHz, CDCII: l
): 1.59 (d, 3H, J・6.8 H2, C
6)! 3), 3.42 (ddd, IH, J=5.3.
7.1.8.2Hz.

C3H), 3.81 (dd, lH, J・8.2.Il
, 6Hz, Cs! Ill, 4.01(dd, Ill,
, J=5.3. Il, 6Hz, C5)j), 5.00
(quintet, IH, J=7, IHz, C4H)
.

■=-”CNMR (25MHz, CDCl5)’:
C1=167.1, C2=<Example 6> As Example 6, 2,2-dichloro-3-chloromethyl-4-ethyl-γ-butyrolactone shown by the above formula (6) will be explained.

As a starting material for the photosensitive material of Example 6, 1-ethyl allyl trichloroacetate was used. The synthesis was carried out in accordance with the method of Example 5, starting from acid chloride. The substance data of the obtained starting material were as follows.

■...R, value: 0.69 (hexane/ethyl ether=]:1 (volume ratio)).

(6)-H'NMR (60MI-1z, cc9.+
): 0.98 (t, 3H, J=7.0H2, C)!
3), 1.78 (quintet, 2H, J=7
．． 0Hz, C)! 2), 5.00-6.2 (m, 4H,
OcH and olefin protons).

■-IR spectrum (neat): 1760.16
50,1245°990.910cm-' ■-B, P,: 68.2-78.5℃/16mmH
q.

■...Synthesis of the photosensitive material of Example 6.

Next, 2,2-dichloro-3-chloromethyl-4-ethyl-γ-butyrolactone, which is the photosensitive material of Example 6, is synthesized from the above-mentioned trichloroacetic acid vj-1-ethyl allyl to synthesize the photosensitive material of Example 1. It was synthesized by a method similar to that described above. The photosensitive material of Example 6 was obtained as a mixture of cis and jrans forms (diastereomer mixture).

In addition, diastereomer E: diastereomer F=92
: It was 8. The data for each substance was as follows.

dd, IH1J□4.6.7.8.9.2Hz, C3H
), 3.73 (dd, IH, J□7.8.I2.O
Hz, C5H), 4.01 (dd, IH, J=4.
6,12.0Hz.

C5) ri, 4.34(ddd, lH,, C3,3,8
,2,9,2t(z,C4)j).

■-13CNMR (25MHz, CDC(+3)
: C+=166.4, C2=80.3, C3257.4, C4283.0, Cs”3
9.0, C6=26.3, C? =9.4° Note that C5 to C1 in each of the above N-locked 8 dekes correspond to carbon in the following structural formula (the same applies to diastereomer F below).

○ (Diastereomer E) ■...R, @: 0.56 (hexane: ethyl ether = 1:1 (volume ratio)).

■...H'NMR (100MHz, CDC(+3)
:'1.11 (t, 3H, J・7, I H2, C?
j3), 1.5-2.3 (m, 2H, Cs+) I2),
2.96 (d ■ JR spectrum (neat):
1800 (C=O group), 1220 cm-' ■... Elemental analysis CtHe02C (L: +: Calculated value (C・36°32°H・3.92. rule・45.94%
), analysis value (C・36.75.8=4,+2.CQ=4
7.22%).

(Diastereomer F) ■...R, (a: 0.56 (hexane:ethyl ether 1.1 (volume ratio)).

■-H'NMR (lQOMHz, CDC(C3)
: 1.28(t, 31(, J□6.9 H2, C?H
3), 1.6-2.3 (m, 2H, CaH2), 3,5
3(ddd, 1ike 5extet, IH, J=4.
9,7.2.7.2Hz, C3H), 3.8-4.2
(two dd, 2H, J c+eminalO,
9Hz, Ca)+2), 4.79(ddd, IH, J
=4.5.7.2,9.9Hz, C4H).

■'-' 13CNMR (25MHz, CDC(13
): C+ = 167.2, C2=78.4, C
3=54.9, C,=82.0, C3=38.5,
C,=22.3,C,=IO,6.

■-IR spectrum (CDCII 3): 1800
cm-' (C□0 groups).

Example 7 As Example 7, a photosensitive material represented by the above formula (7) was synthesized using the same synthesis method as in Example 1 using trichloroacetic acid-1-isopropropane and luaryl as starting materials. The starting material was synthesized by a synthesis method starting from acid chloride in accordance with the method of Example 5.

Only the material data for the starting material, 1-inpropyl allyl trichloroacetate, are shown below.

■...R,i20.75 (hexane:ethyl ether = 11 (volume ratio)).

■・H'NMR (60MHz, CC11,):
0.97 (d, 6H, J=6.0H2, C(CH3)2
), 2.02 (sextet, IH, J=6.0Hz
, C(CH3)2CH), 4.8-6.2(m, 4H
,0Cji and olefin protons).

■・IR spectrum (neat): 1765.16
45.1245980.915.900cm-' ■・8. P: 60.0-60.5°C, / 4
mmh.

<Example 8> As Example 8, a photosensitive material represented by the above-mentioned formula (8) was synthesized using the same synthesis method as in Example 1 using methylallyl dichloroacetate as a starting material. Note that the starting material was synthesized by a synthesis method starting from acid chloride in accordance with the method of Example 5. Only the material data of the starting material, dichloroacetic acid 1-methylanor, is shown below.

The details are shown below.

■...R,@: 0.77 (hexane, ethyl ether 1.1 (volume ratio)).

■-H'NMR (60MHz, CCL):
1.37 (d, 3H1 = 6.0) 1z, cQ3) , 5
．． 0 to 6.2 (m, 3H, olefin proton), 5
．． 86 (s, IH, CHCQ2).

■・IR spectrum (neat): 1760.16
45.1280990cm-' ■-B, P, : 62.2-66.2℃/l Im
mHq.

Example 9 As Example 9, a photosensitive material represented by the above formula (9) was synthesized using the same synthesis method as in Example 1 using 2-cyclohexyl trichloroacetate as a starting material. Note that the starting materials are based on the literature (J, l'1. Qilmore etal J,
Chem, Soc, (cX 1971) p.
2-cyclohexene-1 by the synthesis method described in 2355)
-Synthesized from ol. The starting material, trichloroacetic acid-2-cyclohexyl...Rf(a・0.71 (
Hexane/ethyl ether 1] (volume ratio)).

■-H'NMR (60MHz, CCQ4): 1.
5-2.4 (br, m6H, -(CH2)3), 5
．． 40 (br, IH, 0cH), 5.7-6.4 (
m.

2H,n olefin proton).

■-IR spectrum (neat): 1760.12
40cm■-8,P: 70.5~72.0°G
/ 3 mmH9°Evaluation of each of the photosensitive materials of Examples 1 to 9 thus obtained was performed by using them as photosensitive materials of photosensitive compositions (resists). The results will be explained in the section of Examples of the second invention below.

Theory of Photosensitive Composition 8 Next, regarding an example of the photosensitive composition of the second invention of this application containing at least one kind of photosensitive material of the first invention represented by the above-mentioned general formula (I), negative-tone This will be explained using examples of positive type and positive type.

<Example of negative photosensitive composition> Marcene Resin M (Boisdoylphenol 1 molecule 318000, manufactured by Maruzen Petrochemical Co., Ltd.) 109 as a base resin and the photosensitive material of Example 1 (2,2 to dichloro3) -Chloromethyl-γ-butyrolactone) 39 was dissolved in 20 ml of ethyl cellosolve acetate, and this solution was dissolved in 0.2 um
A photosensitive injection composition (resist solution) was prepared by filtration through a membrane filter having pores.

Apply this resist solution to 3 inches (1 inch is approximately 2.54 cm)
) on a silicon substrate with a film thickness of I
A plurality of such substrates 18 were prepared in the same manner.

Then line and space (L/
A chrome mask having the test pattern of S) was successively adhered to these substrates, and the exposure time was changed for each substrate, using light with a wavelength of 220 to 280 nm from a CM250 cold mirror equipped Xe-Hq lamp. exposure was performed.

Each exposed substrate was developed by immersing it in a developer having a ratio of inamyl acetate/cyclohexane-372 (volume ratio) for 30 seconds, and then rinsed with cyclohexane for 20 seconds. Next, each substrate was subjected to a post-hake at a temperature of 100° C. for 1 minute using a hot plate.

Next, the film thickness of the resist remaining on each substrate is measured using a film thickness meter, and these film thicknesses are calculated as the initial film thickness (in this case,
), which indicates the film thickness immediately after pre-baking, was standardized to determine the normalized residual film rate. In Figure 1, the horizontal axis shows the exposure amount (m
It is a characteristic curve diagram in which the normalized film remaining rate (%) is plotted against the exposure amount, and the vertical axis is the normalized film remaining rate (%). As can be understood from FIG. 1, the photosensitive composition of this example had an exposure amount of 100% at IQ.
It has high sensitivity of OmJ/cm2, and its contrast value γ
It was also found that the value was as high as 3.

In addition, a sample for a scanning electron microscope was prepared from a silicon substrate exposed at an exposure dose of 150 mJ/cm2, and when the resist pattern formed on this sample was observed, it was found that the L/S was 0.35 um. I found that the image was clearly resolved.

Example of a positive-type photosensitive composition As the base resin, poly-α-methylhydroxystyrene (represented by the following formula (■), where n is a positive integer) was used instead of the above-mentioned Maruzen Resin M. A photosensitive composition (17-dist solution) was otherwise prepared in the same manner as in the above-mentioned Example of the negative-type photosensitive composition.

Next, this resist solution was applied to a plurality of silicon substrates in the same manner as in the above-mentioned Example of the negative photosensitive composition, and furthermore, each of these substrates was exposed to different amounts of light. However, as a light source, rF excimer laser (
The exposure amount was controlled by the number of pulses. Each substrate exposed in this way was treated with a metal-free developer (Toshiba McDermitt T).
RD51-50) for 70 seconds, washed with water for 30 seconds, and then post-haked at a temperature of 100°C for 1 minute.

Next, in the same manner as in the examples of the negative photosensitive compositions, a characteristic curve diagram of the residual film rate versus the exposure amount was prepared. Figure 2 shows its characteristic curve diagram. As can be understood from Figure 2, the negative resist of this example has a comparatively high E sensitivity (sensitivity at which the residual film becomes zero) of 200 mJ/cm2. It turned out to be expensive.

In addition, a sample for a scanning electron microscope was prepared from a silicon substrate exposed at an exposure dose of 320 mJ/cm2, and when the resist pattern formed on this sample was observed, it was found that L/S was 0.4 um. I found that even the bangs were clearly resolved.

Although the explanation is omitted here, the photosensitive compositions prepared using the photosensitive materials of Examples 2 to 9 also have the same resolution as the photosensitive compositions explained in the examples, although they differ in sensitivity. was gotten.

Further, the above-mentioned embodiments have been explained using examples in which only one of the photosensitive materials represented by formula (1) is contained in the photosensitive injection composition. However, α-halo γ- shown in formula (I)
Of course, it is also possible to use a plurality of butyrolactone derivatives together as photosensitive materials and to include them in the photosensitive composition.

(Effects of the Invention) As is clear from the above description, the photosensitive material of the first invention of this application exhibits high sensitivity particularly to light having a wavelength of 310 nm or less, and upon receiving such light, generates halogen radicals. is emitted and the polarity changes significantly. Therefore, if a photosensitive composition (resist) is constructed by using this photosensitive material together with a base resin having a crosslinking site, a negative resist can be obtained; A positive resist can be obtained by using these together to form a resist.

Further, according to the photosensitive composition of the second invention of this application, it exhibits high sensitivity to light with a wavelength of 310 nm or less, and
Since it is possible to obtain a pattern with an image line and a high aspect ratio, it is useful for phosphorography technology using an excimer laser beam, which has been attracting attention recently. In general, since the photosensitive materials according to the first and second inventions also react with other beams such as electron beams and X-rays, which have higher energy than deep ultraviolet rays, the photosensitive compositions according to the second invention It can also be used as a beam material or as a material for forming battens in lithography.

[Brief explanation of the drawing]

FIG. 1 is a characteristic curve diagram showing the relationship between the exposure amount and the residual film rate after development of a negative photosensitive composition of the second invention using the photosensitive material of the first invention; The figure is a characteristic curve diagram showing the relationship between the exposure amount and the residual film rate after development of the positive photosensitive composition of the second invention using the photosensitive material of the first invention. Patent applicant: Oki Electric Industry Co., Ltd.

Claims (5)

[Claims] (1) A photosensitive material characterized by being composed of an α-halo-γ-butyrolactone derivative represented by the following general formula (I) (However, in formula (I), at least one of X_1 and X_2 is a halogen atom. Furthermore, R_1 and R_2 are mutually the same or different groups selected from an alkyl group, an aralkyl group, an aryl group, an aryl group having a substituent, a haloalkyl group, and hydrogen, and these R_1 and R_2 together form a ring. Furthermore, at least one of R_3 and R_4 is a haloalkyl group, and the other is selected from an alkyl group, an aralkyl group, an aryl group, an aryl group having a substituent, a haloalkyl group, and hydrogen. and the R_3 and R_4
One of R_1 and R_2 may be integrated with one of R_1 and R_2 to form a ring. ). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (2) In a photosensitive composition containing a solvent, a base resin, and a photosensitive material, α represented by the following general formula (I) as the photosensitive material.
- A photosensitive composition characterized by containing at least one type of halo-γ-butyrolactone derivative (However, in formula (I), at least one of X_1 and X_2 is a halogen atom. Furthermore, R_1 and R_2 are an alkyl R_1 and R_
2 may be integrated to form a ring. Furthermore, R
At least one of _3 and R_4 is a haloalkyl group, and the other is a group selected from an alkyl group, an aralkyl group, an aryl group, an aryl group having a substituent, a haloalkyl group, and hydrogen, and the R_3 and One of R_4 may be integrated with one of R_1 and R_2 to form a ring. ). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (3) The positive photosensitive composition according to claim 2, wherein the base resin is an alkali-soluble base resin. (4) The negative photosensitive composition according to claim 2, wherein the base resin is a base resin having a crosslinking site. (5) In the photosensitive composition according to any one of claims 2 to 5, the content of the α-halo-γ-butyrolactone derivative with respect to the base resin is within the range of 5 to 50% by weight. A photosensitive composition characterized by the following.