JPS5868036A - Sensitizer for photoresist or radiation resist - Google Patents

Abstract

PURPOSE:To attain enhanced solubility in a polar solvent or an alkali soln., enhanced resist sensitivity or the like by using a specified bisazido compound as a sensitizer. CONSTITUTION:A bisazido compound represented by formulaI[where n is 0 or 1; X is -R<1>-OH, -COOR<2>, -SiR3<3>, -OR<4> or halogen (R<1> is lower alkylene; R<2> is H or lower alkyl; and each of R<3> and R<4> is lower alkyl); each of Y and Z is H, -N3, or -SO2N3, when Y is H, Z is -N3 or -SO2N3, and when Z is H, Y is -N3 or -SO2N3], e.g., the compound of formula II or III is used as a sensitizer for a photoresist or a radiation resist. A compound contg. -R<1>-OH (A) as a substituent X in formulaIhas enhanced solubility in a polar solvent. A compound contg. -COOR<2> (B) has enhanced solubility in an alkali soln. A compound contg. -SiR3<3> (C) results in an increased adhesive property to a semiconductor substrate. A compound contg. -OR<4> (D) has enhanced solubility in a polar solvent and enhanced compatibility with a polar polymer. A compound contg. halogen (E) results in increased radiation sensitivity and enhanced resist sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bisazide photosensitizer for use in negative type photo or radiation resists.

Compounds that are credibly related to the photosensitizers of the present invention include those described in U.S. Pat. No. 2,940,853;
6-bis(p-azidobenzylidene)cyclohexanone, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone or U.S. Patent No. 374971
2゜6-bis(p-azidobenzylidene)-4-hydroxyclohexanone, 2,6-
Examples include bis(p-azidocinnamiiden)-4-hydroxychlorohegisanone, which differs from the present invention in the difference in the substituent at the 4-position (X) of the compound represented by the general formula CI of the cyclohexanone ring. ing.

In the field of microfabrication technology in the semiconductor industry, bisazide compounds are usefully used as photosensitizers in photo or radiation resists used to form fine patterns. With the rapid progress of the semiconductor industry in recent years, a wide range of functions have been developed in the production of photoresists1.
First of all, bisazide compounds are used in rubber thread photoresists such as poly-11 isoprene and poly-11 butadine due to their solubility in organic solvents and compatibility with base resins. Use was limited.

The second group of compounds cited above is one that has been added to the above-mentioned bis 52 compound from the point of view of solubility.
- Significantly low yield of hydroxycin clohexanone from commercially available raw materials (165%, D, E Emmertand
D, Lednicer, orB, Prep,
Procedl., 1(2), 127-129(19
69) There were problems with practicality.

In this case, the following improvements in Q or properties are desired for the currently used bisazide compounds.

Development with an alkali aqueous solution is known as an effective method for forming fine patterns because it causes little resist swelling, but this dust-producing method cannot be used because a bisazide compound has poor bath properties compared to an alkali aqueous solution. I can't.

Father, the adhesion between the semiconductor substrate and the resist is the element microbar 11.
It is a property that is desired to be improved because it plays an important role in the first step of processing, but the functional bis-recipitate compound has the following properties:
Since it has poor interaction with the i-surface (inorganic), it makes little contribution in terms of adhesiveness.

Bisazide compounds are sensitive not only to light but also to radiation, but this is due to their low energy absorption efficiency. Resists have low sensitivity when used.

The object of the present invention is to provide a photosensitizer for radiation resists that eliminates the drawbacks of the above-mentioned bisazide compounds.

As a result of intensive studies to achieve the above objectives, we found that the general formula % -3iR;, -OR', halogen (R lower arykylene group, R2 is hydrogen or lower alkyl group, R5, Rt are lower alkyl Y and Z represent hydrogen, -N, or -3o2N, and when Y is hydrogen, 1ff-N, nu is -3o2N, and when Z is hydrogen, Yfl- N3 or 1d-3o2N. It was discovered that the bisazide compounds represented by the following formula can be used as photosensitizers for photo or radiation resists that meet the above-mentioned individual objectives depending on the difference in the substituent X, and these were synthesized.

The present invention will be explained in detail below.

When the substituent X is -R'-OH (where R1 represents a lower alkylene group), a polar hydroxyl group is introduced into one molecule, so the compound CI
) in polar solvents is significantly improved. In this case, CI) is a primary alcohol, so if X = -OH, which is a secondary alcohol, it becomes more polar,
The solubility in polar solvents is greatly improved, and the compatibility with polar polymers is also reduced.As a result, the base plate 117 for photo or radiation suppression can now be selected from a wide range including polar polymers. .

When the substituent X'f-COOH is used, an acidic group is introduced into the molecule of the bisazide compound, so that the solubility in an alkaline aqueous solution increases. Therefore, the alkali 11 development, which has been problematic with conventional photoresists using bisazide compounds, has become extremely easy with the use of this compound.

When the substituent X is -3iR: (where R3 represents a lower alkyl group), the interaction with the inorganic substance underlying the substrate is increased compared to the bisazide compound consisting only of organic components, so it is not exposed to light. The adhesiveness of the resist used as the agent to the semiconductor substrate is significantly the same as above.

Since the substituent X is 10R4 (however, R'fl represents a lower alkyl group) and a polar methoxy group is introduced into one molecule, Improves solubility in polar solvents and compatibility with polar polymers. However, compared to the case where X is a hydroxyl group, the effects tend to be slightly lower in all of the above characteristics.

However, the yield of the precursor is extremely low even though the present compound has a large percentage value, and from an industrial perspective, the effect is extremely large. That is, the precursor 4-methoxycyclohexanone can be obtained from P-methoxyphenol with a high yield of 70% or more by hydrogenation and chromic acid oxidation.

# When the substituent X is a halogen, unlike conventional bisacyto compounds, the atomic group that makes up the molecule contains a high-density halogen. Radiation radiation absorption efficiency increases - "Ru. This fcW>
When JZ3 is used as a sensitizing agent for irradiation, the radiation sensitivity is increased and the irradiation sensitivity is improved compared to that containing no halogen.

Below, the 1R-benzened compound provided by Kimiaki Kizu and its synthesis method will be explained with reference to Examples.

Example 12.6-di(4'-azidobenzal)-4-hydroquinemethylen clohexanone ttE, jung,
The method of R, W Brown et al. (Tetrahadro
nLet, t,, 2771-2774 (1978))
1 g of 4-hytrogine methylun clohegizanone synthesized according to the method.

3 i 'x 10 m of ethanol dissolved in 10 m of ethanol, 0.49 sodium hydroxide II
04ml(1)/KM fc4 V L fc solution w175ii- was added thereto, and the mixture was allowed to react in a brown flask at room temperature for 2 days. The L fc crystals were collected by suction, washed with ethanol, and then recrystallized from ethyl cellosolve to give yellow crystals with a decomposition point of 145-155°C (differential thermal analysis, heating rate 5°C/m1n). 05I was obtained. This product was confirmed to be the title compound by spectral analysis, and infrared absorption spectrum data and elemental analysis values characteristic of the structure of the product were shown below 0. Infrared absorption.

16oocm' (\C=O), 2130cm' (N3
). Element / Analysis” Calculated value as 21H1802N6: C
,65,3;H.

4.7; N, 21.8 Empirical value: C, 65.5; H, 4,
7; N; 22.0° 2.6-di(4'-7didobenzal)-4-hydroxyl The product showed more than 6 times the solubility in methyl cellosolve compared to clohexanone.

Actual ts Example 22.6-di(4'-azidocinnamylidene)
-4- and Droxymethyl cyclohexanone 4-Hydroxymethyl i Noglohexanone 12゜Bara 7 Didocinnamate Altehy)' 3.5 g, 1.IIium hydroxide 7052, water in a suspension consisting of 15 m2 of ethanol. A solution consisting of 0.8y was added and stirred at room temperature for 2 days in a brown flask. The formed gauze crystal was filtered through a suction port, washed with ethanol, and then recrystallized from ethyl cellosolve with a decomposition point of 160-165°C (differential thermal analysis, heating rate 5°C/m1n). Orange crystal 0.6, q'
ltr, j. Spectral analysis revealed that this product had the title H.
0 infrared absorption to confirm that it is a compound of No. 1: 160
0cm' (\C=O), 2150cm' (-N
3).

/ Elemental analysis” Calculated value as 2SH2202Nd: C,
68,5; H, 5, Oi N , 19. 2
'4ノ; f test i @: C, 68, 7; H, 4
,7; 0 Implementation fl13 2,6-di(4'-7,dobenzal)-4-carpogynornoglohexanone 4-methquine carbonylcyclohexanone 52° paraazidobenzterdehyde 1011 was dissolved in 50 mA ethanol, A solution of 2 tons of sodium hydroxide dissolved in 4 m2 of water was added and refluxed for 6 hours in a brown flask. The crystals generated by filtration through the suction port were collected, and then treated with dilute hydrochloric acid several times, washed with zero water, and then recrystallized from methanol with a decomposition point of 150 to 155°C (differential thermal analysis, heating rate). 5℃/m1n) yellow-orange crystals t e 1
y,, (particularly 0) This product was confirmed to be the above compound by spectral analysis, elemental analysis, and colorimetric test of carboxyl group with bromothymol blue. Infrared absorption: 1600 cm'("C= 0), 2130cm'
(-N5). Element/ Analysis ゛C21H460, Calculated value as N6: C, 63
,[l;H.

4.0; N, 2 +, o, actual value: C, 62,
6;H,3,9;H,20,6゜Example 42,6-di(
4'-azidocinnamylidene)-4-carboxylcyclohexanone 4-methoxycarbonylcyclohexanone 12, paraazidocinnamaldehyde 2y', r10J2
'fR shorefL, 0.4 p(7)Na to the ethanol 7Nol
The bath solution was added to 4 mR of OH water and reacted in a brown flask at 50°C for 6 hours. A portion of the crystals generated in U was collected through a suction port, and then treated with dilute hydrochloric acid several times. After washing with water, the cellosolve was recrystallized with a decomposition point of 165-170°C (differential thermal analysis, temperature increase,
+l += 5℃/m1n) orange crystal 031? 0%
This product (rl svegtol fraction analysis, 9-element analysis, bromothymol blue 1-color test shows that it is the compound listed in the list).
'(ゝc=o).

/2140cm-'(-N5). Elemental analysis C2, H2o
31 p“11 white C,66, as O3N6
4; H, 4, 4; dimensions, 18.6. Actual IP
C.

59.9: H, 4, 5; N, 18.2° Implementation A row 5 2
．． 6-,/(4'-azidobenzal)-4-carboxylcarbonylcyclohexanone In Example 5, 2,6-di(4'-azidobenzal)-4-carboxylcarbonylcyclohexanone 0.81 was added to 10 mR of ethanol to make a suspension. Next is Hatake sulfuric acid? A few drops were added and then refluxed for an hour. After cooling, the obtained crystals were filtered through a suction port, washed with water, and then recrystallized from alcohol to give a yellow-orange color with a decomposition point of 150-155°C (differential thermal analysis, heating rate 5°C/m1n). Crystals of 0.5 f'lax were obtained. This product was confirmed to be the compound mentioned above from spectral analysis. Infrared absorption 1595cm'
('C-0), 2140cm' (-N5). Elemental analysis' C27H2405/ Profit value as N C,67,5,H,5,O;N,1
7.5゜ Actual value: C, 67,3; H, 4,9; N, 16
．． 9゜Example 62,6-di(4'-azidobenzal)-
4-Trimethylsilylcyclohexanone 4-trimethylsilylcyclohexanone 17t.

Dissolve paraazidobenzaldehyde in 22#'& 100n12 of ethanol, add 1 t of sodium hydroxide to 11 mR of water and react for 2 days at room temperature in a brown flask, and pass through the R0 suction port. The formed crystals were collected for a while, recrystallized from a mixture of ethanol and ethyl cellosolve, and decomposed at 145-150°C.
(differential thermal analysis, heating rate 5°C/m1n) yellow crystal 4
．． 29''; 0 at f7i° This product was confirmed to be the compound listed above through spectral analysis and elemental analysis. Infrared absorption: 1600 cm' (C=0), 2
130aml'/ (-old). Elemental analysis Calculated value as C, H24ON6S engineering.

C, 64,5; H, 5, 6; N, 196, Experiment I: C, 64, 7; H.

5.2; N, 19.5° Example 72.6-di(4'-azidocinnamylidene)-
4-Triphthylcyclohexanone 4-Trimethylsilylcyclohexanone To a suspension consisting of 152゜ azidocinnamic aldehyde 2.5y and ethanol 15m2 was added a solution consisting of sodium hydroxide and 2yt water 049, in a brown flask.12 at room temperature. A woman who stirred for two days. The formed crystals were filtered through a suction port, washed with ethanol, recrystallized from ethyl cellosolve and decomposed, yielding orange crystals of 1.165-170°C (differential thermal analysis, heating rate 5°C/m1n). 042 was obtained. This product was confirmed to be the compound mentioned above by spectral analysis and elemental analysis. Infrared absorption: 159
5cm' (ゝC=0), 2150cm'(-
N,).

/ Elemental analysis ゛Calculated value as C27H28ON6S1: C
,67,5iH,5,8;N,17.5. Experimental value C,
67,4,H,5,7:N.

172゜Example 82. 6-di(4'-azidobenzal)-4-methoxine clohexanone 10# of 4-methoxycyclohexanone and 30# of baraazidobenzaldehyde in 100 mf of ethanol! .

A solution of 1 t of sodium hydroxide dissolved in 71 nJ of water? The mixture was then allowed to react in a brown flask at room temperature for two days. Separation of the crystals generated by the suction port IIY,
After washing with ethanol, remove 1 liter of FS Mr□ from ethyl cellosolve. 1I (y:, i 145-150°C (differential thermal analysis, Y1 temperature 5°C/nn1n) yellow crystal 471
Get it.

This main component was identified by spectral analysis and elemental analysis.
'x 1m: W2 0 infrared absorption 1600cm'-'(\[:=O), 2130cm
'(-N3). Elemental content/(Blue) C21H1802N6 calculation: C
,65,3;H,4,7;N,21.8. Experimental value C,
65,1; H, 4,7; N, 21.5° Example 92.6
~Di(4'-azidocinnamylidene)-4-methoxy 7 to xanone 4-methoxin chlor to xanone 1! IJY from 05t of sodium hydroxide and 08g of water to Kenshu 1+ consisting of 35F of roseazide cinnamic aldehyde and 15mρ of ethanol.
RuMU? After stirring in a brown flask for 2 days, crystals were formed. After 17 filtration of suction, the fraction was collected, washed with ethanol, and then recrystallized from ethyl cellosolve.
I,',, i + 65 170°C (differential thermal analysis method).

Orange crystal 051 was obtained at a heating rate of 5°C/m1n).This product was confirmed by spectral analysis to be the same compound as described above. Infrared absorption.

1100cm' (-0CHx), 1600cm (/
C=0).

2150 cm' (-Na). Elemental analysis' C25H
2202N/, calculated value as C,68,5iH
,5,OiN,19.2. Experimental value.

C, 68,1; H, 4,8; N, 19.0° Example 10
2.6-Di(4'-azidobenzal)-4-chlorocyclo-xanone 4-chlorocyclohegizanone 1f, barazidobenzaldehyde 3tr Dissolved in ethanol 10mβ, 0.1f
Add a solution of sodium hydroxide dissolved in 0.1 ml of water, react in a brown flask at room temperature for 2 days, remove the formed crystals by filtration with zero suction, and wash with ethanol. Recrystallized from the mixed solution with a decomposition point of 145-150°C (differential thermal analysis wide, contract temperature rate 5
℃/min) Yellow crystals 5 0 filtration 11 r ft a This product was subjected to Bayrunutain test (positive result was IC) and spectral analysis was conducted to confirm that it was a compound. A voice. Infrared absorption 1
595 cm' (, c=o), 2 Gem' (-
N3).

'Example 11 2,6-di(4'-azidobenzal)-
4-butomonk [J-\xanone 4-)゛omo7ri [1 Dissolve 1g of hexane and 33% of barazidobenzaldehyde in 10mR of ethanol, 012
Sodium hydroxide 4 Y o, 1 mρ dissolved in kC solution? The mixture was added and reacted for 2 days at room temperature in a brown flask. The crystals generated by filtration through the suction port were removed, washed with ethanol, recrystallized from a mixture of ethanol and ethyl cellosolve, and decomposed, giving a yellow color of +j, 5140150°C (differential thermal analysis, rate of increase 11.1 5°C/m1n). crystal 031
'l? 'j ft: 0 This product was found to be a compound of ElytLMe in the Pailungutaine test (positive) and spectral analysis.
60Dcm'°16 (\C=O), 2130cm' (-Ng).

/ As described in detail above, the present invention provides a photo or radiation resin material with significantly improved properties such as solubility in polar bath agents, alkaline developability, contact with inorganic square substrates, and radiation sensitivity. Photosensitizer? I was able to provide it.

Continuation of page 1 @From Yokono Junior High School 292 Yoshida-cho, Totsuka-ku, Yokohama Production technology research company Hitachi, Ltd. Inside the office @Publisher Tokio Isogai 292 Yoshida-cho, Totsuka-ku, Yokohama Production technology research company Hitachi, Ltd. Inside the office Q) Initiator Mitsumasa Kojima Hitachi 4-13-1 Higashimachi, Hitachi City Kasei Kogyo Co., Ltd. Yamazaki Factory 0 applicants Hitachi Chemical Co., Ltd. 2-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 1 210-

Claims (1)

[Claims] General formula % -8iR5, -OR', halogen (R1 is a lower argylene group, R2 is hydrogen and a lower argyl group, R', R'
represents a lower argyl group. ), the group selected from Y. Z represents hydrogen or -N, N represents -3o2N, l, Y
is 11 for hydrogen, -N for Z, -3O2N for N,, Z
When is hydrogen, Y is -N or -3O2N. ] A compound represented by! Four Nu, selected from IT, was optically polished to Sharay resist II. 2 General formula CI), R1 is -CH2-, R2 is -CH, hydrogen is -C2H5, R', R' is -CH,
The photosensitizer for photo- or radiation resists according to claim 11, wherein the halogen is Br or C2.