JPS60168144A - Peeling soluting composition - Google Patents

Abstract

PURPOSE:To provide a resist peeling soln. compsn. superior in peeling performance by incorporating a nonionic fluorinated surfactant in an org. solvent. CONSTITUTION:A nonionic fluorinated surfactant is an oil-soluble fluorinated compd. capable of lowering the surface tension of an org. solvent, and the following cmpds. can be enumerated: C9F19CONHC12H25, C8F17SO2NH(C2H4O)6H, C9F17O(''Pluronic L-35'')C9H17, C9F17O(''Pluronic P-84'')C9F17, and C9F7(''Te tronic-704'')(C9F17)2. As the org. solvent, a good solvent for a polymer to be used as an essential component of a resist is optimal. This peeling soln. composn. can peel resists obtained by photocross-linking negative type photoresists made of natural rubber, polyisoprene, polybutadiene, etc., and positive type photoresists composed essentially of alkali-soluble resins, such as novolak resins.

Description

[Detailed description of the invention] The present invention relates to a resist stripper composition.

Resists are used in metal processing and integrated circuit manufacturing due to their chemical and plasma resistance, and their materials include, for example, cyclized materials such as natural rubber, polyisoprene, and polybutadiene. There are negative-working photoresists, which contain negative photoresists, and positive-working photoresists, whose main component is alkali-soluble resins such as novolac resins.

These resists must be removed after exposure, development, baking, and etching processes in lid metal processing and integrated circuit manufacturing, and research has been conducted on stripping solutions for this purpose, and many patents have been filed. I'm sheltering you. For example, exfoliation IVL (Special Publication No. 41-2
Publication No. 369, Publication No. 41-2370, Publication No. 45-12
No. 925, No. 46-5961), stripping liquids mainly containing alkyl glycols and alkyl ethers (Japanese Patent Publications No. 7695-1980, No. 45-2524, No. 46-18922), dodecylbenzenesulfone A stripping solution mainly containing an acid (Japanese Patent Application Laid-open No. 72503/1983, US Pat. No. 3,582,401) is known.

When removing a resist obtained by photo-crosslinking a negative photoresist whose main component is a natural rubber compound or a polyisoprene compound using the conventionally proposed stripping solution as described above, the processing temperature is 120 to 130℃. It must be heated to a relatively high temperature, for example, at 110° C. for 10 minutes or less, and peeling is difficult, resulting in problems in terms of safety and courtesy.

The stripping solution conventionally proposed by Equation et al. has a problem in that its stripping ability is relatively low and that part or all of the stripping solution must be replaced frequently.

Furthermore, the stripping solution described in the above-mentioned patent has the drawback that it cannot strip a resist that is photocrosslinked and crushed by a photoresist containing a polybutadiene cyclized product as a main component. The present invention was made against the background of these conventional technical problems, and involves photo-crosslinking a negative photoresist whose main component is a natural rubber cyclide or polyimprene cyclide, and then peeling off the resist at a relatively low temperature. To provide a stripping liquid composition that has excellent stripping ability and that can strip and apply +1 pressure to a resist obtained by photo-crosslinking an I-Ga type photoresist containing a polybutadiene cyclized product as a main component. The purpose is to

That is, the present invention provides a stripper composition characterized by comprising an organic solvent containing a nonionic fluorosurfactant.

In the present invention, the nonionic fluorine-based surfactant is an oil-soluble fluorine compound that has the effect of lowering the surface tension of organic solvents, such as C2F1. C01 insect Cl2H2
,,C3F17So2NH+C2H40+6H9C2F
170 (Pluronic L-35) C21li”1.
.

C2F17S (Pluronic P-84) C9F17
.

C,F, <Tetronic-704) (C,Fl,)
2. (Here, Pluronic L-35: Polyoxypropylene (50%) manufactured by Asahi Denka Kogyo Co., Ltd.
-shiy (50%) block polymer, average molecular weight 19
00; Pluronic P-84: Asahi Denka Kogyo Co., Ltd. Polyoxypropylene (60%) - Polyoxyethylene (
40%)・Block polymer, average molecular weight 4200; Tetronic-704: Asahi Denka Kogyo @tm N-N-N'-
1-tetrakis (polyoxypropylene-polyoxyethylene block polymer) ethylene diamine, polyoxyethylene content in molecule 40% by weight, average molecular weight 500
It is 0. ) such as CnF2n+1X)1 (where n is an integer from 4 to 25, X is C0NH, 5O21'JH, 50
2NR2゜() (7' Ruronic) or (Tetronic) 几2゜几1 and R2 are CtH2z-HI CKF
+1 or ((gH2JU +-r) IH, L,
K is an integer of 4 to 25, J is an integer of 2 to 4, m is 2 to 2
o is an integer. ) can be mentioned.

In addition, Surflon S-382 and 5C manufactured by Asahi Glass Co., Ltd.
-101, F-TOP EF-122 manufactured by Shinjuyou Kasei Co., Ltd.
B, Florado FC-4'3 manufactured by Resident 3M C Co., Ltd.
0 and FC-431.

The proportion of the nonionic fluorine-based surfactant to the total amount of the stripping solution composition is o, o o i to 5o wt%, preferably 0.005 to 40 wt%, and if o,oo is less than 1 wt%, the present invention The stripper composition has a poor resist stripping effect, and on the other hand, even if the amount exceeds 50M, the stripping effect does not increase proportionally, and it is not economical.

→-/Pmtm 朶客+l Ll Inoto 1 H・-ri to small key 1 A good solvent of polymer is optimal, for example 0-
Halogenated hydrocarbons such as dichlorobenzene, α-chlornaphthalene, and tetrachloroethylene, aromatic hydrocarbons such as xylene and impropylbenzene, carbonyl compounds such as acetone, methyl ethyl ketone, methylseron lubacetate, and ethylseron lupacetate, N-
A nitrogen-containing compound such as methyl-2-pyrrolidone or N-vinyl-2-pyrrolidone is used, and the proportion of the total weight of the stripper composition is preferably 10 to 99.99% by weight, particularly preferably 20 to 99.95% by weight. %.

The stripping liquid composition of the present invention is further mixed with at least one compound selected from the group of phenols, sulfonic acids, sulfuric esters, and phosphoric esters to remove resists; The effect can be further enhanced.

Here, examples of phenols include phenol, 0-cresol, m-cresol, P-cresol, and α-nactol-β-naphthol 3)'-&.

Examples of the sulfonic acid include alkylarylsulfonic acid, alkylsulfonic acid, phenolsulfonic acid, amide-bonded sulfonic acid, and ester-bonded sulfone tR, but alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid and stearylbenzenesulfonic acid or phenol Sulfonic acids are preferred.

The sulfuric acid acid ester is one having -0S (J, H), and includes sulfuric esters of higher alcohols, ester-bonded sulfuric esters, and the like.

Phosphoric esters are those represented by the general formula PO(0几)2 or PO(0几)((JH)2,
Particularly preferred is a polyoxyethylene alkyl (aryl) ether phosphate represented by the general formula C, where I is an alkyl group or an alkylaryl group, A is an aqueous or aqueous group, and n is the number of moles of ethylene oxide added.

These compounds may be used alone or in combination in the stripping solution composition of the present invention, and their proportion to the total amount of the stripping solution composition is 0 to 80% by weight, preferably 0 to 70% by weight, particularly preferably 0 to 70% by weight. ~60% by weight.

In order to strip a resist using the stripping solution composition of the present invention, the stripping solution is heated to, for example, about 90 to 1"C, and the substrate with the resist to be stripped is immersed in it. do it.

As described above, the stripper composition of the present invention comprises: 1) natural rubber;
It is possible to remove resists in general, such as photo-crosslinked negative photoresists whose main components are cyclized products such as polyisoprene and polybutadiene, and positive photoresists whose main components are alkali-soluble resins such as novolac resins.

11) The peeling treatment conditions are also 90 to 110 when peeling a resist obtained by photocrosslinking a negative photoresist whose main component is a cyclized product of natural rubber or polyisoprene, or a positive photoresist whose main component is a novolac resin. ℃
Peeling is possible in a short time at a processing temperature of .

111) The stripping ability is superior to that of previously proposed stripping solutions.

It is also superior to conventional stripping solutions.

The present invention will be explained in more detail below with reference to Examples.

Example 1 Cis-1,4-polybutadiene cyclized product (cyclization rate 65%,
[η] = 0.45 dt/y) and 2,6 as a photocrosslinking agent.
- 3% by weight of bis(4-azidobenzal)cyclohexanone and 2,6-p-f-p- as a stabilizer.
A xylene bath solution of a negative photoresist containing 1% by weight each of cresol and phenyl-α-naphthylamine was prepared. This hemolysis was applied onto a silicon wafer, a fine pattern was baked with ultraviolet light, and after development, heat treatment was performed at 150° C. for 60 minutes to form a resist pattern.

0-dichlorobenzene 60y, tetrachlorethylene 3
A stripping solution composition consisting of O and a nonionic fluorosurfactant (EF-, 122B, manufactured by Shin-Akita Kasei C Co., Ltd.) 3P was heated to 130°C, and a wafer having the resist pattern obtained above was heated. When immersed, the resist could be completely removed in 5 minutes.

Example 2 The same process as in Example 1 was performed except that a photoresist mainly composed of polyimprene cyclized product (C11 (,701) manufactured by Japan Synthetic Rubber Co., Ltd.) was used, and the stripping liquid composition was heated to 11Q°C. The resist could be completely removed in 1 minute.

Example 6 As a stripper composition, polyoxyethylene alkylaryl ether phosphate ester (Plysurf A-212E, manufactured by Daiichi Kogyo Seiyaku C Co., Ltd.) 301, and a nonionic fluorine-based surfactant (Shin Akita Kasei Co., Ltd.) were used. ) made by EF-122B)
When treated in the same manner as in Example 2 except that a mixed solution of 50 y of 3F and O-dichlorobenzene was used, the resist was completely removed in 5 minutes at 110° C. with the stripping solution composition.

Example 4 As a stripper composition, 0-dichlorobenzene 50F, tetrachloroethylene 50y, and a nonionic fluorine-based surfactant (EF-122A manufactured by Shinjuyo Kasei Co., Ltd.) 3
When treated in the same manner as in Example 1 except that a mixed solution of Y- was used, the resist was completely removed and the resist was removed in 15 minutes at 130° C. with the stripping solution composition.

Example 5 U-dichlorobenzene 40y1 as a stripper composition
Tetrachloroethylene 10y, stearylbenzenesulfonic acid 101-U-cresol 15F and nonionic fluorosurfactant (Shin Akita Kasei C Co., Ltd.) EF-122
B) When the same treatment as in Example 2 was carried out except that the mixed number of 2F was used, the stripping liquid composition was able to completely strip the resist in 1 minute at 110°C.

Example 6 Except for using a mixed solution of 50 y of 0-dichlorobenzene, 1 y of tetrachloroethylene, 5 y of dodecylbenzenesulfonic acid, and 3 y of a nonionic fluorine-based surfactant (S-382 manufactured by Asahi Glass Co., Ltd.) as the stripper composition. ,
When treated in the same manner as in Example 2, the stripper composition was able to completely strip the resist at 90° C. in 1 minute.

Example 7 As a peeling liquid composition, 0-dichlorobenzene 50y,
'7'-) dichloroethylene 20F, 0-lyl/sol 20F-dodecylbenzenesulfonic acid io, p and C
2F1. The process was carried out in the same manner as in Example 2, except that a mixture of nonionic fluorosurfactant 1F was used.
The resist could be completely removed in 1 minute using Matato's stripper composition. Even when 100 2-inch diameter wafers with resist patterns were processed, no decrease in stripping ability was observed. Ta.

Example 8 As a stripper composition, 0-dichlorobenzene 6oj,u
-Cresol 20F and stearylbenzenesulfonic acid 20y08F17S02NH+C2H4 [with] 1'' A mixture of nonionic fluorosurfactant 1y was used, but the same procedure as in Example 2 was used. The resist could be completely peeled off in 1 minute at 90°C. Example 9 Alkali-soluble novolak resin 4.3°, 2.3° 4-
Trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone p-triester was dissolved in 0.7 y of ethyl seron lupacetate 151 to prepare a positive resist solution.

This solution was applied onto a silicon wafer, a fine pattern was baked with ultraviolet rays, and after development, heat treatment was performed at 150° C. for 1 hour to form a resist pattern. When treated with the same fine stripping composition as in Example 8, the stripping liquid composition was heated to 90°C.
The resist could be completely removed in 1 minute.

Example 10 As a stripper composition, 20 y of U-dichlorobenzene, 5 y of tetrachloroethylene, 30 y of O-cresol, and m2 y of phenolsulfone were used.

The stripping solution was treated in the same manner as in Example 2, except that a mixture of stearylbenzenesulfonic acid 25F and a nonionic fluorosurfactant (Florard I!'C-43111P manufactured by Jujutsu 3M Co., Ltd.) was used. The composition is 9
The resist could be completely peeled off in 1 minute at 0°C.

Example 11 As a stripper composition, U-dichlorobenzene 4oy, O
-Cresol 30y, dodecylbenzenesulfone ra3
oy and nonionic fluorosurfactant (C, F'1
．． (J<Pluronic P-84) C2F17; Pluronic p-s4: Asahi Denka Kogyo Co., Ltd. Polyquinepropylene (60%) - Polyoxyethylene (40%)
Processing 1-1 was carried out in the same manner as in Example 2 except that the mixed solution of block M coalescence 10.1y was used. Comparative Example 1 In Examples 1 to 11, it was not possible to peel off the "C resist" under the same conditions using a peeling agent to which a nonionic fluorine-based surfactant was not added.

Comparative Example 2 In Example 7, the resist could be removed by processing for 1 minute at 120°C using a removal solution to which no nonionic fluorosurfactant was added, but this removal pj
When 30 wafers with a resist pattern of 2 inches in diameter were processed with the W solution, there were some areas where the wafers could not be peeled off.

Patent Applicant: Japan Synthetic Rubber Co., Ltd., Agent, Patent Attorney: Shigetaka Shirai Procedural Amendment (Voluntary) July 3, 1972 Commissioner of the Patent Office Wakasugi Wainu 1, Indication of Case 1980 Patent Application No. 022780 2. Name of the invention @ synergic composition 3. Relationship with the case of the person making the amendment Patent applicant address 2-11-24 Tsukiji, Chuo-ku, Tokyo Name (4)
17) Japan Synthetic Rubber Co., Ltd. Representative Hisashi Yoshimitsu 4, Agent Postal code: 107 Address Valle Royale Akasaka No. 1 315, 2-17-54 Akasaka, Minato-ku, Tokyo "Detailed description of the invention" in the specification Column 6, Contents of the amendment (1) Change the term “courtesy” in the first line of page 3 of the specification to “
Utility”.

(2) "1, etc." on page 5, lines 1 to 7 of the specification.

1. Compounds can be mentioned. ” is corrected as follows.

"CI such as F tn++ X R' (where n is an integer from 4 to 25, X is -CONH-, -3OzNH-.

-SO□NR"-, -0-(Pluronifuku)- or-
(tetronic) R2, RI and R2 are -(4Hz1
++, C*F z*+r or one+CjH2,O+,
H and N are integers of 4 to 25, j is an integer of 2 to 4, and m is an integer of 2 to 20. ), and a nonionic surfactant consisting of a compound represented by , methyl group or methyl trifluoride group, R4 is a hydrogen atom, a fluorine atom, a methyl group, a methyl trifluoride group, +Cb Htb O+ a
H or -C, Ho, i, 4 R5 is a hydrogen atom, a fluorine atom, a methyl group, a methyl trifluoride group, 4 C* Hz
90 + h Hl Ci Hz (i-p) or 1, +
CqHzaO+ r, cgFz(s-t)++ or CuH! (u-v) CyFz(y-*+++s X is 10- or -COz-1m' and d' is 0 or 1
,b.

g and q are 2, 3. or 4, d, h and r are 0
or an integer from 1 to 20, e, i and U are O or 1 to
23 integer, f is 0 or an integer from 1 to e/2, p is 0 or an integer from 1 to i/2, V is O or an integer from 1 to u/2, S and y are 4 to 20. , t is O or an integer of 1 to s / 2, 2 is 0 or an integer of 1 to y / 2), and R5 is a hydrogen atom,
A repeating structural unit that is a fluorine atom, a methyl group, or a methyl trifluoride group (hereinafter referred to as rA-IJ), R5 is + C
9H290+h H- or -Ct Hz (i-p)
+1 repeating structural unit (hereinafter referred to as rA-2J)
and repeating structural units other than (A-1') and (A-2) (hereinafter referred to as rA-3J) account for 0 to 70%, 0 to 70%, and 1% of the total repeating structural units in the polymer, respectively.
It is present in a proportion of 0 to 100% and has a number average molecular weight of 500 to 500.
10,000, a nonionic fluorosurfactant consisting of a polymer having a molecular weight of 10,000. "that's all

Claims (1)

[Scope of Claims] 1. A stripping liquid composition comprising an organic solvent containing a nonionic fluorosurfactant. 2. Claim 1 comprising at least one compound selected from the group of phenols, sulfone e, sulfur acid ester 2, and phosphorous ester.
The stripping liquid composition described in Section 1.