JPS58160348A - Photo- or radiation-sensitive polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn, capable of forming a coating film which is highly sensitive and has excellent shelf stability and heat resistance, consisting of a polyamic acid, a functional group-contg. compd. and a quinonediazide compd. CONSTITUTION:A polymer (A) having repeating unit of formulaI, II or III (wherein R<1>, R<3> are each a trivalent or tetravalent org. group; R<2>, R<4>, R<5> are each a bivalent org. group; n is 1,2) such as a polyamic acid obtd. by reacting pyromellitic dianhydride with 4, 4'-diaminodiphenyl ether, a compd. (B) having a hydroxy group (or an arom, amino group) and an amino group such as a compd. of formula IV, and a quinonediazide compd. (C) such as p- 3-(N, N- dimethylamino)-propyloxy phenol are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to novel light- or radiation-sensitive plastic composite compositions.

Conventionally, photosensitive orthoquinone diand or 5-toquinone diazide, aromatic dianhydride and aromatic.

Photoresist composition consisting of polyamine rR condensation cut with di-oamine! Polyoxazole oligomers and/or polyoxazole oligomers.

describes a method for producing a thermostable relief structure using a polymer precursor, a thermostable positive resist consisting of a photosensitive azoquinone or In, and a thermostable relief structure using this resist (Japanese Patent Laid-Open No. 56-27140) However, the former positive resist composition is known.

The difference in solubility between the exposed area and the unexposed area is extremely small. In other words, the sensitivity is low. Also, is the latter a strong acid or a weak acid alkali metal salt in the alkaline nature and source solution of Bonresist? use.

Therefore, there is a risk that the characteristics of semiconductors may be adversely affected.

0,・1・
The purpose of the present invention is to eliminate the disadvantages of conventional ridge techniques.

It is an object of the present invention to provide a novel light- or radiation-sensitive adhesive composition that has high sensitivity, stability, heat resistance, and has no adverse effects on semiconductor properties. .

The object of the present invention is to prepare 2M with a novel composition consisting of the following (1) to 1ll).

(IJ general formula % formula % () ) ) ) [However, in the formula, Rx and Rs are 31 or a tetravalent organic group, ・R2, R4, and R1 are divalent organic groups, and Ru is 1 or 2. be. ] A polymer whose product is a repeating unit represented by , ,! ()(1
1) A light- or radiation-sensitive composite composition comprising a compound having a hydroxy group or an aromatic amino group and an amino group, and a compound having a photosensitive quinone diand group 'Ik'lf.

It has excellent storage stability and heat resistance, with high sensitivity and no negative impact on custom-made semiconductors.

I discovered that. That is, light or radiation aVc.

Reactive quinone diandation-f* and hydrox.

Using an amine compound having M group, the above ゛(I)~
The polyamic acid (iii) is imparted with photosensitivity and then exposed to radiation Ns using a light fork.

I discovered that. Furthermore, the above composition is
An ion of an amine compound having a hydroxyl group is attached to the carboxyl group of the polyamide acid of the above general formulas (I) to (flI), and a quinone di-15-and compound is generated by absorbing light or radiation.

active species ketene and hydroxy groups or aromatics.

It reacts with the amino group and becomes insoluble in the #tll solution.

It is. The reaction is generally shown for example in 5.

It becomes like a low-level self. 2()
5.(A)I 1 The materials used in this study will be explained below.

Boria represented by the general formula (I) + U) + (tn).

Midic acid is heat-treated with 4VC to produce polyimide and polype.

nzoxazinone, polybenzoquinasilidione.

It is something that becomes. These polymers are heated at 1° in air or in a violet atmosphere at a temperature below 460°C, preferably at .

Even if heated for 1 hour below 460℃, the number of eggs does not decrease.

It is preferable to use a material with a high degree of heat resistance. Also, this.

No IQ gun is added to the backbone of these polymers as necessary.

atoms, alkyl groups, aryl groups and their 2+14
・Halogen 1 is substituted with & substituents such as amine group, amide group, human a/xy group, carboxyl group, etc.

However, it is desirable to select a range that does not significantly impair the heat resistance of the polymer. Furthermore, the general formula (I
) , (n) I (m) It may be made of boria 5-amic acid represented by (m), or it may be a co-electroposition of these and other repeating/units.

The polyamic acid used in the present invention has the following composition?
It is advantageous to use it as the main component. General/Formula
1′
□(-CO-R'-Co-NH-R"-NH+ ・
...[IJ.

(COOH).

In the formula, R' is, for example, (In the formula, the bond is the carbonyl 11 of the polymer chain.

It represents a bond with a group, and the carboxyl group is located at the ortho position to the bond. ) Natoga et al.

It will be done.

In addition, R2 is, for example,
28, -G-CU-G-, >04, -◎(), ÷◎(n), -o-O-o-O-o-, etc.

In addition, as the polyamic acid 9 represented by the general formula (I), for example, pyromellitic dianhydride and 4. .

4'-Diaminodiphenyl ether, Pia Meritz.

trianhydride and 3,5',4,4'-be/
Schiff.

Enonetetracarboxylic two-yan water proboscis and 4,4'-sia.

Minodiphenyl ether, pyromellitic monohydrate and 3,6',4,4'-benzophenone tetrahydrocytate.

Rubonic dianhydride and 4,4'-diaminophenyl.

ether and 4,4'-diaminodiphenyl-del-6-carbonamide, pyromellitic dianhydride and/or 5,5',4,4'-benzophenonetetracarboxylic dianhydride and 4,4 ′-diamino.

Diphenyl ether and bis(3-amitube 1(10
pyromellitic dianhydride and 3,5',4,4'-benzophenone tetracarboxylic dianhydride,
-aminophenoxy)phenyl]propane and 4,4
'-Diaminodiphenyl ether, 1,2,2-bis(
3,4-nocarpoxyphenyl).

Hexafluoropropanihydride and 4,4'-diami.

Poly sweetened with nodiphenyl ether, etc.

Examples include amic acid.

The polyamide IR2 represented by the general formula CI) in the upper ml,
.

・7・ is,・U, S, pattnt5, 179, 6
17, same 6.゛740, 305, same 5, 356,
648, 3, 959, '350, 4, l
it, No. 906, and Japanese Patent Publication No. 48-2956.

Further, as the polyamic acid used in the present invention, 5 has the following structure as a product component.

General formula % formula % ) In the formula, Bs is, for example, 10 (
t, ×γ, 9, -G-Nisebezawa・-0-Ikoma, -0-O-0- (wherein, the bond (represents the bond with the amino group of the back polymer chain, The amino group is located in the ortho position with respect to the #i position.
Rareru 1rf. 20.8. Polyamic acid represented by general formula (11).

As, 3,3'-benzidine dicarbon.

+R and isophthalic acid and/or terephthalic acid.

A polyamic acid synthesized from dichloride, 5,5'-methylene dianthranilic acid, isophthalic acid and/or terental acid dichloride, etc.

Examples of the polyamic acid represented by the above general formula (n) include those described in Puko Publication No. 44-27756.

It is framed by law. Usually, diaminodicarboxylic acid l·゛ and/carboxylic acid halogen partition are the usual i condensation.

In the same way as in the reaction, the reaction is carried out in equimolar relation, but it is preferable to use -10,000 in excess of several percent.

I'm going to have a good time.

In addition, the solvent used in 1° of the polyamic acid represented by (n) is the same as that used in the above [1].

Same as solvent, pour into IJL tray if necessary.

Diethylaniline, triethylamine, pyridine.

Organic amines such as chlorine or sodium hydroxide.

Presence of inorganic salts such as sodium carbonate in the system 2.1
You can leave it there.

Thus, a polyamide of the general formula [l[] was obtained.

Acids include halogen compounds or inorganic salts.

Therefore, Id for the cow conductor! ! When used for anti-film applications,
.

The alkali metal ions contained in the polymer must be removed to the extent that they do not adversely affect the semiconductor properties.

Further, the polyamic acid used in the present invention has the following structure as a product component. .

General formula 10% formula %() ) In the formula, Bs is as defined above. Ma・taR1
is as defined in R2 and colleagues above. ·In addition,
The polyamic acid 15 represented by the general formula (III) is, for example, 6,3'-benzidinedicarboxylic acid.

and 4,4'-diphenylmethanoisocyanate.

5.5'-methylenetzanthranilic acid and 4,4',-
Schiff.

Manufactured from enylmethane diisocyanate.

Things can be mentioned. These polyamic acids are WIJ 2
．． 1 is preserved and published in the same manner as published on DVD in Jiko No. 44-27677.

Hydroxy group or aromatic group used in the present invention.

As an amino group and a compound that has /W an amino group.

(In the formula, R6 is a divalent aliphatic, alicyclic, aromatic group,
X is a hydroxy group, genus y-q, l<7. R%X is a secondary alkyl group. ) is a compound represented by λ (carrier 1, in which R9 is 511 fli aliphatic, alicyclic, aromatic).

Group group, X is hydroxy group, genus Cφ, R7, R8 are above.

It is exactly as it appears. ] Compound 1 is represented by the proboscis. These 11S sweet → Nakotoji ℃ are vII.

11・CE2礪N(even),,MO(gn0-CH,,C74A
'(genus G)2゜go-Q-oCIilctr,cg,N
(ca), , Io@-o ctr, c4ct4y
.

CC114)2, CHO%C#Cl4Cl4N
CCHs)2.

(E working CW pot Cl2N (C, genus), , CHO soup C-Tsuru C genus N (even),.

CHs NO@-0cH2CHt A'c CHs )t +
Examples include "@04"2"("a'211°, etc.), and at least one angle is used.

A quinonediazide compound used in the present invention.

is the general formula % formula % (in the formula, P is benzene series quinonediazide 1°)
M and Z are sulfonyl (-so, -) and carbonyl.

(-CO-), carbonyloxy (-COO-) 1, sulfonyloxy (-8020-), and RIO are 21 aliphatic, alicyclic, and aromatic groups. ).

Preference is given to compounds that Specifically, 12
, 4.6) - Compounds are mentioned, and at least one or more compounds are used.

It will be done. Preferably these quinonediazides are on top.

The group of the present invention has a good compatibility Yf of 1° with the polyamic acid of the general formula DJ * (II) + (it).

It must not precipitate from acids.　　.

According to the invention, to form a relief structure.

Coat the base or radiation-sensitive composite oxide substrate.

cloth, provide a thin film, and mask the source or radiation.

Akira 7:! 0: Irradiate. The part of the thin film that was irradiated and the part of the thin film that was not irradiated? The unirradiated part was removed by folding or removing it with a developing bulb solution, and the relief structure/structure Hironen L was obtained.

The light or radiation sensing injector assembly 5 used in the wood coating shall be coated with an organic solvent and applied to the substrate.

Can be done. This composition solution was prepared in step 11.

Baku no Youn ζ, Jt Katcho, 1. oN-Methyl-2-pia-lidone, N,N-dimethyl 1 cetamide, N-.

Cyclohexyl-2-pyrrolidone, 1,6-dime.

Aprotic such as thyl-2-imidazolidinone.

The above general formula (L), (ffl
t.

Quinonediazide compound in the polyamide relative solution of (nl).

Begin to mix homogeneously, then hydroxyl or.

Of course, the aromatic amino group and amino 4 are converted to M.

This is a method of mixing. Polyamic acid and hydroxyl group or aromatic amine group of soil Bb and a.

The mixing ratio of mino groups to 1 carboxyl group of the polyamic acid is 0.2 to 2 parts, preferably 0.5 to 1.5 parts.

Reed, polyamic acid and hydroxyl group of upper item d.

Or 1 to 100 violets for the 100 liters of aromatic amino acid and 100 liters of mixed partitions that are converted into aromatic amino acids and amines.

The quinon noaside of the pupil μ is 1 oto sweet.

The above-mentioned binding and cutting process is carried out using the known spreading method 4, the swivel coating method, the 2-reaction coating method, and the spray coating method.

Coating from L1 to 10 μm using the roller violet method.

A strain can be applied to improve the film thickness. .

The relief pattern formed by m'j*vc is then cleaned with a rinsing solution to remove 10% of the relief pattern. Don't mix it with the VC liquid and the 1st liquid liquid*! / 7 <)' 1 m of non-bath medium or methanol, ethanol, alcohol, benzene, toluene, xylene, methyl selon, etc. are used as Il and the temperature is raised to ℃. . 1. Relief Para--
The polymer of this is a polyamic acid, and it is treated in a cold oven at 150℃ to 4℃ to 0℃. .

Kinazozorinon Prefecture and other Horibōki Kaoru were shocked...i
・15 ・Relief pattern of heat-injected polymer and 7. .

Example 4 Example 1 (1) Sweet acid 4,4'-diaminone phenyl ether of polyamic acid 50! IC0,
25% 7 N-methyl-2-biride 7
8951', cooled to -10°C, and directly exchanged the base metal with nitrogen.

TF6 hit, Piromeri Qi Eryan Water Mono.

545, y (0.25 mol) Kaoru ↓ IS once 10℃
Below is Hiroju.

Add gradually so that it lasts. After I lost my strength.

After reacting at about 15°C for 6 hours, it becomes highly viscous when mixed at N10 (20°C) for 5 or 8 hours.

become. This polymer is heated at ¥80℃.

Polyamide (2) with varnish viscosity 410 poise (25°C)
Polyamide m bath (polymer, solid content 15 t%, common liquid Ti 藻 10 boas) 10y.

and ethylene glycol bis-naphthoquinone.

-(1,2)-diazide-(2) -5-sulfo211
16. Sweeten the relative ester L1.7.9'i, then add para-[
.

5-(N,N-metheramino)propyloxy-1phenol 2.5y was added to the tip of a knife and stirred evenly. This bath liquid was filtered through a 1 μm filter and used for one house.

Diluted bath solution (use for 1' time).

The prepared bath solution was spun onto silicon wafer soil using a spinner, and then dried at 1°C for 50 minutes.

A 60 μm thick violet was obtained. Using a photomask on the soda glass surface of this film-woven fabric, I made a temporary mask.

Irradiation was performed for 5 minutes using a 500F Xe-N5 lamp. lf1
The degree of separation on the nine sides is 25°η in the 565nm range.
LηC failed. Fukimoto/Haku, N-methyl-2゛-pyrrolidone 56. A mixed basin consisting of one valley of water.

Apply one glass of water, then rinse with ethanol
(The relief pattern is a monk.

-(2) -5-sulfur ester 0. Mix B5/.

Para~(3-(N,N-nmetherami20))
Bulk into q-biruoxy. This bath solution was filtered through a 1 μm filter and the P-treated bath solution was used.

Silicone wafers in a spinner with the resulting bath solution.

The top layer was dried for 7Q"C, 5 (J minutes) to obtain a 2.05 μm thick layer. This layer was temporarily covered with a soda glass photomask made by a craftsman, and then dried at 500F. Xe-
Illuminated the outside of the cable for 6 minutes using a Hl lamp. Outside the system on the joyful side.

The thigh is a temporary great wall of 365μm and is 25mi; F'/cm2
I failed. .

After editing, a mixture of 4 volumes of N-methyl-2-pyrrolidone and 101 volumes of water was developed, and then washed with a rinse solution (isogumivir alcohol) to obtain the Lely 17 pattern. .

A large painting? A bath solution of 7 pores (25 DEG C.) of polyamide was obtained from 5,5'-methylene dianthranilic acid and prephthalyl dichloride. The obtained polyamitopo (polymer solid content 15 weight Jt%) 10! and ethylene glycol bis-naphthoquinone.

(1.2)-Diazido-(2J-5-sulfonic acid di.

Mix 0.6 da of ster, then para-C3-('N
, N-nomethylaminoglobyloxy)] a.

Grind 15g of Nirin evenly with the tip of the knife. Actual below)#
Y! A rice milling and relay 7 pattern pattern was obtained using the same operations as in No. 11.

Ratio 41￥￥1 Polyamic acid 10 obtained from Hyromellitic dianhydride and 4,4'-diaminodiphenyl ether [Example 1) 94.6 9 and N-dehyabiethyl-6
A photosensitive material is prepared by mixing 16.5y of (5H)-nazo5C6H)-oxo-1-suphthalene sulfonamide and 1oorrLl of dimethylpho. I met an uncle. - The following procedure was carried out in the same manner as in Example 1, and 7 Otre 15 cysts were suspended in water at a volume ratio of 1:15 at about 25°C.

from a 10% aqueous solution of diethylethanolamine.

After stirring for 20 seconds, I developed it three times.

Ta. Relief from Example 1 of the polished rice, Kimoto 4.

The pattern was clear and continuous.

・19・ According to the present invention, the photosensitivity achieved in the conventional problem is the same as above, and it can be applied to a staple film resist for semiconductors.

0 Agent Masukonshi Hiroshi 1) Toshiyuki,・ ・20・

Claims (1)

[Claims] (1) General formula % Formula % ) () ) (However, in the formula, R1 and R8 are trivalent or tetravalent oxidizing groups.
*, tz is i or 152. ) consists mainly of repeating units. a polymer containing a fill hydroxy group or an aromatic amine group; A compound having an amino I group. (9.) A radiation-sensitive polymer composition characterized in that the optical fork consists of a quinonediazide compound's proboscis. .