JP2001209190A - Photoresist remover composition and method for using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent or inhibit the corrosion of a-Si and p-Si. SOLUTION: The photoresist remover composition consists essentially of a primary, secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine, a polar organic solvent, water and 2,3,6-trimethylphenol, 2,4-di-tert- butylphenol or a mixture of those.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a semiconductor integrated circuit,
The present invention relates to a photoresist stripping composition used for manufacturing a semiconductor element circuit and the like of a liquid crystal panel and a method of using the same. More specifically, amorphous silicon (hereinafter referred to as a-Si) which is a constituent metal of a thin film transistor,
The present invention relates to a photoresist stripper composition for suppressing dissolution of polysilicon (hereinafter, referred to as p-Si) and a method for using the same.

[0002]

2. Description of the Related Art A stripping composition is used for stripping a photoresist used for manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like. The manufacture of the semiconductor element circuit or the associated electrode unit is performed as follows. First, a-Si, p-Si are formed on a substrate such as silicon or glass.
Are laminated by a method such as CVD or sputtering.
A photoresist is coated on the upper surface, and the photoresist is patterned by exposure, development and the like. The metal film is etched using the patterned photoresist as a mask.
Thereafter, the unnecessary photoresist is stripped and removed using a stripping composition. The element is formed by repeating the operation.

Conventionally, a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, and a polar solvent, a mixed solution thereof, or an aqueous solution thereof has been used as a release agent composition. Also, in order to improve the resist strippability,
It is also well known to use a mixture of an amine and water as a release agent.

[0004] Japanese Unexamined Patent Publication (Kokai) No. 5-259066 also discloses a release agent obtained by adding an anticorrosive to a mixed solution of an amine and water. Specifically, a photoresist stripper comprising an aqueous solution containing at least one compound selected from the group consisting of an aromatic phenol compound and an aromatic carboxylic acid compound and an organic amine is described.

[0005]

For example, a non-aqueous stripping agent comprising a mixture of a monoethanolamine (MEA) and a solvent, which is well known at present, includes a-Si, p-Si
Does not corrode. However, the non-aqueous stripping agent is inferior to the water-containing stripping agent in stripping / removing the resist, and also strips the resist film that has been modified by treatment with a chemical solution such as heat or acid, or exposure to a plasma state.・ Removability is inferior to water-containing release agent. In addition, non-aqueous release agents must be used under higher temperature conditions. On the other hand, a release agent composed of a mixed solution of monoethanolamine and water is used as a liquid crystal display (liquid crystal display).
play, LCD) thin film transistor (thin f
It is not preferable because a-Si and p-Si which are constituent metals of an illuminator (TFT) element are easily corroded.

In JP-A-5-259066, the resist removal performance is not sufficient because a polar organic solvent is not contained. Claim 4 of this publication
When a quaternary ammonium compound is used as the organic amine described in (1), a-Si and p-Si are corroded.

In view of these points, the present inventors have conducted various experiments, and as a result, have found that a release agent comprising a mixed solution of an alkylamine or alkanolamine other than a quaternary ammonium compound, a polar organic solvent and water has an anticorrosive effect. It has been found that by adding a certain compound, corrosion of a-Si and p-Si can be prevented or significantly suppressed, and excellent peeling / removability can be maintained.

The present invention has been made on the basis of the above findings, and an object of the present invention is to provide a primary, secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine and a polar organic solvent. By adding a-Si, a suitable compound as a p-Si anticorrosive to a release agent composition containing water as a main component, corrosion of a-Si, p-Si which is a constituent metal of a thin film transistor is prevented or It is an object of the present invention to provide a photoresist stripping agent composition that can significantly suppress and maintain excellent stripping / removing properties, and a method of using the same.

[0009]

In order to achieve the above-mentioned object, the photoresist stripping composition of the present invention comprises a primary,
A secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine, a polar organic solvent, water and one of 2,3,6-trimethylphenol or 2,4-di-tert-butylphenol It is configured so that the main component is a seed or a mixture thereof.

In the above photoresist stripping composition, the content of primary, secondary or tertiary alkylamine or primary, secondary or tertiary alkanolamine is 3.0 to 50.0% by weight, preferably 5.0-30.0
% By weight, the content of the polar organic solvent is 20.0 to 85.0% by weight, preferably 40.0 to 80.0% by weight, and the water content is 5.0 to 60.0% by weight, preferably 10 0.0-4
0.0 wt%, the content of one of 2,3,6-trimethylphenol or 2,4-di-tert-butylphenol or a mixture thereof is 0.01 to 10.0 wt%, preferably 0.1 to 10.0 wt%. 05 to 5.0% by weight.

When the content of the primary, secondary or tertiary alkylamine or primary, secondary or tertiary alkanolamine is less than the lower limit, there is a disadvantage that the removability of the resist or the deteriorated resist film is reduced. On the other hand, when the ratio exceeds the upper limit, the content of the other release agent component is reduced, so that there is a disadvantage that the removability of the resist or the deteriorated resist film is reduced. Further, when the content of the polar organic solvent is less than the lower limit, there is a disadvantage that the removability of the resist or the deteriorated resist film is reduced, while when the content exceeds the upper limit, the content of other release agent components is reduced. Therefore, there is a disadvantage that the removability of the resist or the deteriorated resist film is reduced. Further, when the content of water is less than the lower limit, there is a disadvantage that the removability of the resist or the deteriorated resist film is reduced, while when the content is more than the upper limit, the content of other release agent components is reduced. In addition, there is a disadvantage that the removability of the resist or the altered resist film is reduced.

When the content of one of 2,3,6-trimethylphenol or 2,4-di-tert-butylphenol or a mixture thereof is less than the lower limit, a-S
i, the effect of suppressing the corrosion of p-Si, that is, a-S
If i, p-Si has a low corrosion resistance, but exceeds the upper limit, there is a disadvantage that the removability of the resist or the altered resist film is reduced.

When phenol is substituted by a methyl group (alkyl group having 1 carbon atom) or a t-butyl group (alkyl group having 4 carbon atoms), only one of the ortho and para positions is a methyl group or t In a compound substituted with a -butyl group, the dissolution of a-Si and p-Si cannot be suppressed. In addition, when the phenol has no substituent,
A compound in which only one ortho position is substituted with a hydroxyl group (=
Catechol) or a compound in which only one ortho position is substituted with a methyl group (= o-cresol),
Dissolution of a-Si and p-Si cannot be suppressed. Furthermore, only in the meta position of the phenol, a hydroxyl group, a carbon number of 1 to 6
For compounds (resorcinol, 3,5-xylenol, phloroglucinol) in which the alkyl group and the alkoxy group having 1 to 6 carbon atoms are substituted, a-Si, p-
The dissolution of Si cannot be suppressed.

In these photoresist stripping compositions, the primary, secondary or tertiary alkylamine or primary, secondary or tertiary alkanolamine is
Monomethylamine, monoethylamine, propylamine, butylamine, 2-ethylhexylamine, 2-ethylhexyloxypropylamine, 2-ethoxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, Tributylamine, 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, tetramethylethylenediamine, tri-n-octylamine, t-butylamine, sec-butylamine, methylaminopropylamine, dimethylaminopropylamine, Methyliminobispropylamine, 3-methoxypropylamine, allylamine, diallylamine, triallylamine, isopropyl Amine, diisopropyl amine, imino propylamine, iminobispropylamine, monoethanolamine (MEA), N, N- dimethylethanolamine, N, N- diethylethanolamine, aminoethylethanolamine, N- methyl -N,
N-diethanolamine, N, N-dibutylethanolamine, N-methylethanolamine (NMEA), 3
-Amino-1-propanolamine, N, N-bis (2
-Hydroxyethyl) cyclohexylamine (BHEC
HA) can be used.

Examples of the polar organic solvent include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and the like.
Methoxymethyl propionate, ethoxyethyl propionate, propylene glycol methyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, isopropyl lactate, ethyl pyruvate, 2-heptanol, 3-
Methyl-1-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, methyldiglyme,
Methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether (butyl diglycol, BD
G), pyridine, dimethyl sulfoxide (DMS
O), N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NM
P), γ-butyrolactone, sulfolane, 1,2-ethanediol (EG), 1,2-propanediol (P
G), 3-methyl-1,3-butanediol (MB
D), 2-methyl-1,3-propanediol (MP
D), 1,3-butanediol, 1,4-butanediol, glycerin and the like can be used.

In the above photoresist stripping composition, it is preferable to use one or a mixture of 2,3,6-trimethylphenol and 2,4-di-tert-butylphenol.

The method of using the photoresist stripping composition of the present invention comprises the steps of: removing a resist residue generated when a wiring is formed on a semiconductor substrate or a glass substrate for liquid crystal; The wiring is formed by peeling and removing the wiring.

[0018]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention. Examples 1 to 60 and Comparative Examples 1 to 32 A film thickness of 300 was formed on a glass substrate by a plasma CVD method.
Ａ Form an a-Si film and perform laser annealing treatment.
p-Si was grown to form a p-Si film. This substrate was immersed in a 0.5% HF aqueous solution (24 ° C.) for 2 minutes,
The substrate pretreatment was performed by removing the natural oxide film on the Si surface.
Then, after being immersed in a release agent composition having a composition shown in Tables 1 to 3 at 40 ° C. for 10 minutes, washed with pure water, the pure water was blown off with an air gun using N ₂ gas, and air-dried. . The state of the Si surface was observed with a scanning electron microscope (SEM) to compare the Si corrosion protection. The results are shown in Tables 1 to 3. In Tables 1 to 3, ◎ indicates “no Si corrosion corrosion”,
The mark "o" indicates "slightly corroded by Si", the mark "x" indicates "confirmed of Si corrosion", and the mark "xx" indicates "disappearing of the Si film". In Tables 1 to 3, BHECHA is N, N-
Bis (2-hydroxyethyl) cyclohexylamine, MEA indicates monoethanolamine, DEAE indicates N, N-diethylethanolamine (diethylaminoethanol), NMEA indicates N-methylethanolamine, and BDG indicates diethylene glycol monoethylene. Butyl ether (butyl diglycol), NMP is N-
Represents methyl-2-pyrrolidone, DEGMEEE represents diethylene glycol monoethyl ether, EG represents 1,
2-ethanediol is shown, and TMAH is tetramethylammonium hydroxide.

On the other hand, a resist having a thickness of 1 μm formed on a glass substrate was baked at 100 ° C. for 2 minutes, exposed, and developed with a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide). In addition, 140
After baking at 2 ° C. for 2 minutes, dry etching was performed using Cl ₂ gas. Then, after immersing in a release agent composition having a composition shown in Tables 1 to 3 at 40 ° C. for 2 minutes, washing with pure water, and blowing off pure water with an air gun using N ₂ gas,
Air dried. The degree of resist removal was observed with a scanning electron microscope (SEM), and the resist stripping properties were compared. The results are shown in Tables 1 to 3. In Tables 1 to 3, ◎ indicates “no resist residue”, “O” indicates “substantially no resist residue”, ×
The mark indicates that "resist residues are often observed".

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

From the results of Tables 1 to 3, it can be seen that a release agent composition comprising a primary, secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine, a polar organic solvent and water (Comparative Example 1) 9 and 13 to 21), the resist stripping property was excellent, but it was found that the corrosion of Si could not be suppressed. In addition, in a release agent composition comprising an organic solvent and water without containing a primary, secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine (Comparative Examples 10 to 12), Si No corrosion is observed,
It turns out that the resist stripping property is poor. Furthermore, in the case of a stripping composition containing no organic solvent and comprising a primary, secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine and water (Comparative Examples 29 and 30), the resist is stripped. It is understood that Si has a poor property and also corrodes Si.
Further, even when 2,3,6-trimethylphenol is added to a stripping composition comprising a quaternary ammonium compound, TMAH (tetramethylammonium hydroxide), a polar organic solvent, and water, corrosion of Si is suppressed. It can be seen that this cannot be done (Comparative Examples 31 and 32). Also,
As shown in Comparative Examples 22, 23 and 27, when phenol has no substituent, when ortho-position is substituted with hydroxyl group (= catechol), when only one ortho-position is substituted with methyl group In the case of (= o-cresol), dissolution of a-Si and p-Si cannot be suppressed. Further, as shown in Comparative Examples 24, 25 and 28, only a hydroxyl group and carbon number 1 to the meta position of phenol
For compounds (resorcinol, 3,5-xylenol, phloroglucinol) in which an alkyl group of 6 and an alkoxy group of 1 to 6 carbon atoms are substituted, a-Si, p
-Dissolution of Si cannot be suppressed.

On the other hand, 2,3,6-dried alkylamine or primary, secondary or tertiary alkanolamine, a polar organic solvent and water as main components Methylphenol or 2,4-di-t
In the release agent composition (Examples 1 to 60) to which one or a mixture of ert-butylphenol was added,
It can be seen that the corrosion of i can be prevented and excellent resist strippability can be maintained.

Next, an example of a method for using the photoresist stripping composition of the present invention will be described. An a-Si or p-Si thin film is formed on a semiconductor substrate or a liquid crystal glass substrate by CVD, sputtering, or the like. After a photoresist is applied on the upper surface, a pattern is formed by processes such as exposure and development. The a-Si or p-Si thin film is etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist is stripped and removed using the stripping agent composition of the present invention to manufacture a semiconductor element on which wiring and the like are formed.

[0026]

As described above, the present invention has the following effects. (1) A release agent composition comprising a primary, secondary or tertiary alkylamine or a primary, secondary or tertiary alkanolamine, a polar organic solvent and water as main components, a-S
i, by adding an appropriate compound as a p-Si anticorrosive, a-Si, a constituent metal of the thin film transistor,
can inhibit or significantly suppress the corrosion of p-Si,
In addition, excellent peeling / removing properties can be maintained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takeshi Kotani 236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagase Electronics Co., Ltd. Hyogo Plant F-term (reference) 2H096 AA00 AA25 AA27 LA02 LA03 5F046 MA02

Claims (3)

[Claims] 1. A primary, secondary or tertiary alkylamine or primary, secondary or tertiary alkanolamine, a polar organic solvent, water, 2,3,6-trimethylphenol or 2,4-dimethylphenol. -A photoresist stripper composition comprising, as a main component, one or a mixture of tert-butylphenols. 2. The content of primary, secondary or tertiary alkylamine or primary, secondary or tertiary alkanolamine is 3.0 to 50.0% by weight, and the content of polar organic solvent is 20.0%. ~ 85.0% by weight, water content is 5.0 ~
The content of one of 60.0% by weight, 2,3,6-trimethylphenol or 2,4-di-tert-butylphenol or a mixture thereof is 0.01 to 10.0% by weight. The photoresist stripper composition according to any one of the preceding claims. 3. A resist residue generated when wiring is formed on a semiconductor substrate or a liquid crystal glass substrate.
Or a method for using a photoresist stripper composition, wherein the wiring is formed by stripping and removing the photoresist stripper composition according to 2.