WO2014094356A1

WO2014094356A1 - Photoresist remover

Info

Publication number: WO2014094356A1
Application number: PCT/CN2013/001501
Authority: WO
Inventors: 刘兵; 彭洪修; 孙广胜; 颜金荔
Original assignee: 安集微电子科技(上海)有限公司
Priority date: 2012-12-17
Filing date: 2013-12-03
Publication date: 2014-06-26
Also published as: TW201426206A; CN103869636A

Abstract

Disclosed is a cleaning solution with low etching ability suitable for cleaning a relatively thick photoresist. The photoresist cleaning solution with low etching ability contains (a) a quaternary ammonium hydroxide, (b) an ethanol amine, (c) a sugar or sugar alcohol, (d) a surfactant, and (e) a solvent. The photoresist cleaning agent with low etching ability can effectively remove the photoresist on a semiconductor wafer, and at the same time fundamentally won't attack a substrate of metals such as aluminum, copper and the like, and has good application prospects in the field of semiconductor wafer cleaning etc.

Description

Photoresist remover

Technical field

The invention relates to a Guanghai IJ glue remover. Background technique

In a typical semiconductor manufacturing process, by forming a mask of photoresist on the surface of some materials, pattern transfer after exposure, after obtaining the desired pattern, it is necessary to remove the residual photoresist before proceeding to the next process. . In this process it is required to completely remove the unnecessary photoresist while not corroding any substrate. For example, in the wafer microsphere implantation technology, a photoresist is required to form a mask, which needs to be removed after the microsphere is successfully implanted, but since the photoresist is thick, it is completely removed. More difficult. A more common method for improving the removal is to extend the soaking time, increase the soaking temperature, and use a more aggressive solution, but this often results in corrosion of the wafer substrate and corrosion of the microspheres, resulting in a significant reduction in wafer yield.

At present, the photoresist cleaning liquid is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning liquid or rinsing the semiconductor wafer with the cleaning liquid. For example, W02006/056298A1 utilizes an alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMS0), ethylene glycol (EG) and water to clean the photoresist of the copper substrate, while Basically non-corrosive to metallic copper, but it is corrosive to metallic aluminum; for example, US5529887 consists of potassium hydroxide (K0H), mercapto diol monodecyl ether, water-soluble fluoride and water, etc. Immersed in the cleaning solution to remove thick film photoresist on metal and dielectric substrates at 4 ° C. The corrosion of the semiconductor wafer substrate is high. With the rapid development of semiconductors, especially the convex ball package In the development of the field, the cleaning requirements for photoresist residues are correspondingly improved; mainly, as the number of pins (I/O) per unit area increases, the removal of photoresist becomes more and more difficult. .

It can be seen that finding a more effective method for suppressing metal corrosion suppression and high efficiency of photoresist removal is a priority for the improvement of such photoresist cleaning solutions. Summary of the invention

The technical problem to be solved by the invention is to provide a thick film photoresist for the defects of the existing thick film photoresist cleaning liquid which has insufficient cleaning ability or strong corrosion to the semiconductor wafer pattern and the substrate. A photoresist cleaner that is highly cleanable and less corrosive to semiconductor wafer patterns and substrates.

The low etchability of the present invention is applicable to cleaning solutions for thicker photoresist cleaning and cleaning methods thereof. The low etch photoresist cleaning solution contains (a) a quaternary ammonium hydroxide, (b) an alcohol amine, (c) a sugar and/or a sugar alcohol (d) surfactant, and (e) a solvent. The low-etching photoresist cleaning agent can efficiently remove the photoresist on the semiconductor wafer, and has no attack on the substrate, such as metal aluminum, copper, etc., and has good application prospects in the field of semiconductor wafer cleaning and the like. .

In the present invention, the concentration of the quaternary ammonium hydroxide is 0.1 to 10% by weight, preferably 1 to 5% by weight; the concentration of the alcoholamine is 0.1 to 30% by weight, preferably 0.1 to 15% by weight; the concentration of the sugar and/or sugar alcohol It is 0.1 to 5 wt%, preferably 0.1 to 3 wt%; the concentration of the surfactant is 0.01 to 3 wt%, preferably 0.1 to 1 wt%; the balance is a solvent.

The mass of component a and component b described in the present invention is preferably between 6:1 and 1:2.5. When the ratio of component a to component b is greater than 6:1, the system may not form a homogeneous solution or form a homogeneous solution for a long time; on the other hand, when the ratio of component a to component b is less than 1 At 2.5 o'clock, too much alcohol amine will cause the removal efficiency of the photoresist to decrease.

The quaternary ammonium hydroxides described in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, hydroxyethyl One or more of trimethylammonium hydroxide, hexadecanyltrimethylammonium hydroxide, and benzyltrimethylammonium hydroxide.

The alcohol amine described in the present invention is one of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanolamine and diglycolamine. Or several. The presence of an alcohol amine facilitates the improvement of the solubility of the quaternary ammonium hydroxide.

The sugar or sugar alcohol described in the present invention is selected from the group consisting of threose, arabinose, xylose, ribose, nucleoside Sugar, xylulose, glucose, II-drum, T-lactose, sugar, allose, A'; sugar, idose, loprose, sorbose, psicose, fructose, sul One of the sugar alcohol, erythritol, ribitol, arabitol, xylitol, talitol, sorbitol, itol, iditol and galactitol or the surface described in the present invention The active agent is selected from the group consisting of polyvinylpyrrolidone. The addition of a surfactant facilitates the removal of the photoresist.

The solvent described in the present invention may be selected from an organic solvent or a mixture of an organic solvent and water. The organic solvent is preferably one or more of sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolidinone, amide and alcohol ether; the sulfoxide is preferably dimethyl sulfoxide. And one or more of methyl ethyl sulfoxide; the sulfone is preferably one or more of methyl sulfone and sulfolane; and the imidazolidinone is preferably 2-imidazolidinone and One or more of 1,3-dimethyl-2-imidazolidinone; the pyrrolidone is preferably N-methylpyrrolidone, N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone One or more; the imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone; the amide is preferably dimethylformamide and dimethylacetamide One or more of the above; the alcohol ether is preferably one or more of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether. When the solvent described in the present invention is selected from a mixture of an organic solvent and water, the water content of the mixture does not exceed 10% by weight.

In the cleaning liquid of the present invention, the photoresist residue on the wafer can be cleaned at 25 ° C to 85 ° C. The specific method is as follows: The wafer containing the photoresist residue is immersed in the cleaning liquid of the present invention, and after being immersed at 25 ° C to 85 ° C for a suitable period of time, it is taken out and rinsed, and then dried by high-purity nitrogen gas.

The technical effects of the present invention are:

a) the selection of a suitable ratio of quaternary ammonium hydroxide / alcohol amine is beneficial to coordinate the photoresist removal ability and corrosion resistance of the metal microspheres;

b) The presence of sugar or sugar alcohol is beneficial to inhibit the corrosion of metallic copper, aluminum, tin, lead and silver; c) the addition of polyvinylpyrrolidone facilitates the removal of photoresist. detailed description

The reagents and raw materials of the present invention are commercially available. The clear liquid of the present invention can be obtained by simply and uniformly mixing the above components.

The advantages of the present invention are further described below by way of specific embodiments. However, the invention includes, but is not limited to, the specific compositions of the following examples. Preparation Examples Table 1 Examples and the components and contents of the cleaning agent in the comparative examples

Vat

Ϊ́3⁄4 two 'Γ N-ring

10 25 2 62.5 0.5 Sugar Pyrrolidine

Chemical

ϊ

Called B

^3⁄4 . B Ten-milk

4 1 1 93.2 0.8 3⁄4 Amine Sugar Pyrrolidine s'i

钕

Attached

1, 3 - 2

i — B. Tag

3 0.5 0.5 _-2 - imiam 95.8 0.2 sugar

Porphyrin »] ammonium

Call 1 person J

Diacetyl Alu II

6 ] 1.5 91 0.5 Amino sugar Amide Ammonium

Ding

TFl people. — B

5 2 Auntie.

1 9 .8 0.2 saccharide amide

Ammonium

Two

Different: Ai: h - ethylene glycol

7 3 1 88.5 0.5 amine sugar single Φ etherification

Ammonium

Hydroxyethyl

2- 1-1

«Two

B

4 Si Tarot 1-Ethyl Alcohol

1.5 1.5 92.4 0.6 ) Ethylene succinyl ether Hydrogen

m

Ammonium

Sixteen

垸^

Two Φ B 3⁄4 — Mountain 3⁄4 One 1 person J-alcohol

8 4 1.5 86 0.5 3⁄4 ethanolamine sugar ether

3⁄4

Ammonium

Benzyl *

Two f?

3⁄4 hydrogen 2 乙阿洛

2 1 94.5 0.5 amine ketose sulfone 3⁄4

Ammonium

1 ,3-- 3⁄4-2-Milk Beer 89

#氢单乙院

3 5 fructose 1.7 0.8 amine

Ammonium

Water 0.5

¥-乙 fff 苏糖

Three E 5 3 1 84 0.2

(]3⁄4 m sulfone U

33⁄4 ' 5.8

1

Benzyl

Two π'

Ribose

!9 5 6 2 环丁 M 86.5 0.5

ο'

3⁄4

Ammonium

Allah

屮 Γ Γ Γ) Sugar 1 81

Sulfone

-B m

20 5 1 1

3⁄4 IK

Ammonium

1

m water 9 two b

Fl called Tarot II f *3⁄4

21 hydrogen 5 T

^ 3 1.4 90 0.6 Amines Drunken Sulfone

Chemical

Ammonium

μ

22 i ίΕι. Prayer Mountain 3⁄4 — 3⁄4 Asia

6 9 1 83.6 0.4 3⁄4 chemistry )]3⁄4 sulfone

Ammonium

^ B ffj: II' dew

23 5 5 1 sulfolane 88.5 0.5 amine drunk

Ηι人人 J alcohol Ai Du 2⁄4 ia

24 3 3 1.5 92 0.5 Amine Sugar Sulfone

Ammonium

«Hydrogen IHl people 乳乳-甲^亚

25 2 6 0.8 90.4 0.8 3⁄4 saccharide ^ sulfone

Ammonium

84 triethyl sulfone

Xylose

26 3⁄4 hydrogen 4 7 1.3 0.2 amine

3⁄4化 m- 钕 water 3.5 attached

Hydrogen, single, drunk, pear

27 1.5 3 0.8 94.4 0.3 Amine Alcohol Sulfone

Ammonium

duck

Comparison

Iso-W alcohol core H 2-imidazole Example ^ Hydrogen 3 7.5 1.5 87.7 Ruthenium Amino sugar

1 (5) anthrone

Ammonium

Compared

ΙΗι人博 Yamanashi

Example 6 9 NA dimethyl

83.6 0.4

3⁄4 amine

(22) sulfoxide

Ammonium In order to further investigate the defects of the type of cleaning liquid, the invention adopts the following technical means: the wafer containing the photoresist is immersed in the cleaning agent, and the constant temperature oscillator is used at 25 ° C 3⁄4 85 ° C. The vibration frequency of 60 rpm was oscillated for 30 90 minutes, then washed with deionized water and then dried with high purity nitrogen. The cleaning effect of the photoresist and the corrosion of the cleaning solution on the wafer are shown in Table 2.

- 2 Comparative examples and part cleaning of some examples

; blue wash photoresist

Wafer i'R wash 3⁄4

R†r cleaning time

Example (°C) (min) Non-metal base

A1 substrate rot

Corrosion situation

Cleaning result

4 25 90 ◎ ◎ ◎

5 35 75 ◎ ◎ ◎

7 50 60 ◎ ©

9 40 50 ◎ ◎ ◎

1 1 30 85 ◎ ◎ ◎

12 45 80 © ◎ ◎

14 55 65 ◎ ◎ ◎

17 60 45 ◎ ◎ ◎

18 65 40 ◎ ◎

20 70 55 ◎ ◎ ◎

21 75 70 ◎ ◎ ◎

22 80 30 ◎ ◎ ◎

24 85 35 © ◎ ◎

26 65 45 ◎ ◎ ◎ Comparative Example 1 35 75 ◎ 〇 ◎

略 slightly corroded: 〇 less residual;

△ medium corrosion; Δ more residual;

X is strictly corroded. X people Remnant. As can be seen from Table 2, the cleaning liquid of the present invention has a good cleaning effect on the photoresist and has a wide temperature range. In addition, the comparison between Example 5 and Comparative Example 1 shows that the addition of polyvinylpyrrolidone facilitates the removal of the photoresist; the comparison of Example 22 with Comparative Example 2 shows that the presence of sugar or sugar alcohol is beneficial for inhibition. Corrosion of metal aluminum.

In summary, the cleaning liquid of the present invention has strong photoresist removal ability; strong corrosion inhibition to metal and non-metal; and large operation window. It should be understood that the wt% of the present invention refers to the mass percentage.

The specific embodiments of the present invention have been described in detail above, but by way of example only, the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions of the present invention are also within the scope of the invention. Accordingly, equivalent changes and modifications may be made without departing from the spirit and scope of the invention.

Claims

Rights request

A photoresist remover comprising: a quaternary ammonium hydroxide, an alkanolamine, a sugar and/or a sugar alcohol, a surfactant, and a solvent.

2. The photoresist remover according to claim 1, wherein: the concentration of the quaternary ammonium hydroxide is 0.1 to 10% by weight, and the concentration of the alcohol amine is 0.1 to 30% by weight, the sugar and The concentration of the sugar alcohol is 0.1 to 5 wt%, the concentration of the surfactant is 0.01 to 3 wt%, and the content of the solvent is

The photoresist remover according to claim 2, wherein: the concentration of the quaternary ammonium hydroxide is 1 to 5 wt%, and the concentration of the alkanolamine is 0.1 to 15 wt%, the sugar and The concentration of the sugar alcohol is 0.1 to 3 wt%, and the concentration of the surfactant is 0.1 to 1 wt%.

The photoresist cleaning agent according to claim 2 or 3, wherein a mass ratio of the quaternary ammonium hydroxide to the alcohol amine is between 6:1 and 1 to 2.5.

5. The photoresist cleaning agent according to claim 1, wherein: the quaternary ammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. One or more of tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, cetyltrimethylhydroxide hinge, and benzyltrimethylammonium hydroxide .

6. The photoresist cleaning agent according to claim 1, wherein: the alcoholamine described in the invention is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2- One or more of (diethylamino)ethanol, ethyldiethanolamine, and diglycolamine.

7. The photoresist cleaning agent according to claim 1, wherein: the sugar and/or sugar alcohol is selected from the group consisting of threose, arabinose, xylose, ribose, ribulose, xylulose, Glucose, mannose, galactose, tagatose, allose, altrose, idose, tarotose, sorbose, psicose, fructose, threitol, erythritol, ribitol, arab One or more of sugar alcohol, xylitol, talitol, sorbitol, mannitol, iditol and galactitol.

The photoresist cleaning agent according to claim 1, wherein the surfactant is polyvinylpyrrolidone.

9. The photoresist cleaning agent according to claim 1, wherein the solvent is selected from the group consisting of an organic solvent or a mixture of an organic solvent and water.

The photoresist cleaning agent according to claim 9, wherein: the organic solvent is one selected from the group consisting of sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolidinone, amide and alcohol ether or A variety.

The photoresist cleaning agent according to claim 0, wherein: the sulfoxide is selected from one or more of dimethyl sulfoxide and methyl ethyl sulfoxide; From one or more of methyl sulfone and sulfolane; said imidazolium is selected from one or more of 2-imidazolidinone and 1,3-dimethyl-2-imidazolium; The pyrrolidone is selected from one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone; the imidazolidinone is 1,3-dimethyl a quinone-2-imidazolidinone; the amide is selected from one or more of dimethylformamide and dimethylacetamide; the alcohol ether is selected from the group consisting of diethylene glycol monomethyl ether, diethyl One or more of diol monobutyl ether and dipropylene glycol monomethyl ether.

The photoresist cleaning agent according to claim 9, wherein the solvent is selected from the group consisting of an organic solvent and water, and the water content of the mixture is not more than 10% by weight.