WO2009155782A1

WO2009155782A1 - Detergent for removing photoresist

Info

Publication number: WO2009155782A1
Application number: PCT/CN2009/000624
Authority: WO
Inventors: 彭洪修
Original assignee: 安集微电子（上海）有限公司
Priority date: 2008-06-27
Filing date: 2009-06-03
Publication date: 2009-12-30
Also published as: CN101614971B; CN101614971A

Abstract

A detergent for removing photoresist includes quaternary ammonium hydroxide, water, aryl alcohol, dimethyl sulphoxide, corrosion inhibitor of polyacrylic acid. The detergent may clean photoresist and other residues on metal, metal alloy and dielectric substrate.

Description

Photoresist cleaning agent

The present invention relates to a cleaning agent in a semiconductor manufacturing process, and more particularly to a photoresist cleaning agent. technical background

In a typical semiconductor manufacturing process, a photoresist coating is first formed on a surface of a metal such as silicon dioxide, Cu (copper), or a low-k material, and exposed and developed using a suitable mask, depending on the photoresist used. The photoresist is removed from the exposed or unexposed portions, a photoresist pattern is formed at a desired portion, and then plasma etching or reactive gas etching is performed on the photoresist pattern to perform pattern transfer. The low temperature and fast cleaning process is an important direction for the development of semiconductor wafer fabrication processes. Negative photoresists with thicknesses above 20μηη are gradually being used in semiconductor wafer fabrication processes. Currently, most of the photoresist cleaners in the industry have better cleaning ability for positive photoresists, but cannot completely remove the wafers. A negative photoresist having a crosslinked network structure after exposure and etching.

In the chemical cleaning of photoresists on semiconductor wafers, cleaning agents often cause corrosion of the wafer pattern and substrate. Especially in the process of removing photoresist and etching residues by chemical cleaning agents, corrosion of metals (especially active metals such as aluminum and copper) is a common and very serious problem, which often leads to a significant decrease in wafer yield. .

At present, the photoresist cleaning composition is mainly composed of a strong base, a polar organic solvent and/or water, etc., and the photoresist on the semiconductor wafer is removed by dipping the semiconductor wafer into the cleaning agent or by using a cleaning agent to punch the semiconductor wafer. .

Strong bases such as quaternary ammonium hydroxides and alcohol amines, capable of dissolving lithography produced by photoresist and/or etching Glue residue. When the content of the strong base is too low, the cleaning agent has insufficient ability to remove the photoresist residue generated by the photoresist and/or the etching; however, when the content of the strong alkali is too high, the cleaning agent is liable to cause corrosion of the wafer pattern and the substrate. . Compared to alcohol amine compounds, quaternary ammonium hydroxides have better ability to remove photoresist residues from photoresists and/or etches.

The polar organic solvent is capable of dissolving the photoresist residues generated by the photoresist and/or etching, and improving the cleaning ability of the chemical cleaning agent for organic substances. When the content of the polar organic solvent is too low, the cleaning agent has insufficient ability to remove the photoresist residue generated by the photoresist and/or the etching; but when the content of the polar organic solvent is too high, the strong alkali content in the cleaning agent Correspondingly, the ability of the cleaning agent to remove photoresist residues from photoresist and/or etching is reduced.

In order to increase the ability of the cleaning agent to hydrolyze and/or dissolve the photoresist residues produced by the photoresist and/or etching, water in the chemical cleaning agent is sometimes necessary. However, when the content is too high, the cleaning agent has insufficient removal ability of the photoresist residue generated by the photoresist and/or etching, and is liable to cause corrosion of the wafer pattern and the substrate.

A photoresist cleaning agent composed of an alkanolamine and an organic polar solvent is proposed in US 4,761,251. The semiconductor wafer was immersed in the cleaning agent, and the positive photoresist on the wafer was removed at 95 °C. However, the cleaning agent does not contain water, and its cleaning ability for negative photoresist is insufficient.

A photoresist cleaning agent composed of an alcohol amine, a water-soluble organic solvent, water, an organic phenol compound, a triazole compound, and a silicone antimony surfactant is proposed in US Pat. No. 6,140,027. The semiconductor wafer is immersed in the cleaning agent, and the photoresist on the wafer and the photoresist residue generated by the etching are removed at 20 to 50 °C. The cleaning agent uses an organic phenol compound and a triazole compound as corrosion inhibitors for inhibiting metal corrosion. Organic phenolic compounds are harmful to the human body and cause environmental pollution. The cleaning agent has insufficient cleaning ability for the negative photoresist. A photoresist cleaning agent consisting of tetramethylammonium hydroxide, N-methylmorpholine oxide, water and 2-mercaptobenzimidazole is proposed in WO2004059700. The semiconductor wafer was immersed in the cleaning agent, and the photoresist on the wafer was removed at 70 °C. The cleaning agent uses N-methylmorpholine-N-oxide as an oxidizing agent and 2-mercaptobenzimidazole as a metal corrosion inhibitor. The cleaning agent needs to clean the photoresist at a relatively high temperature, and the etching of the semiconductor wafer pattern and the substrate is slightly higher, and the cleaning ability of the photoresist is slightly insufficient. '

A photoresist cleaning agent consisting of quaternary ammonium hydroxide, dimethyl sulfoxide, 1,3'-dimethyl-2-imidazolium and water is proposed in U.S. Patent No. 6,040,117. The semiconductor wafer is immersed in the cleaning agent, and a photoresist having a thickness of ΙΟμη or more on the metal (gold, copper, lead or nickel) substrate is removed at 40 to 95 °C. The cleaning agent uses 1,3'-dimethyl-2-imidazolidinone as an organic co-solvent and does not contain a corrosion inhibitor which inhibits corrosion of metals such as more active metals such as aluminum. The cleaning agent needs to clean the photoresist at a relatively high temperature, and the etching of the semiconductor wafer pattern and the substrate is slightly higher.

A photoresist cleaning agent composed of a quaternary ammonium hydroxide, a water-soluble organic solvent, an organic amine, a dihydric alcohol, and water is proposed in JP2001215736. Immerse the semiconductor wafer in the cleaning agent and remove 20μη on the wafer at 20~90 °C! ~ 40μπι thickness of photoresist. The cleaning agent uses a glycol as a corrosion inhibitor for inhibiting metal corrosion, but the diol has a weak ability to inhibit metal corrosion and reduces the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist. The cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.

A photoresist cleaning agent consisting of quaternary ammonium hydroxide, Ν-methylpyrrolidone, diethanolamine or triethanolamine, water and methanol or ethanol is proposed in JP2004093678. The semiconductor wafer is immersed in the cleaning agent, and the photoresist having a thickness of ΙΟμπι or more on the wafer is removed at 15 to 80 °C. The cleaning agent uses methanol or ethanol as a solubilizer for quaternary ammonium hydroxide, but the flash point of methanol or ethanol is too low, and The cleaning ability of the cleaning agent to the photoresist, especially the negative photoresist, is reduced. The cleaning agent does not contain a corrosion inhibitor that inhibits corrosion of metals such as more reactive metals such as aluminum and copper. The cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate. Summary of invention

The technical problem to be solved by the invention is to overcome the conventional photoresist cleaning agent, which has insufficient cleaning ability for the photoresist, especially the negative photoresist, the toxic and harmful components and the environment, the high operating temperature during cleaning, and the semiconductor Defects such as higher corrosion of the wafer pattern and the substrate, and a photoresist (especially thick film negative photoresist) and other etch residues on the metal, metal alloy or dielectric substrate can be removed while A photoresist cleaning agent that is extremely corrosive to metals such as aluminum and copper and non-metallic materials such as silicon dioxide, and is environmentally friendly and can be used over a wide temperature range.

The photoresist cleaning agent of the present invention contains: a quaternary ammonium hydroxide, water, an aryl alcohol, dimethyl sulfoxide, and a polyacrylic acid corrosion inhibitor.

Wherein, the content of the quaternary ammonium hydroxide is preferably 0.1 to 10%, more preferably 0.5 to 5%; and the content of the water is preferably 0.2 to 5%, more preferably 0.5. ~ 3%; the content of the aryl alcohol is preferably from 1 to 30%, more preferably from 3 to 15% _; the content of the dimethyl sulfoxide is preferably from 1 to 98%, more The best is 30~90%. The content of the polyacrylic corrosion inhibitor is preferably from 0.01 to 5%, more preferably from 0.05 to 2.5%; and the percentage is percentage by mass.

In the present invention, the quaternary ammonium hydroxide is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylhydroxide. One or more of ammonium, more preferably one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, most preferably tetramethylammonium hydroxide . In the present invention, the aryl alcohol is preferably selected from the group consisting of benzyl alcohol, phenylethyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, o-methylphenylethanol, m-methylphenylethanol. , p-Methylphenylethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, o-methoxyphenylethanol, m-methoxyphenylethanol, p-methoxyphenylethanol, o One or more of aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, anthranilic ethanol, m-aminophenylethanol, and p-aminophenylethanol, more preferably selected from the group consisting of benzyl alcohol, phenylethyl alcohol, and p-methyl One or more of benzyl alcohol, p-methylphenylethanol, and p-aminobenzyl alcohol.

In the present invention, the polyacrylic corrosion inhibitor is preferably selected from the group consisting of acrylic polymers and copolymers thereof, methacrylic polymers and copolymers thereof, alcohol amine salts of acrylic polymers, and methacrylic polymers. More preferably, the alcoholamine salt, the polyoxyethylene-modified acrylic polymer, and the ester and the alkanolammonium salt thereof, and the polyoxyethylene-modified methacrylic acid polymer and the ester and the alkanolammonium salt thereof are more preferably An acrylic acid polymer or a copolymer thereof, an alcohol amine salt of an acrylic polymer, a polyoxyethylene modified acrylic polymer and an alkanolammonium salt thereof, and a polyoxyethylene modified methacrylic acid polymer and an alkanolammonium thereof One or more of the salts; the polycarboxylic acid compound preferably has a molecular weight of from 500 to 20,000, more preferably from 1,000 to 10,000.

The photoresist cleaning agent of the present invention may further contain one or more of a polar organic cosolvent, a surfactant, and a corrosion inhibitor other than the polyacrylic corrosion inhibitor.

Wherein, the polar organic co-solvent content is preferably less than or equal to 50%, more preferably from 5 to 30%; and the surfactant content is preferably less than or equal to 5%, more preferably The content of the corrosion inhibitor other than the polyacrylic acid is preferably 5% or less, more preferably 0.10 to 3%; the above percentage is a mass percentage, excluding 0%.

In the present invention, the polar organic co-solvent is a polar organic co-solvent commonly used in the art, preferably One or more selected from the group consisting of sulfoxides, sulfones, imidazolium, alcohol amines, and alkyl glycol monoalkyl ethers. Wherein, the sulfoxide is preferably selected from the group consisting of diethyl sulfoxide and/or methyl ethyl sulfoxide; and the sulfone is preferably one or more selected from the group consisting of methyl sulfone, ethyl sulfone and sulfolane. More preferably, it is sulfolane; the imidazolidinone is preferably selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidine One or more of the ketones, more preferably 1,3-dimethyl-2-imidazolidinone; the alkanolamine is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and isopropyl One or more of an alcoholamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine, more preferably one selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine and methyldiethanolamine Or a plurality of; the mercaptodiol monoalkyl ether is preferably selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, two One or more of propylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether are more preferably selected from the group consisting of diethylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether.

In the present invention, the surfactant is a surfactant commonly used in the art, preferably one or more selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and polyoxyethylene ether, more preferably selected from polyethylene. In the pyrrolidone and/or polyoxyethylene ether; the surfactant preferably has a molecular weight of from 500 to 20,000, more preferably from 1,000 to 10,000.

In the present invention, the corrosion inhibitor other than the polycarboxylic acid may be a commonly used corrosion inhibitor in the art, preferably one or more selected from the group consisting of alcohol amines, azoles and phosphonic acid corrosion inhibitors. Kind. Wherein, the alcohol amine corrosion inhibitor is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine. One or more, more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methyldiethanolamine. The azole inhibitor is preferably selected from the group consisting of benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, dimercaptothiadiazole, 3-amino-1,2,4- Triazole, 4-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-diamino-1,2,4-tri One or more of azole, 4-amino-5-mercapto-1,2,4-triazole, 5-amino-tetrazole and 1-phenyl-5-mercaptotetrazole, more preferably Selected from benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt, 3-amino-1,2,4-triazole, 4-amino-1,2,4- One or more of triazole, 3-amino-5-mercapto-1,2,4-triazole and 5-amino-tetrazole. The phosphonic acid corrosion inhibitor is preferably selected from the group consisting of

1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid and two One or more of ethylene triamine penta methylene phosphonic acid, more preferably selected from

One or more of 2-phosphonic acid butane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, and divinylamine penta methylene phosphonic acid.

The reagents and starting materials used in the present invention are commercially available.

The photoresist cleaning agent of the present invention can be obtained by simply and uniformly mixing the components described above.

The method for using the photoresist cleaning agent of the present invention can be as follows: the semiconductor wafer containing the photoresist is immersed in a cleaning agent, slowly shaken at 20 to 85 ° C with a constant temperature oscillator, and then washed with deionized water. Dry with high purity nitrogen.

The positive effects of the present invention are:

(1) The photoresist cleaning agent of the present invention can relatively quickly clean a photoresist (especially a thick film negative photoresist) having a thickness of 20 μm or more on a metal, a metal alloy or a dielectric substrate, and other etching residues. .

(2) The photoresist cleaning agent of the present invention, while being cleaned, contains an aryl alcohol and a polyacrylic acid corrosion inhibitor of the formula I to form a protective film on the wafer pattern and the surface of the substrate to prevent halogen atoms. The attack of the wafer pattern and the substrate by hydroxide ions, etc., thereby reducing the corrosion of the wafer pattern and the substrate, especially the polyacrylic corrosion inhibitor contained therein exhibits good corrosion to the metal aluminum. System role. Therefore, it has extremely weak corrosive properties to metals such as aluminum and copper and non-metal materials such as silica.

(3) The photoresist in the photoresist cleaning agent of the invention has a low water content, further reducing the corrosiveness of the cleaning agent to metals such as aluminum and copper, and improving the cleaning ability of the positive and negative photoresists. In particular, the ability to clean negative photoresists with a high degree of crosslinking.

(4) The photoresist cleaning agent of the present invention is environmentally friendly and can be used over a wide temperature range (20-85 ° C). Summary of the invention

The invention is further illustrated by the following examples, but the invention is not limited thereto.

In the following examples, the percentages are all by mass.

Example 1~26

Table 1 shows the formulations of the photoresist cleaning agents of Examples 1 to 26 of the present invention, which were simply mixed uniformly according to the components and their contents listed in Table 1, to prepare each cleaning agent.

Photoresist embodiment 1~26 of the present invention

1,3-diethyl

Polyoxyethylene changed to 42-methyl-2-imidazolium

Polyacrylic acid

Oxyl

6.5 3.5 15 24.95 ester monoethanolamine 0.05

Benzyl hydroxyethyl ethylenedioxide salt (molecular weight 8 alcohol

5000) amine o-methacrylic acid-horse monoethanolamine 20 tetraethylmethylbenzotriene

Oxytoic acid copolymer 1 Hydroxide 0.5 1 1 75.48 0.02 azole

Phenyl bene (molecular weight is

Ammonium 2- 1500) mercaptobenzoyl

1 thiazole m-methyl methacrylate

Tetrabutyl triethanolamine 3.5 oxy-maleic acid

Hydroxide 1 3 2 90 0.08

Phenyl ethene (molecular benzotriazole hinge 0.42 is 1000) triethanolamine salt p-methyl methacryl

Tetramethyl triethanolamine 1 oxy acid triethanolamine

Oxygen oxidation 1.5 2 5 88.5 1.5

Phenylethyl salt (molecular weight 1-phenyl-5-ammonium ammonium 0.5 alcohol is 10000) tetrazolium

Isopropanolamine 1.5

2-mercaptobenzophenone

0.35 imidazole polyoxyethylene modification

Tetrapropyl ortho-aminopolyvinyl alcohol

Polyacrylic acid

2 3 - base benzene 8 85 0.05 (molecular weight 0.05

(molecular weight is

Ammonium methanol 500)

5000)

Polyvinylpyrrolidone (Molecular Weight 0.05 is 20000) Polyoxyethylene Modified Methyldiethanol Interstitial 5 Polyacrylic Acid Amine

Base hydrogen 8.5 5 base benzene 25 54.5 0.5

Ester (molecular weight 2-mercaptobenzoimidomethanol methanol 1.5 is 5000) thiazole

Dimethylethanol tetraethyl to ammonia polymethyl propylene 7.5 amine

Hydroxide 1.5 1.5 benzene 5 82 acid (molecular weight 0.3

2-mercaptobenzoammonium methanol 2500) 2.2 oxazole polyacrylic acid trishydroxyethyldibutyltetrabutyl ortho-amine 8 ethanolamine salt amine

Hydrogen peroxide 2 2 base benzene 10 73 3

(molecular weight is

Ammonium ethanol 2

20000) azole

Polyoxyethylene to diethylene glycol

30 tetramethylammonium polymethyl propyl ether ether 1 3 benzene 15 50 enoic acid diethanol 0.5 2-nitro-5- guanidine ammonium ethanolamine salt (molecular group-1,3,4-thiazide 0.5 amount 5000) diazole

Diethylene glycol monopolyoxyethylene modified 5 tetrapropyl to ammonia ether

Polyacrylic acid

Hydroxide 2.5 2.5 10 78.5 1 1-hydroxyethylidene

(molecular weight is

Ammonium

5000) keto-1,1-diphosphine 0.5 Polymethacrylic diethylene glycol single

49.8 Pair A

Triethanolamine

22 methyl hydrogen 9 5 30 1 5

Salt (molecular weight aminotrimethylene oxide methanol 0.2 is 10000) phosphinic acid

Propylene glycol monobutyl polyacrylate tri 30 tetrabutyl p-methyl ether

Ethanolamine salt

23 Hydroxide 5 5 Glyphos: it 6 49.9 4 2-phosphonic acid butane

(molecular weight is

Ammonium -1,2,4-tricarboxylate 0.1

20000)

Acid

Polyoxyethylene to dipropylene glycol monotetramethyl to ammonia 20 polyacrylic acid methyl ether

24 Hydroxide 2 2 Benzene 5 70.55 0.4

(Molecular weight is ethylenediaminetetraammonium methanol 0.05

5000) Methylphosphonic acid

Dipropylene glycol monopolyacrylic acid tris 15 tetrapropyl ether

Benzene ethanolamine salt

25 Hydroxide 2.5 2.5 10 67.95 2 Diethylenetriamine

(molecular weight is

Ammonium pentamethylenephosphonate 0.05

20000)

Polymethacrylic acid dipropylene glycol single

25 phenylacetic acid triethanolamine dibutyl ether

26 methyl hydrogen 3 3 10 52.5 1.5

Alkoxide (molecular weight hexapropylene glycol ammonium oxide 5 is 10000) Monobutyl ether effect example Comparative photoresist cleaning agent Γ~7, and the photoresist cleaning agent 1~16 of the present invention Table 2 gives a comparative cleaning agent Γ ~7' and the formulation of the photoresist cleaning agent 1~16 of the present invention are simply mixed uniformly according to the components listed in Table 1 and their contents, that is, each cleaning agent is prepared. Table 2 Comparison of photoresist cleaning agent 1, 7 ' and the composition and content of the photoresist cleaning agent 1-16 of the present invention Polyoxyethylene 1,3-dioxyethylene

Clear tetramethyl dimethyl benzoethylene diamine deprotected benzene modified polypropyl methyl -2- monoethyl ether (molecule

Washing hydroxide nitrotriazine tetramethylene water alcoholic acid (molecular imidazol alcohol amine amount is

Ammonium sulfone azolylphosphonic acid amount 5000) ketone 10000)

Γ 1.00 5.00 1 94.00 1 1 / 1 1 1

2' 1.00 5.00 1 93.50 1 1 1 1 0.50 1

3' 2.00 8.00 1 89.50 1 1 1 1 0.50 1

4' 2.00 5.00 1 92.50 1 1 1 1 0.50 1

5, 2.00 5.00 1 92.50 1 1 1 1 1 0.50

6' 3.00 6.00 5.00 86.00 1 1 1 1 1 1

7' 3.00 6.00 1 91.00 1 1 1 1 1 1

1 1.00 5.00 2.00 91.99 0.01 1 1 1 I 1

2 1.00 5.00 4.00 89.95 0.05 1 1 1 1 1

3 1.50 1.50 4.00 92.95 0.05 10.00 1 1 1 1 4 2.00 2.00 5.00 86.80 0.20 1 4.00 1 1 1

5 2.50 2.50 5.00 82.60 0.30 1 7.00 0.10 1 1

6 3.00 4.00 6.00 76.20 0.60 1 10.00 1 0.20 1

7 3.00 5.00 6.00 65.20 0.60 10.00 10.00 1 1 0.20

8 3.50 3.50 8.00 72.00 0.90 1 12.00 0.10 1 1

9 4.00 4.00 8.00 70.50 0.90 1 12.00 0.10 0.50 1

10 4.50 4.50 10.00 64.70 1.20 1 15.00 1 1 0.10

11 5.00 5.00 10.00 63.00 1.50 1 15.00 1 0.50 1

12 2.30 3.00 6.00 82.00 0.50 1 6.00 0.20 1 1

13 2.90 3.00 6.00 79.20 0.70 1 8.00 0.20 1 1

14 3.50 4.00 9.00 71.90 1.00 I 10.00 1 0.60 1

15 1.80 2.50 7.00 83.00 0.60 1 5.00 1 1 0.10

16 2.60 2.90 8.00 76.40 0.80 1 9.00 0.30 1 1

The components in Table 2 were uniformly mixed in proportion to obtain Comparative Examples 1 to 7, a cleaning agent and Examples 1 to 16 of a cleaning agent. In addition, Comparative Example Γ~6, the cleaning agent and the cleaning agents of Examples 1 to 16 were clear and transparent homogeneous solutions, except that a small amount of tetramethylammonium hydroxide was not dissolved in Comparative Example 7' cleaning agent.

Comparative Example Γ~6' cleaning agent and Examples 1 to 16 cleaning agents were used to clean the blank Qi wafer, and the corrosion of the metal Cu was measured. Test methods and conditions: A 4 X4 cm blank Cu wafer was immersed in a cleaning agent, and oscillated at a vibration frequency of about 60 rpm for 60 minutes at 20 85 ° C using a constant temperature oscillator, then washed with deionized water and then blown with high purity nitrogen gas. Dry, using a quadrupole prober to measure the change in surface resistance of the blank Cu wafer before and after etching. The results are shown in Table 3.

Comparative Example Γ~6' cleaning agent and Examples 1-16 cleaning agent were used to clean the blank A1 wafer, and the corrosion of the metal A1 was measured. Test methods and conditions: The 4X4cm blank A1 wafer was immersed in the cleaning agent, and oscillated at a vibration frequency of about 60 rpm for 60 minutes at 20 to 85 ° C using a constant temperature oscillator, then washed with deionized water and then blown with high purity nitrogen. Dry, using a quadrupole prober to measure the change in surface resistance of the blank A1 wafer before and after etching. The results are shown in Table 3. Comparative Examples Γ~6, cleaning agent and Examples 1-16 cleaning agents were used to clean blank tetraethoxysilane (TEOS) wafers for corrosion of non-metallic TEOS. Test Methods and Conditions: A 4X4 cm blank TEOS wafer was immersed in a cleaning agent, oscillated at a vibration frequency of about 60 rpm for 60 minutes at 20 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then blown with high purity nitrogen. dry. The variation of TEOS thickness before and after cleaning of the blank TEOS wafer was measured by a Nanospe _C 6100 thickness gauge. The results are shown in Table 3.

A method of cleaning a photoresist on a semiconductor wafer with a photoresist cleaning agent is as follows: immersing a semiconductor wafer (containing a pattern) containing a negative acrylate-based photoresist (having a thickness of about 50 μm, exposed and etched) in the cleaning In the solution, the mixture was shaken at a vibration frequency of about 60 rpm for 1 to 30 minutes at 20 to 85 ° C, and then washed with deionized water and then dried with high purity nitrogen. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning agent are shown in Table 3.

Table 3 Comparative Examples 1, -6, cleaning agent and Examples 1 to 16 cleaning agents for metal Cu and A1 and non-metallic TEOS corrosion and cleaning of negative photoresists

Metal Cu metal A1 non-metal TEOS photoresist wafer pattern application temperature cleaning time

Corrosion Corrosion Corrosion Case Corrosion of Cleaning Results Example CC) (min)

Γ 40 X X 〇 30 〇 ◎

2, 35 X X 〇 30 〇 ◎

3' 30 X X 〇 30 ◎ 〇

4, 20 Δ X 〇 25 ◎ Δ

5, 35 X Δ 〇 20 ◎ Δ

6' 50 〇 X ◎ 20 ◎ X

1 35 ◎ 〇 ◎ 30 〇 ◎

2 35 ◎ ◎ ◎ 30 〇 ◎

3 75 ◎ ◎ ◎ 5 ◎ ◎

4 65 ◎ ◎ ◎ 8 ◎ ◎ 5 55 ◎ ◎ ◎ 12 ◎ ◎

6 30 ◎ ◎ ◎ 15 ◎ ◎

7 40 ◎ ◎ ◎ 15 ◎ ◎

8 20 ◎ ◎ ◎ 20 ◎ ◎

9 35 ◎ ◎ ◎ 10 ◎ ◎

10 45 ◎ ◎ ◎ 10 ◎ ◎

11 20 ◎ ◎ ◎ 25 ◎ ◎

12 60 ◎ ◎ ◎ 5 ◎ ◎

13 30 ◎ ◎ ◎ 15 ◎ ◎

14 45 ◎ ◎ ◎ 10 ◎ ◎

15 70 ◎ ◎ ◎ 5 ◎ ◎

16 85 ◎ ◎ ◎ 3 ◎ ◎ Corrosion: ◎ Basically non-corrosive; Cleaning: ◎ Complete removal;

略 slightly corroded; o a small amount of residue;

Δ medium corrosion; Δ more residual;

X is severely corroded. X has a lot of residuals.

As can be seen from Table 2, compared with the comparative examples Γ~6, the cleaning agents of Examples 1 to 16 have good cleaning ability for the negative acrylate-based photoresist, and the use temperature range is wide, and at the same time, the metal Cu and A1 and non-metallic TEOS have low corrosivity and no damage to the wafer pattern.

Claims

Rights request

A photoresist cleaning agent comprising: a quaternary ammonium hydroxide, water, an aryl alcohol, dimethyl sulfoxide and a polyacrylic acid corrosion inhibitor.

The photoresist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is contained in an amount of 0.1 to 10% by mass.

The photoresist cleaning agent according to claim 2, wherein the quaternary ammonium hydroxide is contained in an amount of from 0.5 to 5% by mass.

The photoresist cleaning agent according to claim 1, wherein the water content is 0.2 to 5% by mass.

The photoresist cleaning agent according to claim 4, wherein the water content is 0.5 to 3% by mass.

The photoresist cleaning agent according to claim 1, wherein the content of the aryl alcohol represented by the formula I is 1 to 30% by mass.

The photoresist cleaning agent according to claim 6, wherein the content of the aryl alcohol represented by the formula I is from 3 to 15% by mass.

The photoresist cleaning agent according to claim 1, wherein the dimethyl sulfoxide is in a mass fraction of from 1 to 98%.

The photoresist cleaning agent according to claim 8, wherein the dimethyl sulfoxide is contained in an amount of 30 to 90% by mass.

The photoresist cleaning agent according to claim 1, wherein the polyacrylic acid corrosion inhibitor has a mass fraction of 0.01 to 5%.

The photoresist cleaning agent according to claim 10, wherein: said polypropylene

The photoresist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, or the like. One or more of butylammonium hydroxide and benzyltrimethylammonium hydroxide.

The photoresist cleaning agent according to claim 1, wherein the aryl alcohol is benzyl alcohol, phenethyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, o-Methylphenylethanol, m-methylphenylethanol, p-methylphenylethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, o-methoxyphenylethanol, m-methoxy One or more of phenylethyl alcohol, p-methoxyphenylethanol, o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, anthranilic ethanol, m-aminophenylethanol, and p-aminophenylethanol.

The photoresist cleaning agent according to claim 1, wherein the polyacrylic corrosion inhibitor is an acrylic polymer and a copolymer thereof, a methacrylic polymer and a copolymer thereof, and an acrylic polymer. Alkanolamine salt, alcoholic amine salt of methacrylic acid polymer, polyoxyethylene modified acrylic polymer and ester and alkanolammonium salt thereof, and polyoxyethylene modified methacrylic acid polymer and ester and ammonium alkoxide thereof One or more of the salts.

The photoresist cleaning agent according to claim 1, wherein the polyacrylic acid corrosion inhibitor has a molecular weight of 500 to 20,000.

The photoresist cleaning agent according to claim 15, wherein the polyacrylic acid corrosion inhibitor has a molecular weight of 1,000 to 10,000.

17. The photoresist cleaning agent according to claim 1, wherein: said photoresist cleaning agent further comprises a polar organic co-solvent, a surfactant, and a buffer other than the polyacrylic corrosion inhibitor. One or more of the etchants.

The photoresist cleaning agent according to claim 17, wherein: the content of the polar organic co-solvent is less than or equal to 50% by mass; and the content of the surfactant is less than or equal to The mass fraction is 5%; the content of the corrosion inhibitor other than the polyacrylic acid is less than or equal to 5% by mass; the above percentage does not include 0%.

The photoresist cleaning agent according to claim 18, wherein: the polar organic co-solvent is in a mass fraction of 5 to 30%; and the surfactant is in a mass fraction of 0.05- 3%; the content of the corrosion inhibitor other than the polyacrylic acid is 0.10~3% by mass.

The photoresist cleaning agent according to claim 17, wherein: the polar organic co-solvent is sulfoxide, sulfone, imidazolidinone, alkanolamine and alkyl glycol monodecyl ether. One or more; the surfactant is one or more of polyvinyl alcohol, polyvinylpyrrolidone and polyoxyethylene ether; the corrosion inhibitor other than polyacrylic acid is alcohol One or more of amine, azole and phosphonic acid corrosion inhibitors.

The photoresist cleaning agent according to claim 20, wherein: the sulfoxide is diethyl sulfoxide and/or methyl ethyl sulfoxide; and the sulfone is methyl sulfone or ethyl sulfone. And one or more of sulfolane; the imidazolidinone is 2-imidazolidinone, 1,3-dimethyl-2-imidazolium and 1,3-diethyl-2-imidazolium One or more of the above; the alcohol amine is one of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methyldiethanolamine, dimethylethanolamine, and hydroxyethylethylenediamine. Or a plurality of; the alkyl glycol monoalkyl ether is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, One or more of dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether; the alcohol amine corrosion inhibitor is monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methyldiethanolamine, dimethyl One or more of ethanolamine and hydroxyethylethylenediamine; The azole inhibitors are benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt,

2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, dimercaptothiadiazole, 3-amino-1,2,4-triazole, 4-amino-1,2, 4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 4-amino-5-mercapto-1 One or more of 2,4-triazole, 5-amino-tetrazole and 1-phenyl-5-mercaptotetrazole; the phosphonic acid corrosion inhibitor is 1-hydroxyl Ethyl-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriamine One or more of methylene phosphonic acids.

The photoresist cleaning agent according to claim 17, wherein the surfactant has a molecular weight of 500 to 20,000.

The photoresist cleaning agent according to claim 22, wherein: said surface is alive