CN102117022A - Photoresist detergent composition - Google Patents
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- CN102117022A CN102117022A CN2009102476596A CN200910247659A CN102117022A CN 102117022 A CN102117022 A CN 102117022A CN 2009102476596 A CN2009102476596 A CN 2009102476596A CN 200910247659 A CN200910247659 A CN 200910247659A CN 102117022 A CN102117022 A CN 102117022A
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Abstract
The invention discloses a photoresist detergent composition, which comprises quaternary ammonium hydroxides, water, alkyl diol ether, dimethyl sulfoxide, a corrosion inhibitor and surfactants. The photoresist detergent composition can remove the photoresist (particuarly thick film negative photoresist) with a thickness of over 20 micrometers on the metals, metal alloys or dielectric medium substrates, and other etching residues, and meanwhile, the composition has low causticity to the metals such as aluminum, copper and the like and the nonmetallic materials such as silicon dioxide and the like, thus, the composition has good application prospect in the micro-electronics fields such as semiconductor chip cleaning, and the like.
Description
Technical field
The present invention relates to a kind of cleansing composition in the semiconductor fabrication process, relate to a kind of quaternary ammonium hydroxide that contains particularly, water, alkyl diol aryl ether, dimethyl sulfoxide (DMSO), the photoresist cleansing composition of corrosion inhibiter and surfactant.
Background technology
In common semiconductor fabrication process, at first go up the coating that forms photoresist on surfaces such as silicon dioxide, Cu metals such as (copper) and low-k materials, utilize suitable mask to expose, develop, according to characteristic with photoresist, remove the photoresist of exposure or unexposed portion, form the photoresist pattern at desired position, on this photoresist pattern, carry out plasma etching or reactant gas etching then, carry out figure transfer.Low temperature cleaning fast is the important directions of semiconductor wafer fabrication process development.The negative photoresist of the above thickness of 20 μ m is applied in the semiconductor wafer fabrication process just gradually, and at present industrial most photoresist clean-out system is better to the cleansing power of positive photoresist, but can not thoroughly remove on the wafer especially thick film negative photoresist of the negative photoresist with cross-linked structure after exposure and etching.
Carry out in the chemical cleaning process of photoresist at semiconductor wafer, clean-out system regular meeting causes the corrosion of wafer pattern and base material.Particularly utilizing chemical to remove in the process of photoresist and etch residue, metal (especially aluminium and copper etc. are than the active metal) corrosion is comparatively generally and very serious problem, often causes the remarkable reduction of wafer yield.
At present, the photoresist cleansing composition mainly is made up of highly basic, polar organic solvent and/or water etc., by immersing semiconductor wafer in the clean-out system or utilizing clean-out system flushing semiconductor wafer, removes the photoresist on the semiconductor wafer.
Highly basic such as potassium hydroxide, quaternary ammonium hydroxide and hydramine etc. can dissolve photoresist and/or photoresist residue that etching produced.Highly basic content is crossed when hanging down, and clean-out system is to the removal scarce capacity of photoresist and/or the photoresist residue that etching produced; But during the highly basic too high levels, clean-out system easily causes the corrosion of wafer pattern and base material.Compare with the clean-out system of being made up of hydramine, the clean-out system that contains potassium hydroxide or quaternary ammonium hydroxide is better to the removal ability of photoresist and/or the photoresist residue that etching produced.But the clean-out system that contains potassium hydroxide easily causes the corrosion of wafer pattern and base material, and its to the removal of photoresist to peel off mode, make photoresist form fragment shape overburden or gluey swelling thing, cause deposition or the adhesion of photoresist easily, even cause the damage of wafer pattern in wafer surface.The clean-out system that contains quaternary ammonium hydroxide has concurrently the removal of photoresist and peels off and dissolve two kinds of effects, can not cause deposition or the adhesion of photoresist in wafer surface.
Polar organic solvent can dissolve photoresist and/or photoresist residue that etching produced, improves chemical to organic cleansing power.Polar organic solvent content is crossed when hanging down, and clean-out system is to the removal scarce capacity of photoresist and/or the photoresist residue that etching produced; But during the polar organic solvent too high levels, the corresponding reduction of highly basic content in the clean-out system makes clean-out system weaken the removal ability of photoresist and/or the photoresist residue that etching produced.
In order to improve hydrolysis and/or the dissolving power of clean-out system to photoresist and/or the photoresist residue that etching produced, the water in the chemical is essential sometimes.But when liquid water content was too high, clean-out system was to the removal scarce capacity of photoresist and/or the photoresist residue that etching produced, and easily caused the corrosion of wafer pattern and base material.
The photoresist clean-out system be made up of hydramine and organic polar solvent has been proposed among the US4617251.Semiconductor wafer is immersed in this clean-out system, under 95 ℃, remove the positive photoresist on the wafer.But do not contain water in this clean-out system, and it is to the cleansing power deficiency of negative photoresist.
The photoresist clean-out system be made up of hydramine, water-miscible organic solvent, water, organic phenolic compounds, triazole compounds and polysiloxane surfactant has been proposed among the US6140027.Semiconductor wafer is immersed in this clean-out system, under 20～50 ℃, remove the photoresist residue that photoresist on the wafer and etching are produced.This clean-out system adopts organic phenolic compounds and triazole compounds as the corrosion inhibiter that suppresses metal erosion.Organic phenolic compounds is harmful, and can pollute environment.This clean-out system is to the cleansing power deficiency of negative photoresist.
The photoresist clean-out system be made up of less than 1% water potassium hydroxide, propylene glycol, N-Methyl pyrrolidone, surfactant, 1,3 butylene glycol, diglycolamine and quality percentage composition has been proposed among the US5962197.Semiconductor wafer is immersed in this clean-out system, under 90～110 ℃, remove the photoresist on the wafer.Contain potassium hydroxide in this clean-out system, higher to the corrosion of wafer substrate, and also its stripping photoresist formed fragment shape overburden or gluey swelling thing can deposit or adhesion on wafer surface, causes the damage of the residual and wafer pattern of photoresist.
The photoresist clean-out system be made up of Tetramethylammonium hydroxide, N-methylmorpholine-N-oxide, water and 2-mercaptobenzimidazole has been proposed among the WO2004059700.Semiconductor wafer is immersed in this clean-out system, under 70 ℃, remove the photoresist on the wafer.This clean-out system adopts N-methylmorpholine-N-oxide as oxygenant, adopts 2-mercaptobenzimidazole as metal corrosion inhibitor.This clean-out system needs cleaning photoetching glue under higher temperature, and is slightly high to the corrosion of semiconductor wafer pattern and base material, and slightly inadequate to the cleansing power of photoresist.
The photoresist clean-out system that 3 '-dimethyl-2-imidazolidinone and water are formed has been proposed among the US6040117 by quaternary ammonium hydroxide, dimethyl sulfoxide (DMSO), 1.Semiconductor wafer is immersed in this clean-out system, at the photoresist of removing the above thickness of 10 μ m on metal (gold, copper, lead or the nickel) base material under 40～95 ℃.This clean-out system adopt price comparatively expensive 1,3 '-dimethyl-2-imidazolidinone is as organic cosolvent, and do not contain the corrosion inhibiter that suppresses metal (especially aluminium etc. than the active metal) corrosion.This clean-out system needs cleaning photoetching glue under higher temperature, and is slightly high to the corrosion of semiconductor wafer pattern and base material.
The photoresist clean-out system be made up of quaternary ammonium hydroxide, water-miscible organic solvent, organic amine, binary alcohol and water has been proposed among the JP2001215736.Semiconductor wafer is immersed in this clean-out system, under 20～90 ℃, remove the photoresist of the 20 μ m～40 μ m thickness on the wafer.This clean-out system adopts dibasic alcohol as the corrosion inhibiter that suppresses metal erosion, but dibasic alcohol is very weak to the inhibition ability of metal erosion, and can reduce the cleansing power of clean-out system to photoresist especially negative photoresist.This clean-out system is slightly high to the corrosion of semiconductor wafer pattern and base material.
The photoresist clean-out system be made up of quaternary ammonium hydroxide, N-Methyl pyrrolidone, diethanolamine or triethanolamine, water and methyl alcohol or ethanol has been proposed among the JP2004093678.Semiconductor wafer is immersed in this clean-out system, under 15～80 ℃, remove the photoresist of the above thickness of 10 μ m on the wafer.This clean-out system employing methyl alcohol or ethanol are as the solubilizer of quaternary ammonium hydroxide, but the flash-point of methyl alcohol or ethanol is low excessively, and can reduce the cleansing power of clean-out system to photoresist especially negative photoresist.This clean-out system does not contain the corrosion inhibiter that suppresses metal (especially aluminium and copper etc. are than the active metal) corrosion.This clean-out system is slightly high to the corrosion of semiconductor wafer pattern and base material.
In sum, existing photoresist clean-out system is to the cleansing power deficiency of the higher photoresist of thickness, and perhaps the corrosivity to semiconductor wafer pattern and base material is stronger, has bigger defective.
Summary of the invention
The technical problem to be solved in the present invention be at existing photoresist clean-out system to thick film photolithography glue cleansing power deficiency, to semiconductor wafer pattern and the stronger and environmentally harmful defective of base material corrosivity, provide a kind of to the photoresist cleansing power strong and lower to semiconductor wafer pattern and base material corrosivity, as to be beneficial to environmental protection photoresist cleansing composition.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of photoresist cleansing composition comprises: quaternary ammonium hydroxide, water, alkyl diol aryl ether, dimethyl sulfoxide (DMSO), corrosion inhibiter and surfactant.
Among the present invention, described quaternary ammonium hydroxide is selected from one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH and/or the benzyltrimethylammonium hydroxide.
Among the present invention, the quality percentage composition of described quaternary ammonium hydroxide is 0.1～10%.
Among the present invention, the quality percentage composition of described water is 0.2～15%.
Among the present invention, the carbon atom number of the alkyl diol in the described alkyl diol aryl ether is 3～18.
Among the present invention, described alkyl diol aryl ether is selected from the single phenyl ether of propylene glycol list phenyl ether, Isopropanediol list phenyl ether, diethylene glycol list phenyl ether, dipropylene glycol, di-isopropylene glycol list phenyl ether, triethylene glycol list phenyl ether, tripropylene glycol list phenyl ether, three Isopropanediol list phenyl ethers, six condensed ethandiol list phenyl ethers, six contract in Isopropanediol list phenyl ether, propylene glycol single-benzyl ether, Isopropanediol single-benzyl ether and the hexanediol list naphthyl ether one or more of propylene glycol list phenyl ether, six that contract.
Among the present invention, the quality percentage composition of described alkyl diol aryl ether is 0.1～65%.
Among the present invention, the quality percentage composition of described dimethyl sulfoxide (DMSO) is 1～98%.
Among the present invention, described corrosion inhibiter is selected from one or more in citric acid, citrate and the citrate.
Among the present invention, described citric acid, citrate and citrate are selected from citric acid, the 2-hydroxycitric acid, trimethyl citrate, triethyl citrate, citric acid three propyl ester, tributyl citrate, citric acid three own esters, trioctyl lemon acid, acetyl triethyl citrate, acetyl tributyl citrate three propyl ester, tributyl 2-acetylcitrate, acetyl tributyl citrate three own esters, acetyl tributyl citrate three monooctyl esters, butyryl citric acid three own esters, citric acid bay alcohol ester, citric acid glyceride, citric acid monoethanolamine ester, the citric acid triethanolamine ester, citric acid diglycolamine ester, citric acid isopropanolamine ester, the shitosan citrate, the citric acid imidazoline ester, ammonium dihydrogen citrate, diammonium hydrogen citrate, Triammonium citrate, the citric acid tetramethyl-ammonium, the citric acid tetraethyl ammonium, the citric acid tetrapropyl ammonium, the citric acid TBuA, the citric acid benzyltrimethylammon.um, the monoethanolamine citrate, the diethanolamine citrate, the triethanolamine citrate, the diglycolamine citrate, the isopropanolamine citrate, the methylethanolamine citrate, the methyldiethanolamine citrate, the triethylamine citrate, in piperazine citrate and/or the oxine citrate one or more.
Among the present invention, the gross mass percentage composition of described citric acid, citrate and citrate is 0.01～10%.
Among the present invention, described surfactant is selected from one or more in polydiene alcohol, polyvinylpyrrolidone and the polyoxyethylene ether.
Among the present invention, the number-average molecular weight of described surfactant is 500～20000.
Among the present invention, the quality percentage composition of described surfactant is≤5%.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Photoresist cleansing composition of the present invention can be made by the simple mixing of top described component.
Photoresist cleansing composition of the present invention can use (between 20～85 ℃) in wider temperature range.Cleaning method can be with reference to following steps: the semiconductor wafer that will contain photoresist immerses in the cleansing composition, utilizes constant temperature oscillator slowly to vibrate under 20～85 ℃, dries up with high pure nitrogen behind deionized water wash then.
Positive progressive effect of the present invention is:
(1) comparatively promptly photoresist and other etch residue of the above thickness of 20 μ m on clean metal, metal alloy or the dielectric substrate of photoresist cleansing composition of the present invention.
(2) the alkyl diol aryl ether that contains of photoresist cleansing composition of the present invention can improve the solubleness of quaternary ammonium hydroxide in dimethyl sulfoxide (DMSO), and the increase of quaternary ammonium hydroxide content helps improving cleansing composition among the present invention to the cleansing power of the negative photoresist of photoresist especially high-crosslinking-degree.
(3) the alkyl diol aryl ether that contains in the photoresist cleansing composition of the present invention shows good inhibition effect to the corrosion of metal such as copper.
(4) photoresist cleansing composition of the present invention shows extremely weak corrosivity to nonmetallic materials such as silicon dioxide.
(5) corrosion inhibiter that is selected from citric acid, citrate and citrate that contains in the photoresist cleansing composition of the present invention shows good inhibition effect to corrosion of metal, can effectively suppress to corrode on wafer pattern and the base material generation of dim spot (spot corrosion).
(6) corrosion inhibiter that is selected from citric acid, citrate and citrate that contains in the photoresist cleansing composition of the present invention is easy to biodegradation, helps environmental protection.
(7) the polyacrylic corrosion inhibiter that can contain in the photoresist cleansing composition of the present invention shows extremely strong inhibiting effect to the corrosion of metal especially aluminium, can further suppress the corrosion of wafer pattern and base material.
(8) photoresist cleansing composition of the present invention can dissolve thick film photolithography glue (especially thick film negative photoresist) and other etch residue of the high-crosslinking-degree of removing on the semiconductor wafer, avoid deposition or the adhesion of photoresist, and can not cause the corrosion or the damage of wafer pattern in wafer surface.
(9) photoresist cleansing composition of the present invention can (20～85 ℃) use in wider temperature range.
Embodiment
Mode below by embodiment further specifies the present invention.Among the following embodiment, number percent is mass percent.
Embodiment 1～26
Table 1 has provided the prescription of photoresist cleansing composition embodiment 1～26 of the present invention, presses listed component and content thereof in the table 1, simply mixes, and promptly makes each cleansing composition.
Table 1 photoresist cleansing composition of the present invention embodiment 1～26
Further specify beneficial effect of the present invention below by the preferred effect embodiment of the present invention.
Effect embodiment contrasts cleansing composition 1 '～7 '
Table 2 has provided the prescription of contrast cleansing composition 1 '～7 ', presses listed component and content thereof in the table 2, simply mixes, and promptly makes each cleansing composition.
Component and the content of table 2 contrast cleansing composition 1 '～7 '
| Clean-out system | Tetramethylammonium hydroxide | Deionized water | Propylene glycol list phenyl ether | Dimethyl sulfoxide (DMSO) | Citric acid | The monoethanolamine citrate | Sulfolane | Monoethanolamine | Polyvinylpyrrolidone (number-average molecular weight is 10000) | Methyl benzotriazazole | The polymethylacrylic acid of polyoxyethylene modification (number-average molecular weight is 10000) |
| 1’ | 1.00 | 4.00 | / | 95.00 | / | / | / | / | / | / | / |
| 2’ | 1.50 | 4.00 | / | 94.30 | / | / | / | / | / | 0.20 | / |
| 3’ | 2.00 | 4.00 | / | 93.55 | / | / | / | / | 0.10 | 0.35 | / |
| 4’ | 2.00 | 6.00 | / | 71.65 | / | / | 20.00 | / | / | 0.35 | / |
| 5’ | 2.00 | 3.00 | / | 93.70 | / | / | / | 1.00 | / | 0.30 | / |
| 6’ | 3.00 | 6.00 | 5.00 | 86.00 | / | / | / | / | / | / | / |
| 7’ | 3.00 | 6.00 | / | 91.00 | / | / | / | / | / | / | / |
Various components in the table 2 are proportionally mixed, make contrast cleansing composition 1 '～7 '.Wherein, have in contrast cleansing composition 7 ' a small amount of undissolved granular Tetramethylammonium hydroxide, contrast cleansing composition 1 '～6 ' is the homogeneous phase solution of clear.
Contrast cleansing composition in the table 21 '～6 ' and 11～26 pairs of three kinds of blank wafer of cleansing composition of the present invention are cleaned with the semiconductor wafer that contains photoresist, and test result sees Table 3.
1, contrast cleansing composition in the table 21 '～6 ' and cleansing composition 11～26 of the present invention are used to clean blank Cu wafer, test its corrosion situation metal Cu.Method of testing and condition: the blank Cu wafer of 4 * 4cm is immersed in the cleansing composition, under 20～85 ℃, utilize constant temperature oscillator vibration 60 minutes, behind deionized water wash, dry up then, utilize four utmost point probe machines to measure blank Cu chip etching front and rear surfaces changes in resistance and calculate with high pure nitrogen.The result is as shown in table 3.
2, contrast cleansing composition in the table 21 '～6 ' and cleansing composition 11～26 of the present invention are used to clean blank Al wafer, test its corrosion situation metal A l.Method of testing and condition: the blank Al wafer of 4 * 4cm is immersed in the cleansing composition, under 20～85 ℃, utilize constant temperature oscillator vibration 60 minutes, behind deionized water wash, dry up then, utilize four utmost point probe machines to measure blank Al chip etching front and rear surfaces changes in resistance and calculate with high pure nitrogen.The result is as shown in table 3.
3, contrast cleansing composition in the table 21 '～6 ' and cleansing composition 11～26 of the present invention are used to clean blank tetraethoxysilane (TEOS) wafer, test its corrosion situation nonmetal TEOS.Method of testing and condition: the blank TEOS wafer of 4 * 4cm is immersed in the cleansing composition, under 20～85 ℃, utilize constant temperature oscillator vibration 60 minutes, behind deionized water wash, dry up then with high pure nitrogen.The change calculations of utilizing the Nanospec6100 thicknessmeter to measure blank TEOS wafer cleaning front and back TEOS thickness obtains, and the result is as shown in table 3.
4, the contrast cleansing composition in the table 21 '～6 ' and cleansing composition 11～26 of the present invention are used to clean photoresist on the semiconductor wafer.Cleaning method is as follows: (thickness is about 60 microns will to contain negativity esters of acrylic acid photoresist, and through overexposure and etching) semiconductor wafer (containing pattern) immerse in the cleansing composition shown in the table 2, under 20～85 ℃, utilize constant temperature oscillator vibration 1～30 minute, behind deionized water wash, dry up then with high pure nitrogen.The cleaning performance of photoresist and cleansing composition are as shown in table 3 to the corrosion situation of wafer pattern.
Table 3 contrast cleansing composition 1 '～6 ' is with the corrosivity of 27～42 couples of metal Cu of cleansing composition of the present invention and Al and nonmetal TEOS and to the negative photoresist cleaning situation of (thickness is about 60 microns)
| ? | Cleaning temperature (℃) | The corrosion feelings of metal Cu | The corrosion feelings of metal A l | The corrosion of nonmetal TEOS | The photoresist scavenging period | Photoresist cleans knot Really | Wafer pattern and base material The corrosion situation |
| Condition | Condition | Situation | (min) | ||||
| ? Comparative Examples 1 ' | 40 | × | × | ○ | 30 | ○ | ◎ |
| ? Comparative Examples 2 ' | 35 | △ | × | ○ | 30 | ○ | ◎ |
| ? Comparative Examples 3 ' | 30 | △ | × | ○ | 20 | ◎ | ○ |
| ? Comparative Examples 4 ' | 20 | × | × | ○ | 25 | ◎ | △ |
| ? Comparative Examples 5 ' | 35 | × | × | ◎ | 20 | ◎ | ○ |
| ? Comparative Examples 6 ' | 40 | ○ | × | ◎ | 20 | ◎ | × |
| ? Embodiment 11 | 40 | ◎ | ◎ | ◎ | 30 | ○ | ◎ |
| ? Embodiment 12 | 40 | ◎ | ◎ | ◎ | 30 | ◎ | ◎ |
| ? Embodiment 13 | 55 | ◎ | ◎ | ◎ | 18 | ◎ | ◎ |
| ? Embodiment 14 | 50 | ◎ | ◎ | ◎ | 16 | ◎ | ◎ |
| ? Embodiment 15 | 45 | ◎ | ◎ | ◎ | 13 | ◎ | ◎ |
| ? Embodiment 16 | 75 | ◎ | ◎ | ◎ | 5 | ◎ | ◎ |
| ? Embodiment 17 | 35 | ◎ | ◎ | ◎ | 15 | ◎ | ◎ |
| ? Embodiment 18 | 65 | ◎ | ◎ | ◎ | 9 | ◎ | ◎ |
| ? Embodiment 19 | 30 | ◎ | ◎ | ◎ | 20 | ◎ | ◎ |
| ? Embodiment 20 | 25 | ◎ | ◎ | ◎ | 25 | ◎ | ◎ |
| ? Embodiment 21 | 20 | ◎ | ◎ | ◎ | 30 | ◎ | ◎ |
| ? Embodiment 22 | 85 | ◎ | ◎ | ◎ | 1 | ◎ | ◎ |
| ? Embodiment 23 | 70 | ◎ | ◎ | ◎ | 6 | ◎ | ◎ |
| ? Embodiment 24 | 55 | ◎ | ◎ | ◎ | 10 | ◎ | ◎ |
| ? Embodiment 25 | 80 | ◎ | ◎ | ◎ | 3 | ◎ | ◎ |
| ? Embodiment 26 | 60 | ◎ | ◎ | ◎ | 8 | ◎ | ◎ |
| The corrosion situation: | ◎ does not have corrosion substantially; | The cleaning situation: | ◎ removes fully; | |
| Zero slightly corrosion; | Zero small portion of residual; | |||
| The △ moderate corrosion; | The more remnants of △; | |||
| * heavy corrosion. | * abundant residues. |
In addition, (thickness is about 150 microns will to contain the negativity esters of acrylic acid photoresist of high-crosslinking-degree, and through overexposure and etching) semiconductor wafer (containing pattern) immerse in the cleansing composition of the present invention 16～26 shown in the table 2, under 40～85 ℃, utilize constant temperature oscillator vibration 10～60 minutes, behind deionized water wash, dry up then with high pure nitrogen.The cleaning performance of photoresist and cleansing composition are as shown in table 4 to the corrosion situation of wafer pattern.
32～42 pairs of negativity esters of acrylic acids of cleansing composition of the present invention in table 4 table 2
The cleaning situation of photoresist (thickness is about 150 microns)
| Embodiment | Cleaning temperature (℃) | The photoresist scavenging period (min) | Photoresist cleans knot Really | Wafer pattern and base material Corrosion situation 200910247659.6 |
| 16 | 75 | 15 | ◎ | ◎ |
| 17 | 55 | 35 | ◎ | ◎ |
| 18 | 65 | 25 | ◎ | ◎ |
| 19 | 50 | 48 | ◎ | ◎ |
| 20 | 45 | 54 | ◎ | ◎ |
| 21 | 40 | 60 | ◎ | ◎ |
| 22 | 85 | 10 | ◎ | ◎ |
| 23 | 70 | 20 | ◎ | ◎ |
| 24 | 55 | 42 | ◎ | ◎ |
| 25 | 80 | 12 | ◎ | ◎ |
| 26 | 60 | 30 | ◎ | ◎ |
The corrosion feelings
◎ does not have corrosion substantially;Clean feelings
◎ removes fully;
Condition:
Condition:
Zero slightly corrosion;
Zero small portion of residual;
The △ moderate corrosion;
The more remnants of △;
* heavy corrosion.
* abundant residues.
From table 3 and table 4 as can be seen, compare with contrast cleansing composition 1 '～6 ', 11～26 pairs of thick film negativity of cleansing composition of the present invention esters of acrylic acid photoresist has good cleansing power, the serviceability temperature scope is wide, corrosivity to metal Cu and Al and nonmetal TEOS is very low simultaneously, and wafer pattern is not had corrosion or damage.
In sum, photoresist cleansing composition among the present invention, can be at thick film photolithography glue and other etch residue of removing under 20～85 ℃ more than the 20 μ m, and its alkyl diol aryl ether that contains and the corrosion inhibiter that is selected from citric acid, citrate and citrate can form layer protecting film at wafer pattern and substrate surface, stop the attack to wafer pattern and base material such as halogen atom, hydroxide ion, thereby reduce the corrosion of wafer pattern and base material; Especially the corrosion inhibiter that is selected from citric acid, citrate and citrate that it contains shows good inhibition effect to corrosion of metal, can effectively suppress to corrode on wafer pattern and the base material generation of dim spot (spot corrosion).The corrosion inhibiter that is selected from citric acid, citrate and citrate that contains in the photoresist cleansing composition of the present invention is easy to biodegradation, helps environmental protection.Photoresist cleansing composition of the present invention shows extremely weak corrosivity to nonmetallic materials such as silicon dioxide.The polyacrylic corrosion inhibiter that can contain in the photoresist cleansing composition of the present invention shows extremely strong inhibiting effect to the corrosion of metal especially aluminium, can further suppress the corrosion of wafer pattern and base material.Photoresist cleansing composition among the present invention can dissolve the thick film negative photoresist of the high-crosslinking-degree of removing on the semiconductor wafer, avoids deposition or the adhesion of photoresist in wafer surface, and can not cause the corrosion or the damage of wafer pattern and base material.
Claims (14)
1. a photoresist cleansing composition comprises: quaternary ammonium hydroxide, water, alkyl diol aryl ether, dimethyl sulfoxide (DMSO), corrosion inhibiter and surfactant.
2. photoresist cleansing composition as claimed in claim 1, described quaternary ammonium hydroxide is selected from one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH and/or the benzyltrimethylammonium hydroxide.
3. photoresist cleansing composition as claimed in claim 1, the quality percentage composition of described quaternary ammonium hydroxide is 0.1～10%.
4. photoresist cleansing composition as claimed in claim 1, the quality percentage composition of described water is 0.2～15%.
5. photoresist cleansing composition as claimed in claim 1, the carbon atom number of the alkyl diol in the described alkyl diol aryl ether is 3～18.
6. photoresist cleansing composition as claimed in claim 5, described alkyl diol aryl ether are selected from the single phenyl ether of propylene glycol list phenyl ether, Isopropanediol list phenyl ether, diethylene glycol list phenyl ether, dipropylene glycol, di-isopropylene glycol list phenyl ether, triethylene glycol list phenyl ether, tripropylene glycol list phenyl ether, three Isopropanediol list phenyl ethers, six condensed ethandiol list phenyl ethers, six contract in Isopropanediol list phenyl ether, propylene glycol single-benzyl ether, Isopropanediol single-benzyl ether and the hexanediol list naphthyl ether one or more of propylene glycol list phenyl ether, six that contract.
7. photoresist cleansing composition as claimed in claim 1, the quality percentage composition of described alkyl diol aryl ether is 0.1～65%.
8. photoresist cleansing composition as claimed in claim 1, the quality percentage composition of described dimethyl sulfoxide (DMSO) is 1～98%.
9. photoresist cleansing composition as claimed in claim 1, described corrosion inhibiter is selected from one or more in citric acid, citrate and the citrate.
10. photoresist cleansing composition as claimed in claim 9, described citric acid, citrate and citrate are selected from citric acid, the 2-hydroxycitric acid, trimethyl citrate, triethyl citrate, citric acid three propyl ester, tributyl citrate, citric acid three own esters, trioctyl lemon acid, acetyl triethyl citrate, acetyl tributyl citrate three propyl ester, tributyl 2-acetylcitrate, acetyl tributyl citrate three own esters, acetyl tributyl citrate three monooctyl esters, butyryl citric acid three own esters, citric acid bay alcohol ester, citric acid glyceride, citric acid monoethanolamine ester, the citric acid triethanolamine ester, citric acid diglycolamine ester, citric acid isopropanolamine ester, the shitosan citrate, the citric acid imidazoline ester, ammonium dihydrogen citrate, diammonium hydrogen citrate, Triammonium citrate, the citric acid tetramethyl-ammonium, the citric acid tetraethyl ammonium, the citric acid tetrapropyl ammonium, the citric acid TBuA, the citric acid benzyltrimethylammon.um, the monoethanolamine citrate, the diethanolamine citrate, the triethanolamine citrate, the diglycolamine citrate, the isopropanolamine citrate, the methylethanolamine citrate, the methyldiethanolamine citrate, the triethylamine citrate, in piperazine citrate and/or the oxine citrate one or more.
11. photoresist cleansing composition as claimed in claim 1, the gross mass percentage composition of described citric acid, citrate and citrate is 0.01～10%.
12. photoresist cleansing composition as claimed in claim 1, described surfactant is selected from one or more in polydiene alcohol, polyvinylpyrrolidone and the polyoxyethylene ether.
13. photoresist cleansing composition as claimed in claim 1, the number-average molecular weight of described surfactant are 500～20000.
14. photoresist cleansing composition as claimed in claim 1, the quality percentage composition of described surfactant is≤5%.
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| CN102981379A (en) * | 2012-12-19 | 2013-03-20 | 青岛华电高压电气有限公司 | Cleaning agent composition for photoresist |
| CN104450280A (en) * | 2014-11-17 | 2015-03-25 | 如皋市大昌电子有限公司 | Cleaning liquid special for diode semiconductor |
| US20150212414A1 (en) * | 2012-11-30 | 2015-07-30 | Rohm And Haas Electronic Materials Llc | Ionic thermal acid generators for low temperature applications |
| CN105297046A (en) * | 2014-06-16 | 2016-02-03 | 上海蓝浦清洗技术有限公司 | Environment-friendly neutral cleaning agent |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150212414A1 (en) * | 2012-11-30 | 2015-07-30 | Rohm And Haas Electronic Materials Llc | Ionic thermal acid generators for low temperature applications |
| US9541834B2 (en) * | 2012-11-30 | 2017-01-10 | Rohm And Haas Electronic Materials Llc | Ionic thermal acid generators for low temperature applications |
| CN102981379A (en) * | 2012-12-19 | 2013-03-20 | 青岛华电高压电气有限公司 | Cleaning agent composition for photoresist |
| CN105297046A (en) * | 2014-06-16 | 2016-02-03 | 上海蓝浦清洗技术有限公司 | Environment-friendly neutral cleaning agent |
| CN104450280A (en) * | 2014-11-17 | 2015-03-25 | 如皋市大昌电子有限公司 | Cleaning liquid special for diode semiconductor |
| CN104450280B (en) * | 2014-11-17 | 2017-06-06 | 如皋市大昌电子有限公司 | A kind of diode semiconductor special cleaning |
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