WO2014079145A1 - 一种去除光刻胶的清洗液 - Google Patents
一种去除光刻胶的清洗液 Download PDFInfo
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- WO2014079145A1 WO2014079145A1 PCT/CN2013/001375 CN2013001375W WO2014079145A1 WO 2014079145 A1 WO2014079145 A1 WO 2014079145A1 CN 2013001375 W CN2013001375 W CN 2013001375W WO 2014079145 A1 WO2014079145 A1 WO 2014079145A1
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- WIPO (PCT)
- Prior art keywords
- cleaning solution
- cleaning
- hydroxide
- photoresist
- solution according
- Prior art date
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- 238000004140 cleaning Methods 0.000 title claims abstract description 52
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 36
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 15
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 8
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 235000010356 sorbitol Nutrition 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000811 xylitol Substances 0.000 claims description 8
- 235000010447 xylitol Nutrition 0.000 claims description 8
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 8
- 229960002675 xylitol Drugs 0.000 claims description 8
- 239000004386 Erythritol Substances 0.000 claims description 7
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 7
- -1 alcohol amine Chemical class 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 7
- 235000019414 erythritol Nutrition 0.000 claims description 7
- 229940009714 erythritol Drugs 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 7
- 150000003457 sulfones Chemical class 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- 229930195725 Mannitol Natural products 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000594 mannitol Substances 0.000 claims description 6
- 235000010355 mannitol Nutrition 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229940102253 isopropanolamine Drugs 0.000 claims description 5
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- NKAWWXQVDJITSK-UHFFFAOYSA-M ethyl-(hydroxymethyl)-dimethylazanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CO NKAWWXQVDJITSK-UHFFFAOYSA-M 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 229960001855 mannitol Drugs 0.000 claims description 2
- 229960002920 sorbitol Drugs 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims 3
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical group CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 claims 2
- 239000012530 fluid Substances 0.000 claims 2
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KCOPAESEGCGTKM-UHFFFAOYSA-N 1,3-oxazol-4-one Chemical compound O=C1COC=N1 KCOPAESEGCGTKM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ULWOJODHECIZAU-UHFFFAOYSA-N n,n-diethylpropan-2-amine Chemical compound CCN(CC)C(C)C ULWOJODHECIZAU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Definitions
- the present invention relates to a cleaning liquid, and more particularly to a cleaning liquid for removing a photoresist. Background technique
- 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.
- 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.
- WO2006/056298A1 utilizes an alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMS0), ethylene glycol (EG) and water for cleaning a copper substrate photoresist, 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. Immersion in the cleaning solution removes the thick film photoresist on the metal and dielectric substrates at 40-90 °C. It has a high corrosion to the semiconductor wafer substrate.
- TMAH tetramethylammonium hydroxide
- DMS0 dimethyl sulfoxide
- EG ethylene glycol
- water water for cleaning a copper substrate photoresist
- K0H potassium hydroxide
- mercapto diol monodecyl ether
- the technical problem to be solved by the present invention is to provide a thick film photoresist cleaning for 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 capable and less corrosive to semiconductor wafer patterns and substrates.
- the present invention provides a cleaning liquid containing a quaternary ammonium hydroxide, an alcohol amine, a c 4 -c 6 polyol, and a solvent.
- the content of the quaternary ammonium hydroxide is 0.1 to 10% by weight (mass%), preferably 1 to 5 wt%
- the content of the alkanolamine is not more than 5% by weight, i.e., less than 5% by weight.
- the content of the C 4 -C 6 polyol is 0.1 to 10 wt %, preferably 0. b 5 wt %
- the remaining portion of the cleaning liquid is a solvent.
- the cleaning liquid for removing photoresist residues disclosed in the present invention does not contain abrasive particles.
- the quaternary ammonium hydroxide is preferably a quaternary ammonium hydroxide including tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylamine.
- ammonium hydroxide and hydroxyethyltrimethylammonium hydroxide One or more of ammonium hydroxide and hydroxyethyltrimethylammonium hydroxide.
- sodium hydroxide, potassium hydroxide or the like is generally used as an alkaline component, but such a substance has a tendency to absorb co 2 in the air to generate a solid, which affects side effects such as washing, and therefore, quaternary ammonium hydroxide is used in the present application. Things.
- the alkanolamine is preferably an alcoholamine which is monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanolamine and diglycolamine. One or several of them.
- the presence of an alkanolamine is advantageous for increasing the solubility of the quaternary ammonium hydroxide.
- the C 4 -C 6 polyol is preferably one or more of erythritol, xylitol, glucose, sorbitol, and mannitol.
- the organic solvent is preferably one or more of sulfoxide, sulfone, imidazolium, imidazolidinone, and amide; wherein the sulfoxide is preferably dimethyl sulfoxide; the sulfone is preferably Sulfolane; imidazolium is preferably 1,3-dimethyl-2-imidazolium; imidazolidinone is preferably 1,3-dimethyl-2-imidazole
- the amide is preferably one or more of dimethylformamide and dimethylacetamide.
- the photoresist on the wafer can be cleaned at 25 ° C to 90 ° C.
- the specific method is as follows: The photoresist containing the photoresist is immersed in the low-etching photoresist cleaning agent of the present invention, and after immersing at 25 ° C to 90 ° C for a suitable period of time, it is taken out and washed, and then dried by high-purity nitrogen gas.
- the positive progress of the invention is as follows:
- the cleaning liquid of the invention has strong photoresist removal ability; strong corrosion inhibition ability to metal and non-metal; and large operation window. detailed description
- the polishing liquid was prepared in accordance with the ingredients of the respective examples in Tables 1 and 2 and the comparative examples, and the mixture was uniformly mixed.
- Table 1 Formulations of Examples 1-20 of the present invention are examples of the present invention.
- the present invention adopts the following technical means: immersing the wafer containing the photoresist in the cleaning agent, and using a constant temperature oscillator at 25 to 90 ° C to vibrate at about 60 rpm. The frequency was oscillated for 5 to 60 minutes, then washed with deionized water and then dried with high purity nitrogen.
- Table 3 The cleaning effect of the photoresist and the corrosion of the cleaning solution on the wafer are shown in Table 3.
- Table 3 compare wafer cleaning of the embodiment and some embodiments
- Corrosion ⁇ Basically non-corrosive; Cleaning condition: ⁇ Completely removed;
- the cleaning liquid of the present invention has a good cleaning effect on the photoresist and has a wide temperature range.
- Example 1 As can be seen from the comparison of Example 1 with Comparative Example 1, the addition of no C 4 -C 6 polyol in the solution system caused moderate corrosion to the AI substrate.
- Example 7 As can be seen from the comparison of Example 7 with Comparative Example 1, the addition of quaternary ammonium hydroxide in the solution system caused a large amount of residual photoresist.
- the cleaning liquid of the present invention has strong photoresist removal ability; strong corrosion inhibition ability to metal and non-metal; and large operation window.
- wt% of the present invention refers to the mass percentage.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
本发明提供了一种低蚀刻性的适用与较厚光刻胶清洗的清洗液及其清洗方法。这种低蚀刻性的光刻胶清洗液含有季铵氢氧化物,醇胺,C4-C6多元醇,以及溶剂。这种低蚀刻性的光刻胶清洗剂能够高效的去除半导体晶圆上的光刻胶,同时对于基材基本没有攻击如金属铝、铜等,在半导体晶圆清洗等领域具有良好的应用前景。
Description
一种去除光刻胶的清洗液 技术领域
本发明涉及一种清洗液, 更具体地说, 涉及一种去除光刻胶的清洗液。 背景技术
在通常的半导体制造工艺中,通过在一些材料的表面上形成光刻胶的掩 膜, 曝光后进行图形转移, 在得到需要的图形之后, 进行下一道工序之前, 需要剥去残留的光刻胶。 在这个过程中要求完全除去不需要的光刻胶, 同时 不能腐蚀任何基材。例如, 在晶圆微球植入工艺(bumping technology)中, 需要光刻胶形成掩膜, 该掩膜在微球成功植入后同样需要去除, 但由于该光 刻胶较厚, 完全去除常较为困难。 改善去除效果较为常用的方法是采用延长 浸泡时间、提高浸泡温度和采用更富有攻击性的溶液, 但这常会造成晶片基 材的腐蚀和微球的腐蚀, 从而导致晶片良率的显著降低。
目前, 光刻胶清洗液主要由极性有机溶剂、强碱和 /或水等组成, 通过将 半导体晶片浸入清洗液中或者利用清洗液冲洗半导体晶片, 去除半导体晶片 上的光刻胶。 如 WO2006/056298A1利用由四甲基氢氧化铵(TMAH ) 、 二 甲基亚砜 (DMS0 ) , 乙二醇 (EG ) 和水组成碱性清洗液, 用于清洗铜基 板的光刻胶, 同时对金属铜基本无腐蚀, 但其对金属铝有腐蚀; 又例如 US5529887由氢氧化钾 (K0H ) 、 垸基二醇单垸基醚、 水溶性氟化物和水 等组成碱性清洗液, 将晶片浸入该清洗液中, 在 40~90°C下除去金属和电介 质基材上的厚膜光刻胶。 其对半导体晶片基材的腐蚀较高。
由此可见, 寻找更为有效抑制金属腐蚀抑制方法和高效的光刻胶去除能 力是该类光刻胶清洗液努力改进的优先方向。 发明内容
本发明所要解决的技术问题是针对现有的厚膜光刻胶清洗液存在的清 洗能力不足或者对半导体晶片图案和基材腐蚀性较强的缺陷, 而提供一种对 厚膜光刻胶清洗能力强且对半导体晶片图案和基材腐蚀性较低的光刻胶清 洗剂。
为了解决上述技术问题, 本发明提供了一种清洗液, 其含有季铵氢氧化 物, 醇胺, c4-c6多元醇以及溶剂。
其中, 季铵氢氧化物的含量为 0.1 ~10wt% (质量百分比), 优选为 1 ~5wt
%。
其中, 醇胺的含量为不超过 5wt%, 即小于 5wt%。
其中, C4-C6多元醇的含量为 0.1 ~10wt %, 优选为 0.卜 5 wt %
其中, 上述清洗液的余量部分为溶剂。
上述含量均为质量百分比含量; 且本发明所公开的去除光阻残留物的清 洗液中不含有研磨颗粒。
本发明中, 季铵氢氧化物较佳的为季铵氢氧化物包括四甲基氢氧化铵、 四乙基氢氧化铵、 四丙基氢氧化铵、 四丁基氢氧化铵、 甲基三乙基氢氧化铵 和羟乙基三甲基氢氧化铵等中的一种或者几种。传统清洗液中, 通常使用氢 氧化钠, 氢氧化钾等作为碱性组分, 但是这类物质具有易吸收空气中的 co2 产生固体, 影响清洗等副作用, 因此在本申请采用季铵氢氧化物。
本发明中, 醇胺较佳地为醇胺为单乙醇胺、 二乙醇胺、 三乙醇胺、 正丙 醇胺、 异丙醇胺、 2- (二乙氨基) 乙醇、 乙基二乙醇胺和二甘醇胺中的一种 或几种。 醇胺的存在有利于提高季铵氢氧化物的溶解度。
本发明中, C4-C6多元醇较佳的为赤藓糖醇、 木糖醇、 葡萄糖、 山梨醇、 甘露醇中的一种或多种。
本发明中, 有机溶剂较佳的为亚砜、 砜、 咪唑垸酮、 咪唑啉酮、 酰胺中 的一种或多种; 其中亚砜较佳的为二甲基亚砜; 砜较佳的为环丁砜; 咪唑垸 酮较佳的为 1 ,3-二甲基 -2-咪唑垸酮; 咪唑啉酮较佳的为 1,3-二甲基 -2-咪唑
啉酮; 酰胺较佳的为二甲基甲酰胺、 二甲基乙酰胺中的一种或多种。
本发明中的清洗液, 可以在 25°C至 90°C下清洗晶圆上的光刻胶。 具体 方法如下: 将含有光刻胶的晶片浸入本发明中的低蚀刻性的光刻胶清洗剂, 在 25°C至 90 C下浸泡合适的时间后, 取出洗涤后用高纯氮气吹干。
本发明的积极进步效果在于: 本发明的清洗液具有光刻胶去除能力强; 对金属和非金属的腐蚀抑制能力强; 具有较大的操作窗口。 具体实施方式
下面通过具体实施例进一步阐述本发明的优点,但本发明的保护范围不 仅仅局限于下述实施例。
按照表 1 和表 2中各实施例以及对比实施例的成分及其比例配制抛光 液, 混合均匀。 表 1 本发明实施例 1-20的配方
季铵氢氧化物 醇胺 c4-c6多元醇 溶剂 实施例
名称 含量 名称 含量 名称 含量 名称 s m. 四甲基氢 二甲基亚
1 3 单乙醇胺 3.5 赤藓糖醇 0.5 93 氧化铵 砜 甲基三乙
二甲基甲
2 基氢氧化 1.5 异丙醇胺 4 甘露醇 1.5 93
酰胺
铵
1 ,3-二甲 四丙基氢
3 3 三乙醇胺 2 木糖醇 2 基 -2-咪 93 氧化铵
唑烷酮
1 ,3-二甲 四丁基氢 乙基二乙
4 2 2.5 山梨醇 5 基 -2-咪 90.5 氧化铰 醇胺
唑啉酮
2- (二乙
四乙基氢
5 1 氨基) 乙 1 山梨醇 6 环丁砜 92 氧化铰
醇
羟乙基三
二甲基亚
6 甲基氢氧 0.1 异丙醇胺 0.1 葡萄糖 0.8 99
砜
化铵
四丙基氢
7 3 三乙醇胺 4
氧化铵 t薩 8 环丁砜 85 四乙基氢 二甲基乙
8 7.5 二甘醇胺 4.5 木糖醇 5.5 82.5 氧化铵 酰胺
四甲基氢 二甲基亚
9 10 单乙醇胺 4.9 赤藓糖醇 10 75.1 氧化铰 砜 四甲基氢 二甲基乙
10 5 正丙醇胺 3.5 木糖醇 4.5 87 氧化铰 酰胺 四甲基氢 二甲基亚
1 1 3 二乙醇胺 4.5 甘露醇 2.5 90 ¾化铵 砜 四甲基氢 二甲基乙
12 4.5 二甘醇胺 3.5 木糖醇 1.5 90.5 氧化铵 酰胺
1 ,3-二甲 四乙基氢 乙基二乙
13 2 2.5 山梨醇 0.1 基 -2-咪 95.4 ¾化铰 醇胺
唑烷酮 四丙基氢
14 3 二乙醇胺 2 葡萄糖 8 环丁砜 87 氧化铰
甲基三乙
二甲基乙
15 基氢氧化 4 单乙醇胺 1 赤藓糖醇 3 92
酰胺 铵
四甲基氢 二甲基亚
16 5.5 单乙醇胺 3 葡萄糖 3.5 88 氧化铰 砜 甲基二乙
17 基氢氧化 3.5 异丙醇胺 4.5 山梨醇 4.5 环丁砜 12.5
铵
2- (二乙 1 ,3-二甲 四丁基氢
18 1.5 氨基) 乙 1.5 甘露醇 4 基 -2-咪 93 氧化铵
醇 唑垸酮 羟乙基三
二甲基亚
19 甲基氢氧 3.5 正丙醇胺 2.5 木糖醇 6.5 87.5
砜
化铵
1 ,3-二甲 四乙基氢
20 2.5 单乙醇胺 3 山梨醇 5 基 -2-咪 89.5 氧化铵
唑啉酮
表 2本发明对比例的配方
季铵氢氧化物 醇胺 C4-C6多.元醇 溶剂 对比例 A
名称 a 名称 含量 名称 含量 名称 含量 四甲基氢 二甲基亚
1 3 单乙醇胺 3.5 赤藓糖醇 1 93 氧化铵 砜 四丙基氢
7 1 三乙醇胺 4 甘露醇 8 环丁砜 85 氧化铰
四甲基氢 二甲基乙
10 5 正丙醇胺 1 木糖醇 4.5 87 氧化铵 酰胺 甲基三乙
二甲基乙
15 基氢氧化 4 单乙醇胺 10 赤藓糖醇 3 92
酰胺 铰
1 ,3-二甲 四乙基氢
20 2.5 单乙醇胺 7 山梨醇 5 基 -2-咪 89.5 氧化铵
唑啉酮
效果实施例 1
为了进一步考察该类清洗液的清洗情况, 本发明采用了如下技术手段: 即将含有光刻胶的晶片浸入清洗剂中, 在 25~90°C下利用恒温振荡器以约 60转 /分的振动频率振荡 5~60分钟, 然后经去离子水洗涤后用高纯氮气吹 干。 光刻胶的清洗效果和清洗液对晶片的腐蚀情况如表 3所示。
表 3对比实施例和部分实施例的晶片清洗情况
0 略有腐蚀; o 少量残余;
△ 中等腐蚀; △ 较多残余;
X 严重腐蚀。 X 大量残余。
从表 3可以看出, 本发明的清洗液对光刻胶具有良好的清洗效果, 使用 温度范围广。
从实施例 1与对比例 1 比较可以看出, 在溶液体系中没有 C4-C6多元醇 的加入对 AI基材产生中等腐蚀。
从实施例 7与对比例 1比较可以看出,在溶液体系中没有季铵氢氧化物 的加入使光刻胶有大量的残留。
从实施例 10与对比例 10比较可以看出,在溶液体系中没有醇胺的加入 对晶片清洗和基材的腐蚀都有影响。
从实施例 15、 20与对比例 15、 20比较可以看出, 在溶液体系中醇胺 的含量超过 5%光刻胶会有残留,并随着醇胺含量的增加光刻胶的残留越多。
实施例与对比例的比较可以看出, 实施例对金属和非金属基板等有较好 的腐蚀抑制作用, 光刻胶去除能力强。
综上, 本发明的积极进步效果在于: 本发明的清洗液具有光刻胶去除能 力强; 对金属和非金属的腐蚀抑制能力强; 具有较大的操作窗口。
应当理解的是, 本发明所述 wt%均指的是质量百分含量。
以上对本发明的具体实施例进行了详细描述, 但其只是作为范例, 本发 明并不限制于以上描述的具体实施例。 对于本领域技术人员而言, 任何对本 发明进行的等同修改和替代也都在本发明的范畴之中。 因此, 在不脱离本发 明的精神和范围下所作的均等变换和修改, 都应涵盖在本发明的范围内。
Claims
权利要求 、 一种去除光刻胶的清洗液, 其特征在于, 所述清洗液包含季铵氢氧 化物, 醇胺, c4-c6多元醇以及溶剂。
、 如权利要求 1所述的清洗液, 其特征在于, 所述季铵氢氧化物的含 量为 0.1 ~10wt%。
、 如权利要求 2所述的清洗液, 其特征在于, 所述季铵氢氧化物的含 量为 1 ~5wt%。
、 如权利要求 1所述的清洗液, 其特征在于, 所述醇胺的含量为小于
5wt%。
、 如权利要求 1所述的清洗液, 其特征在于, 所述 C4-C6多元醇的含 量为 0.1 ~10wt%。
、 如权利要求 5所述的清洗液, 其特征在于, 所述 C4-C6多元醇的含 量为 0.1 ~5 wt%。
、 如权利要求 1所述的清洗液, 其特征在于, 所述清洗液中的余量为 溶剂。
、 如权利要求 1所述的清洗液, 其特征在于, 所述的季铵氢氧化物选 自季铵氢氧化物包括四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化 铵、四丁基氢氧化铵、甲基三乙基氢氧化铵和羟乙基三甲基氢氧化铵等 中的一种或者几种。
、 如权利要求 1所述的清洗液, 其特征在于, 所述的醇胺选自单乙醇 胺、 二乙醇胺、三乙醇胺、 正丙醇胺、异丙醇胺、 2- (二乙氨基)乙醇、 乙基二乙醇胺和二甘醇胺中的一种或几种。
0、 如权利要求 1所述的清洗液, 其特征在于, 所述的 C4-C6多元醇选 自赤藓糖醇、 木糖醇、 葡萄糖、 山梨醇、 甘露醇。
1、 如权利要求 1所述的清洗液,其特征在于,所述的溶剂为亚砜、砜、 咪唑烷酮、 咪唑啉酮、 酰胺中的一种或多种。
2、 如权利要求 11 所述的清洗液, 其特征在于, 所述的亚砜为二甲基 亚砜; 所述的砜为环丁砜; 所述的咪唑垸酮为 1,3-二甲基 -2-咪唑垸酮; 所述的咪唑啉酮为 1,3-二甲基 -2-咪唑啉酮; 所述的酰胺选自二甲基甲 酰胺、 二甲基乙酰胺中的一种或多种。
3、 如权利要求 1所述的清洗液, 其特征在于, 所述清洗液不含有研磨
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