CN1904016A - 除残留物的含有阳离子盐的组合物及其使用方法 - Google Patents
除残留物的含有阳离子盐的组合物及其使用方法 Download PDFInfo
- Publication number
- CN1904016A CN1904016A CNA200610107693XA CN200610107693A CN1904016A CN 1904016 A CN1904016 A CN 1904016A CN A200610107693X A CNA200610107693X A CN A200610107693XA CN 200610107693 A CN200610107693 A CN 200610107693A CN 1904016 A CN1904016 A CN 1904016A
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- China
- Prior art keywords
- composition
- ether
- glycol
- acid
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims description 19
- 125000002091 cationic group Chemical group 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical class CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 organic acid salt Chemical class 0.000 claims description 62
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 50
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 21
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 20
- 239000012964 benzotriazole Substances 0.000 claims description 19
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 17
- 238000005260 corrosion Methods 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 12
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 12
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 12
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- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 6
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 6
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 4
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229940079877 pyrogallol Drugs 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019439 ethyl acetate Nutrition 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- RJLKIAGOYBARJG-UHFFFAOYSA-N 1,3-dimethylpiperidin-2-one Chemical compound CC1CCCN(C)C1=O RJLKIAGOYBARJG-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- FVRSWMRVYMPTBU-UHFFFAOYSA-M 1-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCC(O)[N+](C)(C)C FVRSWMRVYMPTBU-UHFFFAOYSA-M 0.000 claims description 2
- NAFPAOUIKZHXDV-UHFFFAOYSA-N 1-propan-2-yloxy-2-(2-propan-2-yloxypropoxy)propane Chemical compound CC(C)OCC(C)OCC(C)OC(C)C NAFPAOUIKZHXDV-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 2
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 2
- CRAFBOZKMVZBDP-UHFFFAOYSA-N [OH-].C(C)[NH3+].C[NH+](C)C.[OH-] Chemical compound [OH-].C(C)[NH3+].C[NH+](C)C.[OH-] CRAFBOZKMVZBDP-UHFFFAOYSA-N 0.000 claims description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
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- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 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
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
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- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 claims 1
- 229940035024 thioglycerol Drugs 0.000 claims 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 36
- 238000004140 cleaning Methods 0.000 abstract description 22
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
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- 239000000356 contaminant Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
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- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
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- 239000002253 acid Substances 0.000 description 14
- 238000005530 etching Methods 0.000 description 14
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- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
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- 125000003118 aryl group Chemical group 0.000 description 9
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- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 7
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- 150000002500 ions Chemical class 0.000 description 6
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- 229910021641 deionized water Inorganic materials 0.000 description 5
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- XPOLVIIHTDKJRY-UHFFFAOYSA-N acetic acid;methanimidamide Chemical compound NC=N.CC(O)=O XPOLVIIHTDKJRY-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 125000000623 heterocyclic group Chemical group 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- 229910052721 tungsten Inorganic materials 0.000 description 3
- OTXHZHQQWQTQMW-UHFFFAOYSA-N (diaminomethylideneamino)azanium;hydrogen carbonate Chemical compound OC([O-])=O.N[NH2+]C(N)=N OTXHZHQQWQTQMW-UHFFFAOYSA-N 0.000 description 2
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- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- HSTOVACXCNVBDY-UHFFFAOYSA-N methanimidamide Chemical compound C(=N)N.C(=N)N HSTOVACXCNVBDY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 229960002238 methylpentynol Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000002911 monocyclic heterocycle group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical class [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 230000005328 spin glass Effects 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- JOFWLTCLBGQGBO-UHFFFAOYSA-N triazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1Cl JOFWLTCLBGQGBO-UHFFFAOYSA-N 0.000 description 1
- 229960003386 triazolam Drugs 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/50—Derivatives of urea, thiourea, cyanamide, guanidine or urethanes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/24—Organic compounds containing halogen
- C11D3/245—Organic compounds containing halogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/3927—Quarternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3272—Urea, guanidine or derivatives thereof
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
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Abstract
本发明涉及一种含水的清洗用组合物,其用于从基底上,例如,半导体基底上除去不需要的有机和无机残留物和污染物。该清洗用组合物包括按重量计约0.01%至约40%的选自胍盐、乙脒盐、甲脒盐和其混合物的盐;水;和任选的可溶性有机溶剂。根据本发明的组合物不含有氧化剂和磨粒,并且可以从基底,尤其是从具有含硅BARC和/或光刻胶残留物的基底上除去残留物。
Description
相关申请的参照
根据35 U.S.C.§119(e),本申请要求享有较早的于2005年6月23日提交的美国临时专利申请序列号为60/693,205的优先权,在此引入其全部公开内容作为参考。
技术领域
本发明提供了清洗用组合物,它能用于多种应用中包括例如,除去半导体基底上的不需要的光刻胶膜、蚀刻之后、BARC和灰化之后的残留物。特别地,本发明提供了清洗用组合物,其含有选自胍盐、乙脒盐(acetamidinium)、甲脒盐(formamidinium)及其混合物的盐作为清洗剂。
将结合它在清洗上的应用,包括集成电路的制造,描述本发明的背景。然而可以理解,本发明拥有更宽的应用。
背景技术
在集成电路的制造中,有时必须要在薄膜中蚀刻开口或其它的几何形状,该薄膜沉积或生长在硅、砷化镓、玻璃或正在加工的集成电路晶片上的其他基底上。用本方法蚀刻该薄膜时需要将该薄膜暴露在化学蚀刻剂中除去薄膜部分。用于除去薄膜部分的特定蚀刻剂取决于薄膜的性质。例如对于氧化膜,蚀刻剂可能是氢氟酸。对于多晶硅薄膜,一般是氢氟酸或硝酸和乙酸的混合物。
为了保证除去的仅仅是所希望的薄膜部分,使用了光蚀刻法,通过这种方法,将在电脑中起草的光掩模图案转移到薄膜的表面上。该掩模用来确定将被选择性除去的薄膜的区域。用光刻胶(photoresist)材料形成这种图案,该材料是旋涂在薄膜上的正在加工的集成电路晶片上的感光材料并且在通过光掩模投影的高强度辐射中曝光。取决于光刻胶材料的组成,一般用显影剂溶解曝光或未曝光的光刻胶材料,留下能在选定区域里进行蚀刻的图案,而防止蚀刻其它区域。例如阳性类型的光刻胶(resist)已经被广泛地作为掩模物质在基底上画出图案,当进行蚀刻时它会变成导通孔、沟道、接触孔等。
半导体装置的小型化趋势导致了使用精密多级的体系来克服与上述小型化有关的如下的困难。在光蚀刻法中使用高吸收性的抗反射涂层是减少从高反射基底的光背反射所造成的问题的比较简单的方法。背反射率的两个不利的作用是薄膜干涉和反射凹槽。薄膜干涉导致光刻胶膜中因总光强度的变化所引起的临界行距尺寸的变化如光刻胶厚度的变化。行距的变化和振幅比(S)成正比,因此为了更好地控制行距必须将其最小化。振幅比被定义成S=4(RaRb)1/2eαD,其中Ra是在光刻胶/空气或光刻胶/顶涂层界面间的反射率,Rb是在光刻胶/基底界面间的反射率,α是光刻胶的吸光系数,并且D是膜厚度。
底部抗反射层(“BARC”)的功能在于吸收用来曝光光刻胶的辐射,由此减少Rb从而减少振幅比。反射凹槽变深是因为光刻胶在含有地形特征的基底上形成图案,它通过光刻胶薄膜使光散射,造成行距的变化,并且在极端情况中,会形成完全损失光刻胶的区域。同样地,着色的顶端抗反射涂层会通过减少Ra而减少振幅比,其中该涂层对于折射率和吸收特征,例如吸收波长和强度具有最佳值。
日益地,干蚀刻工艺例如等离子蚀刻、活性离子蚀刻或离子铣削被用来腐蚀基底上的光刻胶未保护的区域以形成导通孔、沟道、接触孔等。作为等离子蚀刻工艺的结果,光刻胶、蚀刻气和蚀刻材料的副产物作为残留物沉积在基底上的蚀刻开口的侧壁或四周。
上述干蚀刻工艺一般会使光刻胶掩模非常难除去。例如,在复杂的半导体装置如高级DRAMS和具有多层互连导线的末端线路的逻辑设备中,活性离子刻蚀(RIE)被用来制造穿过层间电介体材料的导通孔来提供一级硅、硅化物或金属导线与下一级导线的联系。这些导通孔一般使Al、AlCu、Cu、Ti、TiN、Ta、TaN、硅或硅化物如钨、钛或钴的硅化物曝光。RIE方法在所涉及的含有复杂混合物的基底留下残留物,这种混合物可以包括例如,再溅射的氧化物材料、由蚀刻气产生的聚合物材料和用来画出导通孔的光刻胶的有机材料。
另外,刻蚀步骤结束之后,必须从晶片的保护区中除去光刻胶(包括BARC或其他防反射涂层)和蚀刻残留物使最后的整理操作能够进行。可以通过使用适当的等离子灰化气体在等离子“灰化”步骤中完成。一般在高温,如高于200℃下进行。灰化是将大部分的有机残留物转化成挥发性的种类,但是之后在基底上留下的主要是无机残留物。这种残留物一般不仅残留在基底的表面上,而且可能出现在导通孔的内壁上。因此,经常用一般被称为“液体剥离组合物”的清洁用组合物处理灰处理后的基底以除去基底上高粘附性的残留物。寻找一种合适的清洁用组合物来除去该残留物而不产生负面作用,例如,已经证明侵蚀、溶解或钝化金属电路是有问题的。不能完全除去或中和残留物会导致电路导线的中断并且使电阻不令人满意地增大。
现有技术中的剥离组合物已经包括,例如:(a)基于有机磺酸的剥离溶液,它含有作为主要的剥离组份的烷基苯磺酸;以及(b)基于有机胺的剥离溶液,其含有作为主要的剥离组份的胺如单乙醇胺。然而,现有技术中的上述用于除去蚀刻残留物的剥离组合物具有明显的缺点。例如,使用它们往往会腐蚀暴露在导通孔底部上的铜丝。
因此,在本领域中需要一种用于包括剥离光刻胶和等离子灰残留物的最后清洗操作的清洗用组合物,其能够选择性地除去上述残留物而不会蚀刻底层的和暴露的基底。底层的和暴露的基底包括,例如,金属、高介电常数的材料(这里被称为“high-k”)、硅、硅化物和/或层间电介质材料包括低介电常数材料(这里被称为“low-k”),如沉积氧化物、HSQ膜、MSQ膜、Fox膜、黑金刚石膜和正硅酸四乙酯(“TEOS”)膜。
发明内容
在此公开的组合物能够选择性的除去残留物例如,来自基底的光刻胶、填隙物、BARC和/或其它聚合材料,和/或无机材料和加工的残留物而不会腐蚀任何不希望的范围的也可能暴露于该组合物的金属、low-k电介质材料、和/或high-k电介质材料。在特定的实施方案中,在此公开的组合物能够有效地从基底上除去BARC残留物同时对暴露的底层的电介质材料造成最小的腐蚀。
一方面,本发明提供了从基底上除去残留物的组合物,该组合物包括:选自胍盐、乙脒盐、甲脒盐和其混合物的盐;水;和任选的水溶性有机溶剂,条件是该组合物不含有氧化剂和磨粒。
另一方面,本发明提供了从含有BARC的基底上除去残留物的组合物,该组合物包括:按重量计约0.01%至约40%的选自胍盐、乙脒盐、甲脒盐、和其混合物的盐;水;和任选的水溶性有机溶剂,条件是该组合物不含有氧化剂和磨粒。在特定的实施方案中,该组合物还包括至少一种选自下列的物质:季铵化合物、氟离子源、胺、羟胺或其酸性盐;有机酸、磺酸或其盐或腐蚀抑制剂。
在另一方面,本发明提供了从含有电介体材料的基底上除去包括BARC的残留物的方法,该方法包括:将基底与组合物接触,该组合物包括:按重量计约0.01%至约40%的选自胍盐、乙脒盐、甲脒盐、和其混合物的盐;水;和任选的水溶性有机溶剂,条件是该组合物不含有氧化剂和磨粒。
本发明提供了一种组合物,它的组分的含量足以有效地除去基底例如半导体基底上的残留物。在涉及半导体基底的应用中,上述残留物包括,例如,光刻胶(固化的或其他的)、填隙物、底部防反射涂层(BARC)及其他聚合材料(例如,含C-F的聚合物、低分子量聚合物和高分子量聚合物)和/或加工的残留物例如由蚀刻和灰化工艺产生的残留物、无机化合物例如金属氧化物、化学机械平整(CMP)淤浆中的陶瓷颗粒及其他无机蚀刻残留物、包括金属的化合物例如,有机金属残留物和有机金属化合物。在一个实施方案中,根据本发明的组合物对于从半导体基底上除去含硅的BARC残留物特别地有效。
残留物一般存在在基底上,该基底可以包括金属、硅、硅酸盐和/或层间电介质材料例如,沉积的硅氧化物和衍生的硅氧化物如HSQ、MSQ、FOX、TEOS和旋压玻璃、化学蒸汽沉积的电介体材料、low-k材料和/或high-k材料例如硅酸铪、氧化铪、钛酸锶钡(BST)、TiO2、TaO5,其中残留物和金属、硅、硅化物、层间电介体材料、low-k材料和/或high-k材料都和清洁用组合物接触。根据本发明的组合物适用于上述物质,并且因此可被用于选择性地除去例如那些如上所述的残留物,而不会明显地腐蚀金属、硅、二氧化硅、层间电介质材料、low-k材料和/或high-k材料。在特定的实施方案中,基底可以包括金属,例如,但不限于,铜、铜合金、钛、氮化钛、钽、氮化钽、钨、和/或钛/钨合金。
根据本发明的组合物不含有氧化剂、磨粒或任何对组合物的剥离和清洗能力起不利作用的或损害底层基底的一个或多个表面的其他组分。氧化剂的例子子包括,但不限于,过氧化氢(H2O2)、单过硫酸盐、碘酸盐、过邻苯二甲酸镁、过乙酸及其他过酸、过硫酸盐、溴酸盐、高碘酸盐、硝酸盐、硝酸、铁盐、铈盐、Mn(III)、Mn(IV)和Mn(VI)盐、银盐、Cu盐、铬盐、钴盐、卤素次氯酸盐及其混合物。磨粒的例子包括金刚石微粒和金属氧化物、硼化物、碳化物、氧化铝、二氧化铈和硅石及其混合物。在特定的实施方案中,该组合物用作除去残留物如包含在来自CMP处理的CMP溶液中的磨粒。此处公开的组合物优选不含有上述微粒。
本发明的组合物是水基的,因而,包含水。在本发明中,水的功能是多方面的,例如,作为溶剂溶解组合物中的一种或多种固体组份、作为组份的载体、作为除去残留物的辅助剂、作为组合物的粘度调节剂和作为稀释剂。
可以确信,在大多数应用中,可以含有,例如,按组合物的重量计约1%至约95%的水。根据本发明的其它优选组合物含有按重量计约1至约75%的水。根据本发明的其它更优选的组合物含有按重量计约1至约50%的水。
本发明中的水分可以作为其它要素的组分附带地存在,例如,含有氟化物离子源或季铵化合物的水溶液,或者它可以单独地加入。非限制性的水的例子包括去离子(Dl)水、超高纯水、蒸馏水、二次蒸馏水或低金属含量的蒸馏水。优选的,组合物中的水包括去离子水。
根据本发明的组合物包括选自胍盐、乙脒盐、甲脒盐,和其混合物的盐。该盐起清洗剂的作用,主要是溶解或帮助溶解存在于基底上的有机残留物。这些盐包括由下列式(I)至式(III)表示的下列之一的阳离子,即分别是胍阳离子、甲脒阳离子或乙脒阳离子,其中m是1或2:
形成上述盐的阴离子的例子包括,但不限于卤离子例如Cl-、Br-、F-、I-;硫离子;亚硫酸根;硫酸根、碳酸根、亚硝酸根、醋酸根和其他本领域公知的阴离子。提供上述阴离子的酸源包括,但不限于,盐酸、氢溴酸、氢氟酸、氢硫酸、亚硫酸或硫酸。
优选的根据本发明组合物中使用的盐包括,但不限于,盐酸胍、硫酸胍、盐酸氨基胍、乙酸胍、碳酸胍、硝酸胍、甲脒亚胺(formanimide)、亚硫酸甲脒、醋酸甲脒、碳酸氨基胍、盐酸碳酸氨基胍、氯化甲脒及其混合物。
可以确信,在大多数应用中,盐的量按组合物的重量计为约0.01%至约40%。优选地,盐按组合物的重量计为约0.01%至约30%,并且更优选为约0.01%至约25%。
根据本发明的组合物任选地包括至少一种有机溶剂。该有机溶剂优选能和水混溶。在本发明的各种实施方案中,一般基底上的金属线路确定是否使用能和水混溶的有机溶剂。例如,当铝线路出现在基底上时,水和卤素离子的结合一般趋向于腐蚀铝。在这些实施方案中,使用能和水混溶的有机溶剂即使不能消除也能显著地减少对铝的腐蚀。
能和水混溶的有机溶剂的例子包括,但不限于,二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)、二甲亚砜(DMSO)、二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、二甲基-2-哌啶酮(DMPD)、四氢糠基醇、甘油、乙二醇及其他酰胺、醇或硫氧化物, 或多官能化合物,例如羟基酰胺或氨基醇。能和水混溶的有机溶剂的其他例子包括二醇和多元醇例如(C2-C20)烷烃二醇和(C3-C20)烷烃三醇、环醇和被取代的醇。这些能和水混溶的有机溶剂的具体例子包括丙二醇、四氢糠基醇、双丙酮醇和1,4-环己烷二甲醇。在特定的实施方案中,能和水混溶的有机溶剂可以是DMSO、NMP和/或DMAC。以上列举的能和水混溶的有机溶剂可以单独使用或和两种或多种的溶剂联合使用。
在本发明的特定优选方案中,能和水混溶的有机溶剂可以包含二醇醚。二醇醚的例子包括乙二醇一甲醚、乙二醇一乙醚、乙二醇一丁醚、乙二醇二甲醚、乙二醇二乙醚、二甘醇一甲醚、二甘醇一乙醚、二甘醇一丙醚、二甘醇一异丙醚、二甘醇一丁醚、二甘醇一异丁基醚、二甘醇一苯甲醚、二甘醇二甲醚、二甘醇二乙醚、三甘醇单甲醚、三甘醇二甲醚、多乙二醇一甲醚、二甘醇甲基乙醚、三甘醇乙二醇一甲醚醋酸酯、乙二醇单乙基醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇一甲醚、丙二醇二甲醚、丙二醇一丁醚、丙二醇、一丙醚、二丙二醇一甲醚、二丙二醇一丙醚、二丙二醇一异丙醚、二亚丙基一丁基醚、二丙二醇二异丙醚、三丙二醇一甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。
可以确信,在大多数应用中,能和水混溶的有机溶剂的量按组合物的重量计为约0%至约60%。优选地,能和水混溶的有机溶剂按组合物的重量计为约0至约55%,并且更优选为约0至约50%。
根据本发明的组合物可以任选地包括季铵化合物。如果使用,该季铵化合物的功能在于辅助除去有机和无机残留物。
根据本发明的组合物中所使用的季铵化合物的例子是具有式[N-R1R2R3R4]+OH-的季铵化合物,其中R1、R2、R3和R4各自独立地是具有1至20个碳原子的烷基基团。术语“烷基”指具有1至20个碳原子,或1至8个碳原子,或1至4个碳原子的直链或支链的未取代的烃基团。合适的烷基基团的例子包括甲基、乙基、丙基、异丙基、丁基和叔丁基。词语“低级烷基”指具有1至4个碳原子的烷基。合适的季铵化合物的例子包括氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵和氢氧化苄基三甲基铵。
可以确信,在大多数应用中,季铵化合物的量按组合物的重量计为约0%至约50%。优选地,季铵化合物按组合物的重量计为约0%至约40%,并且更优选为约0至约30%。
根据本发明的组合物可以任选地包含至少一种氟化物离子源。氟化物离子的功能主要在于从基底上辅助性除去无机残留物。根据本发明的提供氟化物离子源的典型化合物是氢氟酸及其盐、氟化铵、氟化季铵盐例如,氟化四甲铵和氟化四丁铵、氟硼酸盐、氟硼酸、四氟硼酸四丁铵和六氟化铝。此外,也可以使用脂肪族伯、仲或叔胺的氟化盐,例如,式为R5R6R7R8NF的胺,其中R5、R6、R7和R8各自独立地是氢、链烷醇基团、烷氧基基团、烷基基团或其混合物。上述化合物的例子包括氟化铵、氟化四甲基铵、氟化四乙基铵、氟化四丁基胺和其混合物。氟化物离子源的更进一步的例子包括氟硼酸、氢氟酸、氟硼酸盐、氟硼酸、四氟硼酸四丁铵、六氟化铝和氟化胆碱。在更进一步的实施方案中,可以使用的氟化物离子源是脂肪族伯、仲或叔胺的氟化盐。
在一个优选实施方案中,氟化物离子源是烷基氟化物例如,氟化四甲基铵、氟化四乙基铵、氟化四丁基铵及其混合物。
在选择氟化物离子源时,应当考虑该源是否会趋于释放对被清洗的表面产生不利作用的离子。例如,清洗半导体元件时,在清洁用组合物中存在钠或钙离子对元件表面产生不利的作用。
可以确信,在大多数应用中, 清洁用组合物中作为氟化物离子源的化合物的量按重量计为约0至约10%。更优选地,该化合物按组合物的重量计为约0至约5%。然而,应当理解一般根据被清洗的基底的具体情况确定氟化物离子的用量。例如,在特定的清洗应用中,当被清洗的基底中含有对氟化物腐蚀具有高抵抗力的电介质材料时,氟化物离子的用量会相对地高。相反地,在其它应用中,例如,当被清洗的基底中包含对氟化物腐蚀具有低抵抗力的电介质材料时,氟化物离子的量会相对地低。
根据本发明的组合物可以任选地包含至少一种胺化合物。如果使用,胺化合物的功能在于辅助除去特定的有机残留物,例如,有机聚合物残留物如,光刻胶。
适用于本发明的胺化合物包括,例如,链烷醇胺、烷基胺、环状非芳族胺、由式NR9R10R11代表的化合物其中R9、R10和R11各自独立地选自H、脂肪基团、醚基团、烷基单氨基基团、烷基二氨基基团、烷基三氨基基团和在环上任选地含有至少一种选自N、O和S的其他杂原子的N-杂环基基团和其它胺化合物。
在本发明的优选实施方案中,胺化合物是链烷醇胺。优选的链烷醇胺包括低级链烷醇胺其是具有1至5个碳原子的伯、仲和叔链烷醇胺。上述链烷醇胺的例子包括N-甲基乙醇胺(NMEA)、单乙醇胺(MEA)、二乙醇胺、一、二和三异丙醇胺、2-(2-氨基乙基氨基)乙醇、2-(2-氨基乙氧基)乙醇、三乙醇胺等。其他优选的胺包括环状非芳族胺如吗啉、环己胺和哌啶低级烷基胺如丁胺、低级亚烷基二胺如乙二胺等。
本发明的其他优选实施方案中,胺化合物是由式NR9R10R11代表的化合物,其中每个R9、R10和R11各自独立地选自H、脂肪基团、醚基团、烷基单氨基基团、烷基二氨基基团、烷基三氨基基团和在环上任选地含有至少一种选自N、O和S的其它杂原子的N杂环基团和其它胺化合物。上述胺的例子包括,例如,氨基烷基吗啉如氨基丙基吗啉和氨基烷基哌嗪如氨基乙基哌嗪。参照上面的胺化合物的式子,合适的脂肪基团包括直链或支链烷基基团、亚烷基基团、炔、芳基、芳基-烷基、烷基-芳基和被取代的芳基基团。醚基团包括一般具有1至12个碳原子的丙烯酸醚。一些醚基团的例子是甲氧基、乙氧基、丙氧基、丁氧基、异丙氧基、异丁氧基、仲丁氧基和叔丁氧基。氨基基团包括伯、仲和叔胺以及高级烷基氨基官能团如二-和三-胺。
可以确信在多数应用中,组合物中胺化合物的量按组合物的重量计为约0%至约20%。优选地,胺化合物的重量百分数为约0%至约10%,并且更优选按组合物的重量计为约0至5%。
如在此所用的,术语“烷基”指具有1至20个碳原子,或1至10个碳原子的直链或支链未取代的烃基。如在此所用的,术语“链烯基”和“炔基”指一般具有2至8个碳原子的直链或支链不饱和的烃基团。如在此所用的,术语“芳基”指在环部分含有6至12个碳原子的单环或双环芳烃基,如苯基、萘基、联苯基和二苯基基团,其中每个可以是被取代的。一些一般在环中含有5或6个原子的单环杂环基的例子包括吗啉代、哌嗪、异噻唑、咪唑啉、吡唑啉、吡唑烷、嘧啶、吡嗪。如在此所用的,术语“芳烷基”或“烷基芳基”指直接与烷基连接的芳基,如苯甲基或苯乙基。如在此所用的、术语“取代的芳基”或“取代的烷基芳基”指被例如一至四个下述取代基取代的芳基基团或烷基芳基基团:如烷基;取代的烷基、卤素、三氟甲氧基、三氟甲基、羟基、烷氧基、叠氮基、环烷氧基、杂环氧基、烷酰基、烷酰氧基、氨基、烷基氨基、芳烷基氨基、羟烷基、氨基烷基、叠氮烷基、链烯基、炔基、丙二烯基、环烷基氨基、杂环氨基、二烷基氨基、硫醇、烷基硫醇、环烷基硫醇、杂环烷基硫醇、脲基、硝基、氰基、羧基、羧基烷基、氨基甲酰基、烷氧基羰基、烷基硫碳、芳基硫碳、烷基磺酰基、氨磺酰基、芳氧基等。这些取代基可以更进一步的被卤素、羟基、烷基、烷氧基、芳基、取代的芳基、取代的烷基或芳烷基所取代。如在此所用的,术语“取代的苯甲基”指被例如,任何上述的对于取代的芳基所列举的基团所取代的苯甲基基团。除非在特殊例子中另有限定,个别地或作为更大的基团的一部分,上述术语的定义适用于整个说明书。
根据本发明的组合物可以任选地包含至少一种羟胺化合物或其酸性盐。如果使用,该羟胺的功能在于辅助抑制对铜的腐蚀。根据本发明所使用的羟胺的例子包括二乙基羟胺及其乳酸盐和柠檬酸盐。
可以确信在大多数应用中,组合物中羟胺化合物的量按组合物的重量计为约0%至约5%。优选地,如果使用,羟胺化合物为组合物重量百分数的约0.1%至约5%。
根据本发明的组合物可任选地包含至少一种有机酸。如果使用,该有机酸起腐蚀抑制剂的作用。有机酸的例子包括柠檬酸、邻氨基苯甲酸、没食子酸、苯甲酸、丙二酸、马来酸、富马酸、D,L-苹果酸、异酞酸、邻苯二甲酸和乳酸。
可以确信在大多数应用中,组合物中有机酸的量按组合物的重量计为约0%至约10%。优选地,羟胺化合物为组合物重量百分数的约0%至约2%。
根据本发明的组合物可任选地包含至少一种磺酸。如果使用,该磺酸起清洗辅助剂和腐蚀抑制剂的作用。适于在本发明中使用的磺酸的例子包括对-甲苯磺酸、1,5-萘基二磺酸、4-乙基苯磺酸、苯胺磺酸、苯胺-2-磺酸、十二烷基苯磺酸、异丙基苯磺酸、甲基乙基苯磺酸、二甲苯磺酸的异构体和上述磺酸相应的盐。磺酸盐的例子包括对-甲苯磺酸乙醇铵和对-甲苯磺酸三乙醇铵。磺酸或其相应的盐可以以单独的酸或盐,或磺酸的混合物或相应的盐存在于组合物中。
可以确信在大多数应用中,组合物中磺酸的量按组合物的重量计为约0%至约20%。优选地,磺酸按重量计约0%至约10%并且更优选为组合物的约0%至约5%。
根据本发明的组合物可任选地包含至少一种腐蚀抑制剂。优选当用该组合物清洗金属基底时使用腐蚀抑制剂。腐蚀抑制剂的例子包括芳族羟基化合物、炔醇、含有羧基基团的有机化合物及其酐和三唑化合物。
芳族羟基化合物的例子包括苯酚、甲酚、二甲苯酚、邻苯二酚、间苯二酚、对苯二酚、焦性没食子酸、1,2,4-苯三醇、水杨醇、对-羟基苯甲醇、邻-羟基苯甲醇、对-羟基苯乙醇、对-氨基苯酚、间-氨基苯酚、二氨基苯酚、氨基间苯二酚、对-羟基苯甲酸、邻-羟基苯甲酸2,4-二羟基苯甲酸、2-5-二羟基苯甲酸、3,4-二羟基苯甲酸和3,5-二羟基苯甲酸。
炔醇的例子包括2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4-7,9-四甲基-5-癸炔-4,7-二醇和2,5-二甲基-3-己炔2,5-二醇。
含有羧基基团的有机化合物和其酸酐的例子包括甲酸、乙酸、丙酸、丁酸、异丁酸、草酸、丙二酸、丁二酸、戊二酸、马来酸、富马酸、苯甲酸、邻苯二甲酸、1,2,3-苯三羧酸、羟基乙酸、乳酸、马来酸柠檬酸、乙酸酐和水杨酸。
三唑化合物的例子包括苯并三唑、邻-甲苯基三唑、间-甲苯基三唑、对-甲苯基三唑、羧基苯并三唑、1-羟基苯并三唑、硝基苯并三唑和二羟基丙基苯并三唑。
优选的抑制剂是邻苯二酚、没食子酸、苯并三唑、焦性没食子酸、4-甲基邻苯二酚富马酸和二乙基羟胺(DEHA);清洗含铜的基底时优选使用除苯并三唑之外的抑制剂,因为苯并三唑具有与铜结合的趋向。
可以确信在大多数应用中,组合物中腐蚀抑制剂的量按组合物的重量计为约0.01至约5%。优选地,其按重量计为约0.01至约4%,并且最优选按组合物重量计约0.01至约3%。
根据本发明优选的腐蚀抑制剂包括有机酸盐、苯并三唑(BZT)、间苯二酚、其他的酚、酸或三唑马来酸酐、邻苯二甲酸酐、邻苯二酚、焦性没食子酸、没食子酸酯、羧基苯并三唑、果糖、硫代硫酸铵、甘氨酸、四甲基胍、亚氨基二乙酸、二甲基乙酰基乙酰胺、三羟基苯、二羟基苯、水杨基羟氨(salicyclohydroxamic)及其混合物。
该组合物可以同时包括一个或多个下列的添加剂:表面活性剂、螯合剂、化学调节剂、染料、抗微生物剂及其他添加剂。可以将添加剂加入到在此描述的组合物中,条件其是不会对组合物的剥离和清洗能力或对底层金属、硅、二氧化硅、层间电介质材料、low-k和/或high-k材料的完整性产生不利的作用。例如,如果将该组合物用于处理含铜的基底,该组合物不含有能够增加该组合物对铜的蚀刻速率的其他添加剂。一些代表性的添加剂的例子包括炔醇及其衍生物、炔二醇(非离子烷氧基化的和/或可自乳化的炔二醇表面活性剂)及其衍生物、醇、季铵和二胺、酰胺(包括质子惰性的溶剂如二甲基甲酰胺和二甲基乙酰胺)、烷基链烷醇胺(如二乙醇乙胺)和螯合剂如β-二酮、β-酮亚胺、羧酸、mallic酸和基于酒石酸的酯和二酯及其衍生物、以及叔胺、二胺和三胺。
在本发明的一个实施方案中,本发明提供了用于从含有BARC的基底上除去残留物的组合物,该组合物包括:按重量计约0.01%至约40%的选自胍盐、乙脒盐、甲脒盐和其混合物的盐;水;和任选的水溶性有机溶剂。在特定的实施方案中,该组合物还包括至少一种选自下列的物质:季铵化合物、氟化物离子源、胺、羟胺或其酸性盐;有机酸、磺酸或其盐或腐蚀抑制剂。此处公开的组合物的pH值为4至12.5、或5至12.5或6.5-12.5。
本发明的清洗用组合物一般是将组分在室温下在容器中一起混和直到所有的固体溶于水基介质中而制备得到。
此处公开的组合物适用于含low-k膜的基底如HSQ(FOx)、MSQ、SiLK等,包括那些含氟化物的low-k膜。该组合物在剥离下述物质上有效,包括正反光刻胶的光刻胶和等离子体蚀刻残留物如有机残余物、有机金属残留物、无机残留物、金属氧化物、或在低温时对含铜和/或钛基底具有极低腐蚀的光刻胶络合物。此外,该组合物适用于多种金属、硅、二氧化硅、层间电介质材料、low-k和/或high-k材料。
在生产过程中,光刻胶层是涂覆在基底上的。使用光刻方法,将图案确定在光刻胶层上。于是形成图案的光刻胶层受到等离子体的蚀刻并通过这种方法将图案转移至基底。蚀刻残留物在蚀刻阶段产生。用于本发明的一些基底被灰化了而另一些并没有被灰化。当基底被灰化了时,要清洗的主要残留物是蚀刻剂残留物。如果基底没有被灰化,则要清洗或剥离的主要残留物是蚀刻残留物和光刻胶。
可以通过将含有作为薄膜或残留物存在的金属、有机或金属-有机聚合物、无机盐、氧化物、氢氧化物或络合物或其组合的基底与所述的组合物接触来实施此处描述的方法。实际的条件,如温度、时间等取决于要除去的物质的性质和厚度。通常,将基底在20℃至85℃、或20℃至60℃或20℃到40℃下接触或浸入含有组合物的容器中。将基底暴露在组合物中的时间长度一般是,例如,0.1至60分钟、或1至30分钟、或1至15分钟。和组合物接触后,可以将基底漂洗然后干燥。干燥一般在惰性气氛中进行。在特定的实施方案中,可以在将基底与此处描述的组合物接触之前、期间、和/或之后使用去离子水漂洗或用含有去离子水的其他添加剂漂洗。但是,该组合物可以用于任何本领域公知的使用清洗液除去光刻胶、灰或蚀刻残留物和/或残留物的方法中。
本领域技术人员应当理解可以改变本发明的组合物以达到最佳的清洗而不会损害基底从而能够保持生产过程中清洗的高生产量。例如,本领域技术人员应当理解,例如,改变一些或所有组分的含量取决于将要清洗的基底的组成、将要除去的残留物的性质和所用的具体工艺参数。
虽然本发明主要结合清洗半导体基底进行描述,但是本发明的清洁用组合物可以用于清洗含有有机和无机残留物的任何基底。
提供下列实施例的目的在于进一步描述本发明但不是对其做出限定。
具体实施方式
在下面的实施例中,所有的量以重量百分比给出并且总和为100重量百分比。此处公开的组合物是通过将组分在室温下在容器中一起混和直到所有的固体已经溶解制备得到。此处公开的特定组合物的实施例列在表I中。
下面为表I中所用的简称:
APMt-PGMEDPM(或d-PGME)THFATMAHPGMEDI水DEHAMEANMEADMSONMPPGTMAFBZTTME | 氨基丙基吗啉三丙二醇甲醚二丙二醇甲醚四氢糠基醇氢氧化四甲基铵丙二醇甲醚去离子水二乙基羟基胺乙醇胺N-甲基乙醇胺二甲亚砜N-甲基吡咯烷丙二醇氟化四甲基铵苯并三唑四甲氧基乙烷 |
表I:示例性组合物
实施例A | 实施例B | 实施例C | |||
DI水 | 40 | DI水 | 34 | DI水 | 24 |
TMAF(20%) | 1.5 | TMAF(20%) | 1.5 | TMAF(20%) | 1.5 |
苯胺磺酸 | 0.5 | 苯胺磺酸 | 0.5 | 苯胺磺酸 | 0.5 |
DEHA | 4 | DEHA | 0 | DEHA | 0 |
柠檬酸(29%) | 2 | 柠檬酸(29%) | 4 | 柠檬酸(29%) | 4 |
TMAH(25%) | 42 | TMAH(25%) | 47 | TMAH(25%) | 57 |
碳酸胍 | 10 | 碳酸胍 | 13 | 碳酸胍 | 13 |
实施例D | 实施例E | 实施例F | |||
DI水 | 37 | DI水 | 7 | DI水 | 25 |
TMAF(20%) | 1.5 | TMAF(20%) | 1.5 | TMAF(20%) | 1.5 |
苯胺磺酸 | 0.5 | 苯胺磺酸 | 0.5 | 苯胺磺酸 | 0.5 |
DEHA | 4 | DEHA | 4 | DEHA | 4 |
柠檬酸(29%) | 2 | 柠檬酸(29%) | 2 | 柠檬酸(29%) | 2 |
TMAH(25%) | 30 | TMAH(25%) | 30 | TMAH(25%) | 34 |
碳酸胍 | 10 | 碳酸胍 | 10 | 碳酸胍 | 13 |
PGMA | 15 | THFA | 15 | THFA | 20 |
实施例G | 实施例H | 实施例I | |||
DI水 | 25 | DI水 | 33 | DI水 | 36 |
TMAF.4H2O | 3 | TMAF(20%) | 0 | cobratec 948 | 3 |
苯胺磺酸 | 2.2 | 苯胺磺酸 | 2 | TMAH(25%) | 26 |
DEHA | 5 | 柠檬酸(29%) | 2 | 辛胺 | 0.6 |
柠檬酸(29%) | 3 | TMAH(25%) | 40 | HCl(37%) | 9.8 |
TMAH(25%) | 29 | 碳酸胍 | 13 | 碳酸氨基胍/HCl | 11 |
硫酸胍 | 3 | t-PGME | 10 | d-PGME | 13.6 |
PGMA | 29.8 |
实施例J | 实施例K | 实施例L | |||
DI水 | 30 | DI水 36 | d-PGME | 49 | |
cobratec 948 | 3 | Cobratec948 3 | DI水 | 34.5 | |
TMAH(25%) | 22 | TMAH(25%) 26 | 氟化铵(40%) | 1.8 | |
辛胺 | 0.5 | 辛胺 | 0.6 | PG | 8 |
HCl(37%)) | 12.5 | 碳酸胍/H2SO4(78%) | 17 | 硫酸胍 | 4.2 |
醋酸甲脒/HCl | 9 | d-PGME | 17.4 | BZT | 2.5 |
d-PGME | 23 |
实施例M | 实施例N | 实施例O | |||
d-PGME | 49 | d-PGME | 54 | d-PGME | 53 |
DI水 | 41 | DI水 | 36 | DI水 | 36 |
氟化铵(40%) | 2 | 氟化铵(40%) | 2 | 氟化铵(40%) | 3 |
硫酸胍 | 5 | 硫酸胍 | 5 | 硫酸胍 | 5 |
BZT | 3 | BZT | 3 | BZT | 3 |
实施例P | 实施例Q | 实施例R | |||
壬胺 | 1 | 癸胺 | 1 | DI水 | 33 |
TMAF(20%) | 0.75 | TMAF(20%) | 0.75 | TMAF(20%) | 1.5 |
甘油 | 15 | 甘油 | 15 | 苯胺-2-磺酸 | 0.5 |
BZT | 2 | BZT | 2 | TMAH(25%) | 35 |
TMAH(25%) | 20 | TMAH(25%) | 20 | BZT | 1.8 |
碳酸胍 | 10 | 碳酸胍 | 10 | PG | 10 |
d-PGME | 20 | d-PGME | 20 | 醋酸甲脒 | 10 |
DI水 | 1.25 | DI水 | 1.25 | d-PGME | 8.2 |
实施例S | 实施例T | 实施例U | |||
DI水 | 33 | DI水 | 33 | DI水 | 33 |
TMAF(20%) | 1.5 | TMAF(20%) | 1.5 | TMAF(20%) | 2.5 |
苯胺-2-磺酸 | 0.5 | 苯胺-2-磺酸 | 0.5 | 苯胺-2-磺酸 | 0.5 |
TMAH(25%) | 25 | TMAH(25%) | 35 | TMAH(25%) | 35 |
BZT | 1.8 | BZT | 1.8 | BZT | 1.8 |
PG | 5 | PG | 10 | PG | 5 |
碳酸胍 | 10 | 碳酸胍 | 10 | 碳酸胍 | 10 |
TME | 23.2 | TME | 8.2 | TME | 12.2 |
实施例V | 实施例W | 实施例X | |||
DI水 | 24 | DI水 | 24 | DI水 | 33 |
TMAH(25%) | 48 | TMAH(25%) | 48 | TMAF(20%) | 1.5 |
碳酸胍 | 18 | 碳酸胍 | 18 | 苯胺-2-磺酸 | 0.5 |
DMSO | 10 | NMP | 10 | TMAH(25%) | 35 |
BZT | 1.8 | ||||
PG | 10 | ||||
氯化甲脒 | 10 | ||||
d-PGME | 8.2 |
实施例Y | 实施例Z | 实施例A1 | |||
NMEA | 18 | MEA | 18 | APM | 18 |
TMAH(25%) | 35 | TMAH(25%) | 35 | TMAH(25%) | 35 |
碳酸胍 | 18 | 碳酸胍 | 18 | 碳酸胍 | 18 |
DI水 | 29 | DI水 | 29 | DI水 | 29 |
实施例A2 | 实施例A3 | 实施例A4 | |||
APM | 7.40 | APM | 4.80 | APM | 4.80 |
DPM | 18.50 | DPM | 18.10 | DPM | 18.10 |
辛胺 | 0.01 | 辛胺 | 0.10 | 辛胺 | 0.10 |
TMAH(25%) | 30.70 | TMAH(25%) | 35.00 | TMAH(25%) | 25.00 |
碳酸胍 | 11.10 | 碳酸胍 | 13.00 | 碳酸胍 | 11.00 |
DI水 | 32.29 | DI水 | 29.00 | DI水 | 41.00 |
基底的组成
本发明实施例中所用的每一个基底都包括三层。第一层(即底层)是包含BLACK DIAMOND IITM的ILD材料。接下来的一层是含硅的BARC(193nm)以及顶层是光刻胶(193nm)。该基底随后接受等离子蚀刻。
加工条件
在400ml烧杯中用305mL的清洁用组合物和1/2”的圆聚四氟乙烯搅拌棒并设定为600rpm下进行清洗测试。必要时将清洁用组合物在加热板上加热到下述的所需温度。将尺寸约是1/2”×1/2”的晶片片断浸入下列情况中的组合物中。
10分钟@25℃
20分钟@25℃
10分钟@25℃
20分钟@35℃
将该片断随后在DI水溢出浴中漂洗3分钟然后用过滤氮气干燥。随后用SEM显微镜分析其清洁度。
表II:清洁数据
制剂 | BARC | 光刻胶 | ||
248nm | 193nm | 248nm | 193nm | |
实施例A | √ | √ | √ | √- |
实施例B | √ | √ | √ | √- |
实施例C | √ | √ | √ | √- |
实施例D | √ | √ | √ | √- |
实施例E | √ | √ | √ | √- |
实施例F | √ | √- | √ | √- |
实施例G | √ | √- | √ | √- |
实施例H | √ | √- | √ | √- |
实施例I | √ | × | √ | × |
实施例J | √ | × | √ | × |
实施例K | √ | √- | √ | × |
实施例L | √ | × | √ | × |
实施例M | √ | × | √ | × |
实施例N | √ | × | √ | × |
实施例O | √ | × | √ | × |
实施例P | √ | √ | √ | √- |
实施例Q | √ | √ | √ | √- |
实施例R | √ | × | √ | × |
实施例S | √ | √- | √ | √- |
实施例T | √ | √ | √ | √- |
实施例U | √ | √ | √ | √- |
实施例V | √ | √- | √ | √- |
实施例W | √ | √- | √ | √- |
实施例X | √ | × | √ | × |
实施例Y | √ | × | √ | × |
实施例Z | √ | × | √ | × |
实施例A1 | √ | √- | √ | √ |
实施例A2 | √ | √ | √ | √ |
实施例A3 | √ | √ | √ | √ |
实施例A4 | √ | √ | √ | √ |
√=成功 √-=部分成功 ×=不成功
表II说明了根据本发明的组合物除去BARC残留物和光刻胶残留物的效果。
蚀刻速率测量的步骤
对覆Cu、Co和W晶片试样的金属层的厚度进行测定,这是通过使用产自Creative Design Engineering,Inc的ResMapTM型273电阻率仪测定该层的电阻率而实现。将该试样随后在需要的温度下浸在组合物中不超过1个小时。定时将该试样从组合物中取出,用去离子水漂洗然后干燥并再次测量金属层的厚度。制定了一张厚度作为浸泡时间的函数变化的图表,并且由埃/分钟表示的蚀刻速率由该曲线的斜率确定。
表III:清洁和腐蚀数据
制剂 | 蚀刻速率BARC | 蚀刻速率Cu | 蚀刻速率Co | 蚀刻速率W |
193nm(/min) | (/min) | (/min) | (/min) | |
实施例A | 1867 | 8 | NT | NT |
实施例B | NT | 12 | NT | 2 |
实施例C | NT | 12 | NT | 1 |
实施例H | NT | 25 | NT | 3 |
实施例I | 19 | NT | NT | NT |
实施例J | 1 | NT | NT | NT |
实施例K | 378 | 10 | 1 | NT |
实施例M | 1 | NT | NT | NT |
实施例O | 1 | NT | NT | NT |
实施例Q | 181 | NT | NT | NT |
实施例A2 | NT | 10 | NT | 0 |
实施例A3 | 91 | 6 | 24 | NT |
实施例A4 | 191 | NT | NT | NT |
NT=未测试
表III说明了根据本发明的特定组合物选择性地除去残留物而不明显腐蚀金属基底的效果。
上述实施例和对优选实施方案的描述在于举例说明而不是限定如权利要求所定义的本发明。容易理解,许多的变化和上述特征的组合能在不背离如权利要求所述的本发明下应用。不能认为上述变化是对本发明精神和范围的偏离,上述所有变化都应包括在下面的权利要求的范围之内。
Claims (17)
1、一种用于除去基底的残留物的组合物,该组合物包括:
选自胍盐、乙脒盐、甲脒盐、和其混合物的盐;
水;和
任选的能和水混溶的有机溶剂,
条件是该组合物不含有氧化剂和磨粒。
2、根据权利要求1所述的组合物,其还包括腐蚀抑制剂。
3、根据权利要求2所述的组合物,其中腐蚀抑制剂包括至少一种选自下面的物质:有机酸、有机酸盐、邻苯二酚、间苯二酚、苯酚、马来酸酐、邻苯二甲酸酐、邻苯二酚、焦性没食子酸、没食子酸或其酯、苯并三唑、羧基苯并三唑、果糖、硫代硫酸铵、甘氨酸、四甲基胍、亚氨基二乙酸、二甲基乙酰乙酰胺、三羟基苯、二羟基苯、水杨基羟氨(salicyclohydroxamic)、硫甘油及其混合物。
4、根据权利要求1所述的组合物,其还包括羟胺或其酸性盐。
5、根据权利要求4所述的组合物,其中所述的羟胺包括二乙基羟胺。
6、根据权利要求1所述的组合物,其包括能和水混溶的有机溶剂。
7、根据权利要求6所述的组合物,其中能和水混溶的有机溶剂还包括一种选自下面的物质:二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜、二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、二甲基-2-哌啶酮、四氢糠基醇、二醇醚、甘油及其混合物。
8、根据权利要求7所述的组合物,其中二醇醚选自乙二醇一甲醚、乙二醇一乙醚、乙二醇一丁醚、乙二醇二甲醚、乙二醇二乙醚、二甘醇一甲醚、二甘醇一乙醚、二甘醇一丙醚、二甘醇一异丙醚、二甘醇一丁醚、二甘醇一异丁基醚、二甘醇一苯甲醚、二甘醇二甲醚、二甘醇二乙醚、三甘醇单甲醚、三甘醇二甲醚、多乙二醇一甲醚、二甘醇甲基乙醚、三甘醇乙二醇一甲醚醋酸酯、乙二醇一乙醚醋酸酯、丙二醇一甲醚、丙二醇二甲醚、丙二醇一丁醚、丙二醇、一丙基醚、二丙二醇一甲醚、二丙二醇一丙基醚、二丙二醇一异丙醚、二亚丙基单丁基醚、二丙二醇二异丙醚、三丙二醇一甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。
9、根据权利要求1所述的组合物,其还包括氟化物离子源。
10、根据权利要求9所述的组合物,其中氟化物离子源包括具有通式R5R6R7R8NF的化合物,其中R5、R6、R7和R8独立地是氢、醇基团、烷氧基基团、烷基及其混合物。
11、根据权利要求9所述的组合物,其中含氟化物的化合物选自氟化四甲基铵、氟化四乙基铵、氟化四丁基铵、氟化胆碱及其混合物。
12、根据权利要求9所述的组合物,其中含氟化物的化合物包括氟硼酸。
13、根据权利要求1所述的组合物,其包括季铵化合物。
14、根据权利要求13所述的组合物,其中季铵化合物选自氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵及其混合物。
15、根据权利要求1所述的组合物,其还包括胺。
16、根据权利要求1所述的组合物,其还包括磺酸或其盐。
17、一种从包含电介质材料的基底上除去包括BARC的残留物的方法,其包括:将基底与组合物接触,该组合物包括:按重量计约0.01%至约40%的选自胍盐、乙脒盐、甲脒盐、和其混合物的盐;水;和任选的可与水混溶的有机溶剂,条件是该组合物不含有氧化剂和磨粒。
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Also Published As
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KR100844051B1 (ko) | 2008-07-07 |
US7700533B2 (en) | 2010-04-20 |
TW200700938A (en) | 2007-01-01 |
IL176489A0 (en) | 2006-10-05 |
TWI338199B (en) | 2011-03-01 |
KR20060134868A (ko) | 2006-12-28 |
EP1736534A1 (en) | 2006-12-27 |
CN1904016B (zh) | 2010-10-27 |
SG128635A1 (en) | 2007-06-30 |
US20060293208A1 (en) | 2006-12-28 |
JP2007016232A (ja) | 2007-01-25 |
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