TW202144557A - 用於銅大馬士革工藝的清洗液 - Google Patents
用於銅大馬士革工藝的清洗液 Download PDFInfo
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- TW202144557A TW202144557A TW110116779A TW110116779A TW202144557A TW 202144557 A TW202144557 A TW 202144557A TW 110116779 A TW110116779 A TW 110116779A TW 110116779 A TW110116779 A TW 110116779A TW 202144557 A TW202144557 A TW 202144557A
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- Prior art keywords
- acid
- cleaning solution
- ammonium
- process according
- copper
- Prior art date
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- 238000004140 cleaning Methods 0.000 title claims abstract description 87
- 239000010949 copper Substances 0.000 title claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000008569 process Effects 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- -1 organic acid ammonium salt Chemical class 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 20
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 claims description 11
- 229940090948 ammonium benzoate Drugs 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 4
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004251 Ammonium lactate Substances 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
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- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 3
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- FTEDXVNDVHYDQW-UHFFFAOYSA-N BAPTA Chemical compound OC(=O)CN(CC(O)=O)C1=CC=CC=C1OCCOC1=CC=CC=C1N(CC(O)=O)CC(O)=O FTEDXVNDVHYDQW-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- JBGQIGKEDXHQND-UHFFFAOYSA-M [OH-].[NH4+].C(CC)[N+](CCC)(CCC)CCC.[OH-] Chemical compound [OH-].[NH4+].C(CC)[N+](CCC)(CCC)CCC.[OH-] JBGQIGKEDXHQND-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- 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
- C11D7/3245—Aminoacids
-
- 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
- C11D1/62—Quaternary 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
本發明提供一種用於銅大馬士革工藝的清洗液,包括:氧化劑、螯合劑、有機鹼、表面張力調節劑、金屬緩蝕劑、有機酸銨鹽和水。本發明通過在清洗液中添加表面張力調節劑,在TiN硬掩模完全去除,金屬材料、非金屬材料以及低k介質材料得到很好的保護前提下,進一步降低了清洗液的表面張力,使金屬緩蝕劑易於從晶圓表面脫附,進而使刻蝕殘留物完全去除,進一步增強了清洗效果,提高了半導體器件的良率,且本申請的用於銅大馬士革工藝的清洗液不含氟化物,操作視窗較大(適用於20℃~80℃),PH值適用範圍廣(pH值為5~14),在高端半導體清洗領域具有良好的應用前景。
Description
本發明涉及涉及半導體製造過程中的晶圓清洗領域,尤其涉及一種用於14nm及更小技術節點高端半導體清洗液領域。
銅是一種穩定金屬,在與刻蝕氣體反應時不會產生揮發性的副產物,因而在互連工藝中不能像鋁一樣直接使用乾法刻蝕工藝蝕刻銅,以形成金屬互連線圖形。IBM公司在1997年研發出大馬士革工藝,該工藝通過光刻以及乾法蝕刻工藝在介電材料層上形成金屬互連線圖形的凹槽,再沉積金屬阻擋層、銅籽晶層和金屬銅,再用CMP的方式去除多餘的金屬,形成所需的金屬連線。多層銅互連工藝一般需用使用同時形成互連線溝槽與互連通孔的雙大馬士革工藝。
在積體電路(IC)製造中,銅雙大馬士革工藝應用越來越廣泛,高速旋轉單片機清洗也成為主流清洗方式。隨著互連線特徵尺寸進一步減小到14nm及以下技術節點,去膠等工藝中的等離子體損傷會對低k材料的機械與物化性能產生嚴重影響,使集成結構中k值局部增加,削弱低k介質材料的優勢。此外,由於蝕刻殘留物的低表面能和交聯性質,以及殘留物成分物理和化學性質的變化,加之清洗液與設備膜材料和結構之間的相容性問題,使得尋找能夠有效去除等離子體刻蝕殘留物的同時又能保護低k介質材料、非金屬材料和金屬材料的低表面張力清洗液越來越具有挑戰性。
目前,關於積體電路領域的半導體清洗液的報導主要以國外為主。美國高級技術材料公司在專利CN101366107B中公開了一種用於從微電子器件基底上除去刻蝕殘留物,高選擇性去除含鈦(TiN)硬掩模材料的含水氧化組合物及其製備和使用方法。基板材料主要有低k介電材料如有機聚合物、有機矽酸鹽玻璃OSG、摻碳氧化物(CDO)玻璃、正矽酸四乙酯(TEOS)、FSG等,金屬材料主要是銅和鈷。該清洗液組合物主要以H2O2作為氧化劑,以一級胺、二級胺、三級胺和胺-N-氧化物等胺類物質作為氧化劑穩定劑,任選至少一種有機酸作為金屬螯合劑,任選至少一種唑類作為金屬緩蝕劑,配合以緩衝劑和有機共溶劑以及水,在pH值3~9,30~50℃溫度條件下,從微電子器件上選擇性和有效地除去含鈦等離子體刻蝕後殘留物、側壁聚合殘留物、含銅通孔殘留物和/或含鈦硬掩模層。該清洗液可以穩定6~24h實現從微電子器件上高效清洗殘餘材料,同時不會損壞介電材料和金屬互連材料。
最新報導中,美國Versum Material公司在專利US2020035485A1中公開了一種用於從電子電路器件除去TiN硬掩模的組合物。主要以雙氧水作為氧化劑,大分子有機酸作為雙氧水穩定劑,唑類和多元醇類作為金屬腐蝕抑制劑,四級銨氫氧化物和銨鹽作為蝕刻劑,水作為溶劑,加之以任選氟化物來保證清洗力,在pH值大於5.5的環境下選擇性地除去氮化鈦和來自等離子體刻蝕過程中的殘留物,同時使Cu、Co、低k介電材料等第二材料得到有效保護。在晶片或器件加工過程中通過稀氫氟酸去除後,銅損失受到氧化銅厚度的影響,該發明中提到含有氨基的腐蝕抑制劑可提供更好的氧化銅厚度性能。
為解決現有技術中的用於銅大馬士革工藝的清洗液無法完全去除金屬孔道內的刻蝕殘留物的問題,本申請提供一種用於銅大馬士革工藝的清洗液,包括:氧化劑、螯合劑、有機鹼、表面張力調節劑、金屬緩蝕劑、有機酸銨鹽和水。
進一步地,所述氧化劑的含量為0.1 wt%-30 wt%。
進一步地,所述螯合劑的含量為0.05-1000ppm。
進一步地,所述螯合劑的含量為0.1-10ppm。
進一步地,所述有機鹼的含量為0.1 wt%-20 wt%。
進一步地,所述表面張力調節劑的含量為10ppm-10 wt%。
進一步地,所述表面張力調節劑的含量為10ppm-5 wt%。
進一步地,所述表面張力調節劑的含量為10ppm-3%。
進一步地,所述金屬緩蝕劑的含量為0.01 wt%-20 wt%。
進一步地,所述有機酸銨鹽的含量為0.01 wt%-50 wt%。
進一步地,所述水的含量為35.1 wt%-96.9 wt%。
進一步地,所述氧化劑選自H2
O2
、N-甲基嗎啉氧化物(NMMO或NMO)、過氧化苯甲醯、過乙酸(CH3
(CO)OOH)、過氧化脲((CO(NH2
)2
)H2
O2
)、硝酸、過氧乙酸、過氧苯甲酸或四氧嘧啶中的一種或多種。
進一步地,所述螯合劑選自甘氨酸、絲氨酸、脯氨酸、亮氨酸、丙氨酸、天冬氨酸、天冬醯胺、穀氨醯胺、纈氨酸、賴氨酸、胱氨酸、乙二胺四乙酸(EDTA)、反式-1,2環己二胺四乙酸(CDTA)、尿酸、吡啶甲酸、次氮基三乙酸(NTA)、羥基乙叉二膦酸(HEDP)、乙二胺-N,N’-二琥鉑酸(EDDS)、谷氨酸、二乙烯三胺五乙酸(DTPA)、羥乙基乙二胺三乙酸(HEDTA)、亞氨基二乙酸(IDA)、氨三乙酸、水楊酸、葡萄糖酸、煙酸、酒石酸、檸檬酸、1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸(DOTA)、乙二醇四乙酸(EGTA)、1,2-雙(鄰氨基苯氧基)乙烷-N,N,N’,N’-四乙酸、乙二胺-N,N’-雙(2-羥基苯乙酸)(HDDHA)、或丙二胺四乙酸中的一種或多種。
進一步地,所述有機鹼選自四級胺氫氧化物、有機胺、或有機醇胺中的一種或多種。
進一步地,所述四級胺氫氧化物選自四甲基氫氧化銨(TMAH)、四乙基氫氧化銨(TEAH)、三甲基苯基氫氧化銨(TMPAH)、四丙基氫氧化銨(TPAH)、四丁基氫氧化銨(TBAH)、苄基三甲基氫氧化銨(BTMAH)、苄基三乙基氫氧化銨( BTEAH)、膽鹼氫氧化物、氫氧化銨、十二烷基三甲基氫氧化銨(DTAH)、或十六烷基三甲基氫氧化銨(CTOH)中的一種或多種。
進一步地,所述有機胺選自單乙胺、二乙胺、三乙胺、三丙胺、N,N-二乙基乙二胺、羥乙基乙二胺、環己胺、1,2-丙二胺、或五甲基二乙烯三胺中的一種或多種。
進一步地,所述有機醇胺選自單乙醇胺(MEA)、二乙醇胺(DEA)、三乙醇胺(TEA)、二甘醇胺(DGA)、異丙醇胺、或N-甲基乙醇胺中的一種或多種。
進一步地,所述有機鹼的金屬離子的含量<50ppb。
進一步地,所述表面張力調節劑為極性有機物一元醇和/或極性有機物醚類,所述極性有機物醚類的結構通式為R-O-R、R-O-R'、Ar-O-R、Ar-O-Ar或Ar-O-Ar',其中,R=烴基,R'=烴基,R和R'可以相同,也可以不同,相同為對稱醚,不相同為混合醚,如果R、R'分別是一個有機基團兩端的碳原子則稱為環醚,Ar=芳烴基,Ar'=芳烴基,Ar和Ar'可以相同,也可以不同。
進一步地,所述極性有機物一元醇選自甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、新戊醇、環己醇、辛醇、苯甲醇、香茅醇、或橙花醇中的一種或多種。
進一步地,所述極性有機物醚類選自乙醚、丙二醇甲醚、二丙二醇甲醚(DPM)、丙二醇苯醚、甲基叔丁醚、四氫呋喃(THF)、環氧乙烷、苯甲醚、1,2-環氧丙烷、1,4-二氧六環、甲基烯丙基醚、正丙醚、或丁基縮水甘油醚中的一種或多種。
進一步地,所述金屬緩蝕劑為唑類雜環化合物。
進一步地,所述唑類雜環化合物選自苯並三氮唑(BTA)、1,2,4-三氮唑、5-甲基苯並三氮唑(TTA)、羥基苯並三唑、吡唑、甲苯三唑、3,5-二甲基吡唑、四氮唑、4-氨基-1,2,4-三唑、苯並噻唑、甲基-1H-苯並三唑(TTL)、2-氨基苯並噻唑、2-巰基苯並噻唑、3-氨基-5-羥基吡唑、1-苯基吡唑、巰基苯並咪唑、5-氨基四唑、3-巰基-1,2,4-三唑、 3-異丙基-1,2,4-三唑、2-(5-氨基-戊基)-苯並三唑、5-苯硫醇-苯並三唑、甲基四唑、5-苯基-苯並三唑、5-硝基-苯並三唑、3-氨基-5-巰基-1,2,4-三唑、1-氨基-1,2,4三唑、羥苯並三唑、1-氨基-1,2,3-苯並三唑、或噻唑中的一種或多種。
進一步地,所述有機酸銨鹽選自甲酸銨、草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、氨基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸四銨(EDTA四銨)、EDTA三銨、EDTA二銨、琥珀酸銨、1-H-吡唑-3-甲酸銨、丙二酸銨、己二酸銨、或亞氨基二乙酸銨中的一種或多種。優選地,所述有機酸銨鹽為螯合能力強的有機酸銨鹽。
本申請的所有材料和試劑均市售可得。
與現有技術相比較,本發明的優勢在於:
本發明公開了一種用於銅大馬士革工藝的清洗液,主要用於14nm及更小技術節點高端半導體清洗液領域。本發明通過在清洗液中添加表面張力調節劑,在TiN硬掩模完全去除,金屬材料、非金屬材料以及低k介質材料得到很好的保護前提下,進一步降低了清洗液的表面張力,使金屬緩蝕劑易於從晶圓表面脫附,進而使清洗後晶圓的金屬孔道內的刻蝕殘留物能夠被完全去除,進一步增強了清洗效果,提高了半導體器件的良率,且本申請的用於銅大馬士革工藝的清洗液不含氟化物,操作視窗較大(適用於20℃~80℃),PH值適用範圍廣(pH值為5~14),在高端半導體清洗領域具有良好的應用前景。
下面結合附圖及具體實施例,詳細闡述本發明的優勢。
製備方法:按照下述表1中各個實施例和對比例的配方(特定組分及其對應的特定含量)將各個組分進行簡單混合。
表1. 不同實施例及對比例的配方和清洗溫度
氧化劑 wt% | 螯合劑 ppm | 有機鹼 wt% | 表面張力調節劑 | 金屬緩蝕劑wt | 有機酸銨鹽wt% | 水wt% | 溫度℃ | |
實施例1 | H2 O2 :3.0 | 甘氨酸:0.5 | TMAH:0.4 | 苯甲醇:0.1 wt% | BTA:0.5 | 甲酸銨:0.5 | 95.5 | 50℃ |
實施例2 | H2 O2 :6.0 | EDTA:1.0 | TEAH:1.0 | 正丁醇:0.5 wt% | 1,2,4-三氮唑:1.0 | 草酸銨:0.2 | 91.3 | 50℃ |
實施例3 | H2 O2 :9.0 | CDTA:100 | TBPH:1.0 | 新戊醇:1.0 wt% | TTA:1.0 | 乳酸銨:2.0 | 85.99 | 50℃ |
實施例4 | H2 O2 :12.0 | 尿酸:0.05 | BTMAH:0.5 | 環己醇:2.0 wt% | 羥基苯並三唑:1.0 | 酒石酸銨:1.0 | 83.5 | 50℃ |
實施例5 | H2 O2 :15.0 | 吡啶甲酸:1 | BTEAH:10 | 異丙醇:5.0 wt% | 吡唑:1.0 | 檸檬酸銨:1.0 | 68.0 | 50℃ |
實施例6 | H2 O2 :18.0 | IDA:10 | 異丙醇胺:1 | 辛醇:8.0 wt% | 甲苯三唑:0.5 | 乳酸銨:1 | 71.5 | 50℃ |
實施例7 | H2 O2 :21.0 | EDDS:8 | DTAH:1.0 | 乙醇:10.0 wt% | 四氮唑:5 | 氨基甲酸銨:1.0 | 62.0 | 50℃ |
實施例8 | H2 O2 :24.0 | 谷氨酸:80 | CTOH:1.0 | 正丙醇:0.05 wt% | 苯並噻唑:0.5 | 碳酸銨:0.5 | 73.95 | 50℃ |
實施例9 | H2 O2 :27.0 | DTPA:8 | 單乙胺:10 | 丙二醇甲醚:1.5 wt% | 2-氨基苯並噻唑:0.01 | 苯甲酸銨:1.0 | 60.49 | 50℃ |
實施例10 | NMO:0.1 | HEDTA:8 | 二乙胺:1.0 | DPM:0.5 wt% | 2-巰基苯並噻唑:0.5 | EDTA四銨:1.0 | 96.9 | 20℃ |
實施例11 | 過氧乙酸:30.0 | HEDP:0.1 | 三乙胺:1.0 | 環氧乙烷:2.5 wt% | TTL:0.5 | EDTA三銨:1.0 | 65.0 | 30℃ |
實施例12 | 過氧苯甲酸:5.3 | EGTA:8 | 環己胺:1.0 | 苯甲醚:10ppm | 甲基四唑:0.5 | EDTA二銨:1.0 | 92.2 | 40℃ |
實施例13 | H2 O2 :18.0 | 氨三乙酸:5 | MEA:0.1 | 乙醚:20ppm | 1-氨基-1,2,4三唑:3.5 | 琥鉑酸銨:0.8 | 77.6 | 50℃ |
實施例14 | H2 O2 :16.0 | 煙酸:10 | DEA:0.5 | 正丙醚:50ppm | 羥苯並三唑:5 | 1-H-吡唑-3-甲酸銨:3.5 | 75.0 | 50℃ |
實施例15 | H2 O2 :14.0 | 酒石酸:20 | TEA:1 | 丁基縮水甘油醚:100ppm | 噻唑:0.5 | 丙二酸銨:2.5 | 82.0 | 50℃ |
實施例16 | H2 O2 :18.0 | 檸檬酸:30 | DGA:2 | 香茅醇:200ppm | 3-巰基-1,2,4-三唑:0.05 | 己二酸銨:10 | 69.95 | 20℃ |
實施例17 | 四氧嘧啶:8 | DOTA:40 | 異丙醇胺:4 | 橙花醇:500ppm | 5-硝基-苯並三唑:0.5 | 亞氨基二乙酸銨:2.4 | 85.1 | 30℃ |
實施例18 | H2 O2 :12.0 | 亮氨酸:8 | MEA:2 | DPM:800ppm | 4-氨基-1,2,4-三唑:0.25 | 苯甲酸銨:1 | 84.75 | 50℃ |
實施例19 | 硝酸:5.0 | HDDHA:60 | DEA:8 | 甲醇:0.1 wt% | 巰基苯並咪唑:0.5 | 苯甲酸銨:0.01 | 86.39 | 40℃ |
實施例20 | NMO:5.5 | 天冬氨酸:70 | TMPAH:10 | 正丙醇:0.2 wt% | 3,5-二甲基吡唑:3.5 | 乙酸銨:1 | 79.8 | 60℃ |
實施例21 | H2 O2 :10.0 | 葡萄糖酸:80 | 1,2-丙二胺:12 | 異丁醇:0.5 wt% | 1-苯基吡唑:5 | 檸檬酸銨:5 | 67.5 | 70℃ |
實施例22 | H2 O2 :9.0 | 絲氨酸:90 | TPAH:15 | THF:1.0 wt% | 5-氨基四唑:15 | 酒石酸銨:10 | 50.0 | 80℃ |
實施例23 | 過氧化苯甲醯:8.0 | 水楊酸:5 | 膽鹼氫氧化物:1 | 丙二醇苯醚:1.5 wt% | 3-氨基-5-羥基吡唑:0.5 | 乙酸銨:1.0 | 88.0 | 50℃ |
實施例24 | 過氧化脲:6.0 | 丙二胺四乙酸:200 | N-甲基乙醇胺:20 | 1,4-二氧六環:3.0 wt% | 3-異丙基-1,2,4-三唑:10 | 草酸銨:2 | 58.98 | 50℃ |
實施例25 | 過乙酸:4.0 | 脯氨酸:0.05 | 氫氧化銨:5 | 甲基叔丁醚:5.0 wt% | 1-氨基-1,2,3-苯並三唑:20 | 甲酸銨:30 | 36.0 | 50℃ |
實施例26 | NMMO:2.0 | 天冬醯胺:0.5 | 三丙胺:1.0 | 1,2-環氧丙烷:8.0 wt% | 5-苯基-苯並三唑:0.5 | 酒石酸銨:40 | 48.5 | 50℃ |
實施例27 | H2 O2 :3.0 | NTA:1 | N,N-二乙基乙二胺:1.0 | 甲基烯丙基醚:10.0 wt% | 2-(5-氨基-戊基)-苯並三唑:0.9 | 檸檬酸銨:50 | 35.1 | 50℃ |
實施例28 | H2 O2 :22.0 | 賴氨酸:1000 | 羥乙基乙二胺:0.5 | 二級丁醇:0.5 wt% | 5-苯硫醇-苯並三唑:0.5 | 酒石酸銨:0.5 | 75.9 | 50℃ |
實施例29 | H2 O2 :15.0 | 胱氨酸:3 | 五甲基二乙烯三胺:1.0 | 三級丁醇:0.5 wt% | 3-氨基-5-巰基-1,2,4-三唑:0.5 | 苯甲酸銨:0.5 | 82.5 | 60℃ |
實施例30 | H2 O2 :16.0 | 谷氨酸:3 | TMAH:0.4 | 新戊醇:0.05 wt% | BTA:0.3 | 苯甲酸銨:0.5 | 82.75 | 50℃ |
實施例31 | H2 O2 :16.0 | 谷氨酸:3 | TMAH:0.4 | 新戊醇:0.5 wt% | BTA:0.3 | 苯甲酸銨:0.5 | 82.3 | 50℃ |
實施例32 | H2 O2 :16.0 | EDTA:3 | TEA:0.4 | 丙二醇苯醚:0.1 wt% | TTL:0.3 | 酒石酸銨:0.5 | 82.7 | 50℃ |
實施例33 | H2 O2 :16.0 | EDTA:3 | TEA:0.4 | 丙二醇苯醚:0.3 wt% | TTL:0.3 | 酒石酸銨:0.5 | 82.5 | 50℃ |
對比例1 | H2 O2 :16.0 | 谷氨酸:3 | TMAH:0.4 | / | BTA:0.3 | 苯甲酸銨:0.5 | 82.8 | 50℃ |
對比例2 | H2 O2 :16.0 | EDTA:3 | TEA:0.4 | / | TTL:0.3 | 酒石酸銨:0.5 | 82.8 | 50℃ |
對比例3 | H2 O2 :16.0 | 谷氨酸:3 | TMAH:0.4 | 丙二醇:0.5 wt% | BTA:0.3 | 苯甲酸銨:0.5 | 82.3 | 50℃ |
對比例4 | H2 O2 :16.0 | 谷氨酸:3 | TMAH:0.4 | 山梨醇:0.5 wt% | BTA:0.3 | 苯甲酸銨:0.5 | 82.3 | 50℃ |
效果實施例
用於測試蝕刻速率的測試物件及其來源:
TiN(氮化鈦)空白晶片——Ramco Specialties Inc.(美國拉姆科專業有限公司)
Cu(銅)空白晶片——Ramco Specialties Inc.
Co(鈷)空白晶片——Ramco Specialties Inc.
SiON(氮氧化矽)空白晶片——Ramco Specialties Inc.
TEOS(二氧化矽)空白晶片——Ramco Specialties Inc.
BDII(低介電常數氧化矽)空白晶片——Ramco Specialties Inc.
TiN、Cu、Co等金屬蝕刻速率測試方法:
(1)利用Napson四點探針儀測試5*5cm金屬空白晶片(TiN空白晶片、Cu空白晶片、Co空白晶片)的電阻初值(Rs1);
(2)將該5*5cm金屬空白晶片在迷你單片機mini-SWT上400rpm,TiN空白晶片經清洗液處理5min,Cu空白晶片和Co空白晶片化學處理10min;
(3)取出該5*5cm金屬空白晶片,用去離子水(DIW)清洗,高純氮氣吹幹,再利用Napson四點探針儀測試5*5cm金屬空白晶片的電阻值(Rs2);
(4)將上述電阻值和蝕刻時間輸入到合適的程式可計算出金屬的蝕刻速率。
SiON、TEOS、BDII等非金屬蝕刻速率(Etch Rate)測試方法:
(1)按照標準開啟Nanospec6100測厚儀,選用合適的測試程式,將5*5cm非金屬空白晶片(SiON空白晶片、TEOS空白晶片、BDII空白晶片)放入Nanospec6100測厚儀上測試非金屬空白晶片厚度,將非金屬空白晶片旋轉90°繼續測試,連續測試4次,記錄數值;
(2)若非金屬空白晶片為BDII,需用水沖洗乾淨,馬弗爐350℃處理20min,乾燥器冷卻至室溫再測試前值;(其他晶片無需步驟2)
(3)將該5*5cm非金屬空白晶片在mini-SWT上400rpm,清洗液處理10min;
(4)取出該5*5cm非金屬空白晶片,用DIW清洗,高純氮氣吹幹,在Nanospec6100測厚儀上按程式1測試晶片厚度,記錄數值;
(5)若非金屬空白晶片為BDII,需用水沖洗乾淨,馬弗爐350℃處理20min,乾燥器冷卻至室溫再測試後值;(其他晶片無需步驟5)
(6)將上述前後厚度值和蝕刻時間輸入合適的程式中,蝕刻速率計算為厚度變化除以化學處理時間。
將按照表1的實施例與對比例製備得到的不同清洗液,利用克呂士K100型表面張力儀使用懸滴法測試不同溶液的表面張力。按照上述蝕刻速率測試方法測試不同空白晶片的蝕刻速率,並利用X射線光電子能譜分析儀(XPS)測試金屬緩蝕劑在銅或鈷空白晶片表面的吸附情況,因為金屬緩蝕劑含有N元素, 所以,以銅表面的N元素的含量判斷金屬緩蝕劑在銅表面的吸附量。同時在50℃、400rpm/min的條件下,使用mini-SWT單片機清洗圖案晶圓90s,水漂洗乾淨,氮氣吹幹,Hitachi SU8220型掃描電鏡 (SEM)觀察圖形晶圓的清洗效果。不同空白晶片的蝕刻速率、表面吸附結果、表面張力及清洗效果見表2。
表2 不同實施例與對比例的蝕刻速率、表面吸附結果、表面張力及清洗結果
氮化鈦蝕刻速率 | 金屬蝕刻速率 | 非金屬蝕刻速率 | 表面吸附結果 | 表面張力 | 圖形晶圓 清洗結果 | ||||
TiN ER (Å/min) | Cu ER (Å/min) | Co ER (Å/min) | SiON ER (Å/min) | TEOS ER (Å/min) | BDII ER (Å/min) | XPS (基於N) | 懸滴法 (mN/m) | 大馬士革工藝金屬孔道 | |
實施例30 | 246.31 | 0.68 | 0.22 | 0.13 | 0.31 | -0.17 | ○ | 64.20 | ○ |
實施例31 | 246.83 | 0.71 | 0.18 | 0.12 | 0.27 | 0.11 | ◎ | 53.35 | ◎ |
實施例32 | 253.69 | 0.62 | 0.17 | 0.21 | 0.23 | -0.12 | ○ | 62.56 | ○ |
實施例33 | 255.31 | 0.67 | 0.22 | 0.12 | 0.18 | -0.11 | ◎ | 60.09 | ◎ |
對比例1 | 246.65 | 0.76 | 0.17 | 0.06 | 0.24 | -0.11 | △ | 64.85 | △ |
對比例2 | 254.58 | 0.69 | 0.19 | -0.04 | 0.17 | 0.13 | △ | 63.06 | △ |
對比例3 | 247.04 | 0.62 | 0.05 | 0.13 | 0.11 | -0.08 | ○ | 63.88 | ○ |
對比例4 | 247.37 | 0.58 | 0.17 | -0.05 | -0.09 | 0.14 | ○ | 64.76 | ○ |
表面吸附結果(XPS) | 晶圓清洗結果 |
◎ 完全無吸附 | ◎ 完全清洗乾淨 |
○ 輕微吸附 | ○ 少量殘留物 |
△ 較多吸附 | △ 較多殘留物 |
× 嚴重吸附 | × 大量殘留物 |
從表2中可以看出:本發明的清洗液在TiN硬掩模完全去除的情況下,對半導體制程中所用的金屬(如Cu和Co)和非金屬(SiON、TEOS、BDII)基本不會刻蝕,其腐蝕情況均滿足半導體業界通常在高速旋轉單片機清洗的要求。
對比例1與實施例30對照表明,不添加表面張力調節劑,溶液的表面張力較高,金屬緩蝕劑在空白銅晶片表面的吸附(XPS)較多,晶圓清洗後金屬孔道殘留物較多;添加了表面張力調節劑新戊醇,溶液的表面張力得到一定程度的降低,金屬緩蝕劑在空白銅晶片表面的吸附也比不添加時要少,進而在圖形晶圓的清洗殘留物更少。
實施例30與實施例31表明,添加不同濃度的新戊醇,溶液的表面張力達到可調控,隨著新戊醇濃度的增加,溶液的表面張力下降,相應的清洗液在晶片表面的吸附量和清洗後的殘留物也逐漸減少,有利於提高半導體器件的良率。
對比例3與實施例31對照表明,包含相同品質的丙二醇清洗液和包含相同品質的一元醇清洗液,包含丙二醇的清洗液的表面張力要比包含一元醇的清洗液大的多;對比例4與對比例3、實施例31對照表明,包含相同品質的山梨醇的清洗液的表面張力比包含相同品質的新戊醇(一元醇)的清洗液要大的多,同時,比包含相同品質的丙二醇(二元醇)清洗液的表面張力也要大一些,這會對清洗液在晶圓表面的吸附和脫附過程造成影響,進而影響清洗效果。由表2的實施例31、對比例3和對比例4可知,包含新戊醇的清洗液在晶片表面完全無吸附,金屬孔道殘留物被完全清洗乾淨,而包含丙二醇或山梨醇的清洗液在晶片表面存在輕微吸附,清洗後在金屬孔道內仍然存在少量殘留物。由此可知,清洗液的表面張力越小,清洗液在晶圓表面越容易脫附,清洗後的金屬孔道內的殘留物越少。
對比例2與實施例32對照表明,不添加表面張力調節劑,溶液的表面張力較高,在空白銅晶片表面的吸附較多,晶圓清洗後金屬孔道殘留物較多;添加了表面張力調節劑丙二醇苯醚的體系,可以降低溶液的表面張力,減少溶液在空白銅晶片表面的吸附,提高清洗能力。實施例32與實施例33表明,丙二醇苯醚濃度的增加,溶液的表面張力降低,清洗液在晶片表面的吸附量和殘留物也進一步減少,清洗效果得到明顯的提升。原理為:醇醚類極性有機物,分子內含有親水基,在水溶液中,親水基與水分子接觸,受到水分子向下的吸引力。由於親水基的極性弱于水分子,這種吸引力弱于水分子之間的吸引力,因此在有醇醚分子排列的水溶液表面,比沒有醇醚等極性有機物的水溶液表面受力不平衡的狀態要弱,分子向內部的運動減弱,表面分子密度增加,分子間的有效距離變短,分子間引力減弱,表面「繃緊」程度降低,表面張力下降。
綜上,本發明的積極進步效果在於:本發明開發的一種用於銅大馬士革工藝的清洗液,通過添加表面張力調節劑,在TiN硬掩模完全去除,金屬材料、非金屬材料以及低k介質材料得到很好的保護前提下,進一步降低了清洗液的表面張力,進而使金屬緩蝕劑易於從晶圓表面脫附,使刻蝕殘留物完全去除,進一步增強了清洗效果,提高了半導體器件的良率,操作視窗較大,在高端半導體清洗領域具有良好的應用前景。
以上對本發明的具體實施例進行了詳細描述,但其只是作為範例,本發明並不限制於以上描述的具體實施例。對於本領域技術人員而言,任何對本發明進行的等同修改和替代也都在本發明的範疇之中。因此,在不脫離本發明的精神和範圍下所作的均等變換和修改,都應涵蓋在本發明的範圍內。
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Claims (24)
- 一種用於銅大馬士革工藝的清洗液,其特徵在於,包括:氧化劑、螯合劑、有機鹼、表面張力調節劑、金屬緩蝕劑、有機酸銨鹽、和水。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述氧化劑的含量為0.1 wt%-30 wt%。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述螯合劑的含量為0.05-1000ppm。
- 如請求項3所述的用於銅大馬士革工藝的清洗液,其中,所述螯合劑的含量為0.1-10ppm。
- 如權利請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述有機鹼的含量為0.1 wt%-20 wt%。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述表面張力調節劑的含量為10ppm-10 wt%。
- 如請求項6所述的用於銅大馬士革工藝的清洗液,其中,所述表面張力調節劑的含量為10ppm-5 wt%。
- 如請求項7所述的用於銅大馬士革工藝的清洗液,其中,所述表面張力調節劑的含量為10ppm-3%。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述金屬緩蝕劑的含量為0.01 wt%-20 wt%。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述有機酸銨鹽的含量為0.01 wt%-50 wt%。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述水的含量為35.1 wt%-96.9 wt%。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述氧化劑選自H2 O2 、N-甲基嗎啉氧化物、過氧化苯甲醯、過乙酸、過氧化脲、硝酸、過氧乙酸、過氧苯甲酸、或四氧嘧啶中的一種或多種。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述螯合劑選自甘氨酸、絲氨酸、脯氨酸、亮氨酸、丙氨酸、天冬氨酸、天冬醯胺、穀氨醯胺、纈氨酸、賴氨酸、胱氨酸、乙二胺四乙酸、反式-1,2環己二胺四乙酸、尿酸、吡啶甲酸、次氮基三乙酸、羥基乙叉二膦酸、乙二胺-N,N’-二琥鉑酸、谷氨酸、二乙烯三胺五乙酸、羥乙基乙二胺三乙酸、亞氨基二乙酸、氨三乙酸、水楊酸、葡萄糖酸、煙酸、酒石酸、檸檬酸、1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸、乙二醇四乙酸、1,2-雙(鄰氨基苯氧基)乙烷-N,N,N’,N’-四乙酸、乙二胺-N,N’-雙(2-羥基苯乙酸)、或丙二胺四乙酸中的一種或多種。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述有機鹼選自四級胺氫氧化物、有機胺、或有機醇胺中的一種或多種。
- 如請求項14所述的用於銅大馬士革工藝的清洗液,其中,所述四級胺氫氧化物選自四甲基氫氧化銨、四乙基氫氧化銨、三甲基苯基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨、苄基三甲基氫氧化銨、苄基三乙基氫氧化銨、膽鹼氫氧化物、氫氧化銨、十二烷基三甲基氫氧化銨、或十六烷基三甲基氫氧化銨中的一種或多種。
- 如請求項14所述的用於銅大馬士革工藝的清洗液,其中,所述有機胺選自單乙胺、二乙胺、三乙胺、三丙胺、N,N-二乙基乙二胺、羥乙基乙二胺、環己胺、1,2-丙二胺、或五甲基二乙烯三胺中的一種或多種。
- 如請求項14所述的用於銅大馬士革工藝的清洗液,其中,所述有機醇胺選自單乙醇胺、二乙醇胺、三乙醇胺、二甘醇胺、異丙醇胺、或N-甲基乙醇胺中的一種或多種。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述有機鹼的金屬離子的含量<50ppb。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述表面張力調節劑為極性有機物一元醇和/或極性有機物醚類,所述極性有機物醚類的結構通式為R-O-R、R-O-R'、Ar-O-R、Ar-O-Ar或Ar-O-Ar',其中,R=烴基,R' =烴基,Ar=芳烴基,Ar'=芳烴基。
- 如請求項19所述的用於銅大馬士革工藝的清洗液,其中,所述極性有機物一元醇選自甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、新戊醇、環己醇、辛醇、苯甲醇、香茅醇、或橙花醇中的一種或多種。
- 如請求項19所述的用於銅大馬士革工藝的清洗液,其中,所述極性有機物醚類選自乙醚、丙二醇甲醚、二丙二醇甲醚、丙二醇苯醚、甲基叔丁醚、四氫呋喃、環氧乙烷、苯甲醚、1,2-環氧丙烷、1,4-二氧六環、甲基烯丙基醚、正丙醚、或丁基縮水甘油醚中的一種或多種。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述金屬緩蝕劑為唑類雜環化合物。
- 如請求項22所述的用於銅大馬士革工藝的清洗液,其中,所述唑類雜環化合物選自苯並三氮唑、1,2,4-三氮唑、5-甲基苯並三氮唑、羥基苯並三唑、吡唑、甲苯三唑、3,5-二甲基吡唑、四氮唑、4-氨基-1,2,4-三唑、苯並噻唑、甲基-1H-苯並三唑、2-氨基苯並噻唑、2-巰基苯並噻唑、3-氨基-5-羥基吡唑、1-苯基吡唑、巰基苯並咪唑、5-氨基四唑、3-巰基-1,2,4-三唑、 3-異丙基-1,2,4-三唑、2-(5-氨基-戊基)-苯並三唑、5-苯硫醇-苯並三唑、甲基四唑、5-苯基-苯並三唑、5-硝基-苯並三唑、3-氨基-5-巰基-1,2,4-三唑、1-氨基-1,2,4三唑、羥苯並三唑、1-氨基-1,2,3-苯並三唑、或噻唑中的一種或多種。
- 如請求項1所述的用於銅大馬士革工藝的清洗液,其中,所述有機酸銨鹽選自甲酸銨、草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、氨基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸四銨、乙二胺四乙酸三銨、乙二胺四乙酸二銨、琥珀酸銨、1-H-吡唑-3-甲酸銨、丙二酸銨、己二酸銨、或亞氨基二乙酸銨中的一種或多種。
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