TW202113039A - 蝕刻組成物 - Google Patents
蝕刻組成物 Download PDFInfo
- Publication number
- TW202113039A TW202113039A TW109130771A TW109130771A TW202113039A TW 202113039 A TW202113039 A TW 202113039A TW 109130771 A TW109130771 A TW 109130771A TW 109130771 A TW109130771 A TW 109130771A TW 202113039 A TW202113039 A TW 202113039A
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- TW
- Taiwan
- Prior art keywords
- composition
- acid
- weight
- benzotriazole
- etching
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 238000005530 etching Methods 0.000 title claims abstract description 95
- -1 amine compound Chemical class 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 54
- 239000004065 semiconductor Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000005260 corrosion Methods 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 8
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 7
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 150000001565 benzotriazoles Chemical class 0.000 claims description 7
- 229960003330 pentetic acid Drugs 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 claims description 2
- SJBOEHIKNDEHHO-UHFFFAOYSA-N 2-[2-aminoethyl(carboxymethyl)amino]acetic acid Chemical compound NCCN(CC(O)=O)CC(O)=O SJBOEHIKNDEHHO-UHFFFAOYSA-N 0.000 claims description 2
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 2
- XSFHICWNEBCMNN-UHFFFAOYSA-N 2h-benzotriazol-5-amine Chemical compound NC1=CC=C2NN=NC2=C1 XSFHICWNEBCMNN-UHFFFAOYSA-N 0.000 claims description 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims description 2
- QGCDUBGOXJTXIU-UHFFFAOYSA-N 3-(2h-benzotriazol-4-yl)propane-1,1-diol Chemical compound OC(O)CCC1=CC=CC2=NNN=C12 QGCDUBGOXJTXIU-UHFFFAOYSA-N 0.000 claims description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 2
- PHFUGYFADPADDV-UHFFFAOYSA-N 4-(2-methylpropyl)-2h-benzotriazole Chemical compound CC(C)CC1=CC=CC2=NNN=C12 PHFUGYFADPADDV-UHFFFAOYSA-N 0.000 claims description 2
- DNJANJSHTMOQOV-UHFFFAOYSA-N 4-bromo-2h-benzotriazole Chemical compound BrC1=CC=CC2=C1N=NN2 DNJANJSHTMOQOV-UHFFFAOYSA-N 0.000 claims description 2
- IPIVUPVIFPKFTG-UHFFFAOYSA-N 4-butyl-2h-benzotriazole Chemical compound CCCCC1=CC=CC2=C1N=NN2 IPIVUPVIFPKFTG-UHFFFAOYSA-N 0.000 claims description 2
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 claims description 2
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 claims description 2
- ALDDXGSQUCGTDT-UHFFFAOYSA-N 4-fluoro-2h-benzotriazole Chemical compound FC1=CC=CC2=NNN=C12 ALDDXGSQUCGTDT-UHFFFAOYSA-N 0.000 claims description 2
- OKFSBQOGHYYGRZ-UHFFFAOYSA-N 4-hexyl-2h-benzotriazole Chemical compound CCCCCCC1=CC=CC2=C1N=NN2 OKFSBQOGHYYGRZ-UHFFFAOYSA-N 0.000 claims description 2
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical compound [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 claims description 2
- TVOIATIUZOHKFY-UHFFFAOYSA-N 4-pentyl-2h-benzotriazole Chemical compound CCCCCC1=CC=CC2=NNN=C12 TVOIATIUZOHKFY-UHFFFAOYSA-N 0.000 claims description 2
- KUVZHAJTEJICOW-UHFFFAOYSA-N 4-propan-2-yl-2h-benzotriazole Chemical compound CC(C)C1=CC=CC2=NNN=C12 KUVZHAJTEJICOW-UHFFFAOYSA-N 0.000 claims description 2
- VXDLXVDZTJOKAO-UHFFFAOYSA-N 4-propyl-2h-benzotriazole Chemical compound CCCC1=CC=CC2=C1N=NN2 VXDLXVDZTJOKAO-UHFFFAOYSA-N 0.000 claims description 2
- CSUGYJWSPZKYLY-UHFFFAOYSA-N 5-(2,4,4-trimethylpentan-2-yl)-2h-benzotriazole Chemical compound C1=C(C(C)(C)CC(C)(C)C)C=CC2=NNN=C21 CSUGYJWSPZKYLY-UHFFFAOYSA-N 0.000 claims description 2
- YQTFAYALFNXJFA-UHFFFAOYSA-N 5-(2,4-dimethylpentan-2-yl)-2H-benzotriazole Chemical compound CC(C)CC(C)(C)c1ccc2[nH]nnc2c1 YQTFAYALFNXJFA-UHFFFAOYSA-N 0.000 claims description 2
- DYIFWSZJRUOXBY-UHFFFAOYSA-N 5-(2-methylbutan-2-yl)-2h-benzotriazole Chemical compound C1=C(C(C)(C)CC)C=CC2=NNN=C21 DYIFWSZJRUOXBY-UHFFFAOYSA-N 0.000 claims description 2
- JQSSWPIJSFUBKX-UHFFFAOYSA-N 5-(2-methylpropyl)-2h-benzotriazole Chemical compound C1=C(CC(C)C)C=CC2=NNN=C21 JQSSWPIJSFUBKX-UHFFFAOYSA-N 0.000 claims description 2
- YZTYEGCWRPJWEE-UHFFFAOYSA-N 5-(benzotriazol-2-yl)pentan-1-amine Chemical compound C1=CC=CC2=NN(CCCCCN)N=C21 YZTYEGCWRPJWEE-UHFFFAOYSA-N 0.000 claims description 2
- BQCIJWPKDPZNHD-UHFFFAOYSA-N 5-bromo-2h-benzotriazole Chemical compound C1=C(Br)C=CC2=NNN=C21 BQCIJWPKDPZNHD-UHFFFAOYSA-N 0.000 claims description 2
- ZCFMGIGLXOKMJC-UHFFFAOYSA-N 5-butyl-2h-benzotriazole Chemical compound C1=C(CCCC)C=CC2=NNN=C21 ZCFMGIGLXOKMJC-UHFFFAOYSA-N 0.000 claims description 2
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 claims description 2
- ZWTWLIOPZJFEOO-UHFFFAOYSA-N 5-ethyl-2h-benzotriazole Chemical compound C1=C(CC)C=CC2=NNN=C21 ZWTWLIOPZJFEOO-UHFFFAOYSA-N 0.000 claims description 2
- SYGGDXKMRDPIKQ-UHFFFAOYSA-N 5-fluoro-2h-benzotriazole Chemical compound C1=C(F)C=CC2=NNN=C21 SYGGDXKMRDPIKQ-UHFFFAOYSA-N 0.000 claims description 2
- GAHAURRLKFPBCQ-UHFFFAOYSA-N 5-hexyl-2h-benzotriazole Chemical compound CCCCCCC1=CC=C2NN=NC2=C1 GAHAURRLKFPBCQ-UHFFFAOYSA-N 0.000 claims description 2
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 claims description 2
- KAGBXLIGSMIYGF-UHFFFAOYSA-N 5-pentyl-2h-benzotriazole Chemical compound C1=C(CCCCC)C=CC2=NNN=C21 KAGBXLIGSMIYGF-UHFFFAOYSA-N 0.000 claims description 2
- WXSBVEKBZGNSDY-UHFFFAOYSA-N 5-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC2=NNN=C2C=C1 WXSBVEKBZGNSDY-UHFFFAOYSA-N 0.000 claims description 2
- MBSXHYDCWYCSME-UHFFFAOYSA-N 5-propan-2-yl-2h-benzotriazole Chemical compound C1=C(C(C)C)C=CC2=NNN=C21 MBSXHYDCWYCSME-UHFFFAOYSA-N 0.000 claims description 2
- CCBSHAWEHIDTIU-UHFFFAOYSA-N 5-propyl-2h-benzotriazole Chemical compound CCCC1=CC=C2NN=NC2=C1 CCBSHAWEHIDTIU-UHFFFAOYSA-N 0.000 claims description 2
- JLGADKXBPJXIOQ-UHFFFAOYSA-N 5-tert-butyl-2h-benzotriazole Chemical compound C1=C(C(C)(C)C)C=CC2=NNN=C21 JLGADKXBPJXIOQ-UHFFFAOYSA-N 0.000 claims description 2
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- MKBUQYWFFBCMFG-UHFFFAOYSA-N acetic acid propane-1,1-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CCC(N)N MKBUQYWFFBCMFG-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 claims description 2
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- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims description 2
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- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
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- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
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- 238000001039 wet etching Methods 0.000 description 1
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Abstract
本揭示有關於一種蝕刻組成物,其包含1)至少一種氧化劑;2)至少一種螯合劑;3)至少一種有機溶劑;4)至少一種胺化合物;及5)水。
Description
相關申請案之交叉引用
本申請案主張提申日期2019年9月10日之美國臨時申請案第62/898,069號之優先權,其整體內容在此併入本案以為參考。
本揭示係有關於在其它材料如金屬導體、屏障材料、絕緣材料及銅、鵭和低k介電材料之曝露或底層的存在下,選擇性蝕刻氮化鈦矽之組成物及製程。
發明背景
半導體產業在微電子元件、矽晶片、液晶顯示器、MEMS (微機電系統)、印刷電子板等方面,快速地縮小尺寸及增加電子電路及電子組件的密度。其中的積體電路在分層或堆疊時,各電路層間之絕緣層的厚度不斷減少且特徵尺寸越來越小。因為特徵尺寸縮小,所以圖案變得更小,且元件性能參數更緊緻且更強大。結果,由於較小的特徵尺寸,原本可以忍受的各式各樣的問題變得不再能夠忍受或變成更大的問題。
在先進的積體電路之生產中,為了使與較高密度相關的問題減至最少且優化性能,使用高k及低k絕緣體二者及混雜的障壁層材料。
氮化鈦矽(TiSiN)可用於半導體元件且可作為貴金屬、鋁(Al)及銅(Cu)線之基層及蓋層。在半導體元件方面,其可用作為障壁金屬、硬遮罩或閘金屬。
在此等應用之元件的建構中,常常需要對TiSiN進行蝕刻。在TiSiN之各式各樣的用途及元件環境中,當對TiSiN進行蝕刻時,其它層也會接觸或曝露。在此等其它材料(如,金屬導體、介電質及硬標記)之存在下,為了元件產率及長壽命,對TiSiN之蝕刻必須具有高度選擇性。
針對TiSiN的蝕刻製程,可為電漿蝕刻製程。然而,在TiSiN層上使用電漿蝕刻製程,可能會對閘極絕緣層及半導體基材中之一者或二者造成損害。此外,該蝕刻製程可能通過蝕刻由閘極電極曝露的閘極絕緣層而移除一部分的半導體基材。電晶體的電氣特性可能會受到負面的影響。為避免此蝕刻損害,可使用額外的保護元件製造步驟,但需付出高額的成本。
用於TiSiN之濕式蝕刻方法是已知的。此方法可包括使用含有氫氟酸與其它試劑的組合之蝕刻劑。然而,與矽基介電質和金屬(如,Al)之選擇性不足,且在該元件中之其它曝露的金屬亦可能遭受腐蝕或蝕刻。
因此,需要有對TiSiN具有相對高蝕刻率,但對在蝕刻製程期間曝露的或與TiSiN接觸的其它半導體材料具有相對低蝕刻及腐蝕率之蝕刻溶液。
發明概要
本揭示有關於一種相對於半導體元件中所存在的金屬導體層、硬遮罩層及低k介電材料層,選擇性蝕刻TiSiN之組成物及製程。更具體地,本揭示有關於一種相對於銅、鵭、底部抗反射塗層(BARC)、高k介電質(如,HfOx)及層間介電質(ILD) (如,SiOx或低k介電質),選擇性蝕刻氮化鈦矽之組成物及製程。
在一態樣中,本揭示之特徵在於一種蝕刻組成物(如,一種選擇性移除TiSiN之蝕刻組成物),其包括:1)至少一種氧化劑;2)至少一種螯合劑;3)至少一種有機溶劑;4)至少一種胺化合物;及5)水;其中該組成物具有從約6.5至約9.5之pH。
在一些實施例中,該蝕刻組成物可包括:
1) 至少一種氧化劑,其數量為該組成物之約0.1重量%至約30重量%;
2) 至少一種螯合劑,其數量為該組成物之約0.01重量%至約1重量%;
3) 至少一種有機溶劑,其數量為該組成物之約1重量%至約30重量%;
4) 至少一種胺化合物,其包含二胺、烷醇胺或季銨化合物,該至少一種胺化合物含有1至6個碳原子且數量為該組成物之約0.1重量%至約5重量%;及
5)水;
其中該組成物具有從約6.5至約9.5之pH。
在另一態樣中,本揭示之特徵在於一種方法,其包括
使一含有TiSiN特徵之半導體基材與本文所揭示的蝕刻組成物接觸,以移除該TiSiN特徵。
在又另一態樣中,本揭示之特徵在於一種物件,其由以上所述的方法形成,其中該物件是一半導體元件(如,積體電路)。
本揭示之詳細說明
在本文之定義中,除非另有說明,否則全部表示的百分比應理解為相對於該蝕刻組成物之總重量的重量百分比。除非另有說明,否則環摬溫度定義在約16與約27攝氏度(℃)之間。在本文之定義中,“水溶性”物質(如,水溶性醇、酮、酯或醚)意指在25℃水中具有溶解度至少0.5重量% (如,至少1重量%或至少5重量%)的物質。
在一態樣中,本揭示之特徵在於一種蝕刻組成物(如,一種選擇性移除TiSiN之蝕刻組成物),其包括:1)至少一種氧化劑;2)至少一種螯合劑;3)至少一種有機溶劑;4)至少一種胺化合物;及5)水。
在一些實施例中,本揭示之蝕刻組成物可含有至少一種(如,二種、三種或四種)適合用於微電子清潔組成物之氧化劑。可在本揭示之組成物中使用的氧化劑包括,但不限於,過氧化物(如,過氧化氫、二烷基過氧化物、尿素過氧化氫)、過磺酸(如,六氟丙烷過磺酸、甲烷過磺酸、三氟甲烷過磺酸或對甲苯過磺酸)及其鹽類、臭氧、過碳酸(如,過醋酸)及其鹽類、過磷酸及其鹽類、過硫酸及其鹽類(如,過硫酸銨或四甲基過硫酸銨)、過氯酸及其鹽類(如,過氯酸銨或四甲基過氯酸銨)及過碘酸及其鹽類(如,過碘酸銨或四甲基過碘酸銨)。此等氧化劑可單獨或組合使用。
在一些實施例中,該至少一種氧化劑之數量是本揭示之蝕刻組成物的至少約0.1重量% (如,至少約1重量%、至少約2.5重量%、至少約5重量%、至少約7.5重量%、至少約10重量%、至少約11重量%、至少約12重量%、至少約13重量%、至少約14重量%或至少約15重量%)和/或至多約30重量% (如,至多約25重量%、至多約20重量%、至多約19重量%、至多約18重量%、至多約17重量%或至多約15重量%)。
在一些實施例中,本揭示之蝕刻組成物可含有至少一種(如,二種、三種或四種)螯合劑,其可為,但不限於,聚胺基聚羧酸。為本揭示而言,聚胺基聚羧酸意指具有多個(如,二、三、四或更多個)胺基基團及多個(如,二、三、四或更多個)羧酸基團之化合物。適合的聚胺基聚羧酸螯合劑之種類包括,但不限於,單或聚伸烷基聚胺聚羧酸、聚胺基烷聚羧酸、聚胺基烷醇聚羧酸及羥烷基醚聚胺聚羧酸。
適合的聚胺基聚羧酸螯合劑包括,但不限於,丁二胺四乙酸、二乙三胺五乙酸(DTPA)、乙二胺四丙酸、三乙四胺六乙酸、1,3-二胺基-2-羥丙烷-N,N,N',N'-四乙酸、丙二胺四乙酸、乙二胺四乙酸(EDTA)、反式-1,2-二胺基環己烷四乙酸、乙二胺二乙酸、乙二胺二丙酸、1,6-己二胺-N,N,N',N'-四乙酸、N,N-雙(2-羥苯甲基)乙二胺-N,N-二乙酸、二胺基丙烷四乙酸、1,4,7,10-四氮雜環十二烷-四乙酸、二胺基丙醇四乙酸及(羥乙基)乙二胺三乙酸。
在一些實施例中,該至少一種螯合劑之數量可為本揭示之蝕刻組成物的至少約0.01重量% (如,至少約0.05重量%、至少約0.1重量%、至少約0.15重量%、至少約0.2重量%、至少約0.25重量%或至少約0.3重量%)和/或至多約1重量% (如,至多約0.9重量%、至多約0.8重量%、至多約0.7重量%、至多約0.6重量%、至多約0.5重量%、至多約0.4重量%或至多約0.3重量%)。
在一些實施例中,本揭示之蝕刻組成物可任擇地含有至少一種(如,二、三或四種)選自取代或未取代的苯并三唑類之金屬腐蝕抑制劑。適合的取代的苯并三唑類包括,但不限於,經烷基基團、芳基基團、鹵素基團、胺基基團、硝基基團、烷氧基基團及羥基基團取代的苯并三唑類。取代的苯并三唑類亦包括該等與一或多種芳基(如,苯基)或雜芳基基團融合者。
適合用作金屬腐蝕抑制劑之苯并三唑類包括,但不限於,苯并三唑(BTA)、5-胺基苯并三唑、1-羥基苯并三唑、5-苯硫醇-苯并三唑、5-氯基苯并三唑、4-氯基苯并三唑、5-溴基苯并三唑、4-溴基苯并三唑、5-氟基苯并三唑、4-氟基苯并三唑、萘并三唑、甲苯并三唑、5-苯基-苯并三唑、 5-硝基苯并三唑、4-硝基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-苯并三唑、5-甲基-1H-苯并三唑(5-MBTA)、苯并三唑-5-羧酸、4-甲基苯并三唑、4-乙基苯并三唑、5-乙基苯并三唑、4-丙基苯并三唑、5-丙基苯并三唑、4-異丙基苯并三唑、5-異丙基苯并三唑、4-正丁基苯并三唑、5-正丁基苯并三唑、4-異丁基苯并三唑、5-異丁基苯并三唑、4-戊基苯并三唑、5-戊基苯并三唑、4-己基苯并三唑、5-己基苯并三唑、5-甲氧基苯并三唑、5-羥基苯并三唑、二羥丙基苯并三唑、1-[N,N-雙(2-乙己基)胺甲基]-苯并三唑、5-叔丁基苯并三唑、5-(1',1'-二甲丙基)–苯并三唑、5-(1',1',3'-三甲丁基)苯并三唑、5-正辛基苯并三唑及5-(1',1',3',3'-四甲丁基)苯并三唑。
在一些實施例中,該至少一種金屬腐蝕抑制劑之數量為本揭示之蝕刻組成物的至少約0.05重量% (如,至少約0.1重量%、至少約0.15重量%、至少約0.2重量%、至少約0.25重量%或至少約0.3重量%)和/或至多約1重量% (如,至多約0.9重量%、至多約0.8重量%、至多約0.7重量%、至多約0.6重量%、至多約0.5重量%、至多約0.4重量%或至多約0.3重量%)。不欲受理論之約束,但一般認為在本揭示之蝕刻組成物中包括金屬腐蝕抑制劑,可減少半導體基材中之金屬(如,Co、Cu或W)和/或高k介電材料(如,HfOx)的腐蝕或蝕刻。
在一些實施例中,本揭示之蝕刻組成物可含有至少一種(如,二、三或四種)有機溶劑。較佳地,該有機溶劑係選自於由下列所構成之群組:水溶性醇類、水溶性酮類、水溶性酯類及水溶性醚類(如,二醇二醚類)。
水溶性醇類之種類包括,但不限於,烷二醇類(alkane diols) (包括,但不限於,伸烷基二醇類(alkylene glycols))、二醇類(glycols)、烷氧醇類(包括但不限於二醇單醚類)、飽和脂族一元醇類、不飽和非芳族一元醇類及含有環結構之低分子量醇類(如,C4
-C8
醇類)。
水溶性烷二醇類之例子包括,但不限於,2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇、品納可(pinacol)及伸烷基二醇類。
水溶性伸烷基二醇類之例子包括,但不限於,乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇及四乙二醇。
水溶性烷氧醇類之例子包括,但不限於,3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇及水溶性二醇單醚類。
水溶性二醇單醚類之例子包括,但不限於,乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇單正丁醚(EGBE)、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單丁醚、1-甲氧基-2-丙醇、2-甲氧基-1-丙醇、1-乙氧基-2-丙醇、2-乙氧基-1-丙醇、丙二醇單正丙醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單丁醚、二丙二醇單正丙醚、三丙二醇單乙醚、三丙二單甲醚、乙二醇單苄醚及二乙二醇單苄醚。
水溶性飽和脂族一元醇類之例子包括,但不限於,甲醇、乙醇、正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、叔丁醇、2-戊醇、叔戊醇及1-己醇。
水溶性不飽和非芳族一元醇類之例子包括,但不限於,烯丙醇、炔醇、2-丁烯醇、3-丁烯醇及4-戊烯-2-醇。
含有環結構之水溶性低分子量醇類之例子包括,但不限於,四氫糠醇、糠醇及1,3-環戊二醇。
水溶性酮類之例子包括,但不限於,丙酮、環丁酮、環戊酮、二丙酮醇、2-丁酮、5-己二酮、1,4-環己二酮、3-羥基苯乙酮、1,3-環己二酮及環己酮。
水溶性酯類之例子包括,但不限於,乙酸乙酯、二醇單酯類(如乙二醇單乙酸酯及二乙二醇單乙酸酯)及二醇單醚單酯類(如,丙二醇單甲醚乙酸酯、乙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯及乙二醇單乙醚乙酸酯)。
在一些實施例中,該至少一種有機溶劑之數量為本揭示之蝕刻組成物的至少約1重量% (如,至少約2重量%、至少約3重量%、至少約4重量%、至少約5重量%、至少約6重量%、至少約7重量%、至少約8重量%、至少約9重量%或至少約10重量%)和/或至多約30重量% (如,至多約25重量%、至多約20重量%、至多約15重量%、至多約14重量%、至多約13重量%、至多約12重量%、至多約11重量%或至多約10重量%)。
在一些實施例中,本揭示之蝕刻組成物可含有至少一種(如,二種、三種或四種)胺化合物。該胺化合物可為二胺、烷醇胺或季銨化合物。在一些實施例中,該胺化合物可包括1個、2個、3個、4個、5個或6個碳原子。
在一些實施例中,該二胺可為具有式(I)之化合物:H2
N-R1
-NH2
(I),其中R1
是直鏈或支鏈C2
-C6
烷基。具式(I)之二胺的例子包括乙二胺、1,2-二胺基丙烷及1,3-二胺基丙烷。
在一些實施例中,該烷醇胺可為具有式(II)之化合物:HO-R1
-NH2
(II),其中R1
是直鏈或支鏈C2
-C6
烷基。具式(II)之烷醇胺的例子是乙醇胺(亦稱作單乙醇胺或MEA)。
在一些實施例中,該季銨化合物可為季銨鹽或氫氧化季銨。在一些實施例中,該季銨化合物可為四烷銨化合物(如,鹽或氫氧化物)。在一些實施例中,該季銨化合物可為具有式(III)之化合物:[NR1
R2
R3
R4
]+
X-
(III),其中R1
、R2
、R3
及R4
各獨立地為直鏈或支鏈C1
-C6
烷基及X是OH或鹵基(如,F、Cl、Br或I)。具式(III)之季銨化合物的例子為氟化四甲銨。
在一些實施例中,該至少一種胺化合物之數量為本揭示之蝕刻組成物的至少約0.1重量% (如,至少約0.2重量%、至少約0.3重量%、至少約0.5重量%、至少約0.7重量%、至少約1重量%、至少約1重量%、至少約1.2重量%、至少約1.4重量%或至少約1.5重量%)和/或至多約5重量% (如,至多約4.5重量%、至多約4重量%、至多約3.5重量%、至多約3重量%、至多約2.5重量%、至多約2重量%、至多約1.5重量%或至多約1重量%)。不欲受理論之約束,但一般認為在本揭示之蝕刻組成物中包括胺化合物,可增加半導體基材中TiSiN的蝕刻和/或減少高k介電材料(如,HfOx)的腐蝕或蝕刻。
本揭示之蝕刻組成物可進一步包括水。較佳地,該水是去離子且超純的,不含有機污染物且具有約4至約17百萬歐姆之最小電阻率。更佳地,該水之電阻率為至少約17百萬歐姆。
在一些實施例中,該水的數量為本揭示之蝕刻組成物的至少約35重量% (如,至少約45重量%、至少約50重量%、至少約55重量%、至少約60重量%、至少約65重量%、至少約68重量%或至少約70重量%)和/或至多約98重量% (如,至多約95重量%、至多約90重量%、至多約85重量%、至多約80重量%、至多約75重量%或至多約70重量%)。
在一些實施例中,本揭示之蝕刻組成物可任擇地包括至少一種(如,二種、三種或四種)酸。該酸可為有機酸或無機酸。適合的有機酸可包括羧酸或磺酸,如烷基磺酸或芳基磺酸。適合的烷基磺酸之例子包括甲烷磺酸、三氟甲烷磺酸(或三氟甲磺酸(triflic acid))及2-羥乙烷磺酸(或羥乙磺酸(isethionic acid))。適合的芳基磺酸之例子是對甲苯磺酸。適合的無機酸可包括礦酸類,如氫鹵化物(如,氫氯酸或氫溴酸)。
在一些實施例中,該至少一種酸之數量為本揭示之蝕刻組成物的至少約0.1重量% (如,至少約0.2重量%、至少約0.3重量%、至少約0.5重量%、至少約0.7重量%、至少約1重量%、至少約1重量%、至少約1.2重量%、至少約1.4重量%、至少約1.5重量%、至少約1.6重量%、至少約1.8重量%或至少約2重量%)和/或至多約5重量% (如,至多約4.5重量%、至多約4重量%、至多約3.5重量%、至多約3重量%、至多約2.5重量%、至多約2重量%、至多約1.5重量%或至多約1重量%)。不欲受理論之約束,但一般認為在本揭示之蝕刻組成物中包括酸,可調整該組成物之pH及減少半導體基材中高k介電材料(如,HfOx)的腐蝕或蝕刻。
在一些實施例中,本揭示之蝕刻組成物可具有至少約6.5之pH (如,至少約7、至少約7.5、至少約7.8或至少約8)和/或至多約9.5 (如,至多約9、至多約8.5、至多約8.2或至多約8)。不欲受理論之約束,但一般認為具有低於6.5之pH的蝕刻組成物會顯著地增加鈷的蝕刻率及減少TiSiN的蝕刻率,而具有高於9.5之pH的蝕刻組成物會導致氧化劑(如,過氧化氫)之分解增加及顯著地增加對鎢的腐蝕。為了獲得所需的pH,可調整本揭示之蝕刻組成物中之聚胺基聚羧酸、苯并三唑(或其衍生物)、酸及胺化合物的相對濃度。
在一些實施例中,本揭示之蝕刻組成物可含有添加物,如額外的pH調整劑、額外的腐蝕抑制劑、界面活性劑、額外的有機溶劑、除生物劑及消泡劑作為任擇的組份。
適合的消泡劑之例子包括聚矽氧烷消泡劑(如,聚二甲基矽氧烷)、聚乙二醇甲醚聚合物、環氧乙烷/環氧丙烷共聚物及縮水甘油醚封端的炔二醇乙氧基化物(如美國專利案第6,717,019號中所述,在此併入本案以為參考)。任擇的界面活性劑可為陽離子性、陰離子性、非離子性或兩性的。
在一些實施例中,本揭示之蝕刻組成物可任擇地排除一或多種組份,若超過一種的話,任一組合。可從該蝕刻組成物中排除之此等組份係選自於由下列所構成之群組:有機溶劑、pH調整劑、聚合物(如,陽離子或陰離子性聚合物,或聚醚類,如聚(甲基乙烯基醚)類)、去氧劑、季銨化合物(如,鹽或氫氧化物)、胺類、鹼金屬鹼類(如,鹼金屬氫氧化物)、除消泡劑外之界面活性劑、消泡劑、含氟化物化合物、研磨劑(如,陽離子或陰離子性研磨劑)、矽酸鹽類、羥基羧酸類(如,該等含有超過二個羥基基團者)、單羧酸及聚羧酸(如,該等含有或缺少胺基基團者)、矽烷類(如,烷氧矽烷類)、亞胺類(如,脒類,如1,8-二氮雜二環[5.4.0]-7-十一烯(DBU)及1,5-二氮雜二環[4.3.0]壬-5-烯(DBN))、肼類、環狀化合物(如,唑類(如,二唑類、三唑類或四唑類)、三𠯤類及含有至少二個環之環狀化合物,如取代或未取代的萘,或取代或未取代的聯苯醚)、緩衝劑、非唑腐蝕抑制劑、鹵化物鹽類及金屬鹽類(如,金屬鹵化物)。
在一些實施例中,本文中所述的蝕刻組成物之優點是,其可在不會實質上移除或蝕刻高k介電材料(如,HfOx)之情況下,選擇性地蝕刻TiSiN。
本揭示之蝕刻組成物可通過簡單地將組份混合在一起而製得,或可通過將一套組中之二個組成物摻合而製得。該套組中之第一組成物可為氧化劑(如,過氧化氫)之水溶液。該套組中之第二組成物可含有本揭示之蝕刻組成物的剩餘組份,其等呈按預定比率之濃縮形式,使得該二個組成物之摻合可產生期望的本揭示之蝕刻組成物。
或者,本揭示之蝕刻組成物可通過摻合套組中之三個組成物而製得。在此實施例中,第一組成物可包括濃縮水溶液形式之氧化劑,第二組成物可僅包括水,及第三組成物可包括本揭示之蝕刻組成物中按預定比率之所有的剩餘組份。
本揭示之特徵還在於一種蝕刻含有TiSiN特徵之半導體基材的方法。該方法可包括使含有TiSiN特徵之半導體基材與本揭示之蝕刻組成物接觸,以移除該TiSiN特徵。該方法可進一步包括在該接觸步驟後用一沖洗溶劑沖洗該半導體基材和/或在該沖洗步驟後乾燥該半導體基材。在一些實施例中,該方法不會實質上移除該半導體基材中之HfOx。例如,該方法不會移除超過約5重量% (如,超過約3重量%或超過約1重量%)之該半導體基材中的HfOx。作為另一例子,在使用本文中所述的蝕刻組成物一段時間(如,2分鐘)期間,該半導體基材中HfOx層之膜損失可為至多約1Å (如,至多約0.5Å或0.1Å),以達到期望的TiSiN蝕刻效果。
在一些實施例中,該蝕刻方法包括下列步驟:
(A) 提供含有TiSiN特徵之一半導體基材;
(B) 使該半導體基材與本文中所述的蝕刻組成物接觸;
(C) 用一或多種適合的沖洗溶劑沖洗該半導體基材;及
(D) 任擇地,乾燥該半導體基材(如,通過任何可除去該沖洗溶劑且不會妥協該半導體基材之完整性的適合方法)。
在一些實施例中,該蝕刻方法進一步包括從由以上所述的方法獲得的半導體基材形成一半導體元件(如,積體電路元件,像是半導體晶片)。
在此方法中待蝕刻之含有TiSiN特徵之半導體基材,可包含有機及有機金屬殘留物,及額外地,一系列的金屬氧化物,其亦可在該蝕刻製程期間移除。
半導體基材通常是由矽、矽鍺、III-V族化合物(像GaAs)或其等之任一組合構成。該半導體基材可額外地含有曝露的積體電路結構,如互連特徵,像是金屬線及介電材料。用於互連特徵之金屬及金屬合金包括,但不限於,鋁、鋁銅合金、銅、鈦、鉭、鈷、矽、氮化鈦、氮化鉭及鎢。該半導體基材還可含有層間的介電、氧化矽、氮化矽、碳化矽、氧化鈦及碳摻雜氧化矽層。
該半導體基材可通過任何適合的方法與該蝕刻組成物接觸,如將該蝕刻組成物置於槽中並將該半導體基材浸沒和/或沈埋於該蝕刻組成物中、將該蝕刻組成物噴灑至該半導體基材上、使該蝕刻組成物流動至該半導體基材上、或其等之任一組合。在一些實施例中係將該半導體基材浸沒至該蝕刻組成物中。
本揭示之蝕刻組成物可有效地在高達約85℃之溫度下使用。在一些實施例中,該蝕刻組成物可在從約20℃至約80℃之溫度下使用(如,從約55℃至約65℃,或從約60℃至約65℃)。在此範圍內,TiSiN之蝕刻率隨溫度增加,因此使用較高的溫度的製程可運行較短的時間,而較低溫度的製程需要較長的蝕刻時間。
蝕刻時間可在一大範圍內變化,取決於所使用之特定的蝕刻方法、厚度及溫度。當在浸沒式批次類型製程中蝕刻時,適合的時間範圍為例如多達約10分鐘(如,從約1分鐘至約7分鐘、從約1分鐘至約5分鐘或從約2分鐘至約4分鐘)。
在一些實施例中,單一晶圓製程的蝕刻時間範圍可從約30秒至約5分鐘(如,從約30秒至約4分鐘、從約1分鐘至約3分鐘、從約1分鐘至約2分鐘)。
為進一步促進本揭示之蝕刻組成物的蝕刻能力,可使用機械攪拌方法。適合的攪拌方法之例子包括在該蝕刻製程期間,使該蝕刻組成物在該基材上循環、將該蝕刻組成物流動或噴灑在該基材上及超音波或百萬赫茲音波(megasonic)攪拌。該半導體基材相對於地面之方向可為任一適合的角度。較佳的是水平或垂直方向。
在一些實施例中,於該蝕刻後,在有或無攪拌方法之情況下,用適合的沖洗溶劑沖洗該半導體基材約5秒至多達約5分鐘。可使用使用不同沖洗溶劑之多個沖洗步驟。適合的沖洗溶劑之例子包括,但不限於,去離子(DI)水、甲醇、乙醇、異丙醇、N-甲基吡咯啶酮、γ-丁內酯、二甲基亞碸、乳酸乙酯及丙二醇單甲醚乙酸酯。或者,或此外,可使用具有pH >8之水性沖洗液(如,稀釋的氫氧化銨水溶液)。沖洗溶劑之例子包括,但不限於,稀釋的氫氧化銨水溶液、DI水、甲醇、乙醇及異丙醇。在一些實施例中,該沖洗溶劑是稀釋的氫氧化銨水溶液、DI水及異丙醇。該溶劑之施用,可使用與施用本文中所述的蝕刻組成物相似的方法。該蝕刻組成物在開始該沖洗步驟之前已從該半導體基材上移除,或在開始該沖洗步驟時仍與該半導體基材接觸。在一些實施例中,在該沖洗步驟中使用的溫度介於16℃與27℃之間。
任擇地,在該沖洗步驟之後,乾燥該半導體基材。在此技藝中已知的任何適合的乾燥方法均可使用。適合的乾燥方法之例子包括旋轉乾燥、使乾燥氣體流過該半導體基材或用加熱工具如加熱板或紅外線燈加熱該半導體基材、Marangoni乾燥、Rotagoni乾燥、IPA乾燥或其等之任一組合。乾燥時間將取決於所使用之特定方法,但通常為約15秒至長達數分鐘。
在一些實施例中,該半導體基材之後可經過處理而在該基材上形成一或多個電路,或可通過例如組裝(如,切割及黏接)及包裝(如,晶片封裝)而被處理成半導體晶片。範例
參照下列範例更詳細地說明本揭示,該等範例係供例示說明之目的,不應被解釋作為本揭示之範疇的限制。除非有特別指示,否則任何所列出的百分比是重量百分比(重量%)。除非有特別說明,否則在測試期間之控制攪拌係用1吋的攪拌子以250rpm進行。一般程序1 配方摻合
在攪拌下,將配方中剩餘的組份添加至計算過數量的溶劑中,製備蝕刻組成物之樣本。在達到均勻溶液之後,加入,若有使用的話,任擇的添加物。一般程序2 材料與方法
使用市售未圖案化300mm直徑晶圓經切割供評估用的0.5”x0.5”測試片,進行膜上之包覆膜蝕刻率測量。用於測試的主要包覆膜材料包括1)沈積在矽基材上厚度約52Å之包含19重量%Si的TiSiN膜,2)沈積在矽基材上厚度約56Å之包含23重量%Si的TiSiN膜,及3)沈積在矽基材上厚度20Å的氧化鉿(HfOx)膜。
測量該包覆膜測試片於處理前與處理後之厚度,以測定包覆膜蝕刻率。在TiSiN及HfOx膜方面,通過楕圓偏振技術,使用Woollam M-2000X測量於處理前與處理後之厚度。一般程序3 用燒杯測試之蝕刻評估
所有的包覆膜蝕刻及圖案化測試片蝕刻測試,均於含有200g樣本溶液,在250rpm持續攪拌下60℃加熱的600mL玻璃燒杯中進行,全程用Parafilm®覆蓋到位以便最小化蒸發損失。用鑽石劃線器,將一側曝露於樣本溶液之具有圖案或包覆金屬或介電膜之全部的包覆或圖案化測試片,切成0.5” x 0.5”方形測試片,供進行燒杯規模之測試。使用單個4”長鎖定塑膠鑷子夾,將各個別測試片固定在位置上。使以鎖定鑷子夾固定一邊緣之測試片懸浮在600mL玻璃燒杯中並浸沒於200g測試溶液中,同時在60℃下加熱該溶液且持續以250rpm攪拌。就在將各樣本測試片置於該加熱且攪拌的溶液中之後,立刻用Parafilm®蓋住並封住該600mL玻璃燒杯的頂部。使該測試片保持靜止在該攪拌加熱的溶液中,直到處理時間(如一般程序3A所示)過去。經過在測試溶液中之處理時間後,立即從該600mL玻璃燒杯中移出樣本測試片,然後按照一般程序3A (包覆測試片)沖洗。在最後的DI沖洗步驟後,使用手持氮氣鼓風機對全部的測試片進行過濾氮氣吹出步驟,其會強制除去所有DI水的痕跡,產生最後供測試測量用之乾樣本。一般程序3A ( 包覆測試片)
在按照一般程序3之處理10分鐘後,立即將該測試片浸沒於1000mL體積20℃的超高純度去離子(DI)水中, 以~1升/分溢液速率歷時15秒,之後伴隨溫和攪拌再15秒。處理按照一般程序3完成。範例1
按照一般程序1製備配方範例1-10 (FE-1至FE-10),然後按照一般程序2與3進行評估。在60℃下對TiSiN及HfOx膜進行蝕刻2分鐘。配方總結於表1中,及測試結果總結於表2中。表1
DTPA = 二乙三胺五乙酸 5-MBTA = 5-甲基苯并三唑
EGBE = 乙二醇單正丁醚 EDA =乙二胺
MEA = 單乙醇胺 1,3-DAP = 1,3-二胺基丙烷
1,2-DAP = 1,2-二胺基丙烷 TMAF = 氟化四甲銨
MSA = 甲磺酸 p-TSA = 對甲苯磺酸
TA =三氟甲磺酸 IA = 羥乙磺酸表 2
範例 | H2 O2 | DTPA | EGBE | 5-MBTA | 胺 | 酸 | 水 | pH |
FE-1 | 17.5% | 0.25% | 10.11% | 0.22% | EDA 0.15% | 無 | 71.79% | 7.9 |
FE-2 | 17.5% | 0.23% | 9.2% | 0.2% | MEA 1.54% | MSA 1.61% | 69.72% | 8 |
FE-3 | 17.5% | 0.25% | 10.07% | 0.22% | 1,3-DAP 0.26% | 無 | 71.7% | 8 |
FE-4 | 17.5% | 0.25% | 10.05% | 0.22% | 1,2-DAP 0.34% | 無 | 71.64% | 8 |
FE-5 | 17.5% | 0.23% | 9.23% | 無 | MEA 1.54% | MSA 1.51% | 69.98% | 8 |
FE-6 | 17.5% | 0.23% | 7.9% | 無 | MEA 1.3% | p-TSA 2.39% | 70.68% | 8 |
FE-7 | 17.5% | 0.23% | 9.2% | 無 | MEA 1.5% | TA 2.2% | 69.37% | 8 |
FE-8 | 17.5% | 0.23% | 9.1% | 無 | MEA 1.5% | IA 1.9% | 69.77% | 8 |
FE-9 | 17.5% | 0.23% | 9.4% | 無 | MEA 1.6% | HCl 0.5% | 70.77% | 8 |
FE-10 | 17.5% | 0.23% | 10% | 0.22% | TMAF 1.87% | 無 | 70.18% | 7.5 |
範例 | TiSiN (Si19%) 膜 厚度損失 ( Å ) | TiSiN (Si23%) 膜 厚度損失 ( Å ) | HfOx 膜 厚度損失 ( Å ) |
FE-1 | 50 | - | < 0.1 |
FE-2 | 51 | 46 | < 0.1 |
FE-3 | > 51 | 56 | < 0.1 |
FE-4 | 46 | 43 | < 0.1 |
FE-5 | 50 | 46 | < 0.1 |
FE-6 | 50 | 41 | < 0.1 |
FE-7 | 50 | 30 | < 0.1 |
FE-8 | 51 | 42 | < 0.1 |
FE-9 | 52 | 43 | < 0.1 |
FE-10 | 45 | 39 | < 0.1 |
按照一般程序1製備比較配方範例1-15 (CFE-1至FE-15),然後按照一般程序2與3進行評估。在60℃下對TiSiN及HfOx膜進行蝕刻2分鐘。配方總結於表3中,及測試結果總結於表4中。表 3
HA = 羥胺 DBU = 1,8-二氮雜二環[5.4.0]-7-十一烯
TFBA = 四氟硼酸 NBDEA = N-丁基二乙醇胺
NAPDEA = N-(3-胺丙基)二乙醇胺 NMG = N-甲基葡糖胺
BHEAP = 1-[雙(2-羥乙基)胺基]-2-丙醇 CA = 檸檬酸
SA = 水楊酸 OA = 草酸
GA = 沒食子酸表 4
範例 | HA | H2 O2 | DTPA | EGBE | 5-MBTA | DBU | 酸 | 添加物 | 水 | pH |
CFE-1 | 無 | 17.5% | 0.25% | 10% | 0.22% | 0.56% | 無 | 無 | 71.47% | 7.5 |
CFE-2 | 無 | 17.5% | 0.23% | 9.3% | 無 | 3.3% | HF 0.39% | 無 | 69.28% | 7.5 |
CFE-3 | 0.4% | 17.5% | 0.23% | 9.8% | 0.22% | 0.5% | 無 | 無 | 71.35% | 7.8 |
CFE-4 | 1.5% | 17.5% | 0.23% | 9.3% | 0.2% | 0.5% | 無 | 無 | 70.77% | 7.8 |
CFE-5 | 無 | 17.5% | 0.23% | 9.2% | 0.2% | 2.2% | TFBA 0.8% | 無 | 69.87% | 7.8 |
CFE-6 | 無 | 17.5% | 0.25% | 10% | 0.22% | 0.5% | 無 | NBDEA 0.4% | 71.13% | 7.7 |
CFE-7 | 無 | 17.5% | 0.25% | 10.1% | 0.22% | 0.2% | 無 | NAPDEA 0.4% | 71.33% | 7.6 |
CFE-8 | 無 | 17.5% | 0.25% | 10.1% | 0.22% | 0.3% | 無 | NMG 0.4% | 71.23% | 7.6 |
CFE-9 | 無 | 17.5% | 0.25% | 10% | 0.22% | 0.5% | 無 | BHEAP 0.4% | 71.13% | 7.6 |
CFE-10 | 無 | 17.5% | 0.23% | 9.9% | 0.21% | 1.1% | CA 0.4% | 無 | 70.66% | 7.5 |
CFE-11 | 無 | 17.5% | 0.23% | 10% | 0.21% | 0.7% | SA 0.4% | 無 | 70.96% | 7.5 |
CFE-12 | 無 | 17.5% | 0.23% | 9.7% | 0.21% | 1.6% | OA 0.4% | 無 | 70.36% | 7.5 |
CFE-13 | 無 | 17.5% | 0.7% | 9.8% | 0.22% | 1.2% | 無 | 無 | 70.58% | 8 |
CFE-14 | 無 | 17.5% | 0.23% | 10% | 0.22% | 0.7% | 無 | Catechol 0.4% | 70.96% | 8 |
CFE-15 | 無 | 17.5% | 0.23% | 9.9% | 0.21% | 1.1% | GA 0.4% | 無 | 70.66% | 7.5 |
範例 | TiSiN (Si19%) 膜 厚度損失 (Å) | TiSiN (Si23%) 膜 厚度損失 (Å) | HfOx 膜 厚度損失 (Å) |
CFE-1 | 26 | 15 | < 0.1 |
CFE-2 | 45.3 | 27 | 0.6 |
CFE-3 | 32.2 | 15 | < 0.1 |
CFE-4 | 33.9 | 13.9 | < 0.1 |
CFE-5 | 31.6 | 14.7 | < 0.1 |
CFE-6 | 31 | 16 | < 0.1 |
CFE-7 | 31 | 16 | < 0.1 |
CFE-8 | 33 | 17 | < 0.1 |
CFE-9 | 33 | 16 | < 0.1 |
CFE-10 | 33 | - | < 0.1 |
CFE-11 | 34 | - | < 0.1 |
CFE-12 | 34 | - | < 0.1 |
CFE-13 | 34.7 | - | < 0.1 |
CFE-14 | 33.8 | - | < 0.1 |
CFE-15 | 33.7 | - | 0.2 |
如表2及4所示,與比較配方CFE-1至CFE-15相比,配方FE-1至FE-10表現出增加TiSiN蝕刻及減少HfOx蝕刻。
儘管已經參考本發明的某些實施例對本發明進行了詳細描述,但是應當理解,修改和變化在所描述和要求保護的精神和範疇內。
Claims (26)
- 一種蝕刻組成物,其包含: 1) 至少一種氧化劑,其數量為該組成物之約0.1重量%至約30重量%; 2) 至少一種螯合劑,其數量為該組成物之約0.01重量%至約1重量%; 3) 至少一種有機溶劑,其數量為該組成物之約1重量%至約30重量%; 4) 至少一種胺化合物,其包含二胺、烷醇胺或季銨化合物,該至少一種胺化合物包含1至6個碳原子且數量為該組成物之約0.1重量%至約5重量%;及 5) 水; 其中該組成物具有從約6.5至約9.5之pH。
- 如請求項1之組成物,其中該組成物具有從約7至約9.5之pH。
- 如請求項1之組成物,其中該至少一種氧化劑包含過氧化氫。
- 如請求項1之組成物,其中該至少一種氧化劑之數量為該組成物之約1重量%至約18重量%。
- 如請求項1之組成物,其中該至少一種螯合劑包含聚胺基聚羧酸。
- 如請求項5之組成物,其中該聚胺基聚羧酸是選自於由下列所構成之群組:單或聚伸烷基聚胺聚羧酸、聚胺基烷聚羧酸、聚胺基烷醇聚羧酸及羥烷基醚聚胺聚羧酸。
- 如請求項6之組成物,其中該聚胺基聚羧酸是選自於由下列所構成之群組:丁二胺四乙酸、二乙三胺五乙酸、乙二胺四丙酸、三乙四胺六乙酸、1,3-二胺基-2-羥丙烷-N,N,N',N'-四乙酸、丙二胺四乙酸、乙二胺四乙酸、反式-1,2-二胺基環己烷四乙酸、乙二胺二乙酸、乙二胺二丙酸、1,6-己二胺-N,N,N',N'-四乙酸、N,N-雙(2-羥苯甲基)乙二胺-N,N-二乙酸、二胺基丙烷四乙酸、亞胺基二乙酸、1,4,7,10-四氮雜環十二烷-四乙酸、二胺基丙醇四乙酸及(羥乙基)乙二胺三乙酸。
- 如請求項1之組成物,其中該至少一種螯合劑之數量為該組成物之約0.1重量%至約0.5重量%。
- 如請求項1之組成物,其進一步包含至少一種金屬腐蝕抑制劑。
- 如請求項9之組成物,其中該至少一種金屬腐蝕抑制劑包含取代或未取代的苯并三唑。
- 如請求項10之組成物,其中該至少一種金屬腐蝕抑制劑包含任擇地被至少一種選自於由下列所構成之群組之取代基取代的苯并三唑:烷基基團、芳基基團、鹵素基團、胺基基團、硝基基團、烷氧基基團及羥基基團。
- 如請求項10之組成物,其中該取代或未取代的苯并三唑是選自於由下列所構成之群組:苯并三唑、5-胺基苯并三唑、1-羥基苯并三唑、5-苯硫醇-苯并三唑、5-氯基苯并三唑、4-氯基苯并三唑、5-溴基苯并三唑、4-溴基苯并三唑、5-氟基苯并三唑、4-氟基苯并三唑、萘并三唑、甲苯并三唑、5-苯基-苯并三唑、5-硝基苯并三唑、4-硝基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-苯并三唑、5-甲基-1H-苯并三唑、苯并三唑-5-羧酸、4-甲基苯并三唑、4-乙基苯并三唑、5-乙基苯并三唑、4-丙基苯并三唑、5-丙基苯并三唑、4-異丙基苯并三唑、5-異丙基苯并三唑、4-正丁基苯并三唑、5-正丁基苯并三唑、4-異丁基苯并三唑、5-異丁基苯并三唑、4-戊基苯并三唑、5-戊基苯并三唑、4-己基苯并三唑、5-己基苯并三唑、5-甲氧基苯并三唑、5-羥基苯并三唑、二羥丙基苯并三唑、1-[N,N-雙(2-乙己基)胺甲基]-苯并三唑、5-叔丁基苯并三唑、5-(1',1'-二甲丙基)–苯并三唑、5-(1',1',3'-三甲丁基)苯并三唑、5-正辛基苯并三唑及5-(1',1',3',3'-四甲丁基)苯并三唑。
- 如請求項9之組成物,其中該至少一種金屬腐蝕抑制劑之數量為該組成物之約0.1重量%至約0.5重量%。
- 如請求項1之組成物,其中該至少一種有機溶劑包含選自於由下列所構成之群組之溶劑:水溶性醇類、水溶性酮類、水溶性酯類及水溶性醚類。
- 如請求項1之組成物,其中該組成物包含約5重量%至約25重量%之該至少一種有機溶劑。
- 如請求項1之組成物,其中該至少一種胺化合物包含乙二胺、1,2-二胺基丙烷、1,3-二胺基丙烷、乙醇胺或氟化四甲銨。
- 如請求項1之組成物,其中該至少一種胺化合物之數量為該組成物之約1重量%至約5重量%。
- 如請求項1之組成物,其中該水之數量為該組成物之約35重量%至約98重量%。
- 如請求項1之組成物,其進一步包含至少一種酸。
- 如請求項19之組成物,其中該至少一種酸包含無機酸或磺酸。
- 如請求項19之組成物,其中該至少一種酸之數量為該組成物之約0.1重量%至約5重量%。
- 如請求項1之組成物,其中該組成物實質上不含聚合物、亞胺、肼或脒。
- 一種方法,其包含使一含有TiSiN特徵之半導體基材與一蝕刻組成物接觸,以移除該TiSiN特徵; 其中該組成物包含至少一種氧化劑、至少一種螯合劑、至少一種有機溶劑、至少一種包含1至6個碳原子之胺化合物及水,及該組成物具有從約6.5至約9.5之pH。
- 如請求項23之方法,其進一步包含在該接觸步驟後,用一沖洗溶劑沖洗該半導體基材。
- 如請求項24之方法,其進一步包含在該沖洗步驟後,乾燥該半導體基材。
- 如請求項23之方法,其中該方法不會實質上移除該半導體基材中之HfOx。
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US8092707B2 (en) | 1997-04-30 | 2012-01-10 | 3M Innovative Properties Company | Compositions and methods for modifying a surface suited for semiconductor fabrication |
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WO2007120259A2 (en) | 2005-11-08 | 2007-10-25 | Advanced Technology Materials, Inc. | Formulations for removing copper-containing post-etch residue from microelectronic devices |
TWI516573B (zh) * | 2007-02-06 | 2016-01-11 | 安堤格里斯公司 | 選擇性移除TiSiN之組成物及方法 |
US20110318928A1 (en) | 2010-06-24 | 2011-12-29 | Jinru Bian | Polymeric Barrier Removal Polishing Slurry |
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SG192574A1 (en) | 2011-03-11 | 2013-09-30 | Fujifilm Electronic Materials | Novel etching composition |
US20140134778A1 (en) * | 2011-08-09 | 2014-05-15 | Basf Se | Aqueous alkaline compositions and method for treating the surface of silicon substrates |
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US20140100151A1 (en) * | 2012-10-08 | 2014-04-10 | Air Products And Chemicals Inc. | Stripping and Cleaning Compositions for Removal of Thick Film Resist |
WO2014197808A1 (en) * | 2013-06-06 | 2014-12-11 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
US10428271B2 (en) * | 2013-08-30 | 2019-10-01 | Entegris, Inc. | Compositions and methods for selectively etching titanium nitride |
WO2015054464A1 (en) | 2013-10-11 | 2015-04-16 | E. I. Du Pont De Nemours And Company | Removal composition for selectively removing hard mask and methods thereof |
US20150104952A1 (en) * | 2013-10-11 | 2015-04-16 | Ekc Technology, Inc. | Method and composition for selectively removing metal hardmask and other residues from semiconductor device substrates comprising low-k dielectric material and copper |
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