JP2019511842A - コロイドシリカ成長阻害剤及び関連する方法及びシステム - Google Patents
コロイドシリカ成長阻害剤及び関連する方法及びシステム Download PDFInfo
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- JP2019511842A JP2019511842A JP2018551103A JP2018551103A JP2019511842A JP 2019511842 A JP2019511842 A JP 2019511842A JP 2018551103 A JP2018551103 A JP 2018551103A JP 2018551103 A JP2018551103 A JP 2018551103A JP 2019511842 A JP2019511842 A JP 2019511842A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 238000000034 method Methods 0.000 title claims abstract description 88
- 239000008119 colloidal silica Substances 0.000 title claims abstract description 83
- 239000003966 growth inhibitor Substances 0.000 title claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 65
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 63
- 239000000126 substance Substances 0.000 claims abstract description 57
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 17
- 238000012544 monitoring process Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 78
- 230000008569 process Effects 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 28
- 238000012993 chemical processing Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001039 wet etching Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004377 microelectronic Methods 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- 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 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229940024606 amino acid Drugs 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 claims description 3
- JEUFWFJKIXMEEK-UHFFFAOYSA-N carboxy-[2-(dicarboxyamino)ethyl]carbamic acid Chemical compound OC(=O)N(C(O)=O)CCN(C(O)=O)C(O)=O JEUFWFJKIXMEEK-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229960002885 histidine Drugs 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000000084 colloidal system Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 13
- 230000000996 additive effect Effects 0.000 abstract description 8
- 125000000129 anionic group Chemical group 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 43
- 239000004065 semiconductor Substances 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000011282 treatment Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 150000004767 nitrides Chemical group 0.000 description 3
- -1 silicate ester Chemical class 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003631 wet chemical etching Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011260 co-administration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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Abstract
Description
本開示は、リン酸(H3PO4)溶液中でのシリコン基板の処理に関する。特に、これは、リン酸中での処理中に基板表面上のコロイドシリカ堆積物の成長を防止するための新規な方法を提供する。
リン酸(H3PO4)において処理された表面上のコロイドシリカ堆積物の成長を抑制する革新的な方法が本明細書に記載されている。一実施形態では、開示される技術は、前記リン酸溶液に対する添加剤としてのコロイドシリカ成長阻害剤の使用を包含する。いくつかの実施形態において、前記添加剤は、強いアニオン性基を含有し得る化学的性質(a chemistry)を有し得る。可能性のあるアニオン性基としては、−COOH及び−PO3H2が含まれるが、これらに限定されない。これらの化学基は、コロイドシリカネットワーク中のSi中心と反応して、ケイ酸エステルR−C(O)−SiOxの形成をもたらし、溶液中にコロイドシリカが残る。他のコロイドシリカ成長阻害剤も利用できる。いくつかの実施形態では、処理中に前記リン酸中の前記シリカ濃度及び/又は前記成長阻害剤濃度を監視し、必要に応じてそれらの成分の量を調整する方法及び装置が提供される。本明細書に記載される技術は、露出した表面上にコロイドシリカ堆積物の成長を伴わずに、二酸化ケイ素に対する(towards)窒化ケイ素の高い選択性エッチングを提供する。
基板を湿式化学処理システムに装填するステップであって、前記基板が第1の構造体及び第2の構造体を有するステップと、
前記基板上にウェットエッチング溶液を分配するステップと、
を含むことができる。前記ウェットエッチング溶液は、水と、リン酸と、コロイドシリカ成長阻害剤と、を含み、前記湿式化学処理システムは、前記基板上の前記第1の構造体又は第2の構造体の露出した表面上にコロイドシリカ堆積物の成長を生じさせることなく、前記基板上の前記第2の構造体を超えて(over)、前記基板上の前記第1の構造体を選択的にエッチングするように構成される。
本発明及びその利点のより完全な理解は、添付の図面と併せた以下の説明を参照することによって得ることができ、同様の参照番号は同様の特徴を示す。しかしながら、添付の図面は、開示された概念の例示的な実施形態を示しているだけであり、及びしたがって、開示された概念は他の同等に有効な実施形態を認めることができるため、範囲の限定とみなされるべきではないことに留意されたい。
ある半導体構造の窒化ケイ素のリン酸エッチング中に、露出した二酸化ケイ素領域上に堆積するコロイドシリカの不利な成長は、処理中に窒化ケイ素の除去を妨げる可能性があることが判明している。より具体的には、狭いギャップ、狭いトレンチ、及び/又は高いアスペクト比を有する構造内に形成された窒化ケイ素は、特に問題がある。本明細書で使用される高アスペクト比の構造は、少なくとも4:1又はそれ以上のアスペクト比を有する。このような構造は、ロジックデバイス、相互接続構造、フィン電界効果トランジスタ(FinFET)、3D半導体構造、フラッシュメモリデバイス、例えばNot AND(NAND)タイプのメモリデバイスなど、多種多様な半導体構造において見られる。
Claims (26)
- 水と、
リン酸と、
コロイドシリカ成長阻害剤と、
を含む、マイクロ電子基板上の構造体のウェットエッチングのための化学組成物であって、
前記マイクロ電子基板は、少なくとも第1の構造体及び第2の構造体を包含し、当該化学組成物は、前記第1又は第2の構造体の露出した表面上にコロイドシリカ堆積物の成長を生じさせることなく、前記第2の構造体と比較して(to)、前記第1の構造体を選択的にエッチングする、化学組成物。 - 硫酸をさらに含む、請求項1に記載の化学組成物。
- 前記コロイドシリカ成長阻害剤が、少なくとも1つの−COOH基又は少なくとも1つの−PO3H2基、又はその両方を含有する、請求項1に記載の化学組成物。
- 前記コロイドシリカ成長阻害剤がポリカルボキシレートである、請求項1に記載の化学組成物。
- 前記コロイドシリカ成長阻害剤が、クエン酸、酢酸、シュウ酸、リンゴ酸、2−ホスホノブタン−1,2,4−トリカルボキシレート(PBTC)、ジエチレントリアミンペンタアセテート(DETPA)、エチレンジアミンテトラカルボキシレート(EDTA)、1,2,3,4−ブタンテトラカルボキシレート(BTC)、アミノ酸、L−ヒスチジン、L−フェニルアラニン、アンモニウムビフルオリド、及び/又はフッ化アンモニウムから選択される少なくとも1つの化合物を含む、請求項1に記載の化学組成物。
- 前記コロイドシリカ成長阻害剤の濃度が0.1体積%〜10体積%である、請求項5に記載の化学組成物。
- 前記コロイドシリカ成長阻害剤の濃度が0.2体積%〜1体積%である、請求項5に記載の化学組成物。
- クエン酸の濃度が0.2体積%〜1体積%である、請求項5に記載の化学組成物。
- アンモニウムビフルオリドの濃度が0.01体積%〜10体積%である、請求項5に記載の化学組成物。
- アンモニウムビフルオリドの濃度が0.02体積%〜1体積%である、請求項5に記載の化学組成物。
- フッ化アンモニウムの濃度が0.01体積%〜10体積%である、請求項5に記載の化学組成物。
- フッ化アンモニウムの濃度が0.02体積%〜1体積%である、請求項5に記載の化学組成物。
- 前記第1の構造体が窒化ケイ素構造であり、前記第2の構造体が酸化ケイ素構造である、請求項1に記載の化学組成物。
- マイクロ電子基板上の構造体のウェットエッチング方法であって、
前記マイクロ電子基板を湿式化学処理システムに装填するステップであって、前記マイクロ電子基板が第1の構造体及び第2の構造体を有するステップと、
前記基板上にウェットエッチング溶液を分配するステップと、
を含み、
前記ウェットエッチング溶液は、
水と、
リン酸と、
コロイドシリカ成長阻害剤と、
を含み、
前記湿式化学処理システムは、前記基板上の前記第1の構造体又は第2の構造体の露出した表面上にコロイドシリカ堆積物の成長を生じさせることなく、前記マイクロ電子基板上の前記第2の構造体を超えて(over)、前記マイクロ電子基板上の前記第1の構造体を選択的にエッチングするように構成される、方法。 - 前記ウェットエッチング溶液は硫酸をさらに含む、請求項14に記載の方法。
- 前記コロイドシリカ成長阻害剤が、少なくとも1つの−COOH基又は少なくとも1つの−PO3H2基、又はその両方を含有する、請求項14に記載の方法。
- 前記コロイドシリカ成長阻害剤がポリカルボキシレートである、請求項14に記載の方法。
- 前記コロイドシリカ成長阻害剤が、クエン酸、酢酸、シュウ酸、リンゴ酸、2−ホスホノブタン−1,2,4−トリカルボキシレート(PBTC)、ジエチレントリアミンペンタアセテート(DETPA)、エチレンジアミンテトラカルボキシレート(EDTA)、1,2,3,4−ブタンテトラカルボキシレート(BTC)、アミノ酸、L−ヒスチジン、L−フェニルアラニン、アンモニウムビフルオリド、及び/又はフッ化アンモニウムから選択される少なくとも1つの化合物を含む、請求項14に記載の方法。
- 前記第1の構造体は窒化ケイ素の層を含む、請求項14に記載の方法。
- 前記第2の構造体は二酸化ケイ素の層を含む、請求項19に記載の方法。
- 湿式化学処理システムであって、
基板を受け取り、前記基板をウェットエッチング化学組成物に曝すように構成されたチャンバと、
前記チャンバに結合された化学薬品供給システムであって、前記化学薬品供給システムは、前記チャンバに前記ウェットエッチング化学組成物を供給し、前記ウェットエッチング化学組成物は、水と、リン酸と、コロイドシリカ成長阻害剤とを含む、化学薬品供給システムと、
少なくとも前記化学薬品供給システムを包含する前記湿式化学処理システムの構成要素を制御するように構成されたコントローラと、
を含む、システム。 - 前記コントローラは、前記ウェットエッチング化学組成物の少なくとも1つの化学成分の濃度を監視することによって前記湿式化学処理システムの構成要素を制御するように構成される、請求項21に記載のシステム。
- 前記少なくとも1つの化学成分がシリカ又は前記コロイドシリカ成長阻害剤である、請求項22に記載のシステム。
- 前記湿式化学処理システムは単一基板処理システムである、請求項21に記載のシステム。
- 前記湿式化学処理システムが、前記リン酸及び前記コロイドシリカ成長阻害剤のための別個の分配ノズルを含む、請求項24に記載のシステム。
- 前記湿式化学処理システムは、複数の基板を同時に処理するように構成されている、請求項21に記載のシステム。
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TWI731790B (zh) | 2021-06-21 |
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JP2019510379A (ja) | 2019-04-11 |
US10325779B2 (en) | 2019-06-18 |
KR20180121793A (ko) | 2018-11-08 |
CN109072077A (zh) | 2018-12-21 |
SG11201808546YA (en) | 2018-10-30 |
KR102172305B1 (ko) | 2020-10-30 |
KR102196944B1 (ko) | 2020-12-30 |
KR102353264B1 (ko) | 2022-01-18 |
US10763120B2 (en) | 2020-09-01 |
CN108885989A (zh) | 2018-11-23 |
CN109072077B (zh) | 2021-04-27 |
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