JP6914107B2 - ボロン膜の除去方法 - Google Patents
ボロン膜の除去方法 Download PDFInfo
- Publication number
- JP6914107B2 JP6914107B2 JP2017111209A JP2017111209A JP6914107B2 JP 6914107 B2 JP6914107 B2 JP 6914107B2 JP 2017111209 A JP2017111209 A JP 2017111209A JP 2017111209 A JP2017111209 A JP 2017111209A JP 6914107 B2 JP6914107 B2 JP 6914107B2
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- boron
- boron film
- film
- gas
- film according
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 179
- 229910052796 boron Inorganic materials 0.000 title claims description 179
- 238000000034 method Methods 0.000 title claims description 48
- 239000007789 gas Substances 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 230000001590 oxidative effect Effects 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 238000004093 laser heating Methods 0.000 claims description 11
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 238000000206 photolithography Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 3
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 188
- 229910052810 boron oxide Inorganic materials 0.000 description 35
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 35
- 230000008569 process Effects 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000007261 regionalization Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 238000001312 dry etching Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- 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
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- 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
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- Computer Hardware Design (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
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- Formation Of Insulating Films (AREA)
- Semiconductor Memories (AREA)
- Drying Of Semiconductors (AREA)
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Description
最初に、本発明に係るボロン膜の除去方法の概要について説明する。
ボロン膜は、従来からハードマスクとして用いられていたアモルファスシリコン膜やアモルファスカーボン膜よりもドライエッチング耐性が高いため、厚い積層膜をエッチングする際のハードマスクに適している。
ボロンは化学的に安定な物質であるが、酸化ボロン(加水物)は水溶性(水溶性に近い性質)であるため、ボロンを酸化させれば容易に除去することができる。実際、酸化ボロンの薬液処理では、薬液により酸化ボロンが形成され、その後の純水洗浄により酸化ボロンが除去されていると考えられる。
次に、本発明の一実施形態に係るボロン膜除去方法について説明する。図1は本発明の一実施形態に係るボロン膜除去方法を示すフローチャートである。
上述したように、CVDにより成膜されたボロン膜は、成膜ガスとしてB2H6ガスのようなボロンと水素を含有するものを用いるので、膜中には成膜ガス由来の水素が相当量含まれる。この状態のボロン膜を従来のようにO2プラズマにより処理しても酸素はボロン膜中には入り込めずボロンと酸素との反応はほとんど生じない。
次に、上記実施形態のボロン膜除去方法をボロン膜によるパターン形成に応用した実施形態について説明する。
まず、パターン形成への応用の第1の例について説明する。
図5は、本例のパターン形成方法を示す工程断面図である。
次に、パターン形成への応用の第2の例について説明する。
図6は、本例のパターン形成方法を示す工程断面図である。
次に、ウエハ端部におけるボロン膜の局所的除去について説明する。
半導体素子の形成において微細加工を行うためにはフォトリソグラフィーを用いてパターン形成を行っているが、近年、パターンのさらなる微細化にともなって行われている短波長化(ArF、λ=193nm)や、光屈折を利用した液浸露光では、パーティクルや汚染問題の観点からウエハ端部(エッジ・ベベル)での膜の管理が強く求められている。
まず、ウエハ端部の局所的除去への応用の第1の例について説明する。
図7は、本例のウエハ端部の局所的除去を示す工程断面図である。
次に、ウエハ端部の局所的除去への応用の第2の例について説明する。
図8は、本例のウエハ端部の局所的除去を示す工程断面図である。
次に、実験結果について説明する。
[実験1]
ここでは、シリコンウエハ上に、成膜原料ガスとしてジボラン(B2H6)ガスを用い、温度:300℃、圧力:50mTorr(6.67Pa)の条件でプラズマCVDにより厚さ140nmのボロン膜を形成したサンプルを準備し、O2ガス雰囲気800℃で30minの熱処理を行った後、超音波振動させた純水中に30分浸漬するボロン膜除去処理を行った。図9にその際の処理前と処理後のSEM写真を示す。この写真に示すように、熱処理と純水処理によるボロン膜除去処理によって、ボロン膜が完全に除去されていることが確認された。
ここでは、実験1と同様、シリコンウエハ上に、成膜原料ガスとしてジボラン(B2H6)ガスを用い、温度:300℃、圧力:50mTorr(6.67Pa)の条件でプラズマCVDによりボロン膜を形成したサンプルを複数準備し、温度を400℃、500℃、600℃と変化させて、O2ガス雰囲気で30分の熱処理を行った後、超音波振動させた純水中に30分浸漬するボロン膜除去処理を行った。図11に処理前、および各温度で熱処理を行った処理後のSEM写真を示す。この図に示すように、熱処理温度が500℃および600℃のサンプルについては、熱処理と純水処理によるボロン膜除去処理によって、ボロン膜が完全に除去されていることが確認された。また、熱処理温度が400℃のサンプルについては、ボロン膜除去処理によって多少ボロン膜が除去されたが、完全に除去するには、さらに長時間の処理が必要であると考えられる。
ここでは、実験1と同様、シリコンウエハ上に、成膜原料ガスとしてジボラン(B2H6)ガスを用い、温度:300℃、圧力:50mTorr(6.67Pa)の条件でプラズマCVDによりボロン膜を形成したサンプルを複数準備し、温度を400℃、600℃、800℃、時間を1min、10min、20min、30minと変化させて、O2ガス雰囲気での熱処理を行った後、超音波振動させた純水中に30分浸漬するボロン膜除去処理を行った。図12に処理前、および熱処理を各温度および各時間で行った処理後のSEM写真を示す。この図に示すように、熱処理温度が800℃では、処理時間が1minでボロン膜がほぼ除去されていた。また、熱処理温度が600℃では、処理時間が1minでボロン膜が厚さ140nmから120nmまで減膜し、処理時間が10minでボロン膜がほぼ除去されていた。さらに、熱処理温度が400℃では、実験2と同様、処理時間が30minで多少ボロン膜が除去されたが、完全に除去するには、さらに長時間の処理が必要であると考えられる。
以上、本発明の実施の形態について説明したが、本発明は上記実施形態に限定されることなく本発明の思想の範囲内で種々変形可能である。
2;絶縁膜
3;CVDボロン膜
4;酸化ボロン
5,25;レジストまたはマスク材料の膜
11;酸素ノズル
12;レーザー光源
13;レーザー
14;ランプ光源
21;ウエハ
23;ボロン膜
Claims (15)
- CVDにより基板上に形成されたボロン膜を除去するボロン膜の除去方法であって、
前記ボロン膜を、酸化雰囲気でレーザー加熱により部分的に熱処理し、熱処理した部分を酸化させる工程と、
前記ボロン膜の酸化された部分を水または電解質イオンを含む水溶液により除去する工程と
を有し、
前記レーザー加熱により部分的に熱処理して酸化させる工程と、前記酸化された部分を除去する工程とにより、フォトリソグラフフィー工程を行うことなく、前記ボロン膜を部分的に除去することを特徴とするボロン膜の除去方法。 - 前記酸化雰囲気は酸素またはオゾンを含むことを特徴とする請求項1に記載のボロン膜の除去方法。
- 前記電解質イオンは、H+、NH4 +、F−、Cl−、NO3 −、SO4 2−、OH−のいずれかを含むことを特徴とする請求項1または2に記載のボロン膜の除去方法。
- 前記電解質イオンの水溶液は、酸化性を有する酸以外であることを特徴とする請求項3に記載のボロン膜の除去方法。
- 前記ボロン膜は、ボロンと水素を含む原料ガスを用いて成膜されたものであることを特徴とする請求項1から請求項4のいずれか1項に記載のボロン膜の除去方法。
- 前記ボロン膜は、プラズマCVDにより成膜されたものであることを特徴とする請求項1から請求項5のいずれか1項に記載のボロン膜の除去方法。
- 前記熱処理は、400〜1000℃の範囲の温度で行うことを特徴とする請求項1から請求項6のいずれか1項に記載のボロン膜の除去方法。
- 前記熱処理は、1〜60分の期間行うことを特徴とする請求項1から請求項7のいずれか1項に記載のボロン膜の除去方法。
- 前記熱処理は、酸素ガスまたはオゾンガス濃度が20〜100%の雰囲気で行われることを特徴とする請求項1から請求項8のいずれか1項に記載のボロン膜の除去方法。
- 前記除去する工程は、前記基板を純水または電解質イオンを含む水溶液に浸漬することにより行うことを特徴とする請求項1から請求項9のいずれか1項に記載のボロン膜の除去方法。
- 前記基板が浸漬された純水または電解質イオンを含む水溶液に超音波振動を与えることを特徴とする請求項10に記載のボロン膜の除去方法。
- 前記除去する工程は、前記基板に純水または電解質イオンを含む水溶液の流水を供給することにより行うことを特徴とする請求項1から請求項9のいずれか1項に記載のボロン膜の除去方法。
- 前記ボロン膜を部分的に除去することにより、パターンを形成することを特徴とする請求項1から請求項12のいずれか一項に記載のボロン膜の除去方法。
- 前記ボロン膜の基板の端部に対応する部分を部分的に除去することを特徴とする請求項1から請求項12のいずれか一項に記載のボロン膜の除去方法。
- 前記ボロンと水素を含むガスは、三塩化ホウ素(BCl 3 )ガスと水素との混合ガス、トリメチルボラン(B(CH 3 ) 3 )ガス、トリエチルボラン(B(C 2 H 5 ) 3 )ガスから選択されたものであることを特徴とする請求項5に記載のボロン膜の除去方法。
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KR1020180063972A KR102071794B1 (ko) | 2017-06-05 | 2018-06-04 | 붕소막의 제거 방법 및 붕소막에 의한 패턴 형성 방법 |
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