JP2017092101A - パターン形成方法 - Google Patents
パターン形成方法 Download PDFInfo
- Publication number
- JP2017092101A JP2017092101A JP2015216524A JP2015216524A JP2017092101A JP 2017092101 A JP2017092101 A JP 2017092101A JP 2015216524 A JP2015216524 A JP 2015216524A JP 2015216524 A JP2015216524 A JP 2015216524A JP 2017092101 A JP2017092101 A JP 2017092101A
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- JP
- Japan
- Prior art keywords
- film
- metal
- pattern
- mnox
- etched
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 97
- 238000000059 patterning Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 93
- 239000002184 metal Substances 0.000 claims abstract description 93
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 72
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims abstract description 69
- 238000011282 treatment Methods 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 56
- 238000005530 etching Methods 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims description 86
- 239000007789 gas Substances 0.000 claims description 79
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 36
- 150000002697 manganese compounds Chemical class 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 230000007261 regionalization Effects 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 6
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 48
- 230000015572 biosynthetic process Effects 0.000 description 12
- -1 hydrogen radicals Chemical class 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- 125000006850 spacer group Chemical group 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- HDWDVUXQIOWBEP-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Ru] Chemical compound C(C)C1(C=CC=C1)[Ru] HDWDVUXQIOWBEP-UHFFFAOYSA-N 0.000 description 1
- LGJJVJDDNWYROS-UHFFFAOYSA-N C1(C=CC=C1)[Ru]C=C(C=C(C)C)C Chemical compound C1(C=CC=C1)[Ru]C=C(C=C(C)C)C LGJJVJDDNWYROS-UHFFFAOYSA-N 0.000 description 1
- XOSBQSGUNCVAIL-UHFFFAOYSA-N CC(=C[Ru]C1(C=CC=C1)CC)C=C(C)C Chemical compound CC(=C[Ru]C1(C=CC=C1)CC)C=C(C)C XOSBQSGUNCVAIL-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QKOHYQVZNLEAJH-UHFFFAOYSA-N oxomethylidenemanganese Chemical class O=C=[Mn] QKOHYQVZNLEAJH-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- 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
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Abstract
【解決手段】被エッチング膜11上にメタルパターン12が形成されてなる基板上に、MnOx膜13をALDにより形成し、MnOx膜13の表面に水素ラジカル処理を施し、次いで、Ru膜15をCVDにより形成し、次いで、メタルパターン12をエッチング除去し、Ru/Mn反転材16の反転パターンを得る。MnOx膜13のメタルパターン12に対応する部分は、水素ラジカル処理により酸化物のままの第1Mn含有膜14aとなり、MnOx膜13の被エッチング膜11に対応する部分は、水素ラジカル処理により表面に金属Mnが形成された第2Mn含有膜14bとなり、Ru膜15は第2Mn含有膜14b上に選択的に形成される。
【選択図】図1
Description
本実施形態では、最初に、FEOL(Front End Of Line)工程により得られた下部構造10(詳細な構造は省略)上に、被エッチング膜11を有し、その上に、マルチパターニング技術、例えば上述したSADP法、SAQP法、またはLEx法によりメタル膜がパターニングされて形成されたメタルパターンとして、TiN膜がパターニングされて形成されたTiNパターン12を有する基板、例えば半導体ウエハ(以下、単にウエハと記す)Wを準備する(ステップ1、図2(a))。被エッチング膜11は、特に限定されないが、例えばSiO2膜(TEOS膜等)、低誘電率(Low−k)膜(SiCO、SiCOH等)、SiN膜等のSi含有物質からなり、例えば層間絶縁膜として形成される。
次に、以上の工程のうち、主要工程であるステップ3〜5について詳細に説明する。
まず、ステップ3のMnOx膜13を形成する工程について説明する。
MnOx膜13は、メタルパターン膜であるTiN膜12との間で、水素ラジカル処理では金属まで還元されない結合の強い酸化膜を生成する酸化膜として形成される。
次に、ステップ4の水素ラジカル処理について説明する。
水素ラジカル処理は、MnOx膜13を還元して表面を金属Mnに改質する処理であり、この処理によりRu膜15が成膜されやすくなる。すなわち、Ru膜は下地が酸化膜であるとRu核形成密度が低くなり堆積され難いが、下地が金属であるとRu核形成密度が高くなって堆積されやすいことから、水素ラジカル処理により表面が金属Mnに改質された部分にRu膜15が成膜されやすくなるのである。
次に、ステップ5のRu膜15を形成する工程について説明する。
CVD−Ru膜15は、ルテニウムカルボニル(Ru3(CO)12)を成膜原料として用いて熱CVDにより好適に形成することができる。これにより、高純度で薄いRu膜を高ステップカバレッジで成膜することができる。この場合に、成膜温度が175〜230℃の範囲、圧力が1.3〜133Paの範囲であることが好ましい。
以上のように、ステップ3〜5によってRu膜15が被エッチング膜11上に選択的に成膜されるメカニズムをまとめると、図5に示すようになる。すなわち、図5(a)に示すように、ステップ3において被エッチング膜11を構成する例えばTEOS膜上およびTiNパターン12を構成するTiN膜上にALDによりMnOx膜13を成膜すると、TEOS膜ではMnOx膜13の表面はMnOxのままであるが、TiN膜上ではMnOx膜中のMnとTiN膜中のTiとH2Oとが反応してOの結合が強いMnTiO3またはMn2TiO4が生成される。
次に、上記ステップ2〜5の実施に好適な処理システムについて説明する。
図6はそのような処理システムを示す平面図である。
下部構造上に、被エッチング膜11を有し、その上に、SADP法によりTiN膜がパターニングされて形成されたTiNパターンを有するウエハを収容したキャリアCを成膜システム20へ搬送し、接続ポート52または53に接続する。そして、キャリアCから大気搬送用搬送機構56によりウエハWを取り出し、アライメント室54でアライメントを行った後、ロードロック室44aまたは44bに搬送する。そのロードロック室を第2の真空搬送室41と同程度の真空度に減圧した後、第2の搬送機構46によりロードロック室のウエハWを取り出し、第2の真空搬送室41を介してデガス室33に搬送し、ウエハWのデガス処理を行う。その後、第1の搬送機構36によりデガス室33のウエハWを取り出し、第1の真空搬送室31を介してMnOx膜成膜装置32a、32b、32c、32dのいずれかに搬入し、上述したような反転材の一部となるMnOx膜をALDにより成膜する。
次に、上記処理システム20に用いられるALDによりMnOx膜を成膜するMnOx膜成膜装置32a,32b,32c,32dに好適に用いることができる成膜装置について説明する。図7は、成膜装置の一例を示す断面図である。なお、この成膜装置は、CVDによりRu膜を成膜するRu膜成膜装置42a,42bにも適用することができる。
次に、上記処理システム20に用いられる水素ラジカル処理装置の一例について説明する。
図8は、水素ラジカル処理装置の一例を示す断面図であり、リモートプラズマ処理により処理容器内に水素ラジカルを生成するものを例にとって説明する。
以上、本発明の実施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種々変形可能である。例えば、上記実施形態では、メタルパターンとしてTiNパターンを用いたが、他のTi含有膜を好適に用いることもでき、また、Ti含有膜に限らず、金属酸化膜成膜時に還元処理で実質的に還元されない強固な結合を持った酸化物が形成されるものであればよい。
12;TiNパターン
13;MnOx膜
14a;第1Mn含有膜
14b;第2Mn含有膜
15;Ru膜
16;反転材
17;エッチングパターン
18;凹部
W;半導体ウエハ
Claims (16)
- 被エッチング膜上にメタルパターンが形成されてなる基板上に、反転材の一部となる金属酸化膜を形成し、前記メタルパターン上に、前記被エッチング膜上よりもOの結合が強い酸化膜が形成されるようにする第1工程と、
次いで、還元処理を行って、前記メタルパターン上の前記金属酸化膜を、酸化物のままの第1金属含有膜とし、前記被エッチング膜上の前記金属酸化膜を、表面が金属に還元された第2金属含有膜とする第2工程と、
次いで、金属上には形成されやすく、酸化物上には形成され難い性質を有する金属膜を、反転材の一部として前記被エッチング膜上の前記第2金属含有膜上のみに選択的に形成する第3工程と、
次いで、前記メタルパターンをエッチング除去し、前記金属酸化膜から得られた前記第1金属含有膜および前記第2金属含有膜と前記金属膜とで構成される反転材を残存させ、反転材からなる反転パターンを得る第4工程と
を有することを特徴とするパターン形成方法。 - 前記金属酸化膜を形成する工程は、ALDによりMnOx膜を形成することを特徴とする請求項1に記載のパターン形成方法。
- 前記メタルパターンは、Ti含有膜で構成され、前記メタルパターン上の前記MnOx膜が、MnTiO3またはMn2TiO4となることを特徴とする請求項2に記載のパターン形成方法。
- 前記メタルパターンは、TiN膜で構成されることを特徴とする請求項3に記載のパターン形成方法。
- 前記還元処理は水素ラジカル処理であり、この水素ラジカル処理により、前記メタルパターン上の前記金属酸化膜としてのMnOx膜を、酸化物のままの第1金属含有膜である第1Mn含有膜とし、前記被エッチング膜上の前記金属酸化膜としてのMnOx膜を、前記第2金属含有膜である表面が金属Mnに還元された第2Mn含有膜とすることを特徴とする請求項2から請求項4のいずれか1項に記載のパターン形成方法。
- 前記金属膜は、Ru膜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項に記載のパターン形成方法。
- 被エッチング膜上にメタルパターンが形成されてなる基板上に、反転材の一部となるMnOx膜をALDにより形成する第1工程と、
次いで、前記MnOx膜の表面に水素ラジカル処理を施す第2工程と、
次いで、反転材の一部となるRu膜をCVDにより形成する第3工程と、
次いで、前記メタルパターンをエッチング除去し、前記MnOx膜に水素ラジカル処理を施した後の物質および前記Ru膜とで構成される反転材を残存させ、前記被エッチング膜をエッチングするための、反転材からなる反転パターンを得る第4工程と
を有し、
前記メタルパターンは、前記MnOx膜が形成された際に、前記水素ラジカル処理では実質的に金属Mnに還元されない酸化物が形成される材料からなり、
前記MnOx膜の前記メタルパターンに対応する部分は、前記水素ラジカル処理により酸化物のままの第1Mn含有膜となり、
前記MnOx膜の前記被エッチング膜に対応する部分は、前記水素ラジカル処理により還元されて表面に金属Mnが形成された第2Mn含有膜となり、
前記Ru膜は、前記第1Mn含有膜上には実質的に形成されず、前記第2Mn含有膜上に選択的に形成されることを特徴とするパターン形成方法。 - 前記メタルパターンは、Ti含有膜で構成され、前記メタルパターン上の前記MnOx膜が、MnTiO3またはMn2TiO4となることを特徴とする請求項7に記載のパターン形成方法。
- 前記メタルパターンは、TiN膜で構成されることを特徴とする請求項8に記載のパターン形成方法。
- 前記MnOx膜は、基板を配置した処理容器内に、マンガン化合物ガスおよび酸素含有ガスを、前記処理容器内のパージを挟んで交互に供給することにより成膜し、その際の基板温度を、前記マンガン化合物の熱分解温度よりも低い温度とすることを特徴とする請求項7から請求項9のいずれか1項に記載のパターン形成方法。
- 前記水素ラジカル処理は、基板温度を200〜400℃にして100sec以上の期間行われることを特徴とする請求項7から請求項10のいずれか1項に記載のパターン形成方法。
- 前記水素ラジカル処理は、水素ガスを含むガスのプラズマにより生成した水素ラジカルを前記基板に供給することにより行われることを特徴とする請求項11に記載のパターン形成方法。
- 前記Ru膜を形成する際に、成膜原料としてルテニウムカルボニルを用いることを特徴とする請求項7から請求項12のいずれか1項に記載のパターン形成方法。
- 前記第1工程から前記第3工程は、真空を破ることなく連続的に行うことを特徴とする請求項7から請求項13のいずれか1項に記載のパターン形成方法。
- 前記メタルパターンは、SADP法、SAQP法、またはLEx法によりパターニングされて形成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14のいずれか1項に記載のパターン形成方法。
- 前記被エッチング膜は、Si含有膜で構成されていることを特徴とする請求項1から請求項15のいずれか1項に記載のパターン形成方法。
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