JP6815158B2 - 酸化チタン膜の成膜方法およびハードマスクの形成方法 - Google Patents
酸化チタン膜の成膜方法およびハードマスクの形成方法 Download PDFInfo
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- JP6815158B2 JP6815158B2 JP2016201538A JP2016201538A JP6815158B2 JP 6815158 B2 JP6815158 B2 JP 6815158B2 JP 2016201538 A JP2016201538 A JP 2016201538A JP 2016201538 A JP2016201538 A JP 2016201538A JP 6815158 B2 JP6815158 B2 JP 6815158B2
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- titanium oxide
- oxide film
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- gas
- forming
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 85
- 238000000034 method Methods 0.000 title claims description 57
- 239000007789 gas Substances 0.000 claims description 170
- 230000015572 biosynthetic process Effects 0.000 claims description 65
- 239000007800 oxidant agent Substances 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 238000005530 etching Methods 0.000 claims description 23
- 125000006850 spacer group Chemical group 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 8
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 61
- 210000002381 plasma Anatomy 0.000 description 52
- 238000000231 atomic layer deposition Methods 0.000 description 26
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 238000010926 purge Methods 0.000 description 15
- 239000011162 core material Substances 0.000 description 11
- 229910004356 Ti Raw Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000000059 patterning Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000003028 elevating effect Effects 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen peroxide Chemical compound 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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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- C23C16/22—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 deposition of inorganic material, other than metallic material
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Description
最初に、本発明に係る酸化チタン膜(TiO2膜)の成膜方法の一実施形態について図1のフローチャートを参照して説明する。
上述したように、本実施形態で成膜したTiO2膜は、所定の膜をパターンエッチングする際のハードマスクに適用することが好ましい。その際のハードマスクの製造方法は、下層のSiの上に上述したステップ2の第1段階のTiO2膜の成膜を行い、さらに上述したステップ3の第2段階のTiO2膜の成膜を行った後、所定のパターニングを行い所定パターンのハードマスクを製造する。このとき、第1段階の成膜と第2段階の成膜はコンフォーマルに成膜することが好ましい。
まず、図2に示すように、シリコン基体201上にエッチング対象膜である低誘電率膜(Low−k膜)202、反射防止膜(ARC)203、TiN膜204、TEOS膜(SiO2膜)205が形成され、さらに、その上にフォトリソグラフィにより所定のパターンで形成された芯材となるSi膜206が形成された被処理基板である半導体ウエハWを準備する。Si膜206としては、CVDにより成膜されたポリSi膜を好適に用いることができる。
以下、実験例について説明する。
ここでは、Ti原料ガスとしてTiCl4ガスを用い、酸化剤としてH2Oを用いて熱ALDによりSi上にTiO2膜を成膜した場合(ケースA)と、Ti原料ガスとしてTiCl4ガスを用い、酸化剤としてO2プラズマを用いてプラズマALDによりSi上にTiO2膜を成膜した場合(ケースB)のSi上の界面SiO2膜の厚さを調査した。
(1)ケースA
H2O=300sccm、TiCl4=20sccm、4Torr
(2)ケースB
O2ガス=1000sccm、TiCl4=50sccm、
RF=300W、2Torr
次に、上記TiO2膜の成膜方法に好適な成膜装置の一例について説明する。図13は本発明のTiO2膜の成膜方法に好適な成膜装置の一例を示す断面図である。
(1)第1段階の成膜
圧力:1〜10Torr(133〜1333Pa)
温度:室温〜250℃
TiCl4ガス流量:5〜100sccm(mL/min)
H2Oガス流量:50〜1000sccm(mL/min)
Arガス流量:1000〜10000sccm(mL/min)
T1の時間(1回あたり):0.01〜0.5sec
T3の時間(1回あたり):0.2〜5sec
T2(パージ)の時間(1回あたり):0.05〜2sec
T4(パージ)の時間(1回あたり):0.2〜5sec
圧力:0.1〜10Torr(13〜1333Pa)
温度:50〜250℃
TiCl4ガス流量:10〜100sccm(mL/min)
O2ガス流量:250〜2500sccm(mL/min)
高周波電力:100〜1000W
Arガス流量:2000〜10000sccm(mL/min)
T11の時間(1回あたり):0.01〜0.5sec
T13の時間(1回あたり):0.1〜1.0sec
T12(パージ)の時間(1回あたり):0.05〜1.0sec
T14(パージ)の時間(1回あたり):0〜0.5sec
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、被処理体として半導体ウエハを用いた場合を示したが、本発明では、被処理体は少なくとも表面がシリコンであるものであればよく、例えば、化合物半導体やガラス基板、セラミックス基板の上にシリコン膜が形成されたものであってもよい。
2;サセプタ
3;シャワーヘッド
4;排気部
5;ガス供給機構
6;プラズマ生成機構
7;制御部
100;成膜装置
201;シリコン基体
202;Low−k膜(エッチング対象膜)
203;反射防止膜
204;TiN膜
205;TEOS膜
206;Si膜
207;TiO2膜
208;側壁スペーサ(ハードマスク)
210;界面SiO2膜
W;半導体ウエハ(被処理基板)
Claims (12)
- 表面にシリコン部分を有する被処理基板に酸化チタン膜を形成する酸化チタン膜の成膜方法であって、
前記被処理基板の前記シリコン部分を含む表面に、チタン含有ガスと、酸化剤である水素および酸素を含むガスとを交互に供給して熱ALDにより第1の酸化チタン膜を成膜する第1段階の酸化チタン膜成膜工程と、
前記第1の酸化チタン膜の上に、チタン含有ガスと、酸化剤である酸素含有ガスのプラズマとを交互に供給してプラズマALDにより第2の酸化チタン膜を成膜する第2段階の酸化チタン膜成膜工程と
を有し、
前記第1段階の酸化チタン膜成膜工程は、前記シリコン部分の表面酸化が抑制されるように行われ、前記第1の酸化チタン膜は、前記第2段階の酸化チタン膜成膜工程の際における前記シリコン部分の表面酸化のバリアとして機能し、その厚さが1nm以上6nm以下であることを特徴とする酸化チタン膜の成膜方法。 - ハードマスクとなる酸化チタン膜を成膜することを特徴とする請求項1に記載の酸化チタン膜の成膜方法。
- 前記第1段階の酸化チタン膜成膜工程において酸化剤として用いられる水素および酸素を含むガスは、H2Oガスであることを特徴とする請求項1または請求項2に記載の酸化チタン膜の成膜方法。
- 前記第2段階の酸化チタン膜成膜工程において酸化剤として用いられる酸素含有ガスのプラズマは、O2ガスのプラズマであることを特徴とする請求項1から請求項3のいずれか1項に記載の酸化チタン膜の成膜方法。
- 前記第1段階の酸化チタン膜の成膜と、前記第2段階の酸化チタン膜の成膜とは、同一のチャンバー内で行われ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項に記載の酸化チタン膜の成膜方法。
- 表面に所定のパターンのシリコン部分を有し、かつ被エッチング膜を有する被処理基板において、前記被エッチング膜をパターンエッチングするためのハードマスクの形成方法であって、
前記被処理基板の前記シリコン部分を含む表面に、チタン含有ガスと、酸化剤である水素および酸素を含むガスとを交互に供給して熱ALDにより第1の酸化チタン膜を成膜する第1段階の酸化チタン膜成膜工程と、
前記第1の酸化チタン膜の上に、チタン含有ガスと、酸化剤である酸素含有ガスのプラズマとを交互に供給してプラズマALDにより第2の酸化チタン膜を成膜する第2段階の酸化チタン膜成膜工程と、
前記第1段階の酸化チタン膜成膜工程で成膜された前記第1の酸化チタン膜と、前記第2段階の酸化チタン膜成膜工程で成膜された前記第2の酸化チタン膜とで構成された酸化チタン膜をエッチングして所定パターンのハードマスクを形成する工程と
を有し、
前記第1段階の酸化チタン膜成膜工程は、前記シリコン部分の表面酸化が抑制されるように行われ、前記第1の酸化チタン膜は、前記第2段階の酸化チタン膜成膜工程の際における前記シリコン部分の表面酸化のバリアとして機能し、その厚さが1nm以上6nm以下であることを特徴とするハードマスクの形成方法。 - 前記シリコン部分は凸部を有し、前記ハードマスクを形成する工程は、前記凸部の側壁スペーサとしてハードマスクを形成することを特徴とする請求項6に記載のハードマスクの形成方法。
- 前記第1の酸化チタン膜および前記第2の酸化チタン膜は、前記凸部上にコンフォーマルに堆積することを特徴とする請求項7に記載のハードマスクの形成方法。
- 前記ハードマスクを形成する工程の後、前記シリコン部分をエッチング除去する工程をさらに有することを特徴とする請求項6から請求項8のいずれか1項に記載のハードマスクの形成方法。
- 前記第1段階の酸化チタン膜成膜工程において酸化剤として用いられる水素および酸素を含むガスは、H2Oガスであることを特徴とする請求項6から請求項9のいずれか1項の記載のハードマスクの形成方法。
- 前記第2段階の酸化チタン膜成膜工程において酸化剤として用いられる酸素含有ガスのプラズマは、O2ガスのプラズマであることを特徴とする請求項6から請求項10のいずれか1項に記載のハードマスクの形成方法。
- 前記第1段階の酸化チタン膜の成膜と、前記第2段階の酸化チタン膜の成膜とは、同一のチャンバー内で行われることを特徴とする請求項6から請求項11のいずれか1項に記載のハードマスクの形成方法。
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