JP5917351B2 - 金属膜の成膜方法 - Google Patents
金属膜の成膜方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims description 62
- 239000002184 metal Substances 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 210
- 239000007789 gas Substances 0.000 claims description 113
- 229910052759 nickel Inorganic materials 0.000 claims description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 230000015572 biosynthetic process Effects 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000003446 ligand Substances 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 13
- 230000005587 bubbling Effects 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 238000000137 annealing Methods 0.000 description 8
- 238000010926 purge Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- -1 nickel nitride Chemical class 0.000 description 4
- 229910021334 nickel silicide Inorganic materials 0.000 description 4
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- SDIXRDNYIMOKSG-UHFFFAOYSA-L disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
Description
本実施形態では、金属膜としてニッケル膜を形成する場合について説明する。図1は、本発明の一実施形態に係る金属膜の成膜方法を実施するための成膜装置の一例を示す模式図である。
まず、ゲートバルブ25を開け、図示せぬ搬送装置によりウエハWを、搬入出口24を介してチャンバー1内に搬入し、サセプタ2上に載置する。次いで、チャンバー1内を排気装置23により排気してチャンバー1内を所定の圧力にし、サセプタ2を所定温度に加熱する。
すなわち、核となるNiにアミジネート配位子が結合しており、Niは実質的にNi2+として存在している。
(1)成膜原料であるニッケルアミジネートと非共有電子対を有する還元ガスであるNH3とで初期成膜を行って初期Ni膜を成膜した後は、還元ガスとしてH2ガスを用いてもその上にNi膜を成膜することが可能である。
(2)還元ガスとしてH2を用いた場合には、膜中へNが取り込まれないため、NixNが形成されずに純度の高いNi膜を形成することができる。
(3)還元ガスであるH2ガスの存在により、初期Ni膜に含まれるNを除去することができる。
(4)成膜原料としてニッケルアミジネートを用い、還元ガスとしてH2を用いて初期Ni膜の上にNi膜を成膜する場合には、ニッケルアミジネートとNH3とを用いて成膜するよりも成膜レートが高い。
ここでは、成膜原料としてNi(II)(tBu−AMD)2を用い、還元ガスとしてNH3を用いて、Siウエハ上に約30nmのNi膜(初期Ni膜に相当)を成膜したサンプルと、同様にしてNi膜を成膜した後、H2ガスを供給して水素処理を行ったサンプルについてX線光電子分光(XPS)により、膜厚方向の組成分析を行った。その結果を図4、5に示す。これらの図において、横軸は厚さ方向のエッチングサイクルを示し、1回のエッチングで約1.7nmエッチングしている。なお、水素処理は、ウエハ温度:250℃、圧力:1333Pa(10Torr)、H2ガス流量:500mL/min(sccm)、処理時間:180secの条件で行った。
2;サセプタ
5;ヒーター
10;シャワーヘッド
30;ガス供給機構
31;成膜原料タンク
42;NH3ガス供給源
43;H2ガス供給源
50;制御部
51;プロセスコントローラ
53;記憶部
W;半導体ウエハ
Claims (10)
- 処理容器内に被処理基板を配置し、被処理基板上に、分子構造中に窒素−炭素結合をもつ配位子を有し、配位子中の窒素が金属に配位した構造を有する金属含有化合物からなる成膜原料と、アンモニア、ヒドラジン、およびこれらの誘導体から選択された少なくとも1種からなる還元ガスとを供給して、CVDにより初期金属膜を成膜する第1工程と、
その後、前記処理容器内に水素ガスを供給して被処理基板に対して水素処理を行う第2工程と、
被処理基板に形成された初期金属膜の上に、分子構造中に窒素−炭素結合をもつ配位子を有し、配位子中の窒素が金属に配位した構造を有する金属含有化合物からなる成膜原料と、水素ガスからなる還元ガスを供給して、CVDにより主金属膜を成膜する第3工程と
を有することを特徴とする金属膜の成膜方法。 - 前記金属含有化合物は、金属アミジネート系化合物であることを特徴とする請求項1に記載の金属膜の成膜方法。
- 前記金属アミジネート系化合物はニッケルアミジネートであり、前記金属膜はニッケル膜であることを特徴とする請求項2に記載の金属膜の成膜方法。
- 前記第2工程は、160〜500℃で行われることを特徴とする請求項3に記載の金属膜の成膜方法。
- 前記第2工程を実施する際の圧力は、333〜13330Paであることを特徴とする請求項3または請求項4に記載の金属膜の成膜方法。
- 前記第2工程を実施する際の水素ガス流量は、25〜5000mL/min(sccm)であることを特徴とする請求項3から請求項5のいずれか1項に記載の金属膜の成膜方法。
- 前記第1工程および前記第3工程は、200〜350℃で行われることを特徴とする請求項3から請求項6のいずれか1項に記載の金属膜の成膜方法。
- 前記第1工程および前記第3工程を実施する際の圧力は、133.3〜2000Paであることを特徴とする請求項3から請求項7のいずれか1項に記載の金属膜の成膜方法。
- 前記第2工程は、前記第1工程および前記第3工程と同一温度および同一圧力で行われることを特徴とする請求項7または請求項8に記載の金属膜の成膜方法。
- コンピュータ上で動作し、成膜装置を制御するためのプログラムが記憶された記憶媒体であって、前記プログラムは、実行時に、請求項1から請求項9のいずれかの金属膜の成膜方法が行われるように、コンピュータに前記成膜装置を制御させることを特徴とする記憶媒体。
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