JP2015074831A - TDMAT又はTDEATを用いてPEALDによりTi含有膜を形成する方法 - Google Patents
TDMAT又はTDEATを用いてPEALDによりTi含有膜を形成する方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 73
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 50
- 239000012495 reaction gas Substances 0.000 claims abstract description 47
- VJDVOZLYDLHLSM-UHFFFAOYSA-N diethylazanide;titanium(4+) Chemical compound [Ti+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VJDVOZLYDLHLSM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 239000013078 crystal Substances 0.000 claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000151 deposition Methods 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229910010282 TiON Inorganic materials 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 54
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- 239000001257 hydrogen Substances 0.000 description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- 239000010410 layer Substances 0.000 description 26
- 239000012528 membrane Substances 0.000 description 26
- 239000002243 precursor Substances 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 13
- 238000001039 wet etching Methods 0.000 description 13
- 238000001312 dry etching Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000003247 decreasing effect Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052756 noble gas Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910011208 Ti—N Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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Abstract
Description
Ti含有膜は、図6に図示されたシーケンス及び図1に図示された装置を用いて、以下の表7及び8で示される条件下でパターン(アスペクト比:2:1)を有する基板に堆積された。
Ti含有膜は、図6に図示されたシーケンス及び図1に図示された装置を用いて、以下の表8及び10で示される条件下でパターン(アスペクト比:2:1)を有する基板に堆積された。
積層体によって構成されるTi含有膜は、図6に図示されたシーケンス及び図1に図示された装置を用いて、以下の表14及び15で示される条件下でパターン(アスペクト比:2:1)を有する基板に堆積された。
膜は、実施例11、12及び14と同一の条件下で形成され、ドライエッチング速度及びウェットエッチング速度は、膜ごとに測定された。図8は、実施例18で形成されたTiN膜、実施例17で形成されたTiO膜及び実施例19で形成されたTiON膜のドライエッチング速度を示すグラフである。TiON膜のドライエッチング速度は、TiN膜及びTiO膜のドライエッチング速度よりも著しく低かった。図9は、実施例18で形成されたTiN膜、実施例17で形成されたTiO膜及び実施例19で形成されたTiON膜のウェットエッチング速度を示すグラフである。TiON膜のウェットエッチング速度は、TiN膜及びTiO膜のウェットエッチング速度よりも著しく高かった。
膜は、膜形成プロセスの後に、膜を約600℃で、約2時間アニールしたことを除いて実施例6と同一条件下で形成された。図3は、アニールされた膜のX線回折分析の結果を示し、膜がアナターゼ型結晶であることを示す。
Ti含有膜は、図6に図示されたシーケンス及び図1に図示された装置を用いて、以下の表8及び17で示される条件下でパターン(アスペクト比:2:1)を有する基板に堆積された。
Ti含有膜は、図6に図示されたシーケンス及び図1に図示された装置を用いて、以下の表8及び19で示される条件下でパターン(アスペクト比:2:1)を有する基板に堆積された。
Ti含有膜は、図6に図示されたシーケンス及び図1に図示された装置を用いて、以下の表8及び20で示される条件下でパターン(アスペクト比:2:1)を有する基板に堆積された。
Claims (18)
- テトラキス(ジメチルアミノ)チタニウム(TDMAT)又はテトラキス(ジエチルアミノ)チタニウム(TDEAT)を用いてプラズマエンハンスト原子層堆積(PEALD)により基板にTi含有膜を形成する方法であって、
(i)前記基板が配置される反応空間にパルス状に前記TDMAT及び/又は前記TDEATを導入するステップと、
(ii)NH3フリーの反応ガスを前記反応空間に連続的に導入するステップと、
(iii)前記TDMATのパルス及び/又は前記TDEATのパルスと重複せずに、RFパワーを前記反応空間にパルス状に印加するステップと、
(iv)前記ステップ(i)から(iii)を繰り返して、前記基板に前記Ti含有膜を堆積するステップと、を備える方法。 - 前記NH3フリーの反応ガスは、H2及び/又はN2である請求項1に記載の方法。
- 前記NH3フリーの反応ガスは、窒素又は酸素を含まない請求項1に記載の方法。
- 前記NH3フリーの反応ガスは、酸素を含む請求項1に記載の方法。
- 前記NH3フリーの反応ガスは、H2及び希ガスからなり、それにより、前記ステップ(iv)の前記Ti含有膜としてTiN結晶膜を堆積する請求項2に記載の方法。
- 前記NH3フリーの反応ガスは、H2、N2及び希ガスからなり、それにより、前記ステップ(iv)の前記Ti含有膜としてTiCNアモルファス膜を堆積する請求項2に記載の方法。
- 前記Ti含有膜は、−2,500MPaから800MPaの膜応力を有する請求項1に記載の方法。
- 前記ステップ(ii)の前記反応ガスで用いられるH2の基準流量、前記ステップ(iii)で用いられる基準RFパワー、及び前記ステップ(i)から(iii)にわたる基準堆積温度を含む堆積条件下で前記ステップ(i)から(iv)により堆積されるTiN結晶膜の膜応力よりも大きい前記Ti含有膜に対して対象となる膜の応力を設定するステップと、
前記ステップ(ii)の前記反応ガスで用いられるH2の基準流量、前記ステップ(iii)で用いられる基準RFパワー、及び前記ステップ(i)から(iii)にわたる堆積温度を設定するステップと、をさらに備え、
前記H2の基準流量、前記基準RFパワー及び前記堆積温度の一又はそれ以上のみが前記膜応力を変化させるための制御パラメータとして用いられ、かつ前記H2の基準流量、前記基準RFパワー及び前記基準堆積温度とは異なっており、
その後に、前記Ti含有膜を堆積する前記ステップ(i)から(iv)を処理する、
請求項1に記載の方法。 - 前記Ti含有膜は、引っ張り膜応力を有する請求項8に記載の方法。
- 設定された前記H2の流量は、前記TiN結晶膜に用いられるH2の前記基準流量よりも低い請求項9に記載の方法。
- 設定された前記RFパワーは、前記TiN結晶膜に用いられる前記基準RFパワーよりも低い請求項9に記載の方法。
- 設定された前記堆積温度は、前記TiN結晶膜に用いられる前記基準堆積温度よりも高い請求項9に記載の方法。
- 前記Ti含有膜は、約4%から約9%の炭素を含む請求項9に記載の方法。
- 前記Ti含有膜は、フーリエ変換赤外分光光度計(FT−IR)のグラフにおいて2,000cm−1でピークを示し、1,400cm−1でほぼピークを示さない請求項9に記載の方法。
- 前記NH3フリーの反応ガスは、酸素を含まない反応ガス及び酸素を含む反応ガスを含み、前記ステップ(iv)では、前記ステップ(i)から(iii)が繰り返される場合、NH3フリーで酸素フリーの反応ガス及びNH3フリーで酸素を含む反応ガスは、設定された間隔で交互に使用される、請求項1に記載の方法。
- 前記NH3フリーで酸素フリーの反応ガスは、窒素ガスを含まない水素ガスであり、前記NH3フリーで酸素を含む反応ガスは、酸素ガスであり、それにより、設定された間隔で交互に堆積されたTiO膜及びTiN膜からなるTiON膜を形成する請求項15に記載の方法。
- 前記NH3フリーで酸素フリーの反応ガスは、水素ガス及び窒素ガスであり、前記NH3フリーで酸素を含む反応ガスは、酸素ガスであり、それにより、設定された間隔で交互に堆積されたTiO膜及びTiCN膜からなるTiOCN膜を形成する請求項15に記載の方法。
- 前記ステップ(iv)における前記Ti含有膜としてアナターゼ型の結晶を有するTiO膜を形成するように、前記ステップ(iv)の後に、酸素雰囲気で前記基板の前記Ti含有膜をアニールするステップをさらに備える請求項1に記載の方法。
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TWI625414B (zh) | 2018-06-01 |
JP6472203B2 (ja) | 2019-02-20 |
US9556516B2 (en) | 2017-01-31 |
KR20150041755A (ko) | 2015-04-17 |
US20150099072A1 (en) | 2015-04-09 |
KR102332870B1 (ko) | 2021-11-29 |
TW201527579A (zh) | 2015-07-16 |
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