JP2008182187A - 半導体デバイスにおけるDyScO材料の選択的除去 - Google Patents
半導体デバイスにおけるDyScO材料の選択的除去 Download PDFInfo
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- JP2008182187A JP2008182187A JP2007275170A JP2007275170A JP2008182187A JP 2008182187 A JP2008182187 A JP 2008182187A JP 2007275170 A JP2007275170 A JP 2007275170A JP 2007275170 A JP2007275170 A JP 2007275170A JP 2008182187 A JP2008182187 A JP 2008182187A
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- 239000000463 material Substances 0.000 title claims abstract description 154
- 239000004065 semiconductor Substances 0.000 title claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 89
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 69
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 46
- 238000000059 patterning Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 238000001039 wet etching Methods 0.000 claims description 16
- 238000003384 imaging method Methods 0.000 claims description 14
- 238000001312 dry etching Methods 0.000 claims description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 205
- 239000000460 chlorine Substances 0.000 abstract description 57
- 229910052801 chlorine Inorganic materials 0.000 abstract description 20
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052706 scandium Inorganic materials 0.000 abstract description 16
- -1 rare earth scandium oxide Chemical class 0.000 abstract description 11
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 3
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical class Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 description 26
- 238000005530 etching Methods 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000031709 bromination Effects 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910004129 HfSiO Inorganic materials 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 2
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- NJOPPKGMYWXXLJ-UHFFFAOYSA-N COCC(C)(O[Dy](OC(COC)(C)C)OC(COC)(C)C)C Chemical compound COCC(C)(O[Dy](OC(COC)(C)C)OC(COC)(C)C)C NJOPPKGMYWXXLJ-UHFFFAOYSA-N 0.000 description 1
- ABEMZNOFHMYEKL-UHFFFAOYSA-N COCC(C)(O[Sc])C Chemical compound COCC(C)(O[Sc])C ABEMZNOFHMYEKL-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical class [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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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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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28035—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
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Abstract
【解決手段】Si若しくはSiO2上で、例えば希土類スカンジウム酸化物高k材料(具体的にはDyScO3)を選択的に除去する方法を開示する。希土類元素ベースの高k材料層2の上面において、TiN及びTaNを含有する金属ゲートをパターニングするため、塩素含有ガスを使用することができる。塩化チタニウム及び塩化タンタルが揮発性であり、ウェハ上に存在する他の材料に対して適度な選択性を得ることができるからである。Dy及びScの塩化物は揮発性を有さないが、それらは水溶性を有するので、Dy及びSc含有高k材料の表面層は、Cl若しくはBr含有プラズマをさらす間に塩化物化(臭化物化)され、エッチング後ウォータリンスにより取り除くことができる。
【選択図】図3
Description
DyScO3層を原子層堆積装置(AVD(登録商標))により形成する。AVD(登録商標)は、分離した、独立のインジェクタから、パルスモードで前駆物質を導入する。DI H2O/O3溶液中で形成された薄いSiO2層上に全ての層を形成した。この処理により、約0.8nmの膜厚のSiO2層が得られ、通常これは”IMEC−クリーン”出発表面と称される。実験において、AVD(登録商標)によりDyScO層を形成するために使用される前駆物質は、Dy(mmp)3(トリス(1−メトキシ−2−メチル−2−プロポキシ)ディスプロシウム、Dy(OC(CH3)2CH2OCH3)3)及びSc(mmp)3([トリス(1−メトキシ−2−メチル−2−プロポキシ)スカンジウム、Sc(OC(CH3)2CH2OCH3)3])である。図2において、Dy/Scの比率が80/20であるDyScOについての成長曲線を示す。膜厚と注入されたパルスの全体の回数との間には、直線関係が見られる。Scパルスに対して注入されたDyの割合を変化させることにより、形成される層の組成を変更することができ、これらの前駆物質により、純粋なDy2O3から純粋なSc2O3までの範囲に及ぶ層を析出することができることが示された。Sc前駆物質の効率は、Dy前駆物質と比較して6倍以上高いことが分かった。結果として、0.86と等しい前駆物質のパルス比率[Dy/(Dy+Sc)]では、50/50の組成が得られる。5nm未満の膜厚の層について3〜5%の実効膜厚値を有する層は、原子間力顕微鏡による測定により、非常に滑らかであることが分かった。前駆物質は、0.1Mの濃度のトルエンに(安定化剤としてテトラグリムを使用して)溶解した。
原子層堆積法(AVD(登録商標))により形成されたDyScO3層を備えるウェハをラム ヴェルシス2300TCPエッチング反応炉内でエッチングした。当該炉は、プラズマのパワー及び基板のバイアスを別々に制御することができる。当該エッチングは、2つのガス、Cl2若しくはBCl3のいずれかを使用して、プラズマパワー450W、基板バイアス−30V、圧力10mTで30秒間実行した。エッチングの前及び後の当該層の厚さを分光偏光解析法により測定した。その後、当該エッチングされた層を10分間DIウォータリンスにさらし、膜厚を再び測定した。
Claims (20)
- 基板上で希土類元素含有層を少なくとも部分的に除去するための方法であって、
基板を準備する工程と、
上記基板上に上記希土類元素含有層を形成する工程と、
上記希土類元素含有層の少なくとも一部を露呈するために、感光性イメージング層を形成しマスク構造を形成する工程と、
上記の希土類元素含有層の露呈部分にCl含有及び/又はBr含有プラズマをさらし、上記の露呈される希土類元素含有層の少なくとも一部を塩化物化(臭化物化)する工程と、
上記の希土類元素含有層の塩化物化(臭化物化)された部分をウェットエッチングを用いて除去する工程と、
を備えることを特徴とする方法。 - 上記の希土類元素含有層の露呈部分にさらす工程が、異方性ドライエッチングプラズマを使用して実行されることを特徴とする請求項1記載の方法。
- 上記の希土類元素含有層の少なくとも一部の除去が、希土類元素含有層にゲート構造をパターニングすることに関連することを特徴とする請求項1記載の方法。
- 上記希土類元素含有層が高kゲート誘電体層であり、
その構造が半導体デバイスにおけるゲート構造であることを特徴とする請求項3記載の方法。 - 上記希土類元素含有層が高k誘電体層であり、
上記高k誘電体層の形成工程の後、さらに、
上記高k誘電体層上にゲート電極層を形成する工程と、
ゲート構造を形成するため、感光性イメージング層を形成し、上記感光性イメージング層にフォトリソグラフパターンを転写する工程と、
上記ゲート電極層に上記ゲート構造のパターンを転写する工程と、
を備えることを特徴とする請求項1記載の方法。 - 上記ゲート電極層がTaN、TiN、TaN/TiN層の一つであることを特徴とする請求項5記載の方法。
- 上記の希土類元素含有層の露呈部分にさらす工程が、上記のゲート電極層に上記ゲート構造を転写する工程の間に、Cl及び/又はBr含有プラズマを使用して、異方性ドライエッチングプラズマにより実行され、上記希土類元素含有層の露呈部分が塩化物化(臭化物化)されることを特徴とする請求項5記載の方法。
- 上記希土類元素含有層は、DyScO3、LaScO3、PrScO3、NdScO3、GdScO3、TbScO3、HoScO3、ErScO3、TmScO3、YbScO3、及びLuScO3の少なくとも1種から選択されるスカンジウム酸化物を含む高k材料であることを特徴とする請求項1記載の方法。
- 上記希土類元素含有層は、DyO3、LaO3、PrO3、NdO3、GdO3、TbO3、HoO3、ErO3、TmO3、YbO3、及びLuO3の少なくとも1種から選択される希土類元素酸化物を含む高k材料であることを特徴とする請求項1記載の方法。
- 上記希土類元素含有層が、DyScO3を含む高k材料層であることを特徴とする請求項1記載の方法。
- 上記Cl含有プラズマがCl2若しくはBCl3含有プラズマであることを特徴とする請求項1記載の方法。
- 上記Br含有プラズマが、Br2若しくはHBr含有プラズマであることを特徴とする請求項1〜11のいずれかに記載の方法。
- 上記の塩化物化(臭化物化)された希土類元素含有層の一部を取り除く工程の後、さらに、上記感光性イメージング層の残りの部分を除去する工程を備えることを特徴とする請求項1記載の方法。
- 上記基板が、シリコンウェハであることを特徴とする請求項1記載の方法。
- 上記ウェットエッチングが、ウォータベースのリンスにより行われることを特徴とする請求項1記載の方法。
- 上記の高k材料層の露呈部分にCl及び/又はBr含有プラズマをさらす工程の間の基板バイアスが、−30Vであることを特徴とする請求項1記載の方法。
- 上記の高k材料層の露呈部分にCl及び/又はBr含有プラズマをさらす工程の間のプラズマパワーが、100W〜1200Wの範囲にあることを特徴とする請求項1記載の方法。
- 上記の高k材料層の露呈部分にCl及び/又はBr含有プラズマをさらす工程の間のプラズマパワーが、約450Wであることを特徴とする請求項1記載の方法。
- 上記の高k材料層の露呈部分にCl及び/又はBr含有プラズマをさらす工程の間のプラズマ圧力が、最大10mT(1.333Pa)、最大80mT(10.665Pa)であることを特徴とする請求項1記載の方法。
- 半導体装置においてゲート構造をパターニングするための、請求項1に係る方法の使用。
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