JP2005109450A - 高誘電率膜の堆積のための界面層を制御するための方法 - Google Patents
高誘電率膜の堆積のための界面層を制御するための方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000008021 deposition Effects 0.000 title description 9
- 239000002243 precursor Substances 0.000 claims abstract description 45
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
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- 239000000463 material Substances 0.000 claims description 29
- 238000010926 purge Methods 0.000 claims description 29
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- 230000001590 oxidative effect Effects 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910003855 HfAlO Inorganic materials 0.000 claims description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910007875 ZrAlO Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 13
- 238000002161 passivation Methods 0.000 abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000640 hydroxylating effect Effects 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- KCKNXXPGQDHWIG-UHFFFAOYSA-N hafnium;nitric acid Chemical compound [Hf].O[N+]([O-])=O KCKNXXPGQDHWIG-UHFFFAOYSA-N 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 68
- 239000010408 film Substances 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
【解決手段】 水素パッシベーションした表面上に界面層を形成する方法が提供される。これらの方法は、界面層の形成の間、硝酸金属ベースプリカーサ(例えば、硝酸ハフニウムまたは硝酸ジルコニウム)を水酸化剤または酸化剤(例えば、水)を導入することなく組み込む原子層堆積技術を利用する。また、最初に、水素パッシベート基板の表面上に界面層を形成し、その後、1つ以上のhigh−k誘電体膜を堆積することによって、high−k膜を形成する方法が提供される。
【選択図】 図6
Description
従って、最初に、水素パッシベート表面の上にある界面層を形成することによってhigh−k材料を堆積するための方法が提供される。水素パッシベート表面は、水酸化ガス(hydrating gas)または酸化ガス(oxidizing gas)を有しないプリカーサを含む硝酸金属に晒され、このプリカーサを含む硝酸金属は、界面層が自己限界厚さであり得る所望の厚さに形成されるまで導入される。H2Oは酸化ガスまたは水酸化ガスとして作用し得るため、界面層の形成中に導入されない。
水素パッシベーションした表面上に界面層を形成する方法が提供される。これらの方法は、界面層の形成の間、硝酸金属ベースプリカーサ(例えば、硝酸ハフニウムまたは硝酸ジルコニウム)を水酸化剤または酸化剤(例えば、水)を導入することなく組み込む原子層堆積技術を利用する。また、最初に、水素パッシベート基板の表面上に界面層を形成し、その後、1つ以上のhigh−k誘電体膜を堆積することによって、high−k膜を形成する方法が提供される。
16 フィールド酸化物
20 界面層
30 high−k誘電体膜
Claims (13)
- 基板上にhigh−k誘電体膜を形成する方法であって、
a)原子層堆積チャンバ内で、半導体基板上に、水素パッシベーションした表面を提供するステップと、
b)該基板を摂氏200度未満まで加熱することによって界面層を形成し、該界面層の形成の間、水酸化ガスまたはさらなる酸化ガスを導入することなく、無水硝酸ハフニウムを該チャンバに導入するステップと、
c)該界面層上にあるhigh−k膜を形成するステップと
を包含する、方法。 - 前記基板は、シリコン表面を有する、請求項1に記載の方法。
- 前記界面層の形成の間、前記基板は、約30〜200℃の範囲内の温度まで加熱される、請求項1に記載の方法。
- 前記界面層を形成するステップは、窒素パージを用いて、無水硝酸ハフニウムをサイクルさせる、請求項1に記載の方法。
- 前記high−k膜を形成するステップは、ハフニウム含有プリカーサを前記チャンバに導入するステップと、該チャンバをパージするステップと、H2Oを該チャンバに導入するステップと、所望の膜厚が得られるまで該チャンバをパージするステップとを繰り返すステップをさらに包含する、請求項1に記載の方法。
- 前記ハフニウム含有プリカーサは、無水硝酸ハフニウム、ハフニウム塩化物、または、ハフニウム(tmhd)xである、請求項5に記載の方法。
- 前記界面層上にhigh−k膜を形成するステップは、HfCl4プリカーサを前記チャンバに導入するステップと、該チャンバをパージするステップと、Hf(NO3)4を該チャンバに導入するステップと、所望の膜厚が得られるまで該チャンバをパージするステップとを繰り返すステップをさらに包含する、請求項1に記載の方法。
- 前記high−k膜を形成するステップは、ZrO2、Gd2O3、La2O3、CeO2、TiO2、Y2O3、Ta2O5、Al2O3、HfAlOx、ZrAlOx、およびHfZrOxからなる群から選択されるhigh−k金属酸化物膜を形成する、請求項1に記載の方法。
- 前記high−k膜を形成するステップは、ZrO2、Gd2O3、La2O3、CeO2、TiO2、Y2O3、Ta2O5、Al2O3、HfAlOx、ZrAlOx、およびHfZrOxからなる群から選択される金属酸化物膜の交互の層を含む多層膜を形成する、請求項1に記載の方法。
- 基板上にhigh−k誘電体膜を形成する方法であって、
a)原子層堆積チャンバ内で、半導体基板上に、水素パッシベーションした表面を提供するステップと、
b)該水素パッシベーションした表面を、硝酸金属含有プリカーサに、該プリカーサの熱分解温度未満の温度で、水酸化ガスまたは酸化ガスなしに、晒して、自己限界high−k界面層を生成するステップと、
c)該表面を金属含有プリカーサに晒すステップ、該チャンバをパージするステップ、該表面を水酸化ガス、酸化ガスまたはプリカーサに晒すステップ、ならびにパージするステップを繰り返して、さらなるhigh−k材料を堆積するステップと、
を包含する、方法。 - 前記硝酸金属含有プリカーサは、化学式M(NO3)xを有し、ここで、MはHf、Zr、Gd、La、Ce、Ti、Y、Ta、およびAlからなる群から選択される金属であり、xはMの価数である、請求項10に記載の方法。
- 前記さらなるhigh−k材料は、前記界面層と同じ材料である、請求項10に記載の方法。
- 前記さらなるhigh−k材料は、前記界面層と異なる、請求項10に記載の方法。
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KR20220076343A (ko) | 2020-11-30 | 2022-06-08 | 에이에스엠 아이피 홀딩 비.브이. | 기판 처리 장치의 반응 챔버 내에 배열되도록 구성된 인젝터 |
CN114639631A (zh) | 2020-12-16 | 2022-06-17 | Asm Ip私人控股有限公司 | 跳动和摆动测量固定装置 |
TW202231903A (zh) | 2020-12-22 | 2022-08-16 | 荷蘭商Asm Ip私人控股有限公司 | 過渡金屬沉積方法、過渡金屬層、用於沉積過渡金屬於基板上的沉積總成 |
USD980814S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas distributor for substrate processing apparatus |
USD981973S1 (en) | 2021-05-11 | 2023-03-28 | Asm Ip Holding B.V. | Reactor wall for substrate processing apparatus |
USD980813S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas flow control plate for substrate processing apparatus |
USD1023959S1 (en) | 2021-05-11 | 2024-04-23 | Asm Ip Holding B.V. | Electrode for substrate processing apparatus |
USD990441S1 (en) | 2021-09-07 | 2023-06-27 | Asm Ip Holding B.V. | Gas flow control plate |
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US6020243A (en) * | 1997-07-24 | 2000-02-01 | Texas Instruments Incorporated | Zirconium and/or hafnium silicon-oxynitride gate dielectric |
US6620713B2 (en) * | 2002-01-02 | 2003-09-16 | Intel Corporation | Interfacial layer for gate electrode and high-k dielectric layer and methods of fabrication |
US6750066B1 (en) * | 2002-04-08 | 2004-06-15 | Advanced Micro Devices, Inc. | Precision high-K intergate dielectric layer |
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