CN111630204A - 使用双(烷基芳烃)钼前体的钼气相沉积 - Google Patents
使用双(烷基芳烃)钼前体的钼气相沉积 Download PDFInfo
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- CN111630204A CN111630204A CN201980009112.4A CN201980009112A CN111630204A CN 111630204 A CN111630204 A CN 111630204A CN 201980009112 A CN201980009112 A CN 201980009112A CN 111630204 A CN111630204 A CN 111630204A
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- molybdenum
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- carbide
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 178
- 239000011733 molybdenum Substances 0.000 title claims abstract description 172
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000002243 precursor Substances 0.000 title claims abstract description 78
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 96
- 238000000151 deposition Methods 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 35
- ZEMJULNQFSGMTN-UHFFFAOYSA-N ethylbenzene;molybdenum Chemical compound [Mo].CCC1=CC=CC=C1.CCC1=CC=CC=C1 ZEMJULNQFSGMTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims description 55
- 229910039444 MoC Inorganic materials 0.000 claims description 45
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 43
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- -1 molybdenum halide Chemical class 0.000 claims description 11
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical compound C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 claims description 6
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 3
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 14
- 238000000231 atomic layer deposition Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000004377 microelectronic Methods 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000005137 deposition process Methods 0.000 description 5
- 239000005078 molybdenum compound Substances 0.000 description 5
- 150000002752 molybdenum compounds Chemical class 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 229910015255 MoF6 Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910015686 MoOCl4 Inorganic materials 0.000 description 2
- 150000004996 alkyl benzenes Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910015221 MoCl5 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- RLCOZMCCEKDUPY-UHFFFAOYSA-H molybdenum hexafluoride Chemical compound F[Mo](F)(F)(F)(F)F RLCOZMCCEKDUPY-UHFFFAOYSA-H 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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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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Abstract
本发明描述通过使用双(烷基芳烃)钼作为用于这类沉积的前体将钼材料沉积到衬底上的气相沉积方法,所述双(烷基芳烃)钼在本文中又称为(烷基芳烃)2Mo,例如双(乙基苯)钼((EtBz)2Mo);以及含有所沉积材料的结构。
Description
相关申请案的交叉引用
本申请案要求2018年1月19日申请的美国临时专利申请案第62/619,363号在35USC 119下的权益,出于所有目的,所述申请案的公开内容特此以全文引用的方式并入本文中。
技术领域
本发明涉及通过使用双(烷基芳烃)钼将含钼材料沉积到衬底上的气相沉积方法,所述双(烷基芳烃)钼本文中又称为(烷基芳烃)2Mo,例如双(乙基苯)钼((EtBz)2Mo),作为用于这类沉积的前体。
背景技术
半导体及微电子装置及制备这些装置的方法与用于例如电极、通孔、势垒层、互连件、晶种层及各种其它结构的装置结构中的金属及含金属材料有关。在制造期间,金属或含金属材料通过沉积,意谓例如通过原子层沉积、化学气相沉积或其修改或衍生物放置到装置上。将沉积材料以“前体”形式提供到沉积工艺,沉积材料可为当在恰当条件下蒸发且暴露于衬底时将单独或与另一材料组合沉积到衬底上的无机或有机金属试剂。
通常用于传导结构的一种金属为钨。根据沉积钨的常用方法,将六氟化钨(WF6)用作衍生沉积钨的前体。通过使用六氟化钨沉积的钨的不足之处在于氟与氢(H2)反应以形成氟化氢(HF),其可例如通过引起对硅晶片的蚀刻而对衬底有害。
钼为已用于微电子装置中例如作为钨的替代物的低电阻率耐火金属。钼具有高熔点、高热导率、低热膨胀系数及低电阻率。钼已用作或提议用作扩散势垒、电极、光屏蔽、互连件,或用作低电阻率栅极结构。钼为用于替换内存芯片、逻辑芯片及包含多晶硅-金属栅极电极结构的其它装置中所用的钨的候选物。含有钼的薄膜也可用于一些有机发光二极管、液晶显示器,以及薄膜太阳电池及光伏打装置中。
各种前体材料及气相沉积技术已用于将金属材料沉积到微电子装置衬底上。沉积技术可包含化学气相沉积(CVD)及原子层沉积(ALD)以及这些工艺的多种修改,例如UV激光光离解CVD、等离子体辅助CVD及等离子体辅助ALD。CVD及ALD工艺正愈来愈多地用于微电子行业中,这是由于这些方法可允许高度非平面微电子装置几何结构上的极佳保形步阶式覆盖。
半导体及微电子行业中的研究人员不断探索用于将金属沉积到衬底上以提供适用金属或含金属层及结构的改进材料及方法。目前,研究人员对避开六氟化钨的方法及材料感兴趣,包含使用除钨以外的金属,例如钼。已描述适用于钼的化学气相沉积的一些材料及技术。参见例如国际专利公开案WO2017/143246(PCT/US2017/018455)。研究工作仍继续朝着以下进行:鉴别用于将钼沉积到微电子装置衬底上的气相沉积方法中的其它适用材料及技术。
发明内容
根据以下描述,申请人已确定钼材料可通过使用双(烷基芳烃)钼化合物作为沉积工艺中的钼前体来沉积到微电子衬底表面上,双(烷基芳烃)钼化合物在本文中又称为(烷基芳烃)2Mo,例如双(乙基苯)钼((EtBz)2Mo)。钼可以将适用作微电子装置衬底的部分,例如适用作含有钼以及另一材料(例如,碳,以形成碳化钼)的晶种层,或适用作导电块体钼结构(即,元素钼)的任何形式或结构沉积。
其它处于开发中的可能钼前体(例如卤化钼及卤氧化钼前体)已展示为可有效地沉积具有极低电阻率的极高纯度金属钼膜。然而,已发现使用这些前体使金属钼膜成核于氮化钛或其它所需衬底表面上可能受限。将改进金属钼于衬底上的成核的来从卤化钼及卤氧化钼前体的晶种层或晶核层将期望有助于这些前体用于沉积具有极低电阻率的极高纯度金属钼膜的用途。
根据所描述的气相沉积方法,可通过使衬底与来源于(烷基芳烃)2Mo,例如(EtBz)2Mo的蒸气在气相沉积条件下接触而将钼材料沉积到衬底表面上。在特定实施例中,沉积的钼材料为沉积为晶种层的碳化钼,块体(元素)钼的后续层涂覆到所述晶种层上。使用(EtBz)2Mo前体沉积的碳化钼晶种层可在相对较低温度(例如低于300摄氏度,或低于250摄氏度或270摄氏度)下涂覆,其中所述碳化钼晶种层在涂覆到三维结构时具有良好保形性。根据实例结构及方法,可将碳化钼涂覆到三维衬底的氮化钛表面作为在通过使用卤化物前体沉积元素钼的后续步骤期间向氮化钛材料提供呈抗蚀刻性形式的保护的晶种层。使用(EtBz)2Mo前体涂覆的碳化钼晶种层在沉积元素钼的后续(下一个)步骤期间同样允许相对较低或降低的温度,这导致复杂结构(例如高纵横比三维结构或开口,例如通孔或互连件)的经改进保形填充。举例来说,在沉积金属钼的后续步骤期间衬底温度可为至少50摄氏度,低于将金属钼沉积到不包含碳化钼晶种层的衬底上所需的温度。
根据在三维衬底上制备保形钼涂层的一个实例方法(其中所述衬底含有氮化钛表面),通过使用(EtBz)2Mo前体将碳化钼晶种层沉积到氮化钛表面上。在以下步骤中,通过使用任何所需或适用前体(例如MoOCl4、MoCl5或MoF6)将块体(元素)钼涂覆到晶种层。可在低于300摄氏度或低于250摄氏度或270摄氏度的沉积温度(即,衬底温度)下进行沉积晶种层的步骤。尽管必要时可使用较高温度,但仍可在低于500摄氏度或低于450摄氏度的沉积温度(即,衬底温度)下进行沉积块体(元素)钼的步骤。即使在涂覆到高度三维表面(例如高纵横比表面)时,晶种层及块体(元素)钼层仍呈现良好的均一性及保形性。
如本文中所使用,“气相沉积”工艺是指任何类型的气相沉积技术,例如CVD或ALD。在各种实施例中,CVD可采取常规(即,连续流动)CVD、液体注入CVD或光辅助CVD的形式。CVD也可采取脉冲技术,即,脉冲CVD的形式。在其它实施例中,ALD可采取常规(例如,脉冲注入)ALD、专用ALD、液体注入ALD、光辅助ALD或等离子体辅助ALD的形式。
在一个方面,本发明涉及一种在衬底上形成含钼材料的方法。所述方法包含在气相沉积条件下使衬底与双(烷基芳烃)钼(即,(烷基芳烃)2Mo)蒸气接触以将含钼材料沉积于衬底上。
附图说明
图1说明来自MoOCl4的钼于具有各种表面组合物(包含如所描述的碳化钼的一个表面)的衬底上的沉积速率的比较。
图2说明在气相沉积期间钼(来自双(乙基苯)钼)在各种温度及压力条件下的沉积速率。
具体实施方式
以下描述涉及适用于通过使用双(烷基芳烃)钼化合物作为钼前体将呈各种形式的钼沉积到衬底上的气相沉积方法。双(烷基芳烃)钼化合物(络合物)在本文中又称为(烷基芳烃)2Mo化合物。发现适用作前体的这类化合物的物种的一个实例为双(乙基苯)钼(即,(EtBz)2Mo)。前体可用于气相沉积(例如,化学气相沉积)工艺中,以将钼以任何形式沉积到衬底上,例如作为含有钼的化合物或混合物,例如呈碳化钼晶种层形式;作为呈导电结构形式的元素钼;或作为含有钼的另一沉积材料。
化学气相沉积(CVD)通常为化学材料(衍生自“前体”)任选地与一或多种其它材料(例如共反应物)组合在将使得蒸气组分在衬底表面上形成材料薄膜的条件下作为蒸气引入到衬底的化学工艺。
必要或需要时,将例如还原气体(在本文中称为“反应气体”),例如氢的共反应物连同前体引入到沉积腔室中以促进钼以所需形式沉积。提供到沉积腔室的反应气体的量(即,流动速率)可视需要且可有效地产生沉积于衬底表面处的所需形式的钼材料,其中与沉积工艺的其它参数组合选择特定沉积工艺的流动速率,其它参数例如前体的流动速率、衬底温度及腔室压力。
根据本说明书,钼前体连同任选的反应气体可放置于含有衬底的沉积腔室中,以实现钼于衬底上的气相沉积。沉积腔室的条件将使得来自前体的钼以所需形式及量沉积到衬底上。举例来说,作为反应气体的氢及钼前体可以使得衍生自钼前体的钼沉积到衬底表面上的方式组合(例如,反应)。在某些实例方法中,钼前体可通过引起碳化钼(即,具有Mo2C或MoC的结晶学结构的钼及碳)沉积的反应与氢反应气体组合。在其它实例方法中,钼前体可通过引起元素(金属)钼(即,具有Mo的晶体结构的钼)沉积的反应与氢反应气体组合。
通常,可通过使用载体气体将作为蒸气的前体载送到沉积腔室,载体气体可为惰性气体,例如氦气、氩气、氮气、氖气、氙气、氪气或其组合。载体气体可通过含有一定量的例如呈液体形式的前体的密闭容器(例如,密闭容器或“安瓿”)。随着载体气体通过容器,前体蒸气由载体气体载送,且可将组合(“载体气体-前体混合物”提供到沉积腔室。递送到沉积腔室的载体气体-前体混合物可包括以下、由以下组成或基本上由以下组成:载体气体及前体(作为蒸气)。
如所描述的工艺的其上沉积钼的衬底可为具有三维或二维表面的任何衬底,例如二维或三维微电子或半导体装置。根据某些当前适用方法,如所描述的实例方法可尤其适用于将钼涂覆到三维衬底表面上,包含涂布衬底表面,或填充高纵横比三维开口。在实例方法中,可将钼作为碳化钼的电导晶种层沉积到三维衬底上。可衍生自任何前体,优选地衍生自卤化钼或卤氧化钼前体的元素(金属)钼可接着作为呈导电结构形式的元素(金属)钼沉积到晶种层上。
本文中所描述的前体化合物双(烷基芳烃)钼化合物(或“络合物”)(在本文中又称为(烷基芳烃)2Mo)属于又称为双(η6-芳烃)钼络合物的一类化合物,其包含在络合物的芳基(例如,苯)上具有烷基取代基的化合物。这些络合物的实例可通过已知方法合成,已知方法包含使双(η6-苯)钼的芳烃配体复分解以及其它技术。参见:通过芳烃复分解合成双(η6-烷基苯)钼(Synthesis of Bis(η6-alkylbenzene)molybdenum by Arene Metathesis),Victor S.Asirvatham及Michael T.Ashby,《有机金属(Organometallics)》,2001,20(8),第1687-1688页,DOI:10.1021/om001010b,公开日期(网络):2001年3月15日。
这些前体化合物可表示为具有包含以下的结构:在钼原子的第一侧面上与钼原子相结合的第一经取代芳基(例如,烷基苯)以及在同一钼原子的第二侧面上与所述钼原子相结合的第二经取代芳基(例如,烷基苯)。所述化合物或络合物包含围绕在两个烷基经取代芳烃化合物的相对侧上的单个钼原子。具有一个位于两个经取代芳烃化合物之间的钼原子的化合物有时称为“夹层”结构:
芳烃(R)-Mo-芳烃(R)
各芳烃化合物可经相同或不同烷基R取代。举例来说,各烷基(R)可独立地为甲基、乙基、丙基、丁基等,且可为分支链的或直链的。一个实例前体为双(乙基苯)钼(即,(EtBz)2Mo):
这种化合物以适用作如所描述的前体的量及形式(即,具有纯度)市售。
在某些当前优选实例方法中,前体可沉积到衬底上以形成碳化钼的晶种层。晶种层为含有钼(例如碳化钼)且可有效地促进块体金属导电钼层于衬底上的后续沉积的层。晶种层在块体钼材料(例如,元素(金属)钼)将沉积到其上的衬底的整个表面上应为连续的,且应允许钼大块沉积的后续步骤覆盖或填充衬底的整个表面,优选地与块体钼在不存在晶种层的情况下于下层衬底上的沉积相比,允许在较低沉积温度下或以更优选质量成核且覆盖。
优选晶种层的厚度可为5到100埃,例如5或6埃到30、40或50埃。
优选的碳化钼晶种层可包括以下、由以下组成或基本上由以下组成:原子比在1:99到60:40,例如4:96到40:60(碳:钼)范围内的钼及碳。基本上由碳及钼组成的晶种层是指含有不超过1百分比(原子),例如不超过0.5、0.1或0.01百分比(原子)的除碳及钼以外的任何材料的晶种层。与金属钼相反,碳化钼晶种层将含有大量呈Mo2C、MoC或两者的形式的钼及碳。
碳化钼晶种层沉积于其上的衬底可为任何衬底,例如如本文中所描述,作为一个特定实例,包含具有氮化钛表面的三维衬底。
如所描述的方法可在以下沉积腔室中进行:在使用期间基本上仅含有气态前体、任选的载体气体、额外的惰性气体及一或多种反应气体,例如,沉积腔室内部可供应有及含有包括以下、由以下组成或基本上由以下组成的气氛:气态前体、任选的载体气体及反应气体。出于本发明的目的,认为基本上由气态材料(例如,前体蒸气、任选的载体气体及反应气体)的指定组合组成的沉积腔室或相关气流或气流组合含有气态材料的指定组合及不超过非显著量的任何其它气态材料,例如不超过5、2、1、0.5、0.1、0.05百分比(按质量计)的任何其它气态材料。
供应到沉积腔室的气态前体(又称为前体蒸气)的量及反应气体的量可为各自将适用于将所需量的钼及钼组合物(例如以碳化钼形式)沉积到衬底表面上的量。就两种气体的相应流速来说,可基于包含以下的因素选择所述两种气体的量及相对量:沉积晶种层的所需形式及组合物、衬底性质(例如,形状)、所需沉积速率、衬底温度、沉积腔室的大小(容积)及沉积腔室的内部压力。
根据已鉴别为适用的某些方法的非限制性实例,钼前体的流动速率可在2到20微摩尔/分钟的范围内,这速率是基于容积在2,000到20,000立方厘米范围内的沉积腔室,且在10到50托范围内的内部压力下操作。与这些值及其它参数一致,前体蒸气可以任何适用或所需浓度(例如在80到25,000百万分率(ppm)范围内)包括于如所描述的载体气体中。
根据已鉴别为适用的某些方法的非限制性实例,例如氢的反应气体的流动速率可在8,000到25,000微摩尔/分钟的范围内,这速率是基于容积在2,000到20,000立方厘米范围内的沉积腔室,且在10到50托范围内的内部压力下操作。
沉积腔室的内部压力可为对钼沉积为晶种层有效的内部压力。通常,用于化学气相沉积的沉积腔室在低于环境压力,例如低于或远低于760托的压力下操作。用于沉积碳化钼晶种层的本说明书的适用或优选方法可在基本上低于大气压,例如低于约200托的沉积腔室压力,例如不超过50、80或100托,例如在5、10或15最多20、30、40或50托范围内的压力下进行。
在沉积期间,衬底可保持在能有效将碳化钼作为晶种层沉积到衬底上的任何温度下。根据特定实例方法,可通过使用期望或有利的低沉积温度将钼作为碳化钼晶种层沉积到衬底上。在沉积碳化钼晶种层的步骤期间,适用或优选的衬底温度的实例可在150℃到400℃范围内,或在200℃到300℃范围内,优选不超过250℃或270℃的温度。
申请人已确定使用双(烷基芳烃)钼前体,例如双(乙基苯)钼沉积的碳化钼晶种层的存在,允许在将元素钼沉积到晶种层上的步骤期间有效或有利地进一步处理衬底。在特定方法中,将元素钼沉积到晶种层上的步骤可在期望或有利的低温下进行,所述晶种层是使用双(烷基芳烃)钼前体,例如双(乙基苯)钼进行沉积。因此,元素钼的沉积层在沉积到三维衬底表面上时可具有期望或有利的保形性,以及元素钼结构的其它所需功能特性,包含低电阻率及良好均一性。
因此,根据如所描述的使用含有双(乙基苯)钼(例如,(EtBz)2Mo)的前体沉积碳化钼晶种层的方法,在将晶种层沉积到衬底上之后,可将元素钼沉积到所述晶种层上。术语元素钼是指具有金属结构的钼;元素(金属)钼例如在不超过5、3、2或1原子百分比下是导电的但可包含非钼,例如碳。
可通过使用任何钼前体,例如双(乙基芳烃)钼前体(例如,(EtBz)2Mo),或发现适用于沉积钼的另一钼前体来沉积元素钼。其它前体的实例包含卤化钼及卤氧化钼前体,例如五氯化钼(MoCl5)、四氯氧化钼(MoOCl4)及六氟化钼(MoF6)。卤化物及卤氧化物前体已展示为尤其适用于沉积具有极低电阻率的极高纯度金属钼膜。然而,Mo金属膜于TiN或其它所需衬底表面上的成核可能会受限。因此,如所描述的晶种层可作为允许通过使用卤化钼或卤氧化钼前体进行元素钼的经改进沉积的有效手段。
沉积的元素钼可呈金属形式,且可具有高纯度或极高纯度,例如至少95、98、99、99.5、99.9或99.99百分比(原子)钼或更高。一定量的非钼材料(即,沉积的元素钼层中的一般杂质)对于全部此类非钼杂质可优选的低于5、2、1、0.5、0.1或0.01百分比(原子)。例如氢、氯、氧、氮碳及氟的特定杂质可优选地以低于l×1020个原子每立方厘米的沉积钼(对于氢及氯),例如低于l×1021个原子每立方厘米的沉积钼(对于氧及碳)的含量存在。
实例方法可通过使用卤化钼或卤氧化钼前体,例如五氯化钼(MoCl5)、四氯氧化钼(MoOCl4)及六氟化钼(MoF6)将元素(金属)钼沉积到如所描述的由双(烷基芳烃)钼前体涂覆的碳化钼晶种层上。元素(金属)钼可通过使用卤化钼或卤氧化钼前体在低于800摄氏度、700摄氏度或500摄氏度,例如低于450摄氏度或低于400摄氏度的沉积温度(即,衬底温度)下涂覆。
沉积元素钼层可具有低电阻率,例如不超过20μΩ·cm或不超过15μΩ·cm的电阻率,其中钼膜的厚度为40纳米。
沉积的元素钼层可具有任何所需厚度,例如在30到500埃或40到400埃范围内的厚度。
在所描述方法的各种实例实施例中,通过在存在载体气体及氢气作为反应气体的情况下在使得钼沉积为碳化钼势垒层的条件下使衬底表面与双(乙基苯)钼接触而将钼作为晶种层沉积到含有氮化钛的衬底的三维(例如,高纵横比)表面上。在晶种层沉积期间的沉积温度(即,在沉积期间的衬底温度)可低于约300摄氏度、270摄氏度或250摄氏度。
在以下步骤中,通过使用例如MoOCl4、MoOCl5或MoF6的前体的沉积工艺在晶种层上方将钼沉积到衬底表面上。有利地,将元素钼沉积到衍生自双(乙基苯)钼的晶种层上的步骤可在有利的低工艺(衬底)温度及有效沉积速率下进行,具有所需或有利的结果(例如,元素钼的保形性)。
举例来说,图1展示元素钼沉积到三个衬底上的步骤的沉积速率的比较,一个衬底具有无晶核层的TiN表面,一个衬底具有使用B2H6前体沉积到氮化钛上作为晶核层的硼(B)表面,且一个衬底具有通过使用双(乙基苯)钼作为前体沉积于氮化钛上方作为晶种层的碳化钼表面。与具有TiN表面的衬底相比,及与具有硼表面作为晶核层的衬底相比,包含通过使用双(乙基苯)钼前体沉积的碳化钼晶种层的衬底允许元素钼在相对较低温度下的有效沉积速率。
图2展示在各种压力及温度条件下将碳化钼作为晶种层沉积到具有氮化钛表面的衬底上产生一系列沉积速率的工艺实例。在10到30托之间的压力及在200摄氏度与300摄氏度之间的温度展示为有效的,其中30托及200摄氏度的组合尤其适用于保形碳化钼晶种层沉积。在较低温度下沉积的膜具有特别良好的保形性。在较高温度下沉积的膜并未呈现相同有利的保形性,但仍可适用作不太复杂的不难覆盖整个表面的结构上的晶种层。
大体而言,如本文中所描述,使用双(烷基芳烃)钼化合物(例如,(EtBz)2Mo)沉积的钼可沉积到任何所需衬底表面(例如半导体或微电子装置衬底的表面)上,且可适于作为装置的部分执行任何有效功能或便于处理装置。使用如所描述的前体沉积的钼的功能的实例包含:作为晶核或“晶种”层、作为势垒层或作为导电层(例如,作为互连件或“通孔”),以及其它。所沉积的钼可具有例如可有效执行所需功能的组成及厚度的特征。
使用如所描述的前体将呈各种形式的钼沉积到其上的衬底及表面的实例包含任何二维或三维结构,其中特定实例包含微电子装置衬底,例如DRAM装置、3D NAND装置或三维表面具有高纵横比的另一装置。在特定实例中,可通过使用如本文中所描述的前体作为晶种层在三维表面(例如,涂布有氮化钛)上沉积钼,接着使用任何前体在晶种层上沉积元素元素钼。衬底可包含高纵横比开口,例如通孔,其中首先涂覆碳化钼晶种层,接着用元素钼填充开口。举例来说,开口可具有在2:1到200:1,例如5:1到100:1或20:1到30:1范围内的纵向与横向尺寸的纵横比。替代地,3D NAND装置衬底的表面可包含由槽孔分离的经氮化钛涂布的竖直壁,所述壁包含水平延伸的肋及凹部,且所述方法可包含在肋及凹部的氮化钛表面上方形成碳化钼晶种层的均一及保形层(或“膜”),接着在晶种层上方沉积元素钼。通过特定实例方法,可使用例如MoOCl4、MoOCl5或MoF6的前体沉积元素钼以提供具有良好、适用或有利保形性的元素钼层。
根据如所描述的方法的某些适用或当前优选实施例,对于将碳化钼作为双(烷基芳烃)钼前体的晶种层沉积到衬底表面上,适用(非限制性)工艺参数包含以下各者(视整体工艺特征而定,由于如本文通常所描述的方法能够在以超出规定范围的这些参数值操作时使用,因此将指定值称为非限制性的):
传递到沉积腔室中的钼前体蒸气的温度:100摄氏度到140摄氏度;
衬底温度:低于300摄氏度,例如200摄氏度到250摄氏度或270摄氏度;
在沉积步骤期间的沉积腔室压力:10到50托,例如10到20托;
前体-载体气体混合物的流动速率:20到100sccm(标准立方厘米/分钟);
反应气体(例如,氢气)的流动速率:100到1,000sccm。
在这些实例方法中,在沉积晶种层之后,可使用例如MoOCl4、MoOCl5或MoF6的前体将元素钼沉积到晶种层上。适用(非限制性)工艺参数的实例包含以下各者(视整体工艺特征而定,由于如本文通常所描述的方法能够在以超出规定范围的这些参数值操作时使用,因此将指定值称为非限制性的):
传递到沉积腔室中的钼前体的温度:30摄氏度到100摄氏度;
平台(衬底)温度:300摄氏度到800摄氏度;
在沉积步骤期间的沉积腔室压力:10到100托,例如20到80托;
前体-载体气体混合物的流动速率:20到1000sccm;
反应气体(例如,氢气)的流动速率:500到5,000sccm。
Claims (19)
1.一种在衬底上形成含钼材料的方法,所述方法包括使所述衬底与双(烷基芳烃)钼蒸气在气相沉积条件下接触以将含钼材料沉积到所述衬底上。
2.根据权利要求1所述的方法,其中所述双(烷基芳烃)钼为双(乙基苯)钼((EtBz)2Mo)。
3.根据权利要求1所述的方法,其中所述含钼材料为碳化钼。
4.根据权利要求3所述的方法,其包括在不大于300摄氏度的衬底温度下通过化学气相沉积将所述碳化钼沉积到所述衬底上。
5.根据权利要求3所述的方法,其包括在具有10与50托之间的内部压力的沉积腔室中将所述碳化钼沉积到所述衬底上。
6.根据权利要求3所述的方法,其包括将所述碳化钼沉积为厚度在6到100埃范围内的晶种层。
7.根据权利要求3所述的方法,其中所述碳化钼包括呈1:99到60:40(碳:钼)原子比的碳及钼。
8.根据权利要求3所述的方法,其中所述碳化钼沉积到包含氮化钛的所述衬底的表面上。
9.根据权利要求3所述的方法,其中所述碳化钼沉积到所述衬底的三维表面上。
10.根据权利要求9所述的方法,其中所述三维表面为包括由槽孔分离的竖直壁的3DNAND的特征,所述壁包含水平延伸的肋及凹部,且所述方法可包括在肋及凹部的表面上方沉积钼层。
11.根据权利要求9所述的方法,其中所述三维表面包含纵向与横向尺寸的纵横比在2:1到200:1范围内的开口。
12.根据权利要求3所述的方法,其包括将金属钼沉积到所述碳化钼上。
13.根据权利要求12所述的方法,其中所述金属钼衍生自卤化钼前体或卤氧化钼前体。
14.根据权利要求12所述的方法,其中所述金属钼衍生自选自五氯化钼(MoCl5)、四氯氧化钼(MoOCl4)及六氟化钼(MoF6)的前体。
15.根据权利要求12所述的方法,其包括在至少50摄氏度的衬底温度下通过化学气相沉积将所述金属钼沉积到所述衬底上,所述衬底温度小于将元素钼沉积到不包含所述碳化钼的衬底上所需要的温度。
16.根据权利要求12所述的方法,其中所述金属钼具有至少50埃的厚度。
17.根据权利要求1所述的方法,其中所述含钼材料为金属钼。
18.根据权利要求17所述的方法,其包括以至少50埃的厚度沉积元素钼。
19.一种衬底,其包括:
碳化钼晶种层,其沉积到氮化钛上,所述碳化钼晶种层衍生自双(烷基芳烃)钼前体,及
金属钼,其沉积于所述晶种层上,所述金属钼衍生自卤化钼前体或卤氧化钼前体。
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CN111630204B (zh) | 2023-05-23 |
TW201932637A (zh) | 2019-08-16 |
US11560625B2 (en) | 2023-01-24 |
TW202212610A (zh) | 2022-04-01 |
JP7203111B2 (ja) | 2023-01-12 |
TWI830083B (zh) | 2024-01-21 |
TWI748153B (zh) | 2021-12-01 |
KR20200091469A (ko) | 2020-07-30 |
KR20230008894A (ko) | 2023-01-16 |
US20190226086A1 (en) | 2019-07-25 |
WO2019143632A1 (en) | 2019-07-25 |
US20230128330A1 (en) | 2023-04-27 |
EP3740600A4 (en) | 2022-01-26 |
JP2021510770A (ja) | 2021-04-30 |
EP3740600A1 (en) | 2020-11-25 |
KR102622565B1 (ko) | 2024-01-10 |
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