TW201932637A - 使用雙(烷基芳烴)鉬前驅物之鉬蒸氣沉積 - Google Patents
使用雙(烷基芳烴)鉬前驅物之鉬蒸氣沉積 Download PDFInfo
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- TW201932637A TW201932637A TW108102107A TW108102107A TW201932637A TW 201932637 A TW201932637 A TW 201932637A TW 108102107 A TW108102107 A TW 108102107A TW 108102107 A TW108102107 A TW 108102107A TW 201932637 A TW201932637 A TW 201932637A
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- molybdenum
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 174
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000011733 molybdenum Substances 0.000 title claims abstract description 168
- 239000002243 precursor Substances 0.000 title claims abstract description 80
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 88
- 239000000758 substrate Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910039444 MoC Inorganic materials 0.000 claims description 40
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 13
- -1 molybdenum halide Chemical class 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910015275 MoF 6 Inorganic materials 0.000 claims description 7
- 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 3
- CNRRZWMERIANGJ-UHFFFAOYSA-N chloro hypochlorite;molybdenum Chemical compound [Mo].ClOCl CNRRZWMERIANGJ-UHFFFAOYSA-N 0.000 claims description 2
- ZGHDMISTQPRNRG-UHFFFAOYSA-N dimolybdenum Chemical compound [Mo]#[Mo] ZGHDMISTQPRNRG-UHFFFAOYSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 62
- ZEMJULNQFSGMTN-UHFFFAOYSA-N ethylbenzene;molybdenum Chemical compound [Mo].CCC1=CC=CC=C1.CCC1=CC=CC=C1 ZEMJULNQFSGMTN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000000231 atomic layer deposition Methods 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 12
- 238000004377 microelectronic Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- 239000005078 molybdenum compound Substances 0.000 description 6
- 150000002752 molybdenum compounds Chemical class 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 238000005137 deposition process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 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
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- FNQLUENNOIHEFE-UHFFFAOYSA-N CCC(C=CC=C1)=C1[Mo]C1=C(CC)C=CC=C1 Chemical group CCC(C=CC=C1)=C1[Mo]C1=C(CC)C=CC=C1 FNQLUENNOIHEFE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method 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
- UTMHHUFPABSAHZ-UHFFFAOYSA-N ethylbenzene molybdenum Chemical compound [Mo].CCC1=CC=CC=C1 UTMHHUFPABSAHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 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
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 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
- 238000005121 nitriding Methods 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
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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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- 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
- C23C16/06—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 deposition of metallic material
- C23C16/18—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 deposition of metallic material from metallo-organic compounds
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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
- 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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- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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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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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
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- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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Abstract
本發明描述藉由使用雙(烷基芳烴)鉬將鉬材料沉積至基板上之蒸氣沉積方法,以及含有該沉積材料之結構,該雙(烷基芳烴)鉬在本文中亦稱為(烷基芳烴)2
Mo,例如雙(乙基苯)鉬((EtBz)2
Mo),作為用於此類沉積之前驅物。
Description
本發明係關於藉由使用雙(烷基芳烴)鉬將含鉬材料沉積至基板上之蒸氣沉積方法,該雙(烷基芳烴)鉬本文中亦稱為(烷基芳烴)2
Mo,例如雙(乙基苯)鉬((EtBz)2
Mo),作為用於此類沉積之前驅物。
半導體及微電子裝置及製備此等裝置之方法與用於諸如電極、通孔、障壁層、互連件、晶種層及各種其他結構之裝置結構中的金屬及含金屬材料有關。在製造期間,金屬或含金屬材料藉由沉積,意謂例如藉由原子層沉積、化學蒸氣沉積或其修改或衍生物置放至裝置上。將經沉積材料以「前驅物」形式提供至沉積製程,該經沉積材料可為當在恰當條件下蒸發且暴露於基板時將單獨或與另一材料組合沉積至基板上之無機或有機金屬試劑。
通常用於傳導結構的一種金屬為鎢。根據沉積鎢之常用方法,將六氟化鎢(WF6
)用作自其衍生經沉積鎢之前驅物。藉由使用六氟化鎢沉積之鎢的不足之處在於氟與氫(H2
)反應以形成氟化氫(HF),其可例如藉由引起對矽晶圓之蝕刻而對基板有害。
鉬為已用於微電子裝置中例如作為鎢之替代物的低電阻率耐火金屬。鉬具有高熔點、高熱導率、低熱膨脹係數及低電阻率。鉬已用作或提議用作擴散障壁、電極、光遮罩、互連件,或用作低電阻率閘極結構。鉬為用於替換記憶體晶片、邏輯晶片及包括多晶矽-金屬閘極電極結構之其他裝置中所用的鎢之候選物。含有鉬之薄膜亦可用於一些有機發光二極體、液晶顯示器,以及薄膜太陽電池及光伏打裝置中。
各種前驅物材料及蒸氣沉積技術已用於將金屬材料沉積至微電子裝置基板上。沉積技術可包括化學蒸氣沉積(CVD)及原子層沉積(ALD)以及此等製程之多種修改,諸如UV雷射光離解CVD、電漿輔助CVD及電漿輔助ALD。CVD及ALD製程正愈來愈多地用於微電子行業中,此係由於此等方法可允許高度非平面微電子裝置幾何結構上之極佳保形步階式覆蓋。
半導體及微電子行業中之研究人員不斷探索用於將金屬沉積至基板上以提供適用金屬或含金屬層及結構之改良材料及方法。目前,研究人員對避開六氟化鎢之方法及材料感興趣,包括使用除鎢以外的金屬,例如鉬。已描述適用於鉬之化學蒸氣沉積的一些材料及技術。參見例如國際專利公開案WO2017/143246 (PCT/US2017/018455)。研究工作仍繼續朝著以下進行:鑑別用於將鉬沉積至微電子裝置基板上之蒸氣沉積方法中的其他適用材料及技術。
根據以下描述,申請人已確定鉬材料可藉由使用雙(烷基芳烴)鉬化合物作為沉積製程中之鉬前驅物來沉積至微電子基板表面上,雙(烷基芳烴)鉬化合物在本文中亦稱為(烷基芳烴)2
Mo,例如雙(乙基苯)鉬((EtBz)2
Mo)。鉬可以將適用作微電子裝置基板的部分,例如適用作含有鉬以及另一材料(例如,碳,以形成碳化鉬)之晶種層,或適用作導電塊體鉬結構(亦即,元素鉬)之任何形式或結構沉積。
其他處於開發中之可能鉬前驅物(諸如鹵化鉬及鹵氧化鉬前驅物)已展示為可有效地沉積具有極低電阻率之極高純度金屬鉬膜。然而,已發現使用此等前驅物使金屬鉬膜成核於氮化鈦或其他所需基板表面上可能受限。將改良金屬鉬於基板上之成核的來自鹵化鉬及鹵氧化鉬前驅物之晶種層或晶核層將期望有助於此等前驅體用於沉積具有極低電阻率之極高純度金屬鉬膜的用途。
根據所描述之蒸氣沉積方法,可藉由使基板與來源於(烷基芳烴)2
Mo,例如(EtBz)2
Mo之蒸氣在蒸氣沉積條件下接觸而將鉬材料沉積至基板表面上。在特定實施例中,經沉積鉬材料為沉積為晶種層之碳化鉬,塊體(元素)鉬之後續層塗覆至該晶種層上。使用(EtBz)2
Mo前驅物沉積之碳化鉬晶種層可在相對較低溫度(例如低於攝氏300度,或低於攝氏250度或攝氏270度)下塗覆,其中該碳化鉬晶種層在塗覆至三維結構時具有良好保形性。根據實例結構及方法,可將碳化鉬塗覆至三維基板之氮化鈦表面作為在藉由使用鹵化物前驅物沉積元素鉬之後續步驟期間向氮化鈦材料提供呈抗蝕刻性形式之保護的晶種層。使用(EtBz)2
Mo前驅物塗覆之碳化鉬晶種層在沉積元素鉬之後續(下一個)步驟期間亦允許相對較低或降低之溫度,這導致複雜結構(諸如高縱橫比三維結構或開口,例如通孔或互連件)之經改良保形填充。舉例而言,在沉積金屬鉬之後續步驟期間基板溫度可為至少攝氏50度,低於將金屬鉬沉積至不包括碳化鉬晶種層之基板上所需的溫度。
根據在三維基板上製備保形鉬塗層的一個實例方法(其中該基板含有氮化鈦表面),藉由使用(EtBz)2
Mo前驅物將碳化鉬晶種層沉積至氮化鈦表面上。在以下步驟中,藉由使用任何所需或適用前驅物(諸如MoOCl4
、MoCl5
或MoF6
)將塊體(元素)鉬塗覆至晶種層。可在低於攝氏300度或低於攝氏250度或攝氏270度之沉積溫度(亦即,基板溫度)下進行沉積晶種層之步驟。儘管必要時可使用較高溫度,但仍可在低於攝氏500度或低於攝氏450度之沉積溫度(亦即,基板溫度)下進行沉積塊體(元素)鉬之步驟。即使在塗覆至高度三維表面(諸如高縱橫比表面)時,晶種層及塊體(元素)鉬層仍呈現良好的均一性及保形性。
如本文中所使用,「蒸氣沉積」製程係指任何類型之蒸氣沉積技術,諸如CVD或ALD。在各種實施例中,CVD可採取習知(亦即,連續流動) CVD、液體注入CVD或光輔助CVD之形式。CVD亦可採取脈衝技術,亦即,脈衝CVD之形式。在其他實施例中,ALD可採取習知(例如,脈衝注入) ALD、專用ALD、液體注入ALD、光輔助ALD或電漿輔助ALD之形式。
在一個態樣中,本發明係關於一種在基板上形成含鉬材料之方法。該方法包括在蒸氣沉積條件下使基板與雙(烷基芳烴)鉬(亦即,(烷基芳烴)2
Mo)蒸氣接觸以將含鉬材料沉積於基板上。
相關申請案之交叉參考
本申請案主張2018年1月19日申請之美國臨時專利申請案第62/619,363號在35 USC 119下之權益,出於所有目的該申請案之揭示內容特此以全文引用之方式併入本文中。
以下描述係關於適用於藉由使用雙(烷基芳烴)鉬化合物作為鉬前驅物將呈各種形式之鉬沉積至基板上的蒸氣沉積方法。雙(烷基芳烴)鉬化合物(錯合物)在本文中亦稱為(烷基芳烴)2
Mo化合物。發現適用作前驅物之此類化合物之物種的一個實例為雙(乙基苯)鉬(亦即,(EtBz)2
Mo)。前驅物可例如作為含有鉬之化合物或混合物,諸如呈碳化鉬晶種層形式;作為呈導電結構形式之元素鉬;或作為含有鉬之另一沉積材料用於蒸氣沉積(例如,化學蒸氣沉積)製程中,以將呈任何形式之鉬沉積至基板上。
化學蒸氣沉積(CVD)通常為化學材料(衍生自「前驅物」)視情況與一或多種其他材料(諸如共反應物)組合在將使得蒸氣組分在基板表面上形成材料薄膜的條件下作為蒸氣引入至基板的化學製程。
必要或需要時,將諸如還原氣體(在本文中稱為「反應氣體」),例如氫之共反應物連同前驅物引入至沉積腔室中以促進鉬以所需形式沉積。提供至沉積腔室之反應氣體之量(亦即,流動速率)可視需要且可有效地產生沉積於基板表面處之所需形式的鉬材料,其中與沉積製程之其他參數組合選擇特定沉積製程之流動速率,其他參數諸如前驅物之流動速率、基板溫度及腔室壓力。
根據本說明書,鉬前驅物連同視情況選用之反應氣體可置放於含有基板之沉積腔室中,以實現鉬於基板上之蒸氣沉積。沉積腔室之條件將使得來自前驅物之鉬以所需形式及量沉積至基板上。舉例而言,作為反應氣體之氫及鉬前驅物可以使得衍生自鉬前驅物之鉬沉積至基板表面上的方式組合(例如,反應)。在某些實例方法中,鉬前驅物可藉由引起碳化鉬(亦即,具有Mo2
C或MoC之結晶學結構的鉬及碳)沉積之反應與氫反應氣體組合。在其他實例方法中,鉬前驅物可藉由引起元素(金屬)鉬(亦即,具有Mo之晶體結構的鉬)沉積之反應與氫反應氣體組合。
通常,可藉由使用載體氣體將作為蒸氣之前驅物載送至沉積腔室,載體氣體可為惰性氣體,諸如氦氣、氬氣、氮氣、氖氣、氙氣、氪氣或其組合。載體氣體可通過含有一定量的例如呈液體形式之前驅物之密閉容器 (例如,密閉容器或「安瓿」)。隨著載體氣體通過容器,前驅物蒸氣由載體氣體載送,且可將組合(「載體氣體-前驅物混合物」提供至沉積腔室。遞送至沉積腔室之載體氣體-前驅物混合物可包含以下、由以下組成或基本上由以下組成:載體氣體及前驅物(作為蒸氣)。
如所描述之製程之其上沉積鉬的基板可為具有三維或二維表面之任何基板,諸如二維或三維微電子或半導體裝置。根據某些當前適用方法,如所描述之實例方法可尤其適用於將鉬塗覆至三維基板表面上,包括塗佈基板表面,或填充高縱橫比三維開口。在實例方法中,可將鉬作為碳化鉬之電導晶種層沉積至三維基板上。可衍生自任何前驅物,較佳地衍生自鹵化鉬或鹵氧化鉬前驅物之元素(金屬)鉬可接著作為呈導電結構形式之元素(金屬)鉬沉積至晶種層上。
本文中所描述之前驅物化合物雙(烷基芳烴)鉬化合物(或「錯合物」) (在本文中亦稱為(烷基芳烴)2
Mo)屬於亦稱為雙(η6
-芳烴)鉬錯合物的一類化合物,其包括在錯合物之芳基(例如,苯)上具有烷基取代基的化合物。此等錯合物之實例可藉由已知方法合成,已知方法包括使雙(η6
-苯)鉬之芳烴配體複分解以及其他技術。參見:Synthesis of Bis(η6
-alkylbenzene)molybdenum by Arene Metathesis
, Victor S. Asirvatham and Michael T. Ashby, Organometallics, 2001, 20(8), 第1687-1688頁, DOI: 10.1021/om001010b, 公開日期(網路): 2001年3月15日。
此等前驅物化合物可表示為具有包括以下之結構:在鉬原子之第一側面上與鉬原子相結合之第一經取代芳基(例如,烷基苯)以及在同一鉬原子之第二側面上與該鉬原子相結合之第二經取代芳基(例如,烷基苯)。該等化合物或錯合物包括圍繞在兩個烷基經取代芳烴化合物之相對側上的單個鉬原子。具有一個位於兩個經取代芳烴化合物之間的鉬原子之化合物有時稱為「夾層」結構:
芳烴(R)-Mo-芳烴(R)
各芳烴化合物可經相同或不同烷基R取代。舉例而言,各烷基(R)可獨立地為甲基、乙基、丙基、丁基等,且可為分支鏈的或直鏈的。一個實例前驅物為雙(乙基苯)鉬(亦即,(EtBz)2 Mo):
此化合物以適用作如所描述之前驅物的量及形式(亦即,具有純度)市售。
芳烴(R)-Mo-芳烴(R)
各芳烴化合物可經相同或不同烷基R取代。舉例而言,各烷基(R)可獨立地為甲基、乙基、丙基、丁基等,且可為分支鏈的或直鏈的。一個實例前驅物為雙(乙基苯)鉬(亦即,(EtBz)2 Mo):
此化合物以適用作如所描述之前驅物的量及形式(亦即,具有純度)市售。
在某些當前較佳實例方法中,前驅物可沉積至基板上以形成碳化鉬之晶種層。晶種層為含有鉬(例如碳化鉬)且可有效地促進塊體金屬導電鉬層於基板上之後續沉積的層。晶種層在塊體鉬材料(例如,元素(金屬)鉬)將沉積至其上之基板之整個表面上應為連續的,且應允許鉬大塊沉積之的後續步驟覆蓋或填充基板的整個表面,較佳地與塊體鉬在不存在晶種層的情況下於下層基板上之沉積相比,允許在較低沉積溫度下或以更佳品質成核且覆蓋。
較佳晶種層之厚度可為5至100埃,例如5或6埃至30、40或50埃。
較佳的碳化鉬晶種層可包含以下、由以下組成或基本上由以下組成:原子比在1:99至60:40,例如4:96至40:60 (碳:鉬)範圍內之鉬及碳。基本上由碳及鉬組成之晶種層係指含有不超過1百分比(原子),例如不超過0.5、0.1或0.01百分比(原子)之除碳及鉬以外的任何材料之晶種層。與金屬鉬相反,碳化鉬晶種層將含有大量呈Mo2
C、MoC或兩者之形式的鉬及碳。
碳化鉬晶種層沉積於其上之基板可為任何基板,例如如本文中所描述,作為一個特定實例,包括具有氮化鈦表面之三維基板。
如所描述之方法可在以下沉積腔室中進行:在使用期間基本上僅含有氣態前驅物、視情況選用之載體氣體、額外的惰性氣體及一或多種反應氣體,例如,沉積腔室內部可供應有及含有包含以下、由以下組成或基本上由以下組成的氛圍:氣態前驅物、視情況選用之載體氣體及反應氣體。出於本發明之目的,認為基本上由氣態材料(例如,前驅物蒸氣、視情況存在之載體氣體及反應氣體)之指定組合組成的沉積腔室或相關氣流或氣流組合含有氣態材料之指定組合及不超過非顯著量之任何其他氣態材料,例如不超過5、2、1、0.5、0.1、0.05百分比(按質量計)之任何其他氣態材料。
供應至沉積腔室之氣態前驅物(亦稱為前驅物蒸氣)的量及反應氣體的量可為各自將適用於將所需量之鉬及鉬組合物例如以碳化鉬形式沉積至基板表面上的量。就兩種氣體之各別流速而言,可基於包括以下之因素選擇該兩種氣體的量及相對量:沉積晶種層之所需形式及組合物、基板性質(例如,形狀)、所需沉積速率、基板溫度、沉積腔室之大小(容積)及沉積腔室之內部壓力。
根據已鑑別為適用的某些方法之非限制性實例,鉬前驅物之流動速率可在2至20微莫耳/分鐘的範圍內,此速率係基於容積在2,000至20,000立方公分範圍內之沉積腔室,且在10至50托範圍內之內部壓力下操作。與此等值及其他參數一致,前驅物蒸氣可以任何適用或所需濃度(諸如在80至25,000百萬分率(ppm)範圍內)包含於如所描述之載體氣體中。
根據已鑑別為適用的某些方法之非限制性實例,例如氫之反應氣體之流動速率可在8,000至25,000微莫耳/分鐘的範圍內,此速率係基於容積在2,000至20,000立方公分範圍內之沉積腔室,且在10至50托範圍內之內部壓力下操作。
沉積腔室之內部壓力可為對鉬作為晶種層之沉積有效的內部壓力。通常,用於化學蒸氣沉積之沉積腔室在低於環境壓力,例如低於或遠低於760托之壓力下操作。用於沉積碳化鉬晶種層的本說明書之適用或較佳方法可在基本上低於大氣壓,諸如低於約200托之沉積腔室壓力,例如不超過50、80或100托,諸如在5、10或15至多20、30、40或50托範圍內之壓力下進行。
在沉積期間,基板可保持在能有效將碳化鉬作為晶種層沉積至基板上之任何溫度下。根據特定實例方法,可藉由使用期望或有利的低沉積溫度將鉬作為碳化鉬晶種層沉積至基板上。在沉積碳化鉬晶種層之步驟期間,適用或較佳的基板溫度之實例可在150℃至400℃範圍內,或在200℃至300℃範圍內,較佳不超過250℃或270℃的溫度。
申請人已確定使用雙(烷基芳烴)鉬前驅物,例如雙(乙基苯)鉬沉積之碳化鉬晶種層的存在,允許在將元素鉬沉積至晶種層上之步驟期間適用或有利地進一步處理基板。在特定方法中,將元素鉬沉積至晶種層上之步驟可在期望或有利的低溫下進行,該晶種層係使用雙(烷基芳烴)鉬前驅物,例如雙(乙基苯)鉬進行沉積。因此,元素鉬之沉積層在沉積至三維基板表面上時可具有期望或有利的保形性,以及元素鉬結構之其他所需功能特性,包括低電阻率及良好均一性。
因此,根據如所描述之使用含有雙(乙基苯)鉬(例如,(EtBz)2
Mo)之前驅物沉積碳化鉬晶種層的方法,在將晶種層沉積至基板上之後,可將元素鉬沉積至該晶種層上。術語元素鉬係指具有金屬結構之鉬;元素(金屬)鉬例如在不超過5、3、2或1原子百分比下係導電的但可包括非鉬,諸如碳。
可藉由使用任何鉬前驅物,諸如雙(乙基芳烴)鉬前驅物(例如,(EtBz)2
Mo),或發現適用於沉積鉬之另一鉬前驅物來沉積元素鉬。其他前驅體之實例包括鹵化鉬及鹵氧化鉬前驅物,例如五氯化鉬(MoCl5
)、四氯氧化鉬(MoOCl4
)及六氟化鉬(MoF6
)。鹵化物及鹵氧化物前驅物已展示為尤其適用於沉積具有極低電阻率之極高純度金屬鉬膜。然而,Mo金屬膜於TiN或其他所需基板表面上之成核可能會受限。因此,如所描述之晶種層可作為允許藉由使用鹵化鉬或鹵氧化鉬前驅物進行元素鉬之經改良沉積的有效手段。
經沉積元素鉬可呈金屬形式,且可具有高純度或極高純度,例如至少95、98、99、99.5、99.9或99.99百分比(原子)鉬或更高。一定量的非鉬材料(亦即,經沉積元素鉬層中之一般雜質)對於全部此類非鉬雜質可較佳低於5、2、1、0.5、0.1或0.01百分比(原子)。諸如氫、氯、氧、氮碳及氟之特定雜質可較佳地以低於l × 1020
個原子每立方公分之沉積鉬(對於氫及氯),例如低於l × 1021
個原子每立方公分之沉積鉬(對於氧及碳)的含量存在。
實例方法可藉由使用鹵化鉬或鹵氧化鉬前驅物,例如五氯化鉬(MoCl5
)、四氯氧化鉬(MoOCl4
)及六氟化鉬(MoF6
)將元素(金屬)鉬沉積至如所描述之由雙(烷基芳烴)鉬前驅物塗覆之碳化鉬晶種層上。元素(金屬)鉬可藉由使用鹵化鉬或鹵氧化鉬前驅物在低於攝氏800度、攝氏700度或攝氏500度,例如低於攝氏450度或低於攝氏400度之沉積溫度(亦即,基板溫度)下塗覆。
沉積元素鉬層可具有低電阻率,諸如不超過20 µΩ•cm或不超過15 µΩ•cm之電阻率,其中鉬膜的厚度為40奈米。
經沉積元素鉬層可具有任何所需厚度,例如在30至500埃或40至400埃範圍內之厚度。
在所描述方法之各種實例實施例中,藉由在存在載體氣體及氫氣作為反應氣體的情況下在使得鉬沉積為碳化鉬障壁層之條件下使基板表面與雙(乙基苯)鉬接觸而將鉬作為晶種層沉積至含有氮化鈦之基板的三維(例如,高縱橫比)表面上。在晶種層沉積期間之沉積溫度(亦即,在沉積期間之基板溫度)可低於約攝氏300度、攝氏270度或攝氏250度。
在以下步驟中,藉由使用諸如MoOCl4
、MoOCl5
或MoF6
之前驅物的沉積製程在晶種層上方將鉬沉積至基板表面上。有利地,將元素鉬沉積至衍生自雙(乙基苯)鉬之晶種層上的步驟可在有利的低製程(基板)溫度及有效沉積速率下進行,具有所需或有利的結果(例如,元素鉬之保形性)。
舉例而言,圖1展示將元素鉬沉積至三個基板上之步驟之沉積速率的比較,一個基板具有無晶核層之TiN表面,一個基板具有使用B2
H6
前驅物沉積至氮化鈦上作為晶核層之硼(B)表面,且一個基板具有藉由使用雙(乙基苯)鉬作為前驅物沉積於氮化鈦上方作為晶種層之碳化鉬表面。與具有TiN表面之基板相比,及與具有硼表面作為晶核層之基板相比,包括藉由使用雙(乙基苯)鉬前驅物沉積之碳化鉬晶種層的基板允許元素鉬在相對較低溫度下之有效沉積速率。
圖2展示在各種壓力及溫度條件下將碳化鉬作為晶種層沉積至具有氮化鈦表面之基板上產生一系列沉積速率之製程實例。在10至30托之間的壓力及在攝氏200度與攝氏300度之間的溫度展示為有效的,其中30托及攝氏200度之組合尤其適用於保形碳化鉬晶種層沉積。在較低溫度下沉積之膜具有特別良好的保形性。在較高溫度下沉積之膜並未呈現相同有利的保形性,但仍可適用作不太複雜的不難覆蓋整個表面的結構上之晶種層。
大體而言,如本文中所描述,使用雙(烷基芳烴)鉬化合物(例如,(EtBz)2
Mo)沉積之鉬可沉積至任何所需基板表面(諸如半導體或微電子裝置基板之表面)上,且可適於作為裝置之部分執行任何有效功能或便於處理裝置。使用如所描述之前驅物沉積之鉬的功能之實例包括:作為晶核或「晶種」層、作為障壁層或作為導電層(例如,作為互連件或「通孔」),以及其他。所沉積之鉬可具有諸如可有效執行所需功能之組成及厚度之特徵。
使用如所描述之前驅物將呈各種形式之鉬沉積至其上的基板及表面之實例包括任何二維或三維結構,其中特定實例包括微電子裝置基板,諸如DRAM裝置、3D NAND裝置或三維表面具有高縱橫比之另一裝置。在特定實例中,可藉由使用如本文中所描述之前驅物作為晶種層在三維表面(例如,塗佈有氮化鈦)上沉積鉬,接著使用任何前驅物在晶種層上沉積元素鉬。基板可包括高縱橫比開口,諸如通孔,其中首先塗覆碳化鉬晶種層,接著用元素鉬填充開口。舉例而言,開口可具有在2:1至200:1,例如5:1至100:1或20:1至30:1範圍內的縱向與橫向尺寸之縱橫比。替代地,3D NAND裝置基板之表面可包括由槽孔分離的經氮化鈦塗佈之豎直壁,該等壁包括水平延伸之肋及凹部,且該方法可包括在肋及凹部之氮化鈦表面上方形成碳化鉬晶種層之均一及保形層(或「膜」),接著在晶種層上方沉積元素鉬。藉由特定實例方法,可使用諸如MoOCl4
、MoOCl5
或MoF6
之前驅物沉積元素鉬以提供具有良好、適用或有利保形性的元素鉬層。
根據如所描述之方法之某些適用或當前較佳實施例,對於將碳化鉬作為雙(烷基芳烴)鉬前驅物之晶種層沉積至基板表面上,適用(非限制性)製程參數包括以下各者(視整體製程特徵而定,由於如本文通常所描述之方法能夠在以超出規定範圍之此等參數值操作時使用,因此將指定值稱為非限制性的):
傳遞至沉積腔室中之鉬前驅物蒸氣的溫度:攝氏100度至攝氏140度;
基板溫度:低於攝氏300度,例如攝氏200度至攝氏250度或攝氏270度;
在沉積步驟期間之沉積腔室壓力:10至50托,例如10至20托;
前驅物-載體氣體混合物之流動速率:20至100 sccm (標準立方公分/分鐘);
反應氣體(例如,氫氣)之流動速率:100至1,000 sccm。
傳遞至沉積腔室中之鉬前驅物蒸氣的溫度:攝氏100度至攝氏140度;
基板溫度:低於攝氏300度,例如攝氏200度至攝氏250度或攝氏270度;
在沉積步驟期間之沉積腔室壓力:10至50托,例如10至20托;
前驅物-載體氣體混合物之流動速率:20至100 sccm (標準立方公分/分鐘);
反應氣體(例如,氫氣)之流動速率:100至1,000 sccm。
在此等實例方法中,在沉積晶種層之後,可使用諸如MoOCl4
、MoOCl5
或MoF6
之前驅物將元素鉬沉積至晶種層上。適用(非限制性)製程參數之實例包括以下各者(視整體製程特徵而定,由於如本文通常所描述之方法能夠在以超出規定範圍之此等參數值操作時使用,因此將指定值稱為非限制性的):
傳遞至沉積腔室中之鉬前驅物的溫度:攝氏30度至攝氏100度;
平台(基板)溫度:攝氏300度至攝氏800度;
在沉積步驟期間之沉積腔室壓力:10至100托,例如20至80托;
前驅物-載體氣體混合物之流動速率:20至1000 sccm;
反應氣體(例如,氫氣)之流動速率:500至5,000 sccm。
傳遞至沉積腔室中之鉬前驅物的溫度:攝氏30度至攝氏100度;
平台(基板)溫度:攝氏300度至攝氏800度;
在沉積步驟期間之沉積腔室壓力:10至100托,例如20至80托;
前驅物-載體氣體混合物之流動速率:20至1000 sccm;
反應氣體(例如,氫氣)之流動速率:500至5,000 sccm。
圖1說明來自MoOCl4
之鉬於具有各種表面組合物(包括如所描述之碳化鉬的一個表面)之基板上的沉積速率之比較。
圖2說明在蒸氣沉積期間鉬(來自雙(乙基苯)鉬)在各種溫度及壓力條件下之沉積速率。
Claims (10)
- 一種在基板上形成含鉬材料之方法,該方法包含使該基板與雙(烷基芳烴)鉬蒸氣在蒸氣沉積條件下接觸以將含鉬材料沉積於該基板上。
- 如請求項1之方法,其中該雙(烷基芳烴)鉬為雙(乙基苯)鉬((EtBz)2 Mo)。
- 如請求項1之方法,其中該含鉬材料為碳化鉬。
- 如請求項3之方法,其包含將該碳化鉬沉積為厚度在6至100埃範圍內之晶種層。
- 如請求項3之方法,其包含將金屬鉬沉積至該碳化鉬上。
- 如請求項5之方法,其中該金屬鉬衍生自鹵化鉬前驅物或鹵氧化鉬前驅物。
- 如請求項5之方法,其中該金屬鉬衍生自選自五氯化鉬(MoCl5 )、四氯氧化鉬(MoOCl4 )及六氟化鉬(MoF6 )之前驅物。
- 如請求項1之方法,其中該含鉬材料為金屬鉬。
- 如請求項8之方法,其包含以至少50埃的厚度沉積該元素鉬。
- 一種基板,其包含: 碳化鉬晶種層,其沉積至氮化鈦上,該碳化鉬晶種層衍生自雙(烷基芳烴)鉬前驅物,及 金屬鉬,其沉積於該晶種層上,該金屬鉬衍生自鹵化鉬前驅物或鹵氧化鉬前驅物。
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2019
- 2019-01-11 US US16/245,791 patent/US11560625B2/en active Active
- 2019-01-15 JP JP2020539718A patent/JP7203111B2/ja active Active
- 2019-01-15 CN CN201980009112.4A patent/CN111630204B/zh active Active
- 2019-01-15 EP EP19741829.6A patent/EP3740600A4/en active Pending
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JP2021510770A (ja) | 2021-04-30 |
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CN111630204A (zh) | 2020-09-04 |
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TWI748153B (zh) | 2021-12-01 |
EP3740600A1 (en) | 2020-11-25 |
JP7203111B2 (ja) | 2023-01-12 |
WO2019143632A1 (en) | 2019-07-25 |
KR20200091469A (ko) | 2020-07-30 |
CN111630204B (zh) | 2023-05-23 |
US20230128330A1 (en) | 2023-04-27 |
US20190226086A1 (en) | 2019-07-25 |
US11560625B2 (en) | 2023-01-24 |
EP3740600A4 (en) | 2022-01-26 |
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