TW202041702A - 層形成方法及設備 - Google Patents
層形成方法及設備 Download PDFInfo
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- TW202041702A TW202041702A TW109111909A TW109111909A TW202041702A TW 202041702 A TW202041702 A TW 202041702A TW 109111909 A TW109111909 A TW 109111909A TW 109111909 A TW109111909 A TW 109111909A TW 202041702 A TW202041702 A TW 202041702A
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- reactant
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- reaction chamber
- precursor
- molybdenum
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- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000000376 reactant Substances 0.000 claims abstract description 111
- 239000000758 substrate Substances 0.000 claims abstract description 104
- 239000002243 precursor Substances 0.000 claims abstract description 94
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 80
- 239000011733 molybdenum Substances 0.000 claims abstract description 80
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052796 boron Inorganic materials 0.000 claims abstract description 33
- 238000000231 atomic layer deposition Methods 0.000 claims description 36
- 238000000151 deposition Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 229910000085 borane Inorganic materials 0.000 claims description 9
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 claims description 5
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 1
- ASLHVQCNFUOEEN-UHFFFAOYSA-N dioxomolybdenum;dihydrochloride Chemical compound Cl.Cl.O=[Mo]=O ASLHVQCNFUOEEN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 84
- JCFNAADCQWXIJD-UHFFFAOYSA-L dioxomolybdenum(2+);dichloride Chemical compound Cl[Mo](Cl)(=O)=O JCFNAADCQWXIJD-UHFFFAOYSA-L 0.000 description 17
- 238000010926 purge Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 13
- 235000012431 wafers Nutrition 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- CNRRZWMERIANGJ-UHFFFAOYSA-N chloro hypochlorite;molybdenum Chemical compound [Mo].ClOCl CNRRZWMERIANGJ-UHFFFAOYSA-N 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000003877 atomic layer epitaxy Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
- UYEGPKGLVUUIGD-UHFFFAOYSA-J tetrachloro(oxo)molybdenum Chemical compound Cl[Mo](Cl)(Cl)(Cl)=O UYEGPKGLVUUIGD-UHFFFAOYSA-J 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004871 chemical beam epitaxy Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000171 gas-source molecular beam epitaxy Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- -1 nanolaminates Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76876—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for deposition from the gas phase, e.g. CVD
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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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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Abstract
提供一種在一基材上沉積一含鉬層之方法及設備,其係藉由供應包括二氯二氧化鉬(VI)之一前驅物及包括硼及氫之一第一反應物至一反應室中之基材以起反應並形成鉬層。包括硼及氫之第一反應物可係二硼烷。
Description
本揭露大致上係關於一種在一基材上形成一層之方法及設備。更具體地,本揭露係關於一種用於在一反應室中之一基材上沉積一含鉬層之方法及設備。
沉積方法可包括供應包括二氯二氧化鉬之一前驅物及一第一反應物至反應室中之基材以使得前驅物及第一反應物之一部分起反應以形成鉬層。基材上之此層可用於製造一半導體裝置。
在原子層沉積(atomic layer deposition,ALD)及化學氣相沉積(chemical vapor deposition,CVD)中,基材係遭受適於在基材上起反應成為所欲層的前驅物及第一反應物。可在基材上之特徵的製造期間所產生的間隙中沉積層以填充間隙。
在原子層沉積中,基材係暴露至前驅物之脈衝,且前驅物之單層可經化學吸附在基材表面上。表面位點(surface sites)可由前驅物之整體或由前驅物之片段佔據。反應可係化學自限制的(chemically self-limiting),因為前驅物可不吸附或不與已經吸附在基材表面上的前驅物部分起反應。接著,過量的前驅物係例如藉由提供惰性氣體而從反應室吹掃及/或使用泵從反應室移除。隨後,基材係暴露至第一反應物之脈衝,其與經吸附之前驅物的整體或片段(fragment)起化學反應,直到反應完成且表面經覆以反應產物的單層。
已發現,可能存在對改善用於鉬層之沉積製程的品質的需求。
提供本發明內容以簡化形式來介紹一系列概念。這些概念將在下文之揭露的實例實施例之詳細描述中進一步詳述。本發明內容並非意欲鑑別所主張之標的之關鍵特徵或基本特徵,亦非意欲用以限制所主張之標的之範疇。
可能存在對用以在一基材上形成一沉積鉬層之一改善方法的需求。因此,在一實施例中,可提供一種在一反應室中之一基材上沉積一含鉬層之方法。此方法可包括供應包括二氯二氧化鉬(VI) (molybdenum(VI) dichloride dioxide,MoO2
Cl2
)之一前驅物至反應室中之基材。此方法可包括供應一第一反應物至反應室中之基材以使得前驅物及第一反應物之一部分起反應以形成鉬層。第一反應物可包括硼及氫。
藉由使第一反應物包括硼及氫,可改善第一反應物與包括二氯二氧化鉬(VI) (MoO2
Cl2
)之前驅物的反應性。可因而改善鉬層之沉積。可改善總體層(total layer)的品質及/或可改善沉積製程的速度。
在一些其他實施例中,提供一種用於半導體處理之方法。此方法包括將一金屬層沉積至基材中之一間隙中,從而填充間隙。
根據一進一步的實施例,提供一種用以在一基材上沉積一含鉬層之沉積設備,其包括:
一反應室,其具有一基材固持器以固持一基材;
一加熱系統,其經構成及佈置以控制基材的溫度;
一分配系統,其包括閥以在反應室中提供一前驅物及至少一第一反應物;及
一序列控制器,其可操作地連接至此等閥,且經程式化以致能使用前驅物及第一反應物在反應室中之基材上沉積鉬,其中分配系統具有一前驅物輸送裝置及一第一反應物輸送系統,前驅物輸送裝置用以輸送一二氯二氧鉬(VI)蒸氣,第一反應物輸送系統經構成及佈置以輸送包括硼及氫之一第一反應物之一蒸氣。
雖然在下文揭示某些實施例及實例,所屬技術領域中具有通常知識者將了解本發明延伸超出本發明及其明顯的修改與等同物之具體揭示的實施例及/或用途。因此,希望所揭示之本發明之範疇不應受下文所述的特定揭示實施例之限制。
本文呈現之圖解說明並非意謂任何特定材料、結構或裝置的實際視圖,而僅為用於描述本揭示案之實施例的理想表示。
如本文中所使用,用語「基材(substrate)」可指可使用或在其上可形成裝置、電路、或膜之任何(多個)下伏(underlying)材料。
如本文中所使用,用語「循環沉積(cyclic deposition)」可指將一或多個前驅物(反應物)循序引入反應室中以在基材上方沉積膜,並包括沉積技術,諸如原子層沉積及循環化學氣相沉積(cyclical chemical vapor deposition)。
如本文中所使用,用語「循環化學氣相沉積」可指任何製程,其中基材係循序暴露至一或多個揮發性前驅物,其在基材上起反應及/或分解,以製造所欲沉積。
如本文中所使用,用語「原子層沉積」可指氣相沉積製程,其中沉積循環(較佳的係複數個接續的沉積循環)係在反應室中實施。一般而言,在各循環期間,前驅物係化學吸附至沉積表面(例如基材表面或先前沉積的下伏表面,諸如來自先前原子層沉積循環的材料),形成不易與額外前驅物起反應的單層或次單層(亦即,自限制反應(self-limiting reaction))。其後,若有必要,可隨後將反應物(例如,另一前驅物或反應氣體)引入至製程室中,以用於在沉積表面上將經化學吸附之前驅物轉化為所欲材料。通常,此反應物能夠進一步與前驅物反應。此外,亦可在每個循環期間利用吹掃步驟自處理室移除過量前驅物,及/或在轉化經化學吸附之前驅物之後自處理室移除過量反應物及/或反應副產物。進一步地,當使用(多個)前驅物組成物、反應性氣體、及吹掃(例如惰性載體)氣體的交替脈衝施行時,如本文中所使用之用語「原子層沉積」亦意指包括由相關用語指定的製程,諸如「化學氣相原子層沉積(chemical vapor atomic layer deposition)」、「原子層磊晶(atomic layer epitaxy)」(ALE)、分子束磊晶(molecular beam epitaxy,MBE)、氣體源分子束磊晶(gas source MBE)、或有機金屬分子束磊晶(organometallic MBE)、及化學束磊晶(chemical beam epitaxy)。
如本文中所使用,用語「層」可指藉由本文所揭示之方法形成之任何連續或不連續的結構及材料。例如,「層」可包括二維材料(2D materials)、奈米層壓體(nanolaminates)、奈米棒(nanorods)、奈米管(nanotubes)、或奈米粒子(nanoparticles)、或甚至部分或完整分子層、或部分或完整原子層、或原子及/或分子團簇。「層」可包括具有針孔(pinholes),但仍係至少部分連續的材料或層。
鉬層可作為半導體裝置中之想要的導電層。可因此使用一種在反應室中之基材上沉積含鉬層之方法。此方法可包括供應包括二氯二氧化鉬(VI)之前驅物至反應室中之基材。前驅物可包括氧鹵化鉬(molybdenum oxyhalide),但並非氧四氯化鉬(molybdenum oxytetrachloride,MoOCl4
)。前驅物可包括氧氯化鉬(molybdenum oxychloride),但並非氧四氯化鉬(MoOCl4
)。前驅物可具有鉬氧(Mo-O)及鉬氯(Mo-Cl)鍵,但並非氧四氯化鉬。前驅物可包括氧鹵化鉬,其具有與鍵結至鉬之氯化物原子相同數目的氧。前驅物可包括氧鹵化鉬,其具有鍵結至鉬的兩個氧及兩個氯化物原子。
此方法可更包括供應包括硼及氫之第一反應物至反應室中的基材以使得前驅物及第一反應物的一部分起反應,以在基材上形成鉬層。包括硼及氫之第一反應物可選自具有化學式Bn
H(n+x)
之硼烷(boranes)所組成之群組,其中n係從1至10之整數,且x係偶數。
包括硼及氫之第一反應物可例如選自由具有化學式Bn
H(n+4)
之巢式硼烷(nido-boranes)所組成之群組。
包括硼及氫之第一反應物可例如選自由具有化學式Bn
H(n+6)
之網式硼烷(arachno-boranes)所組成之群組。
包括硼及氫之第一反應物可例如選自由具有化學式BnH(n+8)
之敞網式硼烷(hypho-boranes)所組成之群組。
包括硼及氫之第一反應物可例如選自由聯式硼烷(conjuncto-boranes)Bn
Hm
所組成之群組。在上述實例中,n係從1至10之整數,且m係不同於n之從1至10之整數。
包括硼及氫之第一反應物可係二硼烷(diborane)(B2
H6
)。二硼烷可具有帶有四個末端及兩個橋接(bridging)氫原子的結構。介於硼與末端氫原子之間的鍵係習知的共價鍵。硼原子與橋接氫原子之間的鍵結可係不同的,因為兩個電子已用於鍵結至末端氫原子,各硼原子具有一個餘留的價電子以用於額外鍵結。橋接氫原子各自提供一個電子,因此二硼烷中的硼原子可藉由四個電子來固持在一起。硼氫(B-H)橋鍵的長度可長於硼氫端鍵(terminal bonds)。這些鍵結之長度差可反映其等之強度差。二硼烷之硼氫橋鍵可相對較弱。
以二硼烷還原二氯二氧化鉬可具有下列的反應路徑:MoO2
Cl2
+ ½ B2
H6
-> Mo (s) + BOCl + HCl + H2
O。使二硼烷之硼氫橋鍵斷裂可係必要的,以將二硼烷切半以供反應之用。相較於MoO2
Cl2
+ 3H2
-> Mo (s) + 2HCl + 2H2
O之反應路徑,亦可包含可具有較弱氫鍵之較少分子,有利於二氯二氧化鉬與二硼烷之反應。以二硼烷還原氧四氯化鉬遵循MoOCl4
+ ½ B2
H6
-> Mo (s) + BOCl + 3HCl,其可造成反應室中之蝕刻劑氯化氫(HCl)的濃度較高,導致非所要的蝕刻及/或降低沉積率。
二硼烷可係高度反應性且萬用的反應物。二硼烷已在半導體產業中例如用作摻雜劑。二硼烷可因此輕易地在產業中採用作為用於二氯二氧化鉬(VI)之反應物以用於沉積鉬。
可在其上沉積鉬之表面可包括一個類別的沉積材料。或者,表面可包括不同類別之沉積材料。表面可例如包括氧化鋁及/或氮化鈦。當可想要例如鉬導電層時,可能會難以將鉬沉積在不同材料上。通常被稱為種晶層或成核層(seed or nucleation layer)之第一層可能更難以沉積。因此,可係較佳的是提供二氯二氧化鉬(VI)至反應室中之基材;並供應包括硼及氫之第一反應物至反應室中之基材,以使得前驅物及第一反應物的一部分起反應以在基材上形成鉬種晶層。
在積體電路裝置特徵之製造期間所產生的間隙可填以金屬層(例如,以鉬製成)。間隙可具有高深寬比率(aspect ratio),因為其等之深度遠大於其等之寬度。間隙可在已製造之具有實質上水平之頂部表面的層中垂直地延伸。在垂直方向上且填以金屬的間隙可例如用在動態隨機存取記憶體(dynamic random access memory,DRAM)型之記憶體積體電路之字線(word line)中。在垂直方向上且填以金屬之間隙亦可例如用在邏輯積體電路中。例如,金屬填充間隙可用作P型金屬氧化物半導體(P-type metal oxide semiconductor,PMOS)或互補金屬氧化物半導體(complementary metal oxide semiconductor,CMOS)積體電路中或源極/汲極溝槽接觸(source/drain trench contact)中之閘極填充(gate fill)。
間隙亦可在已製造之層中佈置在水平方向上。再一次地,間隙可具有高深寬比率,因為其等之深度(現在水平方向上)遠大於其等之寬度。在水平方向上且填以金屬的間隙可例如用在3D NAND型之記憶體積體電路之字線中。間隙亦可佈置在垂直方向與水平方向之組合上。
間隙之表面可包括一個類別之沉積材料。或者,間隙之表面可包括不同類別之沉積材料。間隙之表面可例如包括氧化鋁及/或氮化鈦。當例如間隙中可以想要鉬導電層時,可能難以將鉬沉積在間隙中之不同材料上。可想要的是鉬層可充分覆蓋間隙表面且完全填充間隙。進一步地,可係想要的是鉬層可充分覆蓋包括不同類別的材料之間隙表面。
欲完全填充間隙,鉬種晶層可沉積在間隙中且鉬主體層(bulk layer)可沉積在鉬種晶層上。種晶層可藉由循序重複預處理原子層沉積循環來形成。因此,可係較佳的是提供二氯二氧化鉬(VI)至反應室中之基材;並供應包括硼及氫之第一反應物至反應室中之基材,以使得前驅物及第一反應物的一部分起反應以在基材上之間隙中形成鉬種晶層。
或者,種晶層可由化學氣相沉積製程形成。化學氣相沉積製程可係脈衝式,其中第一前驅物係在連續供應第一反應物至基材上的同時以脈衝供應至基材上。
主體層可藉由循序地重複主體原子層沉積循環來沈積在種晶層上。可藉由供應包括二氯二氧化鉬(VI)之前驅物及包括氫之第二反應物至反應室中之基材而在鉬種晶層之頂部上提供主體鉬層,其中前驅物及第二反應物的一部分起反應以形成主體鉬層。第二反應物可包括氫氣(H2
)。第二反應物可不包括硼。氫氣可係相對便宜且常見的反應物。
或者,可藉由化學氣相沉積製程將主體鉬層沉積在鉬種晶層上。化學氣相沉積製程可係脈衝式,其中第二前驅物係在連續供應第二反應物至基材上的同時以脈衝供應至基材上。
第1a圖及第1b圖顯示流程圖,其繪示根據一實施例之一種沉積鉬層之方法。
鉬層可沉積作為種晶層。鉬層可沉積在間隙中。鉬主體層可沉積在種晶層上。
用於鉬種晶層之第一原子層沉積循環1可顯示於第1a圖中。用於鉬主體層之第二原子層沉積循環2可顯示於第1b圖中。
具有間隙之基材可在步驟3中於反應室中提供。包括二氯二氧化鉬(VI)之第一前驅物可在步驟5中供應至基材持續第一供應週期T1(參見第1a圖)。隨後,可例如藉由在步驟7中從反應室吹掃一部分的第一前驅物持續第一移除週期R1來停止至基材之第一前驅物的額外供應。
進一步地,第一循環可包括供應9第一反應物至基材持續第二供應週期T2。第一反應物可包括硼及氫。第一反應物在一個分子中可包括硼及氫原子,例如,其可係二硼烷。可將氫氣添加至第一反應物之氣體流。第一前驅物及第一反應物的一部分可起反應以在基材上形成鉬種晶層的至少一部分。在開始沉積種晶層之前可耗費若干個(約50個)循環。可例如藉由在步驟10中從反應室吹掃一部分的第一反應物持續第二移除週期R1來停止至基材之第一反應物的額外供應。
可選地,第一反應物可在沉積種晶層之前用以清潔基材。二硼烷反應物在清潔基材表面的過程中可極具反應性及效率。
第一前驅物及第一反應物可經選擇以在間隙表面上具有適當成核作用。第一原子層沉積循環1可重複N次以沉積鉬種晶層,其中N經選擇為介於100與1000之間、較佳介於200與800之間、且更佳介於300與600之間。種晶層可具有的厚度係介於1與20奈米(nm)之間、較佳介於2與10奈米之間、更佳介於3與7奈米之間。
在第一原子層沉積循環1經重複N次之後,可在步驟11中將包括二氯二氧化鉬(VI)之第一前驅物在主體原子層沉積循環2中供應至基材持續第三供應週期T3(參見第1b圖)。此可在與第1a圖之第一原子層沉積循環1相同之反應室中或在不同反應室中完成。
當針對第一循環之溫度要求可係不同時,在不同於第一原子層沉積循環之反應室中進行主體原子層沉積循環可係有利的。基材轉移因而可能係必要的。
隨後,至基材之第一前驅物的額外供應可停止並從反應室移除。此可藉由在步驟13中從反應室朝反應室的排氣泵吹掃一部分的第一前驅物持續第三移除週期R3來完成。
進一步地,循環可包括供應15第二反應物至基材持續第四供應週期T4。第一前驅物及第二反應物的一部分可起反應以在基材上形成主體鉬層的至少一部分。可例如藉由在步驟17中從反應室吹掃一部分的第二反應物持續第四移除週期R4來停止至基材之第二反應物的額外供應。
第一前驅物及第二反應物可經選擇以具有適當的電子性質。例如,以具有低電阻率。鉬膜可具有的電阻率係低於3000微歐姆-公分(μΩ-cm)、或低於1000微歐姆-公分、或低於500微歐姆-公分、或低於200微歐姆-公分、或低於100微歐姆-公分、或低於50微歐姆-公分、或低於25微歐姆-公分、或低於15微歐姆-公分、或甚至低於10微歐姆-公分。
用於主體層之第二原子層沉積循環2可重複M次,其中M經選擇為介於200與2000之間、較佳介於400與1200之間、且更佳介於600與1000之間。主體鉬層可具有的厚度係介於1與100奈米之間、較佳介於5與50奈米之間、更佳介於10與30奈米之間。
在用於種晶鉬層之第一原子層沉積循環期間,製程溫度可介於300與800°C之間、較佳介於400與700°C之間、且更佳介於500與650°C之間。第一前驅物在其中汽化之容器可維持在20與150°C之間、較佳在30與120°C之間、且更佳在40與110°C之間。
在用於主體鉬層之第二原子層沉積循環期間,製程溫度可介於300與800°C之間、較佳介於400與700°C之間、且更佳介於500與650°C之間。第一前驅物在其中汽化之容器可維持在20與150°C之間、較佳在30與120°C之間、且更佳在40與110°C之間。
供應第一前驅物至反應室中可花費持續時間T1、T3,其等係在0.1與10秒之間、較佳在0.5與5秒之間、且更佳在0.8與2秒之間選擇。例如,T1可係1秒且T3可係1.3秒。第一或第二前驅物至反應室中之流量可在50與1000單位時間標準毫升數(sccm)之間、較佳在100與500單位時間標準毫升數之間、且更佳在200與400單位時間標準毫升數之間選擇。反應室中之壓力可在0.1與100托耳(Torr)之間、較佳在1與50托耳之間、且更佳在4與20托耳之間選擇。
供應第一及/或第二反應物至反應室中之持續時間T2、T4可花費介於0.5與50秒之間、較佳介於1與10秒之間、且更佳介於2與8秒之間。第一或第二前驅物至反應室中之流量可介於50與50000單位時間標準毫升數之間、較佳介於100與20000單位時間標準毫升數之間、且更佳介於500與10000單位時間標準毫升數之間。
亦可考慮將矽烷用於第二反應物。用於矽烷之通式係Six
H2(x+2)
,其中x係整數1、2、3、4……。矽烷(SiH4
)、二矽烷(Si2
H6
)、或三矽烷(Si3
H8
)可係用於具有氫原子之第二反應物的合適實例。
從反應室吹掃第一前驅物、第一反應物、及第二反應物之至少一者的一部分之持續時間R1、R2、R3、或R4可在0.5與50秒之間、較佳在1與10秒之間、且更佳在2與8秒之間選擇。
可在供應第一前驅物至基材之後;供應第一反應物至基材之後;及供應第二反應物至反應室之後使用吹掃,以從反應室移除第一前驅物、第一反應物、及第二反應物之至少一者的一部分,吹掃持續時間係R1、R2、R3、或R4。吹掃可藉由泵送及/或藉由提供吹掃氣體來完成。吹掃氣體可係惰性氣體(諸如氮)。
此方法可用在單晶圓或批量晶圓原子層沉積設備中。
此方法可包括在反應室中提供基材,且反應室中之第一原子層沉積循環可包括:供應第一前驅物至反應室中之基材;從反應室吹掃一部分的第一前驅物;供應第一反應物至反應室中之基材;及從反應室吹掃一部分的第一反應物。
進一步地,此方法可包括在反應室中提供基材,且反應室中之主體原子層沉積循環可包括:供應第二前驅物至反應室中之基材;從反應室吹掃一部分的第二前驅物;供應第二反應物至反應室中之基材;及從反應室吹掃一部分的第二反應物。
經特別設計以施行原子層沉積製程之例示性單晶圓反應器可以購自ASM International NV (Almere, The Netherlands)下的商標名Pulsar®、Emerald®、Dragon®、Synergis®、及Eagle®。此方法亦可在批量晶圓反應器(例如垂直熔爐)中施行。例如,沉積製程亦可在可購自ASM International N.V.之A400TM或A412TM垂直熔爐中施行。熔爐可具有製程室,其可容納超過100個半導體基材或晶圓(具有200或300毫米(mm)直徑)之負載。
晶圓反應器可具有可控制反應器之控制器及記憶體。記憶體可以程式加以程式化,在控制器上施行此程式時,根據此揭露之實施例在反應室中供應前驅物及反應物。
可使用此揭露之方法填以鉬之間隙可具有高深寬比率,因為垂直及或水平的深度遠大於寬度。例如,間隙的深寬比率(間隙深度/間隙寬度)可大於約2、大於約5、大於約10、大於約20、大於約50、大於約75,或者在一些情況下甚至大於約100、或大於約150、或大於約200。深寬比率可小於1000。
可注意,可難以針對間隙判定深寬比率,但在此上下文中可以表面增強比率(surface enhancement ratio)來取代深寬比率,表面增強比率可係晶圓或晶圓之部分中之間隙的總表面積相對於晶圓或晶圓部分之平面表面積的比率。間隙的表面增強比率(表面間隙/表面晶圓)可大於約2、大於約5、大於約10、大於約20、大於約50、大於約75,或在一些情況下甚至大於約100、或大於約150、或大於約200。表面增強比率可小於1000。
間隙的表面可包括不同類別的沉積材料。表面可例如包括Al2
O3
或TiN。
可藉由使用第一前驅物及第一反應物循序地重複第一原子層沉積循環來沉積種晶層以在間隙表面上沉積保形鉬金屬層。進一步地,可藉由使用第一前驅物及第二反應物循序地重複第二原子層沉積循環而在種晶層上沉積保形鉬主體層。
所用方法之細節係顯示於第1圖及第1b圖以及相關描述中。在一些實施例中,經沉積之含Mo膜可具有之階梯覆蓋率(step coverage)大於約50%、大於約80%、大於約90%、大於約95%、大於約98%、大於約99%。
此方法可在原子層沉積設備中施行。例如,一種用以在一基材上沉積一含鉬層之沉積設備可包括:
一反應室,其具有一基材固持器以固持一基材;
一加熱系統,其經構成及佈置以控制基材的溫度;
一分配系統,其包括閥以在反應室中提供一前驅物及至少一第一反應物;及
一序列控制器,其可操作地連接至此等閥且經程式化以致能使用前驅物及第一反應物在反應室中之基材上沉積鉬。
分配系統可具有前驅物輸送裝置及第一反應物輸送系統,前驅物輸送裝置經構成及佈置以輸送二氯二氧鉬(VI)蒸氣,第一反應物輸送系統經構成及佈置以輸送包括硼及氫之第一反應物的蒸氣(例如二硼烷)。
第一反應物可係二硼烷,並可以50至50000(例如495)單位時間標準毫升數的流量在反應室中供應,其供應持續時間T2、T4係5秒。可在供應第一前驅物之後;在供應第一前驅物之後並且在5秒的持續時間R1、R2、R3、或R4持續供應第一反應物之後使用氮吹掃氣體。
在預處理及主體原子層沉積循環期間,製程溫度可係例如約550°
C,且壓力可係約10托耳。第一前驅物可在其中汽化之容器可係約70°
C。
此方法亦可用在空間原子層沉積設備中。在空間原子層沉積中,前驅物及反應物係在不同的實體區段(physical sections)中連續地供應,且基材係在區段之間移動。可提供至少兩個區段,其中,在基材存在時,可發生半反應(half-reaction)。若基材存在於此一半反應區段中,則可由第一或第二前驅物形成單層。接著,基材經移動至第二個半反應區,其中原子層沉積循環係使用第一或第二反應物完成以形成一個原子層沉積單層。或者,基材位置可固定且氣體供應可移動,或此兩者之某一組合。欲得到較厚的膜,可重複此序列。
根據空間原子層沉積(spatial ALD apparatus)設備中之一個實施例,此方法包括:
將基材放入包括複數個區段之反應室中,各區段係藉由氣體幕與相鄰區段分開;
供應第一前驅物(例如,二氯二氧化鉬(VI))至反應室的第一區段中之基材;
(例如,側向地)相對於反應室移動基材表面通過氣體幕至反應室之第二區段;
供應包括硼及氫之第一反應物(例如二硼烷)至反應室的第二區段中之基材以形成鉬種晶層;
(例如,側向地)相對於反應室移動基材表面通過氣體幕;及
重複供應第一前驅物及反應物,包括(例如,側向地)相對於反應室移動基材表面以形成鉬種晶層。
欲形成主體層,此方法可更包括:
將基材放入包括複數個區段之反應室中,各區段係藉由氣體幕與相鄰區段分開;
供應第一前驅物(例如,二氯二氧化鉬(VI))至反應室的第一區段中之基材;
(例如,側向地)相對於反應室移動基材表面通過氣體幕至反應室之第二區段;
供應第二反應物(例如,氫氣)至反應室的第二區段中之基材以形成鉬主體層;
(例如,側向地)相對於反應室移動基材表面通過氣體幕;及
重複供應第一前驅物及第二反應物,包括(例如,側向地)相對於反應室移動基材表面以形成鉬主體層。
第一反應物可係包括氫及硼(例如二硼烷)。第二反應物可係氫氣。
在額外實施例中,種晶鉬層或主體鉬層可包括小於約40原子百分率(at.%)、小於約30原子百分率、小於約20原子百分率、小於約10原子百分率、小於約5原子百分率、或甚至小於約2原子百分率的氧。在進一步的實施例中,種晶層或主體層可包括小於約30原子百分率、小於約20原子百分率、小於約10原子百分率、或小於約5原子百分率,或小於約2原子百分率、或甚至小於約1原子百分率的氫。
在一些實施例中,種晶鉬層或主體鉬層可包括小於約10原子百分率、或小於約5原子百分率、小於約1原子百分率、或甚至小於約0.5原子百分率的鹵素或氯。在更進一步的實施例中,種晶鉬層或主體鉬層可包括小於約10原子百分率,或小於約5原子百分率,或小於約2原子百分率,或小於約1原子百分率、或甚至小於約0.5原子百分率的碳。在本文所概述之實施例中,元素之原子百分率(atomic percentage,at.%)濃度可利用盧瑟福背向散射(Rutherford backscattering,RBS)來判定。
在本揭露之一些實施例中,形成半導體裝置結構(諸如半導體裝置結構)可包括形成包括鉬膜之閘電極結構(gate electrode structure),閘電極結構具有的有效工作函數(effective work function)係大於約4.9電子伏特(eV)、或大於約5.0電子伏特、或大於約5.1電子伏特、或大於約5.2電子伏特、或大於約5.3電子伏特、或甚至大於約5.4電子伏特。在一些實施例中,對包括具有小於約100埃(Angstroms)、或小於約50埃、或小於約40埃、或甚至小於約30埃厚度的鉬層之電極結構而言,可論證上文所給定的有效工作函數值。
在所屬領域中具有通常知識者將理解,在不偏離本發明範疇的情況下,可對上述製程及結構作出各種省略、添加、及修改。預期可作出實施例之特定特徵及態樣的各種組合或子組合,且其等仍落在本說明書之範疇內。揭示實施例之各種特徵及態樣可依序相互組合或彼此取代。所有此類修改及變化係意欲歸屬於如由隨附之申請專利範圍所定義之本發明的範疇內。
1:循環
2:循環
3:步驟
5:步驟
7:步驟
9:供應
10:步驟
11:步驟
13:步驟
15:供應
17:步驟
R1:第一移除週期,第二移除週期,持續時間
R2:持續時間
R3:第三移除週期,持續時間
R4:第四移除週期,持續時間
T1:第一供應週期,持續時間
T2:第二供應週期,持續時間
T3:第三供應週期,持續時間
T4:第四供應週期,持續時間
雖然本說明書以特別指出且明確主張被視為本發明實施例之權利的申請專利範圍作為結論,但是當結合伴隨圖式閱讀時,可從本揭露的實施例之某些實例的描述更容易地探知本揭露之實施例的優點,其中:
第1a圖及第1b圖顯示流程圖,其繪示根據一實施例之一種沉積層之方法。
1:循環
3:步驟
5:步驟
7:步驟
9:供應
10:步驟
Claims (21)
- 一種在一反應室中之一基材上沉積一含鉬層之方法,包括: 供應包括二氯二氧化鉬(VI) (MoO2 Cl2 )之一前驅物至該反應室中之該基材;以及 供應一第一反應物至該反應室中之該基材以使得一部分之該前驅物及該第一反應物起反應以形成該鉬層,其中該第一反應物包括硼及氫。
- 如請求項1之方法,其中該鉬層係一種晶層。
- 如請求項2之方法,更包括藉由一方法提供一主體鉬層至該種晶層,該方法包括: 供應包括二氯二氧化鉬(VI)之該前驅物至該反應室中之該基材;以及 供應包括氫氣之一第二反應物至該反應室中之該基材,其中一部分之該前驅物及該反應物起反應以形成該主體鉬層。
- 如請求項3之方法,其中該第二反應物包括氫氣(H2 )。
- 如請求項1之方法,其中該前驅物係以脈衝供應至該反應室中且該等脈衝係介於0.1與10秒之間。
- 如請求項1之方法,其中該前驅物至該反應室中之流量係介於50與1000單位時間標準毫升數之間。
- 如請求項1之方法,其中該第一反應物至該反應室中之流量係介於50與50000單位時間標準毫升數之間。
- 如請求項1之方法,其中該反應室中之壓力係介於0.1與100托耳之間。
- 如請求項1之方法,其中製程溫度係介於300與800° C之間。
- 如請求項1之方法,其中沉積該鉬層包括重複一原子層沉積循環,該原子層沉積循環包括循序地供應該前驅物及該第一反應物至該基材。
- 如請求項10之方法,其中在供應該第一前驅物與該第一反應物之間,該基材係經吹掃介於0.5與50秒之間的時間。
- 如請求項11之方法,其中供應該第一反應物至該反應室中花費介於0.5與50秒之間的時間。
- 如請求項1之方法,其中包括硼及氫之該第一反應物係選自由具有化學式Bn H(n+x) 之硼烷所組成的群組,其中n係從1至10的一整數,且x係一偶數。
- 如請求項13之方法,其中包括硼及氫之該第一反應物係選自由具有化學式Bn H(n+4) 之巢式硼烷所組成之群組。
- 如請求項13之方法,其中包括硼及氫之該第一反應物係選自由具有化學式Bn H(n+6) 之網式硼烷所組成之群組。
- 如請求項13之方法,其中包括硼及氫之該第一反應物係選自由具有化學式Bn H(n+8) 之敞網式硼烷所組成之群組。
- 如請求項13之方法,其中包括硼及氫之該第一反應物係二硼烷(B2 H6 )。
- 如請求項1之方法,其中包括硼及氫之該第一反應物係選自由具有化學式Bn Hm 之聯式硼烷所組成的群組,其中n係從1至10的一整數,且m係從1至10之不同於n的一整數。
- 如請求項1之方法,其中在提供該前驅物至該反應室之前,在該反應室中提供包括硼及氫之該第一反應物以製備該基材表面。
- 如請求項1之方法,其中該基材包括在製造該基材上之一特徵期間所產生的一或多個間隙,且該一或多個間隙係藉由該在一反應室中之一基材上沉積一含鉬層之方法而至少部分地填充。
- 一種在一基材上沉積一含鉬層之沉積設備,包括: 一反應室,具有一基材固持器以固持一基材; 一加熱系統,構成及佈置以控制該基材的溫度; 一分配系統,包括閥以在該反應室中提供一前驅物及至少一第一反應物;以及 一序列控制器,可操作地連接至該等閥,且經程式化以致能使用該前驅物及該第一反應物在該反應室中之該基材上沉積鉬,其中該分配系統具有一前驅物輸送裝置及一第一反應物輸送系統,該前驅物輸送裝置用以輸送二氯二氧鉬(VI) (MoO2 Cl2 )蒸氣,該第一反應物輸送系統構成及佈置以輸送包括硼及氫之一第一反應物之一蒸氣。
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