TWI682057B - 使用四碘化鈦前驅物在低溫下沉積純鈦薄膜的方法及設備 - Google Patents
使用四碘化鈦前驅物在低溫下沉積純鈦薄膜的方法及設備 Download PDFInfo
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- TWI682057B TWI682057B TW104126934A TW104126934A TWI682057B TW I682057 B TWI682057 B TW I682057B TW 104126934 A TW104126934 A TW 104126934A TW 104126934 A TW104126934 A TW 104126934A TW I682057 B TWI682057 B TW I682057B
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- titanium
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- semiconductor substrate
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- 239000010936 titanium Substances 0.000 title claims abstract description 114
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 88
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 title claims description 32
- 239000010409 thin film Substances 0.000 title description 4
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 238000000151 deposition Methods 0.000 claims abstract description 56
- 238000010926 purge Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 40
- 239000004065 semiconductor Substances 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000012159 carrier gas Substances 0.000 claims description 21
- 238000000231 atomic layer deposition Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910021341 titanium silicide Inorganic materials 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 230000008676 import Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 62
- 238000012545 processing Methods 0.000 description 62
- 230000008021 deposition Effects 0.000 description 23
- 239000007788 liquid Substances 0.000 description 16
- 239000000376 reactant Substances 0.000 description 16
- 235000012431 wafers Nutrition 0.000 description 16
- 238000002156 mixing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- 238000005240 physical vapour deposition Methods 0.000 description 9
- 238000009834 vaporization Methods 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000012546 transfer Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005137 deposition process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 238000000560 X-ray reflectometry Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 238000001636 atomic emission spectroscopy Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- -1 nitrogen-containing compound Chemical class 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012163 sequencing technique Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010386 TiI4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 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
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 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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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- 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
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Abstract
本文提供在低溫下沉積高度保形及高純度之鈦膜的方法。該方法涉及以下步驟:將基板曝露於四碘化鈦、清除腔室、將基板曝露於電漿、清除腔室、及重複該等操作。鈦膜沉積於低於約450℃的低溫。
Description
本揭露內容係關於半導體基板處理,更具體而言,係關於使用四碘化鈦前驅物在低溫下沉積純鈦薄膜的方法及設備。
半導體生產製程通常涉及鈦或含鈦化合物之沉積。在習知情況下,已藉由物理氣相沉積濺鍍方法來沉積鈦薄膜。隨著半導體裝置縮放至越來越小的技術節點,縮小特徵部的尺寸使沉積高度保形且高純度的鈦膜更具挑戰性。增加之縱橫比可導致特徵部表面上不完整的階梯覆蓋率,造成半導體裝置中不良的阻障性能。針對沉積鈦薄膜所使用之其他方法已造成具有由於所使用的前驅物所致之雜質的鈦膜,或已造成熱預算的問題。
本說明書中所提供的係沉積鈦或含鈦化合物之方法。一態樣包含在低於約450℃的溫度下,藉由使用原子層沉積循環,在腔室中將鈦沉積於半導體基板上,此處之每一循環包含:(i)將該基板曝露於四碘化鈦、(ii)清除該腔室、(iii)將該基板曝露於引燃之電漿、及(iv)清除該腔室、及重複(i)至(iv)直至所需厚度之鈦已沉積於該基板上為止。每一循環可沉積具有厚度約為0.5 Å的鈦。
在各種實施例中,該方法更包含在將該基板曝露於四碘化鈦之前,將該基板預潔淨。在某些實施例中,在(i)至(iv)之整個期間使該基板曝露於載氣。該載氣係可選自由氬、氫、及其組合所組成之群組。該電漿可遠端產生或在該腔室中產生。
在各種實施例中,該方法更包含將所沉積之鈦回火以形成鈦矽化物。在某些實施例中,在(i)中該基板曝露於四碘化鈦達一段介於1秒與約30秒之間的持續時間,在(ii)及(iv)中清除該基板各達一段介於1秒與5秒之間的持續時間,而在(iii)中該基板曝露於電漿達一段介於1秒與10秒之間的持續時間。
在某些實施例中,所沉積之鈦具有少於約1%的摻雜物,或少於約0.1%的摻雜物。在某些實施例中,所沉積之鈦具有至少約4.0 g/cc的膜密度。所沉積之鈦可具有介於約70%與約100%之間的階梯覆蓋率。在某些實施例中,該腔室壓力係可介於約0.1 Torr與約20 Torr之間。在某些實施例中,該基板上之特徵部可具有介於約3:1與約10:1之間的縱橫比。
在各種實施例中,該方法更包含在低於約450℃的溫度下,使用原子層沉積循環來鈦氮化物,此處之每一循環包含:(i)將該基板曝露於四碘化鈦、(ii)清除該腔室、(iii) 將該基板曝露於含氮氣體並引燃電漿、及(iv)清除該腔室;及重複(i)至(iv)直至所需厚度之鈦氮化物已沉積於該基板上為止。在某些實施例中,該氣體係選自由氮、氨、聯氨、及胺類所組成之群組。
另一態樣涉及用於在半導體基板上沉積鈦之設備,此處該設備包含一反應之腔室,包含用以支撐該基板之基座;至少一排氣口,用於連接至真空;一或更多的製程氣體進氣口,其連接至一或更多個前驅物源;一射頻(RF, radio frequency)產生器;及一控制器,用於控制該設備中之操作。該控制器包含機器可讀取之指令,該等指令用於:(a)將該反應之腔室中之該基座的溫度設定至低於約450℃的溫度、(b)將四碘化鈦導入至該腔室、(c)清除該腔室、(d)在該腔室中提供電漿、及(e)清除該腔室、及(f)重複(b)至(e)。
在某些實施例中,該等指令係配置成在每一(b)至(e)的循環中沉積約0.5 Å的鈦。在各種實施例中,該控制器更包含機器可讀取之指令,該指令用於:(g)將四碘化鈦導入至該腔室、(h)清除該腔室、(i)在該腔室中提供電漿、(j)將含氮氣體導入至該腔室、及(k)清除該腔室;及(l)重複(g)至(k)。在某些實施例中,該氣體係選自由氮、氨、聯氨、及胺類所組成之群組。
該等及其他態樣係參照圖示進一步敘述於下。
在以下敘述中,為提供對於所呈現實施例之完整瞭解,將提出許多具體細節。在不具有這些具體細節之部分或全部者的情況下,仍可實施本揭露實施例。在其他情況下,為避免不必要地混淆本揭露實施例,因此已不詳細描述眾所周知的程序操作。雖然本揭露實施例將結合具體實施例而描述,但應瞭解其並非意欲限制本揭露實施例。
對於半導體裝置製造而言,沉積純、薄的保形鈦膜係為關鍵性的。在前段製程(FEOL, front end of the line)及後端製程(BEOL, back end of line)兩者之金屬化作用中,鈦膜及鈦化合物係作為阻障層來使用。尤其,鈦膜係作為接點中的阻障來使用,如鎢或銅接點。在習知情況下,在接點中所使用的阻障層已包含鉭及氮化鉭,或兩者之組合。沉積方法一般包含物理氣相沉積(PVD, physical vapor deposition)濺鍍。然而,由於鈦作為低電阻材料,對於半導體裝置之各種元件的廣泛應用性,因此具有鈦阻障層的接點係受到特別關注。
隨著產業移向發展越來越小的半導體裝置,特徵部縮小,且特徵部(鈦將沉積於該處)的縱橫比係為高。此類特徵部可具有約30 nm或更小的特徵部開口。高縱橫比之範例包含介於約3:1與10:1之間的縱橫比,如5:1。當使用習知技術來將鈦沉積於高縱橫比的特徵部中時,階梯覆蓋率低。由於濺鍍方法之方向性性質,階梯覆蓋率僅介於約15%及約20%之間,且所沉積的薄膜之均勻度係為低。
針對將鈦沉積於高縱橫比的特徵部中,已提出化學氣相沉積(CVD, Chemical vapor deposition)方法,以形成高度保形膜。然而。藉由CVD來沉積涉及金屬有機鈦前驅物(如TDMAT、TEMAT、TDEAT等)之使用、或四氯化鈦(TiCl4
, titanium chloride)之使用。使用金屬有機前驅物時,通常會由於結合有機物種而造成該鈦膜中的雜質,而使該鈦膜包含碳及氮摻雜物。使用TiCl4
來進行沉積牽涉分解TiCl4
,其於高溫(如:超過約600℃)下執行,以防止氯結合至所沉積的鈦膜中。使用習知技術來沉積鈦之製程條件可能超出該裝置的熱預算,如此一來當基板曝露於高溫下,該基板之既存下層可能受到損害或失效。
本說明書中所提供的係為針對用於半導體處理,於低溫下在高縱橫比的特徵部中沉積高度保形及高純度鈦膜的方法。該方法涉及使用含鈦前驅物(如此一來該前驅物具有通式Tix
Ry
)來進行鈦的沉積。儘管可使用其他含鈦化合物,針對本揭露實施例,四碘化鈦(TiI4
, titanium tetraiodide)係作為一範例來使用。本揭露實施例的優點包含以下各項:在低溫下使用TiI4
來進行沉積、沉積無雜質或幾乎無雜質之實質上的純鈦膜、及在FEOL及BEOL兩者之應用中,用以沉積鈦及鈦化合物兩者之該沉積方法的廣泛應用性。
由於雖然碘較某些其他鹵化物更不易揮發,但鈦-碘鍵結較其他鍵結(如:鈦-氯鍵結)更易斷裂,因此四碘化鈦係為特別有用的鈦前驅物。此情況係由於鈦-碘鍵結之較低的吉布斯自由能(ΔG, Gibbs free energy)( TiI4
之ΔG = -370.69 kJ/mol;TiCl4
之ΔG = -725.3 kJ/mol;TiI4
之生成熱焓(ΔH, enthalpy of formation) = -375.72 kJ/mol;TiCl4
之ΔH = -762.32 kJ/mol)所造成。
圖1提供操作之流程圖,其係用於執行依據所揭露之實施例的方法。圖1之操作針對FEOL應用,可在低於約450℃的溫度下執行,或針對BEOL應用,可在低於約400℃的溫度下執行。在各種實施例中,執行圖1之操作的腔室之溫度係低於約350℃。該腔室之壓力可為介於約0.1 Torr與約20 Torr之間,或介於約1 Torr與約3 Torr之間。於圖1之操作期間,可流動載氣。該載氣可為任何惰性氣體(如氬),其可以介於約100 sccm與約300 sccm之間的流率來流動。例如氬之氣體係特別適於高純度鈦膜之沉積。在鈦化合物將沉積於基板上的實施例中,第二氣體可與該載氣一起使用,或以第二氣體替代該載氣來使用,例如針對沉積TiN,第二氣體可為氮氣(N2
)、或含氮氣體。
在圖1的操作102中,可選擇性地將基板預潔淨。預潔淨可包含以下各項:熱處理、一段高達約2分鐘時間之電漿處理(例如利用Ar、或以反應性F或Cl為基底的化學物)、或任何其他合適的預潔淨處理。
在操作104中,將該基板曝露於含鈦前驅物,如TiI4
。該含鈦前驅物被吸附至該基板表面之活性位置上。在某些實施例中,將該基板曝露一段足以覆蓋實質上所有該活性位置的持續時間,例如該活性位置之至少約80%,或至少約90%。在各種實施例中,將該基板曝露於含鈦前驅物達一段介於約1秒與約30秒之間的時間。
該含鈦前驅物可具有高蒸氣壓,例如在約85℃下,大於約110 mTorr之壓力。含鈦前驅物之範例包含具有化學式TiXn
之化合物,其中n為介於2至4之間且包含2與4之整數,而X為鹵化物。具體範例包含TiI4
、TiCl4
、TiF4
、及TiBr4。在各種實施例中,將該基板曝露於TiI4。在某些實施例中,該含鈦前驅物為非有機化合物。該含鈦前驅物可儲存於在沉積腔室上游的起泡器中。該起泡器可設定在介於約80℃與約160℃之間、或低於約100℃的溫度。
操作104可於含電漿或不含電漿之情況下執行。若使用電漿,則該電漿可為遠端電漿或原位電漿。該電漿可具有介於約13.56 MHz與約27 MHz之間的頻率。在某些實施例中,該電漿具有27 MHz之頻率。該電漿之功率係可介於約0.3 W/cm2
與約0.6 W/cm2
之間。
在操作106中,將腔室內留在氣相中的任何殘餘之含鈦前驅物清除。就此而言,在此操作期間,停止流動該含鈦前驅物,而該載氣則持續流至該腔室中。此操作可執行一段介於約1秒與約5秒之間的時間。
在操作108中,將該基板曝露於電漿。在此操作期間,可流動任何惰性氣體,如氬或H2
。在某些實施例中,當該電漿引燃時,流動氬及H2
之混合物。該電漿可為遠端電漿或原位電漿,且可具有上述關於操作104之頻率及功率之任一者。在許多實施例中,此電漿劑量可執行一段介於約1秒與約10秒之間的持續時間。在此操作期間,可使鈦與任何配位基(如碘原子)之間的鍵結斷裂,俾固體的、且實質上純的(少於約1%之摻雜物)鈦留在該基板上。
在操作110中,關閉該電漿且清除該腔室,而僅使該載氣(其在操作104與108之整段期間持續流動)持續流至該腔室中。此清除過程可執行一段介於約1秒與約5秒之間的持續時間。在此操作期間,可將任何自操作108期間所移除之配位基所形成之化合物清除。舉例而言,在此操作期間,可將碘(I2
)移除。該電漿可為原位電漿或遠端電漿。
在操作112中,決定該所沉積之膜是否已沉積成足夠的厚度,該厚度可為沉積高度保形的純鈦所需之任何合適的厚度。若尚未達成,則重複操作104至110直至該膜沉積成足夠的厚度為止。
圖2係為具有各種曝露及清除階段的時序方案之示意圖。如所示,在方案200中,第一沉積循環210A可包含一系列的四個操作(220A、240A、260A、280A),其分別對應圖1中的操作104、106、108、及110。操作104對應220A中之TiI4
曝露階段。應注意,在該曝露期間,氬係作為載氣流動,TiI4
流至該腔室中,而該電漿關閉。操作106對應清除階段240A,此時該TiI4
曝露關閉,該電漿為關閉狀態,而僅有氬持續流動。操作108對應電漿曝露階段260A,此時該電漿開啟,該TiI4
流動維持關閉,而氬持續流動。該電漿協助移除任何附於所沉積之鈦上的配位基(如碘原子),以產生高純度的鈦膜。操作110對應清除階段280A,此時該電漿關閉,該TiI4
流動維持關閉狀態,而氬持續流動以將任何殘餘之TiI4
或電漿清除。沉積循環210B顯示重複之沉積循環的範例,其用於若該鈦膜在基板上尚未沉積足夠的厚度。在沉積循環210B中,重複圖1中之操作104至110,分別造成TiI4
曝露階段220B、清除階段240B、電漿曝露階段260B、及清除階段280B。必要時可重複另外的沉積循環。
該所沉積的高純度鈦膜可具有介於約70%與約100%之間的階梯覆蓋率,或對於具有約為3:1的縱橫比之特徵部,其具有至少約90%的階梯覆蓋率。在縱橫比約為5:1之某些實施例中,該鈦膜之階梯覆蓋率係可介於約50%與約70%之間。使用本說明書中所揭露之方法來進行沉積,通常不會造成該膜有超出位於特徵部開口處之邊緣的突出部分。
在各種實施例中,所沉積之鈦膜可具有少於約0.1%的原子碘雜質,或少於約1%的摻雜物。該鈦膜可沉積至任何所需厚度,如介於約2 nm與20 nm之間,或少於約5 nm。每循環所沉積的膜之厚度可約為0.5 Å。可視對於該期望之鈦膜所需的次數而重複循環。該所沉積的膜具有至少約4.0 g/cc或約4.2 g/cc之密度。在某些實施例中,使用本說明書中所敘述之方法所沉積之該鈦膜,具有相當於使用PVD濺鍍直接在基板上所沉積之鈦膜的特性及屬性,除了在高縱橫比的特徵部中,該使用本說明書中所敘述之方法所沉積的膜,較使用PVD濺鍍所沉積的膜而言,具有更高的階梯覆蓋率。在某些實施例中,對於140 Å的鈦膜而言,其電阻可為小於約400 µΩ-cm。
圖3描繪本說明書中所敘述方法之應用的實例之流程圖。鈦/鈦氮化物膜可使用該所敘述的方法之變化來沉積,俾可於基板上之高縱橫比的特徵部中沉積具有高階梯覆蓋率之薄、高度保形的膜。在沉積金屬以形成接點之前,鈦/鈦氮化物膜可沉積於特徵部中作為阻障。
具有各種高縱橫比之特徵部的基板,首先可使用如上述關於圖1中操作102之條件及化學物來進行預潔淨。在某些實施例中,該預潔淨操作可為選擇性的。在該選擇性的預潔淨之後,在操作312中,使用如該等上述有關圖1中操作104至110的方法及條件來沉積薄鈦層。例如,高純度、高度保形之鈦可沉積成小於約2 nm之厚度,且具有至少4.0 g/cc的密度。
在操作314中,可於低於約450℃下,使用熱回火來選擇性地後處理該所沉積之高純度鈦,此造成鈦矽化物(TiSix
,在某些情況下,此處的x=2)或TiSix
Gey
(0 < x+y < 2)的形成。
在該選擇性的後處理之後,在操作316中,可藉由原子層沉積法(ALD, atomic layer deposition),使用脈衝法來沉積鈦氮化物。在此沉積過程中,該腔室之壓力、溫度、及載氣流率與類型,可與在鈦沉積過程中的相同。
藉由首先將該基板曝露於一前驅物劑量,可沉積鈦氮化物,其中電漿可為開啟或關閉狀態,達一段介於約1秒至30秒之間的時間。藉由載氣氣流或第二氣體氣流,可將該前驅物導入至該基板。可將該前驅物清除,而使該前驅物之流動停止,而該電漿關閉,但該載氣氣流或第二氣體氣流則持續流動達約1秒至約5秒。隨後,將該基板曝露於一電漿劑量,此時該載氣或第二氣體持續流動,無額外的前驅物流動被導入,而該電漿開啟達一段介於約1秒與約10秒之間的時間。接著該電漿關閉,而該載氣或第二氣體持續流動達約1秒至5秒。該等順序可映射至圖1中之操作104至110。如圖1,該等操作可重複直至該鈦氮化物膜沉積成足夠的厚度為止。
應注意,欲沉積鈦氮化物以替代純鈦,該載氣或第二氣體包含含氮化合物。在某些實施例中,該含氮化合物係為金屬有機化合物。尤其,可使用反應性之含氮反應物。在使用反應性之含氮反應物之某些實施例中,該電漿劑量可降低其時間或功率、或可消除該電漿劑量。可使用之含氮化合物的範例包含氮(N2
)、氨(NH3
)、聯氨家族、及胺類。金屬有機前驅物之範例為(四(二乙基醯胺基)鈦)(TDEAT,tetrakisdiethylamidotitanium)。
在該鈦氮化物層沉積於基板後,在操作318中,將鎢沉積於該基板上以形成接點或鎢插塞。在各種實施例中,藉由CVD來沉積鎢。在操作320中,該基板可選擇性地平坦化以形成完整的鎢接點或鎢插塞。
本說明書中所揭露之實施例可用於沉積高度保形及實質上純的鈦,以及鈦化合物,如鈦氮化物、鈦矽化物、及鈦氧化物。設備
圖4描繪具有處理腔室體402的ALD處理站400之實施例的示意圖示。多個ALD處理站400可包含於一般的處理工具環境。舉例而言,圖5描繪多站處理工具500之實施例。在某些實施例中,可藉由一或更多的電腦控制器450,程式性地調整ALD處理站400之一或更多的硬體參數,包含該等以下詳加討論的參數。
ALD處理站400與用於遞送製程氣體至分配噴淋頭406之反應物遞送系統401a流體連通。反應物遞送系統401a包含用於混合及/或調節遞送至噴淋頭406之製程氣體的混合容器404。一或更多的混合容器進氣閥420可控制製程氣體至混合容器404之導入。該站400包含安瓿盒413,其經由安瓿線連接至腔室402。舉例而言,可使用反應物遞送系統401a來遞送TiI4
。
作為實例,圖4之實施例包含用於汽化欲供應至混合容器404之液態反應物的汽化點403。在某些實施例中,汽化點403可為加熱之汽化器。由此類汽化器所產生的飽和反應物蒸氣可在下游遞送管道中凝結。不相容氣體曝露於該凝結反應物可能產生小顆粒。該等小顆粒可能會阻塞管道、妨礙閥操作、污染基板等。用以解決該等問題的一些方法涉及清除及/或排空遞送管道以移除殘留之反應物。然而,清除遞送管道可能增加處理站的循環時間,而降低處理站的產量。因此,在某些實施例中,可對汽化點403下游之遞送管道進行加熱保溫。在某些實例中,混合容器404亦受到加熱保溫。在一非限制性的實例中,汽化點403下游之管道具有在混合容器404處自約100℃延伸至約150℃之遞增的溫度曲線。
在某些實施例中,液體前驅物或液體反應物可於液體注入器進行汽化。例如,液體注入器可將液體反應物之脈衝注入該混合容器上游之載氣氣流中。在一實施例中,液體注入器可藉由將液體從較高壓力急驟蒸發至較低壓力而使該反應物汽化。在另一實施中,液體注入器可使該液體霧化為分散微滴,該分散微滴隨後於加熱的遞送管道中汽化。較小的液滴可較較大液滴更快汽化,而縮短液體注入與完全汽化之間的延遲。較快的汽化可縮短自汽化點403下游之管道的長度。在一情況下,液體注入器可直接安裝至混合容器404。在另一情況下,液體注入器可直接安裝至噴淋頭406。
在某些實施例中,汽化點403上游之液體流量控制器(LFC, liquid flow controller)係設置以控制汽化並遞送至處理站400之液體的質流。舉例而言,該LFC可包含位於LFC下游之熱質量流量計(MFM, thermal mass flow meter)。該LFC之活塞閥係因應由與該MFM電性連通之比例-積分-微分(PID, proportional-integral-derivative)控制器所提供之反饋控制信號而調整。然而,使用反饋控制來使液體流量穩定需要1秒鐘或更久。此情況可能延長施用液體反應物的時間。因此,在某些實施例中,該LFC係於反饋控制模式與直接控制模式之間進行動態切換。在某些實施例中,藉由停止該LFC的感測管及該PID控制器,可執行該動態切換。
噴淋頭406朝向基板412分配製程氣體。在圖4所示之實施例中,基板412係位於噴淋頭406之下方,且係顯示為置於基座408上。噴淋頭406可具有任何合適的形狀,且可具有用於將製程氣體分配至基板412之任何合適的數目及配置之埠口。
選擇性地,於部分製程期間,基座408可下降及/或上升以調節製程壓力、反應物濃度等。應瞭解,在某些實施例中,藉由合適的電腦控制器450,可程式性地調整基座高度。
在另一情況下,調整基座408的高度可允許於包含於該製程中之電漿活化及/或處理循環期間改變電漿密度。在該製程階段結束時,於另一基板搬運階段期間,使基座408下降以允許自基座408移去基板412。
再者,應瞭解,在本揭露內容之範圍內,可藉由任何合適的機制來改變基座408及/或噴淋頭406的垂直位置。在某些實施例中,基座408可包含用以轉動基板412之方向的轉軸。應瞭解,在某些實施例中,藉由一或更多的合適的電腦控制器450,可程式性地執行該等例示性調整之一或更多者。
在某些實施例中,其中可使用如上討論之電漿,噴淋頭406及基座408與射頻(RF, radio frequency)電源414及匹配網路416電性連通以對電漿供電。在某些實施例中,藉由控制處理站壓力、氣體濃度、RF源功率、RF源頻率、及電漿功率脈衝時序之其中一或多者,而可控制該電漿能量。例如,RF電源414及匹配網路416可在任何適當的功率下操作,以形成具有期望之自由基物種組成物的電漿。合適功率之範例包含於上。同樣地,RF電源414可提供任何合適的頻率之RF功率。在某些實施例中,RF電源414係可配置以互相獨立地控制高頻及低頻RF電源。例示性低頻RF頻率可包含(但不限於)介於50 kHz與500 kHz之間的頻率。例示性高頻RF頻率可包含(但不限於)介於1.8 MHz與2.45 GHz之間的頻率。應瞭解,可不連續或連續地調節任何合適的參數以對表面反應提供電漿能量。在一非限制性之實例中,相對於連續地對電漿供電,可間歇地以脈衝輸送電漿功率以降低基板表面之離子轟擊。
在某些實施例中,可藉由一或更多的電漿監視器來原位監測電漿。在一情況下,可藉由一或更多的電壓、電流感測器(如:VI探針)來監視電漿功率。在另一情況下,可藉由一或更多的光學放射光譜(OES, optical emission spectroscopy)感測器來量測電漿密度及/或製程氣體濃度。在某些實施例中,可基於來自此類原位電漿監視器之量測而程式性地調整一或更多的電漿參數。舉例而言,OES感測器可用於用以提供電漿功率之程式性控制的反饋迴路中。應瞭解,在某些實施例中,可使用其他監視器來監視該電漿及其他製程特性。此類監視器可包含(但不限於)紅外線(IR, infrared)監視器、聲波監視器、及壓力傳感器。
在某些實施例中,可經由輸入/輸出控制(IOC, input/output control) 定序指令來提供控制器450之指令。在一實例中,設定製程階段之條件的指令可包含於製程配方的對應配方階段中。在某些情況下,可依序安排製程配方階段,以使製程階段的所有指令與該製程階段同時執行。在某些實施例中,設定一或更多的反應器參數之指令可包含於配方階段中。例如,第一配方階段可包含設定惰性氣體及/或反應氣體(如:如TiI4
之第一前驅物)之流率的指令、設定載氣(如氬或氮)之流率的指令、及第一配方階段之時間延遲指令。隨後的第二配方階段可包含調整或停止惰性氣體及/或反應氣體之流率的指令、及調整載氣或清除氣體之流率的指令、及第二配方階段之時間延遲指令。第三配方階段可包含設定惰性氣體及/或反應氣體 (其可與用於第一配方階段中之氣體相同或不同)(如:如氬之第二前驅物)之流率的指令、調整載氣之流率的指令、及第三配方階段之時間延遲指令。第四配方階段可包含調整或停止惰性氣體及/或反應氣體之流率的指令、調整載氣或清除氣體之流率的指令、及第四配方階段之時間延遲指令。應瞭解,在本揭露內容之範圍內可以任何合適的方式進一步再分割及/或重複該等配方階段。
在某些實施例中,可經由加熱器410對基座408進行溫度控制。例如,在沉積高度保形及高純度鈦層之期間,可於低溫(如300℃)下使用加熱器410來加熱基座408。再者,在某些實施例中,藉由蝶形閥418,可提供針對處理站400之壓力控制。如圖4實施例中所示,蝶形閥418調節由下游真空泵(未顯示)所提供之真空。然而,在某些實施例中,藉由改變被導入至處理站400之一或更多的氣體的流率,亦可調整處理站400之壓力控制。
如上所述,一或更多的處理站可包含於多站處理工具中。圖5顯示具有入站負載鎖室502及出站負載鎖室504(其中一者或兩者可包含遠端電漿源)之多站處理工具500的示意圖。處於大氣壓力下之機械臂506係配置成將晶圓自通過箱體508而載入之卡匣,經由大氣埠510,移至入站負載鎖502室中。藉由機械臂506將晶圓放置於入站負載鎖室502中的基座512上,關閉大氣埠510、並將負載鎖室抽空。其中入站負載鎖室502包含遠端電漿源,在將晶圓導入處理腔室514之前,可將晶圓曝露至負載鎖室中的遠端電漿處理。再者,亦可於入站負載鎖室502中將晶圓加熱,以例如去除水分及吸附之氣體。接著,開啟通往處理腔室514之腔室傳送埠516,而另一機械臂(未顯示)將晶圓放置於反應器中之該反應器中所示第一站的基座上以供處理。雖然圖5中所描繪之實施例包括負載鎖室,但應瞭解,在某些實施例中,可提供晶圓至處理站之直接進入。
該所描繪之處理腔室514包含四個處理站,在圖5中所示之實施例中,從1至4編號。各站皆具有加熱基座(顯示於站1的518處)、及氣體管線入口。應瞭解,在某些實施例中,各處理站可具有不同或多種目的。例如,在某些實施例中,處理站可在ALD與電漿輔助ALD處理模式之間進行切換。此外或或者,在某些實施例中,處理腔室514可包含ALD與電漿輔助ALD處理站之一或更多的匹配對。雖然該所描繪之處理腔室514包含四個處理站,但應瞭解,依據本揭露內容之處理腔室可具有任何合適數量的站。例如,在某些實施例中,處理腔室可具有五或更多的站,而在其他實施例中,處理腔室可具有三或更少的站。
圖5描繪在處理腔室514內用以傳送晶圓之晶圓搬運系統的實施例。在某些實施例中,晶圓搬運系統可在各種處理站之間及/或在處理站與負載鎖室之間傳送晶圓。應瞭解,可使用任何合適的晶圓搬運系統。非限制性之實例包含晶圓旋轉料架及晶圓搬運機械臂。圖5亦描繪系統控制器550之實施例,該系統控制器係用以控制處理工具500之製程條件與硬體狀態。系統控制器550可包含一或更多的記憶裝置556、一或更多的大量儲存裝置554、及一或更多的處理器552。處理器552可包含CPU或電腦、類比及/或數位輸入/輸出連接部、步進馬達控制器板等。
在某些實施例中,系統控制器550控制處理工具500的所有作業。系統控制器550執行系統控制軟體558,該系統控制軟體儲存於大量儲存裝置554中、載入至記憶體裝置556中、並於處理器552上執行。或者,可將控制邏輯硬碼化於控制器550中。特殊應用積體電路、可編程邏輯裝置(如:場可程式化閘陣列(FPGAs, field-programmable gate arrays))等,可用於該等用途。在下列討論中,無論「軟體」或「編碼」用於何種情況,功能上相當之硬碼化邏輯皆可用於該狀況。系統控制軟體558可包含用以控制時序、氣體之混合、不完全飽和之氣體氣流的量、腔室及/或站壓力、腔室及/或站溫度、晶圓溫度、目標功率位準、RF功率位準、基板基座、夾具及/或載具位置、及由處理工具500所執行的特定製程之其他參數的指令。系統控制軟體558可以任何合適的方式來配置。例如,可寫入各種處理工具元件子程式或控制目標,以控制執行各種處理工具製程必要之該處理工具元件的操作。系統控制軟體558可以任何合適的電腦可讀取程式語言來進行編碼。
在某些實施例中,系統控制軟體558可包含用以控制上述各種參數之IOC定序指令。在某些實施例中,可使用儲存於與系統控制器550相關聯之大量儲存裝置554及/或記憶裝置556上的其他電腦軟體及/或程式。用於此用途之程式或程式片段的範例包括基板定位程式、製程氣體控制程式、壓力控制程式、加熱器控制程式、及電漿控制程式。
基板定位程式可包含處理工具元件的程式碼,該處理工具元件係用以將基板裝載至基座518上,並控制基板與處理工具500其他部分之間的間距。
製程氣體控制程式可包含編碼,該編碼係用以控制氣體組成物(如:TMA、氨、及如本說明書中所敘述之清除氣體)、及流率、及選擇性地用以在沉積前將氣體流入一或更多的處理站以使該處理站中之壓力穩定。壓力控制程式可包含編碼,該編碼係藉由調節例如該處理站之排氣系統中的節流閥、進入該處理站之氣體氣流等,以控制該處理站中之壓力。
加熱器控制程式可包含編碼,該編碼係用以控制通往用於加熱基板之加熱單元的電流。或者,該加熱器控制程式可控制熱傳氣體(如氦)至基板之遞送。
電漿控制程式可包含編碼,該編碼係用以設定施加至依據本說明書中之實施例之一或更多處理站中之處理電極的RF功率位準。
壓力控制程式可包含編碼,該編碼係用以維持依據本說明書中之實施例的反應腔室中之壓力。
在某些實施例中,可存在有與系統控制器550相關聯之使用者介面。該使用者介面可包含顯示螢幕、設備及/或製程條件之圖形化軟體顯示器、及使用者輸入裝置(例如指向裝置、鍵盤、觸控螢幕、麥克風等)。
在某些實施例中,由系統控制器550所調整之參數可與製程條件有關。非限制性之範例包含製程氣體組成物及流率、溫度、壓力、電漿條件(如RF偏壓功率位準)等。可以配方的形式將該等參數提供給使用者,並可利用使用者介面來輸入該等參數。
可藉由系統控制器550之類比及/或數位輸入連接部,而自各種處理工具感測器提供用以監視製程的信號。可於處理工具500之類比及數位輸出連接部上,輸出用以控制製程之信號。可受到監測之處理工具感測器的非限制性範例包含質量流量控制器、壓力感測器(如壓力計)、熱電偶等。適當程式化之反饋及控制演算法可與來自該等感測器的資料一起使用,以維持製程條件。
系統控制器550可提供用以實施上述沉積製程的程式指令。該等程式指令可控制種種製程參數,如DC功率位準、RF偏壓功率位準、壓力、溫度等。該等指令可控制該等參數,以操作根據本說明書中所揭露之各種實施例的原位沉積或膜堆疊。
該系統控制器一般包含配置以執行該等指令之一或更多的記憶裝置及一或更多的處理器,以使該設備能執行依據該等所揭露之實施例之方法。包含依據該等所揭露之實施例來控制製程操作之指令的機器可讀取之媒體,可連接至系統控制器。
用以執行本說明書中所揭露之方法的適當裝置係更進一步於以下案中討論與敘述:申請於2011年4月11日的美國專利申請案第13/084,399號,發明名稱為「PLASMA ACTIVATED CONFORMAL FILM DEPOSITION」;及申請於2011年4月11日的美國專利申請案第13/084,305號,發明名稱為「SILICON NITRIDE FILMS AND METHODS」。上述申請案之各者整體併入本文中以作為參考文獻。
本說明書中所敘述之該裝置/製程可與例如用以製造或生產半導體元件、顯示器、LED、光伏面板等之微影圖案化工具或製程結合使用,一般而言(儘管非必然),此類工具/製程將於共同的製造設施中一起使用或執行。膜的微影圖案化一般包含部分或所有下列操作(每一個操作係以若干合適的工具來達成):(1)使用旋轉塗佈或噴霧塗佈工具將光阻塗佈於工件(例如基板)上;(2)使用加熱板、或加熱爐、或UV固化工具將光阻固化;(3)以例如晶圓步進機之工具將光阻曝露於可見光、或UV光、或x射線光;(4)使用例如溼式清洗台之工具將光阻顯影以選擇性地移除光阻,藉以將之圖案化;(5)藉由使用乾式或電漿輔助蝕刻工具將光阻圖案轉移至下層之膜或工件中;及(6)使用例如RF或微波電漿光阻剝除機之工具將光阻移除。實驗 實驗 1
實施一實驗以評估使用本說明書中所敘述之方法所沉積之鈦膜的特性。使用TiI4
(作為前驅物)及Ar/H2
電漿,藉由ALD在5 kÅ的矽氧化物(如:TEOS)基板上沉積鈦膜。該膜於基座溫度300℃及壓力3 Torr的情況下沉積。
圖6A顯示當鈦膜602沉積時的穿透式電子顯微鏡(TEM, transmission electron microscopy)影像。圖6B顯示該相同之膜的放大TEM影像。該ALD鈦膜與矽氧化物之間的介面看起來係平滑的。膜密度係藉由x射線反射率(XRR, X-ray reflectometry)分析而量測為4.2 g/cc,該測值相當於習知PVD鈦膜所量測之結果。對於140 Å厚的膜而言,該膜的電阻率係量測為約300 µΩ-cm,該測值僅稍微高於習知PVD鈦膜。該毯覆式膜觀察顯示,在低溫下使用TiI4
作為前驅物可沉積合適的鈦膜。實驗 2
使用本說明書中所敘述之方法,藉由ALD以TiI4
作為前驅物來沉積鈦氮化物膜。將該TiI4
前驅物與作為反應物之N2
一起導入腔室。所沉積之TiN膜具有對於60 Å的膜之200µΩ-cm的電阻率,其相當於PVD的TiN之電阻率。該膜之密度係藉由XRR分析而量測為4.6 g/cc,該測值亦相當於PVD的TiN膜之測值。該結果顯示,如本說明書中所敘述之方法中的TiN膜之電阻率係較使用金屬有機前驅物(TDMAT、TEMAT等)所沉積之TiN膜為低。結論
儘管已為了清楚理解之目的而詳加敘述前述實施例,但顯而易見的,在所附請求項之範圍內,可實施某些變更及改質。應注意,實施本實施例之製程、系統、及設備有許多替代方式。因此,應將本發明實施例視為說明性的,而非限制性的,且不將該等實施例限於本說明書中所提出的細節。
102‧‧‧操作
104‧‧‧操作
106‧‧‧操作
108‧‧‧操作
110‧‧‧操作
112‧‧‧操作
200‧‧‧方案
210A‧‧‧沉積循環
220A‧‧‧TiI4曝露階段
240A‧‧‧清除階段
260A‧‧‧電漿曝露階段
280A‧‧‧清除階段
210B‧‧‧沉積循環
220B‧‧‧TiI4曝露階段
240B‧‧‧清除階段
260B‧‧‧電漿曝露階段
280B‧‧‧清除階段
312‧‧‧操作
314‧‧‧操作
316‧‧‧操作
318‧‧‧操作
320‧‧‧操作
400‧‧‧處理站/站
401a‧‧‧反應物遞送系統
402‧‧‧處理腔室體/腔室
403‧‧‧汽化點
404‧‧‧混合容器
406‧‧‧噴淋頭
408‧‧‧基座
410‧‧‧加熱器
412‧‧‧基板
413‧‧‧安瓿盒
414‧‧‧RF電源
416‧‧‧匹配網路
420‧‧‧混合容器進氣閥
450‧‧‧控制器
500‧‧‧處理工具
502‧‧‧入站負載鎖室
504‧‧‧出站負載鎖室
506‧‧‧機械臂
508‧‧‧箱體
510‧‧‧大氣埠
512‧‧‧基座
514‧‧‧處理腔室
516‧‧‧腔室傳送埠
518‧‧‧基座
550‧‧‧系統控制器
552‧‧‧處理器
554‧‧‧大量儲存裝置
556‧‧‧記憶裝置
558‧‧‧系統控制軟體
602‧‧‧鈦膜
圖1依據各種實施例,係為一流程圖,繪示沉積鈦之方法中的操作。
圖2依據各種實施例,繪示脈衝之時序圖。
圖3依據各種實施例,係為一流程圖,繪示方法之應用的實例中之操作。
圖4依據所揭露之實施例,係為適用於沉積製程之處理腔室的一示意圖。
圖5依據所揭露之實施例,係為適用於沉積製程之處理系統的一示意圖。
圖6A及6B依據所揭露之實施例的實驗,係為所沉積之膜的穿透式電子顯微鏡(TEM, transmission electron microscopy)影像。
200‧‧‧方案
210A‧‧‧沉積循環
220A‧‧‧TiI4曝露階段
240A‧‧‧清除階段
260A‧‧‧電漿曝露階段
280A‧‧‧清除階段
210B‧‧‧沉積循環
220B‧‧‧TiI4曝露階段
240B‧‧‧清除階段
260B‧‧‧電漿曝露階段
280B‧‧‧清除階段
Claims (20)
- 一種在腔室中將鈦沉積於半導體基板上之方法,該方法包含:(a)在低於約450℃的溫度下使用原子層沉積循環來沉積鈦,每一循環包含:(i)將該基板曝露於四碘化鈦,(ii)清除該腔室,(iii)將該基板曝露於引燃之電漿,及(iv)清除該腔室;及(b)重複(i)至(iv)直至所需厚度之鈦已沉積於該基板上為止,其中該電漿係於一遠端電漿產生器中引燃。
- 如申請專利範圍第1項之在腔室中將鈦沉積於半導體基板上之方法,更包含在將該基板曝露於四碘化鈦之前,將該基板預潔淨。
- 如申請專利範圍第1項之在腔室中將鈦沉積於半導體基板上之方法,其中在(i)至(iv)之整個期間使該基板曝露於載氣。
- 如申請專利範圍第1項之在腔室中將鈦沉積於半導體基板上之方法,更包含將所沉積之鈦回火以形成鈦矽化物。
- 如申請專利範圍第1項之在腔室中將鈦沉積於半導體基板上之方法,其中該電漿於遠端產生。
- 如申請專利範圍第1項之在腔室中將鈦沉積於半導體基板上之方法,其中該電漿在該腔室中產生。
- 如申請專利範圍第3項之在腔室中將鈦沉積於半導體基板上之方法,其中該載氣係選自由氬、氫、及其組合所組成之群組。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中在(i)中該基板曝露於四碘化鈦達一段介於1秒與約30秒之間 的持續時間,在(ii)及(iv)中清除該基板各達一段介於1秒與5秒之間的持續時間,而在(iii)中該基板曝露於電漿達一段介於1秒與10秒之間的持續時間。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中所沉積之鈦具有少於約1%的摻雜物。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中所沉積之鈦具有至少約4.0g/cc的膜密度。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中每一循環沉積具有厚度約為0.5Å的鈦。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中所沉積之鈦具有介於約70%與約100%之間的階梯覆蓋率。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中該腔室具有介於約0.1Torr與約20Torr之間的腔室壓力。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,其中該基板包含具有介於約3:1與約10:1之間的縱橫比之特徵部。
- 如申請專利範圍第1-7項中任一項之在腔室中將鈦沉積於半導體基板上之方法,更包含:(a)在低於約450℃的溫度下使用原子層沉積循環來沉積鈦氮化物,每一循環包含:(i)將該基板曝露於四碘化鈦,(ii)清除該腔室,(iii)將該基板曝露於含氮氣體並引燃電漿,及(iv)清除該腔室;及(b)重複(i)至(iv)直至所需厚度之鈦氮化物已沉積於該基板上為止。
- 如申請專利範圍第15項之在腔室中將鈦沉積於半導體基板上之方法,其中該含氮氣體係選自由氮、氨、聯氨、及胺類所組成之群組。
- 一種用於將鈦沉積於半導體基板上之設備,該設備包含:一反應之腔室,包含用以支撐該基板之基座;至少一排氣口,用於連接至真空;一或更多的製程氣體進氣口,其連接至一或更多個前驅物源;一遠端射頻(RF,radio frequency)產生器;及一控制器,用於控制該設備中之操作,該控制器包含機器可讀取之指令,該等指令用於:(a)將該反應之腔室中之該基座的溫度設定至低於約450℃的溫度,(b)將四碘化鈦導入至該腔室,(c)清除該腔室,(d)從該遠端射頻產生器在該腔室中提供電漿,及(e)清除該腔室,及(f)重複(b)至(e)。
- 如申請專利範圍第17項之用於將鈦沉積於半導體基板上之設備,其中該等指令係配置成在每一(b)至(e)的循環中沉積約0.5Å的鈦。
- 如申請專利範圍第17或18項之用於在半導體基板上沉積鈦之設備,其中該控制器更包含機器可讀取之指令,該指令用於:(g)將四碘化鈦導入至該腔室,(h)清除該腔室,(i)在該腔室中提供電漿,(j)將含氮氣體導入至該腔室,及(k)清除該腔室;及 (l)重複(g)至(k)。
- 如申請專利範圍第19項之用於將鈦沉積於半導體基板上之設備,其中該含氮氣體係選自由氮、氨、聯氨、及胺類所組成之群組。
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US9478438B2 (en) | 2016-10-25 |
KR20160022792A (ko) | 2016-03-02 |
US20160056053A1 (en) | 2016-02-25 |
TW201623680A (zh) | 2016-07-01 |
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