TWI781143B - 用於在基板上形成氮化矽膜之方法及相關半導體裝置結構 - Google Patents
用於在基板上形成氮化矽膜之方法及相關半導體裝置結構 Download PDFInfo
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- TWI781143B TWI781143B TW107105980A TW107105980A TWI781143B TW I781143 B TWI781143 B TW I781143B TW 107105980 A TW107105980 A TW 107105980A TW 107105980 A TW107105980 A TW 107105980A TW I781143 B TWI781143 B TW I781143B
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- silicon nitride
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 223
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 239000000758 substrate Substances 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims abstract description 107
- 239000004065 semiconductor Substances 0.000 title claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000376 reactant Substances 0.000 claims abstract description 53
- 238000005137 deposition process Methods 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- -1 silicon halide Chemical class 0.000 claims abstract description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 114
- 238000000151 deposition Methods 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 230000008021 deposition Effects 0.000 claims description 71
- 239000002243 precursor Substances 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 33
- 238000000231 atomic layer deposition Methods 0.000 claims description 25
- 238000009832 plasma treatment Methods 0.000 claims description 25
- 238000012545 processing Methods 0.000 claims description 24
- 239000001307 helium Substances 0.000 claims description 16
- 229910052734 helium Inorganic materials 0.000 claims description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000002161 passivation Methods 0.000 claims description 6
- JHGCXUUFRJCMON-UHFFFAOYSA-J silicon(4+);tetraiodide Chemical compound [Si+4].[I-].[I-].[I-].[I-] JHGCXUUFRJCMON-UHFFFAOYSA-J 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910003691 SiBr Inorganic materials 0.000 claims description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 2
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 2
- CIEKVFFSPFYSHN-UHFFFAOYSA-N triiodo(triiodosilyl)silane Chemical compound I[Si](I)(I)[Si](I)(I)I CIEKVFFSPFYSHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000009257 reactivity Effects 0.000 claims 1
- 238000001039 wet etching Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 35
- 235000012431 wafers Nutrition 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000011010 flushing procedure Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
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- 230000007246 mechanism Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 230000004048 modification Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000012686 silicon precursor Substances 0.000 description 3
- 241000579895 Chlorostilbon Species 0.000 description 2
- 229910004480 SiI4 Inorganic materials 0.000 description 2
- 238000003877 atomic layer epitaxy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000011982 device technology Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 229910052876 emerald Inorganic materials 0.000 description 2
- 239000010976 emerald Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
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- 241000894007 species Species 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004871 chemical beam epitaxy Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000171 gas-source molecular beam epitaxy Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
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Abstract
揭示一種用於在基板上形成氮化矽膜之方法。該方法可包括:藉由循環沉積製程在該基板上形成循環氮化矽膜,其中該循環沉積製程包含以下中之至少一者:使該基板與包含鹵化矽源之第一反應物接觸及使該基板與包含氮源之第二反應物接觸。該方法亦可包括使該循環氮化矽膜暴露於電漿。亦揭示包含氮化矽膜之半導體裝置結構。
Description
本揭示大體上係關於用於在基板上形成氮化矽膜之方法及包括氮化矽膜之相關半導體裝置結構。
在半導體裝置技術領域中,可在製造半導體積體電路期間利用氮化矽膜。舉例而言,氮化矽膜可在製造半導體裝置結構(諸如電晶體、記憶單元、邏輯裝置、記憶體陣列等)期間用作絕緣材料。
在半導體裝置技術領域中針對高品質氮化矽膜需要低溫沉積製程;此類低溫沉積製程也應該提供對於膜厚度、厚度均一性及保形性的精確控制。
常見氮化矽膜沉積製程要求高溫沉積,亦即大約600℃至800℃,以實現諸如二氯矽烷(DCS)之前驅體與氨氣(NH3)之間的反應。習知技藝的裝置結構可能無法經受住此高熱預算,高熱預算會進一步導致裝置性能降低且會造成裝置集成問題。
高溫沉積製程的替代解決方案可為利用電漿來活化前驅體,該前驅體可繼而允許低溫反應且降低氮化矽膜的沉積溫度。然而,基於電漿的沉積製程會限制沉積性能,亦即,可用於高縱橫比結構之膜品質的步階覆蓋率、均一性,且基於電漿的沉積製程會損壞底下的裝置結構。因此,可能需要用於氮化矽膜及包括此類氮化矽膜之半導體裝置結構的低溫沉積製程以改良半導體裝
置性能。
根據本揭示之至少一個具體例,提供一種用於在基板上形成氮化矽膜之方法。該方法可包含:藉由循環沉積製程在基板上形成循環氮化矽膜,其中該循環沉積製程包含至少一個循環:使基板與包含鹵化矽源之第一反應物接觸,及使基板與包含氮源之第二反應物接觸。所提供之方法亦可包含使循環氮化矽膜暴露於電漿。
100:方法
102:循環沈積製程
104:使基板與第一反應物接觸
106:使基板與第二反應物接觸
108:所達到之厚度
110:將循環氮化矽暴露於電漿
112:所達到之厚度
114:離開
200:WER資料
202:WER資料
300:氮化矽樣品晶圓
302:氮化矽膜
402:資料
404:資料
406:資料
408:資料
410:資料
412:資料
502:資料曲線
504:資料曲線
602:氮化矽膜
604:矽基板
700:裝置結構
702:基板
704:抗蝕或硬質遮罩
706:氮化矽膜
800:反應系統
802:反應腔室
804:前驅體反應物源
804A:管道
806:前驅體反應物源
806A:管道
808:沖洗氣體源
808A:管道
810:系統操作及控制機構
儘管本說明書以具體指出且明確主張視為本發明之具體例的申請專利範圍作結,但在結合隨附圖式理解時可更容易自本揭示之具體例之某些實施例的描述來確定本揭示之具體例的優勢,在隨附圖式中:圖1說明根據本揭示之具體例之例示性沉積方法的製程流程圖;圖2說明藉由本揭示之具體例所形成之氮化矽膜的濕式蝕刻速率(WER);圖3說明橢圓偏振量測資料,該資料顯示由藉由本揭示之具體例所形成之氮化矽膜所引發的基板弓曲;圖4說明「所沉積之」氮化矽膜及藉由本揭示之具體例所形成之氮化矽膜的盧瑟福後向散射(Rutherford backscattering)資料;圖5說明「所沉積之」氮化矽膜及藉由本揭示之具體例所形成之氮化矽膜的傅里葉變換紅外光譜(Fourier Transform Infrared spectroscopy)資料;圖6說明具有形成於其上之保形氮化矽膜的矽基板之掃描電子顯微鏡影像;圖7說明包括藉由本揭示之具體例所形成之氮化矽膜的實施例半導體裝置結構之示意圖;
圖8說明經組構以執行本揭示之具體例的反應系統之示意圖。
應瞭解,圖式中之構件係為簡單及清楚起見而展示且未必按比例繪製。舉例而言,可相對於其他構件將圖式中之一些構件的尺寸擴大以幫助改良對所說明之本揭示之具體例的理解。
儘管在下文中揭示特定具體例及實施例,但彼等熟悉此項技術者應理解,本發明延伸超出本發明所具體揭示之具體例及/或用途及其明顯修改及等效物。因此,希望所揭示之本發明之範疇不應受下文所描述之具體揭示之具體例限制。
如本文所使用,術語「基板」可指代可使用或在其上可形成裝置、電路或膜之任何底層材料。
如本文所使用,術語「循環沉積」可指代將前驅體(反應物)連續引入至反應腔室中以在基板上方沉積一層且包括諸如原子層沉積及循環化學氣相沉積之加工技術。
如本文所使用,術語「原子層沉積(ALD)」可指代在處理腔室中實施沉積循環,較佳地複數個連續沉積循環的氣相沉積製程。通常地,在各循環期間,前驅體化學吸附至沉積表面(例如基板表面或先前所沉積之底層表面,諸如來自先前ALD循環之材料),從而形成不容易與其他前驅體反應(亦即自我限制反應)的單層或亞單層。之後,必要時可接著將反應物(例如另一前驅體或反應氣體)引入至處理腔室中以用於將經化學吸附之前驅體轉化為沉積表面上的所需材料。通常地,此反應物能夠進一步與前驅體反應。此外,亦可在各循環期間利用沖洗步驟自處理腔室移除過量前驅體及/或在轉化經化學吸附之前驅體之後自處理腔室移除過量反應物及/或反應副產物。此外,如本文中所使用之術語「原子層沉積」在用前驅體組合物、反應氣體及沖洗(例如惰性載劑)氣體之交流脈衝
執行時還意欲包括由相關術語指示之製程,諸如「化學氣相原子層沉積」、「原子層磊晶法(ALE)」、分子束磊晶法(MBE)、氣體源MBE或有機金屬MBE及化學束磊晶法。
如本文所使用,術語「循環化學氣相沉積」可指代其中基板依序暴露於兩種或更多種揮發性前驅體之任何製程,該等前驅體在基板上反應及/或分解以產生所需沉積物。
如本文所使用,術語「基板」可指代可使用或在其上可形成裝置、電路或膜之任何底層材料。基板可包含晶圓,諸如矽晶圓、玻璃基板或任何其他類型之基板。
本揭示之具體例可包括用於在基板上形成氮化矽膜且尤其用於在減小之沉積溫度下在基板上形成高品質氮化矽膜的方法。作為本揭示之非限制性實施例具體例,在基板上形成氮化矽膜之方法可包括多個完整的沉積循環,其中各完整的沉積循環包括使循環氮化矽膜沉積至所需厚度且接著將循環氮化矽膜暴露於電漿。本揭示之具體例已展示將循環氮化矽膜暴露於電漿改良了循環氮化矽膜的特性,諸如改良了所形成之經電漿處理之氮化矽膜的濕式蝕刻速率。多個完整的沉積循環(亦即循環的氮化矽沉積及電漿暴露)可執行以沉積具有改良品質之高品質氮化矽膜。
可參考圖1理解本揭示之方法,該圖說明用於在基板上形成氮化矽膜之方法之非限制性實施例具體例。舉例而言,圖1可說明藉由兩個或更多個完整的沉積循環在基板上形成氮化矽膜之方法100。方法100可包含循環沈積製程102,該程序塊可包含用於在基板上形成循環氮化矽膜之循環沉積製程。更詳細地,用於形成循環氮化矽之循環沉積製程可包含原子層沉積製程或替代地可包含循環化學氣相沉積製程。循環沉積製程之非限制性實施例具體例可包括ALD,其中ALD係基於典型地自我限制反應,由此使用反應物之連續且交替的
脈衝以於每個沉積循環沉積約一個原子(或分子)單層材料。沉積條件及前驅體通常選擇以提供自飽和反應,以使得一種反應物之吸附層離開同一反應物之不與氣相反應物反應的表面終端。接著使基板與不同反應物接觸,該不同反應物與先前終端反應以實現持續沉積。因此,交替脈衝之各循環通常留下不超過約一個單層的所需材料。然而,如上文所提及,熟習此項技術者將認識到在一或多個ALD循環中可沉積超過一個單層材料,例如在不管製程之交替性質如何進行一些氣相反應時。
在沉積循環氮化矽膜之ALD型製程中,一個ALD循環可包含如圖1之程序塊104中所示之使基板與第一反應物接觸,如圖1之程序塊106所示之自反應空間移除任何未反應之第一反應物及反應副產物且使基板與第二反應物接觸,接著第二移除步驟。第一反應物可包含鹵化矽源且第二反應物可包含氮源。
前驅體可藉由惰性氣體(諸如氬氣(Ar)或氮氣(N2))分離以避免在反應物之間的氣相反應並可實現自飽和表面反應。然而,在一些具體例中,基板可移動以單獨地接觸第一氣相反應物及第二氣相反應物。由於反應自飽和,所以基板之嚴格的溫度控制及前驅體之精確的劑量控制通常係不需要的。然而,基板溫度較佳使得入射氣體物種不冷凝至單層或多單層中亦不在表面上熱分解。在基板與下一種反應性化學物質接觸之前,過剩的化學物質及反應副產物(若存在)諸如藉由沖洗反應空間或藉由移動基板自基板表面移除。非所需氣態分子可藉助於惰性沖洗氣體有效地自反應空間排出。真空泵可用於輔助沖洗。
能夠用於生長循環氮化矽膜的反應器可用於沉積。該等反應器包括ALD反應器、以及配備有用以提供前驅體之適宜設備及構件的CVD反應器。根據一些具體例,可使用噴淋頭反應器。
可使用之合適反應器的實例包括市售單基板(或單晶圓)沉積設
備,諸如可購自亞利桑那州菲尼克斯之ASM America,Inc.及ASM Europe B.V.,Almere,Netherlands之Pulsar®反應器(諸如Pulsar® 2000及Pulsar® 3000及Pulsar® XP ALD)以及EmerALD® XP及EmerALD®反應器。其他市售反應器包括來自ASM Japan K.K(日本東京)商品名為Eagle® XP及XP8之彼等反應器。在一些具體例中,反應器為空間ALD反應器,其中基板在加工期間移動或旋轉。
在一些具體例中,可使用批式反應器。合適批式反應器包括(但不限於)來自ASM Europe B.V(荷蘭阿爾梅勒)市售之商品名為A400及A412 PLUS的Advance®400系列反應器。在一些具體例中,利用諸如A412之垂直批式反應器,其中舟皿在加工期間旋轉。因此,在一些具體例中,晶圓在加工期間旋轉。在其他具體例中,批式反應器包含經組構以容納10個或更少晶圓、8個或更少晶圓、6個或更少晶圓、4個或更少晶圓、或2個晶圓的小型批式反應器。在其中使用批式反應器之一些具體例中,晶圓間之均勻度小於3%(1 σ)、小於2%、小於1%或甚至小於0.5%。
本文中所描述之沉積製程可視情況在連接至群集工具的反應器或反應空間中進行。在群集工具中,由於各反應腔室係專用於一種類型之製程,因此各模組中之反應腔室的溫度可維持恆定,其相較於在各次運轉前將基板加熱至製程溫度的反應器可改良生產量。另外,在群集工具中,可減少在基板之間將反應腔室泵至期望製程壓力水準之時間。
獨立式反應器可配備有負載鎖定。在該情況下,在各次運轉之間不需冷卻反應空間。在一些具體例中,用於沉積薄循環氮化矽膜之沉積方法可包含複數個ALD循環。
在一些具體例中,循環沉積製程用於在基板上形成循環氮化矽膜且循環沉積製程可為ALD類型製程。在一些具體例中,該循環沉積可為混合ALD/CVD或循環CVD製程。舉例而言,在一些具體例中,ALD製程之生長率與
CVD製程相比可較低。一種增加生長率之途徑可為在比ALD製程中通常採用之溫度更高的基板溫度下操作,導致化學氣相沉積過程,但仍利用前驅體之連續引入,該製程可被稱為循環CVD。
根據一些具體實例,ALD製程用於在基板(諸如積體電路工件)上形成循環氮化矽膜。在本揭示之一些具體例中,各ALD循環包含兩種不同的沉積步驟或階段。
在循環沉積之第一階段(「矽階段」)中,使需要沉積之基板表面與包含化學吸附至該基板表面上之矽前驅體之第一氣相反應物接觸(圖l之程序塊104),從而在基板表面上形成不超過約一個單層的反應物物種。應瞭解在一些具體例中,在前進至後續加工步驟之前,亦即在後續接觸步驟或移除/沖洗步驟之前,可重複各接觸步驟一或多次。
在一些具體例中,矽前驅體,在本文中亦被稱作「矽化合物」可包含鹵化矽源。在一些具體例中,第一反應物可包含鹵化矽源且可進一步包含以下中之至少一者:四碘化矽(SiI4)、四溴化矽(SiBr4)、四氯化矽(SiCl4)、六氯二矽烷(Si2Cl6)、六碘二矽烷(Si2I6)、八碘三矽烷(Si3I8)。在其中鹵化矽源包含四碘化矽(SiI4)之具體例中,四碘化矽源可經預加熱以提供充足的蒸氣壓以遞送至反應腔室,例如在一些具體例中,四碘化矽前驅體源可經預加熱至約90℃與約125℃之間的溫度,或在一些具體例中,四碘化矽可經預加熱至約100℃之溫度。
在一些具體例中,使基板暴露於鹵化矽源可包含在基板上方脈衝矽前驅體(例如四碘化矽(SiI4))持續約0.5秒與約30秒之間,或約0.5秒與約10.0秒之間,或約0.5秒與約5.0秒之間的時間時間段。此外,在基板上方脈衝鹵化矽源期間,鹵化矽源之流速可小於2000sccm,或小於1000sccm,或小於500sccm,或小於250sccm或甚至小於100sccm。
過量鹵化矽源及反應副產物(若存在)可例如藉由用惰性氣體沖
洗而自基板表面移除。舉例而言,在本揭示之一些具體例中,該方法可包括其中基板表面經沖洗小於約5.0秒之時間段的沖洗循環。過量鹵化矽源及任何反應副產物可藉助於由抽汲系統產生之真空來移除。
在循環沉積之第二階段,例如ALD循環(「氮氣階段」)中,使基板與包含氮源之第二氣相反應物接觸(圖1之程序塊106)。在本揭示之一些具體例中,方法可進一步包含選擇氮源以包含氨氣(NH3)、醯肼(N2H4)或烷基-醯肼中之至少一者,其中烷基-醯肼可指代可包含烷基官能基且亦可包含額外官能基之醯肼衍生物,烷基-醯肼之非限制性實施例具體例可包含以下中之至少一者:三丁基肼(C4H9N2H3)、甲基肼(CH3NHNH2)或二甲基肼((CH3)2N2H2)。
在一些具體例中,使基板暴露於氮源可包含在基板上方脈衝氮源(例如氨氣(NH3))持續約0.5秒至約30.0秒之間,或約0.5秒至約10秒之間,或約0.5秒至約5秒之間的時間段。在基板上方脈衝氮源期間,氮源之流速可小於4000sccm,或小於2000sccm,或小於1000sccm,或甚至小於250sccm。
包含氮源之第二氣相反應物可與基板表面上留下之含矽分子反應。在一些具體例中,第二階段氮源可與基板表面上留下之含矽分子反應以沉積循環氮化矽膜。
過量第二源化學物質及反應副產物,若存在的話,可例如藉由沖洗氣體脈衝及/或由抽汲系統產生之真空自基板表面移除。沖洗氣體較佳為任何惰性氣體,非限制性地諸如氬氣(Ar)、氮氣(N2)或氦氣(He)。若插入沖洗(亦即沖洗氣體脈衝)或其他反應物移除步驟,則通常考慮一個階段緊接著在另一階段之後。
儘管如圖1之方法100中所示,循環沉積製程102可包含使基板與第一反應物接觸104,之後接著使基板與第二反應物接觸106,應瞭解本揭示之具體例可逆轉接觸順序且可首先使基板與第二反應物接觸106,接著使基板與第
一反應物接觸104。亦應理解在使基板與第二反應物接觸之前基板可與第一反應物接觸多次,且反之亦然。
本揭示之具體例可進一步包含在循環沉積製程102期間加熱基板,例如在基板上沉積循環氮化矽膜之ALD製程期間加熱基板。在一些具體例中,方法可包含將基板加熱至約小於200℃之溫度,或至小於約250℃之溫度,或至小於約300℃之溫度,或至小於約350℃之溫度,或至小於約400℃之溫度,或至小於約450℃之溫度,或甚至至小於約500℃之溫度。
本揭示之具體例可進一步包含降低用於藉由循環沉積製程沉積循環氮化矽之反應腔室中之壓力。舉例而言,在一些具體例中,循環沉積可在小於50托之反應腔室壓力下,或在小於25托之反應腔室壓力下,或在小於10托之反應腔室壓力下,或甚至在小於5托之反應腔室壓力下執行。
藉由循環沉積製程,例如ALD型製程沉積循環氮化矽膜之速率通常呈現為埃/脈衝循環,取決於多個因素,包括例如取決於表面上之可用反應性表面位點或活性位點之數目及以化學方式吸附之分子的膨鬆度。在一些具體例中,此類膜之沉積速率可介於約0.1至約5.0埃/脈衝循環之範圍內。在一些具體例中,沉積速率可為約0.1、0.2、0.3、0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0、4.5、5.0埃/脈衝循環。
用於在基板上形成循環氮化矽膜之循環沉積製程可重複一或多次直至達到循環氮化矽之所需厚度。參考圖1,程序塊108說明用於決定循環沉積製程應或不應重複之決策門,該決策門藉由循環氮化矽膜之所需厚度來確定。舉例而言,在一些具體例中,藉由循環沉積製程在基板上形成循環氮化矽膜包含形成厚度介於約5埃與約30埃之間的的循環氮化矽膜。在一些具體例中,該方法可包含在基板上形成具有以下厚度之循環氮化矽膜:小於50埃、或小於40埃、或小於30埃、或小於20埃,或甚至小於10埃。在一些具體例中,該方法
可包含藉由循環沉積製程在基板上形成厚度為約15埃之循環氮化矽膜。
在本揭示之其他具體例中,循環氮化矽可形成至更大厚度,例如若底層基板包含易碎裝置結構或經部分地製造之易碎裝置結構,則循環氮化矽可在厚度上增加以保護易碎材料避免後續電漿處理,在此等具體例中,循環氮化矽膜可具有大於5nm、或大於10nm、或甚至大於25nm的厚度。
在獲得循環氮化矽膜之所需厚度後,循環氮化矽膜可暴露於電漿以便改良經沉積循環氮化矽膜之材料特徵,亦即,諸如改良所沉積之氮化矽膜的濕式蝕刻速率。因此,本揭示之方法可包含使循環氮化矽暴露於電漿,如藉由圖1之程序塊110所示。更詳細地,在已獲得循環氮化矽膜之所需厚度後,基板可轉移至經組構以使基板及特定的循環氮化矽膜暴露於電漿,亦即電漿處理的另一反應腔室。在一些具體例中,同一反應腔室可用於循環氮化矽膜之循環沉積及使循環氮化矽膜暴露於電漿兩者。在替代具體例中,用於循環氮化矽膜之循環沉積之反應腔室及用於使循環氮化矽膜暴露於電漿之反應腔室可彼此不同。在不同反應腔室用於循環沉積製程及電漿處理製程的具體例中,基板及上覆循環氮化矽膜可自第一反應腔室(用於循環氮化矽膜沉積)轉移至第二反應腔室(用於電漿處理)而不暴露於環境氛圍。換言之,本揭示之方法可包含藉由循環沉積製程在基板上形成循環氮化矽膜及利用同一半導體加工設備使循環氮化矽膜暴露於電漿。用於循環沉積及電漿處理之半導體加工設備可包含群集工具,該群集工具包含兩個或更多個反應腔室且該群集工具可進一步包含基板可在第一反應腔室與第二反應腔室之間傳輸的轉移腔室。在一些具體例中,可控制轉移腔室內之環境,亦即,溫度、壓力及環境氣體,以使得基板及尤其循環氮化矽不暴露於環境氛圍。在一些具體例中,經組構以使循環氮化矽膜暴露於電漿之反應腔室可經組構以具有電容耦合式電漿(CCP)源、感應耦合電漿(ICP)源或遠程電漿(RP)源。
在基板及相關上覆循環氮化矽膜定位於經組構用於電漿處理之適當反應腔室中後,本揭示之方法可包含使循環氮化矽膜暴露於電漿。在一些具體例中,產生電漿之源氣體可包含以下中之一或多者:氮氣(N2)、氦氣(He)、氫氣(H2)及氬氣(Ar)。在本揭示之特定具體例中,產生電漿之源氣體可包含氦氣(He)及氮氣(N2)之混合物且氦(He)氣體與氮(N2)氣體之比例可相等,亦即50%氦氣(He)比50%氮氣(N2)(50:50)。在替代具體例中,氦(He)氣體與氮氣(N2)之比例可為:10%:90%、或20%:80%、或30%:70%、或40%:60%、或60%:40%、或70%:30%、或80%:20%,或甚至90%:10%。
在本揭示之一些具體例中,使循環氮化矽膜暴露於電漿可包含為電漿源氣體(es)施加以下電力:大於約150W、或大於300W、或大於600W,或甚至大於900W。此外,用於使循環氮化矽膜暴露於電漿之反應腔室可在減壓下操作,例如在一些具體例中,用於使循環氮化矽暴露於電漿之反應腔室可在約小於4托下操作,或可在約小於2托之壓力下操作,或可甚至在約1托之壓力下操作。在一些具體例中,基板可在電漿處理過程期間加熱,例如使循環氮化矽膜暴露於電漿可包含將基板及相關循環氮化矽膜加熱至大於約100℃之溫度、或至大於約200℃之溫度,或甚至至大於約250℃之溫度。
在本揭示之一些具體例中,使循環氮化矽膜暴露於電漿包含使循環氮化矽暴露於電漿持續小於約300秒之時間段,或持續小於150秒之時間段,或甚至小於90秒之時間段。在本揭示之某些具體例中,循環氮化矽可暴露於電漿處理持續更長時間段,例如持續大於2分鐘、或大於5分鐘,或甚至大於10分鐘之時間段。應注意基板及相關循環氮化矽膜暴露於電漿愈久,電漿處理之有利效應更可能飽和且非常長的電漿暴露時間可甚至對循環氮化矽表面造成損壞。
作為本揭示之非限制性實施例具體例,使循環氮化矽膜暴露於電
漿可包含在包含電容耦合式電漿(CCP)源之反應腔室中之氦氣(He)及氮氣(N2)(50%:50%)氣體電漿在600W之電漿電力、2托之反應腔室壓力下持續90秒時間段。
在循環氮化矽暴露於電漿之後,已執行一個完整的沉積循環,因此單個完整的沉積循環包含藉由循環沉積製程在基板上形成循環氮化矽膜及使循環氮化矽膜暴露於電漿。本揭示之具體例可包含重複完整的沉積循環兩次或更多次。舉例而言,在完成第一個完整的沉積循環後,亦即在完成循環氮化矽之電漿處理後,圖1之方法100可繼續進行決策門112,其中繼續進行另一個完整的沉積循環的決策係基於所達到的氮化矽膜之厚度。在(圖1之)決策門112產生重複完整的沉積循環一或多次之決策的具體例中,基板及上覆氮化矽膜可返回(亦即轉移)至經組構用於循環沉積製程102之反應腔室,例如經組構用於ALD型製程之反應腔室。如先前所描述,基板可自電漿處理反應腔室轉移至循環沉積反應腔室而不使基板暴露於環境氛圍,可在經控制環境條件下利用包含轉移腔室之群集工具實現此類基板傳輸。
儘管藉由圖1中之方法100示出之完整的沉積循環示出循環沉積製程102之後接著使基板暴露於電漿,但可瞭解本揭示之具體例亦可包括其中在執行循環沉積製程102之前首先使基板暴露於電漿處理的方法,換言之,該等具體例之方法可進一步包含在藉由循環沉積循環在基板上形成循環氮化矽膜之前使基板暴露於電漿。不受理論束縛,但認為包含在循環氮化矽沉積之前使基板暴露於電漿處理之預處理可藉由改變其上待沉積循環氮化矽膜之基板的表面能來改良循環氮化矽沉積製程,且從而改良循環氮化矽膜凝核。在本揭示之一些具體例中,基板之電漿預處理可包含氮氣(N2)、氦氣(He)、氬氣或氮氣/氦氣(例如50%/50%)電漿法中之一或多者,在約0.5托至約4托之間的反應腔室壓力下,在約600W之電漿電力下執行持續約10秒與約90秒之間的時間段。亦應理解可在
單個完整的沉積循環中執行多個電漿處理以及可在單個沉積循環期間執行多個循環沉積製程102。
在其他具體例中,各完整的沉積循環可不同於正在進行及/或後續完整的沉積循環或替代地各沉積循環可包含相同的製程參數。在兩個或所有完整的沉積循環不同於彼此之具體例中,包含循環氮化矽膜沉積及電漿處理之一個或所有製程之製程參數在各完整的沉積循環之間可改變。作為非限制性實施例,在一些具體例中,底層基板可包含易碎裝置結構或易碎的經部分地製造之裝置結構且因此初始循環氮化矽膜可沉積至更大的厚度以在後續電漿處理期間確保對易碎材料的保護。
在本揭示之一些具體例中,完整的沉積循環可重複超過兩次,或超過五次,或超過十次,或甚至超過二十次。在一些具體例中,完整的沉積循環可重複直至氮化矽層之厚度大於約5nm,或大於約10nm,或甚至大於約25nm。利用本揭示之一或多個完整的沉積循環之氮化矽膜沉積可改良厚度不均勻性,其中所沉積之氮化矽膜的厚度不均勻性小於15% 1-σ、或小於10% 1-σ、或小於5% 1-σ,或甚至小於2% 1-σ。
在已利用多個完整的沉積循環(如圖1中所說明)沉積所需厚度之氮化矽膜後,基板及其上所形成之相關氮化矽膜可自半導體加工設備移除。然而,在自半導體加工設備移除氮化矽膜之前,氮化矽膜可進行其他加工。舉例而言,使循環氮化矽暴露於電漿可具有如本文所描述之有利效應,然而,循環氮化矽表面之電漿處理可呈現此類表面高度反應性且因此所沉積之氮化矽在暴露於環境條件之前會需要鈍化處理以實質上防止發生氧化處理。因此,在本揭示之一些具體例中,在完成最終完整的沉積循環後,方法可包含在自半導體加工設備移除氮化矽膜之前使氮化矽膜與氮前驅體接觸。本揭示之其他具體例可包含選擇氮前驅體以包含氨氣或氮氣(N2)電漿中之至少一者,例如低電力遠程電
漿處理。在一些具體例中,氮化矽膜可暴露於氮前驅體約5秒與約60秒之間的時間段以確保氮化矽表面之鈍化。
藉由本文中之本揭示之具體例所沉積之氮化矽膜的高品質可以多種方法來測定。舉例而言,藉由本文中所揭示之具體例所沉積之氮化矽膜可經受濕式化學蝕刻製程來測定所沉積之氮化矽膜之濕式蝕刻速率(WER)。作為非限制性實施例,藉由(圖1之)方法100之兩個或更多個完整的沉積循環所形成的氮化矽膜在2000:1水(H2O)比氫氟酸(HF)之溶液中可具有約小於5埃/分鐘的WER。作為對照,在不利用本文所描述之方法的情況下所沉積之氮化矽膜在2000:1水(H2O)比氫氟酸(HF)之溶液中呈現60埃/分鐘的WER,因此本文中所描述之具體例能夠沉積與藉由替代方法所形成之氮化矽膜相比對濕式化學蝕刻具有大致十二(12)倍多抗性之氮化矽膜。
作為另一非限制性實施例具體例,圖2說明藉由利用電漿處理製程之不同電漿源氣體的本文中所描述之具體例所形成的氮化矽膜之在2000:1(H2O:HF)中之WER。利用包含氫氣(H2)及氮氣(N2)(50%:50%)之電漿源氣體所沉積之氮化矽膜及所處理之電漿的WER資料標記為200且展現介於約35埃/分鐘與約32埃/分鐘之間的WER。利用包含氦氣(He)及氮氣(N2)(50%:50%)之電漿源氣體所沉積之氮化矽膜及所處理之電漿的WER資料標記為202且展現介於約12埃/分鐘與約3埃/分鐘之間的WER。
在一些具體例中,本揭示之方法亦可用於改變所沉積之氮化矽膜中之應力及底層基板之所得弓曲。舉例而言,本揭示之方法可利用不同數目之完整沉積循環來形成氮化矽層,沉積循環之數目及尤其電漿處理之頻率對所沉積之氮化矽膜中之應力及基板之所得弓曲具有直接影響。
表1說明五(5)種不同的氮化矽膜,在不電漿處理之情況下藉由習知方法沉積之對照樣品(標記「沉積時」)及四(4)種氮化矽膜標稱地沉積至同一厚度,亦即約90埃,但在電漿處理之遞增頻率下。應注意用於獲取表1中之資料的電漿處理包含在600W之電力、2托之反應腔室壓力及九十(90)秒之電漿暴露時間段下的氦氣(He)、氮氣(N2)(50%:50%)電漿。表1清楚地展現氮化矽膜之WER在遞增電漿處理頻率之情況下改良,如先前提及。此外,表1清楚地展現所沉積之氮化矽膜中之應力亦可直接利用本揭示之方法來控制。舉例而言,「沉積時」氮化矽膜展現590MPa之拉伸應變,而藉由本揭示之具體例用七(7)個電漿處理循環所形成之氮化矽展現-1034MPa之壓縮應變。因此,在本揭示之一些具體例中,循環氮化矽暴露於電漿進一步包含改變氮化矽膜中之應力且可進一步包含將氮化矽膜中之應力自拉伸狀態改變為壓縮狀態。
作為本揭示之具體例之另一非限制性實施例,圖3說明藉由上覆氮化矽膜中之應力在基板上所誘發之晶圓弓曲的橢偏儀量測值且展現利用各種電漿化學反應所獲得之應力。「沉積時」氮化矽樣品晶圓(標記300)中之晶圓弓曲展現具有約-3微米之最大晶圓弓曲的拉伸應力。相比之下,藉由本揭示之具體例,尤其藉由使循環氮化矽暴露於氫氣(H2)及氮氣(N2)電漿化學法所形成之氮化矽膜(標記302),產生壓縮應力及約7微米之最大晶圓弓曲。因此,本揭示之具體例可包含使循環氮化矽暴露於電漿且可進一步包含改變基板之弓曲度。
在本揭示之一些具體例中,利用多個完整沉積循環(包括循環氮
化矽沉積及電漿處理)形成氮化矽膜之方法可用於改變所沉積之氮化矽膜的組成。舉例而言,圖4說明自六種(6)氮化矽膜收集之盧瑟福後向散射資料,標記為資料402、404、406及408之初始四(4)種氮化矽膜為「沉積時」,亦即不採用電漿處理,而標記為資料410及412之最終兩(2)種氮化矽膜藉由本文中所描述之具體例之方法形成,亦即經受一或多個電漿處理。「沉積時」氮化矽膜之資料展現隨著沉積溫度自250℃增加至480℃,氫(標記c)之原子百分比減小且矽(標記a)及氮(標記b)之原子百分比增加。不受理論束縛,但認為氮化矽膜中之過量氫會產生具有較差品質(亦即增加的WER及較差的電特性)之氮化矽膜。「沉積時」氮化矽膜之資料表明更高品質的氮化矽膜可在更高沉積溫度下形成,然而,如先前所述,此類高沉積溫度會損害最先進的半導體裝置結構。相比之下,標記410及412之資料展現藉由本文中所描述之具體例之方法所形成之氮化矽膜且資料410及412皆包含在250℃之低沉積溫度下所沉積之氮化矽膜。如圖4中所見,經H2-N2電漿處理之氮化矽膜(資料410)及經He-N2電漿處理之氮化矽膜(資料412)展現類似於資料408之高溫氮化矽膜的組成。因此,本文中所描述之方法允許低溫沉積具有改良組成之氮化矽膜,類似於在非常高的溫度(例如大於400℃)下所沉積之氮化矽膜的改良組成。
本揭示之具體例可包含在基板上形成氮化矽膜同時將該板加熱至小於約250℃之溫度,其中基板上之氮化矽膜具有小於25%的氫原子百分比,或具有小於20%的氫原子百分比,或具有小於15%的氫原子百分比,或具有小於10%的氫原子百分比,或甚至具有小於5%的氫原子百分比。
本揭示之其他具體例可包含在基板上形成氮化矽膜同時將該板加熱至小於約250℃之溫度,其中基板上之氮化矽膜具有大於25%的矽原子百分比,或具有大於30%的矽原子百分比,或具有大於35%的矽原子百分比,或甚至具有大於40%的矽原子百分比。
本揭示之其他具體例可包含在基板上形成氮化矽膜同時將該基板加熱至小於約250℃之溫度,其中基板上之氮化矽膜具有大於35%的氮原子百分比,或具有大於40%的氮原子百分比,或具有大於45%的氮原子百分比,或具有大於50%的氮原子百分比,或甚至具有大於55%的氮原子百分比。
如本文中先前所描述,本揭示之具體例可減小所沉積之氮化矽膜中之氫原子百分比。特定言之,本文所描述之方法可減小氫結合至氮之量,亦即N-H結合基團。作為非限制性實施例,圖5說明「沉積時」氮化矽膜及藉由本文所描述之方法所沉積之氮化矽膜之傅里葉變換紅外光譜(FTIR)資料。更詳細地,資料曲線502說明「沉積時」氮化矽膜之FTIR光譜學且清楚地表明由於對應於N-H鍵位置之資料中之峰值而導致N-H鍵之存在。持續參考圖5,該資料曲線504說明藉由本文所描述之方法所形成之氮化矽之FTIR光譜學,且尤其經氦氣(He)、氮氣(N2)電漿處理。該資料曲線504展示在N-H鍵位置處無可見峰且因此認為電漿處理自氮化矽膜有效地移除N-H鍵。
在本揭示之一些具體例中,藉由本文所描述之方法所形成之氮化矽膜可沉積於三維結構上。作為非限制性實施例,圖6說明已經蝕刻以使其包含具有約220奈米之深度的表面通孔的矽基板604之掃描電子顯微鏡(SEM)橫截面影像。藉由本文中所描述之具體例所形成之保形性氮化矽膜602沉積於經蝕刻矽基板604之表面上方。如藉由圖6之SEM橫截面影像展現,藉由本揭示之具體例所形成之氮化矽膜對於底層表面構形為保形性的。因此,在一些具體例中,在具有縱橫比(高度/寬度)大於約2、大於約5、大於約10、大於約25、大於約50或大於約100之結構中,氮化矽膜之步驟覆蓋可等於或大於約50%、大於約80%、大於約90%、約95%、約98%或約99%或更大。
熟習此項技術者將認識到本文中所描述之製程適用於多種情況,包括製造半導體裝置結構,諸如(但不限於)記憶體裝置(例如電阻式記憶體、
DRAM及VNAND),包括發光二極體之二極體及包括平面裝置以及多種閘極電晶體之電晶體,諸如FinFET。作為非限制性實施例,本揭示之氮化矽膜可在製造半導體裝置結構中用作有用層。舉例而言,本揭示之氮化矽膜可用作犧牲性膜或硬式光罩以用於與多重圖案化處理相關之應用,諸如雙倍或四倍圖案化應用。舉例而言,本揭示之具體例可允許在減小的沉積溫度下形成具有增加蝕刻速率阻抗的氮化矽膜。因此,藉由本揭示之方法所形成之氮化矽膜可適用於微影/圖案化相關應用,諸如多重圖案化應用。因此,本揭示之一些實施例可包含經部分地製造之裝置結構,該裝置結構包含經組構以對底層進行連續圖案化之遮罩結構,該遮罩結構包含藉由本揭示之方法所形成之氮化矽膜。更詳細地且參考圖7,經部分地製造之裝置結構700可包含經組構以連續圖案化及蝕刻的基板702。藉由光微影方法所形成之抗蝕或硬質遮罩704可安置於基板702上方且藉由本揭示之方法所形成之氮化矽膜706可安置於抗蝕或硬質遮罩704上方。
本揭示之具體例亦可包括經組構以形成本揭示之氮化矽膜的反應系統。更詳細地,圖8示意性地說明包括反應腔室802之反應系統800,該反應腔室進一步包括用於在預定壓力、溫度及環境條件下固持基板(未示出)且用於將基板選擇性暴露於各種氣體的機構。前驅體反應物源804可藉由管道或其它適當管道804A耦接至反應腔室802,且可進一步耦接至集管、閥門控制系統、質量流控制系統,或機構以控制氣態前驅體來源於前驅體反應物源804。藉由前驅體反應物源804供應之前驅體(未示出)、反應物(未示出)在室溫及標準常壓條件下可為液體或固體。此前驅體可在反應物源真空容器內氣化,該容器可維持在前驅體源腔室內之氣化溫度或高於該氣化溫度下。在此等具體例中,氣化前驅體可用運載氣體(例如非活性或惰性氣體)傳輸且接著經由管道804A饋入至反應腔室802中。在其他具體例中,前驅體在標準條件下可為蒸氣。在此等具體例中,前驅體不需要蒸發且可不需要運載氣體。舉例而言,在一個具體例中,前驅體可儲
存於貯氣瓶中。反應系統800亦可包括額外前驅體反應物源,此類前驅體反應物源806亦可藉由如上文所描述之管道806A耦接至反應腔室。
沖洗氣體源808亦可經由管道808A耦接至反應腔室802,且為反應腔室802選擇性地供應各種惰性或稀有氣體以輔助自反應腔室移除前驅氣體或廢料氣體。可供應之各種惰性或稀有氣體可來源於固態、液態或儲存氣態形式。
圖8之反應系統800亦可包含提供電子電路及機械組件以選擇性地操作閥、集管、泵及反應系統800中所包括之其他設備的系統操作及控制機構810。此類電路系統及組件操作以自對應的前驅體反應物源804、806及沖洗氣體源808引入前驅體、沖洗氣體。該系統操作及控制機構810亦控制氣體脈衝順序之時間安排、基板及反應腔室之溫度,及反應腔室之壓力及設置反應系統800之恰當操作所必需之各種其他操作。系統操作及控制機構810可包括控制軟體及電力地或氣動地控制閥以控制前驅體、反應物及沖洗氣體進入及離開反應腔室802之流動。控制系統可包括執行特定任務之模組,諸如軟體或硬體組件,例如FPGA或ASIC。模組可有利地經組構以駐留於控制系統之可尋址儲存媒體中,且經組構以執行一或多個程序。
熟悉相關技術者理解本反應系統之其他構形為可能的,包括不同數目及類別之前驅體反應物源及沖洗氣體源。此外,此類人員亦將理解存在可用於實現將氣體選擇性地饋入至反應腔室802中之目標的閥、管道、前驅體源沖洗氣體源之多種配置。此外,作為反應系統之示意性圖示,為簡單說明起見已省去多種組件,且此類組件可包括例如各種閥、集管、純化器、加熱器、容器、通風口及/或支路。在一些具體例中,反應系統800可包括兩個或更多個反應腔室,其中各反應腔室可經組構用於所需製程,例如第一反應腔室可經組構用於循環沉積製程且第二反應腔室可經組構用於電漿製程。此外,反應系統800可包
含用於在經控制條件下將基板自第一反應腔室轉移至第二反應腔室之轉移腔室。
上文所描述之本揭示之實施例具體例並不限制本發明的範疇,此係由於此等具體例僅為本發明之具體例之實施例,其由所附申請專利範圍及其法定等效物定義。任何等效具體例意欲處於本發明之範疇內。實際上,除彼等所示及本文中所描述之外,本揭示之各種修改(諸如所描述之元件的替代性適用組合)根據描述對熟習此項技術者而言將變得顯而易見。該等修改及具體例同樣意欲屬於所附申請專利範圍之範疇內。
100‧‧‧方法
102‧‧‧循環沈積製程
104‧‧‧使基板與第一反應物接觸
106‧‧‧使基板與第二反應物接觸
108‧‧‧所達到之厚度
110‧‧‧將循環氮化矽暴露於電漿
112‧‧‧所達到之厚度
114‧‧‧離開
Claims (23)
- 一種用於在基板上形成氮化矽膜之方法,該方法包含:藉由循環沉積製程在該基板上形成循環氮化矽膜,其中該循環沉積製程包含至少一個以下循環:使該基板與包含鹵化矽源之第一反應物接觸,及使該基板與包含氮源之第二反應物接觸;在該至少一個循環之後,使該循環氮化矽膜暴露於電漿以完成完整的沉積循環且形成經電漿處理之氮化矽膜,其中該暴露步驟致使該經電漿處理之氮化矽膜之表面具有反應性,且其中該經電漿處理之氮化矽膜之濕式蝕刻速率小於該循環氮化矽膜之濕式蝕刻速率;在該完整的沉積循環之後且因此在形成該經電漿處理之氮化矽膜之後,重複該形成步驟及該暴露步驟以執行多個完整的沉積循環,從而形成多個經電漿處理之氮化矽膜;及在重複該形成步驟及該暴露步驟以執行多個完整的沉積循環之後,使該經電漿處理之氮化矽膜之表面鈍化,其中該鈍化步驟包含一或多個電漿處理及使該經電漿處理之氮化矽膜暴露於氮氣(N2),其中該鈍化步驟與該使該循環氮化矽膜暴露於該電漿之步驟不同,且其中該鈍化步驟降低該經電漿處理之氮化矽膜之表面之反應性。
- 如請求項2之方法,其中該方法包含循環原子層沉積製程。
- 如請求項2之方法,其中重複該完整的沉積循環兩次或更多次。
- 如請求項1之方法,其中重複該循環沉積製程直至該循環氮化矽膜具有第一所需厚度,其中執行重複該形成步驟及該暴露步驟直至該多個經電漿處理之氮化矽膜具有第二所需厚度。
- 如請求項1之方法,其中該鈍化步驟包含在自半導體加工設備移 除該氮化矽膜之前使該氮化矽膜與暴露於遠程電漿之氮氣接觸。
- 如請求項1之方法,其進一步包含選擇該鹵化矽源以包含以下中之至少一者:四碘化矽(SiI4)、四溴化矽(SiBr4)、四氯化矽(SiCl4)、六氯二矽烷(Si2Cl6)、六碘二矽烷(Si2I6)或八碘三矽烷(Si3I8)。
- 如請求項1之方法,其進一步包含選擇該氮源以包含以下中之至少一者:氨(NH3)、醯肼(N2H4)或烷基-醯肼。
- 如請求項1之方法,其中使該循環氮化矽膜暴露於該電漿包含使該循環氮化矽膜暴露於該電漿持續小於約90秒之時間段。
- 如請求項1之方法,其中使該循環氮化矽膜暴露於該電漿包含使該循環氮化矽膜暴露於包含以下中之至少一者的電漿源:氮氣(N2)、氦氣(He)、氫氣(H2)及氬氣(Ar)。
- 如請求項1之方法,其中使該循環氮化矽膜暴露於該電漿包含使該循環氮化矽膜暴露於包含氦氣(He)及氮氣(N2)之電漿源。
- 如請求項10之方法,其中包含氦氣(He)及氮氣(N2)之該電漿源包含氦氣(He)比氮氣(N2)之50%:50%比率。
- 如請求項1之方法,其進一步包含將該基板加熱至小於約250℃之溫度。
- 如請求項12之方法,其中該氮化矽膜之氫原子百分比小於15%。
- 如請求項1之方法,其中該氮化矽膜在2000:1 H2O:HF溶液中之濕式蝕刻速率為約小於5埃/分鐘。
- 如請求項1之方法,其中藉由該循環沉積製程在該基板上形成該循環氮化矽膜及使該循環氮化矽膜暴露於該電漿係在同一半導體加工設備中執行。
- 如請求項1之方法,其進一步包含在藉由該循環沉積製程在該基 板上形成該循環氮化矽膜之前使該基板暴露於該電漿。
- 如請求項1之方法,其中使該循環氮化矽膜暴露於該電漿進一步包含改變該循環氮化矽膜中之應力。
- 如請求項17之方法,其中改變該循環氮化矽膜中之應力進一步包含將應力自拉伸狀態改變為壓縮狀態。
- 如請求項1之方法,其中使該循環氮化矽膜暴露於該電漿進一步包含改變該基板之弓曲度。
- 如請求項1之方法,其中該鈍化步驟包含在自半導體加工設備移除該氮化矽膜之前使該經電漿處理之氮化矽膜與氮前驅體接觸。
- 如請求項20之方法,其進一步包含選擇該氮前驅體以包含至少一種氨氣或氮氣電漿。
- 一種半導體裝置結構,其包含藉由請求項1之方法所形成的氮化矽層。
- 一種反應系統,其經組構以執行請求項1之方法。
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US9214333B1 (en) * | 2014-09-24 | 2015-12-15 | Lam Research Corporation | Methods and apparatuses for uniform reduction of the in-feature wet etch rate of a silicon nitride film formed by ALD |
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US10892156B2 (en) | 2021-01-12 |
US20180323056A1 (en) | 2018-11-08 |
KR20180123436A (ko) | 2018-11-16 |
KR102663011B1 (ko) | 2024-05-02 |
TW201907448A (zh) | 2019-02-16 |
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