TWI810405B - 形成紫外輻射反應性含金屬氧化物膜之方法 - Google Patents
形成紫外輻射反應性含金屬氧化物膜之方法 Download PDFInfo
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- TWI810405B TWI810405B TW108141828A TW108141828A TWI810405B TW I810405 B TWI810405 B TW I810405B TW 108141828 A TW108141828 A TW 108141828A TW 108141828 A TW108141828 A TW 108141828A TW I810405 B TWI810405 B TW I810405B
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- metal oxide
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- oxide
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- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
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- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims 2
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- 229910005898 GeSn Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
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- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- HJYACKPVJCHPFH-UHFFFAOYSA-N dimethyl(propan-2-yloxy)alumane Chemical compound C[Al+]C.CC(C)[O-] HJYACKPVJCHPFH-UHFFFAOYSA-N 0.000 description 2
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 2
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- NSYDOBYFTHLPFM-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3,6,2-dioxazasilocan-6-yl)ethanol Chemical compound C[Si]1(C)OCCN(CCO)CCO1 NSYDOBYFTHLPFM-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 description 1
- CLQPEJKJHMMRRW-UHFFFAOYSA-N N-silylpropan-2-amine Chemical compound CC(C)N[SiH3] CLQPEJKJHMMRRW-UHFFFAOYSA-N 0.000 description 1
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- KAJBHOLJPAFYGK-UHFFFAOYSA-N [Sn].[Ge].[Si] Chemical compound [Sn].[Ge].[Si] KAJBHOLJPAFYGK-UHFFFAOYSA-N 0.000 description 1
- MNEVZRBZSZELSW-UHFFFAOYSA-N [Zn+]C.CC(C)[O-] Chemical compound [Zn+]C.CC(C)[O-] MNEVZRBZSZELSW-UHFFFAOYSA-N 0.000 description 1
- VEZYCISMGXNHOV-UHFFFAOYSA-N [dimethyl-[(trimethylsilylamino)silylamino]silyl]methane Chemical compound C[Si](C)(C)N[SiH2]N[Si](C)(C)C VEZYCISMGXNHOV-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OCFSGVNHPVWWKD-UHFFFAOYSA-N butylaluminum Chemical group [Al].[CH2]CCC OCFSGVNHPVWWKD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004871 chemical beam epitaxy Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 238000000171 gas-source molecular beam epitaxy Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- TWVSWDVJBJKDAA-UHFFFAOYSA-N n-[bis(dimethylamino)silyl]-n-methylmethanamine Chemical compound CN(C)[SiH](N(C)C)N(C)C TWVSWDVJBJKDAA-UHFFFAOYSA-N 0.000 description 1
- NWINXQYZVMLCMI-UHFFFAOYSA-N n-ethyl-n-[tris(diethylamino)germyl]ethanamine Chemical compound CCN(CC)[Ge](N(CC)CC)(N(CC)CC)N(CC)CC NWINXQYZVMLCMI-UHFFFAOYSA-N 0.000 description 1
- JKUUTODNPMRHHZ-UHFFFAOYSA-N n-methyl-n-[tris(dimethylamino)germyl]methanamine Chemical compound CN(C)[Ge](N(C)C)(N(C)C)N(C)C JKUUTODNPMRHHZ-UHFFFAOYSA-N 0.000 description 1
- ZWRHKBMGGAGXHE-UHFFFAOYSA-N n-methyl-n-tris[ethyl(methyl)amino]germylethanamine Chemical compound CCN(C)[Ge](N(C)CC)(N(C)CC)N(C)CC ZWRHKBMGGAGXHE-UHFFFAOYSA-N 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
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 235000013616 tea Nutrition 0.000 description 1
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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
- H01L21/02172—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 the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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
- H01L21/02172—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 the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
本發明揭示一種用來形成紫外(UV)輻射反應性含金屬氧化物膜之方法。該方法可包括:經由將基板加熱至低於400°C之沉積溫度將UV輻射反應性含金屬氧化物膜沉積於基板上方,使基板與包含金屬組分、氫組分、及碳組分之第一氣相反應物接觸,及使基板與包含含氧前驅物之第二氣相反應物接觸,其中UV輻射反應性含金屬氧化物膜於UV照射後之區域具有第一蝕刻速率及UV輻射反應性含金屬氧化物膜之未經UV輻射照射之區域具有第二蝕刻速率,其中第二蝕刻速率不同於第一蝕刻速率。
Description
本揭示大致係關於形成紫外(UV)輻射反應性含金屬氧化物膜之方法。本揭示亦大致關於直接形成圖案化含金屬氧化物硬質光罩之方法及包括圖案化含金屬氧化物硬質光罩之半導體結構。
隨著趨勢將半導體裝置結構推向越來越小的幾何形狀,出現了不同的圖案化技術。此等技術包括自對準多重圖案化、間隔物界定四倍圖案化、及可包括深紫外線微影(DUVL)、極紫外線微影(EUVL)、及DUVL/EUVL組合間隔物界定雙倍圖案化的紫外線微影。另外,定向自組裝(DSA)已被視為未來微影術應用之選項。
上文所描述之圖案化技術可利用至少一種設於基板上之有機聚合物阻劑以實現基板之高解析度圖案化。為了滿足高解析度與低線邊緣粗糙度二者之需求,聚合物阻劑通常可為薄層。然而,此類薄聚合物阻劑可能具有若干缺點。尤其,高解析度聚合物阻劑可能具有低抗蝕刻性,即高蝕刻速率。聚合物阻劑之此低抗蝕刻性使得圖案化阻劑轉印至下層更加困難。當先進的高解析度聚合物阻劑需進一步縮小尺寸時,低抗蝕刻性的問題變大,因為聚合物阻劑可能具有甚至更低的抗蝕刻性及蝕刻選擇性。
在一些應用中,將聚合物阻劑之圖案轉印至硬質光罩可能為有利的。硬質光罩為半導體處理中用來作為蝕刻遮罩之材料,以代替聚合物或其他有機「軟質」阻劑材料,或是除了聚合物或其他有機「軟質」阻劑材料之外所使用的材料。相較於聚合物阻劑,硬質光罩材料一般具有較高的抗蝕刻性及較高的蝕刻選擇性。然而,硬質光罩圖案化方法一般涉及通過使用中間聚合物阻劑來界定硬質光罩圖案的間接圖案化技術。
因此,需要用來形成可直接圖案化及隨後利用作為硬質光罩材料之紫外(UV)輻射反應性材料的方法。
提供本發明內容來以簡化形式介紹一系列之概念。此等概念在下文本揭示實例具體例之詳細描述中進行進一步詳述。本發明內容並非意欲識別所主張之主題的關鍵特徵或基本特徵,亦非意欲用以限制所主張之主題的範疇。
在本揭示之一些具體例中,揭示一種用來形成紫外(UV)輻射反應性含金屬氧化物膜之方法。該方法可包括:將UV輻射反應性含金屬氧化物膜沉積於基板上方,該UV輻射反應性含金屬氧化物膜具有實質上均勻的蝕刻速率,其中沉積包括:將基板加熱至低於400℃之沉積溫度;使基板與包含金屬組分、氫組分、及碳組分之第一氣相反應物接觸;及使基板與包含氧前驅物之第二氣相反應物接觸,其中UV輻射反應性含金屬氧化物膜於UV照射後之區域具有第一蝕刻速率及UV輻射反應性含金屬氧化物膜之未經UV輻射照射之區域具有第二蝕刻速率,其中第二蝕刻速率不同於第一蝕刻速率。
為了概述本發明及所達成之優於先前技術的優點,本發明之某些目標及優點已在本文中於上文描述。當然,應了解的是,可無須根據本發明之任何特定具體例來達成所有此類目標或優點。因此,例如,本領域技術人士將
瞭解到,本發明可以達成或優化如本文中所教示或提示的一個優點或一群優點的方式來實施或進行,但未必達成如本文中所教示或提示的其他目的或優點。
所有該等具體例皆意欲屬於本文所揭示之本發明範疇中。藉由參考附圖之某些具體例的下述詳細說明,該等及其他具體例對本領域技術人士來說將變得更加明顯易懂,且本發明並不限於所揭示之任何特定具體例。
100:製程
100B:化學氣相沉積製程
110:製程方塊
110A:循環沉積製程
110B:化學氣相沉積製程
120:製程方塊
130:製程方塊
200:子製程方塊
210:子製程方塊
220:子製程方塊
230:決定閘口
240:循環沉積階段
250:製程方塊
300:子製程方塊
310:子製程方塊
320:子製程方塊
330:製程方塊
340:製程方塊
400:基板
402:膜;未經照射部分
402A:經UV照射部分
404:半導體結構
406:半導體結構
408:基板表面
500:製程
510:製程方塊
520:製程方塊
530:製程方塊
600:製程方塊
610:子製程方塊
620:子製程方塊
630:決定閘口
640:循環沉積階段
650:製程方塊
雖然本說明書以特別指出且明確主張被視為本發明的具體例的申請專利範圍作為結論,但是當結合伴隨圖式閱讀時,可從本揭示的具體例之某些實例的描述更容易地探知本揭示之具體例的優點,其中:圖1繪示說明根據本揭示之具體例用來沉積、照射、及圖案化UV反應性含金屬氧化物膜之方法的非限制性例示性製程流程;圖2繪示說明根據本揭示之具體例用來沉積UV反應性含金屬氧化物膜之循環沉積方法的非限制性例示性子製程流程;圖3繪示說明根據本揭示之具體例用來沉積UV反應性含金屬氧化物膜之化學氣相沉積方法的非限制性例示性子製程流程;圖4A-4D繪示藉由根據本揭示之具體例形成、照射、及顯影UV反應性含金屬氧化物膜之製程所形成的半導體結構的橫截面示意圖;圖5繪示說明根據本揭示之具體例用來沉積、照射、及圖案化UV反應性混合材料膜之方法的非限制性例示性製程流程;及圖6繪示說明根據本揭示之具體例用來沉積UV反應性混合材料膜之循環沉積方法的非限制性例示性子製程流程。
雖然在下文中揭示特定具體例及實例,但是該項技藝者可以理解,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其均等物。因此,其目的在於所揭示之本發明的範疇不應受下文所描述的特定揭示之具體例的限制。
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具體例的理想表示。
如本文所使用,術語「基板」可指可使用或在其上可形成裝置、電路或膜之任何下層材料。
如本文所使用,術語「化學氣相沉積」可以意指任何一個製程,其中將基板暴露於一種或更多種揮發性前驅物,該等前驅物在基板表面上反應及/或分解,以產生所要的沉積物。
如本文所使用,術語「循環沉積」可指將前驅物(反應物)依序引入至反應室中以在基板上方沉積一膜且包含諸如原子層沉積及循環化學氣相沉積之沉積技術。
如本文所使用,術語「循環化學氣相沉積」可以意指任何一個製程,其中將基板依序暴露於兩種或更多種揮發性前驅物,該等前驅物在基板上反應及/或分解,以產生所要的沉積物。
如本文所使用,術語「原子層沉積」(ALD)可指在反應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,在每個循環期間,前驅物被化學吸附至沉積表面(例如,基板表面或諸如來自前一個ALD循環之材料的先前所沉積之底層表面),從而形成不容易與其它前驅物反應(亦即,自限制反應(self-limiting reaction))的分子單層或次單層。之後,若需要,則可隨後將反應物(例如,另一種前驅物或反應氣體)引入至製程腔室中,以用於在沉積表面上將經化學吸附之前驅物轉化為所要材料。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沖洗步驟,自製程腔室移除過量前驅物,及/或在轉化經化學吸附之前驅物之後,自製程腔室移除過量反應物及/或反應副產物。此外,當用前驅物組合物、反應性氣體及沖洗(例如,惰性載體)氣體之交替脈衝執行時,如本文所使用之術語「原子層沉積」亦意謂包括由相關術語所表示之製程,例如,「化學氣相原子層沉積」、「原子層磊晶」(ALE)、分子束磊晶(MBE)、氣體源MBE或有機金屬MBE及化學束磊晶。
本文中所使用之術語「膜」及「薄膜」可指藉由本文中所揭示方法而沉積之任何連續或不連續結構及材料。舉例而言,「膜」及「薄膜」可包括2D材料、奈米層合物、奈米棒、奈米管、或奈米粒子或甚至部分或完全分子層或部分或完全原子層或原子及/或分子之群集。「膜」及「薄膜」可包含具有針孔,但仍為至少部分連續之材料或層。
如本文中所使用,術語「金屬有機」或「有機金屬」係可互換地使用且可指含有金屬組分或類金屬組分之有機化合物。有機金屬化合物可被視為具有直接金屬-碳鍵之金屬有機化合物的亞類。
如本文中所使用,術語「含金屬氧化物膜」可指包含至少一種金屬組分及一氧組分之膜。術語「含金屬氧化物膜」亦可指包含一或多種額外金屬組分、一或多種摻雜劑物種、及/或雜質之含金屬氧化物膜。
如本文中所使用,術語「金屬組分」可指元素金屬組分及類金屬組分兩者,其中類金屬組分可包括,但不限於,矽組分、鍺組分、硼組分、或銻組分。
如本文中所使用,術語「UV反應性含金屬氧化物膜」可指當經UV輻射照射時可吸收UV輻射之至少一部分,並回應於UV輻射刺激經歷物理或化學變化中之至少一者的含金屬氧化物膜。
如本文中所使用,術語「結晶膜」可指展現至少短程規則或甚至
長程規則之結晶結構的膜,且包括單晶膜以及多晶膜。相對地,如本文中所使用,術語「非晶膜」可指實質上未展現膜結構之規則的膜。
如本文中所使用,術語「摻雜劑前驅物」可指包含當經UV輻射照射時可改變UV輻射反應性含金屬氧化物膜之反應性之摻雜劑物種的前驅物。
如本文中所使用,術語「蝕刻速率」可指藉由濕式蝕刻製程、乾式蝕刻製程、或熱蝕刻製程中之一或多者的膜移除速率。
在本揭示的所有具體例中給出一些實例材料,應注意針對每個實例材料所給出之化學式不應被視為限制性且所給出之非限制性實例材料不應受給定的實例化學計量所限制。
本揭示之具體例可提供用來形成及照射UV輻射反應性含金屬氧化物膜之方法。經照射的含金屬氧化物膜隨後可經顯影以形成含金屬氧化物之硬質光罩,而不需要中間有機聚合物阻劑且不需要用來形成及圖案化有機聚合物的相關光微影製程。
紫外線微影(UVL)通常利用有機聚合物遮罩材料。舉例來說,UVL製程可使有機聚合物遮罩材料暴露至UV輻射,該UV輻射至少部分被吸收於有機遮罩材料中且亦被吸收於下層基板中,從而產生高能光電子及繼而產生低能二次電子之級聯。此等二次電子增加有機聚合物遮罩材料中之化學反應,從而提高其對UV輻射的敏感性。然而,二次電子型態的性質係無規的,且其重疊於光學影像上,從而導致喪失解析度、提高線條邊緣粗糙度(LER)、及線寬變化。因此,需要對UV輻射具反應性,但較不易受到二次電子暴露效應影響的替代性遮罩材料。此外,需要對UV輻射具反應性,同時當經暴露至常於半導體裝置製造期間使用之蝕刻劑時仍維持結構剛性及高抗蝕刻性的遮罩材料。此外,需要對下層基板具有經改良的黏著力,其可免除對中間黏著促進層之需求,藉此簡化半導體裝置製造過程的UV反應性遮罩材料。
因此,本揭示之具體例提供用來形成及照射UV輻射反應性含金屬氧化物膜之方法。該等方法可包括:將紫外(UV)輻射反應性含金屬氧化物膜沉積於基板上方,該UV輻射反應性含金屬氧化物膜具有實質上均勻的蝕刻速率,其中沉積包括:將基板加熱至低於400℃之沉積溫度,使基板與包含金屬組分、氫組分、及碳組分之第一氣相反應物接觸;及使基板與包含氧前驅物之第二氣相反應物接觸,其中UV輻射反應性含金屬氧化物膜於UV照射後之區域具有第一蝕刻速率及UV反應性含金屬氧化物膜之未經UV輻射照射之區域具有第二蝕刻速率,其中第二蝕刻速率不同於第一蝕刻速率。
如本文中所使用,「UV輻射」可指具有小於250奈米、或小於200奈米、或小於100奈米、或小於50奈米、或小於25奈米、或甚至小於20奈米之波長,或具有介於大約10奈米與大約400奈米之間之波長、或具有介於大約10奈米與大約200奈米之間之波長的電磁輻射。在一些具體例中,電磁輻射可在低於13.5奈米之範圍內。作為非限制性實例,UV輻射可具有193奈米、248奈米、或13.5奈米之波長。
本揭示之具體例進一步參照圖1作說明,其繪示用來沉積UV反應性含金屬氧化物膜,利用UV輻射照射UV反應性含金屬氧化物之選定部分,及直接形成圖案化含金屬氧化物硬質光罩遮罩(即不需要中間有機聚合物阻劑)的例示性製程100。更詳言之,例示性製程100可始於製程方塊110,其包括沉積UV輻射反應性含金屬氧化物膜。參照圖2及圖3更詳細地繪示製程方塊110,其中圖2繪示用來沉積UV反應性含金屬氧化物膜之例示性循環沉積製程110A及圖3繪示用來沉積UV反應性含金屬氧化物膜之例示性化學氣相沉積製程110B。
作為一非限制性實例,UV反應性含金屬氧化物膜可藉由如參照圖2說明於文中之循環沉積方法來沉積,圖2繪示沉積製程110A及其組成子製程。例示性沉積製程110A可始於子製程方塊200,其包括將基板提供至反應腔室
中並將基板加熱至沉積溫度。
於本揭示之一些具體例中,該基板可包括平坦基板(如圖4A之基板400所繪示)或包含高縱橫比特徵(諸如,比方說,溝槽結構及/或鰭片結構)之圖案化基板。基板可以包括一種或多種材料,包含但不限於矽(Si)、鍺(Ge)、鍺錫(GeSn)、矽鍺(SiGe)、矽鍺錫(SiGeSn)、碳化矽(SiC)或第III族-第V族半導體材料,例如砷化鎵(GaAs)、磷化鎵(GaP)或氮化鎵(GaN)。在一些具體例中,基板可包括一或多種介電材料,諸如,但不限於,金屬氧化物,氧化矽、氮化矽、及氮氧化矽。在一些具體例中,基板可進一步包括一或多種金屬、金屬氮化物、金屬碳化物、或其混合物。在本揭示之一些具體例中,基板可包括工程化基板,其中表面半導體層設置在塊體支撐件上方,其間設置有插入的掩埋氧化物(BOX)。
圖案化基板可以包括如下基板:其可以包含形成在基板表面之中或之上的半導體裝置結構,例如,圖案化基板可以包含部分製造的半導體裝置結構,諸如,比方說,電晶體及/或記憶體元件。在一些具體例中,基板可含有單晶表面及/或一個或多個可包含非單晶表面(諸如多晶表面及/或非晶表面)之第二表面。單晶表面可包含,例如,矽(Si)、矽鍺(SiGe)、碳化矽(SiC)、鍺錫(GeSn)、鍺(Ge)、或第III族-第V族半導體中之一者或多者。多晶或非晶表面可包括介電材料,諸如氧化物、氮氧化物或氮化物,諸如,比方說,氧化矽及氮化矽。
在一些具體例中,可將基板設置於經組構用於循環沉積製程之反應腔室,諸如,比方說,經組構用於原子層沉積製程之反應腔室或經組構用於循環化學氣相沉積製程之反應腔室中。舉例來說,可利用經組構用來以依序方式提供前驅物之ALD反應器以及CVD反應器來使用循環沉積製程沉積UV輻射反應性含金屬氧化物膜。依據一些具體例,可以使用噴灑頭式反應器。依據一些具體例,可以使用交叉流動式、批式、小型批式或空間式AID反應器。
於本揭示之一些具體例中,例示性循環沉積製程110A可於批式反應室中進行。在一些具體例中,可使用垂直批式反應器。在其他具體例中,批式反應器包括小型批式反應器,其經組構成容納10個或更少晶圓、8個或更少晶圓、6個或更少晶圓、4個或更少晶圓或者2個或更少晶圓。在使用批式反應器之一些具體例中,晶圓間之不均勻度小於3%(1 σ)、小於2%、小於1%或甚至小於0.5%。
本文中所描述之例示性循環沉積製程110A可視情況在連接至集束型製程設備的反應器或反應腔室中進行。在集束型製程設備中,因為每個反應腔室專用於一種類型的製程,所以每個模組中之反應腔室的溫度可維持恆定,其相較於在每次運轉前將基板加熱至製程溫度的反應器可改善生產量。此外,在集束型製程設備中,可減少將反應腔室抽汲至基板間所要的製程壓力位準之時間。在本揭示之一些具體例中,用來形成文中揭示之UV輻射反應性含金屬氧化物膜的例示性循環沉積製程可以在包括多個反應腔室之集束型製程設備中進行,其中可利用每個個別反應腔室來使基板暴露於個別的前驅物氣體,並且可使基板在不同的反應腔室之間輸送,以便暴露於多種前驅物氣體,基板的輸送係在受控環境下進行,以防止基板的氧化/污染。在本揭示之一些具體例中,當前揭示之循環沉積製程可在包括多個反應腔室之集束型製程設備中進行,其中每個個別反應腔室可經組構以將基板加熱至不同溫度。
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腔室。
在一些具體例中,循環沉積製程可為混合ALD/CVD或循環CVD製程。例如,在一些具體例中,ALD製程之生長速率相較於CVD製程可能是較低的。一種增加生長速率之方法可以在比ALD製程中通常使用之溫度更高的基板溫度下操作,從而導致一些部分的化學氣相沉積製程,但是仍利用前驅物的
依序引入,此一製程可稱為循環CVD。在一些具體例中,循環CVD製程可包括將兩種或更多種前驅物依序引入至反應腔室中,其中在反應腔室中在兩種或更多種前驅物之間可存在一重疊時間段,從而導致沉積的ALD組分及沉積的CVD組分兩者。
一旦將基板設置於適當反應腔室中,則子製程200(圖2)可經由在膜沉積之前將基板加熱至期望的沉積溫度來繼續。舉例而言,基板可經加熱至低於大約800℃、或低於大約600℃、或低於大約400℃、或低於大約350℃、或低於大約300℃、或低於大約250℃、或低於大約200℃、或低於大約150℃、或低於大約100℃、或低於大約50℃、或甚至低於大約25℃之基板溫度。在本揭示之一些具體例中,沉積製程期間之基板溫度可在介於25℃與250℃之間、或介於100℃與200℃之間。在一些具體例中,沉積製程期間之基板溫度可在介於15℃與350℃之間、或介於20℃與300℃之間。
除了達到所欲沉積溫度(即,所欲之基板溫度)之外,例示性循環沉積製程110A亦可調節反應腔室內之壓力,以獲得所沉積UV反應性含金屬氧化物膜之期望特性。例如,在本揭示的一些具體例中,例示性循環沉積製程110A可於經調節至低於100托(Torr)、或低於10托、或低於1托、或低於0.1托、或低於0.01托、或甚至低於0.0001托之反應腔室壓力的反應腔室內進行。
循環沉積製程之非限制性實例具體例可包含原子層沉積(ALD),其中ALD係基於典型地自限制反應,從而使用反應物之依序及交替脈衝來於每個沉積循環沉積約一個原子(或分子)單層材料。沉積條件及前驅物通常經選擇以提供自飽和反應,使得一種反應物之吸收層留下不與相同反應物之氣相反應物反應的表面終端。接著使基板與一種不同的反應物接觸,此不同的反應物與先前終端反應,以便能夠持續沉積。因此,交替脈衝的每個循環通常留下不超過約一個單層的所要材料。然而,如上文所提及,熟習此項技術者將認知
到在一或多個ALD循環中可沉積超過一個單層的材料,例如在不管製程之交替性質如何發生一些氣相反應時。
在利用於形成UV輻射反應性含金屬氧化物膜之ALD類型製程中,一個沉積循環可包括使基板暴露於第一氣相反應物,自反應腔室移除任何未反應之第一反應物及反應副產物,及使基板暴露於第二氣相反應物,繼而為第二移除步驟。在本揭示之一些具體例中,第一氣相反應物可包含金屬組分、氫組分、及碳組分,及第二氣相反應物可包含含氧前驅物。
前驅物可藉由惰性氣體(諸如氬氣(Ar)或氮氣(N2))分離,以避免反應物之間的氣相反應且能夠進行自飽和表面反應。然而,在一些具體例中,可以移動基板,以與第一氣相反應物及第二氣相反應物個別接觸。由於反應在某種程度上自飽和,因此可以不需要基板之嚴格的溫度控制及前驅物之精確的劑量控制。然而,基板溫度較佳使得入射氣體物種不會凝結成單層亦不會在表面上分解。在使基板與下一種反應性化學物質接觸之前,例如藉由沖洗反應空間或藉由移動基板來從基板表面移除過剩的化學物質及反應副產物(如果有的話)。不需要的氣態分子可以藉助於惰性沖洗氣體有效地從反應空間排出。真空泵可以用於輔助沖洗。
在將基板加熱至期望沉積溫度後,例示性循環沉積製程110A可藉由子製程方塊210繼續進行循環沉積階段240,其包括使基板與第一氣相反應物接觸,及特定言之,在一些具體例中,使基板與包含金屬組分、氫組分、及碳組分的第一氣相反應物接觸。
在本揭示之一些具體例中,第一氣相反應物可包含金屬有機前驅物,其中該金屬有機前驅物包含金屬組分、氫組分、及碳組分。在一些具體例中,第一氣相反應物可包含金屬有機前驅物,其包括選自包含下列之群的金屬組分:鋁、鋅、銦、鉍、或銻。在一些具體例中,第一氣相反應物可包含金屬
有機前驅物,其包括選自包含下列之群的類金屬組分:矽或鍺。
在本揭示之一些具體例中,第一氣相反應物可包含鋁(Al)組分,即鋁金屬有機前驅物。舉例而言,鋁金屬有機前驅物可包含三甲基鋁(TMA)、三乙基鋁(TEA)、氫化二甲基鋁(DMAH)、異丙氧化二甲基鋁(DMAI)、或三-第三丁基鋁(TTBA)中之至少一者。
在本揭示之一些具體例中,第一氣相反應物可包含鋅(Zn)組分,即鋅金屬有機前驅物。舉例來說,鋅金屬有機前驅物可包括二甲基鋅(ZnMe2)、二乙基鋅(ZnEt2)、異丙氧化甲基鋅(ZnMe(OPr))或醋酸鋅(Zn(CH3CO2)2)中的至少一者。
在本揭示之一些具體例中,第一氣相反應物可包含銦(In)組分,即銦金屬有機前驅物。舉例來說,銦金屬有機前驅物可包括三甲基銦(TMI)、三乙基銦(TEI)、二異丙基甲基銦(DIPMeIn)或乙基二甲基銦(EDMIn)中的至少一者。
在本揭示之一些具體例中,第一氣相反應物可包含鉍(Bi)組分,即鉍金屬有機前驅物。舉例來說,鉍金屬有機前驅物可包括鉍-烷氧化物或鉍-甲矽烷基醯胺基的至少一者。在一些具體例中,金屬有機鉍前驅物可選自包括下列之群:[(dmb)2Bi-O-Bi(dmb)2]2、參(2,3-二甲基-2-丁氧基)鉍(III)、參(第三丁氧基)鉍(III)、或參(異丙氧基)鉍(III)。在一些具體例中,金屬有機鉍前驅物可選自包括下列之群:Bi(N(SiMe3)2)3、Bi(thd)3、Bi(OtBu)3、Bi(dmb)3、或Bi(CH2SiMe3)3。在發給Hatanpaa等人之美國專利案號7,713,584中描述金屬有機鉍前驅物,該案以引用方式併入本文。
在本揭示之一些具體例中,第一氣相反應物可包含銻(Sb)組分,即銻金屬有機前驅物。舉例來說,銻金屬有機前驅物可包括烷氧化銻、銻烷基胺、或銻烷基中的至少一者。在一些具體例中,銻金屬有機前驅物可包括Sb(N(CH3)2)3、Sb(NMe2)3、Sb(NEr2)3、或Sb(NPr2)3中之至少一者。在發給Matero
等人之美國專利案號9,006,112中描述金屬有機銻前驅物,該案以引用方式併入本文。
在本揭示之一些具體例中,第一氣相反應物可包含矽組分,即矽金屬有機前驅物。舉例來說,矽金屬有機前驅物可包括烷基胺基矽烷,諸如,比方說,雙烷基胺基矽烷(例如,雙-二乙基胺基矽烷)、烷基胺基矽烷(例如,二異丙基胺基矽烷)、或三烷基胺基矽烷(例如,參-二甲基胺基矽烷)。
在本揭示之一些具體例中,第一氣相反應物可包含鍺組分,即鍺金屬有機前驅物。舉例來說,鍺金屬有機前驅物可包括肆(二甲基胺基)鍺(TDMAGe)、肆(二乙基胺基)鍺(TDEAGe)、或肆(乙基甲基胺基)鍺(TEMAGe)中之至少一者。
在本揭示之一些具體例中,使基板與第一氣相反應物(例如,金屬有機前驅物)接觸可包含使基板接觸介於約0.01秒與約60秒之間、介於約0.05秒與約10秒之間或介於約0.1秒與約5.0秒之間的時間段。此外,在基板與第一氣相反應物接觸期間,第一氣相反應物的流速可小於2000sccm、或小於500sccm、或甚至小於100sccm。此外,在第一氣相反應物與基板接觸期間,第一氣相反應物的流速可在約1至2000sccm、約5至1000sccm、或約10至約500sccm之範圍內。
圖2之例示性循環沉積製程110A可藉由沖洗反應腔室來繼續。舉例來說,過量的第一氣相反應物及反應副產物(若存在)可例如藉由用惰性氣體泵送而自基板表面移除。在本揭示之一些具體例中,該沖洗製程可包括一沖洗循環,其中將基板表面沖洗低於大約5.0秒、或低於大約3.0秒或甚至低於大約2.0秒的時間段。過量的第一氣相反應物及任何可能的反應副產物可藉助由與反應腔室流體連通之泵送系統產生的真空來移除。
在利用沖洗循環沖洗反應腔室時,例示性循環沉積製程110A可藉由子製程方塊220來繼續進行循環沉積階段240之第二階段,其包括使基板與
第二氣相反應物接觸,及特定而言使基板與包括含氧前驅物(「氧前驅物」)之第二氣相反應物接觸。
在本揭示之一些具體例中,含氧前驅物可包含水(H2O)、臭氧(O3)、過氧化氫(H2O2)、分子氧(O2)、原子氧(O)、一氧化二氮(N2O)、二氧化氮(NO2)、三氧化硫(SO3)、或基於氧之電漿中之至少一者,其中該基於氧之電漿包含原子氧(O)、氧離子、氧自由基、及激發氧物種,且可藉由激發(例如,經由施加RW功率)含氧氣體來產生。應注意,如本文所使用,術語「氣相反應物」包括激發電漿且激發物種包含該電漿。
在本揭示之一些具體例中,使基板與含氧前驅物接觸可包括:使氧前驅物與基板接觸介於約0.01秒與約60秒之間,介於約0.05秒與約10秒之間,或介於約0.1秒與約5.0秒之間的時間段。此外,於氧前驅物與基板之接觸期間,氧前驅物的流速可低於2000sccm,或低於500sccm,或甚至低於100sccm。此外,於基板與氧前驅物之接觸期間,氧前驅物的流速可在約1至2000sccm,約5至1000sccm,或約10至約500sccm之範圍內。
當基板一經與氧前驅物接觸,例示性循環沉積製程110A可經由沖洗反應腔室來繼續進行。舉例來說,過量的氧前驅物及反應副產物(若存在)可例如藉由在使惰性氣體流動之同時泵送而自基板表面移除。在本揭示之一些具體例中,沖洗製程可包括沖洗基板表面持續介於大約0.1秒與大約10秒之間、或介於大約0.5秒與大約3秒之間、或甚至介於大約1秒與2秒之間的時間段。
在完成自反應腔室沖洗第二氣相反應物(即氧前驅物(及任何反應副產物))後,循環沉積階段240可藉由決定閘口230來繼續,其中該決定閘口230係取決於所沉積之UV輻射反應性含金屬氧化物膜之厚度。舉例來說,如UV輻射反應性含金屬氧化物膜就期望應用而言係以不足夠的厚度沉積,則循環沉積階段240可經由返回至子製程方塊210及繼續通過再一沉積循環來重複,其中一單
位沉積循環可包括使基板與第一氣相反應物(諸如,比方說,金屬有機前驅物)接觸(子製程方塊210),沖洗反應腔室,使基板與含氧前驅物接觸(子製程方塊220),及再次沖洗反應腔室。可重複循環沉積階段240之單位沉積循環一或多次,直至於基板上方沉積期望厚度的UV輻射反應性含金屬氧化物膜為止。一旦UV輻射反應性含金屬氧化物膜已經沉積至期望厚度,則例示性沉積製程110可經由製程方塊250離開,且可使其上具有UV輻射反應性含金屬氧化物膜之基板接受進一步加工以形成含金屬氧化物之硬質光罩材料。
應明瞭在本揭示之一些具體例中,基板與第一氣相反應物(例如,金屬有機前驅物)及第二氣相反應物(例如,氧前驅物)接觸之順序可為使基板先與第二氣相反應物接觸及接著再與第一氣相反應物接觸。此外,在一些具體例中,例示性循環沉積製程110A之循環沉積階段240可包括使基板與第一氣相反應物接觸一或多次,隨後再使基板與第二氣相反應物接觸一或多次。此外,在一些具體例中,例示性循環沉積製程110A之循環沉積階段240可包括使基板與第二氣相反應物接觸一或多次,隨後再使基板與第一氣相反應物接觸一或多次。
在一些具體例中,循環沉積階段240可進一步包括使基板與包含至少一金屬組分之第三氣相反應物接觸,其中該第三氣相反應物中之金屬組分可不同於第一氣相反應物中之金屬組分。添加包含至少一金屬組分之第三氣相反應物容許沉積混合金屬氧化物、或混合類金屬氧化物、或金屬氧化物及類金屬氧化物之混合物。
在本揭示之替代具體例中,UV輻射反應性含金屬氧化物膜可藉由化學氣相沉積製程來沉積,且例示性的化學氣相沉積製程110B及化學氣相沉積製程110B之組成子製程參照圖3來說明。
更詳言之,例示性的化學氣相沉積製程110B可始於子製程方塊300,其包括將基板提供至經組構用於化學氣相沉積製程之半導體加工設備的反
應腔室中及將基板加熱至期望的沉積溫度。基板可包括如參照圖2之例示性循環沉積製程110A所描述之所有形式的基板及基板材料。用來沉積UV輻射反應性含金屬氧化物膜之一例示性化學氣相沉積製程可包括將基板加熱至低於800℃、或低於600℃、或低於400℃、或低於350℃、或低於300℃、或低於250℃、或低於200℃、或低於150℃、或低於100℃、或低於50℃、或甚至低於25℃之沉積溫度。在本揭示之一些具體例中,沉積製程期間之基板溫度可係介於25℃與250℃之間,或介於100℃與200℃之間。
除了達到期望沉積溫度(即,期望的基板溫度)之外,例示性CVD沉積製程110B亦可調整反應腔室內之壓力,以獲得所沉積UV反應性含金屬氧化物膜之期望特性。例如,在本揭示的一些具體例中,例示性CVD製程110B可在經調節至低於100托、或低於10托、或低於1托、或低於0.1托、或低於0.01托、或甚至低於0.0001托之反應腔室壓力的反應腔室內進行。
當達到期望沉積溫度及反應器壓力時,例示性化學氣相沉積製程110B可繼續進行子製程方塊310及子製程方塊320,其包括使基板與包含金屬組分、氫組分、及碳組分之第一氣相反應物接觸(子製程方塊310),及進一步包括使基板與包含氧前驅物之第二氣相反應物接觸(子製程方塊320)。
在本揭示之一些具體例中,子製程方塊310及子製程方塊320係同時進行,換言之,可使基板同時與第一氣相反應物及第二氣相反應物兩者接觸。舉例來說,可將第一氣相反應物引入至反應腔室中,同時亦將第二氣相反應物引入至反應腔室中,使得第一氣相反應物及第二氣相反應物同時地共同流入至反應腔室中,且包含至少第一氣相反應物及第二氣相反應物之氣體混合物可與設置於反應腔室中之基板接觸。
在一些具體例中,第一氣相反應物之流速可小於2000sccm、或小於500sccm、或甚至小於100sccm。在一些具體例中,第一氣相反應物之流速
可係約1至約2000sccm、約5至約1000sccm、或約10至約500sccm。在一些具體例中,第二氣相反應物之流速可小於2000sccm、或小於500sccm、或甚至小於100sccm。在一些具體例中,第二氣相反應物之流速可係約1至約2000sccm、約5至約1000sccm、或約10至約500sccm。
在替代具體例中,例示性CVD製程110B可首先將第一氣相反應物引入至反應腔室中(子製程方塊310),隨後接著將第二氣相反應物引入至反應腔室中(子製程方塊320)。或者,例示性CVD製程100B可首先將第二氣相反應物引入至反應腔室中(子製程方塊320),隨後接著將第一氣相反應物引入至反應腔室中(子製程方塊310)。
在例示性化學氣相沉積製程110B及尤其在包括使基板與第一氣相反應物接觸之子製程方塊310中,第一氣相反應物可包含金屬有機前驅物,其包含金屬組分、氫組分、及碳組分。在一些具體例中,第一氣相反應物可包含金屬有機前驅物,其包括選自包含下列之群的金屬組分:鋁、鋅、銦、鉍、或銻。在一些具體例中,第一氣相反應物可包含金屬有機前驅物,其包括選自包含下列之群的類金屬組分:矽或鍺。
例示性化學氣相沉積製程100B及尤其子製程方塊310可利用如先前參照循環沉積製程110A所描述之所有金屬有機前驅物,因此不針對例示性CVD製程110B再次說明。
此外,在例示性化學氣相沉積製程110B及尤其在包括使基板與第二氣相反應物接觸之子製程方塊320中,第二氣相反應物可包含氧前驅物,且可利用先前參照循環沉積製程110A所描述之所有氧前驅物,因此不針對例示性CVD製程110B再次說明。
例示性化學氣相沉積製程110A可藉由製程方塊330繼續,其包括將UV反應性含金屬氧化物膜沉積至期望厚度。舉例來說,使基板(於期望基板溫
度下)與第一氣相反應物及第二氣相反應物接觸可導致將UV反應性含金屬氧化物膜沉積於基板的經暴露上表面上,且例示性CVD製程可繼續一時間段,直至沉積得足夠厚度之UV反應性含金屬氧化物膜為止,此時例示性化學氣相沉積製程110B可經由製程方塊340離開,且可使UV反應性含金屬氧化物膜接受進一步的製程以形成圖案化含金屬氧化物硬質光罩。
例示性循環沉積製程110A(圖2)及例示性化學氣相沉積製程110B(圖3)皆可進一步包括額外的子製程,其包括使基板與一或多種摻雜劑前驅物接觸。
作為一非限制性實例,循環沉積製程110A可進一步包括在循環沉積階段240之任何階段使基板與一或多種摻雜劑前驅物接觸。舉例來說,可在使基板與第一氣相反應物接觸之前,或在使基板與第二氣相反應物接觸之前,或在使基板與第二氣相反應物接觸之後,使基板與一或多種摻雜劑前驅物接觸。或者,可在使基板與第一氣相反應物接觸的同時使基板與一或多種摻雜劑前驅物接觸及/或可在使基板與第二氣相反應物接觸的同時使基板與一或多種摻雜劑前驅物接觸。或者,可在使基板與一或多種摻雜劑前驅物接觸之前進行循環沉積階段240之一或多個單位循環,例如,可將循環沉積階段240之單位循環重複一或多次、二或更多次、五或更多次,及接著可使基板與一或多種摻雜劑前驅物接觸。
作為再一非限制性實例,化學氣相沉積製程110B可進一步包括在化學氣相沉積製程110B之任何階段使基板與一或多種摻雜劑前驅物接觸。舉例來說,可將第一氣相反應物、第二氣相反應物、及一或多種摻雜劑前驅物同時引入至反應腔室中並作為包含至少第一氣相反應物、第二氣相反應物、及一或多種摻雜劑前驅物之氣體混合物與基板接觸。或者,一或多種摻雜劑前驅物可在第一氣相反應物之前接觸基板,繼而為第二氣相反應物,或相反地,一或
多種摻雜劑前驅物可在第二氣相反應物之前接觸基板,繼而為第一氣相反應物,或可設想任何及所有用來使基板與第一氣相反應物、第二氣相反應物、及一或多種摻雜劑前驅物接觸的順序。
一或多種摻雜劑前驅物可與基板接觸以將一或多種摻雜劑引入至UV反應性含金屬氧化物膜中,其可改變UV輻射反應性含金屬氧化物膜當經UV輻射照射時的反應性。舉例來說,在一些具體例中,將一或多種摻雜劑引入至UV反應性含金屬氧化物膜中可使含金屬氧化物膜之UV反應性提高大於50%,或大於100%,或甚至大於200%。
在本揭示之一些具體例中,一或多種摻雜劑前驅物可向UV輻射反應性含金屬氧化物膜中引入額外的金屬氧化物摻雜劑、額外的金屬摻雜劑、或烷基矽化合物摻雜劑。舉例來說,添加摻雜劑至UV輻射反應性含金屬氧化物膜中會向含金屬氧化物膜引入改良含金屬氧化物膜之UV反應性的結構及/或鍵及/或基團。
在本揭示之一些具體例中,使基板與一或多種摻雜劑前驅物接觸可進一步包括將額外的金屬氧化物摻雜劑引入至UV反應性含金屬氧化物膜中。舉例來說,額外的金屬氧化物摻雜劑可包含氧化鋁、氧化鋅、氧化銦、氧化鉍、氧化銻、氧化矽、或氧化鍺中之至少一者。在一些具體例中,額外的金屬氧化物摻雜劑可包含與構成含金屬氧化物之材料者不同的金屬氧化物。舉例來說,可利用金屬有機前驅物來引入額外的金屬氧化物摻雜劑,且此一金屬有機前驅物可與利用作為用來沉積含金屬氧化物膜之第一氣相反應物者不同。
在本揭示之一些具體例中,使基板與一或多種摻雜劑前驅物接觸可進一步包括將額外的金屬摻雜劑引入至UV反應性含金屬氧化物膜中。舉例來說,額外的金屬摻雜劑可包含鋁、鋅、銦、鉍、銻、矽、或鍺中之至少一者。在一些具體例中,額外的金屬摻雜劑可包含錫。
在本揭示之一些具體例中,使基板與一或多種摻雜劑前驅物接觸可進一步包括將烷基矽化合物摻雜劑引入至UV反應性含金屬氧化物膜中。在一些具體例中,烷基矽化合物摻雜劑可選自包含下列之群:DSBAS二-第二丁基胺基矽烷(sBu2N)SiH3、BDEAS雙(二乙胺基)矽烷SiH2(NEt2)2、BDMAS雙(二甲胺基)矽烷SiH2(NMe2)2、TriDMAS參(二乙胺基)矽烷SiH(NMe2)3、雙(三甲基矽烷基胺基)矽烷SiH2(NHSiMe3)2、TEAS肆(乙胺基)矽烷Si(NHEt)4、TEOS肆(乙氧基)矽烷Si(OEt)4、BTESE雙(三乙氧矽烷基)乙烷(EtO)3Si-CH2-CH2-Si(OEt)3。
在本揭示之一些具體例中,矽化合物摻雜劑係通式(R1R2N)nSiH4-x之胺基矽烷,其中x包含在1及4之間,其中R1及R2獨立地為H或C1-C6直鏈、分支鏈或環狀碳鏈。較佳地,矽化合物摻雜劑係通式(R1R2N)nSiH2之胺基矽烷,其中R1及R2較佳獨立地選自C1-C4直鏈、分支鏈或環狀碳鏈。在一些具體例中,烷基胺基矽烷係雙(二乙胺基)矽烷(BDEAS)、雙(二甲胺基)矽烷(BDMAS)或參(二甲胺基)矽烷(TriDMAS)。
在本揭示之一些具體例中,UV反應性含金屬氧化物膜可經沉積至大於1奈米、或大於5奈米、或大於10奈米、或大於20奈米之厚度。在一些具體例中,UV反應性含金屬氧化物膜可經沉積至介於0.5奈米至50奈米之間之厚度、或介於1奈米至30奈米之間之厚度、或介於1奈米至20奈米之間之厚度、或甚至介於2奈米至15奈米之間之厚度。
在本揭示之一些具體例中,UV反應性含金屬氧化物膜,如圖4A之膜402所繪示,可沉積於基板400之上表面的大部分上。在一些具體例中,UV反應性含金屬氧化物膜可僅沉積於基板400之上表面的選定部分上(未圖示)。在一些具體例中,UV反應性含金屬氧化物膜402可具有實質上均勻的剛沉積蝕刻速率,即在任何UV照射製程之前的均勻蝕刻,其中實質上均勻的蝕刻速率可指
在大於1奈米/分鐘、或大於5奈米/分鐘、或大於10奈米/分鐘、或大於20奈米/分鐘、或大於30奈米/分鐘、或大於50奈米/分鐘、或大於100奈米/分鐘或甚至大於150奈米/分鐘之範圍內之總體UV反應性含金屬氧化物膜的蝕刻速率。在其他具體例中,輻射後之UV反應性含金屬氧化物膜材料可具有在大於1奈米/分鐘、或大於5奈米/分鐘、或大於10奈米/分鐘、或大於20奈米/分鐘、或大於30奈米/分鐘、或大於50奈米/分鐘、或大於100奈米/分鐘或甚至大於150奈米/分鐘之範圍內之蝕刻速率。
在本揭示之一些具體例中,沉積UV輻射反應性含金屬氧化物膜可包括沉積氧化鋁、氧化鋅、氧化銦、氧化鉍、氧化矽、氧化鍺、或氧化銻、及其對應經摻雜對等物中之至少一者。根據本揭示之具體例沉積的UV輻射反應性含金屬氧化物膜由於雜質濃度、濕式蝕刻速率、電性質等,而習慣上可被視為品質不良的膜。然而,根據本揭示之具體例沉積的UV輻射反應性含金屬氧化物膜可被利用作為高度UV反應性膜。相對於形成含金屬氧化物膜之先前方法,當前揭示之方法可利用產生一般將被稱為「不良品質」膜的製程條件,該等製程條件包括,例如,不完全反應、部分CVD反應、前驅物分解、或不完全前驅物飽和。然而,採用該等通常不被考慮用來形成含金屬氧化物膜之製程條件產生UV反應性含金屬氧化物膜。
在一些具體例中,UV輻射反應性含金屬氧化物膜係經沉積至具有期望原子百分比(原子%)的碳,例如,碳可自具有碳組分的第一氣相前驅物引入至膜中。舉例來說,UV反應性含金屬氧化物膜可具有大於1原子%、或大於5原子%、或大於10原子%、或大於20原子%、或大於30原子%、或甚至大於40原子%之碳濃度。此外,在一些具體例中,UV輻射反應性含金屬氧化物膜係經沉積至具有期望原子百分比(原子%)的氫,例如,氫可自具有氫組分的第一氣相前驅物引入至膜中。舉例來說,UV反應性含金屬氧化物膜可具有大於1原子%、或
大於5原子%、或大於10原子%、或大於20原子%、或大於30原子%、或甚至大於40原子%之氫濃度。此外,在一些具體例中,UV反應性含金屬氧化物膜係經沉積至具有期望原子百分比(原子%)的摻雜劑物種,諸如,比方說,額外的金屬氧化物摻雜劑、額外的金屬摻雜劑、或烷基矽化合物摻雜劑。因此,UV反應性含金屬氧化物膜可具有大於1原子%、或大於5原子%、或大於10原子%、或大於20原子%、或大於30原子%、或甚至大於40原子%之故意納入摻雜劑物種的濃度。
在一些具體例中,UV反應性含金屬氧化物膜可實質上不含錫(Sn)。舉例來說,UV反應性含金屬氧化物膜可具有低於20原子%、或低於10原子%、或低於5原子%、或低於1原子%、或低於0.5原子%、或低於0.1原子%、或甚至低於0.001原子%之錫濃度。
在本揭示之一些具體例中,沉積UV反應性含金屬氧化物膜可進一步包括沉積非晶形UV反應性含金屬氧化物膜,即膜實質上未展現膜的結構規則。舉例來說,剛沉積UV反應性含金屬氧化物膜之x射線繞射(XRD)分析可產生不包含對應於膜中之結晶方向之可辨識峰的數據。在替代性具體例中,沉積UV反應性含金屬氧化物膜可進一步包括沉積結晶UV反應性含金屬氧化物膜,即膜可展現至少短程規則或甚至長程規則且包括單晶膜以及多晶膜。舉例來說,剛沉積UV反應性含金屬氧化物膜之x射線繞射(XRD)分析可產生其中觀察到對應於特性結晶方向之可辨識峰的數據。
在沉積UV輻射反應性含金屬氧化物膜後,圖1之例示性製程100可繼續進行製程方塊120,其包括利用UV輻射照射UV反應性含金屬氧化物膜之選定部分。
更詳言之,可將其上具有UV反應性含金屬氧化物膜402之基板400(圖4B)設置於UV圖案化工具內。在一些具體例中,可將UV反應性含金屬氧化物膜沉積於第一反應腔室內及隨後輸送至UV圖案化工具。在一些具體例中,
經組構用來沉積UV反應性含金屬氧化物膜之反應腔室及UV圖案化工具可形成集束型製程設備,使得其上設置有UV反應性含金屬氧化物膜之基板的輸送係在受控環境(即未暴露至外部條件)下進行。
一旦設置於UV圖案化工具內,則本揭示之方法可包括利用UV輻射照射UV輻射反應性含金屬氧化物膜之選定部分,藉此形成包含具有第一蝕刻速率之經照射部分及具有不同於第一蝕刻速率之第二蝕刻速率之未經照射部分的含金屬氧化物膜。舉例來說,圖4C繪示半導體結構404,其包含基板400、UV反應性含金屬氧化物膜402之未經照射部分、及UV反應性含金屬氧化物膜之經UV照射部分402A。在一些具體例中,經UV照射部分402A具有低於未經照射部分402之第二蝕刻速率的第一蝕刻速率。在一些具體例中,經UV照射部分402A具有高於未經照射部分402之第二蝕刻速率的第一蝕刻速率。在本揭示之一些具體例中,經照射部分402A與未經照射部分402之間的蝕刻選擇性可大於2:1、或大於5:1、或大於8:1、或大於10:1、或大於15:1、或大於20:1、或甚至大於50:1。在替代具體例中,未經照射部分402與經照射部分402A之間的蝕刻選擇性可大於2:1、或大於5:1、或大於8:1、或大於10:1、或大於15:1、或大於20:1、或甚至大於50:1。
在一些具體例中,利用UV輻射照射UV反應性含金屬氧化物膜之選定部分進一步包括使經UV照射部分402A至少部分結晶。在一些具體例中,利用UV輻射照射UV反應性含金屬氧化物膜之選定部分進一步包括提高經UV照射部分402A之抗蝕刻性或剛性。舉例來說,在一些具體例中,UV反應性含金屬氧化物膜可經沉積為非晶形膜,及照射UV反應性含金屬氧化物膜之選定部分可刺激UV反應性含金屬氧化物膜之結晶。
一旦UV反應性含金屬氧化物膜之選定區域已受UV輻射照射,則圖1之例示性方法100可繼續進行製程方塊130,其包括直接形成圖案化含金屬氧
化物硬質光罩。舉例來說,本揭示之方法可進一步包括經由使UV反應性含金屬氧化物膜顯影以移除經照射部分或未經照射部分中之一者來直接形成圖案化含金屬氧化物硬質光罩。
更詳言之,在本揭示之一些具體例中,圖4C之半導體結構404可經顯影以移除經照射部分402A或未經照射部分402。舉例來說,用來移除UV反應性含金屬氧化物膜之選定部分的顯影製程可包含蝕刻製程,諸如,比方說,濕式蝕刻製程(例如,暴露至濕式蝕刻劑溶液)、乾式蝕刻製程(例如,暴露至基於電漿之蝕刻劑或於氣相中非基於電漿之蝕刻劑)、或熱蝕刻製程(例如,加熱半導體結構404)中之一或多者。作為一非限制性實例,經照射部分402A可具有第一蝕刻速率,其可低於未經照射部分402之第二蝕刻速率,及因此,在暴露至蝕刻製程期間,未經照射部分將以較經照射部分402A高的速率移除,從而容許完全移除未經照射部分402A,同時仍保留至少一部分的照射部分402A,如由圖4D之半導體結構406所繪示,其包含基板400及覆蓋基板400之表面之選定部分的圖案化含金屬氧化物硬質光罩402A,同時基板表面408的剩餘部分暴露至後續的加工。作為一非限制性實例,移除經UV照射之含金屬氧化物膜之選定部分可包括利用氯化學物質或氟化學物質中之一或多者的乾式電漿蝕刻製程。作為再一非限制性實例,移除經UV照射之含金屬氧化物膜之選定部分可包括,例如,利用氫氯酸之濕式蝕刻製程。在一些具體例中,圖案化含金屬氧化物硬質光罩402A可包含至少部分結晶膜。
在本揭示之替代具體例中,利用來形成圖案化硬質光罩之沉積UV反應性膜可包含混合材料,其中混合材料包含無機組分及有機組分兩者,且包括諸如,比方說,無機/有機奈米層合物及金屬有機框架之材料。如同文中關於UV反應性含金屬氧化物膜所揭示之例示性具體例,可沉積UV反應性混合材料,使其選擇性地暴露至UV輻射,及圖案化形成混合材料硬質光罩。
更詳言之,圖5繪示例示性製程500,其係用來沉積UV反應性混合材料,利用UV輻射照射UV反應性混合材料膜之選定部分,及直接形成圖案化混合材料硬質光罩遮罩,即無需中間有機聚合物阻劑。更詳言之,例示性製程500可始於製程方塊510,其包括沉積UV輻射反應性混合材料。參照圖6更詳細地繪示製程方塊510,圖6繪示用來沉積UV反應性混合材料之例示性循環沉積製程510。
利用來沉積UV反應性混合材料之圖6之例示性循環沉積製程510可由製程方塊600開始,其包括將基板提供至反應腔室中並將基板加熱至沉積溫度。基板及基板材料可包括先前參照圖1之方法100說明於文中之彼等。在一些具體例中,可將基板設置於經組構用於循環沉積製程之反應腔室,諸如經組構用於原子層沉積製程之反應腔室、或經組構用於循環化學氣相沉積製程之反應腔室中。在一些具體例中,基板可經加熱至低於大約800℃、或低於大約600℃、或低於大約400℃、或低於大約350℃、或低於大約300℃、或低於大約250℃、或低於大約200℃、或低於大約150℃、或低於大約100℃、或低於大約50℃、或甚至低於大約25℃之沉積溫度。在本揭示之一些具體例中,沉積製程期間之基板溫度可在介於25℃與250℃之間、或介於100℃與200℃之間。於一些具體例中,沉積製程期間之基板溫度可在介於15℃與350℃之間、或介於20℃與300℃之間。
在將基板加熱至期望沉積溫度後,例示性的循環沉積製程510可藉由子製程方塊610繼續進行循環沉積階段640,其包括使基板與第一氣相反應物接觸,及特定言之,在一些具體例中,使基板與包含金屬組分的第一氣相反應物接觸。
在本揭示之一些具體例中,第一氣相反應物可包含金屬有機前驅物,其中該金屬有機前驅物包含金屬組分、氫組分、及碳組分。在一些具體例
中,第一氣相反應物可包含金屬有機前驅物,該金屬有機前驅物包括選自包含下列之群之金屬組分:鋁、鋅、銦、矽、鍺、鉍、或銻。利用於混合材料之循環沉積之金屬有機前驅物可與先前參照圖2之循環沉積製程110A所描述之彼等相同,及因此不針對例示性循環沉積製程510來重複。在替代具體例中,第一氣相反應物可包含鹵化物前驅物,諸如金屬氯化物、金屬碘化物、金屬溴化物、或金屬氟化物中之至少一者。
在本揭示之一些具體例中,使基板與第一氣相反應物(例如,金屬前驅物)接觸可包含使基板接觸介於約0.01秒與約60秒之間、介於約0.05秒與約10秒之間、或介於約0.1秒與約5.0秒之間的時間段。此外,在基板與第一氣相反應物接觸期間,第一氣相反應物的流速可小於2000sccm、或小於500sccm、或甚至小於100sccm。此外,在第一氣相反應物與基板接觸期間,第一氣相反應物的流速可在約1至2000sccm、約5至1000sccm、或約10至約500sccm之範圍內。
圖6之例示性循環沉積製程510可藉由沖洗反應腔室來繼續。舉例來說,過量的第一氣相反應物及反應副產物(若存在)可例如藉由用惰性氣體泵送而自基板表面移除。在本揭示之一些具體例中,該沖洗製程可包括一沖洗循環,其中將基板表面沖洗低於大約5.0秒、或低於大約3.0秒、或甚至低於大約2.0秒的時間段。過量的第一氣相反應物及任何可能的反應副產物可藉助由與反應腔室流體連通之泵送系統產生的真空來移除。
在利用沖洗循環沖洗反應腔室後,例示性循環沉積製程510可藉由子製程方塊620繼續進行循環沉積階段640之第二階段,其包括使基板與第二氣相反應物接觸,及特定而言使基板與包含有機前驅物之第二氣相反應物(「有機前驅物」)接觸。
在本揭示之一些具體例中,有機前驅物可包含同雙官能化合物,諸如,比方說,二醇或二胺。在一些具體例中,有機前驅物可包含乙二醇或乙
二胺中之至少一者。在本揭示之一些具體例中,有機前驅物可包含異雙官能化合物,諸如,醇胺(例如,乙醇胺)。在一些具體例中,有機前驅物可包含酐,諸如,順丁烯二酸酐。在本揭示之一些具體例中,有機前驅物可基於利用於暴露UV反應性混合材料之UV波長來選擇或調整。在本揭示之一些具體例中,有機前驅物可包含利用諸如-OH或-NH2之至少兩個官能基官能化之飽和或不飽和、脂族或芳族、環狀或非環狀C1-C10烴、C2-C10烴、C3-C10烴、C4-C10烴、C5-C10烴、C1-C5烴、C2-C5烴、C3-C5烴、C4-C6烴、C5-C7烴、C1-C3烴、C2-C4烴。在一些具體例中,有機前驅物係官能化C2烴諸如乙醇胺。
在本揭示之一些具體例中,使基板與有機前驅物接觸可包括:使有機前驅物與基板接觸介於約0.01秒與約60秒之間,介於約0.05秒與約10秒之間,或介於約0.1秒與約5.0秒之間的時間段。此外,於基板與有機前驅物接觸期間,有機前驅物的流速可低於2000sccm,或低於500sccm,或甚至低於100sccm。此外,於基板與有機前驅物接觸期間,氧前驅物的流速可在約1至2000sccm,約5至1000sccm,或約10至約500sccm之範圍內。
在基板與有機前驅物接觸後,例示性循環沉積製程510可經由沖洗反應腔室來繼續進行。舉例來說,過量的有機前驅物及反應副產物(若存在)可例如藉由在使惰性氣體流動之同時泵送而自基板表面移除。在本揭示之一些具體例中,沖洗製程可包括沖洗基板表面持續介於大約0.1秒與大約10秒之間、或介於大約0.5秒與大約3秒之間、或甚至介於大約1秒與2秒之間的時間段。
在完成自反應腔室沖洗第二氣相反應物(即有機前驅物(及任何反應副產物))後,循環沉積階段640可繼續進行決定閘口630,其中該決定閘口630係取決於所沉積之UV輻射反應性混合材料膜之厚度。舉例來說,如UV輻射反應性混合材料膜就期望應用而言係以不足夠的厚度沉積,則循環沉積階段640可經由返回至子製程方塊610及繼續通過再一沉積循環來重複,其中一單位沉積循環
可包括使基板與第一氣相反應物(諸如,比方說,金屬前驅物)接觸(子製程方塊610),沖洗反應腔室,使基板與有機前驅物接觸(子製程方塊620),及再次沖洗反應腔室。可重複循環沉積階段640之單位沉積循環一或多次,直至於基板上方沉積期望厚度的UV輻射反應性混合材料膜為止。一旦UV輻射反應性混合材料膜已經沉積至期望厚度,則例示性沉積製程510可經由製程方塊650離開,且可使其上具有UV輻射反應性混合材料膜之基板接受進一步加工以形成混合材料硬質光罩材料。
應明瞭在本揭示之一些具體例中,基板與第一氣相反應物(例如,金屬前驅物)及第二氣相反應物(例如,有機前驅物)接觸之順序可為使基板先與第二氣相反應物接觸及接著與第一氣相反應物接觸。此外,在一些具體例中,例示性循環沉積製程510之循環沉積階段640可包括使基板與第一氣相反應物接觸一或多次,隨後再使基板與第二氣相反應物接觸一或多次。此外,在一些具體例中,例示性循環沉積製程510之循環沉積階段640可包括使基板與第二氣相反應物接觸一或多次,隨後再使基板與第一氣相反應物接觸一或多次。
例示性循環沉積製程510可進一步包括額外子製程,其包括使基板與一或多種摻雜劑前驅物接觸。使基板與一或多種摻雜劑接觸之製程及特定摻雜劑物種之細節已參照圖2之循環沉積製程110A作說明,及因此針對循環沉積製程510不再重複。
在一些具體例中,UV反應性混合材料係經沉積至具有期望原子百分比(原子%)的碳。舉例來說,UV反應性混合材料可具有大於1原子%、或大於5原子%、或大於10原子%、或大於20原子%、或大於30原子%、或甚至大於40原子%之碳濃度。此外,在一些具體例中,UV反應性混合材料可具有大於1原子%、或大於5原子%、或大於10原子%、或大於20原子%、或大於30原子%、或甚至大於40原子%之氫濃度。
在一些具體例中,UV反應性混合材料可實質上不含錫(Sn)。舉例來說,UV反應性混合材料可具有低於20原子%、或低於10原子%、或低於5原子%、或低於1原子%、或低於0.5原子%、或低於0.1原子%、或甚至低於0.001原子%之錫濃度。
在沉積UV輻射反應性混合材料膜後,圖5之例示性製程500可繼續進行製程方塊520,其包括利用UV輻射照射UV反應性混合材料膜之選定部分。
更詳言之,可將具有UV輻射反應性混合材料膜之基板設置於UV圖案化工具中及可利用UV照射UV輻射反應性混合材料膜之選定部分,藉此形成包含具有第一蝕刻速率之經照射部分及具有不同於第一蝕刻速率之第二蝕刻速率之未經照射部分的混合材料膜。在一些具體例中,經UV照射部分具有低於未經照射部分之第二蝕刻速率的第一蝕刻速率。在一些具體例中,經UV照射部分具有高於未經照射部分之第二蝕刻速率的第一蝕刻速率。
在一些具體例中,利用UV輻射照射UV反應性混合材料膜之選定部分進一步包括使經UV照射部分至少部分結晶。在一些具體例中,利用UV輻射照射UV反應性混合材料膜之選定部分進一步包括提高UV反應性混合材料之結晶度。在一些具體例中,利用UV輻射照射UV反應性混合材料膜之選定部分進一步包括提高UV反應性混合材料之抗蝕刻性或結構剛性。
舉例來說,在一些具體例中,UV反應性混合材料膜可經沉積為非晶形膜,及照射UV反應性混合材料膜之選定部分可刺激UV反應性混合材料膜之結晶。
一旦UV反應性混合材料膜之選定區域已受UV輻射照射,則圖5之例示性方法500可繼續進行製程方塊530,其包括直接形成圖案化混合材料硬質光罩。舉例來說,本揭示之方法可進一步包括經由使UV反應性混合材料膜顯影以移除經照射部分或未經照射部分中之一者來直接形成圖案化混合材料硬質
光罩。在一些具體例中,用來移除UV反應性混合材料膜之選定部分的顯影製程可包含蝕刻製程,諸如,比方說,濕式蝕刻製程、乾式蝕刻製程、或熱蝕刻製程中之一或多者。作為一非限制性實例,經照射部分可具有第一蝕刻速率,其可低於未經照射部分之第二蝕刻速率,及因此,在暴露至蝕刻製程期間,未經照射部分將以較經照射部分高的速率移除,從而容許完全移除未經照射部分,同時仍保留至少一部分的照射部分。在一些具體例中,利用來顯影UV反應性混合材料之濕式蝕刻製程及/或乾式蝕刻製程可實質上與先前針對UV反應性含金屬氧化物膜之顯影所描述之彼等相似,及因此在此不作重複。在一些具體例中,UV反應性混合材料可以圖案顯影製程蝕刻,該圖案顯影製程利用包括使UV反應性混合材料暴露至氧基電漿的灰化製程。在一些具體例中,圖案化混合材料硬質光罩可包含至少部分結晶膜。
上述揭示內容之實例具體例並未限制本發明的範疇,因為此等具體例僅為本發明之具體例之實例,本發明的範疇係由隨附申請專利範圍及其合法均等物來界定。任何等效具體例皆旨在本發明之範疇內。實際上,熟習此項技術者自前述描述將明白除了本文展示且描述以外的本揭示之各種修飾,諸如所述元件之替代有用組合。該等修飾及具體例亦旨在落在隨附申請專利範圍之範疇內。
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Claims (26)
- 一種用來形成紫外(UV)輻射反應性含金屬氧化物膜之方法,該方法包含:沉積UV輻射反應性含金屬氧化物膜於基板上方,該UV輻射反應性含金屬氧化物膜具有實質上均勻的蝕刻速率,其中沉積包含:將該基板加熱至低於400℃之沉積溫度;使該基板與包含金屬組分、氫組分、及碳組分之第一氣相反應物接觸;及使該基板與包含含氧前驅物之第二氣相反應物接觸;及經由選擇性地UV照射該UV輻射反應性含金屬氧化物膜以提供經照射區域及未經照射區域,以及經由顯影該UV輻射反應性含金屬氧化物膜以移除該等經照射區域或該等未經照射區域中之一者,來形成圖案化含金屬氧化物硬質光罩,其中該等經照射區域具有第一蝕刻速率,且該等未經照射區域具有不同於該第一蝕刻速率的第二蝕刻速率,及其中該沉積UV輻射反應性含金屬氧化物膜進一步包含使該基板與一或多種不同於該第一氣相反應物的摻雜劑前驅物接觸,以使該UV輻射反應性含金屬氧化物膜的UV反應性增加至少50%。
- 如請求項1之方法,其中該第一蝕刻速率與該第二蝕刻速率之間的蝕刻選擇性係大於2:1。
- 如請求項1之方法,其中該第一蝕刻速率與該第二蝕刻速率之間的蝕刻選擇性係大於10:1。
- 如請求項1之方法,其中該選擇性地UV照射該UV輻射反應性含金屬氧化物膜包含利用波長為13.5奈米之UV輻射進行照射。
- 如請求項1之方法,其中該第一氣相反應物包含金屬有機前驅物, 該金屬有機前驅物係選自包含下列之群:三甲基鋁(TMA)、三乙基鋁(TEA)、及二乙基鋅。
- 如請求項1之方法,其中該UV輻射反應性含金屬氧化物膜具有大於10原子%之碳濃度。
- 如請求項1之方法,其中該UV輻射反應性含金屬氧化物膜具有大於20原子%之氫濃度。
- 如請求項1之方法,其中該UV輻射反應性含金屬氧化物膜包含非晶形膜。
- 如請求項1之方法,其中該一或多種摻雜劑前驅物包含額外的金屬氧化物摻雜劑、額外的金屬摻雜劑、或烷基矽化合物摻雜劑中之至少一者。
- 如請求項9之方法,其中該額外的金屬摻雜劑係選自包含下列之群:鋁(Al)、鋅(Zn)、銦(In)、銻(Sb)、或鉍(Bi)。
- 如請求項9之方法,其中該額外的金屬摻雜劑包含錫(Sn)。
- 如請求項9之方法,其中該烷基矽化合物摻雜劑包含Si(CH3)xCl4-x或(CH3)3SiNHSi(CH3)3(HMDS)中之至少一者。
- 如請求項2之方法,其中該選擇性地UV照射該UV輻射反應性含金屬氧化物膜包含使該經UV照射區域至少部分結晶。
- 如請求項1之方法,其中該圖案化含金屬氧化物硬質光罩包含至少部分結晶膜。
- 如請求項1之方法,其中該UV輻射反應性含金屬氧化物膜包含氧化鋁、氧化鋅、氧化銦、氧化鉍、或氧化銻中之至少一者。
- 如請求項1之方法,其中該第一蝕刻速率低於該第二蝕刻速率。
- 如請求項1之方法,其中該第二蝕刻速率低於該第一蝕刻速率。
- 如請求項1之方法,其中使該基板與該第一氣相反應物接觸及使 該基板與該第二氣相反應物接觸係藉由循環沉積製程依序地進行。
- 如請求項1之方法,其中使該基板與該第一氣相反應物接觸及使該基板與該第二氣相反應物接觸係藉由化學氣相沉積製程同時進行。
- 如請求項1之方法,其中該UV輻射反應性含金屬氧化物膜實質上不含錫(Sn)。
- 如請求項1之方法,其中該沉積UV輻射反應性含金屬氧化物膜係於第一反應腔室中進行,及該選擇性地UV照射該UV輻射反應性含金屬氧化物膜係於UV圖案化工具中進行,其中該第一反應腔室及該UV圖案化工具係組構於集束型半導體製程設備上,使得於該第一反應腔室與該UV圖案化工具之間進行該基板之輸送係未使該基板暴露至外部環境條件。
- 一種半導體結構,其包含藉由請求項1形成之圖案化含金屬氧化物硬質光罩膜。
- 一種用來形成紫外(UV)輻射反應性含金屬氧化物膜之方法,該方法包含:沉積UV輻射反應性含金屬氧化物膜於基板上方,該UV輻射反應性含金屬氧化物膜具有實質上均勻的蝕刻速率,其中沉積包含:將該基板加熱至低於400℃之沉積溫度;使該基板與包含金屬組分、氫組分、及碳組分之第一氣相反應物接觸;及使該基板與包含含氧前驅物之第二氣相反應物接觸;及使用UV圖案化工具選擇性地UV照射該UV輻射反應性含金屬氧化物膜以提供經照射區域及未經照射區域,其中該等經照射區域具有第一蝕刻速率,且該等未經照射區域具有不同於該第一蝕刻速率的第二蝕刻速率, 其中該第一氣相反應物包含金屬有機前驅物,該金屬有機前驅物係包含三乙基鋁(TEA)或二乙基鋅,及其中該沉積UV輻射反應性含金屬氧化物膜進一步包含使該基板與一或多種不同於該第一氣相反應物的摻雜劑前驅物接觸,以使該UV輻射反應性含金屬氧化物膜的UV反應性增加至少50%。
- 如請求項23之方法,其中該一或多種摻雜劑前驅物包含額外的金屬氧化物摻雜劑、額外的金屬摻雜劑、或烷基矽化合物摻雜劑中之至少一者。
- 如請求項24之方法,其中該額外的金屬摻雜劑係選自包含下列之群:鋁(Al)、鋅(Zn)、銦(In)、銻(Sb)、或鉍(Bi)。
- 如請求項24之方法,其中該烷基矽化合物摻雜劑包含Si(CH3)xCl4-x或(CH3)3SiNHSi(CH3)3(HMDS)中之至少一者。
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US20220102140A1 (en) | 2022-03-31 |
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KR20200066556A (ko) | 2020-06-10 |
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