TWI769291B - 使用鹵素去活化之選擇性膜沉積 - Google Patents
使用鹵素去活化之選擇性膜沉積 Download PDFInfo
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- TWI769291B TWI769291B TW107127962A TW107127962A TWI769291B TW I769291 B TWI769291 B TW I769291B TW 107127962 A TW107127962 A TW 107127962A TW 107127962 A TW107127962 A TW 107127962A TW I769291 B TWI769291 B TW I769291B
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- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 34
- 150000002367 halogens Chemical class 0.000 title claims abstract description 34
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- 230000008021 deposition Effects 0.000 title abstract description 5
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- 239000002243 precursor Substances 0.000 claims abstract description 108
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- 238000003672 processing method Methods 0.000 claims abstract 23
- 239000007789 gas Substances 0.000 claims description 91
- 238000000034 method Methods 0.000 claims description 38
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
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- 239000001301 oxygen Substances 0.000 claims description 17
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 16
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- 239000002184 metal Substances 0.000 claims description 14
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 238000007254 oxidation reaction Methods 0.000 claims description 7
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- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UCRXQUVKDMVBBM-UHFFFAOYSA-N benzyl 2-amino-3-(4-phenylmethoxyphenyl)propanoate Chemical compound C=1C=CC=CC=1COC(=O)C(N)CC(C=C1)=CC=C1OCC1=CC=CC=C1 UCRXQUVKDMVBBM-UHFFFAOYSA-N 0.000 claims description 2
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 claims description 2
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
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- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
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- 230000005284 excitation Effects 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 229910021480 group 4 element Inorganic materials 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 150000003235 pyrrolidines Chemical class 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
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- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical group CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
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- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
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- SYCZCVFOEPCWBF-UHFFFAOYSA-N n,n'-di(propan-2-yl)ethanimidamide Chemical compound CC(C)NC(C)=NC(C)C SYCZCVFOEPCWBF-UHFFFAOYSA-N 0.000 description 1
- ZUHLLHJBEFJMKQ-UHFFFAOYSA-N n,n'-ditert-butylethanimidamide Chemical compound CC(C)(C)NC(C)=NC(C)(C)C ZUHLLHJBEFJMKQ-UHFFFAOYSA-N 0.000 description 1
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- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
- H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
-
- 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
- H01L21/02123—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 silicon
- H01L21/02126—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/02131—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being halogen doped silicon oxides, e.g. FSG
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
本發明的實施例提供使用鹵素去活化在基板的凹入特徵部中選擇性膜沉積。基板處理方法包含:a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;b)將基板曝露於第一前驅物氣體,以在基板上形成第一前驅物層;c)將基板曝露於經電漿激發的含鹵素氣體,以去活化或至少部分地移除基板之場區及凹入特徵部之底部上的第一前驅物層;及d)將基板曝露於第二前驅物氣體,該第二前驅物氣體與第一前驅物層反應以在凹入特徵部的側壁上、但不在已被經電漿激發的含鹵素氣體去活化之場區及凹入特徵部的底部上形成材料層。
Description
本發明關於半導體製造及半導體元件的領域,且更特別地,關於使用鹵素去活化之選擇性膜沉積。 [相關申請案]
本申請案關於且主張於2017年8月11日申請之美國臨時專利申請案第62/544,460號的優先權,其全部內容於此藉由參照納入本案揭示內容。
當製造更小的電晶體時,圖案化之特徵部的臨界尺寸(CD)或解析度對於製造變得更具挑戰性。自對準圖案化需取代覆蓋驅動(overlay-driven)圖案化,使得具有成本效益的縮放即使在極紫外線(EUV)微影引入之後仍可繼續。需要實現降低的變異性、擴展的縮放及加強的CD及製程控制的圖案化選項。薄膜的選擇性形成在高度縮放之技術節點中的圖案化中係關鍵的步驟。
本發明的實施例提供使用鹵素去活化在基板的凹入特徵部中選擇性膜沉積。根據一實施例,提供一基板處理方法,該方法包含:a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;b)將基板曝露於第一前驅物氣體,以在基板上形成第一前驅物層;c)將基板曝露於經電漿激發的含鹵素氣體,以去活化或至少部分地移除基板之場區及凹入特徵部之底部上的第一前驅物層;及d)將基板曝露於第二前驅物氣體,該第二前驅物氣體與第一前驅物層反應以在凹入特徵部的側壁上、但不在已被經電漿激發的含鹵素氣體去活化之場區及凹入特徵部的底部上形成材料層。步驟b)-d)可重複至少一次,以在凹入特徵部中的側壁上沉積額外量的材料層。
根據另一實施例,提供一基板處理方法,該方法包含:a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;b)將基板曝露於第一前驅物氣體,以在基板上形成第一前驅物層;c)在不存在電漿的情況下將基板曝露於含鹵素氣體,以使基板之場區上的第一前驅物層去活化;及d)將基板曝露於第二前驅物氣體,該第二前驅物氣體與第一前驅物層反應以在側壁及凹入特徵部的底部上、但不在已被含鹵素氣體去活化的場區上形成材料層。可重複步驟b)-d)至少一次,以在凹入特徵部中的側壁及底部上沉積額外量的材料層。在一示例中,材料層可實質上填充凹入特徵部。
圖1係根據本發明的實施例之用於處理基板的製程流程圖,而圖2A-2F透過橫剖面圖示意性地顯示根據本發明實施例之處理基板的方法。
製程流程1包含:在步驟100中,提供包含第一膜202及第二膜200的基板2。此係在圖2A中示意性地顯示。第一膜202具有圍繞凹入特徵部204的場區201,其中凹入特徵部204具有側壁208及底部206。凹入特徵部204可例如具有小於200 nm、小於100 nm、小於50 nm、小於25 nm、小於20 nm、或小於10 nm的寬度207。在其他示例中,凹入特徵部204的寬度207可在5 nm與10 nm之間、在10 nm與20 nm之間、在20 nm與50 nm之間、在50 nm與100 nm之間、在100 nm與200 nm之間、在10 nm與50 nm之間、或在10 nm與100 nm之間。寬度207亦可稱為臨界尺寸(CD)。凹入特徵部204可例如具有25 nm、50 nm、100 nm、200 nm、或更大的深度。
在一些示例中,第一膜202及第二膜200可包含相同材料或由相同材料所組成。在一示例中,第一膜202及第二膜200可包含Si或由Si所組成。在一些示例中,第一膜202可包含介電材料,例如:SiO2
、SiON、SiN、高k材料、低k材料、或超低k材料。凹入特徵部204可使用眾所周知的微影術及蝕刻製程形成。儘管圖案化的遮罩層未在圖2A中顯示,但圖案化的遮罩層可存在於場區201上且定義凹入特徵部204的開口。
製程流程1更包含:在步驟102中,將基板2曝露於第一前驅物氣體,以在基板2上(包含在場區201、側壁208、及底部206上)形成第一前驅物層210。此係在圖2B中示意性地顯示。曝露可為飽和曝露,其在基板2上形成第一前驅物層210的飽和覆蓋。在一示例中,第一前驅物氣體可包括含金屬的前驅物,且第一前驅物層210可形成該含金屬前驅物的吸附保形層,其係約一原子層厚。含金屬的前驅物可例如包含鹼土元素、鈦、鉿、鋯、鋁、稀土元素、或其二或更多者的組合。
本發明的實施例可利用各式各樣的鉿及鋯前驅物。舉例而言,具代表性的示例包含:Hf(Ot
Bu)4
(叔丁醇鉿,HTB)、Hf(NEt2
)4
(四(二乙胺基)鉿,TDEAH)、Hf(NEtMe)4
(四(乙基甲基胺基)鉿,TEMAH)、Hf(NMe2
)4
(四(二甲胺基)鉿,TDMAH)、Zr(Ot
Bu)4
(叔丁醇鋯,ZTB)、Zr(NEt2
)4
(四(二乙胺基)鋯,TDEAZ)、Zr(NMeEt)4
(四(乙基甲基胺基)鋯,TEMAZ)、Zr(NMe2
)4
(四(二甲胺基)鋯,TDMAZ)、Hf(mmp)4
、Zr(mmp)4
、HfCl4
、ZrCl4
、ZrCp2
Me2
、Zr(tBuCp)2
Me2
、及Zr(NiPr2
)4
。在一示例中,鉿及鋯前驅物可具有相同的配位基(例如HTB及ZTB),藉此防止前驅物間之任何可能有害的配位基交換。
本發明的實施例可利用各式各樣的不同鋁前驅物。舉例而言,許多鋁前驅物具有下列化學式: AlL1
L2
L3
Dx
其中L1
、L2
、L3
係個別的陰離子配位基,而D係中性予體配位基,其中x可為0、1、或2。每個L1
、L2
、L3
配位基可分別選自烷氧化物、鹵化物、芳氧化物(aryloxide)、醯胺、環戊二烯基、烷基、矽基、脒鹽(amidinate)、β-二酮酸鹽、酮亞胺鹽(ketoiminate)、矽烷醇酸鹽(silanoate)、及羧酸鹽的群組。D配位基可選自醚、呋喃、吡啶、吡咯、吡咯烷、胺、冠醚、二甲氧乙烷、及腈的群組。
鋁前驅物的其他示例包含:Al2
Me6
、Al2
Et6
、[Al(OsBu)3
]4
、Al(CH3
COCHCOCH3
)3
、AlBr3
、AlI3
、Al(OiPr)3
、[Al(NMe2
)3
]2
、Al(iBu)2
Cl、Al(iBu)3
、Al(iBu)2
H、AlEt2
Cl、Et3
Al2
(OsBu)3
、Al(THD)3
。
本發明的實施例可利用各式各樣的不同稀土前驅物。舉例而言,許多稀土前驅物具有下列化學式: ML1
L2
L3
Dx
其中M係選自釔(Y)、鎦(Lu)、鑭(La)、鈰(Ce)、鐠(Pr)、釹(Nd)、釤(Sm)、銪(Eu)、釓(Gd)、鋱(Tb)、鏑(Dy)、鈥(Ho)、鉺(Er)、銩(Tm)、及鐿(Yb)之群組的稀土金屬元素。L1
、L2
、L3
係個別的陰離子配位基,而D係中性予體配位基,其中x可為0、1、2、或3。每個L1
、L2
、L3
配位基可分別選自烷氧化物、鹵化物、芳氧化物、醯胺、環戊二烯基、烷基、矽基、脒鹽、β-二酮酸鹽、酮亞胺鹽、矽烷醇酸鹽、及羧酸鹽的群組。D配位基可選自醚、呋喃、吡啶、吡咯、吡咯烷、胺、冠醚、二甲氧乙烷、及腈的群組。
L基團之烷氧化物的示例包含叔丁醇鹽、異丙醇鹽、乙醇鹽、1-甲氧基-2,2-二甲基-2-丙酸鹽(mmp)、1-二甲胺基-2,2’-二甲基丙酸鹽、戊醇鹽、及新戊醇鹽。鹵化物的示例包含氟化物、氯化物、碘化物、及溴化物。芳氧化物的示例包含酚鹽、及2,4,6-三甲基酚鹽。醯胺的示例包含雙(三甲基矽基)醯胺、二叔丁基醯胺、及2,2,6,6-四甲基哌啶(TMPD)。環戊二烯基的示例包含環戊二烯基、1-甲基環戊二烯基、1,2,3,4-四甲基環戊二烯基、1-乙基環戊二烯基、五甲基環戊二烯基、1-異丙基環戊二烯基、1-正丙基環戊二烯基、及1-正丁基環戊二烯基。烷基的示例包含雙(三甲基矽基)甲基、三(三甲基矽基)甲基、及三甲基矽基甲基。矽基的示例為三甲基矽基。脒鹽的示例包含N,N’-二叔丁基乙脒鹽、N,N’-二異丙基乙脒鹽、N,N’-二異丙基-2-叔丁基脒、及N,N’-二叔丁基-2-叔丁基脒。β-二酮酸鹽的示例包含2,2,6,6-四甲基-3,5-庚二酮酸鹽(THD)、六氟-2,4-戊二酮酸鹽、及6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛二酮酸鹽(FOD)。酮亞胺鹽的示例為2-異丙基亞胺基-4-戊酸鹽。矽烷醇酸鹽的示例包含三叔丁基矽醇鹽(tri-tert-butylsiloxide)、及三乙基矽醇鹽(triethylsiloxide)。羧酸鹽的示例為2-乙基己酸鹽。
D配位基的示例包含四氫呋喃、二乙醚、1,2-二甲氧基乙烷、二乙二醇二甲醚、三甘醇二甲醚、四乙二醇二甲醚、12-冠醚-6、10-冠醚-4、吡啶、N-甲基吡咯烷、三乙胺、三甲胺、乙腈、及2,2-二甲基丙腈。
稀土前驅物之代表性示例包含:
Y前驅物:Y(N(SiMe3
)2
)3
、Y(N(i
Pr)2
)3
、Y(N(t
Bu)SiMe3
)3
、Y(TMPD)3
、Cp3
Y、(MeCp)3
Y、((nPr)Cp)3
Y、((nBu)Cp)3
Y、Y(OCMe2
CH2
NMe2
)3
、Y(THD)3
、Y[OOCCH(C2
H5
)C4
H9
]3
、Y(C11
H19
O2
)3
CH3
(OCH2
CH2
)3
OCH3
、Y(CF3
COCHCOCF3
)3
、Y(OOCC10
H7
)3
、Y(OOC10
H19
)3
、及Y(O(i
Pr))3
。
La前驅物:La(N(SiMe3
)2
)3
、La(N(i
Pr)2
)3
、La(N(t
Bu)SiMe3
)3
、La(TMPD)3
、((i
Pr)Cp)3
La、Cp3
La、Cp3
La(NCCH3
)2
、La(Me2
NC2
H4
Cp)3
、La(THD)3
、La[OOCCH(C2
H5
)C4
H9
]3
、La(C11
H19
O2
)3
·CH3
(OCH2
CH2
)3
OCH3
、La(C11
H19
O2
)3
·CH3
(OCH2
CH2
)4
OCH3
、La(O(i
Pr))3
、La(OEt)3
、La(acac)3
、La(((t
Bu)2
N)2
CMe)3
、La(((i
Pr)2
N)2
CMe)3
、La(((iPr)2
N)2
CH)3
、La(((t
Bu)2
N)2
C(t
Bu))3
、La(((i
Pr)2
N)2
C(t
Bu))3
、及La(FOD)3
。
Ce前驅物:Ce(N(SiMe3
)2
)3
、Ce(N(i
Pr)2
)3
、Ce(N(t
Bu)SiMe3
)3
、Ce(TMPD)3
、Ce(FOD)3
、((i
Pr)Cp)3
Ce、Cp3
Ce、Ce(Me4
Cp)3
、Ce(OCMe2
CH2
NMe2
)3
、Ce(THD)3
、Ce[OOCCH(C2
H5
)C4
H9
]3
、Ce(C11
H19
O2
)3
·CH3
(OCH2
CH2
)3
OCH3
、Ce(C11
H19
O2
)3
·CH3
(OCH2
CH2
)4
OCH3
、Ce(O(i
Pr))3
、及Ce(acac)3
。
Pr前驅物:Pr(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Pr、Cp3
Pr、Pr(THD)3
、Pr(FOD)3
、(C5
Me4
H)3
Pr、Pr[OOCCH(C2
H5
)C4
H9
]3
、Pr(C11
H19
O2
)3
·CH3
(OCH2
CH2
)3
OCH3
、Pr(O(i
Pr))3
、Pr(acac)3
、Pr(hfac)3
、Pr(((t
Bu)2
N)2
CMe)3
、Pr(((i
Pr)2
N)2
CMe)3
、Pr(((t
Bu)2
N)2
C(t
Bu))3
、及Pr(((i
Pr)2
N)2
C(t
Bu))3
。
Nd前驅物:Nd(N(SiMe3
)2
)3
、Nd(N(i
Pr)2
)3
、((i
Pr)Cp)3
Nd、Cp3
Nd、(C5
Me4
H)3
Nd、Nd(THD)3
、Nd[OOCCH(C2
H5
)C4
H9
]3
、Nd(O(i
Pr))3
、Nd(acac)3
、Nd(hfac)3
、Nd(F3
CC(O)CHC(O)CH3
)3
、及Nd(FOD)3
。
Sm前驅物:Sm(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Sm、Cp3
Sm、Sm(THD)3
、Sm[OOCCH(C2
H5
)C4
H9
]3
、Sm(O(i
Pr))3
、Sm(acac)3
、及(C5
Me5
)2
Sm。
Eu前驅物:Eu(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Eu、Cp3
Eu、(Me4
Cp)3
Eu、Eu(THD)3
、Eu[OOCCH(C2
H5
)C4
H9
]3
、Eu(O(i
Pr))3
、Eu(acac)3
、及(C5
Me5
)2
Eu。
Gd前驅物:Gd(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Gd、Cp3
Gd、Gd(THD)3
、Gd[OOCCH(C2
H5
)C4
H9
]3
、Gd(O(i
Pr))3
、及Gd(acac)3
。
Tb前驅物:Tb(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Tb、Cp3
Tb、Tb(THD)3
、Tb[OOCCH(C2
H5
)C4
H9
]3
、Tb(O(i
Pr))3
、及Tb(acac)3
。
Dy前驅物:Dy(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Dy、Cp3
Dy、Dy(THD)3
、Dy[OOCCH(C2
H5
)C4
H9
]3
、Dy(O(i
Pr))3
、Dy(O2
C(CH2
)6
CH3
)3
、及Dy(acac)3
。
Ho前驅物:Ho(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Ho、Cp3
Ho、Ho(THD)3
、Ho[OOCCH(C2
H5
)C4
H9
]3
、Ho(O(i
Pr))3
、及Ho(acac)3
。
Er前驅物:Er(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Er、((nBu)Cp)3
Er、Cp3
Er、Er(THD)3
、Er[OOCCH(C2
H5
)C4
H9
]3
、Er(O(i
Pr))3
、及Er(acac)3
。
Tm前驅物:Tm(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Tm、Cp3
Tm、Tm(THD)3
、Tm[OOCCH(C2
H5
)C4
H9
]3
、Tm(O(i
Pr))3
、及Tm(acac)3
。
Yb前驅物:Yb(N(SiMe3
)2
)3
、Yb(N(i
Pr)2
)3
、((i
Pr)Cp)3
Yb、Cp3
Yb、Yb(THD)3
、Yb[OOCCH(C2
H5
)C4
H9
]3
、Yb(O(i
Pr))3
、Yb(acac)3
、(C5
Me5
)2
Yb、Yb(hfac)3
、及Yb(FOD)3
。
Lu前驅物:Lu(N(SiMe3
)2
)3
、((i
Pr)Cp)3
Lu、Cp3
Lu、Lu(THD)3
、Lu[OOCCH(C2
H5
)C4
H9
]3
、Lu(O(i
Pr))3
、及Lu(acac)3
。
仍參照圖1,製程流程1更包含:在步驟104中,將基板2曝露於經電漿激發的含鹵素氣體203,以使基板2之場區201上及凹入特徵部204之底部206上的第一前驅物層210去活化。去活化可在基板2的場區201及凹入特徵部204的底部206上形成鹵化的第一前驅物層205。此係在圖2C及2D中示意性地顯示。根據另一實施例,曝露於經電漿激發的含鹵素氣體203可移除基板2的場區201上及凹入特徵部204的底部206上之第一前驅物層210的至少一部分。含鹵素氣體的非限制性示例包含Cl2
、BCl3
、CCl4
、HCl、HBr、TiCl4
、及其組合。含鹵素氣體可更包含諸如氬(Ar)的惰性氣體。在一些示例中,電漿激發可利用例如感應式耦合電漿(ICP)源或微波電漿源的高密度電漿源執行。基板可經由基板支架被施加偏壓,以進一步增強電漿曝露的非等向性特徵。此外,可選擇諸如基板溫度、氣體壓力、及電漿功率的製程條件以控制第一前驅物層210的去活化且使對於基板的損壞最小化。
製程流程1更包含:在步驟106中,將基板2曝露於第二前驅物氣體,該第二前驅物氣體與第一前驅物層210反應以在凹入特徵部204的側壁208上、但不在已被經電漿激發的含鹵素氣體去活化之場區201及凹入特徵部204的底部206上形成材料層212。在一示例中,第二前驅物氣體可包括含氧氣體、含氮氣體、含氧和氮的氣體、或其組合。含氧氣體可選自由H2
O、O2
、O3
、H2
O2
、及其組合所組成之群組。含氧氣體可包含但不限於O2
、H2
O、H2
O2
、或其組合、及選用性之諸如Ar的惰性氣體。類似地,含氮氣體可包含但不限於NH3
或聯胺(N2
H4
)、及選用性之諸如Ar的惰性氣體。含氧和氮的氣體可包含但不限於NO、NO2
、或N2
O、或其組合、及選用性之諸如Ar的惰性氣體。所得的基板2示意性地顯示於圖2E中。
之後,可使用熱處理步驟、氧化步驟、或其組合自基板2移除場區201上及底部206上之鹵化的第一前驅物層205。所得的基板2示意性地顯示於圖2F中。熱處理步驟及/或氧化步驟可在比曝露步驟102-106高的基板溫度下執行。此外,氧化步驟可使用比步驟106中使用之氧化條件強的氧化條件執行。
在一示例中,凹入特徵部204之側壁208上的材料層212可用於側壁保護,以防止清潔製程或蝕刻製程期間之凹入特徵部的臨界尺寸之損失。
曝露步驟102-106可如製程箭頭108所示重複至少一次,以在凹入特徵部204中的側壁208上沉積額外量的材料層212。可將曝露步驟102及106描述為原子層沉積(ALD)製程。ALD可沉積具有原子等級厚度控制及先進凸起和凹入特徵部上之極佳保形性的極薄膜。
材料層212可例如包含鹼土元素、鈦、鉿、鋯、鋁、稀土元素、或其任何二或更多者的組合。
根據一實施例,材料層212可包含金屬氧化物膜。金屬氧化物膜可為高k膜。在一示例中,金屬氧化物膜可選自由HfO2
、ZrO2
、TiO2
、Al2
O3
、及其組合所組成之群組。然而,可使用其他金屬氧化物膜。根據另一實施例,材料層212可選自由金屬氧化物膜、金屬氮化物膜、金屬氮氧化物膜、金屬矽酸鹽膜、及其組合所組成之群組。根據又另一實施例,材料層212可包含元素週期表的IV族元素(Ti、Hf、或Zr)及非IV族元素。
在一示例中,圖1中的製程流程可更包含在曝露步驟102與104之間、在曝露步驟104與106之間、及在曝露步驟106與102之間的氣體沖洗步驟。氣體沖洗步驟藉由使惰性氣體流經處理腔室而幫助自處理腔室移除不需要的氣體。
在一些示例中,材料層212的厚度可為10 nm或更少、5 nm或更少、4 nm或更少、在1 nm與2 nm之間、在2 nm與4 nm之間、在4 nm與6 nm之間、在6 nm與8 nm之間、或在2 nm與6 nm之間。側壁208上之材料層212的存在減少凹入特徵部204的寬度207。然而,此寬度中的變化可為相對小,因為材料層212可僅為幾nm厚。
根據一實施例,製程流程1包含:a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;b)將基板曝露於鉿前驅物氣體以在基板上形成鉿前驅物層;c)將基板曝露於經電漿激發的Cl2
氣體,以去活化或至少部分地移除基板之場區及凹入特徵部之底部上的鉿前驅物層;d)將基板曝露於含氧氣體,該含氧氣體與鉿前驅物層反應以在凹入特徵部的側壁上、但不在已被經電漿激發的Cl2
氣體去活化之場區及凹入特徵部的底部上形成鉿氧化物層;及e)重複步驟b)-d)至少一次以在凹入特徵部中的側壁上沉積額外量的鉿氧化物層。
圖3係根據本發明的實施例之用於處理基板的製程流程圖,而圖4A-4F透過橫剖面圖示意性地顯示根據本發明實施例之處理基板的方法。
製程流程3包含:在步驟300中,提供包含第一膜402及第二膜400的基板4。第一膜402具有場區401及凹入特徵部404,凹入特徵部404具有側壁408及底部406。凹入特徵部404可例如具有小於200 nm、小於100 nm、小於50 nm、小於25 nm、小於20 nm、或小於10 nm的寬度407。在其他示例中,凹入特徵部404的寬度407可在5 nm與10 nm之間、在10 nm與20 nm之間、在20 nm與50 nm之間、在50 nm與100 nm之間、在100 nm與200 nm之間、在10 nm與50 nm之間、或在10 nm與100 nm之間。凹入特徵部404可例如具有25 nm、50 nm、100 nm、200 nm、或更大的深度。
在一些示例中,第一膜402及第二膜400可包含相同材料或由相同材料所組成。在一示例中,第一膜402及第二膜400可包含Si或由Si所組成。在一些示例中,第一膜402可包含介電材料,例如:SiO2
、SiON、SiN、高k材料、低k材料、或超低k材料。凹入特徵部404可使用眾所周知的微影術及蝕刻製程形成。儘管圖案化的遮罩層未在圖4A中顯示,但圖案化的遮罩層可存在於場區401上且定義凹入特徵部404的開口。
製程流程3更包含:在步驟302中,將基板4曝露於第一前驅物氣體,以在基板4上(包含在場區401、側壁408、及底部406上)形成第一前驅物層410。此係在圖4B中示意性地顯示。曝露可為飽和曝露,其在基板4上形成第一前驅物層410的飽和覆蓋。在一示例中,第一前驅物氣體可包括含金屬的前驅物,且第一前驅物層410可形成吸附之含金屬前驅物的保形層,其係約一原子層厚。含金屬的前驅物可例如包含鹼土元素、鈦、鉿、鋯、鋁、稀土元素、或其任何二或更多者的組合。
製程流程3更包含:在步驟304中,在不存在電漿的情況下將基板4曝露於含鹵素氣體403,以使基板4之場區401上的第一前驅物層410去活化。含鹵素氣體403在曝露於基板之前不受電漿激發。去活化可在基板4的場區401上形成鹵化的第一前驅物層405。此係在圖4C及4D中示意性地顯示。
根據另一實施例,於不存在電漿的情況下曝露於含鹵素氣體403可移除基板4的場區401上之鹵化的第一前驅物層405的至少一部分。含鹵素氣體的非限制性示例包含Cl2
、BCl3
、CCl4
、HCl、HBr、TiCl4
、及其組合。含鹵素氣體可更包含諸如氬(Ar)的惰性氣體。
含鹵素氣體的非限制性示例包含Cl2
、BCl3
、CCl4
、HCl、HBr、TiCl4
、或其組合。含鹵素氣體可更包含諸如氬(Ar)的惰性氣體。由於含鹵素氣體403進入凹入特徵部404中的有限穿透度,所以在缺乏電漿激發的情況下優先使基板4之場區401上的第一前驅物層410去活化。此外,可選擇氣體曝露期間的製程條件(諸如基板溫度、氣體壓力、氣體成分、及基板旋轉)以控制第一前驅物層410的去活化。在一些示例中,可使用高度稀釋的含鹵素氣體及高的總氣體壓力(例如大於約1托),以提供含鹵素氣體403的高等向性曝露。
製程流程3更包含:在步驟306中,將基板4曝露於第二前驅物氣體,該第二前驅物氣體與第一前驅物層410反應以在側壁408及凹入特徵部404的底部406上、但不在已被含鹵素氣體去活化的場區401上形成材料層412。在一示例中,第二前驅物氣體可包括含氧氣體、含氮氣體、含氧和氮的氣體、或其組合。含氧氣體可選自由H2
O、O2
、O3
、H2
O2
、及其組合所組成之群組。含氧氣體可包含但不限於O2
、H2
O、或H2
O2
、或其組合、及選用性之諸如Ar的惰性氣體。類似地,含氮氣體可包含但不限於NH3
或N2
H4
、及選用性之諸如Ar的惰性氣體。含氧和氮的氣體可包含但不限於NO、NO2
、或N2
O、或其組合、及選用性之諸如Ar的惰性氣體。所得的基板4示意性地顯示於圖2E中。
之後,可使用熱處理步驟、氧化步驟、或其組合自基板4移除鹵化的第一前驅物層405。所得的基板4示意性地顯示於圖4F中。熱處理步驟及/或氧化步驟可在比曝露步驟302-306高的基板溫度下執行。此外,氧化步驟可使用比步驟306中使用之氧化條件強的氧化條件執行。
曝露步驟302-306可如製程箭頭308所示重複至少一次,以在凹入特徵部404中的側壁408及底部406上沉積額外量的材料層412。可將曝露步驟302及306描述為ALD製程。ALD可沉積具有原子等級厚度控制及先進凸起和凹入特徵部上之極佳保形性的極薄膜。
根據一實施例,材料層412可包含金屬氧化物膜。金屬氧化物膜可為高k膜。在一示例中,金屬氧化物膜可選自由HfO2
、ZrO2
、TiO2
、Al2
O3
、及其組合所組成之群組。然而,可使用其他金屬氧化物膜。根據另一實施例,材料層412可選自由金屬氧化物膜、金屬氮化物膜、金屬氮氧化物膜、金屬矽酸鹽膜、及其組合所組成之群組。
在一示例中,圖3中的製程流程可更包含在曝露步驟302與304之間、在曝露步驟304與306之間、及在曝露步驟306與302之間的氣體沖洗步驟。氣體沖洗步驟藉由使惰性氣體流經處理腔室而幫助自處理腔室移除不需要的氣體。
在一些示例中,材料層412的厚度可為10 nm或更少、5 nm或更少、4 nm或更少、在1 nm與2 nm之間、在2 nm與4 nm之間、在4 nm與6 nm之間、在6 nm與8 nm之間、或在2 nm與6 nm之間。
已描述使用鹵素去活化之選擇性膜沉積的複數實施例。本發明實施例之以上描述已為了說明及描述的目的而呈現。其係非意欲為詳盡的或將本發明限制於所揭示的確切形式。此描述及以下申請專利範圍包含僅用於描述性目的而非被理解為限制性的術語。精於相關技術領域之人士可理解,根據上述教示,許多修改及變化是可能的。精於本技術領域之人士將察知對於顯示於圖中之諸多元件的諸多等效組合及替換。因此,意圖使本發明的範圍不由此詳細說明而由此處隨附的申請專利範圍所限定。
1‧‧‧製程流程2‧‧‧基板3‧‧‧製程流程4‧‧‧基板100‧‧‧步驟102‧‧‧步驟104‧‧‧步驟106‧‧‧步驟108‧‧‧製程箭頭200‧‧‧第二膜201‧‧‧場區202‧‧‧第一膜203‧‧‧含鹵素氣體204‧‧‧凹入特徵部205‧‧‧鹵化的第一前驅物層206‧‧‧底部207‧‧‧寬度208‧‧‧側壁210‧‧‧第一前驅物層212‧‧‧材料層300‧‧‧步驟302‧‧‧步驟304‧‧‧步驟306‧‧‧步驟308‧‧‧製程箭頭400‧‧‧第二膜401‧‧‧場區402‧‧‧第一膜403‧‧‧含鹵素氣體404‧‧‧凹入特徵部405‧‧‧鹵化的第一前驅物層406‧‧‧底部407‧‧‧寬度408‧‧‧側壁410‧‧‧第一前驅物層412‧‧‧材料層
由於本發明在關聯於隨附圖式而考量時藉由參照下列詳細的描述而受到更佳理解,因此將輕易獲得本發明之更完整理解及其許多伴隨的優點,其中:
圖1係根據本發明的實施例之用於處理基板的製程流程圖;
圖2A-2F透過橫剖面圖示意性地顯示根據本發明實施例之處理基板的方法;
圖3係根據本發明的實施例之用於處理基板的製程流程圖;及
圖4A-4F透過橫剖面圖示意性地顯示根據本發明實施例之處理基板的方法。
2‧‧‧基板
200‧‧‧第二膜
201‧‧‧場區
202‧‧‧第一膜
204‧‧‧凹入特徵部
205‧‧‧鹵化的第一前驅物層
206‧‧‧底部
208‧‧‧側壁
212‧‧‧材料層
Claims (22)
- 一種基板處理方法,包含:(a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;(b)將該基板曝露於第一前驅物氣體,以在該基板上形成第一前驅物層;(c)將該基板曝露於經電漿激發的含鹵素氣體,以去活化或至少部分地移除該基板之該場區及該凹入特徵部之該底部上的該第一前驅物層;及(d)將該基板曝露於第二前驅物氣體,該第二前驅物氣體與該第一前驅物層反應以在該凹入特徵部的該側壁上、但不在已被經電漿激發的該含鹵素氣體去活化之該場區及該凹入特徵部的該底部上形成材料層。
- 如申請專利範圍第1項之基板處理方法,更包含:(e)重複步驟b)-d)至少一次,以在該凹入特徵部中的該側壁上沉積額外量的材料層。
- 如申請專利範圍第1項之基板處理方法,其中,步驟c)在該基板的該場區及該凹入特徵部的該底部上形成鹵化第一前驅物層,該方法更包含:在步驟d)之後,藉由熱處理、執行氧化步驟、或其組合自該基板移除該鹵化第一前驅物層。
- 如申請專利範圍第1項之基板處理方法,其中,該第一前驅物氣體包括含金屬前驅物。
- 如申請專利範圍第4項之基板處理方法,其中,該含金屬前驅物包含鹼土元素、鈦、鉿、鋯、鋁、稀土元素、或其二或更多者的組合。
- 如申請專利範圍第1項之基板處理方法,其中,該含鹵素氣體包含Cl2、BCl3、CCl4、HCl、HBr、TiCl4、及其組合。
- 如申請專利範圍第1項之基板處理方法,其中,該第二前驅物氣體包括含氧氣體、含氮氣體、或其組合。
- 如申請專利範圍第1項之基板處理方法,其中,該第二前驅物氣體包括含氧和氮的氣體。
- 如申請專利範圍第1項之基板處理方法,其中,將該基板曝露於經電漿激發的含鹵素氣體之步驟更包含對支撐該基板的基板支架施加偏壓,以提供非等向性的電漿曝露。
- 一種基板處理方法,包含:(a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;(b)將該基板曝露於鉿前驅物氣體,以在該基板上形成鉿前驅物層;(c)將該基板曝露於經電漿激發的Cl2氣體,以去活化或至少部分地移除該基板之該場區及該凹入特徵部之該底部上的該鉿前驅物層;(d)將該基板曝露於含氧氣體,該含氧氣體與該鉿前驅物層反應以在該凹入特徵部的該側壁上、但不在已被經電漿激發的該Cl2氣體去活化之該場區及該凹入特徵部的該底部上形成鉿氧化物層;及 (e)重複步驟b)-d)至少一次,以在該凹入特徵部中的該側壁上沉積額外量的鉿氧化物層。
- 如申請專利範圍第10項之基板處理方法,其中,步驟c)在該基板的該場區及該凹入特徵部的該底部上形成氯化層,該方法更包含:在步驟d)之後,藉由熱處理、執行氧化步驟、或其組合自該基板移除該氯化層。
- 如申請專利範圍第10項之基板處理方法,其中,該鉿前驅物包含Hf(OtBu)4(叔丁醇鉿,HTB)、Hf(NEt2)4(四(二乙胺基)鉿,TDEAH)、Hf(NEtMe)4(四(乙基甲基胺基)鉿,TEMAH)、或Hf(NMe2)4(四(二甲胺基)鉿,TDMAH)。
- 如申請專利範圍第10項之基板處理方法,其中,該含氧氣體係選自由H2O、O2、O3、H2O2、及其組合所組成之群組。
- 如申請專利範圍第10項之基板處理方法,其中,將該基板曝露於經電漿激發的Cl2氣體之步驟更包含對支撐該基板的基板支架施加偏壓,以提供非等向性的電漿曝露。
- 一種基板處理方法,包含:(a)提供包含場區及凹入特徵部的基板,該凹入特徵部具有側壁及底部;(b)將該基板曝露於第一前驅物氣體,以在該基板上形成第一前驅物層; (c)在不存在電漿的情況下將該基板曝露於含鹵素氣體,以去活化或至少部分地移除該基板之該場區上的該第一前驅物層;及(d)將該基板曝露於第二前驅物氣體,該第二前驅物氣體與該第一前驅物層反應以在該側壁及該凹入特徵部的該底部上、但不在已被該含鹵素氣體去活化的該場區上形成材料層。
- 如申請專利範圍第15項之基板處理方法,更包含:(e)重複步驟b)-d)至少一次,以在該凹入特徵部中的該側壁及該底部上沉積額外量的材料層。
- 如申請專利範圍第15項之基板處理方法,其中,步驟c)在該基板的該場區上形成鹵化第一前驅物層,該方法更包含:在步驟d)之後,藉由熱處理、執行氧化步驟、或其組合自該基板移除該鹵化第一前驅物層。
- 如申請專利範圍第15項之基板處理方法,其中,該第一前驅物氣體包括含金屬前驅物。
- 如申請專利範圍第18項之基板處理方法,其中,該含金屬前驅物包含鹼土元素、鈦、鉿、鋯、鋁、稀土元素、或其組合。
- 如申請專利範圍第15項之基板處理方法,其中,該含鹵素氣體包含Cl2、BCl3、CCl4、HCl、HBr、TiCl4、及其組合。
- 如申請專利範圍第15項之基板處理方法,其中,該第二前驅物氣體包括含氧氣體、含氮氣體、或其組合。
- 如申請專利範圍第15項之基板處理方法,其中,該第二前驅物氣體包括含氧和氮的氣體。
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