TWI670393B - 減少在反應室釋氣之方法及系統 - Google Patents
減少在反應室釋氣之方法及系統 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 83
- 238000010943 off-gassing Methods 0.000 title abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 162
- 239000000463 material Substances 0.000 claims abstract description 65
- 238000010926 purge Methods 0.000 claims abstract description 29
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 27
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 23
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- 230000008569 process Effects 0.000 claims description 28
- 238000011010 flushing procedure Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 238000012806 monitoring device Methods 0.000 claims description 10
- -1 transition metal nitride Chemical class 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910001507 metal halide Inorganic materials 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
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- 229910052718 tin Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005530 etching 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
-
- 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
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
Abstract
本發明揭示減少反應器之反應室內物質之釋氣的系統及方法。例示性方法包括在該反應室內沈積障壁層及使用清除前驅體以與該反應室表面上之物質反應。例示性系統包括氣相沈積系統,諸如原子層沈積系統,其包括流體地聯接至該系統之反應室的障壁層源及/或清除前驅體源。
Description
本發明大體上係關於氣相反應方法及系統。更特定言之,本發明係關於減少氣相反應室中材料之釋氣的方法及系統。
電子裝置(諸如半導體裝置)及光子裝置(諸如發光及太陽能裝置)通常尤其藉由將薄膜材料沈積在基板上而形成。用於沈積膜之技術包括原子層沈積(atomic layer deposition;ALD)。ALD可為各種應用所需,因為ALD製程為自我限制性的,允許材料精確、保形地沈積在基板上。
原子層沈積典型地包括使用兩種或兩種以上前驅體使膜氣相沈積,其中可使用例如直接或遠程電漿來活化一或多種前驅體。典型ALD製程包括使用兩種前驅體沈積。在此情況下,順序通常包括使基板表面暴露於第一前驅體以與基板表面上之物質在反應室中反應,沖洗反應室以移除第一前驅體,使基板表面暴露於第二前驅體以與來自第一前驅體之物質在反應室中反應且自反應室移除第二前驅體。若各前驅體在另一前驅體引入反應室中之前未經充分沖洗,則可發生非所需氣相反應,該等反應轉而可造成非所需粒子形成或沈積膜之不均勻性。另外或可替代地,前驅體沖洗不足可導致隨後引入之前驅體損耗。
在ALD沈積製程期間,一或多種前驅體可吸附在反應室表
面上所形成之膜上或吸附至該膜中,且隨後在另一前驅體在其間引入反應室中之循環期間釋氣。在此情況下,當一種前驅體在另一前驅體流過反應室時釋氣時可發生非所需氣相反應。
舉例而言,當ALD用於在基板表面上形成金屬氧化物膜時,用於形成金屬氧化物膜之方法可包括使基板表面暴露於含有金屬之前驅體以與基板表面上之化學物質反應,沖洗反應室,使基板表面暴露於諸如氧氣、活性氧、臭氧、水或乙醇之氧化劑,且接著沖洗反應室。重複此等步驟直至在基板表面上形成所需量之金屬氧化物為止。在此等步驟期間,金屬氧化物膜材料除沈積在基板表面外亦沈積在反應室上之表面上。若氧化劑吸附至反應室表面上所沈積之材料中或吸附在該材料上,則在沖洗步驟期間可能無法自反應室完全清除氧化劑,且因此可在使基板表面暴露於含有金屬之前驅體之後續步驟期間釋氣。由於氧化劑釋氣,因此在使基板表面暴露於含有金屬之前驅體之步驟期間該氧化劑可與含有金屬之前驅體反應,從而導致基板表面上之膜之不合需要的不均勻性及/或反應室內之粒子形成。
為減緩前驅體釋氣,ALD製程可在相對低壓(例如低於0.01托)下運作以增強前驅體之沖洗。然而,將反應室之操作壓力降低至如此低壓通常會減少ALD製程之通量,且因此在此等壓力下操作之系統及方法不太適合於裝置之生產。因此,需要用於在氣相反應期間減緩自反應室釋氣之改良之方法及系統。
本發明之各種具體實例係關於用於減緩反應器之反應室內
物質之釋氣的方法及系統。當下文更詳細論述本發明之各種具體實例解決先前技術之方法及系統之缺點的方式時,一般而言,本發明提供用於以下之系統及方法:提供障壁層、使用清除劑以與一或多種否則會釋氣之物質反應或另外阻斷反應室內之物質從而減緩或防止物質在反應室內之後續處理期間釋氣。
根據本發明之各種具體實例,減少物質釋氣之方法包括以下步驟:提供具有反應室之氣相反應器,在反應室內之表面上形成障壁層,將材料沈積在反應室內之基板表面上及自反應室移除基板。障壁層可包括例如過渡金屬氧化物(例如TiO2、Ta2O5、HfO2或Al2O3或SiO2)、過渡金屬氮化物(例如TiN)、過渡金屬氮氧化物(例如TiON)及/或過渡金屬碳化物(例如TiC)。障壁層厚度可根據應用而變化,且可大於一個單層、大於兩個單層或介於約一個單層與約50Å之間、介於約5Å與約20Å之間或介於約10Å與約20Å之間。根據此等具體實例之各種態樣,提供氣相反應器之步驟包含提供原子層沈積(ALD)反應器。根據其他態樣,沈積步驟包括向反應室提供第一前驅體,該第一前驅體與基板表面反應以形成第一表面物質,自反應室沖洗第一前驅體(例如使用低壓及/或載氣),向反應室提供第二前驅體以與第一表面物質反應以形成第二表面物質及自反應室沖洗第二前驅體。當沈積在基板上(及在反應室內之表面上)之材料包括吸濕材料,諸如氧化鑭、氧化鎂、氧化鋇、氧化鍶或其他傾向於吸收或吸附一或多種前驅體之材料時,該等方法尤其可適用。例示性方法改良沈積在基板上之材料之厚度均勻性,增加清洗循環之間反應室內之運作次數且與未在反應室內形成障壁層之情況下產生之類似膜相比,產生較高品質之膜。
根據本發明之其他具體實例,用於將材料沈積在基板上及用於減緩反應室內之物質釋氣的系統包括反應器,諸如ALD反應器,其包括反應室、流體地聯接至反應室之第一前驅體源、流體地聯接至反應室之第二前驅體源、流體地聯接至反應室之沖洗氣體及流體地聯接至反應室之障壁層前驅體。根據此等具體實例之例示性態樣,系統經組態以在基板自反應室移除之後或在基板進入反應室之前在反應室內之表面上形成障壁層。根據其他態樣,障壁層前驅體可選自例如過渡金屬氧化物前驅體、過渡金屬氮化物前驅體、過渡金屬氮氧化物前驅體、過渡金屬碳化物前驅體、氧化矽前驅體及氧化鋁前驅體中之一或多者。
根據本發明之其他具體實例,減少反應室內之物質釋氣之方法包括以下步驟:提供具有反應室之氣相反應器,將材料沈積在反應室內之基板表面上(及在反應室內之表面上)及向反應室提供清除前驅體以與反應室表面上之材料反應。根據此等具體實例之各種態樣,清除氣在到達基板或基板固持器之前消耗或耗盡或實質上消耗或耗盡(例如使用給料控制)。清除前驅體可為例如金屬鹵化物或有機金屬化合物,諸如氯化鉿、氯化矽、氯化鋯或TMA。根據此等具體實例之例示性態樣,將材料沈積在表面上之步驟包括向反應室提供第一前驅體以與基板表面反應以形成第一表面物質,自反應室沖洗第一前驅體,向反應室提供第二前驅體以與第一表面物質反應以形成第二表面物質及沖洗第二前驅體。在此等情況下,提供清除前驅體之步驟可發生在提供第一前驅體之步驟之後及/或在沖洗第一前驅體之步驟之前。或者,提供清除前驅體之步驟可發生在沖洗第一前驅體之步驟之後。方法亦可包括沖洗清除前驅體之步驟,例如在提供第二前驅
體之步驟之前。根據此等具體實例之各種態樣,該等方法可包括給料前監測之步驟,其允許調整製程以減緩或防止清除前驅體與基板上之表面反應。換言之,可調整方法以消耗基板上游之全部或幾乎全部清除前驅體。
根據本發明之其他具體實例,用於將材料沈積在基板上及用於減緩反應室內之物質釋氣的系統包括反應器,諸如ALD反應器,其包括反應室、流體地聯接至反應室之第一前驅體源、流體地聯接至反應室之第二前驅體源、流體地聯接至反應室之沖洗氣體及流體地聯接至反應室之清除前驅體源。根據此等具體實例之例示性態樣,使反應室暴露於第一前驅體且在反應室暴露於第一前驅體之後使反應室暴露於清除前驅體,且在反應室暴露於清除前驅體之後使反應室暴露於第二前驅體。根據此等具體實例之系統可包括給料前監測裝置(諸如一或多個石英晶體微量天平)以調整系統,以使得全部或幾乎全部清除前驅體在基板上游消耗。
以上概述及以下實施方式均僅為例示性及解釋性,且不限制本發明或所主張之發明。
100‧‧‧系統
102‧‧‧反應器
104‧‧‧第一前驅體源
106‧‧‧第二前驅體源
108‧‧‧障壁層前驅體源
110‧‧‧沖洗氣體源
112‧‧‧視情況選用之混合物
114‧‧‧視情況選用之進氣增壓室
116‧‧‧真空源
118‧‧‧管線
120‧‧‧管線
122‧‧‧管線
124‧‧‧管線
126‧‧‧管線
128‧‧‧管線
130‧‧‧管線
132‧‧‧管線
134‧‧‧閥門
136‧‧‧閥門
138‧‧‧閥門
140‧‧‧閥門
142‧‧‧基板
144‧‧‧反應室
200‧‧‧方法
202‧‧‧步驟
204‧‧‧步驟
206‧‧‧步驟
208‧‧‧步驟
300‧‧‧系統
302‧‧‧清除前驅體源
304‧‧‧反應器之下部
400‧‧‧反應室內部之一部分
402‧‧‧第一給料前監測裝置
404‧‧‧第二給料前監測裝置
600‧‧‧方法
602‧‧‧步驟
604‧‧‧步驟
606‧‧‧步驟
700‧‧‧製程
702‧‧‧步驟
704‧‧‧步驟
706‧‧‧步驟
708‧‧‧步驟
710‧‧‧步驟
800‧‧‧製程
802‧‧‧步驟
804‧‧‧步驟
806‧‧‧步驟
808‧‧‧步驟
810‧‧‧步驟
812‧‧‧步驟
藉由當與以下說明性圖式結合考慮時參考實施方式及申請專利範圍,可得出對本發明之具體實例之更加完整的理解。
圖1說明根據本發明之例示性具體實例使用之系統;圖2說明根據本發明之例示性具體實例用於減少物質釋氣之方法;圖3說明根據本發明之例示性具體實例之另一系統;圖4說明根據本發明之例示性具體實例之反應室的一部分;
圖5說明根據本發明之其他例示性具體實例之反應室的另一部分;圖6說明根據本發明之又其他例示性具體實例用於減少物質釋氣之另一方法;圖7說明根據本發明之又其他例示性具體實例之製程;以及圖8說明根據本發明之其他例示性具體實例之另一製程。
應瞭解,圖中之元件為了簡單及清楚起見而說明且未必已按比例繪製。舉例而言,可相對於其他元件將圖中之一些元件之尺寸擴大以幫助增進對本發明之說明性具體實例的理解。
以下所提供之方法及系統之例示性具體實例的描述僅為例示性且僅意欲用於說明之目的;以下描述並不意欲限制本發明或申請專利範圍之範疇。此外,列舉具有所陳述特徵之多個具體實例並不意欲排除具有其他特徵之其他具體實例或併入所陳述特徵之不同組合之其他具體實例。
本發明大體上係關於氣相反應器,系統及方法。更特定言之,本發明係關於減緩物質自反應室之內部表面釋氣之反應器、系統及方法,例如減緩來自反應室之內部表面上所沈積之材料的釋氣。
圖1說明包括反應器102之系統100。在所說明之實施例中,系統100包括第一前驅體源104、第二前驅體源106、障壁層前驅體源108、沖洗氣體源110、視情況選用之混合器112、視情況選用之進氣增壓室114及真空源116。源104-110可使用管線118-132及閥門134-140耦接至混合器
112或反應器102。
反應器102可為獨立反應器或組合設備工具之一部分。此外,反應器102可專用於特定製程,諸如沈積製程,或反應器102可用於其他製程,例如用於層鈍化及/或蝕刻處理。舉例而言,反應器102可包括典型地用於原子層沈積(ALD)處理之反應器,諸如購自ASM之Pulsar 3000,且可包括直接電漿及/或遠程電漿設備。使用電漿可增強一或多個前驅體之反應性。藉助於一個實施例,反應器102包括適用於介電材料ALD沈積在基板142上之反應器。適用於系統100之例示性ALD反應器描述於美國專利申請公開案第US 2012/0266821號中,其內容在此以該等內容並不與本發明衝突之程度上以引用的方式併入本文中。反應器102之反應室144的操作壓力可根據各種因素變化。反應器102可經組態以在接近大氣壓或在更低壓力下操作。舉例而言,在沈積及沖洗步驟期間反應器102之操作壓力在約0.01托至約100托或約1托至約5托範圍內。
用於前驅體源104之例示性第一前驅體包括例如一或多種有機金屬化合物或金屬鹵化物化合物。舉例而言,前驅體源包括一或多種選自由氯化鉿(HfCl4)及三甲基鋁(TMA)組成之群的化合物。
用於前驅體源106之例示性第二前驅體包括氧化劑,諸如氧氣、活性氧、臭氧、水或乙醇。藉助於特定實施例,前驅體源106包括水。
用於障壁層源108之例示性前驅體可包括一或多個與自源104及/或源106所吸收或吸附材料反應以形成較低揮發性之化合物的前驅體。用於源108之適合前驅體包括過渡金屬氧化物、過渡金屬氮化物、過渡金屬氮氧化物及過渡金屬碳化物材料前驅體。舉例而言,前驅體源108
包括金屬鹵化物,諸如HfCl4。
沖洗氣體源110可包括任何適合之沖洗氣體或載氣。例示性氣體包括氮氣、氬氣、氦氣及氫氣。
系統100可包括氣體分佈系統。允許氣體(例如來自源104-110)之間快速轉換之例示性氣體分佈系統闡述於美國專利第8,152,922號(Schmidt等人)中,該專利頒佈於2012年4月10日,標題為「Gas Mixer and Manifold Assembly for ALD Reactor」,其內容在此以該等內容並不與本發明衝突之程度上以引用的方式併入本文中。氣體分佈系統可用於例如在氣體到達增壓室114或反應器102之前混合前驅體氣體及載氣(其可與來自沖洗氣體源108之沖洗氣體相同或不同)。另外,儘管以基板142上之水平流說明(沿圖1中之箭頭方向),但根據替代性具體實例之反應器可包括垂直流,例如由噴淋頭發散出並實質上向下流至基板上之流體。
使用系統(諸如系統100)之例示性ALD沈積製程包括使反應器102之反應室144內之基板142表面暴露於第一前驅體(例如來自源104之有機金屬化合物或金屬鹵化物化合物),該第一前驅體與基板142表面上之物質反應以形成第一表面物質,沖洗第一前驅體(例如使用來自源110之沖洗氣體),使第一表面物質暴露於第二前驅體(例如來自源106之氧化劑,諸如水)以形成第二表面物質及自反應室沖洗第二前驅體。或者,例示性ALD順序可開始於暴露於氧化劑,接著沖洗,接著暴露於第二前驅體,接著沖洗。在圖1中所說明之系統中,前驅體氣體可與載氣(諸如來自源110之沖洗氣體)在混合器112處混合,且前驅體及載氣之混合物可使用增壓室114引入反應室144中。前驅體及沖洗氣體之流動方向一般由圖1
中之箭頭指示。
使用此技術形成之若干膜可吸收或吸附隨後可在膜暴露於另一前驅體時釋氣之前驅體(例如來自源104或源106)。舉例而言,諸如氧化鑭、氧化鎂、氧化鋇及氧化鍶之膜可為吸濕的。在此情況下,若水用作氧化劑,則水可被所沈積膜吸附且在沖洗循環期間可能無法經充分沖洗。因此水可在基板暴露於另一前驅體之步驟期間釋氣。當前驅體之此非所需釋氣發生在膜暴露於另一其他前驅體時,可引起較高粒子計數及沈積在基板上之膜之均勻性降低。
圖2說明減少物質釋氣之方法200。方法200包括以下步驟:提供具有反應室之氣相反應器(步驟202),在反應室表面上形成障壁層以減緩一或多種氣體之釋氣(步驟204),將材料沈積在反應室內之基板表面上(步驟206)及自反應室移除基板(步驟208)。根據此等具體實例之例示性態樣,該方法產生具有相對較低粒子計數(例如在300mm基板上少於10個尺寸大於32nm之粒子)之膜。另外或可替代地,該方法產生具有小於一個西格瑪百分之一之不均勻性值的膜。
步驟202包括提供氣相反應器,諸如系統100之反應器102。如上文所指出,反應器可包括ALD反應器,諸如水平流反應器。反應器可在約0.01托至約100托或約1托至約5托之壓力及約100℃至約600℃或約200℃至約350℃之溫度下操作。
為減緩物質(諸如可藉由反應室之內部表面上所沈積之材料吸收或吸附在該材料上的第一前驅體或第二前驅體)之非所需釋氣,在步驟204期間將障壁層沈積在反應器內之潤濕表面或其部分上。如本文所用,
反應器之潤濕表面係指反應器內暴露於沈積氣體(諸如來自源104及源106之前驅體)之表面。例示性障壁層包括過渡金屬氧化物、氮化物、氮氧化物及碳化物以及氧化矽及氧化鋁。藉助於特定實施例,障壁層包括選自TiO2、TiN、TiON、TiC、Ta2O5、HlO2、SiO2及Al2O3中之一或多者之材料。根據此等具體實例之例示性態樣,障壁層藉由前驅體(例如來自源108)與物質(例如氧化劑)反應以形成障壁層而形成。
在步驟204期間所沈積之障壁層厚度可根據例如沈積在基板表面上之材料、在步驟204期間所沈積之材料厚度、在步驟206期間經處理之基板的數目及其類似因素而變化。舉例而言,障壁層厚度可大於一個單層、大於兩個單層或介於約一個單層與約50Å之間、約5Å至約20Å或約10Å至約20Å。
在步驟206期間,材料沈積在基板(諸如基板142)表面上。基板表面可具有任何適合之表面形狀,包括暴露以用於沈積之平面及/或非平面表面,且基板可包括不同材料(諸如用於形成半導體及/或光子裝置之材料)之層。舉例而言,表面可包括半導體或光子裝置工件或晶圓之頂面或其部分(包括佈局)。步驟206可適當地包括使用ALD製程之沈積材料。在此情況下,步驟206可包括以下子步驟:向反應室提供第一前驅體(例如來自源104),該第一前驅體與基板表面反應以形成第一表面物質,自反應室沖洗第一前驅體(例如使用來自源110之沖洗氣體),向反應室提供第二前驅體(例如來自源106)以與第一表面物質反應以形成第二表面物質及自反應室沖洗第二前驅體。此等步驟可重複所需數目之次數直至在基板表面上形成所需或預定量之材料為止。
在步驟208中,自反應室移除基板。舉例而言,在步驟204期間可藉由將支撐物移動至卸載位置,且隨後自反應器移除基板來自反應器102之反應室144移除基板支撐物上所支撐之基板。儘管如進行至步驟208之製程200所說明,在步驟206期間材料可同時或依次沈積在多個基板上且在步驟208期間自反應器移除。步驟204-208可重複所需數目之次數。
現轉向圖3,說明根據本發明之其他具體實例之系統300。系統300類似於系統100,除系統300包括用於向反應器102之反應室144提供清除前驅體之清除前驅體源302外。
適合與本發明之例示性具體實例一起使用之例示性清除前驅體包括金屬鹵化物,諸如金屬氯化物及有機金屬化合物。藉助於特定實施例,清除前驅體源302包括氯化鉿或氯化矽。
根據本發明之各種具體實例之例示性系統包括一或多個能夠調整系統之給料前監測裝置。圖4說明反應室內部之部分400,諸如腔室144,其包括位於基板142上游(或基板142將駐留於其中之位置)之第一給料前監測裝置402及第二給料前監測裝置404。例示性給料前監測裝置包括石英晶體微量天平。
給料前監測裝置可安裝至反應器102之下部304上及反應室144內。給料前監測裝置可用於調整製程條件,以使得位於基板上游之反應室之潤濕表面可暴露於清除前驅體,且全部或幾乎全部清除前驅體在到達基板142之前經反應室表面上之物質消耗(例如與其反應)。舉例而言,可調整系統以使得清除前驅體前之斯托克斯(Stokes)在基板142上游(例如接近該基板)實質上下降至零。此允許清除前驅體在沈積製程期間使用,
而非在反應室暴露於清除前驅體之前移除基板期間。
圖5說明部分400之另一實例,其中給料前監測器位於更遠處。在所說明之情況下,監測器404位於基板142下游。在此情況下,可能需要其他及/或更複雜的計算來調整反應器以使得全部或幾乎全部清除前驅體在到達基板142之前經消耗。
圖6說明根據本發明之其他例示性具體實例減少反應室內之物質釋氣之方法600。方法600包括以下步驟:提供具有反應室之氣相反應器(步驟602),將材料沈積在反應室內之表面或基板上(步驟604),及向反應室提供清除前驅體以與反應室表面上之材料反應(步驟606)。
提供氣相反應器步驟602可包括提供任何適合之反應器,諸如本文所揭示之反應器。根據各種實施例,步驟602包括提供ALD反應器。
在步驟604期間,可使用例如ALD製程沈積材料。在此情況下,步驟604可包括向反應室提供第一前驅體以與基板表面反應以形成第一表面物質,自反應室沖洗第一前驅體,向反應室提供第二前驅體以與第一表面物質反應以形成第二表面物質及自反應室沖洗第二前驅體。
儘管如獨立步驟604,606所說明,步驟604及606之部分可重疊。圖7說明製程700,其包括步驟604及606之例示性組合。
在所說明之實例中,製程700包括向反應室提供第一前驅體以與基板表面反應以形成第一表面物質(步驟702),向反應室提供清除前驅體以與反應室表面上(例如基板上游)之材料反應(步驟704),自反應室沖洗第一前驅體及清除前驅體(步驟706),向反應室提供第二前驅體以與第一表面物質反應以形成第二表面物質(步驟708)及自反應室沖洗第二
前驅體(步驟710)。步驟704可包括提供清除前驅體以使得全部或幾乎全部清除前驅體在到達基板之前經消耗。製程700可重複所需數目之次數直至在基板上形成所需厚度之材料。且用於此製程之前驅體及沖洗氣體可包括本文所指出之前驅體及沖洗氣體中之任一者。
圖8說明另一製程800,其包括步驟604及606之替代性例示性組合。製程800類似於製程700,除製程800包括另一沖洗步驟804外。步驟802、806、808、810及812可分別對應於製程700之步驟702-710,除由於與步驟706相比在此步驟期間可移除較少前驅體材料,因此步驟808持續時間可較短及/或可在較高壓力下外。
儘管在此闡述本發明之例示性具體實例,但應瞭解本發明並非如此受限。舉例而言,儘管結合各種特定化學物質來描述系統及方法,但本發明未必限於此等實例。另外,除非本文相反地指示,否則儘管以一特定順序說明方法,但該方法不限於該順序之步驟。可在不偏離本發明之精神及範疇之情況下對本文所陳述之系統及方法作出各種修改、變化及增強。
本發明之標的物包括本文所揭示之各種製程、系統及組態,及其他特徵、功能、作用及/或特性,以及其任何及所有等效物的所有新穎及非顯而易見之組合及子組合。
Claims (20)
- 一種減少物質釋氣之方法,該方法包含以下步驟:提供具有反應室之氣相反應器;在該反應室表面上形成障壁層以減緩一或多種氣體之釋氣;將材料沈積在該反應室內之基板表面上;及自該反應室移除該基板。
- 如申請專利範圍第1項之減少物質釋氣之方法,其中提供氣相反應器之該步驟包含提供原子層沈積反應器。
- 如申請專利範圍第1項之減少物質釋氣之方法,其中沈積之該步驟包含:向該反應室提供第一前驅體,該第一前驅體與該基板之表面反應以形成第一表面物質;自該反應室沖洗該第一前驅體;向該反應室提供第二前驅體以與該第一表面物質反應以形成第二表面物質;及自該反應室沖洗該第二前驅體。
- 如申請專利範圍第1項至第3項中任一項之減少物質釋氣之方法,其中形成障壁層之該步驟包含形成選自以下各項中之一或多者的層:過渡金屬氧化物層、過渡金屬氮化物層、過渡金屬氮氧化物層及過渡金屬碳化物層。
- 如申請專利範圍第1項至第3項中任一項之減少物質釋氣之方法,其中形成障壁層之該步驟包含形成包含TiO2、Ta2O5、HfO2、SiO2、Al2O3、 TiN、TiON及TiC中之一或多者之層。
- 如申請專利範圍第1項至第3項中任一項之減少物質釋氣之方法,其中形成障壁層之該步驟包含形成包含HfO2之層。
- 如申請專利範圍第1項至第3項中任一項之減少物質釋氣之方法,其中形成障壁層之該步驟包含在該反應室之該表面上沈積介於約一個單層與約50Å之間的障壁材料。
- 一種減少反應室內物質釋氣之方法,該方法包含以下步驟:提供具有反應室之氣相反應器;將材料沈積在該反應室內之基板表面上;及向該反應室提供清除前驅體以與位於該基板上游之該反應室表面上之該材料反應,其中該清除氣前驅體在到達該基板之前實質上消耗或消耗。
- 如申請專利範圍第8項之方法,其中該清除前驅體係選自由金屬鹵化物及有機金屬化合物組成之群。
- 如申請專利範圍第8項之方法,其中該清除前驅體係選自由HfCl4及SiCl4以及TMA組成之群。
- 如申請專利範圍第1項至第10項中任一項之方法,其中將材料沈積在基板表面上之該步驟包含:向該反應室提供第一前驅體以與該基板之表面反應以形成第一表面物質;自該反應室沖洗該第一前驅體;向該反應室提供第二前驅體以與該第一表面物質反應以形成第二表面 物質;及自該反應室沖洗該第二前驅體。
- 如申請專利範圍第11項之方法,其中提供清除前驅體之該步驟發生在提供第一前驅體之該步驟後。
- 如申請專利範圍第12項之方法,其中提供清除前驅體之該步驟發生在沖洗該第一前驅體之該步驟前。
- 如申請專利範圍第11項之方法,其中提供清除前驅體之該步驟發生在沖洗該第一前驅體之該步驟後。
- 如申請專利範圍第14項之方法,其進一步包含沖洗該清除前驅體之步驟。
- 如申請專利範圍第15項之方法,其中沖洗該清除前驅體之該步驟發生在提供第二前驅體之該步驟前。
- 如申請專利範圍第1項至第10項中任一項之方法,其進一步包含給料前監測之步驟。
- 如申請專利範圍第17項之方法,其中給料前監測之該步驟用於調整製程條件以在該清除前驅體到達該基板之前消耗該清除前驅體。
- 一種用於將材料沈積在基板上之系統,該系統包含:包含反應室之反應器;流體地聯接至該反應室之第一前驅體源;流體地聯接至該反應室之第二前驅體源;流體地聯接至該反應室之沖洗氣體源;及流體地聯接至該反應室之清除前驅體源, 其中該反應室暴露於第一前驅體,及在該反應室暴露於該第一前驅體之後,該反應室暴露於清除前驅體,及在該反應室暴露於該清除前驅體之後,該反應室暴露於第二前驅體。
- 如申請專利範圍第19項之系統,其進一步包含一或多個給料前監測裝置。
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US20040023516A1 (en) * | 2001-10-02 | 2004-02-05 | Londergan Ana R. | Passivation method for improved uniformity and repeatability for atomic layer deposition and chemical vapor deposition |
US20040221807A1 (en) * | 2003-05-09 | 2004-11-11 | Mohith Verghese | Reactor surface passivation through chemical deactivation |
US20040266011A1 (en) * | 2003-06-26 | 2004-12-30 | Samsung Electronics Co., Ltd. | In-situ analysis method for atomic layer deposition process |
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US20150017319A1 (en) | 2015-01-15 |
TW201514336A (zh) | 2015-04-16 |
KR102186335B1 (ko) | 2020-12-04 |
US9790595B2 (en) | 2017-10-17 |
US20150140210A1 (en) | 2015-05-21 |
US8993054B2 (en) | 2015-03-31 |
KR20150007989A (ko) | 2015-01-21 |
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