TWI549958B - 鉬（ｉｖ）醯胺前驅物及其於原子層沈積之用途 - Google Patents
鉬（ｉｖ）醯胺前驅物及其於原子層沈積之用途 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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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]
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Description
本發明係關於鉬(Mo)(IV)醯胺前驅物及採用該等前驅物藉由原子層沈積(ALD)製備MoO2膜之方法。
本申請案主張2010年8月27日申請之美國專利公開案號第61/377,692號之優先權，全文以引用的方式併入本文中。
ALD係沈積薄膜之已知方法。其係一種自限性、序列獨特之成膜技術，該技術以表面反應為基礎且可控制原子層，並由在不同組成之基板上的前驅物提供沈積之仿形薄膜物質。在ALD方法中，於反應期間分離該等前驅物。第一前驅物通過該基板並於該基板上形成一個單層。將任何過量的未反應前驅物泵出該反應室。接著讓第二前驅物通過該基板並與第一前驅物反應，於該基板表面形成單層膜。重覆此循環以得到所需厚度的膜。
ALD方法可應用在奈米技術及製造半導體器件(諸如電容器電機、閘極、黏合劑擴散障壁及積體電路)中。此外，該等具有高介電常數(電容率)之介電薄膜係許多微電子學及光電子學之子區域所要求者。隨著微電子組件之尺寸持續縮小，使得使用此等介電膜之需求日益增加。
Green,J等人報導了鉬錯合物Mo(C5H5)(NMe2)3之合成與分離。J. Chem. Soc.,Dalton Trans.,1997,3219-3224頁。
美國專利案第No. 5,064,686號報導了一種用於化學蒸汽沈積(CVD)之Mo(IV)錯合物。於CAD中嘗試使用Mo[N(Me)(Me)]4。然而於CAD中注意到熱穩定性問題並發現儘管該前驅物在結構上類似，但並不適於沈積MoO2層。
此外，發現Mo(NtBu)2(NMe2)2對藉由ALD形成MoO2膜並不能產生良好效果，原因在於其形成了不適於DRAM的MoO3膜。因此需要發現新穎的Mo前驅物，其應可藉由ALD沈積MoO2膜，具有改善的熱穩定性，易揮發性或提高的沈積速率。
在一項實施例中，提供一種錯合物，其結構對應於式I
其中L為--NR1R2；R1及R2為C1-C6-烷基或氫；R為C1-C6-烷基；且n為0、1、2或3。
在另一實施例中，提供一種藉由ALD形成MoO2膜之方法。該方法包括傳送至少一種前驅物至基板，其中該至少一種前驅物對應於上式I之結構。
在另一實施例中，提供該錯合物Mo[N(Me)(Et)]4及其於ALD中形成MoO2膜之用途。
其他實施例(包括以上概述實施例之特定態樣)將可自以下詳細描述中了解。
在本發明之多種態樣中，提供鉬(IV)醯胺前驅物及以其藉由ALD形成MoO2膜之使用方法。
在一實施例中，本發明之方法可用來產製或形成顯示高介電常數之含Mo薄膜。如本文所用介電薄膜意指具有高電容率之薄膜。
如本文所用，術語「前驅物」意指有機金屬分子、錯合物及/或化合物，其可被傳送至用於沈積之基板，藉由ALD形成薄膜。
術語「Cp」意指與過渡金屬結合之環戊二烯基(C5H5)配體。如本文所用，該Cp配體之全部5個碳原子係藉由π鍵，以η5配位結合至金屬中心，因此本發明之前驅物為π錯合物。
術語「烷基」意指1至約6個碳原子之長度的飽和烴鏈，諸如(但不限於)甲基、乙基、丙基及丁基。該烷基基團可為直鏈或支鏈。例如，如本文所用，丙基包含正丙基及異丙基；丁基包含正丁基、第二丁基、異丁基及第三丁基。此外，如本文所用，「Me」意指甲基，及「Et」意指乙基。
術語「胺基」在本文中意指視需要經取代之單價氮原子(即，-NR1R2，其中R1及R2可相同或相異)。本發明所包括之胺基實例包括(但不限於)。此外，此胺基之氮原子係共價結合至金屬中心，其等一起可稱為「醯胺」基團(即)。此基團又可稱為「氨基(ammono)」基團或無機醯胺。
在第一實施例中，提供一種「琴凳」錯合物，其結構對應式I
其中L為--NR1R2；R1及R2分別為C1-C6-烷基或氫；R為C1-C6-烷基；且n為0、1、2或3。
R1及R2可相同或相異。在特定實施例中，R1及R2皆為甲基。在另一特定實施例中，R1為甲基且R2為乙基。
在另一實施例中，當n為0時，R1與R2係彼此相異。
在一項實施例中，R1及R2分別為甲基、乙基或丙基；R為甲基、乙基或丙基；且n為0、1或2。
在又一實施例中，R1與R2係相同；R為甲基；n為0、1或2。
在又一實施例中，R1為甲基且R2為乙基；R為甲基；且n為0、1或2。
結構上對應於式I之錯合物的實例為(環戊二烯基)Mo(NMe2)3；(甲基環戊二烯基)Mo(NMe2)3；(乙基環戊二烯基)Mo(NMe2)3；(丙基環戊二烯基)Mo(NMe2)3；(甲基環戊二烯基)Mo(NEt2)3；(乙基環戊二烯基)Mo(NEt2)3；(丙基環戊二烯基)MoNEt2)3；(環戊二烯基)Mo(NMeEt)3；(甲基環戊二烯基)Mo(NMeEt)3；(乙基環戊二烯基)Mo(NMeEt)3；及(丙基環戊二烯基)Mo(NMeEt)3。
在又一實施例中，Mo(IV)醯胺錯合物上的環戊二烯基環係被另一醯胺基團取代，形成肆醯胺：Mo[N(Me)(Et)]4。
該等依據式I之錯合物及Mo[N(Me)(Et)]4係用作前驅物，藉由ALD形成MoO2膜。該等本文所揭示之前驅物可依脈衝方式，與合適氧源脈衝(諸如H2O、H2O2、O2、臭氧、iPrOH、tBuOH或N2O)交替傳送沈積至基板上。
在一項實施例中，藉由獨立傳送或與一種共反應劑組合傳送至少一種依據式I之前驅物，供沈積形成MoO2膜。此等共反應劑之實例包括(但不限於)氫、氫電漿、氧、空氣、水、H2O2、氨、肼、烷基肼、硼烷、矽烷、臭氧或其任何組合。
多種基板可用於本發明之方法中。例如，依據式I之前驅物或Mo[N(Me)(Et)]4可傳送至諸如(但不限於)矽、氧化矽、氮化矽、鉭、氮化鉭或銅之基板上沈積。
本發明之ALD方法包含多種類型之ALD製程。例如，在一項實施例中，採用習知ALD形成本發明之含金屬膜。針對習知及/或脈衝注入之ALD製程可參見(例如)George S. M 等人。J. Phys. Chem. 1996. 100:13121-13131。
在又一實施例中，採用液體注入ALD形成含金屬膜，其中液體前驅物不採用(傳統)鼓泡器之蒸汽牽引，反而以直接液體注入方式傳送至反應室。針對液體注入ALD製程可參見(例如)Potter R. J等人。Chem. Vap. Deposition. 2005. 11(3):159。
液體注入ALD成膜條件之實例包括(但不限於)：
(1)基板溫度：Si(100)上160-300℃
(2)蒸汽溫度範圍：約120-200℃
(3)反應壓範圍：約2-50 mbar
(4)溶劑：甲苯，或任何上述溶劑
(5)溶液濃度範圍：約0.05至2 M
(6)注入速率範圍：每脈衝約1-10 μl(每個周期4個脈衝)
(7)惰性氣體流動速率：約50-500 cm3 min-1
(8)脈衝順序(秒)(前驅物/淨化/H2O/淨化)：將依據反應室大小變化
(9)循環次數：將依據所需膜厚度變化
該前驅物可溶解在合適烴或胺溶劑中。合適烴溶劑包括(但不限於)脂族烴，諸如己烷、庚烷及壬烷；芳香烴，諸如甲苯及二甲苯；脂肪族及環醚，諸如二乙二醇二甲醚、三乙二醇二甲醚及四乙二醇二甲醚。合適胺溶劑之實例包括(不限於)辛胺及N,N-二甲基十二胺。例如，該前驅物可溶解於甲苯，以得到0.05至1 M溶液。
在又一實施例中，至少一種結構對應於式I之前驅物及/或Mo[N(Me)(Et)]4可呈「純物質」(未經過運載氣體稀釋)傳送至該基板。
在又一實施例中，採用光輔助ALD來形成含金屬膜。針對光輔助ALD製程，參見(例如)美國專利案第4,581,249號。
在又一實施例中，可採用液體注入及光輔助ALD兩者，使用至少一種結構對應於式I之前驅物及/或Mo[N(Me)(Et)]4來形成含金屬膜。
在又一實施例中，可採用電漿輔助ALD，使用至少一種結構對應於式I之前驅物及/或Mo[N(Me)(Et)]4來形成含金屬膜。
因此，此等方法中所使用之結構對應於式I之有機金屬前驅物及Mo[N(Me)(Et)]4可為液態、固態、或氣態。特定言之，該等前驅物在周圍溫度下為液態，且具有高蒸氣壓以不斷地輸送蒸氣至該處理室。
ALD實質上依賴於化學反應性而非熱分解。因此，對於合適前驅物所需的特徵存在根本差異。該前驅物在所採用之溫度下必需熱穩定，且應具有充分揮發性，使其可沈積在基板上。此外，當沈積金屬氧化物膜時，該金屬前驅物與氧化物源之間需要快速且完全的化學反應。然而，該反應應僅發生在基板表面，以免損壞下層結構，且應可輕易地自表面移除副產物(諸如碳及氫)。
已發現該Cp環上取代作用之變化及連接至金屬中心的3個相同配體針對ALD方法展示有用及改善之性質。例如，式I之前驅物可提高藉由ALD沈積MoO2膜的能力，其成膜速率接近彼等採用簡單金屬醯胺時之結果，但因為熱穩定性提高而可在較高溫下操作，可以改善產品品質。此外，使用Mo(IV)醯胺琴凳型錯合物可藉由極化分子以容許與表面反應，而增強ALD性能，該表面可達飽和狀態之自限成膜，以達到優良的仿形控制。
在特定實施例中，本發明方法係用於在諸如矽晶片之基板上之諸如：動態隨機存取記憶體(DRAM)及互補金屬氧化物半導體(CMOS)的記憶及邏輯應用。
在另一實例中，提供一種用於藉由ALD形成「混合」金屬膜之方法。如本文所用之術語「混合」金屬膜係指由至少兩種不同金屬構成該膜。
在一實施例中，採用ALD，藉由傳送用於沈積之至少一種依據式I之前驅物及/或Mo[N(Me)(Et)]4及至少一種具有不同金屬中心的共前驅物，來形成混合金屬膜。例如，可傳送用於沈積之至少一種依據式I之Mo前驅物及/或Mo[N(Me)(Et)]4及至少一種適合的共前驅物(諸如鉛、鈦、鍶及/或鋇前驅物)至基板，而產生混合金屬膜。
藉由本發明方法得到之薄膜可具有介於10及250間之電容率，較佳至少25至40且更佳至少40至100。此外，高於100之數值可被視為超高電容率。此項技術中一般技術者咸了解，該膜之所得電容率視很多因素而定，諸如用於沈積的金屬、所得膜的厚度、在成膜及後續處理期間所採用的參數及基板。
以下實例僅供說明，並不以任何方式限制本發明。全部操作均在惰性蒙氣下使用手套箱及史蘭克管(schlenk line)技術進行。使用布魯克(Bruker)250 MHz儀器進行NMR分析。
N-乙基，甲基胺化鋰係使用標準方法自nBuLi及HNEtMe製得。在4小時時間內滴加N-乙基甲基胺(65.6 g，1.1莫耳)至nBuLi(680 ml，1.6 M己烷溶液，冰浴冷卻至0℃)中。所有醯胺均添加後，立即加溫該混合物至室溫，接著攪拌一夜。添加THF(250 ml)至此溶液中，並攪拌該混合物1小時，接著於冰浴中冷卻至0℃。於該混合物中添加MoCl5(50.2 g，0.18莫耳，由於混合物會大量放熱及噴濺，因此應以8小時時間以每小份約1-2 g分次添加)。一旦MoCl5添加完畢後，立即將該深褐色(近乎黑色)反應混合物升溫至室溫，接著回流1小時。冷卻該混合物並接著攪拌一夜。使用標準技術使該混合物沉澱(LiCl)並過濾。汽提排除反應混合物中之溶劑，接著讓紫色液體自該反應混合物中昇華/蒸餾排出，產生紫色液體。
蒸餾條件：壓力範圍3.5×10-2鐸及油浴溫度100-110℃。
在於冰浴中冷卻至0℃的Mo(NEtMe)4(如上述製備，3.3 g，0.01莫耳)之深紫色甲苯溶液(60ml)中添加新近裂化的MeCpH(4 g，0.05莫耳，經由注射器添加)。未立即觀察到顏色變化，因此再於室溫下攪拌該混合物2小時。仍未觀察到顏色變化，因而讓該混合物回流3小時，以得到深綠色溶液。汽提排除該反應混合物之甲苯，獲得深綠色液體。
該等MoO2膜係沈積在定製之ALD反應器中。使用Mo(MeCp)(NEtMe)3及臭氧作為前驅物。讓MoO2膜沈積在矽晶圓基板上。在沈積之前，藉由切割該晶圓(1英寸x 英寸)並用1% HF抛光來製備該晶圓基板。
該成膜溫度為200-350℃。該成膜壓力為0.5-1.5鐸。在該反應器中連續通入30 sccm之乾燥氮氣進行淨化。該反應器中全部電腦控制閥均為購自Cajon之氣體操作ALD VCR閥。
將臭氧充分淨化。將鉬儲存在不銹鋼安瓿中。ALD閥與該安瓿直接相連。此ALD閥之出口為與另一用於氮氣注入之ALD閥呈T形。該T形出口端管連接至500 cm3之不銹鋼儲槽。此儲槽之出口再連接至稱為注入閥之第三ALD閥，該閥出口直接通向該反應器。注入氮氣以提高在鉬注入閥之後的總壓力，使得該壓力高於該反應器成膜壓力。使用30微米針孔VCR襯墊完成氮氣注入。該等全部閥門及安瓿均置於爐形箱中，使該安瓿、閥門、導管均勻加熱至50℃至250℃。
在該ALD成膜操作期間，該等閥門之順序如下。將鉬前驅物導入該活化矽表面。接著進行氮氣淨化，其包括抽氣移除剩餘的未黏附於該表面的反應劑分子。接著導入臭氧，隨後再用氮氣進行淨化。接著注入該臭氧，以重覆開始該ALD循環。
該循環總數量一般為300次。
本文所引證之全部專利及公開案之全文係以引用之方式併入此公開案中。
用詞「包括(comprise)」、「包括(comprises)」、「包括(comprise)」應解讀為涵蓋而非獨有。
圖1為顯示Mo[N(Me)(Et)]4之毫克數(mg)相對於溫度/時間之熱解重量分析(TGA)數據之圖示。
Claims (20)
- 一種藉由原子層沈積形成MoO2膜之方法，該方法包括傳送Mo[N(Me)(Et)]4至基板。
- 一種結構對應於式I之Mo(IV)錯合物
- 如請求項2之錯合物，其中R1及R2各自獨立為甲基、乙基或丙基；R為甲基、乙基或丙基；及n為0、1或2。
- 如請求項2之錯合物，其中R1及R2係相同；R為甲基；且n為0、1或2。
- 如請求項2之錯合物，其中 R1為甲基且R2為乙基；R為甲基；且n為0、1或2。
- 如請求項2之錯合物，其中結構對應於式I之該錯合物係選自由以下組成之群：(甲基環戊二烯基)Mo(NMe2)3；(乙基環戊二烯基)Mo(NMe2)3；(丙基環戊二烯基)Mo(NMe2)3；(甲基環戊二烯基)Mo(NEt2)3；(乙基環戊二烯基)Mo(NEt2)3；(丙基環戊二烯基)Mo(NEt2)3；(環戊二烯基)Mo(NMeEt)3；(甲基環戊二烯基)Mo(NMeEt)3；(乙基環戊二烯基)Mo(NMeEt)3；及(丙基環戊二烯基)Mo(NMeEt)3。
- 如請求項2之錯合物，其中結構對應於式I之該錯合物係選自由以下組成之群：(甲基環戊二烯基)Mo(NMe2)3；(甲基環戊二烯基)Mo(NMeEt)3；及(環戊二烯基)Mo(NMeEt)3。
- 一種藉由原子層沈積形成MoO2膜之方法，該方法包括傳送至少一種前驅物至基板，其中該至少一種前驅物結構對應於式I：
- 如請求項8之方法，其中R1及R2各自獨立為甲基、乙基或丙基；R為甲基、乙基或丙基；及n為0、1或2。
- 如請求項8之方法，其中R1及R2係相同；R為甲基；且n為0、1或2。
- 如請求項8之方法，其中R1為甲基且R2為乙基；R為甲基；且n為0、1或2。
- 如請求項8之方法，其中該至少一種結構對應於式I之前驅物係選自由以下組成之群：(環戊二烯基)Mo(NMe2)3； (甲基環戊二烯基)Mo(NMe2)3；(乙基環戊二烯基)Mo(NMe2)3；(丙基環戊二烯基)Mo(NMe2)3；(甲基環戊二烯基)Mo(NEt2)3；(乙基環戊二烯基)Mo(NEt2)3；(丙基環戊二烯基)Mo(NEt2)3；(環戊二烯基)Mo(NMeEt)3；(甲基環戊二烯基)Mo(NMeEt)3；(乙基環戊二烯基)Mo(NMeEt)3；及(丙基環戊二烯基)Mo(NMeEt)3。
- 如請求項8之方法，其中該至少一種結構對應於式I之前驅物係選自由以下組成之群：(甲基環戊二烯基)Mo(NMe2)3；(甲基環戊二烯基)Mo(NMeEt)3；(環戊二烯基)Mo(NMeEt)3；及(環戊二烯基)Mo(NMe2)3。
- 如請求項8之方法，其中該原子層沈積係選自由以下組成之群：光輔助原子層沈積、液體注入原子層沈積及電漿輔助原子層沈積。
- 如請求項8之方法，其中該前驅物係以與選自H2O、H2O2、O2、臭氧、iPrOH、tBuOH及N2O之氧源脈衝交替之脈衝沈積至基板上。
- 如請求項8之方法，其中將至少兩種結構對應於式I之前驅物傳送至基板，以藉由原子層沈積形成MoO2膜。
- 如請求項8之方法，其進一步包括傳送至少一種共前驅物至基板，以藉由原子層沈積形成混合金屬膜。
- 如請求項8之方法，其中先將該至少一種結構對應於式I之前驅物溶解在溶劑中，然後再傳送至基板。
- 如請求項8之方法，其中該至少一種結構對應於式I之前驅物係以純物質傳送至基板。
- 如請求項8之方法，其中該MoO2膜係用於記憶及/或邏輯應用。
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Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2432363B (en) | 2005-11-16 | 2010-06-23 | Epichem Ltd | Hafnocene and zirconocene precursors, and use thereof in atomic layer deposition |
| TWI382987B (zh) | 2007-07-24 | 2013-01-21 | Sigma Aldrich Co | 應用於化學相沉積製程的有機金屬前驅物 |
| KR101560755B1 (ko) | 2007-09-14 | 2015-10-15 | 시그마 알드리치 컴퍼니 엘엘씨 | 모노시클로펜타디에닐 티타늄계 전구체를 이용한 원자층 증착에 의한 티타늄 함유 박막의 제조 방법 |
| TWI467045B (zh) | 2008-05-23 | 2015-01-01 | Sigma Aldrich Co | 高介電常數電介質薄膜與使用鈰基前驅物製造高介電常數電介質薄膜之方法 |
| CN102574884B (zh) | 2009-08-07 | 2016-02-10 | 西格玛-奥吉奇有限责任公司 | 高分子量烷基-烯丙基三羰基钴配合物及其用于制备介电薄膜的用途 |
| JP5873494B2 (ja) | 2010-08-27 | 2016-03-01 | シグマ−アルドリッチ・カンパニー、エルエルシー | モリブデン（ｉｖ）アミド前駆体及び原子層堆積法におけるそれらの使用 |
| US8927748B2 (en) | 2011-08-12 | 2015-01-06 | Sigma-Aldrich Co. Llc | Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films |
| US9175023B2 (en) | 2012-01-26 | 2015-11-03 | Sigma-Aldrich Co. Llc | Molybdenum allyl complexes and use thereof in thin film deposition |
| WO2014140672A1 (en) * | 2013-03-15 | 2014-09-18 | L'air Liquide, Societe Anonyme Pour I'etude Et I'exploitation Des Procedes Georges Claude | Bis(alkylimido)-bis(alkylamido)molybdenum molecules for deposition of molybdenum-containing films |
| WO2015138390A1 (en) | 2014-03-13 | 2015-09-17 | Sigma-Aldrich Co. Llc | Molybdenum silylcyclopentadienyl and silylallyl complexes and use thereof in thin film deposition |
| KR102147190B1 (ko) * | 2015-03-20 | 2020-08-25 | 에스케이하이닉스 주식회사 | 막형성조성물 및 그를 이용한 박막 제조 방법 |
| WO2016191432A1 (en) | 2015-05-27 | 2016-12-01 | Asm Ip Holding B.V. | Synthesis and use of precursors for ald of molybdenum or tungsten containing thin films |
| US10662527B2 (en) | 2016-06-01 | 2020-05-26 | Asm Ip Holding B.V. | Manifolds for uniform vapor deposition |
| KR20180038823A (ko) | 2016-10-07 | 2018-04-17 | 삼성전자주식회사 | 유기 금속 전구체, 이를 이용한 막 형성 방법 및 이를 이용한 반도체 장치의 제조 방법 |
| US10358407B2 (en) | 2016-10-12 | 2019-07-23 | Asm Ip Holding B.V. | Synthesis and use of precursors for vapor deposition of tungsten containing thin films |
| KR102474876B1 (ko) * | 2017-06-15 | 2022-12-07 | 삼성전자주식회사 | 텅스텐 전구체 및 이를 이용한 텅스텐 함유막의 형성 방법 |
| US11560625B2 (en) | 2018-01-19 | 2023-01-24 | Entegris, Inc. | Vapor deposition of molybdenum using a bis(alkyl-arene) molybdenum precursor |
| US11492701B2 (en) | 2019-03-19 | 2022-11-08 | Asm Ip Holding B.V. | Reactor manifolds |
| KR20210048408A (ko) | 2019-10-22 | 2021-05-03 | 에이에스엠 아이피 홀딩 비.브이. | 반도체 증착 반응기 매니폴드 |
| TW202136571A (zh) | 2020-02-10 | 2021-10-01 | 荷蘭商Ａｓｍ Ｉｐ 控股公司 | 高深寬比孔內的氧化鉿之沉積 |
| KR20210119809A (ko) | 2020-03-25 | 2021-10-06 | 삼성전자주식회사 | 몰리브덴 화합물과 이를 이용한 집적회로 소자의 제조 방법 |
| US11434254B2 (en) | 2021-01-12 | 2022-09-06 | Applied Materials, Inc. | Dinuclear molybdenum precursors for deposition of molybdenum-containing films |
| US11459347B2 (en) | 2021-01-12 | 2022-10-04 | Applied Materials, Inc. | Molybdenum(IV) and molybdenum(III) precursors for deposition of molybdenum films |
| US11390638B1 (en) | 2021-01-12 | 2022-07-19 | Applied Materials, Inc. | Molybdenum(VI) precursors for deposition of molybdenum films |
| US11760768B2 (en) | 2021-04-21 | 2023-09-19 | Applied Materials, Inc. | Molybdenum(0) precursors for deposition of molybdenum films |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07107190B2 (ja) | 1984-03-30 | 1995-11-15 | キヤノン株式会社 | 光化学気相成長方法 |
| US5064686A (en) * | 1990-10-29 | 1991-11-12 | Olin Corporation | Sub-valent molybdenum, tungsten, and chromium amides as sources for thermal chemical vapor deposition of metal-containing films |
| GB9929279D0 (en) | 1999-12-11 | 2000-02-02 | Epichem Ltd | An improved method of and apparatus for the delivery of precursors in the vapour phase to a plurality of epitaxial reactor sites |
| GB0017968D0 (en) | 2000-07-22 | 2000-09-13 | Epichem Ltd | An improved process and apparatus for the isolation of pure,or substantially pure,organometallic compounds |
| DE02772548T1 (de) | 2001-10-26 | 2004-11-11 | Epichem Ltd., Wirral | Vorlaeuferverbindungen für chemische dampfphasenabscheidung |
| TW200411923A (en) | 2002-07-19 | 2004-07-01 | Asml Us Inc | In-situ formation of metal insulator metal capacitors |
| WO2004083479A2 (en) | 2003-03-17 | 2004-09-30 | Epichem Limited | Alcoholates of rare earth mtals a precursors for metaloxide layers or films |
| GB0412790D0 (en) | 2004-06-08 | 2004-07-14 | Epichem Ltd | Precursors for deposition of silicon nitride,silicon oxynitride and metal silicon oxynitrides |
| GB2432363B (en) | 2005-11-16 | 2010-06-23 | Epichem Ltd | Hafnocene and zirconocene precursors, and use thereof in atomic layer deposition |
| US7638645B2 (en) | 2006-06-28 | 2009-12-29 | President And Fellows Of Harvard University | Metal (IV) tetra-amidinate compounds and their use in vapor deposition |
| JP5555872B2 (ja) * | 2006-06-28 | 2014-07-23 | プレジデント アンド フェローズ オブ ハーバード カレッジ | 金属（ｉｖ）テトラ−アミジネート化合物ならびに蒸着においての使用 |
| US7956207B2 (en) * | 2006-09-28 | 2011-06-07 | Praxair Technology, Inc. | Heteroleptic organometallic compounds |
| TWI382987B (zh) | 2007-07-24 | 2013-01-21 | Sigma Aldrich Co | 應用於化學相沉積製程的有機金屬前驅物 |
| TWI425110B (zh) | 2007-07-24 | 2014-02-01 | Sigma Aldrich Co | 以化學相沉積法製造含金屬薄膜之方法 |
| KR101560755B1 (ko) | 2007-09-14 | 2015-10-15 | 시그마 알드리치 컴퍼니 엘엘씨 | 모노시클로펜타디에닐 티타늄계 전구체를 이용한 원자층 증착에 의한 티타늄 함유 박막의 제조 방법 |
| CN101815807B (zh) | 2007-09-14 | 2012-06-13 | 西格玛-奥吉奇有限责任公司 | 采用单环戊二烯基三烷氧基铪和锆前体通过原子层沉积制备薄膜的方法 |
| TW200944535A (en) | 2008-03-20 | 2009-11-01 | Sigma Aldrich Co | Purification and preparation of phosphorus-containing compounds |
| TWI467045B (zh) | 2008-05-23 | 2015-01-01 | Sigma Aldrich Co | 高介電常數電介質薄膜與使用鈰基前驅物製造高介電常數電介質薄膜之方法 |
| WO2009143452A1 (en) | 2008-05-23 | 2009-11-26 | Sigma-Aldrich Co. | High-k dielectric films and methods of producing using cerium-based precursors |
| TW200949006A (en) | 2008-05-23 | 2009-12-01 | Sigma Aldrich Co | High-k dielectric films and methods of producing using titanium-based precursors |
| TW200949939A (en) | 2008-05-23 | 2009-12-01 | Sigma Aldrich Co | High-k dielectric films and methods of producing using titanium-based β -diketonate precursors |
| TW200951241A (en) | 2008-05-30 | 2009-12-16 | Sigma Aldrich Co | Methods of forming ruthenium-containing films by atomic layer deposition |
| TW201014925A (en) | 2008-06-20 | 2010-04-16 | Sigma Aldrich Co | Titanium pyrrolyl-based organometallic precursors and use thereof for preparing dielectric thin films |
| WO2010114386A1 (en) * | 2009-03-30 | 2010-10-07 | Universitetet I Oslo | Thin films containing molybdenum oxide |
| SG177710A1 (en) | 2009-07-21 | 2012-02-28 | Sigma Aldrich Co Llc | Compositions and methods of use for forming titanium- containing thin films |
| CN102574884B (zh) | 2009-08-07 | 2016-02-10 | 西格玛-奥吉奇有限责任公司 | 高分子量烷基-烯丙基三羰基钴配合物及其用于制备介电薄膜的用途 |
| US8318572B1 (en) * | 2010-02-19 | 2012-11-27 | Intermolecular, Inc. | Inexpensive electrode materials to facilitate rutile phase titanium oxide |
| WO2011115878A1 (en) | 2010-03-19 | 2011-09-22 | Sigma-Aldrich Co. | Methods for preparing thin fillms by atomic layer deposition using hydrazines |
| JP5873494B2 (ja) | 2010-08-27 | 2016-03-01 | シグマ−アルドリッチ・カンパニー、エルエルシー | モリブデン（ｉｖ）アミド前駆体及び原子層堆積法におけるそれらの使用 |
| US8927748B2 (en) | 2011-08-12 | 2015-01-06 | Sigma-Aldrich Co. Llc | Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films |
| US9175023B2 (en) | 2012-01-26 | 2015-11-03 | Sigma-Aldrich Co. Llc | Molybdenum allyl complexes and use thereof in thin film deposition |
-
2011
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-
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Non-Patent Citations (2)
| Title |
|---|
| 「Synthesis of new amido, alkoxo and η-cyclopentadienylderivatives of molybdenum」, J. Chem. Soc., Dalton Trans., 1997, 2091-2100, DOI: 10.1039/A701096F, Xuefeng Yan 等著 * |
| 「The molybdenum-molybdenum triple bond. 1. Hexakis(dimethylamido)dimolybdenum and some homologs: preparation, structure, and properties」, J. Am. Chem. Soc., 1976, 98 (15), pp 4469–4476, DOI: 10.1021/ja00431a024, Publication Date: July 1976, Malcolm H. Chisholm 等著 * |
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| US20130196065A1 (en) | 2013-08-01 |
| IL224618A (en) | 2015-02-26 |
| KR20130139866A (ko) | 2013-12-23 |
| TW201219405A (en) | 2012-05-16 |
| JP5873494B2 (ja) | 2016-03-01 |
| WO2012027575A1 (en) | 2012-03-01 |
| JP2013540893A (ja) | 2013-11-07 |
| KR101847953B1 (ko) | 2018-04-11 |
| EP2609102B1 (en) | 2014-12-31 |
| EP2609102A1 (en) | 2013-07-03 |
| US9802220B2 (en) | 2017-10-31 |
| SG187920A1 (en) | 2013-03-28 |
| CN103097394B (zh) | 2016-03-02 |
| CN103097394A (zh) | 2013-05-08 |
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