201130857 六、發明說明: 基於35 U.S.C. §119(e),本申請案主張於2007年7 月20日提出之美國臨時申請案第60/961,370號以及於 2008年6月30日提出之非臨時申請案第12215828號之優 先權。 【發明所屬之技術領域】 本發明係關於製備有機金屬化合物(OMC)之方法。特 別地,本發明係針對製備用於諸如化學氣相沉積之製程之 高純度有機金屬化合物的方法。 【先前技術】 可藉由多種手段如化學氣相沉積(CVD)、物理氣相沉 積(PVD)及其他磊晶技術如液相磊晶術(LPE)、分子束磊晶 術(MBE)、化學束磊晶術(CBE)及原子層沉積(ALD),將金屬 膜沉積於表面’如非導電(電子材料應用)表面。化學氣相 沉積製程,如有機金屬化學氣相沉積(MOCVD),係藉由在伸 高之溫度(亦即,超過室溫),於大氣壓力或於減壓下分解 有機金屬前體化合物來沉積金屬層。使用此等CVD或MOCVD 製程可沉積多種金屬。 對於半導體及電子裝置應用來說,有機金屬前體化合 物必須為超純且為實質上不含可測得濃度(level)之金屬 雜質(如;ε夕與鋅)以及其他雜質(包括烴類及經氧化化合 物)°理想地’超純度係指生產具有雜質濃度<0. lwt%,較 佳<lppm ’或甚至<lppb的材料。經氧化雜質典型係來自用 以製備此等有機金屬化合物之溶劑,也來自濕度或氧之其 3 95103 201130857 他不疋來源。當製造電子應用之材料(包括第hi族及第v 族0MC)用於CVD以生產LED用及光電裝置用半導體之化合 物的材料時,或製造ALD用有機金屬前體以生長用於先進 之石夕晶片之薄膜的材料時,達成超純度係重要者。某些雜 質具有對該等有機金屬前體化合物而言為相似之彿點,使 得難以用傳統蒸餾技術達成高純度。 人業經進行很多工作,以改良製備超純有機金屬前體化 5物的合成方法。歷史上,業經藉由批式製程製備有機金 屬前體化合物,但近來,已有如美國專利第6,495,7〇7號 及美國專利公開第2004/0254389號中所揭示之用於生產 有機金屬化合物(如三甲基銦及三曱基鎵)之連續方法。 ^儘管有這些進步,該有機金屬化合物之合成仍困難。 許多該等反應為放熱反應,且大量生產,尤其是以如此高 、吨度之大量生產是困難的。此外,難以規模化(scale)生產 球等材料以適應波動需求’且由於可能引人雜質及降解產 物,因此該等有機金屬化合物之儲存可能為非所欲者。 用於純化之傳統方法係包括蒸顧、結晶、加成物純化、 質量選擇(mass-selective)超離心及與縫合用之化學處 =。雖然此等方法提供某種程度雜質濃度之降低,仍持續 需要生產超純有機金屬化合物,以滿足今天最先進之電子 敦置的效能要求。再者,使用現有方法可達之純度濃度往 轉在經濟限制。㈣科接受之產率敎、能量輸入、 或由於該等雜質及有機金屬化合物之物理及/或化學性質 造成的製程循環時間,過量之資本或操作成本可限制可達 4 95103 201130857 之純度。 舉例而言,可使用芬斯克方程(Fenske Equation)而 基於該等成份之相對揮發性(a )以及所欲純度來計算蒸餾 所需的最小平衡階(stage)數。為了移除最成問題之相近沸 點的雜質(a<l. 2),該階數或理論板相當高度(height equivalent theoretical plate, HETP)數可超過 50、100 或甚至200,以至於即使使用今天最先進之填充(HETp = 0.05至0.20公尺(m)),亦可能需要>1〇公尺之柱高。當 嘗試製備超純材料時,這一尺寸之柱面臨難以擴大規模及 可操作性之挑戰,及就可燃性有機金屬化合物大量存放來 看的安全性問題。 因此,對於製備用作CVD前體之超純有機金屬化合物 的新方法仍有持續的需求。 【發明内容】 、憑藉微通道裝置之益4,本發明滿足前述之需求。微 通道裝置提供製程條件之較佳調控,改善之安全性,以及 自實驗至研發至商業製造之市場化速度。微通道裝置之一 個實例’連續流微反應H,繁助透過傑出之熱及質量傳遞 以調控該反祕件且透過材狀低庫存而最小化反應失控 ί =的溢出之風險,從而達纽善之合成產率及純度。 Γ曰I道裝置進—步藉由增加多個裝置數目,以無效能損 需進行傳統製程規模放大研究而於顯著之時間及成 本=下而滿足市場需要’使得生產規模放大成為可能。 微通道裝置也可以相似之益處用於試劑、溶劑、中間 95103 5 201130857 體或最終產物之分離及純化步驟。於微通道技術中,該等 益處之基礎係來自於該裝置内提供之像得相之間的高交換 率成為可能的高表面積。透過增加介面現象之重要性以及 降低熱及質量傳遞之距離而於該微通道構築維度(典型1 至1000微米)達成分離之提升。於此等裝置中之傑出之熱 及質量傳遞為更有效之分離階段或更低之理論板相當高度 (HETP)提供相之間的高交換率及更佳之溫度調控。這使得 於固定之分離裝置幾何形狀内獲得更高純度之更多階段成 為可能。透過改善能量效率(藉由更佳之熱交換整合),亦 有益於降低資本密集度及降低操作成本。 微通道裝置可用於寬範圍之分離應用,包括蒸餾、吸 附(adsorption)、萃取、吸收(absorption)及氣體汽提β 憑藉微通道裝置之益處,本發明成功地生產超純有機 金屬前體化合物。 於本發明之一個態樣’係提供用於製備超高純度之有 機金屬烧基化合物(organometallie metal alkyl compound)的製程,係包含:將如金屬化鹵化物溶液與燒基 金屬(alkyl metal)溶液於微通道裝置中反應,以產生金属 烧基化合物(metal alkyl compound),其中,所得化合物 係具有化學氣相沉積製程所需之最小純度。 於本發明之第二態樣,係提供製備超高純度之金屬烧 基化合物的方法,係包含:於微通道裝置中純化包含雜質 之有機金屬化合物,以將具有界於0.8〈a<1.5之相對揮發 性(a)之雜質的濃度降低至適用於電子材料應用之濃度。 95103 6 201130857 【實施方式】 如本文中所使用者,術語“金屬函化物,,係指含有金屬 以及至少一個鍵結至該金屬之齒素的化合物。該金屬也可 具有額外之非齒化物取代基。 如本文中所使用者’術語“電子材料應用,,係指包括, 但不限於化學氣相沉積(CVD)、物理氣相沉積(PVD)及其他 蟲晶技術如液相磊晶術(LPE)、分子束磊晶術(MBE)、化學 束磊晶術(CBE)及原子層沉積(ALD)之應用。於電子材料應 用中,具有界於0. 8<a<l. 5之相對揮發性(a)之雜質的濃度 典型係必須低於100 ppm,或者低於lppm。 素”係指氟、氯、溴及碘,且“齒基,,係指氟基、氯 基、溴基及碘基。相似地,“南化”係指氟化、氯化、溴化 及碘化。“烷基”係包括直鏈、分支鏈及環狀的烷基。相似 地,“烯基”及“炔基”係分別包括直鏈、分支鏈及環狀的烯 基及炔基。術語“第IV族金屬,,不意欲包括第1¥族非金屬 如碳。相似地,術語“第vi族金屬,’不意欲包括第VI族砟 金屬如氧及硫。“芳基”係指任何芳香族部份,較佳係芳香 族烴。 冠詞“一’’(外文為“a”或“an”)係指單數及複數。 如本文中所使用者,“CVD,,意欲包括全部形式之化學氣 相沉積,舉例而言:金屬有機化學氣相沉積(M〇CVD)、金屬 有機氣相蟲晶術(M0VPE)、有機金屬氣相磊晶術(〇mvpe)、 有機金屬化學氣相沉積(OMCVD)及遙控電漿化學氣相沉積 (RPCVD)。於CVD製程中,為了滿足使用此等有機金屬化合 95103 7 201130857 物生產之半導體裝置之嚴苛的電效能或光電效能的需求, 有機金屬化合物必須具有至少99. 9999%之純度。 除了另行指明者之外’全部之量係重量百分率,以及 全部比例係莫耳比。全部數值範圍係包括邊值且可以任何 順序組合,除非此等數值範圍明顯限定為其總和至高為 100%。 微通道裝置於化學合成及純化中提供新的機會。微通 道裝置所具有之通遒橫截面維度(寬度)為0. 1至5, 000微 米,較佳1至1,000微米’或更佳1至100微米》微通道 裝置典型係由多個供流體沿平行於主要流動方向流動之通 道所構成。由於通道橫截面維度小,該微通道裝置係具有 高表面積與體積之比,造成高效之質量及熱傳遞。特別地, 質量傳遞係於分子規格上,以及熱傳遞係數可高至25千瓦 /平方米凱氏溫度(square meterKelvin)或更高。供比較 用,傳統外罩反應器之熱傳遞係數典型為〇·丨至〇 2千瓦/ 平方米凱氏溫度。於微通道裝置中之高效質量及熱傳遞允 許對於反應條件如溫度、反應物濃度及停留時間的更緊湊 的調控。對於高純度有機金屬產物之製備而言,溫度調控 係尤其重要者。偏離放熱反應或吸熱反應的恒溫條件可導 致非所欲副產物的量增加,造成較低之產率及產物純度。 於高純度產物之生產中的精確溫度調控降低,或於某些例 中消除對於後續純化之需要,因此降低生產該有機金屬化 合物所需之資源的總量。 由於每一個微通道裝置典型係生產小量之有機金屬 8 95103 201130857 則體,可並聯(in parallel)使用大量微通道裝置。可藉由 在給疋時間點增加或降低微通道裝置的數目來調控藉由該 系列微通道裝置所生產之總體積,因此降低或消除對於產 物儲存之需求。 微通道裝置可自任何傳統材料做成包括’但不限於’ 金屬、聚合物、陶瓷、矽或玻璃。例示性金屬係包括,但 不限於’金屬合金(如來自Haynes International Inc.之 Hastell〇yTM合金,以及沃斯因鐵不鏽鋼(austenitic stainless steels)如 304、312 及 316 不鏽鋼)。製造方法 係包括,但不限於,機械式微機械加工、模製、薄帶成形、 蝕刻、雷射圖形化、沙磨、熱壓花、微影及微立體微影。 該微通道襞置可構築為具有平滑通道壁及/或該通道壁上 具有提升熱及質量傳遞之結構特徵的通道兩者。微反應器 係微通道裝置之一個實例。 於用於施行反應之某些微通道裝置之具體實施態樣 中,該微反應器係包含用於每種試劑之入口。於採用三種 或更多種試劑之反應中,可將兩種或更多種試劑組合並通 過單一入口進料至該微反應器中,其限制條件為試劑之總 數直至位於該微反應區域中才予以組合。舉例而古,當該 反應採用三種試劑時,該等試劑之兩種可通過相同入口共 同進料至該微反應器中,而第三種試劑可通過第二入口進 料。 該微通道裝置可包含經由外部冷卻或加熱來源進行 溫度調控的不同(separate)通道系統。例示性系统包括, 95103 9 201130857 但不限於,熱油、熱水、熱蒸氣、冷油、冷水、冷浴及冷 卻單元。如本文中所使用者,“熱,,係意指超過室溫之溫度, 典型係超過35°C。如本文中所使用者,“冷’,係意指低於室 溫之溫度,典型係低於15。(:。於微反應器之例中,該裝置 係於適用於特定合成反應之溫度操作。 該微通道裝置可復包含用於將入口蒸氣混合之微混 合器。 該微通道裝置可具有1微米至1米或更大範圍之長 度’此係取決於製程需要或裝置製造方法。若需要,可依 序使用多個微通道裝置以達成所欲之總長度。於微反應器 之例中’除了流速及溫度之外,該微通道裝置之長度也藉 由待實施之特定反應的動力學所指定。較慢反應需要較長 之微反應器内停留時間,並據此需要更長之微反應器。此 外’當所欲者係依序反應時,該微反應器可沿著該裝置之 長度或界於裝置之間包含供額外試劑使用之額外入口。 該微通道裝置係包含用於移除產物之出口。於某些具 體實施態樣中’該微通道裝置係包括兩個出口,一個供液 體流使用,另一個供氣體流使用。隨後,來自微反應器之 產物流可使用傳統純化方法、微通道純化或其組合進行純 化。 微反應器之實例係揭示於美國專利第6,537,506號 中’其揭示合併熱傳遞流體路徑、反應物流體路徑、產物 路徑、混合腔及反應腔之堆疊板、多通道反應器。 微通道裝置可視需要含有墊(wick)或膜結構以調控 10 95103 201130857 流體膜厚度並提升介面現象。微通道裝置可用於流體分離 包括蒸餾。微通道裝置於商業重要之蒸餾應用中的應用為 C2分離器,其自乙烯中分離乙烷。該微通道蒸餾製程可減 少用於乙烯生產之能量消耗及資本成本。 本發明係提供用於製備有機金屬化合物之製程,藉由 將金屬鹽與烧基化劑(alkylating agent)於微通道裝置中 反應以生產用於諸如化學氣相沉積之製程的超純烷基金屬 化合物。此外,本發明之烷基化劑自身可為經純化者。 金屬鹽與烷基化劑之組合的實例係包括,但不限於, 於例如微反應器之微通道裝置中將金屬齒化物與三烷基铭 溶液反應’將金屬_化物溶液與鹵化烷基鎂反應,或將金 屬鹵化物溶液與烷基鋰溶液反應,以生產烷基金屬化合 物。於某些具體實施態樣中,烷基化劑與金屬鹽之莫耳比 係大於或等於1。於某些具體實施態樣中,該莫耳比係大 於或等於2。於某些具體實施態樣中,該莫耳比係大於或 等於3。 該金屬S化物可包含第II族、第III族、第Iv族或 第V族之金屬。該金屬齒化物中存在足夠數目之齒素以形 成中性化合物。例示性金屬齒化物係包括,但不限於, Z11CI2、GaCh、InCh、InBn、Inl3、GeCh、SiCl4、snci4、 PC13、AsC13、SbCl3及 BiCh。 該三烷基鋁溶液係包含三個烷基,其可相同或不同。 每個烧基係包含1個至8個碳原子。該等烧基可為直^、 分支鏈或環狀。該i化烷基鎂及烷基鋰化合物係包含具有 95103 11 201130857 1個至8個碳原子之單—㈣基。類似地,該粒基可為 直鏈、分支鏈或環狀。 該金屬鹽溶液及該院基化劑溶液可包含任何有機溶 劑,該溶劑對於該兩種成分間之反應呈惰性以及對自該反 之任何產物亦呈惰性。於某些具體實施態樣中,該 金屬^容液係不含溶劑,亦即,該金屬鹽係已經呈液體形 式且以“純的(neat),,狀態加入。々 该>谷劑應選擇為提供足夠 用Γ使得反應進行。該金屬鹽溶液與魏基化劑 =液相同或不同之溶劑。特別適當之有機溶劑係包 括,但不限於’烴類及芳香族 ^ ,^ ^ ^ 、工類。例示性有機溶劑係包 括但不限於,笨;經院基取代之笨,如甲苯、二甲笨及 (C4-C2°)院基苯如(Cl〇-Cl2)烷基笨及rr 及脂肪族烴類如戊燒、己燒、二该基聯苯;以 ^ s 70辛烷、癸烷、十二烷、 鯊烷、%戊烷、%己烷及環庚⑥;以及 該有機溶劑係笨、甲苯、二甲笼 、代口 較佳也, 庚烧、環戊烧或環己燒。適宜者俜^2。)烧基苯、己院、 有機溶劑。此等有機溶劑通常地使用超過一種 Chemicals (Milwaukee,Wis ) 來/原如 Aldrich 接使用,或較佳地,於使用之此等㈣可直 了此等有機溶劑係於使用之前乾燥以及去氧。 =:段將:==、於真― 句括气贪备-^ 進仃去氣。適當之惰性氣體係 匕括絲、氮減减,較佳錢氣或氣氣。 於另外之具體實施態樣中,將採用離子液體⑹仏 95103 12 201130857 liquid)作為溶劑’係慮及離子液體不與有機金屬合成相立 作用並&供環境友好之綠色環保溶劑離子液體通常為 於低溫為液體之鹽,具有低於10(rc之熔點。多數離子液 體於室溫保持為液相,且稱為室溫離子液體。離子液體完 全由離子構成,且典型地,他們係由大體積有機陽離子及 無機陰離子構成。由於此等化合物中之高庫余引力,離子 液體實際上不具有蒸氣壓。 任何適當之離子液體可用於本發明中。用於離子液體 之例示性陽離子係包括,但不限於,烴基錢 (hydrocarbylammonium)陽離子、烴基填錯 (hydrocarbylphosphonium)陽離子、烴基吼啶鏽 (hydrocarbylpyridinium)陽離子及二烴基咪唑鑷 (dihydrocarbylimidazolium)陽離子。適用於本發明之離 子液體之例示性陰離子係包括,但不限於,氯金屬酸根 (chlorometalate)陰離子、氟硼酸根陰離子如四氟硼酸根 陰離子及經烴基取代之氟硼酸根陰離子、以及氟磷酸根陰 離子如六氟磷酸根陰離子及經烴基取代之氟磷酸根陰離 子。氯金屬酸根陰離子之實例係包括,但不限於,氣鋁酸 根陰離子如四氣鋁酸根陰離子及氯三烷基鋁酸根陰離子、 氣鎵酸根陰離子如氯三曱基鎵酸根及四氯鎵酸根、氣銦酸 根陰離子如四氣銦酸根及氯三甲基銦酸根。 適當之氣鋁酸根系離子液體係包括,但不限於,彼等 具有經烴基取代之i化銨、經烴基取代之磷鏽函化物、經 經基取代之°比°疋錄_化物成經烴基取代之味β坐鐵齒化物 13 95103 201130857 者。例示性氣鋁酸根系離子液體係包括,但不限於,氣鋁 酸三甲基苯基銨(TMPACA)、氣鋁酸苄基三曱基銨(BTMACA)、 氣鋁酸苄基三乙基銨(BTEACA)、氣鋁酸苄基三丁基銨 (BTBACA)、氣鋁酸三曱基苯基磷鏽(TMPPCA)、氣鋁酸苄基 三曱基磷鏽(BTMPCA)、氣鋁酸苄基三乙基磷鏽(BTEPCA)、 氣鋁酸苄基三丁基磷鏽(BTBPCA)、氣鋁酸1-丁基-4-曱基 吡啶鏽(BMPYCA)、氣鋁酸卜丁基吡啶鏽(BPYCA)、氯鋁酸 3-曱基-1-丙基°比咬鏽(MPPYCA)、氯紹酸1-丁基-3-甲基0米 唑鏽(BMIMCA)、氯鋁酸1-乙基-3-曱基咪唑鏽(EMIMCA)、 溴-三氣鋁酸1-乙基-3-甲基咪唑鏽(EMIMBTCA)、氯鋁酸1-己基-3-曱基咪唑鑌(HMIMCA)、氣三曱基鋁酸苄基三曱基銨 (BTMACTMA)、以及氣鋁酸1-曱基-3-辛基咪唑鏽(M0IMCA)。 其他適當之離子液體係包括彼等具有氟硼酸根陰離 子或氟墙酸根陰離子者,例如但不限於,氟删酸三曱基苯 基銨(TMPAFB)、氟硼酸苄基三曱基銨(BTMAFB)、氟硼酸苄 基三乙基銨(BTEAFB)、氟硼酸苄基三丁基銨(BTBAFB)、氟 硼酸三甲基苯基磷鏽(TMPPFB)、氟硼酸苄基三曱基磷鏽 (BTMPFB)、氟硼酸苄基三乙基磷鏽(BTEPFB)、氟硼酸苄基 三丁基礙鏽(BTBPFB)、氟侧酸1-丁基-4-曱基η比咬鑌 (BMPFB)、氟硼酸1-丁基吡啶鏽(BPFB)、氟硼酸3-曱基-1-丙基D比咬鏽(MPPFB)、氟硼酸1-丁基—3-曱基咪唑鏽 (BMIMFB)、氟硼酸1-乙基-3-甲基咪唑鏽(EMIMFB)、溴三 氟代删酸1-乙基-3-曱基咪唑鏽(EMIMBTFB)、氟硼酸卜己 基-3-曱基咪唑鏽(HMIMFB)、氟硼酸卜曱基_3一辛基咪唑鏽 14 95103 201130857 (MOIMFB)、以及氟磷酸苄基三甲基銨(BTMAFp)。 離子液體通常可商業地購得或可藉由該技術領域中 已知之方法製備。此等化合物可直接使用或可經進一步純 化。 此等溶液之濃度及量係經選擇而使得該烷基化劑化 合物與該金屬鹽之莫耳比係大於或等於特定之烷基化反應 之化學計量學之需要。 該金屬鹵化物與三烷基鋁溶液之反應可於_1〇〇c至 100°C施行。可用之壓力為i至10巴(bar)。 該金屬齒化物溶液與齒化烷基鎂或烷基鋰溶液之反 應V於-5(TC至5(TC施行。可用之壓力為1至10巴。 於本發明之另一具體實施態樣中,係提供製備作為適用 於原子層沉積(ALD)之可用來源之金屬脒(metal amidinate) 化合物的方法。該金屬脒化合物係適用於作為ald前體使 用之有機金屬化合物,具有式其 中’V'R2及R3係獨立選自Khto-CO烷基、(C2-C6)烯基、 (o*c〇炔基、二烷基胺基、二(經矽烷基取代之烷基)胺 基、二矽烷基胺基、二(經烷基取代之矽烷基)胺基及芳基; Μ為金屬;L1為陰離子性配位子;l2為中性配位子;m為Μ 之價數;η=0至6 ; ρ=〇至3 ;以及其中,m2 η。金屬脒之 本質可係均配物(homoleptic)或雜配物,亦即,可包含不 同之脒配位子(amidinate ligand)或脒配位子與其他陰離 子性配位子之組合。此等化合物係適用於多種氣相沉積方 法’如化學氣相沉積(CVD),以及特別適用於原子層沉積 15 95103 201130857 (ALD)。亦提供包括上揭化合物與有機溶劑之組成物。此組 成物特別適用於ALD與直接液體注射(dli)製程。 製備有機金屬脉化合物之方法係包含,將金属齒化物 溶液與脒基鋰(amidinato lithium)溶液於諸如微反應器 之微通道裝置中反應,以生產金屬烷基脒(metal alkylamidinate)化合物,其中,該脒基鋰化合物與金屬鹵 化物之莫耳比係大於或等於1。於某些具體實施態樣中, 該莫耳比係大於或等於2。於某些具體實施態樣中,該莫 耳比係大於或等於3。 該金屬_化物可包含第π族至第VIII族之金屬。該 金屬函化物中存在足夠數目之齒素以形成中性化合物。例 示性金屬齒化物係包括,但不限於,ZnCh、GaCh、InBn、 A1C13、HfCl4、ZrCl4 ' GeCl4、SiCl4、TaCl5、WC16、SbCl3 及 R11CI3。 該脉基鐘化合物係包含單一脉基,該肺基係包含具有 1個至8個碳原子之烧基或芳基或環狀基。該等院基可係 直鏈、分支鏈或環狀基。 該金屬齒化物溶液及該脒基鋰溶液可包含任何溶劑, 該溶劑對於金屬齒化物與脒基鐘溶液間之反應呈惰性以及 對自該^應獲得之任何產物亦呈惰性。該等溶劑與試劑必 須被乾燥以及去氧。該溶劑應選擇為提供足夠之溶解度, 以使得反應進行。該金屬齒化物溶液與該脉絲溶液可使 用相同或不同之溶劑。例示性溶劑係包括,但不限於前述 万|1诂去。 95103 16 201130857 樣中’金屬鹵化物溶液係不含溶 ⑷亦即4金屬齒化物係已經呈液體形式且以“純的,,狀 =入。此等减之I度及量係經選擇而使得該脒基裡化 口 =與該金屬自化物之莫耳比係大於或等於之反應 化學計量學之需要。 巴 該反應可於—阶至咐施行。可狀壓力為!至 10 #二=實施態樣中’製備有機金屬化合物之方法 物轉料基金聽祕三級胺、三 置C如;—_之混合物的存在下,於微通道裝 置(如微反應器)中施行。 :- ::I合物於三級胺、三級膦、或三級胺 二=膦之混&物的存在下於有機溶财反應,以提供院 屬化°物’其中,每個R係獨立選自Η、烧基、烯基、 炔基及芳基1係選自第Ιν族金屬及第π族金屬;每個χ 係獨立為鹵素;每個R4係獨立選自(Μ)烧基;Μΐ為第工ι『 族金屬·,每個&係獨立為自素^為^至^以及〇為1 至3。該第IV族金屬齒化物與該第VI族金屬齒化物通常 可自諸如Gelest公司(Tullytown,Pa.)商業地購得,或可 藉由文獻中已知之方法製備。此等化合物可直接使用或於 使用之前先純化。技術領域中具有通常知識者應知悉,可 使用超過一種金屬齒化物、超過一種第111族化合物、以 及其組合。 95103 17 201130857 例示性第i v族金屬係包括,但不限於,石夕、錯及錫。 例示性第VI族金屬係包括,但不限於,碲及硒。Μ較佳係 矽、鍺或錫,更佳係鍺。X可為任何鹵素。每個X可相同 或不同。於一具體實施態樣中,m = 0。當m = 0時,係使 用第IV族或第VI族金屬四鹵化物。於其他具體實施態樣 中,m可為1、2或3。 廣泛種類之烷基、烯基及炔基可用於R。適當之烷基 包括,而不限於,(C1-C12)烧基,典型為(Ci-Ce)烧基,更典 型為(G-C4)烷基。於一具體實施態樣中,該等烷基係大體 積烷基。“大體積烷基”係意指任何空間位阻之烷基。此等 大體積烷基係具有至少3個碳,此基中碳之數目並無特定 之上限。較佳地,該等大體積烷基係個別具有3個至6個 碳原子,更佳3個至5個碳原子。此等大體積烷基較佳係 非直鏈,較佳係環狀或分支鏈。例示性烧基係包括曱基、 乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第 三丁基、戊基、環戊基、己基及環己基。更典型地,適當 之烷基係包括乙基、異丙基及第三丁基、適當之烯基係包 括,但不限於,(C2-Cl2)稀基,典型為(C2-C6)婦基,更典型 為(C2_C4)烯基。例示性烯基係包括乙烯基、烯丙基、曱基 烯丙基及巴豆基。典型之炔基係包括,但不限於,(C2-C12) 炔基,典型為(C2-C6)炔基,更典型為(C2-C4)炔基。適當之 芳基係(C6-Cl0)芳基,包括但不限於,苯基、曱苯基、二曱 苯基、苄基及苯乙基。當存在兩個或更多個烷基、烯基或 炔基時,此等基可相同或不同。 18 95103 201130857 取:,基、块基或芳基可視需要經 其、株A ,一一烷基胺基取代。“經取代,,係意指該烷 ;岑-二^炔基或芳基上之一個或多個氫經-個或多個鹵 素或一燒基胺基置換。 廣泛種類之第111族化合物。可用於本發明之 個田化合物典型係具有式R4nM,XVn,其中,每 :、、蜀立選自(Cl-C6)烧基;M1為第⑴八族金屬;X、 及η為!至3之整數。Ml適當地為蝴、銘、嫁、 :及1:’且較佳為鋁。較佳地’χ1係選自a、氯或溴。適 ;之燒基係包括,但不限於,甲基、乙基、正丙基、 異^土 JE丁基、異丁基及第三丁基。較佳之院基係包括 甲土乙基、正丙基及異丙基。於一具體實施態樣中,n 為3。其中η為3之此第⑴族化合物係包括三烧基棚、 三烷基鋁、三烷基鎵、三烷基銦及三烷基鉈, 化合物係難者。歸狀越實施紐中,以^ 其中η為1至2之此等第⑴請化合物係包括函化二烧基 鋁如氣化二烷基鋁。第ΠΙ族化合物通常可自多種來源如 Gelest公司商業地購得’或可藉由文獻中已知之多種方法 製備。此等化合物可直接使用或於使用之前純化。 適§之二級胺係包括,但不限於,彼等具有通式 者’其中,R5、R6及r7係獨立選自(G-CO燒基、經二(Ci_c6) 烷基胺基取代之(C!-C6)烷基、以及苯基,以及其中^與R6 可與其所連接之氮原子一起形成5員至7員雜環。此雜環 可為芳香族或非芳香族。特別適當之三級胺係包括,但不 95103 19 201130857 限於,三曱胺、三乙胺、三正丙基胺、三正丁基胺、三異 丙基胺、三異丁基胺、二曱胺基環己烷、二乙胺基環己烷、 二甲胺基環戊烷、二乙胺基環戊烷、N-甲基吡咯啶、N_乙 基吡咯啶、N-正丙基吡咯啶、N-異丙基吡咯啶、N-甲基哌 咬、N-乙基α底咬、N-正丙基°底σ定、N-異丙基。底σ定、Ν, Ν’ -二甲基哌哄、Ν, Ν’ -二乙基哌畊、Ν,Ν’ -二丙基哌畊、 Ν,Ν,Ν’,Ν’ -四曱基-1,2-二胺基乙烷、吡啶、吡畊、嘧啶 及其混合物。較佳之胺係包括三曱胺、三乙胺、三正丙基 胺、三異丙基胺、及三正丁基胺。於一具體實施態樣中, 該三級胺係三乙胺或三正丙基胺。 例示性三級膦係包括,而非限制,彼等具有通式R8R9R10P 者,其中,R8、R9及R1(l係獨立選自(G-Ce)烷基、苯基及經 (G-Ce)烷基取代之苯基。適當之三級膦係包括三乙基膦、 三丙基膦、三丁基膦、苯基二甲基膦、苯基二乙基膦及丁 基二乙基膦。 技術領域中具有通常知識者應知悉,可使用超過一種 之三級胺或三級膦。也可使用三級胺及三級膦之混合物。 此等三級胺及三級膦係通常可自多種來源商業地購得。此 等三級胺及三級膦可直接使用,或較佳地,於使用之前進 一步純化。 可使用廣泛種類之有機溶劑。典型地,此等有機溶劑 不含有經氧化者如醚鏈結,且較佳係不含氧。例示性有機 溶劑係包括,但不限於,烴類及芳香族烴類。適當之有機 溶劑係包括,而不限於,苯、甲苯、二甲苯、戊烷、己烷、 20 95103 201130857 庚烧、辛炫、癸烧、十二烧、鯊烧、環戊烧、環己烧、環 庚烷及其混合物。適宜地,較佳可將超過一種之有機溶劑 用於本發明中。於另外之具體實施態樣中,該三級胺可用 作該有機溶劑。此等有機溶劑通常可自多種來源如 Aldrich Chemicals (Milwaukee,Wis.)商業地購得。此等 溶劑可直接使用,或較佳地,於使用之前純化。 較佳地,此等有機溶劑係於使用之前去氧。可藉由各 種手段,如以惰性氣體沖洗、於真空對溶劑進行脫氣或其 組合,將該等溶劑進行去氧。適當之惰性氣體係包括氬氣、 氮氣及氦氣,較佳係氬氣或氮氣。 所使用之具體之三級胺、三級膦及有機溶劑係取決於 所欲之特定之烷基金屬化合物。舉例而言,該有機溶劑及 三級胺可經選擇而使得他們比所欲之烷基金屬化合物具更 多揮發性或更少揮發性。此等揮發性之差異使該烷基金屬 化合物與該胺及有機溶劑兩者更容易分離。該三級胺及該 有機溶劑之選擇係屬於技術領域中具有通常知識者能力範 圍之内。 通常,該三級胺及/或三級膦係以該第IIIA族化合物 之化學計量學之量存在。該金屬化物與該第IIIA族化合 物之莫耳比可於寬範圍内變動,如自l:〇. 1至1:5,特定 之莫耳比係取決於所欲之烷基金屬化合物。另一適當之莫 耳比範圍係自1:0. 5至1:2。亦預期超過1:5之莫耳比係 有效者。 可藉由選擇該金屬鹵化物與該第IIIA族化合物之莫 21 95103 201130857 耳比來調控自本方法獲得之特定之貌基金屬化合物,亦 即,可藉由第III族化合物之莫耳數來調控該金屬齒化物 化合物中被置換之齒素的數目。舉例而言,於如四氣化鍺 之第IV族金屬四齒化物(A)與如三甲基銘之三烧基銘(β) 之反應中,1:0. 5(Α:Β)之莫耳比係提供烷基第丨7族金屬三 鹵化物;1:1(Α:Β)之莫耳比係提供二烷基第IV族金屬二鹵 化物;1:1. 5(Α:Β)之莫耳比係提供三烷基第ιν族金屬鹵化 物;以及1:2(Α:Β)之莫耳比係提供四烷基第ιν族金屬。 因此,根據本發明之方法,該金屬齒化物之一個、兩個、 三個或四個齒素可經置換。 於一具體實施態樣中’可在與該金屬齒化物反應之 前,以任何順序將該第III族化合物、三級胺及/或三級膦 及有機溶劑組合。於再一具體實施態樣中,首先係將該第 111族化合物與該三級胺及/或三級膦組合以形成胺-第 III族加成物或膦-第III族加成物。典型地,該胺-第ill 族加成物可於寬範圍之溫度形成。形成該加成物之適當之 溫度係環境溫度至90°C。隨後,該金屬齒化物與該胺一第 III族加成物反應以形成所欲之烷基金屬化合物。較佳係 將該金屬鹵化物以純化合物或呈烴溶液滴加至該胺-第 III族加成物中。或者,該胺-第III族加成物可以純化合 物或呈烴溶液滴加至該金屬鹵化物中。用以形成該烷基金 屬化合物之適當之溫度係環境溫度至80°C。因此,於一具 體實施態樣中,本發明係提供用於製備烷基金屬化合物之 方法,係包含將第III族化合物與三級胺於不含經氧化之 22 95103 201130857 物質的有機溶劑中反應以形成胺_第HI族加成物;以及將 該胺-第III族加成物與第IV族金屬齒化物、第VIA族金 屬鹵化物或其混合物於該有機溶劑中反應。當於上揭反應 中使用三級膦時’形成膦-第ΠΙ族加成物。 於另一具體實施態樣中,可在與該三級胺及/或三級 膦混合之前,將該金屬齒化物與該第ΙΠ族化合物及視需 要之有機溶劑組合。隨後,使用該微通道裝置内之適當的 混合區域或傳統外部攪動技術將該三級胺及/或三級膦及 視需要之有機溶劑與該金屬_化物_第ΙΙΙΑ族化合物混合 物組合。或者,可將該金屬4化物_第ΠΙ族化合物加入該 二級胺及/或二級膦及視需要之有機溶劑中。雖非欲為理論 所束缚,咸信,直至將該金屬齒化物、第ηΙ族化合物及 二級細組合時’該轉燒基化(transalkylation)反應方才開 始0 或者,可以連續之方式製備該烷基金屬化合物。舉例 而言,可將該金屬i化物與該第ΙΠ族化合物以連續之方 式獨立加入微通道反應器中,並於適當有機溶劑(如芳香族 或脂肪族烴)+與三級胺及/或三級膦接觸。可藉由多種適 當之手段(如藉由使用質量流調控器)調控該金屬_化物與 該第III族化合物之添加。於此連續製程中,可在將該金 屬鹵化物與第ΠΙ族化合物添加至該反應區域中之同時, 藉由諸如蒸餾來回收所欲之烷基金屬化合物。於再一替代 者中,可將該金屬i化物與該第Ιπ族化合物之混合物於 適當之溶劑中與該三級胺及/或三級膦組合。於此連續製程 95103 23 201130857 中,可在將該金屬豳化物/第in族化合物之混合物添加至 該反應區域中之同時,藉由諸如蒸餾來回收所欲之燒美金 屬化合物。 該有機金屬化合物可直接使用或適當地藉由多種技 術如蒸館、昇華及再結晶予以純化。本發明之方法係提供 實質上不含金屬雜質如鋁、鎵、銦、鎘、汞及鋅之有機金 屬化合物。該等有機金屬化合物亦實質上不含經氣化之雜 質如醚化溶劑(ethereal solvent),且較佳係不含此等經 氧化之雜質。“實質上不含”係意指該化合物含有低於〇 5 ppm之此等雜質。本發明之有機金屬化合物係具有至少 99.99重量%之純度,或者99.9999重量%之純度。具體而 言,以重量計,本發明之有機金屬化合物所包含雜質之濃 度係低於lOOppm至低於lppm。 可使用微通道裝置進一步純化用於電子材料應用之 超高純度之有機金屬化合物。該微通道裝置可用以純化該 等反應物、中間體、或最終產物或其組合,以達成用於電 子應用之超高純度化合物。該有機金屬化合物可於如上揭 者之微通道反應器中製備’或於傳統反應器(包括批式攪拌 槽、半批式連續流半槽、連續流管式反應器、反應性蒸 餾反應器)中製備、及其他已知之方法製備。由於傳統方法 之低濃度驅動力,用於電子應用的超高純度材料往往難以 透過傳統熱分離方法如蒸餾及昇華、或質量傳遞分離方法 如萃取、吸收及吸附達成。 含有具相近沸點之雜質(相對揮發性,〇· 8<a<1. 5,其 95103 24 201130857 中’ a=該雜質之蒸乳壓/所欲之純化合物的蒸氣壓)的有機 金屬化合物尤其難以透過具有傳統填充之分段(staged)蒸 餾製程予以純化°該柱可需要大階數如>50、>1〇〇、有時〉 200,或高回流比如>1〇、>20、有時>50,或兩者,這增加 製程之投資及操作成本以及複雜性。該微通道裝置提供此 等問題之經改良的解決方法。小的通道維度生成更高之傳 送梯度以加強熱及質量傳遞,以及增加之柱表面而於固定 之幾何形狀中提供更高之有效交換面積。兩個因素貢獻更 有效之分離(較小的理論板相當高度,HETP)純化,尤其有 益於獲得高純度。 也可藉由吸附性或化學純化技術(如加成物純化)於 微通道裝置生產超高純度有機金屬化合物。可於微通道表 面支撐選擇性吸附劑或加成物形成路易斯鹼 (adduct-forming Lewis base)如胺、膦或醚,提供非常高 之交換面積以接觸含有雜質之流。可提供供熱傳遞流體流 動用的其他微通道,從而精確地調控該裝置之溫度,以有 效地進行吸附步驟與解吸附步驟間的調節及循環。 基於微通道技術之分離製程’如蒸顧、汽提、萃取及 吸附,提供達成超純產物(ppm,ppb)所需之提升的熱及質 量傳遞。此等分離製程額外提供解決將具有相似沸點(相對 揮發性,0.8<a<l. 5)之液體混合物分離成高純度濃度之問 題所需之傳遞階的強化。有利的較佳之操作條件係包括溫 度及壓力,其中,該液體成分之一種或多種係位於該液相 中,且能進行轉變成氣相狀態或至經吸附於吸收劑上之狀 95103 25 201130857 態的相變化。這可包括25°C至250°C之溫度及〇. ipa至10 MPa之壓力。進料雜質濃度可自該流體混合物之lppm高至 10wt%或甚至 50 wt〇/〇。 本發明之有機金屬化合物特別適用於在全部氣相沉 積方法如 LPE、MBE、CBE、ALD、CVD、M0CVD 及 M0VPE 中作 為前體使用。本發明之化合物係適用於沉積含有一種或多 種第IV族、第VI族或第IV族與第VI族金屬的膜。此等 膜係有用於製造電子裝置例如,但不限於,積體電路、光 電裝置及發光二極體。 第IV族及/或第VI族金屬之膜典型係藉由下述者予 以沉積··首先將所欲之烷基金屬化合物(亦即,來源化合物 或前體化合物)置於具有與沉積腔相連接之出口的運輸裝 置(如圓筒柱)中。取決於所使用之特定之沉積設備,·^使 用多種圓筒柱。當該前體化合物為固體時,可使用於美國 專利第6, 444, 038號(Rangarajan等人)及美國專利第 6, 607, 785號(Timmons等人)中揭露之圓筒柱以及其他設 計。對於液體前體化合物,可使用美國專利第4, 506,815 號(Melas等人)及美國專利第5,755,885號(Mikoshiba等 人)中揭露之圓筒柱以及其他液體前體圓筒柱。該來源化合 物係呈液體或固體保持於該等圓筒柱中。固體來源化合物 典型係於傳輸至該沉積腔之前予以蒸發或昇華。 該等來源化合物典型係藉由使載氣穿過該圓筒柱而傳 輸至該沉積腔中。適當之載氣係包括氮氣、氫氣及其混合 物。通常,該載氣係引入該來源化合物之表面下,且上行 26 95103 201130857 通過該來源化合物至其上之頂部空間,將來該來源化合物 之苽氧裹挾或運載至該載氣中。隨後,經裹挾或運載之蒸 氣進入該 >冗積腔中。 該沉積腔典型係其内部配置有至少一種(且可能多種) 基材之經加熱之容器。該沉積腔係具有出口,其典型連接 至真空泵,以將副產物自該腔中抽出且提供適宜之減壓。 可於大氣壓錢壓下施行·VD。該沉積腔絲持於足夠 同之/JBL度以誘發該來源化合物之分解。該沉積腔溫度係 200 C至1200°C ’最適化所選擇之確切溫度以提供有效沉 積。視需要’若該基材係維持於升高之溫度,或如果有 來源產生其他能量如射頻(radio freqUenCy,RF)能量,該 沉積腔内整體之溫度可降低。 於電子裝置製造之例中,用於沉積之適當之基材可為 石夕、钟化鎵、碟化銦等。此等基材可含有—層或多層額外 之材料層例如,但不限於,介電層及導電層如金屬。此等 基材特別適用於製造積體電路、光電裝置及發光二極體。 將沉積持續所欲之時間,以生產具有所欲性質的膜。 典型地’纽積停止時,_之厚度可自幾百埃至幾十奈 米至幾百微米或更厚。 下述實施例係預期以進一步例示性說明本發明之各 種態樣,但非欲以於任何方面限制本發明之料。全部操 作係於惰性氣氛’典型於乾燥氮氣之氣氛下予以施行。’、 [實施例] 比較例#1 95103 27 201130857 根據下述方程式合成四曱基鍺烷:201130857 VI. INSTRUCTIONS: Based on 35 USC § 119(e), this application claims US Provisional Application No. 60/961,370, filed on July 20, 2007, and proposed on June 30, 2008. Priority of Provisional Application No. 12215828. TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of preparing an organometallic compound (OMC). In particular, the present invention is directed to a method of preparing a high purity organometallic compound for use in a process such as chemical vapor deposition. [Prior Art] Various means such as chemical vapor deposition (CVD), physical vapor deposition (PVD), and other epitaxial techniques such as liquid phase epitaxy (LPE), molecular beam epitaxy (MBE), chemistry Beam epitaxy (CBE) and atomic layer deposition (ALD) deposit a metal film on a surface such as a non-conductive (electronic material application) surface. A chemical vapor deposition process, such as organometallic chemical vapor deposition (MOCVD), is deposited by decomposing an organometallic precursor compound at atmospheric pressure (ie, above room temperature) at atmospheric pressure or under reduced pressure. Metal layer. A variety of metals can be deposited using these CVD or MOCVD processes. For semiconductor and electronic device applications, the organometallic precursor compound must be ultrapure and be substantially free of measurable levels of metal impurities (eg, ε and zinc) and other impurities (including hydrocarbons and Oxidized compound) ° ideally 'ultra-purity means that the production has impurity concentration <0. lwt%, better <lppm ’ or even <lppb material. The oxidized impurities are typically derived from solvents used to prepare such organometallic compounds, also from humidity or oxygen. 3 95103 201130857 He does not deplete the source. When manufacturing materials for electronic applications (including hi and v-group 0MC) for CVD to produce materials for compounds for semiconductors for LEDs and optoelectronic devices, or for the production of organometallic precursors for ALD for growth in advanced stone In the case of the material of the film of the wafer, it is important to achieve ultra-purity. Some impurities have similar points for these organometallic precursor compounds, making it difficult to achieve high purity using conventional distillation techniques. A lot of work has been done in the human industry to improve the synthesis of ultrapure organometallic precursors. Historically, organometallic precursor compounds have been prepared by a batch process, but recently, for the production of organometallic compounds as disclosed in U.S. Patent No. 6,495,7,7 and U.S. Patent Publication No. 2004/0254389, A continuous process such as trimethylindium and tris-gallium. ^ Despite these advances, the synthesis of organometallic compounds is still difficult. Many of these reactions are exothermic and are produced in large quantities, especially in such high, tonnage mass production. In addition, it is difficult to scale the production of materials such as spheres to accommodate fluctuations in demand' and because of the potential for introduction of impurities and degradation products, the storage of such organometallic compounds may be undesirable. Conventional methods for purification include steaming, crystallization, adduct purification, mass-selective ultracentrifugation, and chemistry for suturing. Although these methods provide some reduction in the concentration of impurities, there is a continuing need to produce ultrapure organometallic compounds to meet the performance requirements of today's most advanced electronic devices. Furthermore, the purity concentration that can be achieved using existing methods is shifting to economic constraints. (iv) The yields received by the Section, energy input, or process cycle time due to the physical and/or chemical nature of such impurities and organometallic compounds, excessive capital or operating costs may limit the purity up to 4 95103 201130857. For example, the Fenske Equation can be used to calculate the minimum equilibrium number of stages required for distillation based on the relative volatility (a) of the components and the desired purity. In order to remove the most problematic near-boiling impurities (a <l. 2), the order or the theoretical height of the theoretical plate (HETP) can exceed 50, 100 or even 200, so that even with the most advanced filling today (HETp = 0.05 to 0.20 m) (m)) may also require a column height of >1 metre. When attempting to prepare ultrapure materials, columns of this size face the challenge of being difficult to scale and operability, as well as the safety issues associated with the large storage of flammable organometallic compounds. Therefore, there is a continuing need for new methods for preparing ultrapure organometallic compounds for use as CVD precursors. SUMMARY OF THE INVENTION The present invention satisfies the aforementioned needs by virtue of the benefit of the microchannel device 4. Microchannel devices provide better control of process conditions, improved safety, and market speed from experimentation to R&D to commercial manufacturing. An example of a microchannel device 'continuous flow microreaction H, which helps to regulate the anti-mystery through outstanding heat and mass transfer and minimizes the risk of spillage through the low-inventory material, thus reaching New Zealand Synthetic yield and purity. In order to increase the number of devices, it is possible to perform the conventional process scale-up study with ineffective energy loss and meet the market demand at a significant time and cost = making the scale of production possible. Microchannel devices can also be used for similar separations and purification steps for reagents, solvents, intermediate 95103 5 201130857 bodies or final products. In microchannel technology, the basis for such benefits is the high surface area from which high exchange rates between the image phases provided within the device are possible. The separation is achieved in the microchannel construction dimension (typically 1 to 1000 microns) by increasing the importance of the interface phenomenon and reducing the distance of heat and mass transfer. The outstanding heat and mass transfer in these devices provides a high exchange rate between phases and better temperature regulation for a more efficient separation stage or lower theoretical plate equivalent height (HETP). This makes it possible to obtain more stages of higher purity within the fixed separation device geometry. By improving energy efficiency (by better heat exchange integration), it is also beneficial to reduce capital intensity and reduce operating costs. Microchannel devices are useful for a wide range of separation applications, including distillation, adsorption, extraction, absorption, and gas stripping. By virtue of the benefits of microchannel devices, the present invention successfully produces ultrapure organometallic precursor compounds. One aspect of the present invention provides a process for preparing an ultra-high purity organometalliclie metal alkyl compound comprising: a metal halide solution and an alkyl metal solution; The reaction is carried out in a microchannel device to produce a metal alkyl compound, wherein the resulting compound has the minimum purity required for a chemical vapor deposition process. In a second aspect of the invention, there is provided a method of preparing an ultrahigh purity metal alkylate comprising: purifying an organometallic compound comprising an impurity in a microchannel device to have a bound of 0.8 < a <1.5 Relative Volatile (a) The concentration of impurities is reduced to a concentration suitable for electronic material applications. 95103 6 201130857 [Embodiment] As used herein, the term "metal complex" refers to a compound containing a metal and at least one dentate bonded to the metal. The metal may also have an additional non-dentate substitution. As used herein, the term 'electronic material' refers to, but is not limited to, chemical vapor deposition (CVD), physical vapor deposition (PVD), and other insect crystal techniques such as liquid phase epitaxy ( LPE), molecular beam epitaxy (MBE), chemical beam epitaxy (CBE) and atomic layer deposition (ALD) applications. In the case of an electronic material application, having a boundary of 0.88 <a <1.5. Relative volatility (a) The concentration of impurities typically must be less than 100 ppm, or less than 1 ppm. "" means "fluorine, chlorine, bromine and iodine, and "dentate radical" means fluoro, chloro, bromo and iodo. Similarly, "naned" refers to fluorination, chlorination, bromination, and iodination. "Alkyl" is meant to include straight chain, branched chain, and cyclic alkyl groups. Similarly, "alkenyl" and "alkynyl" include straight-chain, branched-chain, and cyclic alkenyl and alkynyl groups, respectively. The term "Group IV metal" is not intended to include a Group 1 non-metal such as carbon. Similarly, the term "Group VII metal" is not intended to include Group VI ruthenium metals such as oxygen and sulfur. "Aryl" means any aromatic moiety, preferably an aromatic hydrocarbon. The article "a" ("a" or "an" in the text) refers to both singular and plural. As used herein, "CVD," is intended to include all forms of chemical vapor deposition, for example: metal organic chemistry Vapor deposition (M〇CVD), metal organic vapor phase microscopy (M0VPE), organometallic vapor phase epitaxy (〇mvpe), organometallic chemical vapor deposition (OMCVD) and remote controlled plasma chemical vapor deposition ( RPCVD). In the CVD process, the organometallic compound must have a purity of at least 99.9999% in order to meet the demand for the electrical or photovoltaic performance of the semiconductor device produced by the use of the organic metal compound 95103 7 201130857. All weights are by weight unless otherwise indicated, and all ratios are molar ratios. All numerical ranges are inclusive and can be combined in any order, unless such numerical ranges are Microchannel devices offer new opportunities in chemical synthesis and purification. The microchannel device has a cross-sectional dimension (width) of from 0.1 to 5,000 micrometers, preferably from 1 to 1,000 micrometers or more preferably from 1 to 100 micrometers. The fluid is formed in a channel that flows parallel to the main flow direction. Due to the small cross-sectional dimension of the channel, the microchannel device has a high surface area to volume ratio resulting in efficient mass and heat transfer. In particular, mass transfer is based on molecular specifications and the heat transfer coefficient can be as high as 25 kilowatts per square meter Kelvin (square meter Kelvin) or higher. For comparison, the heat transfer coefficient of a conventional housing reactor is typically from 〇·丨 to 〇 2 kW/m 2 Kelvin. Efficient mass and heat transfer in microchannel devices allows for more compact regulation of reaction conditions such as temperature, reactant concentration and residence time. Temperature control is especially important for the preparation of high purity organometallic products. Constant temperature conditions that deviate from the exothermic or endothermic reaction can result in an increase in the amount of undesired by-products, resulting in lower yields and product purity. Precise temperature regulation in the production of high purity products reduces, or in some cases eliminates the need for subsequent purification, thereby reducing the total amount of resources required to produce the organometallic compound. Since each microchannel device typically produces a small amount of organometallic 8 95103 201130857, a large number of microchannel devices can be used in parallel. The total volume produced by the series of microchannel devices can be adjusted by increasing or decreasing the number of microchannel devices at the given time point, thereby reducing or eliminating the need for product storage. The microchannel device can be made from any conventional material including, but not limited to, metal, polymer, ceramic, tantalum or glass. Exemplary metal systems include, but are not limited to, 'metal alloys (e.g., Hastell® alloys from Haynes International Inc., and austenitic stainless steels such as 304, 312, and 316 stainless steel). Manufacturing methods include, but are not limited to, mechanical micromachining, molding, ribbon forming, etching, laser patterning, sanding, hot embossing, lithography, and micro-stereolithography. The microchannel device can be constructed to have both a smooth channel wall and/or a channel having structural features that enhance heat and mass transfer on the channel wall. A microreactor is an example of a microchannel device. In a specific embodiment of certain microchannel devices for performing the reaction, the microreactor contains an inlet for each reagent. In a reaction employing three or more reagents, two or more reagents may be combined and fed into the microreactor through a single inlet, with the restriction that the total number of reagents is not in the microreaction region. Combine. For example, when the reaction employs three reagents, two of the reagents can be fed together into the microreactor through the same inlet, and the third reagent can be fed through the second inlet. The microchannel device can include a separate channel system for temperature regulation via an external cooling or heating source. Exemplary systems include, 95103 9 201130857 but are not limited to hot oil, hot water, hot steam, cold oil, cold water, cold bath, and cooling units. As used herein, "heat," means a temperature above room temperature, typically exceeding 35 ° C. As used herein, "cold" means a temperature below room temperature, typical Less than 15. (: In the case of a microreactor, the apparatus is operated at a temperature suitable for a particular synthesis reaction. The microchannel apparatus may comprise a micromixer for mixing inlet vapors. The microchannel apparatus may have 1 micron. Lengths up to 1 m or more 'this depends on process requirements or device manufacturing methods. If desired, multiple microchannel devices can be used sequentially to achieve the desired total length. In the case of microreactors' In addition to the flow rate and temperature, the length of the microchannel device is also specified by the kinetics of the particular reaction to be carried out. Slower reactions require longer residence times in the microreactor and accordingly require longer microreactors In addition, the microreactor may contain additional inlets for additional reagents along the length of the device or between the devices when the desired system is sequentially reacted. The microchannel device is included for removal of the product. In some embodiments, the microchannel device comprises two outlets, one for the liquid stream and the other for the gas stream. Subsequently, the product stream from the microreactor can be Purification by conventional purification methods, microchannel purification, or a combination thereof. An example of a microreactor is disclosed in U.S. Patent No. 6,537,506, which discloses a combined heat transfer fluid path, reactant fluid path, product path, mixing chamber, and reaction chamber. Stacked plates, multi-channel reactors. Microchannel devices may optionally contain a wick or membrane structure to regulate the thickness of the fluid film and enhance the interface phenomenon. The microchannel device can be used for fluid separation including distillation. Microchannel devices are commercially available. An important application in distillation applications is the C2 separator, which separates ethane from ethylene. This microchannel distillation process reduces the energy consumption and capital cost for ethylene production. The present invention provides a process for preparing organometallic compounds. An ultrapure alkyl metal compound for use in a process such as chemical vapor deposition is produced by reacting a metal salt with an alkylating agent in a microchannel device. Further, the alkylating agent of the present invention itself It may be a purified one. Examples of combinations of metal salts and alkylating agents include, but are not limited to, For example, in a microchannel device of a microreactor, a metal dentate is reacted with a trialkylamine solution to react a metal hydride solution with an alkylmagnesium halide or a metal halide solution with an alkyllithium solution to produce an alkyl group. The metal compound. In some embodiments, the molar ratio of the alkylating agent to the metal salt is greater than or equal to 1. In some embodiments, the molar ratio is greater than or equal to 2. In some embodiments, the molar ratio is greater than or equal to 3. The metal s-oxide may comprise a metal of Group II, Group III, Group Iv, or Group V. A sufficient number of the metal dentates are present. The dentate forms a neutral compound. Exemplary metal toothings include, but are not limited to, Z11CI2, GaCh, InCh, InBn, Inl3, GeCh, SiCl4, snci4, PC13, AsC13, SbCl3, and BiCh. The trialkyl aluminum solution contains three alkyl groups which may be the same or different. Each alkyl group contains from 1 to 8 carbon atoms. The alkyl groups may be straight, branched or cyclic. The alkylmagnesium alkyl and alkyllithium compounds comprise a mono-(tetra)yl group having from 1 to 8 carbon atoms of 95103 11 201130857. Similarly, the granules may be linear, branched or cyclic. The metal salt solution and the hospital base solution may comprise any organic solvent which is inert to the reaction between the two components and inert to any product from the reaction. In some embodiments, the metal solution is free of solvent, that is, the metal salt is already in liquid form and is added in a "neat" state. The solvent is selected to provide sufficient hydrazine to cause the reaction to proceed. The metal salt solution is the same as or different from the Wei grouping agent = liquid. Particularly suitable organic solvent systems include, but are not limited to, 'hydrocarbons and aromatics ^ , ^ ^ ^ , Examples of exemplary organic solvents include, but are not limited to, stupid; substituted by a hospital base such as toluene, dimethyl stearate and (C4-C2°) phenyl based such as (Cl〇-Cl2) alkyl stupid and rr and Aliphatic hydrocarbons such as pentane, hexane, bis-biphenyl; s 70 octane, decane, dodecane, squalane, % pentane, % hexane, and cycloheptane 6; and the organic solvent It is stupid, toluene, dimethyl cage, and the mouth is also preferred, and it is suitable for sulphur, cyclopentane or cyclohexane. Suitable for 俜^2.) Benzylbenzene, hexyl, organic solvents. These organic solvents are usually used. More than one Chemicals (Milwaukee, Wis) comes / used as Aldrich, or preferably, in use (4) can be straightforward The organic solvent is dried and deoxygenated before use. =: The segment will: ==, in the true - the sentence is greedy -^ Into the gas. Appropriate inert gas system, including silk, nitrogen reduction, better money Gas or gas. In another specific embodiment, ionic liquid (6) 仏 95103 12 201130857 liquid) will be used as a solvent to ensure that the ionic liquid does not interact with the organometallic synthesis and & environmentally friendly green Solvent ionic liquids are generally liquid salts at low temperatures and have a melting point below 10 (rc. Most ionic liquids remain in the liquid phase at room temperature and are referred to as room temperature ionic liquids. Ionic liquids are composed entirely of ions, and typically They are composed of large volumes of organic cations and inorganic anions. Due to the high residual gravity in these compounds, the ionic liquid does not actually have a vapor pressure. Any suitable ionic liquid can be used in the present invention. The cationic cations include, but are not limited to, hydrocarbylammonium cations, hydrocarbylphosphonium cations, hydrocarbylpyridinium Ionic and dihydrocarbylimidazolium cations. Exemplary anionic groups suitable for use in the ionic liquids of the present invention include, but are not limited to, chlorometalate anions, fluoroborate anions such as tetrafluoroborate anions, and hydrocarbyl groups. a substituted fluoroborate anion, and a fluorophosphate anion such as a hexafluorophosphate anion and a hydrocarbyl-substituted fluorophosphate anion. Examples of chlorometalate anions include, but are not limited to, aeroaluminate anions such as tetra-aluminate Anionic and chlorotrialkylaluminate anions, gas gallate anions such as chlorotrimethylgallate and tetrachlorogallate, gas indium anions such as tetra-indium hydride and chlorotrimethyl indium. Suitable gas aluminate ionic liquid systems include, but are not limited to, those having a hydrocarbyl-substituted i-ammonium, a hydrocarbyl-substituted phosphorous rust, and a trans-substituent ratio. Replace the taste of β sitting iron toothing 13 95103 201130857. Exemplary aluminosilicate ionic liquid systems include, but are not limited to, trimethylphenylammonium sulphate (TMPACA), benzyltrimethylammonium aluminoate (BTMACA), benzyltriethylammonium aluminoate (BTEACA), benzyltributylammonium sulphate (BTBACA), tridecylphenylphosphorus rust (TMPPCA), benzyltrimethylphosphonium sulphate (BTMPCA), benzyl aluminoaluminate Triethylphosphorus rust (BTEPCA), benzyl tributylphosphonate (BTBPCA), 1-butyl-4-mercaptopyridine rust (BMPYCA), aluminosilicate butyl pyridine rust (BPYCA) , 3-mercapto-1-propyl chloroaluminate ratio bite rust (MPPYCA), 1-butyl-3-methyl 0-mazole rust (BMIMCA), 1-ethyl-3 chloroaluminate - mercapthy imidazole rust (EMIMCA), bromine-tri-aluminum acid 1-ethyl-3-methylimidazolium rust (EMIMBTCA), chloroaluminate 1-hexyl-3-mercaptoimidazolium (HMIMCA), gas triterpene Benzyltrimonium aluminate (BTMACTMA), and 1-mercapto-3-octyl imidazole rust (M0IMCA). Other suitable ionic liquid systems include those having a fluoroborate anion or a fluorocerate anion such as, but not limited to, tridecylphenylammonium fluoride (TMPAFB), benzyltrimonium fluoroborate (BTMAFB) Benzyl triethylammonium fluoroborate (BTEAFB), benzyltributylammonium fluoroborate (BTBAFB), trimethylphenylphosphorus fluoroborate (TMPPFB), benzyltrifluorophosphoryl fluoroborate (BTMPFB) Benzyl trifluorophosphate fluoroacetate (BTEPFB), benzyl tributyl chloroborate rust (BTBPFB), 1-butyl-4-fluorenyl fluorobutyrate η ratio (BMPFB), fluoroboric acid 1 -butylpyridinium rust (BPFB), 3-mercapto-1-propyl fluoroborate bismuth rust (MPPFB), 1-butyl-3-mercaptoimidazole fluoroacetate (BMIMFB), fluoroborate 1-B EMI-methylimidazole rust (EMIMFB), bromotrifluoro-decahydrol 1-ethyl-3-mercaptoimidazole rust (EMIMBTFB), fluoroboric acid, hexyl-3-mercaptoimidazole rust (HMIMFB), fluoroboric acid Dimethoprim-3 octyl imidazole rust 14 95103 201130857 (MOIMFB), and benzyltrimethylammonium fluorophosphate (BTMAFp). Ionic liquids are generally commercially available or can be prepared by methods known in the art. These compounds can be used directly or can be further purified. The concentration and amount of such solutions are selected such that the molar ratio of the alkylating agent compound to the metal salt is greater than or equal to the stoichiometry of the particular alkylation reaction. The reaction of the metal halide with the trialkylaluminum solution can be carried out at from 1 to 10 °C. The pressure available is from i to 10 bar. The reaction of the metal dentate solution with the toothed alkylmagnesium or alkyllithium solution is V-5 (TC to 5 (TC can be used. The pressure can be from 1 to 10 bar. In another embodiment of the invention) Providing a method for preparing a metal amidinate compound as a usable source for atomic layer deposition (ALD). The metal ruthenium compound is suitable for use as an organometallic compound for use as an ald precursor, having the formula 'V' R2 and R3 are independently selected from the group consisting of Khto-CO alkyl, (C2-C6) alkenyl, (o*c〇 alkynyl, dialkylamino, di(alkyl-substituted alkyl) amine, dioxane Amino group, a di(alkyl-substituted decyl)amino group and an aryl group; ruthenium is a metal; L1 is an anionic ligand; l2 is a neutral ligand; m is a valence of Μ; η=0 To 6; ρ = 〇 to 3; and wherein m2 η. The nature of the metal ruthenium may be a homoleptic or a heteroligand, that is, may contain different amidate ligands or hydrazines. Combination of a position with other anionic ligands. These compounds are suitable for a variety of vapor deposition methods such as chemical vapor deposition (C VD), and is especially suitable for atomic layer deposition 15 95103 201130857 (ALD). It also provides a composition comprising a compound and an organic solvent. This composition is particularly suitable for ALD and direct liquid injection (dli) processes. The method of the compound comprises reacting a metal dentate solution with a amidinato lithium solution in a microchannel device such as a microreactor to produce a metal alkylamidinate compound, wherein the sulfhydryl lithium The molar ratio of the compound to the metal halide is greater than or equal to 1. In some embodiments, the molar ratio is greater than or equal to 2. In some embodiments, the molar ratio is greater than or Is equal to 3. The metal compound may comprise a metal of Group π to Group VIII. A sufficient number of dentates are present in the metal complex to form a neutral compound. Exemplary metal tooth systems include, but are not limited to, ZnCh, GaCh, InBn, A1C13, HfCl4, ZrCl4 'GeCl4, SiCl4, TaCl5, WC16, SbCl3 and R11CI3. The vein-based compound contains a single vein group, and the lung matrix contains 1 a base or an aryl or a cyclic group of up to 8 carbon atoms. The base group may be a linear chain, a branched chain or a cyclic group. The metal dentate solution and the cerium-based lithium solution may comprise any solvent, The solvent is inert to the reaction between the metal dentate and the sulfhydryl clock solution and is also inert to any product obtained from the solvent. The solvents and reagents must be dried and deoxygenated. The solvent should be selected to provide sufficient solubility. , so that the reaction proceeds. The metal tooth solution may be the same or different solvent as the pulse solution. Exemplary solvent systems include, but are not limited to, the foregoing. 95103 16 201130857 In the sample, the metal halide solution is free of dissolved (4), that is, the 4 metal toothing system is already in liquid form and is "pure, shape = in. The reduction of the degree I and the amount are selected. The sulfhydryl hydration = the reactivity of the metal complex with the molar ratio of greater than or equal to the reaction stoichiometry. The reaction can be carried out from - to 咐. The compressible pressure is! to 10 #二=implementation In the aspect of the method for preparing an organometallic compound, the transesterification fund is used in a microchannel device (such as a microreactor) in the presence of a mixture of a tertiary amine and a triple C. The I compound is dissolved in an organic solvent in the presence of a tertiary amine, a tertiary phosphine, or a tertiary amine bisphosphine mixture to provide a genus, wherein each R is independently selected from the group consisting of An anthracene, an alkyl group, an alkenyl group, an alkynyl group and an aryl group 1 are selected from the group consisting of a Group Ιν group metal and a Group π group metal; each lanthanide is independently halogen; each R4 group is independently selected from the group consisting of (Μ)alkyl; The first work ι 『 group metal ·, each & is independent from ^ ^ ^ ^ ^ and 〇 is 1 to 3. The Group IV metal toothing and the VI Metal dentates are generally commercially available from, for example, Gelest Corporation (Tullytown, Pa.), or can be prepared by methods known in the literature. These compounds can be used directly or purified prior to use. It will be appreciated that more than one metal dentate, more than one Group 111 compound, and combinations thereof can be used. 95103 17 201130857 Exemplary iv group metals include, but are not limited to, Shi Xi, Wrong and Tin. Illustrative VI The metal group includes, but is not limited to, bismuth and selenium. Μ is preferably lanthanum, cerium or tin, more preferably 锗. X can be any halogen. Each X can be the same or different. In a specific embodiment, m = 0. When m = 0, a metal tetrahalide of Group IV or Group VI is used. In other embodiments, m can be 1, 2 or 3. A wide variety of alkyl, alkenyl and An alkynyl group can be used for R. Suitable alkyl groups include, without limitation, (C1-C12) alkyl, typically (Ci-Ce) alkyl, more typically (G-C4) alkyl. In this way, the alkyl groups are bulky alkyl groups. "Large-volume alkyl" means Any sterically hindered alkyl group. These bulky alkyl groups have at least 3 carbons, and the number of carbons in the group has no particular upper limit. Preferably, the bulky alkyl groups individually have from 3 to 6 More preferably 3 to 5 carbon atoms. These bulky alkyl groups are preferably non-linear, preferably cyclic or branched. Exemplary alkyl groups include mercapto, ethyl, n-propyl. Base, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl. More typically, suitable alkyl groups include ethyl, iso The propyl and tert-butyl, suitable alkenyl groups include, but are not limited to, (C2-Cl2), typically (C2-C6), and more typically (C2_C4)alkenyl. Exemplary alkenyl groups include vinyl, allyl, decylallyl, and crotonyl. Typical alkynyl groups include, but are not limited to, (C2-C12)alkynyl, typically (C2-C6)alkynyl, more typically (C2-C4)alkynyl. Suitable aryl (C6-Cl0) aryl groups include, but are not limited to, phenyl, anthracenylphenyl, diphenylphenyl, benzyl and phenethyl. When two or more alkyl, alkenyl or alkynyl groups are present, such groups may be the same or different. 18 95103 201130857 Take: the base, block or aryl group can be replaced by its A, monoalkylamine group as needed. "Substituted," means that the alkane; one or more hydrogens on the fluorene-di-alkynyl or aryl group are replaced by one or more halogen or a monoalkylamine group. A broad variety of Group 111 compounds. The individual compounds which can be used in the present invention typically have the formula R4nM, XVn, wherein each:, erect is selected from (Cl-C6) alkyl; M1 is the (1) octal metal; X, and η are ! to 3 Integral. Ml is suitably butterfly, imprint, marry, and 1: and preferably aluminum. Preferably, 'χ1 is selected from a, chlorine or bromine. Suitable bases include, but are not limited to, Methyl, ethyl, n-propyl, iso-JH butyl, isobutyl and tert-butyl. Preferred hospital bases include methyl ethyl, n-propyl and isopropyl. In the sample, n is 3. wherein the compound of the group (1) wherein η is 3 includes a tricarbyl shed, a trialkyl aluminum, a trialkyl gallium, a trialkyl indium, and a trialkyl fluorene, and the compound is difficult. The more the implementation of New Zealand, to ^ where η is 1 to 2, etc. (1) The compound is composed of a functionalized dialkyl aluminum such as a gasified dialkyl aluminum. The steroids are usually available from a variety of sources such as the Gelest business. Ground It can be prepared by a variety of methods known in the literature. These compounds can be used directly or purified prior to use. Suitable secondary amines include, but are not limited to, those having the formula 'where R5, R6 and r7 are independently selected from (G-CO alkyl, C(C)-C6)alkyl substituted by di(Ci_c6)alkylamino, and phenyl, and the nitrogen atom to which R and R6 may be attached. Forming a 5- to 7-membered heterocyclic ring together. The heterocyclic ring may be aromatic or non-aromatic. Particularly suitable tertiary amine systems include, but are not limited to, 95103 19 201130857, tridecylamine, triethylamine, tri-n-propyl Amine, tri-n-butylamine, triisopropylamine, triisobutylamine, diammonium cyclohexane, diethylaminocyclohexane, dimethylaminocyclopentane, diethylaminocyclopentane Alkane, N-methylpyrrolidine, N-ethylpyrrolidine, N-n-propyl pyrrolidine, N-isopropylpyrrolidine, N-methyl piperidine, N-ethyl alpha bottom bite, N-positive丙基 底 σ 、, N-isopropyl. σ 定 Ν, Ν, Ν ' - dimethyl piperazine, hydrazine, Ν ' - diethyl piper, Ν, Ν ' - dipropyl piper, Ν,Ν,Ν',Ν' - 四曱基-1,2- Aminoethane, pyridine, pyridin, pyrimidine and mixtures thereof. Preferred amines include tridecylamine, triethylamine, tri-n-propylamine, triisopropylamine, and tri-n-butylamine. In an embodiment, the tertiary amine is triethylamine or tri-n-propylamine. Exemplary tertiary phosphines include, but are not limited to, those having the general formula R8R9R10P, wherein R8, R9 and R1 are Independently selected from (G-Ce)alkyl, phenyl and phenyl substituted by (G-Ce)alkyl. Suitable tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, benzene Dimethylphosphine, phenyldiethylphosphine and butyldiethylphosphine. It will be appreciated by those of ordinary skill in the art that more than one tertiary or tertiary phosphine can be used. Mixtures of tertiary amines and tertiary phosphines can also be used. These tertiary and tertiary phosphines are generally commercially available from a variety of sources. These tertiary amines and tertiary phosphines can be used as such or, preferably, further purified prior to use. A wide variety of organic solvents can be used. Typically, such organic solvents do not contain oxidizers such as ether linkages, and preferably contain no oxygen. Exemplary organic solvents include, but are not limited to, hydrocarbons and aromatic hydrocarbons. Suitable organic solvents include, but are not limited to, benzene, toluene, xylene, pentane, hexane, 20 95103 201130857, gypsum, Xinxuan, wolfberry, twelfth, shark, cyclopentane, cycloheximide. , cycloheptane and mixtures thereof. Suitably, more than one organic solvent is preferably used in the present invention. In another embodiment, the tertiary amine can be used as the organic solvent. Such organic solvents are generally commercially available from a variety of sources such as Aldrich Chemicals (Milwaukee, Wis.). These solvents can be used as such or, preferably, purified prior to use. Preferably, such organic solvents are deoxygenated prior to use. The solvents may be deoxygenated by various means such as rinsing with an inert gas, degassing the solvent under vacuum or a combination thereof. Suitable inert gas systems include argon, nitrogen and helium, preferably argon or nitrogen. The particular tertiary amine, tertiary phosphine and organic solvent employed will depend on the particular alkyl metal compound desired. For example, the organic solvent and tertiary amine can be selected such that they are more volatile or less volatile than the desired metal alkyl compound. These differences in volatility allow the alkyl metal compound to be more easily separated from both the amine and the organic solvent. The tertiary amine and the choice of the organic solvent are within the skill of the artisan in the art. Typically, the tertiary amine and/or tertiary phosphine is present in stoichiometric amounts of the Group IIIA compound. The molar ratio of the metal compound to the Group IIIA compound can vary over a wide range, such as from 1:1 to 1:5, and the specific molar ratio depends on the desired metal alkyl compound. Another suitable molar ratio range is from 1:0.5 to 1:2. It is also expected that a molar ratio of more than 1:5 is effective. The specific surface metal compound obtained from the method can be controlled by selecting the metal halide and the Group IIIA compound Mo 21 95103 201130857 ear ratio, that is, by the mole number of the III compound The number of displaced dentates in the metal tooth compound is adjusted. For example, in the reaction of a Group IV metal tetradentate (A) such as a gasified ruthenium with a trimethyl sulphate (β), 1:0.5 (Α:Β) The molar ratio provides an alkyl group 丨7 metal trihalide; the 1:1 (Α: Β) molar ratio provides a dialkyl Group IV metal dihalide; 1:1. 5 (Α: Β The molar ratio provides a trialkyl Group 0 metal halide; and the 1:2 (Α: Β) molar ratio provides a tetraalkyl Group 1 metal. Thus, according to the method of the present invention, one, two, three or four fangs of the metal dentate can be replaced. In a specific embodiment, the Group III compound, the tertiary amine and/or the tertiary phosphine and the organic solvent may be combined in any order before the reaction with the metal dentate. In still another embodiment, the Group 111 compound is first combined with the tertiary amine and/or tertiary phosphine to form an amine-Group III adduct or a phosphine-Group III adduct. Typically, the amine- ll family adduct can be formed at a wide range of temperatures. The appropriate temperature for forming the adduct is ambient temperature to 90 °C. Subsequently, the metal dentate reacts with the amine-Group III adduct to form the desired alkyl metal compound. Preferably, the metal halide is added dropwise to the amine-Group III adduct as a pure compound or as a hydrocarbon solution. Alternatively, the amine-Group III adduct may be purified or added as a hydrocarbon solution to the metal halide. The appropriate temperature for forming the alkyl metal compound is ambient temperature to 80 °C. Accordingly, in one embodiment, the present invention provides a process for the preparation of an alkyl metal compound comprising reacting a Group III compound with a tertiary amine in an organic solvent free of oxidized 22 95103 201130857 To form an amine-Group HI adduct; and react the amine-Group III adduct with a Group IV metal dentate, a Group VIA metal halide or a mixture thereof in the organic solvent. When a tertiary phosphine is used in the above-mentioned uncovering reaction, a phosphine-diterpene adduct is formed. In another embodiment, the metal dentate can be combined with the steroid and, if desired, an organic solvent prior to mixing with the tertiary amine and/or tertiary phosphine. The tertiary amine and/or tertiary phosphine and optionally an organic solvent are then combined with the metal-based steroid mixture using a suitable mixing zone or conventional external agitation technique within the microchannel apparatus. Alternatively, the metal hydride/tertiary compound may be added to the secondary amine and/or the secondary phosphine and optionally the organic solvent. Although it is not intended to be bound by theory, it is not until the metal dentate, the η steroid and the second fine combination that the transalkylation reaction starts 0 or the alkyl can be prepared in a continuous manner. Base metal compound. For example, the metal i compound and the steroid may be separately added to the microchannel reactor in a continuous manner, and in a suitable organic solvent (such as an aromatic or aliphatic hydrocarbon) + with a tertiary amine and / or Tertiary phosphine contact. The addition of the metal compound to the Group III compound can be regulated by a variety of suitable means, such as by using a mass flow regulator. In this continuous process, the desired metal alkyl compound can be recovered by, for example, distillation while the metal halide and the steroid are added to the reaction zone. In still another alternative, a mixture of the metal i compound and the second π compound can be combined with the tertiary amine and/or tertiary phosphine in a suitable solvent. In this continuous process 95103 23 201130857, the desired burnt metal compound can be recovered by, for example, distillation while the mixture of the metal halide/inium compound is added to the reaction zone. The organometallic compound can be used directly or suitably by various techniques such as steaming, sublimation and recrystallization. The process of the present invention provides organic metal compounds that are substantially free of metallic impurities such as aluminum, gallium, indium, cadmium, mercury, and zinc. The organometallic compounds are also substantially free of vaporized impurities such as ethereal solvents, and preferably are free of such oxidized impurities. By "substantially free" is meant that the compound contains less than 5 ppm of such impurities. The organometallic compound of the present invention has a purity of at least 99.99% by weight, or a purity of 99.9999% by weight. Specifically, the organometallic compound of the present invention contains impurities at a concentration of less than 100 ppm to less than 1 ppm by weight. Ultra-high purity organometallic compounds for electronic material applications can be further purified using microchannel devices. The microchannel device can be used to purify the reactants, intermediates, or final products, or a combination thereof, to achieve ultra high purity compounds for electronic applications. The organometallic compound can be prepared in a microchannel reactor as described above or in a conventional reactor (including batch stirred tank, semi-batch continuous flow half tank, continuous flow tubular reactor, reactive distillation reactor) Prepared by preparative, and other known methods. Ultra-high purity materials for electronic applications are often difficult to achieve through conventional thermal separation methods such as distillation and sublimation, or mass transfer separation methods such as extraction, absorption, and adsorption due to the low concentration driving forces of conventional methods. Contains impurities with similar boiling points (relative volatility, 〇·8 <a <1. 5, 95103 24 201130857 The organometallic compound of 'a = the vapor pressure of the impurity or the vapor pressure of the desired pure compound) is particularly difficult to purify through a staged distillation process with conventional filling. ° The column may require a large order such as > 50, > 1 〇〇, sometimes > 200, or a high reflux such as > 1 〇, > 20, sometimes > 50, or both, which increases the process Investment and operating costs and complexity. The microchannel device provides an improved solution to these problems. The small channel dimension produces a higher transfer gradient to enhance heat and mass transfer, as well as an increased column surface to provide a higher effective exchange area in a fixed geometry. Two factors contribute to a more efficient separation (smaller theoretical plate height, HETP) purification, especially for obtaining high purity. Ultrahigh purity organometallic compounds can also be produced in microchannel devices by adsorptive or chemical purification techniques such as addition of adducts. A selective adsorbent or adduct can be supported on the surface of the microchannel to form an adduct-forming Lewis base such as an amine, phosphine or ether, providing a very high exchange area to contact the stream containing impurities. Other microchannels for the flow of heat transfer fluid can be provided to precisely regulate the temperature of the device for efficient adjustment and cycling between the adsorption and desorption steps. The separation process based on microchannel technology, such as steaming, stripping, extraction and adsorption, provides the enhanced heat and mass transfer required to achieve ultrapure products (ppm, ppb). These separate processes provide additional solutions that will have similar boiling points (relative volatility, 0.8 <a <l. 5) Enhancement of the transfer order required for the separation of the liquid mixture into a high purity concentration. Advantageous preferred operating conditions include temperature and pressure, wherein one or more of the liquid components are in the liquid phase and can be converted to a gaseous phase or to a state adsorbed onto the absorbent 95103 25 201130857 Phase change. This may include temperatures from 25 ° C to 250 ° C and pressures from i. ipa to 10 MPa. The feed impurity concentration can be from 1 ppm up to 10 wt% or even 50 wt〇/〇 of the fluid mixture. The organometallic compounds of the present invention are particularly useful as precursors in all gas phase deposition processes such as LPE, MBE, CBE, ALD, CVD, MOCVD, and MOVPE. The compounds of the present invention are useful for depositing films comprising one or more Group IV, Group VI or Group IV and Group VI metals. These films are useful in the manufacture of electronic devices such as, but not limited to, integrated circuits, photovoltaic devices, and light emitting diodes. The film of the Group IV and/or Group VI metal is typically deposited by: first placing the desired metal alkyl compound (ie, the source compound or precursor compound) with the deposition chamber In the transport device (such as a cylindrical column) that is connected to the exit. Depending on the particular deposition equipment used, a variety of cylindrical columns are used. When the precursor compound is a solid, the cylindrical column and other designs disclosed in U.S. Patent No. 6,444,038 (Rangarajan et al.) and U.S. Patent No. 6,607,785 (Timmons et al.) are incorporated. . For the liquid precursor compound, a cylindrical column and other liquid precursor cylindrical columns disclosed in U.S. Patent No. 4,506,815 (Melas et al.) and U.S. Patent No. 5,755,885 (Mikoshiba et al.) are incorporated. The source compound is held in the cylindrical column as a liquid or solid. The solid source compound is typically evaporated or sublimed prior to delivery to the deposition chamber. The source compounds are typically delivered to the deposition chamber by passing a carrier gas through the cylindrical column. Suitable carrier gas systems include nitrogen, hydrogen, and mixtures thereof. Typically, the carrier gas is introduced under the surface of the source compound and upstream 26 95103 201130857 through the source compound to the headspace thereon, and the source compound is later entrained or carried into the carrier gas. The entrained or carried vapor is then passed into the > redundant chamber. The deposition chamber is typically a heated vessel having at least one (and possibly a plurality of) substrates disposed therein. The deposition chamber has an outlet that is typically connected to a vacuum pump to draw by-products from the chamber and provide a suitable reduced pressure. VD can be implemented under atmospheric pressure. The deposition chamber wire is held at a level equal to /JBL to induce decomposition of the source compound. The deposition chamber temperature is 200 C to 1200 ° C' to optimize the exact temperature selected to provide effective deposition. If desired, the substrate temperature is maintained at elevated temperatures, or if there is other source of energy such as radio frequency (RFF) energy, the overall temperature within the deposition chamber can be reduced. In the case of manufacturing an electronic device, a suitable substrate for deposition may be Shi Xi, galvanized, indium disinte, or the like. Such substrates may contain a layer or layers of additional material such as, but not limited to, a dielectric layer and a conductive layer such as a metal. These substrates are particularly useful in the fabrication of integrated circuits, optoelectronic devices, and light emitting diodes. The deposition will be continued for a desired period of time to produce a film of the desired properties. Typically, when the product is stopped, the thickness of _ can range from a few hundred angstroms to several tens of nanometers to several hundred micrometers or more. The following examples are intended to further illustrate the various aspects of the invention, but are not intended to limit the invention in any way. All operations were carried out under an inert atmosphere 'typically under a dry nitrogen atmosphere. ‘, [Examples] Comparative Example #1 95103 27 201130857 Synthesis of tetradecyl decane according to the following equation:
GeCL, + 2(CH3)3AI:Pr3N.-> (CH3)4Ge + 2CH3AlCl2.Pr3N 於氮氣中,將三曱基鋁(40公克(g),0.554莫耳)加 入三頸圓底燒瓶内的150g高沸點直鏈烷基苯中。於室溫將 正丙胺(79. 5g, 0· 554莫耳)滴加至其中。該添加係持續3〇 分鐘,於此期間’該混合物變暖(約50°C)。完成該添加且 該混合物冷卻至室溫之後,於室溫將純氣化鍺(40g,〇. 186 莫耳)滴加至所形成之加成物中。該添加耗時1小時,於此 期間,該反應混合物再次變暖至約60°C。冷卻至室溫後, 將反應物加熱至160至170°C (油浴溫度),於此期間,通 過U管將20g粗產物四甲基鍺烷蒸餾進入經乾冰冷卻之接 收器中。藉由4 NMR(-CH3於〇· 1 ppm共振)完成對該產物 之身分確認,顯示其含有一些三丙胺(<5%)。粗產物之產率 為81.6%。反應釜遺留之殘質的沱NMR表明,存在更多尚 未分離之四曱基鍺烷。 實施例1 根據下述方程式合成四甲基錯烧:GeCL, + 2(CH3)3AI:Pr3N.-> (CH3)4Ge + 2CH3AlCl2.Pr3N Trisyl aluminum (40 g (g), 0.554 mol) was added to a three-necked round bottom flask under nitrogen. 150 g of high boiling linear alkylbenzene. N-propylamine (79. 5 g, 0·554 m) was added dropwise thereto at room temperature. This addition lasted for 3 minutes, during which time the mixture warmed (about 50 ° C). After the addition was completed and the mixture was cooled to room temperature, pure gasified hydrazine (40 g, 〇. 186 mol) was added dropwise to the formed adduct at room temperature. The addition took 1 hour during which time the reaction mixture warmed again to about 60 °C. After cooling to room temperature, the reaction was heated to 160 to 170 ° C (oil bath temperature) during which time 20 g of crude product tetramethyl decane was distilled through a U-tube into a dry ice-cooled receiver. The identity of the product was confirmed by 4 NMR (-CH3 in 〇 1 ppm resonance), which showed that it contained some tripropylamine (< 5%). The yield of the crude product was 81.6%.沱NMR of the residue left in the autoclave indicated that there were more tetradecyldecane which had not been separated. Example 1 Synthesis of tetramethyl malodoration according to the following equation:
GeCL, + 2 (CH3)3AlPr3N (CH3)4Ge + 2 CH3AlCl2Pr3N 於氣氣中,於同沸點直鍵烧基苯溶劑中製備三曱基铭 與正丙胺之等莫耳溶液。於室溫將該三甲基鋁/正丙胺溶液 與純氣化鍺連續加入微通道裝置中。該微通道裝置係對該 等試劑提供不同之流動路徑,且該等流動路徑於混合物區 95103 28 201130857 % 域中彼此連通,於該混合區域中,該等反應劑彼此接觸。 將該等試劑流調控為維持三曱基鋁與氣化鍺之莫耳比為 • 3。該混合物進入該微通道裝置之反應區域,導致該等試劑 之間出現烷基化反應。該反應區域係具有垂直於流動方向 之1至100微米範圍的寬度。該反應區域具有1微米至1 米範圍之長度(於該流動反向),藉由該烷基化反應確定最 佳長度,以達成藉由調節流動速度而設定之足夠的反應時 間(1秒至10分鐘),以及提供至少80%之轉化。藉由熱傳 遞流體(如Therminol)於與該微通道裝置内之反應通道不 同之流動通道流動,將反應溫度調控為+/-1°C。反應產物 流自該微通道反應器流出,收集且於160至170°C蒸顧該 反應產物流以獲得所欲之MeAe產物。藉由FT-NMR及 ICP-AES測量該MeAe產物之純度,預計為99. 9999%純。 實施例2 使用微通道裝置根據下述方程式合成高純度之三甲 基I呂-三丙胺加成物: (CH3)3A1 + Pr3N (CHb):jAl.Pr3N 加成物 於經純化之有機鋁-三級胺加成物之製備中,使用包 含多個平行通道的由316 SS構築之橫截面維度約為1χ3 毫米(mm)且長度大於1米之微通道反應器。微通道襄置之 每一通道係與熱交換區域接觸。於室溫將含有31 (藉由ICP技術測得)之三甲基鋁(TMA)進料流以2 5千克 (kg)/小時(hr)之速度進料入連續流反應器中。於室溫經由 95103 29 201130857 不同之注入口將三丙胺之進料流以5. Okg/hr之速度同時 進料入該反應器中。於該等流動通道内,兩種進料互相混 合。使用於該反應器熱交換通道中循環之冷卻油(4〇。〇調 控反應器溫度,以將製程出口溫度維持為約5〇°C之穩定严 度。將反應器流出物(7.5 kg/hr)進料入連續薄膜蒸發器 以純化該加成物。該蒸發器表面經旋轉葉片連續擦 ' 蒸發器係於2托(torr)操作,且外罩溫度為8〇。" β亥 純化之ΤΜΑ :加成物,產率大於98州,並。吹集經 如 ^析顯示,該產物具有較起始材料顯著降低之^斤。ICP 所示者,石夕自31. 6ppm降至〇 。 雜質, 【圖式簡單說明】 益 【主要元件符號說明】 無 30 95103GeCL, + 2 (CH3)3AlPr3N (CH3)4Ge + 2 CH3AlCl2Pr3N In a gas atmosphere, a molar solution of triterpene and n-propylamine was prepared in a solvent of the same boiling point direct-burning benzene. The trimethylaluminum/n-propylamine solution and pure gasified hydrazine were continuously added to the microchannel apparatus at room temperature. The microchannel device provides different flow paths for the reagents, and the flow paths are in communication with each other in the region of the mixture 95103 28 201130857%, in which the reactants are in contact with each other. The flow of the reagents is controlled to maintain a molar ratio of trimethyl aluminum to gasified hydrazine of ? The mixture enters the reaction zone of the microchannel device resulting in an alkylation reaction between the reagents. The reaction zone has a width ranging from 1 to 100 microns perpendicular to the flow direction. The reaction zone has a length in the range of 1 micrometer to 1 meter (in the reverse direction of the flow), and the optimal length is determined by the alkylation reaction to achieve a sufficient reaction time set by adjusting the flow velocity (1 second to 10 minutes), and provide at least 80% conversion. The reaction temperature is regulated to +/- 1 °C by a heat transfer fluid (e.g., Therminol) flowing in a different flow channel than the reaction channel in the microchannel device. The reaction product stream exits the microchannel reactor, collects and vaporizes the reaction product stream at 160 to 170 ° C to obtain the desired MeAe product. The purity of the MeAe product was estimated to be 99.9999% pure by FT-NMR and ICP-AES. Example 2 A high-purity trimethyl Ilu-tripropylamine adduct was synthesized according to the following equation using a microchannel apparatus: (CH3)3A1 + Pr3N (CHb): jAl.Pr3N adduct in purified organoaluminum- In the preparation of the tertiary amine adduct, a microchannel reactor constructed of 316 SS having a cross-sectional dimension of about 1 χ 3 mm (mm) and a length of more than 1 m is used. Each channel of the microchannel device is in contact with the heat exchange region. A trimethylaluminum (TMA) feed stream containing 31 (measured by ICP techniques) was fed into the continuous flow reactor at a rate of 25 kilograms (kg) per hour (hr) at room temperature. The feed stream of tripropylamine was fed simultaneously into the reactor at a rate of 5. Okg/hr through a different injection port at 95103 29 201130857. Within the flow channels, the two feeds mix with each other. The cooling oil used in the heat exchange channel of the reactor was used to adjust the reactor temperature to maintain the process outlet temperature at a stability of about 5 ° C. The reactor effluent (7.5 kg / hr) Feeding into a continuous thin film evaporator to purify the adduct. The surface of the evaporator is continuously rubbed by a rotating blade. The evaporator is operated in a 2 torr operation, and the temperature of the outer cover is 8 〇. " : The adduct, the yield is greater than 98 states, and the product of the blowdown shows that the product has a significantly lower than that of the starting material. As shown by ICP, Shi Xi is reduced from 31. 6 ppm to 〇. , [Simple diagram description] Benefit [main component symbol description] No 30 95103