TWI755689B - Vi族前驅化合物 - Google Patents
Vi族前驅化合物 Download PDFInfo
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- TWI755689B TWI755689B TW109106622A TW109106622A TWI755689B TW I755689 B TWI755689 B TW I755689B TW 109106622 A TW109106622 A TW 109106622A TW 109106622 A TW109106622 A TW 109106622A TW I755689 B TWI755689 B TW I755689B
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- molybdenum
- compound
- chromium
- tungsten
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Classifications
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- C07—ORGANIC CHEMISTRY
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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- 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
- C23C16/06—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 metallic material
- C23C16/08—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 metallic material from metal halides
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- C—CHEMISTRY; METALLURGY
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明提供用於製備各種VI族前驅化合物之簡便方法,該等VI族前驅化合物可用於將該等VI族金屬氣相沈積於固體基板、尤其微電子半導體裝置基板上。該方法提供獲得該等揮發性材料之有效手段,然後該等揮發性材料可為欲沈積於該等基板上之含鉬、鉻或鎢之材料之來源。另外,本發明提供用於將該等化合物氣相沈積於微電子裝置基板上之方法。
Description
本發明係關於用於某些含VI族材料之氣相沈積之某些前驅物及其製備方法。
由於其極高熔點、低熱膨脹係數、低電阻率及高導熱率之特性,VI族金屬(例如鉬、鉻及鎢)越來越多地用於半導體裝置之製造中,其包括於擴散障壁、電極、光罩、電力電子基板、低電阻率柵極、平板顯示器及互連中之使用。
該實用性已促使努力達成用於該等應用之鉬、鉻及鎢膜之沈積,其特徵在於所沈積膜之高保形性及高沈積速率以適應有效的大批量製造操作。此繼而使得能夠努力開發用於氣相沈積操作之經改良鉬及鎢源試劑以及利用該等試劑之經改良製程參數。
本發明提供用於製備可用於將某些VI族金屬氣相沈積於固體基板、尤其微電子半導體裝置基板上之各種VI族前驅化合物之簡便方法。該方法提供獲得及分離該等揮發性固體或液體材料之有效手段,該等揮發性固體或液體材料然後可作為欲沈積於該等基板上之含鉬、鉻或含鎢材料之來源。另外,本發明提供用於將該等化合物氣相沈積於微電子裝置基板上之方法。
在第一態樣中,本發明提供製備式(I)化合物之方法(I),
其中M選自鉬、鉻及鎢,X選自氟、氯、溴及碘,且每一L1
及L2
相同或不同且構成:
(i) 與M配位之單齒烴基配體,或
(ii) 一起形成與M配位之二齒烴基配體;
該方法包含:
(A)使下式化合物
與以下各項接觸:(a) 含有約0.1% (w/w)至約48% (w/w)式HX化合物之水,及(b) 式L1及/或L2之化合物;隨後
(B) 將該式(I)化合物分離為固體或液體。
如本文所用,術語「烴基」代表包含碳及氫原子且視情況含有至少一個氮、硫或氧原子之C2
-C16
基團。該等烴基可包含直鏈或具支鏈飽和、不飽和及多不飽和伸烷基及伸環烷基且可經(例如)一至五個選自以下之基團取代:C1
-C6
烷氧基、羧基、硝基、胺基、C2
-C6
胺基羰基、C2
-C6
醯胺基、氰基、C2
-C7
-烷氧基羰基、C2
-C7
-烷醯基氧基、羥基、芳基、雜芳基、硫醇、硫醚、C2
-C10
二烷基胺基、C3
-C15
三烷基銨及鹵素。術語「C1
-C6
烷氧基」、「C2
-C7
-烷氧基羰基」及「C2
-C7
-烷醯基氧基」係用於表示分別對應於結構--OR3
、--CO2
R3
及--OCOR3
之基團,其中R3
係C1
-C6
烷基或經取代C1
-C6
烷基。術語「C2
-C16
胺基羰基」及「C2
-C16
醯胺基」係用於表示分別對應於結構--NHCOR4
、--CONHR4
之基團,其中R4
係C1
-C7
烷基。如上所述,L1
及L2
包含該等烴基,且含有至少一個氮、硫或氧原子。
L1
及L2
係獨立地選擇且代表單齒配體或一起形成二齒配體。一般而言,L1
及L2
包含具有至少一個氧、硫或氮原子之烴基。該等配體可選自例如第三丁基腈、甲苯、四氫呋喃及乙腈,且該等基團視情況經一或多個選自以下之基團取代:鹵基、氰基、硝基、C1
-C6
烷基、C1
-C6
烷氧基、四氫呋喃、C1
-C6
烷氧基羰基及苯基。其他實例包括1,2-二甲氧基乙烷;1,2-二乙氧基乙烷;1,2-二甲氧基丙烷;N,N-二甲基乙醯胺;N,N-二甲基甲醯胺;N,N-二甲基氰基乙醯胺;二胺及三胺,例如N,N,N',N'-四甲基乙二胺、乙二胺、六伸乙基二胺、二伸乙基三胺(diethylene triamine)及二伸乙基三胺(diethylenetriamine);二甲亞碸;及二醇,例如乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇及1,6-己二醇。
步驟(B)分離式(I)化合物可藉由以下實施:利用水不混溶溶劑自水性反應混合物萃取化合物,隨後蒸發溶劑或結晶。另一選擇為,可將諸如醇(例如乙醇)之水溶性溶劑添加至水溶液以誘導期望式(I)化合物沈澱。若期望,式(I)之固體化合物可藉由結晶及/或真空昇華來純化。
應瞭解,上文繪示本發明化合物之結構係以二維形式繪製,未必代表其三維定向。
另外,式(I)化合物一旦形成,便可與式L1
及/或L2
之額外/不同化合物反應,以經由置換反應形成不同的式(I)化合物。因此,在另一實施例中,本發明提供上述方法,其包含使式(I)化合物與選自以下之化合物接觸之步驟:第三丁基腈、甲苯、四氫呋喃及乙腈,且該等基團視情況經一或多個選自:鹵基、氰基、硝基、C1
-C6
烷基、C1
-C6
烷氧基、四氫呋喃、C1
-C6
烷氧基羰基及苯基之基團取代;1,2-二甲氧基乙烷;1,2-二乙氧基乙烷;1,2-二甲氧基丙烷;N,N-二甲基乙醯胺;N,N-二甲基甲醯胺;N,N-二甲基氰基乙醯胺;N,N,N',N'-四甲基乙二胺、乙二胺、六伸乙基二胺、二伸乙基三胺(diethylene triamine)及二伸乙基三胺(diethylenetriamine);二甲亞碸;及乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇及1,6-己二醇,
以獲得具有式L1
及/或L2
之不同配體之式(I)化合物。
在其他實施例中,本發明提供式(I)化合物(I),
其中M選自鉬、鉻及鎢,X選自氟、氯、溴及碘,且每一L1
及L2
相同或不同且構成:
(i) 與M配位之單齒烴基配體,或
(ii) 一起形成與M配位之二齒烴基配體;
其呈固體或液體形式。在某些實施例中,式(I)化合物具有小於約3重量%雜質。在其他實施例中,式(I)化合物具有小於1重量%雜質。在其他實施例中,式(I)化合物係以結晶型分離。式(I)化合物之該等結晶型之特定實例包括MoO2
Cl2
(CH3
CN)2
及WO2
Cl2
(CH3
CN)2
及MoO2
Cl2
(四氫呋喃)2
。在另一實施例中,本發明提供具有式MoO2
Cl2
(CH3
CN)2
、呈結晶型且具有如圖1中所示之x射線晶體結構之化合物。在另一實施例中,本發明提供具有式WO2
Cl2
(CH3
CN)2
、呈結晶型且具有如圖2中所示之x射線晶體結構之化合物。在另一實施例中,本發明提供具有式MoO2
Cl2
(四氫呋喃)2
、呈結晶型且具有如圖5中所示之x射線晶體結構之化合物。該等結晶型進一步在以下試驗部分中表徵。
在另一實施例中,本發明提供具有式MoO2
Cl2
(CH3
CN)2
且具有斜方晶系且單位晶胞尺寸約為以下之化合物:
a = 12.0350(8) Å α= 90°
b = 11.5956(9) Å β= 90°
c = 26.5807(15) Å γ = 90°。
在另一實施例中,本發明提供具有式WO2
Cl2
(CH3
CN)2
且具有斜方晶系且單位晶胞尺寸約為以下之化合物:
a = 8.7091(6) Å α = 90°
b = 8.2536(7) Å β = 90°
c = 12.8021(8) Å γ = 90°。
在另一實施例中,本發明提供具有式MoO2
Cl2
(四氫呋喃)2
且具有斜方晶系且單位晶胞尺寸約為以下之化合物:
a = 7.4048(4) Å α = 90°
b = 12.5437(6) Å β = 90°
c = 13.7487(7) Å γ = 90°。
如本文所用,術語「單位晶胞」係指完全代表晶體圖案之單元之晶體的最小且最簡單之體積元素。單位晶胞之尺寸係由六個數值界定:尺寸a、b及c及角度α、β及γ。晶體係許多單位晶胞之有效堆積陣列。
如本文所用,術語「斜方單位晶胞」係指其中a≠b≠c;α=β=γ=90°之單位晶胞。
如本文所用,「晶格」係指由堆積之單位晶胞之頂點界定之點陣列,如藉由單晶x-射線繞射分析所測定。
如本文所用,「空間群」係指單位晶胞之對稱性。在空間群名稱(例如C2)中,大寫字母指示晶格類型,且其他符號代表在不改變其外觀的情況下可對單位晶胞實施之對稱操作。
在本發明之方法中,適宜水不混溶溶劑包括二氯甲烷、乙酸乙酯、二乙醚、甲苯、苯、戊烷及諸如此類。
在一個實施例中,方法係在升高之溫度(例如約20℃至約100℃)下實施。
式(I)化合物亦可藉由利用下式之起始材料來製備:,
即,通式A2
MO4
之化合物,其中M選自鉻、鉬或鎢,且A選自I族及II族金屬或銨陽離子。該等陽離子之實例包括Li+
、Na+
、K+
、NH4 +
、烷基銨化合物及諸如此類。該等化合物可在式L1
及/或L2
之化合物之存在下與HX類似地反應,以獲得期望之前驅化合物。
本發明方法提供某些化合物,其繼而可用於將某些VI族金屬氣相沈積於各種基板、包括微電子半導體裝置基板上。因此,在另一態樣中,本發明提供在基板上形成材料之方法,其包含使基板與式(I)之化合物接觸(I),
其中M選自鉬、鉻及鎢,X選自氟、氯、溴及碘,且每一L1
及L2
相同或不同且構成:
(i) 與M配位之單齒烴基配體,或
(ii) 一起形成與M配位之二齒烴基配體;
在氣相沈積條件下將含鉬、鉻或鎢之材料沈積於基板上。
用於本發明沈積方法中之基板可為任何適宜類型,且可包含(例如)半導體裝置基板,例如矽基板、二氧化矽基板或其他基於矽之基板。在各個實施例中,基板可包含一或多種金屬或電介質基板,例如Co、Cu、Al、W、WN、WC、 TiN、Mo、MoC、SiO2
、W、SiN、、WCN、Al2
O3
、AlN、ZrO2、HfO2
、SiO2
、氧化鑭(La2
O3
)、氮化鉭(TaN)、氧化釕(RuO2
)、氧化銥(IrO2
)、氧化鈮(Nb2
O3
)及氧化釔(Y2
O3
)。
在某些實施例中,例如在氧化物基板(例如二氧化矽)或另一選擇矽或多晶矽基板之情形中,基板可經處理或製作以在其上包括用於後續沈積材料之障壁層(例如氮化鈦)。
在一個實施例中,沈積於基板表面上之含鉬、鉻或鎢之層可係藉由(例如)脈衝化學氣相沈積(CVD)或原子層沈積(ALD)或其他氣相沈積技術形成,而不需預先形成成核層且因此直接利用源自式(I)化合物之蒸氣。各別式(I)蒸氣接觸步驟可交替並重複地實施所期望之循環次數,以形成期望厚度之鉬、鉻或鎢膜。在各個實施例中,基板(例如氮化鈦)層與該蒸氣之接觸係在低至350℃且在其他實施例中在300℃至750℃範圍內之溫度下實施。
利用源自式(I)化合物之蒸氣,含鉬、鉻或鎢之材料可直接沈積於基板上,以形成元素鉬、鉻或鎢或其相應氧化物之塊體沈積物。H2
之濃度對於金屬或氧化物之形成至關重要,此乃因金屬形成需要大於四莫耳當量或過量之H2
。少於四(4)莫耳當量之H2
將導致形成不同量之該等金屬之氧化物,且因此將需要進一步暴露於H2
以還原由此形成之金屬氧化物。
在各個實施例中,含鉬、鉻或鎢之材料係在300℃至750℃範圍內之溫度下沈積於基板表面上。可實施該方法,以使得氣相沈積條件引起元素鉬、鉻或鎢作為含金屬材料於基板上之沈積。氣相沈積條件可具有任何適宜特徵,且可包含(例如)氫氣或其他還原性氣體之存在,以在基板上形成元素鉬、鉻或鎢之塊體層。
更一般而言,根據本揭示內容,在基板上形成含鉬、鉻或鎢之材料之廣泛方法可包含包括存在氫氣或其他還原性氣體之氣相沈積條件。含鉬、鉻或鎢之材料可在存在或不存在氫氣之情形中沈積於障壁層或表面上。舉例而言,障壁層可由氮化鈦構成,且氮化鈦層可在氫氣之存在下與源自式(I)化合物之蒸氣接觸。
在另一實施例中,在使用式(I)化合物作為沈積金屬氧化物薄膜(例如MoO2
、WO3
及Cr2
O3
)之手段時,可將氧化共反應物(例如氧)添加至方法中。
應瞭解,本發明可以許多替代方式並在眾多種製程條件下實施。本發明方法可在(例如)在基板上製造半導體裝置之製程中實施。半導體裝置可為任何適宜類型,且可包含例如DRAM裝置、3-D NAND裝置或其他裝置或裝置積體結構。在各個實施例中,基板可包含含鉬材料沈積於其中之通孔。舉例而言,裝置可具有在10:1至40:1範圍內之深度對橫向尺寸之縱橫比。在其他實施例中,裝置可為用於平板顯示器或行動裝置中之膜。
根據本發明,沈積含鉬材料之製程化學可包括藉由以下反應沈積元素鉬Mo(0):2 MO2
Cl2
[(L1
)(L2
)] + 6H2
→ 2M (其中M = 鉬、鉻或鎢) + 4HCl + 4H2
O。根據本發明方法沈積之含鉬、鉻或鎢之材料(M)可藉由任何適當評估指標及參數來表徵,例如,含鉬、鉻或鎢之材料之沈積速率、所沈積含鉬、鉻或鎢之材料之膜電阻率、所沈積含鉬、鉻或鎢之材料之膜形態、所沈積含鉬、鉻或鎢之材料之膜應力、材料之階梯覆蓋率以及適當處理條件之製程窗或製程包絡。可採用任何適當評估指標及參數來表徵所沈積之材料並將其與具體製程條件相關聯,以能夠大量生產相應半導體產品。有利地,本發明方法能夠將高純度鉬、鉻或鎢之膜沈積於半導體裝置上。因此,在另一態樣中,本發明提供具有沈積於其上之鉬膜之半導體裝置,其中該膜包含大於99%鉬、鉻或鎢。
在某些實施例中,本發明係關於在基板上形成含鉬、鉻或鎢之材料之方法,其包含藉由化學氣相沈積(CVD)製程利用前驅物式(I)化合物將鉬、鉻或鎢沈積於基板表面上,以在該基板上產生含鉬、鉻或鎢之材料。
該等製程可以如本文多方面闡述之任何適宜方式實施。在具體實施例中,該方法可利用包含化學氣相沈積(例如,脈衝化學氣相沈積)之氣相沈積製程實施。該方法可經實施,以使得所得含鉬、鉻或鎢之材料基本上由元素鉬、鉻或鎢構成,且在各個實施例中,鉬、鉻或鎢可在氫氣或其他適宜還原性氣體之存在下沈積於基板表面上。在本發明之其他實施例中,式(I)之前驅物及還原性氣體可相繼以脈衝方式輸送,以脈衝方式沈積鉬膜,其中脈衝序列針對膜保形性及膜電阻率經最佳化。該方法可在半導體裝置產品(例如DRAM裝置、或3-D NAND、邏輯裝置、平板顯示器或IC封裝組件)之製造中實施。
通常,本發明用於在基板上形成含鉬、鉻或鎢之材料之方法可經實施以達成含鉬、鉻或鎢之材料以高程度之階梯覆蓋率(例如,在約75%至約100%範圍內之階梯覆蓋率)之沈積。
本發明可藉由其較佳實施例之下列實例進一步說明,但應理解,除非另外特定指出,否則包括該等實例僅用於說明之目的且並非意欲限制本發明之範圍。
試驗部分
使用以下一般程序,可製備式(I)化合物:
合成程序 1 號 .
將MoO3
(20.0 g, 138 mmol)加載於配備有磁力攪拌棒之500 mL圓底燒瓶中。將HCl (200 mL, 37%)直接添加至MoO3
,反應燒瓶裝備有水冷式冷凝器(5℃),並使用油浴將所得淺綠色懸浮液加熱至接近回流(95℃)。約2小時後,反應呈現為澄清淺綠色溶液。將反應冷卻至室溫,然後置於冰浴中。此時,將DME (50 mL)直接添加至經冷卻之溶液並使反應升溫至室溫並攪拌過夜。第二天早晨,將淺綠色溶液傾倒於1L分液漏斗中並用DCM (2 x 200 mL)萃取。將有機層合併,使用MgSO4
乾燥,過濾,置於配備有磁力攪拌棒之1L圓底燒瓶,並在減壓下去除溶劑,以獲得呈灰白色固體之MoO2
Cl2
(二甲氧基乙烷)。質量= 12.68g,產率 = 31.8%。產物可經真空昇華(80℃,在25毫托(mTorr)下)純化。1
H NMR (400 MHz, C6
D6
, 298K): δ 3.29 (s, 6H);2.78 (s, 4H) ppm。13
C{1H} NMR (100 MHz, C6
D6
, 298K): δ 70.68, 64.13 ppm。
合成程序 2 號
通式A2
MO4
,其中M = 鉻、鉬或鎢且A = 鋰、鈉或鉀。
此處,一般合成程序及後處理極類似於程序1號,
即,通式A2
MO4
之化合物,其中M係選自鉻、鉬或鎢,且A係選自I及II族金屬或銨陽離子。實例包括Li+
、Na+
、K+
、NH4 +
、烷基銨化合物及諸如此類。
合成程序 3 號
可利用配體取代以合成式(I)化合物。舉例而言,可使用上文程序1號製備MoO2
Cl2
(N,N-二甲基甲醯胺)2
錯合物,且然後N,N-二甲基甲醯胺配體經由溶劑分解來取代二甲氧基乙烷以產生MoO2
Cl2
(二甲氧基乙烷)。
如上所述,圖1係MoO2
Cl2
(CH3
CN)2
之三維固態晶體結構繪示。此化合物經受x-射線結晶學分析並獲得以下資料:
表1. MoO2
Cl2
(CH3
CN)2
之晶體資料及結構精修.
識別碼 NB00618-002
經驗式 C4 H6 Cl2 Mo N2 O2
式量 280.95
溫度 100.0 K
波長 0.71073 Å
晶系 斜方
空間群 Pnma
單位晶胞尺寸 a = 12.0350(8) Å α= 90°。
b = 11.5956(9) Å β= 90°。
c = 26.5807(15) Å γ = 90°.
體積 3709.4(4) Å3
Z, Z’ 16, 4
密度(計算值) 2.012 Mg/m3
吸收係數 1.945 mm-1
F(000) 2176
晶體大小 0.24 x 0.19 x 0.18 mm3
用於資料收集之θ範圍 1.857至26.718°.
指數範圍 -15<=h<=15, -14<=k<=14, -33<=l<=32
所收集之反射 22254
獨立反射 4134 [R(int) = 0.0475]
至θ= 25.242°之完整性 99.9 %
吸收校正 由等效值之半經驗校正
最大及最小透射 0.7454及0.6516
精修方法 對F2
之全矩陣最小二乘法
資料/約束/參數 4134 / 0 / 222
對F2
之擬合優度 1.008
最終R指數[I>2σ(I)] R1 = 0.0258, wR2 = 0.0518
R指數(所有資料) R1 = 0.0388, wR2 = 0.0558
消光係數 0.00013(2)
最大繞射峰及谷 0.492及-0.462 e.Å-3
表2. 原子坐標( × 104
)及等效各向同性位移參數(Å2
x 103
)。U(eq)定義為正交化Uij
張量之跡線的三分之一。
表3. MoO2
Cl2
(CH3
CN)之鍵長[Å]及角度[°]。
對稱變換用於生成等效原子:
#1 x,-y+1/2,z #2 x,-y+3/2,z
表4. MoO2
Cl2
(CH3
CN)之各向異性位移參數(Å2
x 103
)。各向異性位移因子指數採取以下形式:-2π2
[ h2
a*2
U11
+ ... + 2 h k a* b* U12
]
表5. MoO2
Cl2
(CH3
CN)之氫坐標( × 104
)及各向同性位移參數(Å2
x 103
)。
如上所述,圖2係WO2
Cl2
(CH3
CN)2
之三維固態晶體結構繪示。
表6. WO2
Cl2
(CH3
CN)2
之晶體資料及結構精修.
識別碼 NB00666-001
經驗式 C4 H6 Cl2 N2 O2 W
式量 368.86
溫度 100.0 K
波長 0.71073 Å
晶系 斜方
空間群 Pbcn
單位晶胞尺寸 a = 8.7091(6) Å α= 90°。
b = 8.2536(7) Å β= 90°。
c = 12.8021(8) Å γ = 90°。
體積 920.23(12) Å3
Z 4
密度(計算值) 2.662 Mg/m3
吸收係數 13.088 mm-1
F(000) 672
晶體大小 0.37 x 0.35 x 0.33 mm3
用於資料收集之θ範圍 3.183至28.277°.
指數範圍 -11<=h<=10, -11<=k<=6, -16<=l<=16
所收集之反射 5168
獨立反射 1139 [R(int) = 0.0281]
至θ= 25.242°之完整性 99.9 %
吸收校正 由等效值之半經驗校正
最大及最小透射 0.6035及0.3693
精修方法 對F2
之全矩陣最小二乘法
資料/約束/參數 1139 / 0 / 52
對F2
之擬合優度 1.133
最終R指數[I>2σ(I)] R1 = 0.0183, wR2 = 0.0431
R指數(所有資料) R1 = 0.0256, wR2 = 0.0459
消光係數 n/a
最大繞射峰及谷 0.641及-1.611 e.Å-3
表7. WO2
Cl2
(CH3
CN)2
之原子坐標( × 104
)及等效各向同性位移參數(Å2
x 103
)。U(eq)定義為正交化Uij
張量之跡線的三分之一。
表8. WO2
Cl2
(CH3
CN)2
之鍵長[Å]及角度[°]。
對稱變換用於生成等效原子:
#1 -x+1,y,-z+1/2
表9. WO2
Cl2
(CH3
CN)2
之各向異性位移參數(Å2
x 103
)。各向異性位移因子指數採取以下形式:-2π2
[ h2
a*2
U11
+ ... + 2 h k a* b* U12
]
表10. WO2
Cl2
(CH3
CN)2
之氫坐標( × 104
)及各向同性位移參數(Å2
x 103
)。
x | y | z | U(eq) | |
Mo(4) | 7248(1) | 2500 | 4414(1) | 10(1) |
Mo(2) | 2330(1) | 7500 | 3151(1) | 10(1) |
Mo(1) | 2455(1) | 2500 | 3069(1) | 11(1) |
Mo(3) | 7667(1) | 7500 | 4464(1) | 12(1) |
Cl(2) | 4372(1) | 2500 | 2868(1) | 17(1) |
Cl(3) | 1038(1) | 7500 | 2486(1) | 19(1) |
Cl(4) | 4104(1) | 7500 | 3531(1) | 15(1) |
Cl(5) | 5845(1) | 7500 | 4786(1) | 20(1) |
Cl(7) | 7535(1) | 2500 | 3536(1) | 17(1) |
Cl(8) | 7804(1) | 2500 | 5264(1) | 16(1) |
Cl(1) | 877(1) | 2500 | 3592(1) | 19(1) |
Cl(6) | 9054(1) | 7500 | 3833(1) | 19(1) |
O(1) | 2102(2) | 3651(1) | 2715(1) | 19(1) |
N(2) | 3254(2) | 6256(2) | 2597(1) | 13(1) |
N(1) | 3109(2) | 3737(2) | 3706(1) | 16(1) |
N(3) | 6849(2) | 8742(2) | 3887(1) | 16(1) |
O(4) | 6389(2) | 1350(2) | 4438(1) | 18(1) |
O(3) | 8142(2) | 6347(2) | 4788(1) | 21(1) |
C(2) | 3871(2) | 5026(2) | 4428(1) | 17(1) |
C(1) | 3436(2) | 4302(2) | 4022(1) | 13(1) |
C(4) | 4342(2) | 4940(2) | 1977(1) | 18(1) |
C(7) | 9534(2) | 4320(2) | 4355(1) | 10(1) |
N(4) | 8773(2) | 3745(2) | 4367(1) | 15(1) |
C(8) | 10517(2) | 5057(2) | 4342(1) | 15(1) |
O(2) | 1813(2) | 8648(2) | 3461(1) | 19(1) |
C(3) | 3728(2) | 5680(2) | 2325(1) | 13(1) |
C(6) | 5822(2) | 10073(2) | 3259(1) | 17(1) |
C(5) | 6407(2) | 9324(2) | 3608(1) | 12(1) |
Mo(4)-Cl(7) | 2.3601(9) | |
Mo(4)-Cl(8) | 2.3561(9) | |
Mo(4)-O(4) | 1.6885(17) | |
Mo(4)-O(4)#1 | 1.6885(17) | |
Mo(4)-N(4)#1 | 2.338(2) | |
Mo(4)-N(4) | 2.338(2) | |
Mo(2)-Cl(3) | 2.3547(9) | |
Mo(2)-Cl(4) | 2.3623(9) | |
Mo(2)-N(2) | 2.343(2) | |
Mo(2)-N(2)#2 | 2.343(2) | |
Mo(2)-O(2) | 1.6846(17) | |
Mo(2)-O(2)#2 | 1.6846(17) | |
Mo(1)-Cl(2) | 2.3672(10) | |
Mo(1)-Cl(1) | 2.3534(10) | |
Mo(1)-O(1)#1 | 1.6867(17) | |
Mo(1)-O(1) | 1.6867(17) | |
Mo(1)-N(1) | 2.355(2) | |
Mo(1)-N(1)#1 | 2.355(2) | |
Mo(3)-Cl(5) | 2.3528(10) | |
Mo(3)-Cl(6) | 2.3671(10) | |
Mo(3)-N(3) | 2.323(2) | |
Mo(3)-N(3)#2 | 2.323(2) | |
Mo(3)-O(3)#2 | 1.6885(17) | |
Mo(3)-O(3) | 1.6885(17) | |
N(2)-C(3) | 1.137(3) | |
N(1)-C(1) | 1.135(3) | |
N(3)-C(5) | 1.134(3) | |
C(2)-C(1) | 1.462(3) | |
C(4)-C(3) | 1.462(3) | |
C(7)-N(4) | 1.133(3) | |
C(7)-C(8) | 1.461(3) | |
C(6)-C(5) | 1.453(3) | |
Cl(8)-Mo(4)-Cl(7) | 155.09(4) | |
O(4)#1-Mo(4)-Cl(7) | 97.26(6) | |
O(4)-Mo(4)-Cl(7) | 97.26(6) | |
O(4)#1-Mo(4)-Cl(8) | 97.95(6) | |
O(4)-Mo(4)-Cl(8) | 97.94(6) | |
O(4)#1-Mo(4)-O(4) | 104.33(13) | |
O(4)#1-Mo(4)-N(4)#1 | 165.97(8) | |
O(4)-Mo(4)-N(4) | 165.97(8) | |
O(4)-Mo(4)-N(4)#1 | 89.70(8) | |
O(4)#1-Mo(4)-N(4) | 89.70(8) | |
N(4)-Mo(4)-Cl(7) | 80.39(5) | |
N(4)#1-Mo(4)-Cl(7) | 80.39(5) | |
N(4)-Mo(4)-Cl(8) | 80.08(5) | |
N(4)#1-Mo(4)-Cl(8) | 80.08(5) | |
N(4)-Mo(4)-N(4)#1 | 76.27(11) | |
Cl(3)-Mo(2)-Cl(4) | 156.61(3) | |
N(2)-Mo(2)-Cl(3) | 80.86(5) | |
N(2)#2-Mo(2)-Cl(3) | 80.86(5) | |
N(2)-Mo(2)-Cl(4) | 80.76(5) | |
N(2)#2-Mo(2)-Cl(4) | 80.76(5) | |
N(2)#2-Mo(2)-N(2) | 76.03(10) | |
O(2)#2-Mo(2)-Cl(3) | 97.08(6) | |
O(2)-Mo(2)-Cl(3) | 97.08(6) | |
O(2)-Mo(2)-Cl(4) | 97.18(7) | |
O(2)#2-Mo(2)-Cl(4) | 97.18(7) | |
O(2)#2-Mo(2)-N(2) | 89.75(8) | |
O(2)-Mo(2)-N(2)#2 | 89.75(8) | |
O(2)-Mo(2)-N(2) | 165.78(8) | |
O(2)#2-Mo(2)-N(2)#2 | 165.78(8) | |
O(2)#2-Mo(2)-O(2) | 104.47(12) | |
Cl(1)-Mo(1)-Cl(2) | 156.82(4) | |
Cl(1)-Mo(1)-N(1)#1 | 81.08(6) | |
Cl(1)-Mo(1)-N(1) | 81.08(6) | |
O(1)-Mo(1)-Cl(2) | 96.88(6) | |
O(1)#1-Mo(1)-Cl(2) | 96.88(6) | |
O(1)#1-Mo(1)-Cl(1) | 97.24(6) | |
O(1)-Mo(1)-Cl(1) | 97.24(6) | |
O(1)#1-Mo(1)-O(1) | 104.56(12) | |
O(1)-Mo(1)-N(1)#1 | 165.24(8) | |
O(1)#1-Mo(1)-N(1)#1 | 90.19(8) | |
O(1)-Mo(1)-N(1) | 90.20(8) | |
O(1)#1-Mo(1)-N(1) | 165.24(8) | |
N(1)#1-Mo(1)-Cl(2) | 80.59(6) | |
N(1)-Mo(1)-Cl(2) | 80.59(6) | |
N(1)#1-Mo(1)-N(1) | 75.05(10) | |
Cl(5)-Mo(3)-Cl(6) | 156.17(4) | |
N(3)#2-Mo(3)-Cl(5) | 81.11(6) | |
N(3)-Mo(3)-Cl(5) | 81.11(6) | |
N(3)-Mo(3)-Cl(6) | 80.24(6) | |
N(3)#2-Mo(3)-Cl(6) | 80.24(6) | |
N(3)#2-Mo(3)-N(3) | 76.59(10) | |
O(3)#2-Mo(3)-Cl(5) | 97.49(7) | |
O(3)-Mo(3)-Cl(5) | 97.49(7) | |
O(3)-Mo(3)-Cl(6) | 97.00(7) | |
O(3)#2-Mo(3)-Cl(6) | 97.00(7) | |
O(3)#2-Mo(3)-N(3) | 89.38(8) | |
O(3)-Mo(3)-N(3) | 165.95(8) | |
O(3)-Mo(3)-N(3)#2 | 89.38(8) | |
O(3)#2-Mo(3)-N(3)#2 | 165.95(8) | |
O(3)#2-Mo(3)-O(3) | 104.65(13) | |
C(3)-N(2)-Mo(2) | 177.7(2) | |
C(1)-N(1)-Mo(1) | 177.7(2) | |
C(5)-N(3)-Mo(3) | 177.0(2) | |
N(1)-C(1)-C(2) | 179.3(3) | |
N(4)-C(7)-C(8) | 179.7(3) | |
C(7)-N(4)-Mo(4) | 177.4(2) | |
N(2)-C(3)-C(4) | 179.7(3) | |
N(3)-C(5)-C(6) | 178.8(3) |
U11 | U22 | U33 | U23 | U13 | U12 | |
Mo(4) | 9(1) | 9(1) | 13(1) | 0 | 2(1) | 0 |
Mo(2) | 9(1) | 10(1) | 10(1) | 0 | 3(1) | 0 |
Mo(1) | 13(1) | 10(1) | 10(1) | 0 | -3(1) | 0 |
Mo(3) | 15(1) | 9(1) | 11(1) | 0 | -4(1) | 0 |
Cl(2) | 16(1) | 18(1) | 17(1) | 0 | 3(1) | 0 |
Cl(3) | 12(1) | 23(1) | 22(1) | 0 | -4(1) | 0 |
Cl(4) | 13(1) | 18(1) | 13(1) | 0 | -1(1) | 0 |
Cl(5) | 20(1) | 19(1) | 21(1) | 0 | 3(1) | 0 |
Cl(7) | 19(1) | 20(1) | 13(1) | 0 | 0(1) | 0 |
Cl(8) | 19(1) | 17(1) | 13(1) | 0 | 2(1) | 0 |
Cl(1) | 15(1) | 20(1) | 23(1) | 0 | 4(1) | 0 |
Cl(6) | 17(1) | 20(1) | 21(1) | 0 | 2(1) | 0 |
O(1) | 21(1) | 16(1) | 21(1) | 5(1) | -4(1) | 1(1) |
N(2) | 11(1) | 12(1) | 17(1) | 1(1) | -1(1) | 2(1) |
N(1) | 18(1) | 14(1) | 17(1) | -2(1) | 0(1) | -1(1) |
N(3) | 18(1) | 13(1) | 17(1) | -2(1) | -1(1) | 1(1) |
O(4) | 17(1) | 15(1) | 21(1) | -1(1) | 3(1) | -5(1) |
O(3) | 25(1) | 16(1) | 22(1) | 4(1) | -2(1) | 4(1) |
C(2) | 20(2) | 16(2) | 17(2) | -5(1) | 0(1) | 1(1) |
C(1) | 11(1) | 13(1) | 15(1) | 5(1) | 4(1) | 4(1) |
C(4) | 21(2) | 16(2) | 16(1) | -2(1) | 4(1) | 2(1) |
C(7) | 16(1) | 9(1) | 6(1) | 1(1) | 1(1) | 3(1) |
N(4) | 17(1) | 14(1) | 13(1) | -1(1) | 0(1) | 2(1) |
C(8) | 14(2) | 16(2) | 15(1) | 3(1) | -3(1) | -4(1) |
O(2) | 17(1) | 21(1) | 20(1) | -4(1) | 5(1) | 3(1) |
C(3) | 12(1) | 13(1) | 13(1) | 3(1) | -4(1) | -2(1) |
C(6) | 18(2) | 15(2) | 18(1) | 7(1) | -3(1) | -1(1) |
C(5) | 13(1) | 10(1) | 14(1) | -2(1) | 2(1) | -2(1) |
x | y | z | U(eq) | |
H(2A) | 3835 | 5837 | 4327 | 26 |
H(2B) | 4645 | 4814 | 4496 | 26 |
H(2C) | 3425 | 4910 | 4732 | 26 |
H(4A) | 3937 | 4884 | 1658 | 27 |
H(4B) | 4422 | 4169 | 2124 | 27 |
H(4C) | 5080 | 5270 | 1916 | 27 |
H(8A) | 10874 | 4995 | 4012 | 22 |
H(8B) | 11040 | 4812 | 4604 | 22 |
H(8C) | 10298 | 5860 | 4402 | 22 |
H(6A) | 6256 | 10150 | 2949 | 26 |
H(6B) | 5722 | 10835 | 3412 | 26 |
H(6C) | 5094 | 9740 | 3181 | 26 |
x | y | z | U(eq) | |
W(1) | 5000 | 3420(1) | 2500 | 7(1) |
Cl(1) | 7382(1) | 4003(1) | 3276(1) | 14(1) |
O(1) | 5680(3) | 2149(3) | 1552(2) | 12(1) |
N(1) | 4324(4) | 5646(4) | 3495(2) | 12(1) |
C(2) | 3798(5) | 8375(4) | 4431(3) | 14(1) |
C(1) | 4080(4) | 6841(4) | 3911(3) | 11(1) |
W(1)-Cl(1)#1 | 2.3502(9) |
W(1)-Cl(1) | 2.3502(9) |
W(1)-O(1)#1 | 1.710(3) |
W(1)-O(1) | 1.710(3) |
W(1)-N(1)#1 | 2.312(3) |
W(1)-N(1) | 2.312(3) |
N(1)-C(1) | 1.141(5) |
C(2)-H(2A) | 0.9800 |
C(2)-H(2B) | 0.9800 |
C(2)-H(2C) | 0.9800 |
C(2)-C(1) | 1.452(5) |
Cl(1)-W(1)-Cl(1)#1 | 156.36(4) |
O(1)-W(1)-Cl(1) | 96.89(9) |
O(1)#1-W(1)-Cl(1) | 97.55(9) |
O(1)-W(1)-Cl(1)#1 | 97.55(9) |
O(1)#1-W(1)-Cl(1)#1 | 96.89(9) |
O(1)-W(1)-O(1)#1 | 104.30(17) |
O(1)-W(1)-N(1) | 165.20(12) |
O(1)-W(1)-N(1)#1 | 90.48(11) |
O(1)#1-W(1)-N(1) | 90.48(11) |
O(1)#1-W(1)-N(1)#1 | 165.20(12) |
N(1)-W(1)-Cl(1)#1 | 81.11(8) |
N(1)#1-W(1)-Cl(1)#1 | 80.15(8) |
N(1)#1-W(1)-Cl(1) | 81.11(8) |
N(1)-W(1)-Cl(1) | 80.15(8) |
N(1)-W(1)-N(1)#1 | 74.75(15) |
C(1)-N(1)-W(1) | 172.6(3) |
H(2A)-C(2)-H(2B) | 109.5 |
H(2A)-C(2)-H(2C) | 109.5 |
H(2B)-C(2)-H(2C) | 109.5 |
C(1)-C(2)-H(2A) | 109.5 |
C(1)-C(2)-H(2B) | 109.5 |
C(1)-C(2)-H(2C) | 109.5 |
N(1)-C(1)-C(2) | 178.8(4) |
U11 | U22 | U33 | U23 | U13 | U12 | |
W(1) | 8(1) | 5(1) | 7(1) | 0 | -1(1) | 0 |
Cl(1) | 11(1) | 14(1) | 16(1) | -1(1) | -4(1) | -1(1) |
O(1) | 12(1) | 11(1) | 14(1) | -1(1) | -2(1) | 1(1) |
N(1) | 10(2) | 12(2) | 12(2) | 0(1) | 0(1) | -1(1) |
C(2) | 21(2) | 8(2) | 12(2) | -3(1) | -3(2) | 2(1) |
C(1) | 11(2) | 11(2) | 11(2) | 1(1) | -4(2) | -2(1) |
x | y | z | U(eq) | |
H(2A) | 3864 | 9258 | 3921 | 16 |
H(2B) | 4569 | 8540 | 4979 | 16 |
H(2C) | 2772 | 8363 | 4744 | 16 |
如上所述,圖5係MoO2
Cl2
(THF)2
(THF = 四氫呋喃)之三維固態晶體結構繪示。此化合物經受x-射線結晶學分析並獲得以下資料:
表11. MoO2
Cl2
(THF)2
之晶體資料及結構精修. 經驗式 C8 H16 Cl2 Mo O4
分子式 C8 H16 Cl2 Mo O4
式量 343.05
溫度 200 K
波長 0.71073 Å
晶系 斜方
空間群 P2 1
2 1
2 1
單位晶胞尺寸 a = 7.4048(4) Å α= 90°。
b = 12.5437(6) Å β= 90°。
c = 13.7487(7) Å γ = 90°。
體積 1277.03(11) Å3
Z 4
密度(計算值) 1.784 Mg/m3
吸收係數 1.437 mm-1
F(000) 688
晶體大小 0.15 x 0.15 x 0.1 mm3
晶體色彩,習性 透明無色塊狀
用於資料收集之θ範圍 2.198至26.382°.
指數範圍 -9<=h<=9, -15<=k<=13, -17<=l<=17
所收集之反射 11549
獨立反射 2611 [R(int) = 0.0731]
至θ = 25.242°之完整性 99.9 %
吸收校正 由等效值之半經驗校正
最大及最小透射 0.4652及0.3891
精修方法 對F2
之全矩陣最小二乘法
資料/約束/參數 2611 / 0 / 136
對F2
之擬合優度 1.065
最終R指數[I>2σ(I)] R1 = 0.0332, wR2 = 0.0838
R指數(所有資料) R1 = 0.0361, wR2 = 0.0858
絕對結構參數 0.00(5)
消光係數 n/a
最大繞射峰及谷 0.360及-0.510 e.Å-3
表12. 實例11之原子坐標(x 104
)及等效各向同性位移參數(Å2
x 103
)。U(eq)定義為正交化Uij
張量之跡線的三分之一。
表13. MoO2
Cl2
(THF)2
之鍵長[Å]及角度[°].
對稱變換用於生成等效原子:
表14. MoO2
Cl2
(THF)2
之各向異性位移參數(Å2
x 103
)。各向異性位移因子指數採取以下形式:-2π2
[ h2
a*2
U11
+ ...+ 2 h k a* b* U12
]
表15. MoO2
Cl2
(THF)2
之氫坐標(x 104
)及各向同性位移參數(Å2
x 103
)。
下表說明某些式(I)化合物之各種物理性質:
縮寫:
x | y | z | U(eq) | |
Mo(1) | 5728(1) | 5036(1) | 4146(1) | 36(1) |
Cl(2) | 6796(2) | 6222(1) | 2947(1) | 42(1) |
Cl(1) | 5665(2) | 3642(1) | 5296(1) | 59(1) |
O(3) | 7484(4) | 3874(3) | 3290(2) | 33(1) |
O(4) | 8555(5) | 5286(3) | 4799(3) | 37(1) |
O(2) | 3868(5) | 4641(4) | 3542(4) | 60(1) |
O(1) | 4986(7) | 6018(4) | 4890(3) | 63(1) |
C(6) | 10956(8) | 5056(5) | 5895(4) | 56(2) |
C(1) | 7073(9) | 2746(4) | 3220(4) | 44(1) |
C(8) | 9173(9) | 6336(5) | 5068(4) | 54(2) |
C(2) | 8331(10) | 2315(4) | 2433(4) | 52(2) |
C(4) | 9009(8) | 4133(5) | 2657(4) | 45(1) |
C(7) | 10698(10) | 6210(6) | 5705(8) | 97(3) |
C(3) | 9888(9) | 3099(5) | 2452(5) | 53(2) |
C(5) | 9912(11) | 4520(5) | 5131(5) | 64(2) |
Mo(1)-Cl(2) | 2.3575(14) |
Mo(1)-Cl(1) | 2.3576(15) |
Mo(1)-O(3) | 2.280(3) |
Mo(1)-O(4) | 2.300(4) |
Mo(1)-O(2) | 1.683(4) |
Mo(1)-O(1) | 1.692(4) |
O(3)-C(1) | 1.451(6) |
O(3)-C(4) | 1.462(6) |
O(4)-C(8) | 1.442(6) |
O(4)-C(5) | 1.463(8) |
C(6)-H(6A) | 0.9900 |
C(6)-H(6B) | 0.9900 |
C(6)-C(7) | 1.483(9) |
C(6)-C(5) | 1.469(8) |
C(1)-H(1A) | 0.9900 |
C(1)-H(1B) | 0.9900 |
C(1)-C(2) | 1.526(8) |
C(8)-H(8A) | 0.9900 |
C(8)-H(8B) | 0.9900 |
C(8)-C(7) | 1.438(9) |
C(2)-H(2A) | 0.9900 |
C(2)-H(2B) | 0.9900 |
C(2)-C(3) | 1.516(9) |
C(4)-H(4A) | 0.9900 |
C(4)-H(4B) | 0.9900 |
C(4)-C(3) | 1.478(8) |
C(7)-H(7A) | 0.9900 |
C(7)-H(7B) | 0.9900 |
C(3)-H(3A) | 0.9900 |
C(3)-H(3B) | 0.9900 |
C(5)-H(5A) | 0.9900 |
C(5)-H(5B) | 0.9900 |
Cl(1)-Mo(1)-Cl(2) | 160.67(6) |
O(3)-Mo(1)-Cl(2) | 81.43(9) |
O(3)-Mo(1)-Cl(1) | 83.31(10) |
O(3)-Mo(1)-O(4) | 76.68(12) |
O(4)-Mo(1)-Cl(2) | 83.21(10) |
O(4)-Mo(1)-Cl(1) | 81.78(10) |
O(2)-Mo(1)-Cl(2) | 96.61(17) |
O(2)-Mo(1)-Cl(1) | 95.55(17) |
O(2)-Mo(1)-O(3) | 91.38(18) |
O(2)-Mo(1)-O(4) | 167.97(18) |
O(2)-Mo(1)-O(1) | 104.3(2) |
O(1)-Mo(1)-Cl(2) | 94.13(16) |
O(1)-Mo(1)-Cl(1) | 97.36(16) |
O(1)-Mo(1)-O(3) | 164.1(2) |
O(1)-Mo(1)-O(4) | 87.7(2) |
C(1)-O(3)-Mo(1) | 122.6(3) |
C(1)-O(3)-C(4) | 109.8(4) |
C(4)-O(3)-Mo(1) | 127.3(3) |
C(8)-O(4)-Mo(1) | 120.9(3) |
C(8)-O(4)-C(5) | 107.6(5) |
C(5)-O(4)-Mo(1) | 131.1(4) |
H(6A)-C(6)-H(6B) | 108.9 |
C(7)-C(6)-H(6A) | 110.8 |
C(7)-C(6)-H(6B) | 110.8 |
C(5)-C(6)-H(6A) | 110.8 |
C(5)-C(6)-H(6B) | 110.8 |
C(5)-C(6)-C(7) | 104.7(5) |
O(3)-C(1)-H(1A) | 110.7 |
O(3)-C(1)-H(1B) | 110.7 |
O(3)-C(1)-C(2) | 105.4(5) |
H(1A)-C(1)-H(1B) | 108.8 |
C(2)-C(1)-H(1A) | 110.7 |
C(2)-C(1)-H(1B) | 110.7 |
O(4)-C(8)-H(8A) | 110.2 |
O(4)-C(8)-H(8B) | 110.2 |
H(8A)-C(8)-H(8B) | 108.5 |
C(7)-C(8)-O(4) | 107.8(5) |
C(7)-C(8)-H(8A) | 110.2 |
C(7)-C(8)-H(8B) | 110.2 |
C(1)-C(2)-H(2A) | 111.2 |
C(1)-C(2)-H(2B) | 111.2 |
H(2A)-C(2)-H(2B) | 109.1 |
C(3)-C(2)-C(1) | 102.9(5) |
C(3)-C(2)-H(2A) | 111.2 |
C(3)-C(2)-H(2B) | 111.2 |
O(3)-C(4)-H(4A) | 110.7 |
O(3)-C(4)-H(4B) | 110.7 |
O(3)-C(4)-C(3) | 105.0(4) |
H(4A)-C(4)-H(4B) | 108.8 |
C(3)-C(4)-H(4A) | 110.7 |
C(3)-C(4)-H(4B) | 110.7 |
C(6)-C(7)-H(7A) | 110.0 |
C(6)-C(7)-H(7B) | 110.0 |
C(8)-C(7)-C(6) | 108.4(6) |
C(8)-C(7)-H(7A) | 110.0 |
C(8)-C(7)-H(7B) | 110.0 |
H(7A)-C(7)-H(7B) | 108.4 |
C(2)-C(3)-H(3A) | 111.0 |
C(2)-C(3)-H(3B) | 111.0 |
C(4)-C(3)-C(2) | 103.7(5) |
C(4)-C(3)-H(3A) | 111.0 |
C(4)-C(3)-H(3B) | 111.0 |
H(3A)-C(3)-H(3B) | 109.0 |
O(4)-C(5)-C(6) | 106.4(5) |
O(4)-C(5)-H(5A) | 110.4 |
O(4)-C(5)-H(5B) | 110.4 |
C(6)-C(5)-H(5A) | 110.4 |
C(6)-C(5)-H(5B) | 110.4 |
H(5A)-C(5)-H(5B) | 108.6 |
U11 | U22 | U33 | U23 | U13 | U12 | |
Mo(1) | 30(1) | 33(1) | 44(1) | -1(1) | 12(1) | 0(1) |
Cl(2) | 47(1) | 32(1) | 46(1) | 7(1) | -1(1) | 0(1) |
Cl(1) | 77(1) | 48(1) | 52(1) | 10(1) | 30(1) | -8(1) |
O(3) | 35(2) | 24(2) | 38(2) | -4(1) | 9(2) | -2(1) |
O(4) | 43(2) | 25(2) | 42(2) | -5(2) | -5(2) | 0(2) |
O(2) | 31(2) | 63(3) | 87(3) | 5(3) | 1(2) | -6(2) |
O(1) | 65(3) | 52(3) | 72(3) | -10(2) | 32(3) | 12(2) |
C(6) | 43(3) | 66(5) | 59(4) | 2(4) | 4(2) | -6(3) |
C(1) | 53(3) | 28(3) | 50(3) | -8(2) | -2(3) | -7(3) |
C(8) | 75(4) | 31(3) | 56(4) | -6(3) | -11(3) | -12(3) |
C(2) | 80(4) | 33(3) | 42(3) | -8(3) | -7(3) | 16(3) |
C(4) | 49(3) | 39(3) | 46(3) | -3(3) | 19(3) | 0(3) |
C(7) | 73(5) | 45(4) | 172(9) | -34(5) | -58(6) | 10(4) |
C(3) | 58(3) | 42(4) | 59(4) | -1(3) | 20(3) | 10(3) |
C(5) | 70(4) | 43(4) | 78(5) | -5(3) | -24(4) | 13(3) |
x | y | z | U(eq) | |
H(6A) | 12249 | 4862 | 5854 | 67 |
H(6B) | 10496 | 4862 | 6548 | 67 |
H(1A) | 5794 | 2636 | 3035 | 52 |
H(1B) | 7299 | 2385 | 3848 | 52 |
H(8A) | 9528 | 6741 | 4481 | 64 |
H(8B) | 8197 | 6730 | 5404 | 64 |
H(2A) | 8745 | 1584 | 2591 | 62 |
H(2B) | 7731 | 2309 | 1790 | 62 |
H(4A) | 9857 | 4623 | 2988 | 54 |
H(4B) | 8586 | 4471 | 2048 | 54 |
H(7A) | 10480 | 6593 | 6324 | 116 |
H(7B) | 11794 | 6512 | 5398 | 116 |
H(3A) | 10766 | 2913 | 2968 | 64 |
H(3B) | 10521 | 3115 | 1817 | 64 |
H(5A) | 10710 | 4310 | 4586 | 76 |
H(5B) | 9322 | 3872 | 5392 | 76 |
化合物 | M.P. | STA-DSC | 實例編號 | |
T50 ( ℃ ) | 殘餘質量 (%) | |||
MoO2 Cl2 (DME) | 128.4 | 184.4 | 1.69 | 1 |
MoO2 Cl2 (DMM) | 200.4 | 46.36 | 2 | |
MoO2 Cl2 (1,2-DMP) | 131.8 | 185.0 | 40.89 | 3 |
MoO2 Cl2 (DMA)2 | 124.7 | 238.3 | 17.06 | 4 |
MoO2 Cl2 (DMF)2 | 162.6 | 232.0 | 9.93 | 5 |
MoO2 Cl2 (MeCN)2 | 112.4 | 143.5 | 2.61 | 6 |
MoO2 Cl2 (tBuCN)x | 95.3 | 135.7 | 4.55 | 7 |
MoO2 Cl2 (iPrCN)x | 69.9 | 134.1 | 3.15 | 8 |
MoO2 Cl2 (DMCA) | n/a | 64.45 | 9 | |
MoO2 Cl2 (TMEN) | n/a | 57.12 | 10 | |
MoO2 Cl2 (THF)2 | 138.1 | 18.77 | 11 |
DME = 1,2-二甲氧基乙烷 |
DMM = 1,2-二甲氧基甲烷 |
1,2-DMP = 1,2-二甲氧基丙烷 |
DMA =N,N -二甲基乙醯胺 |
DMF =N,N -二甲基甲醯胺 |
DMCA = N,N-二甲基氰基乙醯胺 |
TMEN = N,N,N’,N’-四甲基乙二胺 |
CN = 腈 |
THF = 四氫呋喃 |
STA-DSC :
同步熱分析 - 差示掃描量熱法
圖1係MoO2
Cl2
(CH3
CN)2
之三維固態晶體結構繪示。
圖2係WO2
Cl2
(CH3
CN)2
之三維固態晶體結構繪示。
圖3係使用MoO2
Cl2
(二甲氧基乙烷)作為前驅物在氮化鈦基板上鉬沈積速率(Å/循環)對基板溫度(℃)之圖表。
圖4係使用MoO2
Cl2
(二甲氧基乙烷)2
作為前驅物在氮化鈦基板上XRF碳(用於碳之X-射線螢光分析) (µgm/cm2
/100Å Mo)對基板溫度(℃)之圖表。因此,圖3及4圖解說明Mo相對於MoC優先沈積之製程參數。
圖5係MoO2
Cl2
(四氫呋喃)2
之三維固態晶體結構繪示。
Claims (9)
- 如請求項1之方法,其中該烴基配體進一步包含至少一個氧、硫或氮原子。
- 如請求項1之方法,其中L1及L2係獨立地選擇並包含單齒配體,或一起形成二齒配體並選自二胺、三胺及二醇。
- 如請求項1之方法,其中L1及L2係獨立地選擇並包含單齒配體,或一起形成二齒配體並選自第三丁基腈、甲苯、四氫呋喃及乙腈,且該等基團視情況經一或多個選自以下之基團取代:鹵基、氰基、硝基、C1-C6烷基、C1-C6烷氧基、四氫呋喃、C1-C6烷氧基羰基及苯基;1,2-二甲氧基乙 烷;1,2-二乙氧基乙烷;1,2-二甲氧基丙烷;N,N-二甲基乙醯胺;N,N-二甲基甲醯胺;N,N-二甲基氰基乙醯胺;N,N,N',N'-四甲基乙二胺、乙二胺、六伸乙基二胺、二伸乙基三胺(diethylene triamine)及二伸乙基三胺(diethylenetriamine);二甲亞碸;及乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇及1,6-己二醇。
- 如請求項1之方法,其中L1及L2一起形成選自以下之二齒配體:乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、N,N,N',N'-四甲基乙二胺、乙二胺及二伸乙基三胺。
- 如請求項1之方法,其中M係鉬且L1及L2係1,2-二甲氧基乙烷、四氫呋喃或乙腈。
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