TWI739507B - 氧鹵化物前驅物 - Google Patents

氧鹵化物前驅物 Download PDF

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TWI739507B
TWI739507B TW109123232A TW109123232A TWI739507B TW I739507 B TWI739507 B TW I739507B TW 109123232 A TW109123232 A TW 109123232A TW 109123232 A TW109123232 A TW 109123232A TW I739507 B TWI739507 B TW I739507B
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大衛 M 艾曼特
羅柏茲 L 二世 懷特
湯瑪士 H 邦姆
布萊恩 C 漢迪克斯
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Abstract

本發明提供一種製備鉬及鎢氧鹵化物化合物之方法,該氧鹵化物化合物適用於將含有鉬及鎢之薄膜沈積於微電子裝置的各種表面上。在本發明之方法中,在固態介質中或在包含有包含鹼金屬鹽及/或鹼土金屬鹽之共晶摻合物的熔融相反應中加熱三氧化鉬或三氧化鎢。由此形成之鉬或鎢氧鹵化物可以蒸氣形式分離且結晶以提供高度純化前驅物化合物,諸如MoO2 Cl2

Description

氧鹵化物前驅物
本發明係關於用於某些含第VI族材料之氣相沈積之某些前驅物、其製備方法及其新穎晶體結構。
由於其極高熔點、低熱膨脹係數、低電阻率及高熱導率之特徵,諸如鉬及鎢之第VI族金屬日益用於半導體裝置之製造中,包括用於擴散障壁、電極、光罩、電力電子基板、低電阻率閘極及互連件中。
該等效用促進實現用於此類應用之鉬及鎢薄膜的沈積,該等應用的特徵在於經沈積薄膜之高保形性及容納高效大批量加工操作之高沈積速率。此又促進開發適用於氣相沈積操作之改良的鉬及鎢源試劑,以及利用此類試劑之改良的方法參數。
五氯化鉬最常用作含鉬材料之化學氣相沈積之鉬源。另一種源試劑或前驅物為MoO2 Cl2 ,但仍需要以高產率及高純度製備此類試劑以及諸如WOCl4 、WO2 Cl2 、MoOCl4 及其類似物之其他氧鹵化物。
本發明提供一種用於製備某些第VI族金屬氧鹵化物化合物之方法,該等氧鹵化物化合物適用於將含有第VI族之薄膜沈積於微電子裝置的各種表面上。在本發明之方法中,在固態介質中或在包含有包含一或多種鹼金屬鹽及/或鹼土金屬鹽之共晶摻合物的熔融相反應中加熱三氧化鉬或三氧化鎢。由此形成之鉬或鎢氧鹵化物可以蒸氣形式分離且結晶以提供高度純化結晶氧鹵化物,諸如MoO2 Cl2 及WO2 Cl2 ,以提供本發明之另一態樣。
在第一態樣中,本發明提供一種用於製備式MOy Xz 之化合物之方法,其中M選自鉬及鎢,且X選自氯、氟、溴及碘,y為1或2,且z為2或4,該方法包括使以下式之化合物
Figure 02_image003
與至少一種式A-X之化合物在約200℃至約900℃之溫度下接觸,其中A係選自元素週期表之第1族之元素、第2族之元素、過渡金屬及主族元素。
如本文所闡述,A可為能夠形成鹵化物之任何元素。
在一個實施例中,A選自鹼金屬及鹼土金屬。
在一個實施例中,A選自鋰、鈉及鉀。在另一個實施例中,A選自鎂、鈣、鍶、鋇、鈹、鈧、鈦、釩及鉻。在另一個實施例中,A為鋰或鉀。
在一個實施例中,X為氯。
在另一個實施例中,至少一種式A-X之化合物為兩種或更多種化合物之混合物,且在某些實施例中,選擇該等化合物以便形成共晶混合物。
在本發明之方法中,儘管當式A-X化合物在約200℃至約900℃之溫度範圍內呈固態時,式A-X之化合物與式MO3 之化合物可發生相互作用,但式A-X之化合物亦可以有利地選自形成共晶摻合物的彼等鹼金屬鹵化物及鹼土金屬鹵化物。以此方式,兩種或更多種式A-X之化合物之共晶摻合物使得本發明之方法在低於各個別鹼金屬鹵化物或鹼土金屬鹵化物之熔點的處理溫度下以熔融相實施,同時提供促進所形成之式MOy Xz 之化合物昇華的熔融相反應環境,該式MOy Xz 之化合物隨後可以移除且使其冷卻以提供純結晶形態。可選擇式A-X之化合物之各種摻合物,且以不同比例選擇以提供合適之反應介質及鹵化物源,同時提供溫度足夠高的熔融相以促進所需產物在其形成時昇華。在某些實施例中,視在所需溫度範圍內提供熔融相反應介質所必須的摻合物之任一組分之任何濃度而定,個別鹼金屬鹵化物與鹼土金屬鹵化物之比例可為約1:1,但亦可在10:1或1:10之間變化。在其他實施例中,由式A-X定義之混合物可包含形成共晶摻合物之三種或更多種物種,該共晶摻合物在用於形成及昇華式MOy Xz 之產物的所需溫度範圍內形成熔融相。
已知許多式A-X之化合物會形成共晶摻合物,例如LiCl/KCl,如以下實驗部分中所述,以及在G. J. Janz等人之「Molten Salts:Volume 4, Part 2 Chlorides and Mixtures - electrical conductance, density, viscosity, and surface tension data」,Journal of Physical and Chemical Reference Data 4, 871 (1975)中闡述者。
在一個實施例中,式A-X之化合物為氯化鋰與氯化鉀之混合物,其形成熔點為約357℃,以約44重量百分比之氯化鋰與約56重量百分比之氯化鉀的比例構成之共晶混合物。
在某些實施例中,該方法在大氣壓下或在減壓下利用惰性載氣(諸如氮氣、氬氣等)進行,該等參數經選擇以促進式MOy Xz 之所需反應產物的昇華,以及將所需產物之熱分解降至最低。另外,在一個實施例中,當Y為1且Z為4時,選擇化學計量之量的式MO3 之起始物質從而產生較高產量之式MOy Xz 之化合物。在另一個實施例中,當Y為2且Z為2時,選擇化學計量之量的式MO3 之起始物質從而產生較高產量之式MOy Xz 之化合物。在又一個實施例中,該方法在部分昇華之狀態下進行,同時改變壓力及溫度以便在不同壓力/溫度組合下產生既定物種。以此方式,可以將其中Y及Z為2之所需產物的物種與其中Y為1且Z為4之所需產物的物種分離,在冷卻後各自形成純結晶形態。
在第二態樣中,本發明提供具有式MOy Xz 且呈結晶形態之化合物,其中M選自鉬及鎢,X選自氯、氟、溴及碘,且y為1或2,且z為2或4。
在一個實施例中,式MOy Xz 之化合物為MoO2 Cl2 。在另一個實施例中,式MoO2 Cl2 之化合物之結晶形態具有如圖1所描繪之晶體結構;MoO2 Cl2 之此結晶形態為無水的。在另一個實施例中,式MoO2 Cl2 之化合物之結晶形態具有斜方晶晶體系統,且單位晶胞尺寸為約 a = 13.552(5) Å     α= 90° b = 5.456(2) Å  β= 90° c = 5.508(2) Å  γ= 90°。 式MoO2 Cl2 之化合物之結晶形態的大致鍵長度已經如下確定: Mo--Cl       2.278(2) Å Mo--O         1.706(5) - 2.239(5) Å Cl--Mo--Cl  151.78(7) Å O--Mo--O    79.08-102.90 Å。
如本文所使用,術語「單位晶胞」係指晶體之最小且最簡單之體積要素,其完全地表示晶體之圖案單位。單位晶胞之尺寸由六個數字界定:尺寸a、b及c及角度α、β及γ。晶體為許多單位晶胞之有效堆積陣列。
如本文所使用,術語「斜方晶單位晶胞」係指單位晶胞,其中a≠b≠c;α=β=γ=90°。
如本文所使用,「晶格」係指由堆積單位晶胞之頂點界定之點陣列,如由單晶x-射線繞射分析所測定。
如本文所使用,「空間群」係指單位晶胞之對稱性。在空間群命名(例如,C2)中,大寫字母指示晶格類型,且其他符號表示可在不改變單位晶胞之外觀的情況下對單位晶胞進行之對稱性操作。
在另一個實施例中,MoO2 Cl2 之結晶形態展現了粉末XRD圖案,其中該粉末XRD圖案在12.94、23.64、26.10、39.50及/或40.28±0.04°2θ處具有一或多個峰。在另一個實施例中,MoO2 Cl2 之結晶形態具有如圖5所描繪之粉末XRD圖案。在另一個實施例中,結晶MoO2 Cl2 具有含有如自表4所列之單晶單位晶胞參數所測定之一或多個峰的粉末XRD圖案。
在另一個實施例中,具有式MOy Xz 且呈結晶形態之化合物為WO2 Cl2
本發明可以進一步藉由其某些實施例之以下實例來說明,但應理解,除非另外特別指示,否則此等實例僅出於說明之目的包括在內且不欲限制本發明之範疇。 實例 實例1.  MoO2 Cl2 之合成
將氯化鋰與氯化鉀之混合物(以重量計44/56)與MO3 在不鏽鋼安瓿中組合且在減壓(20毫托)下抽真空。在管形爐中將安瓿加熱至475℃。經由配備有圓底燒瓶之短程管收集所得MoO2 Cl2 蒸氣。FTIR及STA分析支持MoO2 Cl2 之合成。
表1.   4(關於使用所描述之方法合成之MoO2 Cl2 的ICP-MS資料。以百萬分之一(ppm)為單位報道資料)。
元素列表 D.L. 樣品A* 樣品B 樣品C
0.041 0.523 0.354 0.571
0.027 0.786 0.690 0.606
0.018 0.019 <0.018 <0.018
1.851 1.851 1.272 0.919
0.027 <0.027 <0.027 <0.027
0.026 <0.026 <0.026 <0.026
0.028 <0.028 <0.028 <0.028
0.028 0.482 0.404 0.704
0.023 <0.023 <0.023 <0.023
0.036 0.238 0.067 0.133
0.032 0.081 0.065 0.092
0.021 <0.021 <0.021 <0.021
0.022 0.033 0.056 0.045
0.019 1.019 2.259 2.731
0.027 <0.027 <0.027 <0.027
0.066 0.083 0.165 0.329
0.043 0.115 0.119 0.409
0.067 <0.067 <0.067 0.068
0.027 <0.027 <0.027 <0.027
*樣品A、B及C中之每一者取自同一批次。
表2 MoO2 Cl2 之晶體資料及結構精修 標識碼                                  NB00657 實驗式                                  Cl2 MoO2 分子量                                  198.84 溫度                                     100.0 K 波長                                     0.71073 Å 晶體系統                              斜方晶 空間群                                  Cmc21 單位晶胞尺寸                        a = 13.552(5) Å  α= 90°. b = 5.456(2) Å    β= 90°. c = 5.508(2) Å    γ = 90°. 體積                                     407.2(3) Å3 Z                                         4 密度(計算值)                         3.243 Mg/m3 吸收係數                              4.342 mm-1 F(000) 368 晶體大小                              0.27 x 0.22 x 0.2 mm3 資料收集之θ範圍                   3.006 至 28.284°. 指數範圍                              -17<=h<=17, -7<=k<=5, -7<=l<=7 所收集之反射                        1579 獨立反射                              523 [R(int) = 0.0274] 相對於θ之完整性 = 25.500°         100.0 % 吸收校正                              來自等效物之半實驗校正 最大及最小傳輸                     0.2627及0.1831 精修方法                              F2 之完全矩陣最小平方法 資料/限定/參數                      523 / 1 / 28 F2 之擬合良好度                     1.144 最終R指數[I>2σ(I)] R1 = 0.0216, wR2 = 0.0540 R指數(所有資料) R1 = 0.0234, wR2 = 0.0556 絕對結構參數                        0.12(5) 消光係數                              n/a 最大繞射峰值及谷值               1.383及-0.853 e.Å-3
表3. 針對MoO2 Cl2 之鍵長[Å]及角度[°]。 Mo(1)-Cl(1)#1                 2.2783(17) Mo(1)-Cl(1)                          2.2783(17) Mo(1)-O(1)                     1.715(5) Mo(1)-O(1)#2                  2.234(6) Mo(1)-O(2)                     1.706(5) Mo(1)-O(2)#3                  2.239(5) Cl(1)#1-Mo(1)-Cl(1)        151.78(7) O(1)#2-Mo(1)-Cl(1)              79.41(4) O(1)-Mo(1)-Cl(1)#1              98.91(5) O(1)-Mo(1)-Cl(1)             98.91(5) O(1)#2-Mo(1)-Cl(1)#1      79.41(4) O(1)-Mo(1)-O(1)#2               88.36(11) O(1)#2-Mo(1)-O(2)#3      79.1(3) O(1)-Mo(1)-O(2)#3               167.4(3) O(2)-Mo(1)-Cl(1)#1              98.54(5) O(2)#3-Mo(1)-Cl(1)              78.92(4) O(2)#3-Mo(1)-Cl(1)#1      78.92(4) O(2)-Mo(1)-Cl(1)             98.54(5) O(2)-Mo(1)-O(1)             103.0(4) O(2)-Mo(1)-O(1)#2               168.6(3) O(2)-Mo(1)-O(2)#3               89.57(6) Mo(1)-O(1)-Mo(1)#4        149.9(4) Mo(1)-O(2)-Mo(1)#5        173.8(4)
用以產生等效原子之對稱性變換: #1 -x+1,y,z    #2 -x+1,-y+1,z+1/2    #3 -x+1,-y,z+1/2 #4 -x+1,-y+1,z-1/2    #5 -x+1,-y,z-1/2
表4.
0.5(Cl4 Mo2 O4 )MoO2 Cl2 .cif MoO2 Cl2
0.5(Cl4 Mo2 O4 ) 斜方晶:Cmc21 (36) [M=8]
晶胞:13.552×5.456×5.508<90.0×90.0×90.0>體積=407.3,Z=4,Dx=3.2428,I/Ic=8.14 oC20
參見Dolomanov, O.V.、Bourhis, L.J.、Gildea, R.J、Howard, J.A.K.和Puschmann, H. (2009)之J. Appl. Cryst. 42, 339-341.以及Sheldrick, G.M. (2008).之Acta Cryst. A64, 112-122。
用於確定晶胞之繞射點數=1075、測量晶胞時之溫度=100(2)、用於確定晶胞的繞射點之最大θ值=28.28、用於確定晶胞的繞射點之最小θ值=3.01
0.0-90.0度數>=0.0%、I/Ic=8.14之99合併線(m=合併線): [繞射儀 LP] [U(i,j)] [F'+F"]
# (hkl) d(Å) I(f) θ 1/(2d) 2pi/d  m
1 (200) 13.055 6.776 57.9 6.527 0.0738 0.9273
2 (110) 17.508 5.0612 0.1 8.754 0.0988 1.2414
3 (111) 23.857 3.7268 100.0 11.929 0.1342 1.6860
4 (310) 25.580 3.4795 0.3 12.790 0.1437 1.8058
5 (400) 26.283 3.3880 8.8 13.142 0.1476 1.8545
6 (311) 30.360 2.9417 10.5 15.180 0.1700 2.1359
7 (2) 32.485 2.7540 8.0 16.242 0.1816 2.2815
8 (20) 32.803 2.7280 12.3 16.401 0.1833 2.3032
9 (202) 35.146 2.5513 7.3 17.573 0.1960 2.4627
10 (220) 35.443 2.5306 1.3 17.722 0.1976 2.4829
11 (21) 36.734 2.4446 0.1 18.367 0.2045 2.5702
12 (510) 37.004 2.4274 0.0 18.502 0.2060 2.5885
13 (112) 37.136 2.4191 0.7 18.568 0.2067 2.5974
14 (221) 39.143 2.2995 0.5 19.571 0.2174 2.7324
15 (600) 39.880 2.2587 13.5 19.940 0.2214 2.7818
16 (511) 40.582 2.2212 19.0 20.291 0.2251 2.8287
17 (312) 41.797 2.1594 0.4 20.898 0.2315 2.9096
18 (402) 42.256 2.1370 4.4 21.128 0.2340 2.9401
19 (420) 42.510 2.1248 0.6 21.255 0.2353 2.9571
20 (421) 45.730 1.9824 0.3 22.865 0.2522 3.1695
21 (22) 46.837 1.9381 10.8 23.419 0.2580 3.2419
22 (222) 48.835 1.8634 8.5 24.418 0.2683 3.3719
23 (710) 49.945 1.8245 0.0 24.973 0.2740 3.4437
24 (512) 50.049 1.8210 0.2 25.025 0.2746 3.4504
25 (130) 50.599 1.8025 0.0 25.299 0.2774 3.4858
26 (602) 52.344 1.7464 3.6 26.172 0.2863 3.5977
27 (620) 52.561 1.7397 5.5 26.280 0.2874 3.6116
28 (711) 52.814 1.7320 9.8 26.407 0.2887 3.6277
29 (113) 53.013 1.7259 5.6 26.507 0.2897 3.6404
30 (131) 53.442 1.7131 9.7 26.721 0.2919 3.6677
31 (800) 54.094 1.6940 1.3 27.047 0.2952 3.7091
32 (330) 54.334 1.6871 0.2 27.167 0.2964 3.7243
33 (422) 54.501 1.6823 5.7 27.250 0.2972 3.7349
34 (621) 55.333 1.6590 0.0 27.666 0.3014 3.7874
35 (313) 56.637 1.6238 8.1 28.319 0.3079 3.8694
36 (331) 57.048 1.6131 1.6 28.524 0.3100 3.8951
37 (23) 60.758 1.5232 0.1 30.379 0.3283 4.1251
38 (712) 60.853 1.5210 0.1 30.426 0.3287 4.1309
39 (530) 61.336 1.5102 0.0 30.668 0.3311 4.1605
40 (132) 61.426 1.5082 0.0 30.713 0.3315 4.1660
41 (223) 62.442 1.4861 0.1 31.221 0.3365 4.2280
42 (622) 63.163 1.4708 7.2 31.581 0.3399 4.2718
43 (513) 63.477 1.4643 3.0 31.739 0.3415 4.2909
44 (531) 63.861 1.4564 4.6 31.930 0.3433 4.3141
45 (910) 64.103 1.4515 0.0 32.052 0.3445 4.3287
46 (802) 64.533 1.4429 1.0 32.266 0.3465 4.3546
47 (820) 64.723 1.4391 0.4 32.361 0.3474 4.3660
48 (332) 64.748 1.4386 0.2 32.374 0.3476 4.3676
49 (911) 66.570 1.4036 0.9 33.285 0.3562 4.4765
50 (821) 67.177 1.3924 0.1 33.589 0.3591 4.5126
51 (423) 67.350 1.3892 0.1 33.675 0.3599 4.5228
52 (4) 68.029 1.3770 0.4 34.014 0.3631 4.5630
53 (40) 68.767 1.3640 1.8 34.384 0.3666 4.6064
54 (10,0,0) 69.277 1.3552 0.3 34.639 0.3689 4.6364
55 (204) 69.617 1.3494 1.8 34.808 0.3705 4.6562
56 (240) 70.348 1.3372 0.8 35.174 0.3739 4.6988
57 (114) 70.864 1.3287 0.0 35.432 0.3763 4.7288
58 (730) 71.059 1.3255 0.0 35.529 0.3772 4.7401
59 (532) 71.143 1.3242 0.0 35.571 0.3776 4.7450
60 (41) 71.153 1.3240 0.1 35.577 0.3776 4.7456
61 (241) 72.711 1.2994 0.3 36.355 0.3848 4.8353
62 (713) 73.054 1.2942 1.8 36.527 0.3863 4.8550
63 (731) 73.412 1.2887 3.4 36.706 0.3880 4.8755
64 (133) 73.578 1.2862 1.6 36.789 0.3887 4.8849
65 (912) 73.723 1.2841 0.0 36.861 0.3894 4.8932
66 (314) 73.971 1.2804 0.1 36.986 0.3905 4.9073
67 (404) 74.291 1.2757 1.6 37.145 0.3920 4.9254
68 (822) 74.304 1.2755 1.9 37.152 0.3920 4.9262
69 (440) 75.003 1.2653 0.5 37.501 0.3952 4.9657
70 (623) 75.174 1.2628 0.1 37.587 0.3959 4.9754
71 (333) 76.643 1.2423 3.1 38.322 0.4025 5.0579
72 (441) 77.311 1.2332 0.2 38.656 0.4055 5.0951
73 (24) 77.603 1.2293 0.3 38.802 0.4067 5.1113
74 (42) 78.130 1.2223 1.2 39.065 0.4091 5.1405
75 (10,0,2) 78.616 1.2160 0.6 39.308 0.4112 5.1673
76 (10,2,0) 78.791 1.2137 0.1 39.396 0.4120 5.1769
77 (224) 79.115 1.2095 2.6 39.558 0.4134 5.1947
78 (242) 79.639 1.2029 1.3 39.820 0.4157 5.2234
79 (11,1,0) 79.730 1.2017 0.0 39.865 0.4161 5.2284
80 (514) 80.053 1.1977 0.0 40.027 0.4175 5.2460
81 (732) 80.321 1.1944 0.0 40.160 0.4186 5.2606
82 (10,2,1) 81.068 1.1853 0.0 40.534 0.4218 5.3011
83 (604) 81.864 1.1757 0.4 40.932 0.4253 5.3441
84 (11,1,1) 82.000 1.1741 1.6 41.000 0.4259 5.3514
85 (640) 82.557 1.1676 2.0 41.279 0.4282 5.3812
86 (533) 82.667 1.1663 1.1 41.334 0.4287 5.3871
87 (930) 83.233 1.1598 0.0 41.617 0.4311 5.4173
88 (424) 83.610 1.1556 2.4 41.805 0.4327 5.4373
89 (442) 84.128 1.1498 1.1 42.064 0.4349 5.4648
90 (641) 84.812 1.1422 0.1 42.406 0.4377 5.5008
91 (913) 85.141 1.1387 2.1 42.571 0.4391 5.5181
92 (931) 85.486 1.1349 0.4 42.743 0.4406 5.5361
93 (823) 85.701 1.1326 0.0 42.851 0.4414 5.5474
94 (12,0,0) 86.013 1.1293 0.9 43.006 0.4427 5.5636
95 (10,2,2) 87.827 1.1106 1.1 43.913 0.4502 5.6574
96 (11,1,2) 88.750 1.1014 0.0 44.375 0.4539 5.7045
97 (714) 88.988 1.0991 0.0 44.494 0.4549 5.7166
98 (43) 89.421 1.0949 0.0 44.710 0.4567 5.7385
99 (134) 89.491 1.0942 0.1 44.745 0.4569 5.7421
表4為使用市售軟體以建模及模擬PXRD資料之單位晶胞(MoO2 Cl2 晶體結構)之模擬粉末X射線繞射(PXRD)光譜。
表5
水合MoO2 Cl2 峰搜尋報告
掃描:10.0/90.0/0.032/43.5(秒),Cu,I(p)=8121,05/22/1 9 11 :28p
峰:1 5(pts)/拋物線過濾器,臨限值=3.0,截止值=0.1%,BG=3/1 0,峰間…
注意:強度=計數值,2T(0)=0.0(度),計算間距之波長=...
# d(Å) BG 高度 H% 面積 A% FWHM
1 12.854 6.8817 1670 876 13.1 8314 15.6 0.258
2 16.045 5.5194 1458 6663 100.0 53209 100.0 0.217
3 19.349 4.5836 1328 1428 21.4 10284 19.3 0.196
4 24.786 3.5891 1403 1421 21.3 10676 20.1 0.204
5 25.738 3.4586 1432 1641 24.6 12382 23.3 0.205
6 26.191 3.3997 1418 1875 28.1 15407 29.0 0.223
7 32.051 2.7902 1292 579 8.7 5877 11.0 0.276
8 32.486 2.7539 1269 181 2.7 3136 5.9 0.472
9 35.509 2.5260 1159 112 1.7 2723 5.1 0.660
10 36.011 2.4920 1122 174 2.6 2305 4.3 0.361
11 44.499 2.0344 1089 251 3.8 3794 7.1 0.411
表5描繪在MoO2 Cl2 暴露於環境氛圍數小時之後獲得之水合MoO2 Cl2 的實驗X射線粉末繞射。
在圖式及說明書中,已揭示本發明之某些實施例,且儘管採用特定術語,但其僅以一般及描述性意義使用且並非出於限制之目的,本發明之範疇闡述於以下申請專利範圍中。
圖1為MoO2 Cl2 單位晶胞之晶體結構描述。
圖2描述了MoO3 及LiCl/KCl混合物之熱解重量分析,該等混合物在MoO3 及LiCl/KCl組合後呈現明顯質量損失。相對於溫度(℃)繪製殘餘質量(%)。
圖3描述了市售MoO2 Cl2 與使用本發明之方法合成之MoO2 Cl2 相比較的熱解重量分析。相對於溫度(℃)繪製殘餘質量(%)。
圖4為購買之MoO2 Cl2 與使用本發明之方法製備的MoO2 Cl2 之FTIR比較。
圖5為MoO2 Cl2 晶體之實驗X射線粉末繞射與使用所獲得之MoO2 Cl2 單位晶胞參數所計算之光譜(黑線)相比較的曲線圖。
圖6為水合MoO2 Cl2 之X射線粉末繞射,其中模擬MoO2 Cl2 如以下豎直實線所繪示。
圖7為所描述方法之耦合的同步熱解重量分析與差示掃描熱量測定(STA-DSC)。此數據顯示熔點在略微不同於僅LiCl/KCl共晶之溫度下發生。

Claims (7)

  1. 一種氧鹵化物化合物,其具有式MoO2Cl2且呈結晶形態,其展現了在12.94、23.64、26.10、39.50及/或40.28±0.04°2 θ處具有一或多個峰之粉末XRD圖案。
  2. 一種用於製備式MOyXz之化合物之方法,其中M選自鉬及鎢,且X選自氯、氟、溴及碘,y為1或2,且z為2或4,該方法包括使以下式之化合物
    Figure 109123232-A0305-02-0016-1
    與至少一種式A-X之化合物在約200℃至約900℃之溫度下接觸,其中A係選自第1族之元素、第2族之元素、過渡金屬及主族元素。
  3. 如請求項2之方法,其中A選自鋰、鈉及鉀。
  4. 如請求項2之方法,其中X為氯。
  5. 如請求項2之方法,其中A選自鎂、鈣、鍶、鋇、鈹、鈧、鈦、釩及鉻。
  6. 如請求項2之方法,其中該式A-X之化合物包含氯化鋰與氯化鉀之混合物。
  7. 如請求項2之方法,其進一步包含收集蒸氣形式之該式MOyXz之化合物且使該蒸氣冷卻,從而形成結晶形態之該式MOyXz之化合物。
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