TWI739507B - 氧鹵化物前驅物 - Google Patents
氧鹵化物前驅物 Download PDFInfo
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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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- molybdenum
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- 239000002243 precursor Substances 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims description 44
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 238000001144 powder X-ray diffraction data Methods 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000011737 fluorine Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 230000005496 eutectics Effects 0.000 abstract description 7
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract description 4
- -1 alkaline earth metal salts Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 abstract 2
- 239000013078 crystal Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 description 3
- 150000008045 alkali metal halides Chemical class 0.000 description 3
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
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- C01G39/04—Halides
-
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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
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
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 |
鋁 | 0.041 | 0.523 | 0.354 | 0.571 |
銻 | 0.027 | 0.786 | 0.690 | 0.606 |
鋇 | 0.018 | 0.019 | <0.018 | <0.018 |
鈣 | 1.851 | 1.851 | 1.272 | 0.919 |
鉻 | 0.027 | <0.027 | <0.027 | <0.027 |
鈷 | 0.026 | <0.026 | <0.026 | <0.026 |
銅 | 0.028 | <0.028 | <0.028 | <0.028 |
鐵 | 0.028 | 0.482 | 0.404 | 0.704 |
鉛 | 0.023 | <0.023 | <0.023 | <0.023 |
鋰 | 0.036 | 0.238 | 0.067 | 0.133 |
鎂 | 0.032 | 0.081 | 0.065 | 0.092 |
錳 | 0.021 | <0.021 | <0.021 | <0.021 |
鎳 | 0.022 | 0.033 | 0.056 | 0.045 |
鉀 | 0.019 | 1.019 | 2.259 | 2.731 |
銀 | 0.027 | <0.027 | <0.027 | <0.027 |
鈉 | 0.066 | 0.083 | 0.165 | 0.329 |
錫 | 0.043 | 0.115 | 0.119 | 0.409 |
鈦 | 0.067 | <0.067 | <0.067 | 0.068 |
釩 | 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) | 2θ | 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=... | ||||||||
# | 2θ | 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)
- 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。
- 如請求項2之方法,其中A選自鋰、鈉及鉀。
- 如請求項2之方法,其中X為氯。
- 如請求項2之方法,其中A選自鎂、鈣、鍶、鋇、鈹、鈧、鈦、釩及鉻。
- 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。
- 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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