化學(xué)氣相沉積

1、Chemical vapour deposition of zeolitic imidazolate framework thin films化學(xué)氣相沉積法制備沸石咪唑框架薄膜作者:Ivo Stassen, Mark Styles 作者單位：比利時(shí)魯汶大學(xué)表面化 學(xué)與催化中心2.內(nèi)容簡(jiǎn)介（1）本文采用化學(xué)氣相沉積法（MOF-CVD）合成ZIF-8薄膜，使用這種方法制備的薄膜材料厚度均勻可控，且具有高深寬比。（2）介紹了使用MOF-CVD方法如何進(jìn)行剝離和沉積MOFs薄膜3.研究現(xiàn)狀（1）金屬有機(jī)框架結(jié)構(gòu)(MOFs)材料:金屬有機(jī)骨架材料（MOFs）是近十年來(lái)發(fā)展迅速的一種配位聚合物，具有三維的

2、孔結(jié)構(gòu)，一般以金屬離子為連接點(diǎn)，有機(jī)配體位支撐構(gòu)成空間3D延伸。在催化，儲(chǔ)能和分離中都有廣泛應(yīng)用。這類材料的比表面積遠(yuǎn)大于相似孔道的分子篩，而且能夠在去除孔道中的溶劑分子后仍然保持骨架的完整性。沸石咪唑酯骨架結(jié)構(gòu)(ZIFs)材料：是多孔晶體材料，在其中，有機(jī)咪唑酯交聯(lián)連接到過(guò)渡金屬上，形成一種四面體框架。是最典型的一種MOFs.3.研究現(xiàn)狀（2）化學(xué)氣相沉積法（CVD）是微型器件制備的基礎(chǔ)方法。近年來(lái)，化學(xué)氣相沉積法制備的范圍已經(jīng)從金屬無(wú)機(jī)物擴(kuò)展到有機(jī)材料及復(fù)合材料。比如，碳的同素異形體、有機(jī)聚合物和混合聚合物4.實(shí)驗(yàn)方法（1）氧化鋅沉積：氧化鋅沉積是二乙基鋅和氧氣等離子體通過(guò)原子層沉積或反應(yīng)

3、濺射得到的。(2)ZIF-氣固反應(yīng)：a.表面涂有氧化鋅的基底和2-甲基咪唑的粉末層在100預(yù)先加熱；b.在反應(yīng)容器中，將基底懸浮在粉末層上方5cm處，100下反應(yīng)30min。c.將基底從反應(yīng)器中轉(zhuǎn)移（100），然后將其放在電熱板上進(jìn)行活化10min.（110，氮?dú)夥諊〧ig.2 Schematic overview of the transformation mechanism.Fig.3 Photographs of ALD zinc oxide films with different thicknesses, before (a) and after (b) 30 min vapour

4、-solid reaction with HmIM. 5.實(shí)驗(yàn)結(jié)果與討論 (1)XRDbdcFig. 3X-ray diffraction of (a)a ZIF-8 CVD film and simulated pattern for ZIF-8 and (b) 15nm (c)6nm (d) 3 nm zinc oxide film before and after 30 min vapour-solid reaction with HmIM.(2)SEMFig.4 SEM cross-sectional imaging of 15 nm zinc oxide film after 30

5、min vapour-solid reaction with HmIM. a, tilted view. b, perpendicular view. Scale bars 1 m.Fig.5 SEM cross-sectional imaging of 6 nm zinc oxide film after 30 min vapour-solid reaction with HmIM. a, tilted view. b, perpendicular view. Scale bars a, 2 m and b, 500 nm.Fig.6 SEM cross-sectional imaging

6、of 3 nm zinc oxide film after 30 min vapour-solid reaction with HmIM. a, tilted view. b, perpendicular view. Scale bars a, 1 m and b, 500 nm.(3)AFMFig.7 AFM analysis of 15 nm zinc oxide film after 30 min vapour-solid reaction with HmIM. Surface roughness calculated over 2 2 m area: Ra = 26.0 nm; Rq

7、= 31.3 nm. Axes top: X and Y -1, 1 m, Z 0 nm, 200 nm, axes bottom: X and Y -250, 250 nm, Z 0 nm, 100 nm, scale bars 500 nm (top) and 100 nm (bottom).aFig.8 AFM analysis of 6 nm zinc oxide film after 30 min vapour-solid reaction with HmIM. Surface roughness calculated over 2 2 m area: Ra = 24.9 nm; R

8、q = 32.5 nm. Axes top: X and Y -1, 1 m, Z 0 nm, 200 nm, axes bottom: X and Y -250, 250 nm, Z 0 nm, 125 nm, scale bars 500 nm (top) and 100nm (bottom).Fig.9 AFM analysis of 3 nm zinc oxide film after 30 min vapour-solid reaction with HmIM. Surface roughness calculated over 2 2 m area: Ra = 15.1 nm; R

9、q = 20.1 nm. Axes top: X and Y -1, 1 m, Z 0 nm, 100 nm, axes bottom: X and Y -250, 250 nm, Z 0 nm, 25 nm, scale bars 500 nm (top) and 100nm (bottom).(3)TEMacbFig.10 TEM cross section of (a)15nm (b)6 nm and (c)3nm zinc oxide film after 30 min vapour-solid reaction with HmIM. The average thickness of

10、the film over the full range of the cross section is (a)ca.124nm (b)ca. 104nm and (c)ca.52nm(4)反應(yīng)前后氧化鋅的表面粗糙度Fig.11 AFM analysis of ALD zinc oxide films with different thicknesses: a, 3 nm, b, 6 nm, c, 15 nm. Surface roughness calculated over 2 2 m area: a, Ra = 1.07 nm; Rq = 1.37 nm, b, Ra = 1.54 nm

11、; Rq = 1.97 nm, c, Ra = 1.34 nm; Rq = 1.66 nm. Axes: X and Y -1, 1 m, Z -5 nm, 5 nm, scale bars 500 nm.(5)不同基底的影響Fig.12 SEM images of ZIF-8 films on different substrates after 30 min vapour-solid reaction with HmIM. Substrates: a, 6 nm zinc oxide on titanium oxide, b, 6 nm zinc oxide on silicon oxide and c, zinc oxide (50 nm, partial conversion). Scale bars: 2 m.(6)不同溫度對(duì)薄膜形態(tài)的影響Fig.13 SEM images of 15 nm zinc oxide film after 30 min vapour-solid reaction at 100(a, c) and 120(b, c). The film resulting from the reaction at 100 is thicker and less confined to th