化学气相沉积

1、Chemical vapour deposition of zeolitic imidazolate framework thin films化学气相沉积法制备沸石咪唑框架薄膜作者:Ivo Stassen, Mark Styles 作者单位：比利时鲁汶大学表面化 学与催化中心2.内容简介（1）本文采用化学气相沉积法（MOF-CVD）合成ZIF-8薄膜，使用这种方法制备的薄膜材料厚度均匀可控，且具有高深宽比。（2）介绍了使用MOF-CVD方法如何进行剥离和沉积MOFs薄膜3.研究现状（1）金属有机框架结构(MOFs)材料:金属有机骨架材料（MOFs）是近十年来发展迅速的一种配位聚合物，具有三维的

2、孔结构，一般以金属离子为连接点，有机配体位支撑构成空间3D延伸。在催化，储能和分离中都有广泛应用。这类材料的比表面积远大于相似孔道的分子筛，而且能够在去除孔道中的溶剂分子后仍然保持骨架的完整性。沸石咪唑酯骨架结构(ZIFs)材料：是多孔晶体材料，在其中，有机咪唑酯交联连接到过渡金属上，形成一种四面体框架。是最典型的一种MOFs.3.研究现状（2）化学气相沉积法（CVD）是微型器件制备的基础方法。近年来，化学气相沉积法制备的范围已经从金属无机物扩展到有机材料及复合材料。比如，碳的同素异形体、有机聚合物和混合聚合物4.实验方法（1）氧化锌沉积：氧化锌沉积是二乙基锌和氧气等离子体通过原子层沉积或反应

3、溅射得到的。(2)ZIF-气固反应：a.表面涂有氧化锌的基底和2-甲基咪唑的粉末层在100预先加热；b.在反应容器中，将基底悬浮在粉末层上方5cm处，100下反应30min。c.将基底从反应器中转移（100），然后将其放在电热板上进行活化10min.（110，氮气氛围）Fig.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.实验结果与讨论 (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)反应前后氧化锌的表面粗糙度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)不同基底的影响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)不同温度对薄膜形态的影响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