Quantification of metallic nanoparticle morphology on TiO2 using HAADF-STEM tomography.

Electron tomography is applied to photocatalytic gold/titanium oxide and gold/silver/titanium oxide samples. In order to obtain a tilt series for the electron tomography measurement, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is used under cryogenic conditions. Dedicated programs have been developed for measuring volume, surface area, thickness distribution and nearest-neighbour distance of metallic nanoparticles on samples. Using these quantification programs, the 3D morphology of gold and silver nanoparticles is accurately characterized. We paid particular attention to the quantitative measurement of surface area. The measurement error of the method and appropriate magnification are defined using spherical nanoparticle models. We measured the 3D morphology of gold nanoparticles supported on titanium oxide (total volume=6.5 x 10(5)[nm(3)], surface area=1.4 x 10(5)[nm(2)], and average nearest-neighbour distance=40[nm]).

[1]  P. Midgley,et al.  Electron tomography of nanoparticle catalysts on porous supports: A new technique based on Rutherford scattering , 2001 .

[2]  Ulrike Ziese,et al.  Three-dimensional localization of ultrasmall immuno-gold labels by HAADF-STEM tomography. , 2002, Journal of structural biology.

[3]  Kenneth H Downing,et al.  Electron tomography: a 3D view of the subcellular world. , 2007, Analytical chemistry.

[4]  P. Buseck,et al.  Comparison of intensity distributions in tomograms from BF TEM, ADF STEM, HAADF STEM, and calculated tilt series. , 2005, Ultramicroscopy.

[5]  B. Inkson,et al.  Spectroscopic electron tomography. , 2003, Ultramicroscopy.

[6]  P. Midgley,et al.  Quantitative electron holographic tomography for the 3D characterisation of semiconductor device structures. , 2008, Ultramicroscopy.

[7]  Satoshi Hata,et al.  Crack tip dislocations revealed by electron tomography in silicon single crystal , 2008 .

[8]  L. Miao,et al.  Direct observation of TiO6 octahedron forming titanate nanotube by advanced transmission electron microscopy , 2009, Nanotechnology.

[9]  P A Midgley,et al.  Magnetite morphology and life on Mars , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[10]  P. Midgley,et al.  3 D characterization of gold nanoparticles supported on heavy metal oxide catalysts by HAADF-STEM electron tomography. , 2009, Angewandte Chemie.

[11]  José-Jesús Fernández,et al.  Three-dimensional real-space crystallography of MCM-48 mesoporous silica revealed by scanning transmission electron tomography , 2006 .

[12]  A. Verkleij,et al.  Three-Dimensional Transmission Electron Microscopy: A Novel Imaging and Characterization Technique with Nanometer Scale Resolution for Materials Science , 2000 .

[13]  Mino Green,et al.  Low-pressure photochemical vapour deposition of gallium metal from an iodide precursor , 1991 .

[14]  M. Iwaki,et al.  Three-dimensional STEM for observing nanostructures. , 2001, Journal of electron microscopy.

[15]  Xiaojing Xu,et al.  Three-dimensional metrology and fractal analysis of dendritic nanostructures , 2008 .

[16]  R. Leapman,et al.  Three-dimensional distributions of elements in biological samples by energy-filtered electron tomography. , 2004, Ultramicroscopy.

[17]  J R Kremer,et al.  Computer visualization of three-dimensional image data using IMOD. , 1996, Journal of structural biology.

[18]  A. Howie,et al.  Image Contrast And Localized Signal Selection Techniques , 1979 .

[19]  J. McIntosh,et al.  Letter. Crystal morphology of MV-1 magnetite , 2002 .

[20]  Joachim Frank,et al.  Electron Tomography , 1992, Springer US.

[21]  Bruce F. McEwen,et al.  Three-Dimensional Reconstructions of Organelles and Cellular Processes , 1992 .

[22]  P. Gilbert.  Iterative methods for the three-dimensional reconstruction of an object from projections. , 1972, Journal of theoretical biology.

[23]  R. Palmer,et al.  Sintering of passivated gold nanoparticles under the electron beam. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[24]  C. Kübel,et al.  Recent Advances in Electron Tomography: TEM and HAADF-STEM Tomography for Materials Science and Semiconductor Applications , 2005, Microscopy and Microanalysis.

[25]  P. Midgley,et al.  3D electron microscopy in the physical sciences: the development of Z-contrast and EFTEM tomography. , 2003, Ultramicroscopy.

[26]  M Godehardt,et al.  Towards a Quantitative Understanding in Electron Tomography , 2009, Microscopy and Microanalysis.

[27]  P. Midgley,et al.  Visualization of the three-dimensional microstructure of TiO2 nanotubes by electron tomography , 2009 .

[28]  N. Tanaka,et al.  Oxygen release and structural changes in TiO2 films during photocatalytic oxidation , 2006 .

[29]  Peter R. Buseck,et al.  Volume and surface-area measurements using tomography, with an example from the Brenham pallasite meteorite , 2008, Comput. Geosci..

[30]  Z. Saghi,et al.  Hybrid Tomography of Nanostructures in the Electron Microscope , 2009 .

[31]  N. Tanaka,et al.  The three-dimensional morphology of nickel nanodots in amorphous silica and their role in high-temperature permselectivity for hydrogen separation , 2009, Nanotechnology.

[32]  Osamu Wada,et al.  Electron tomography of embedded semiconductor quantum dot , 2008 .

[33]  J. E. Murphy,et al.  Nanoparticle shape and configuration analysis by transmission electron tomography , 2008, Journal of microscopy.

[34]  A. Cormack.  Representation of a Function by Its Line Integrals, with Some Radiological Applications , 1963 .

[35]  J. Frank.  Electron tomography : methods for three-dimensional visualization of structures in the cell , 2005 .

[36]  Andrew Leis,et al.  Cryo-electron tomography of cells: connecting structure and function , 2008, Histochemistry and Cell Biology.

[37]  Norio Baba,et al.  A novel "ghost"-free tomographic image reconstruction method applicable to rotary-shadowed replica specimens. , 2008, Ultramicroscopy.

[38]  Z. Horita,et al.  Characterization of TiO2–Ag nanocomposite particles prepared by spray pyrolysis process using transmission electron microscopy and three-dimensional electron tomography , 2005 .