Summary of Research Project Results Under the JSPS FY2000
"Research for the future Program"



1.Research Institution Osaka University
 
2.Research Area Physical and Engineering Sciences
 
3.Research Field Advanced Processes
 
4.Term of Project FY1996〜FY2000
 
5.Project Number 96P00305
 
6.Title of Project Materials Synthesis with Atom Clusters

7.Projetct Leader
Name Institution,Department Title of Position
Mori, Hirotaro Osaka University, Res. Ctr. UHVEM Professor

8.Core Members

Names Institution,Department Title of Position
Yanagida, Shozo Osaka University, Graduate School of Engineering Professor
Hayashi, Shinji Kobe University, Faculty of Engineering Professor
Yamamoto, Keiichi Kobe University, Faculty of Engineering Professor

9.Cooperating Researchers

Names Institution,Department Title of Position
Wada, Yuji Osaka University, Graduate School of Engineering Associate Prof.
Yasuda, Hidehiro Osaka University, Res. Ctr. UHVEM Assistant

10.Summary of Research Results

It is well known that atom clusters consisting of 103〜104 atoms often exhibit properties and structures that are quite different from those of the corresponding bulk materials. Based upon this premise, in the present project, studies on materials synthesis with atom clusters have been carried out. The results obtained can be summarized as follows.
1. It is found that GaSb crystals can be rendered amorphous by MeV electron irradiation. It is also confirmed that such heavy atoms as lead and gold can be implanted into the Al matrix by MeV electron irrandiation.
2. It is confirmed that spontaneous alloying in atom clusters takes place in a variety of binary alloy systems and therefore is a phenomenon of wide generality. It is revealed that the phase equilibrium in nanometer-sized atom clusters is quite different from that in bulk materials.
3. ZnS and CdS nanoclusters have been successfully prepared and stabilized in DMF. It is confirmed that the nanoclusters catalyzed selective photoreduction of CO2.
4. Porous TiO2 films with narrow pore-size distribution and high optical transmittance have been successfully prepared using 2 kinds of titanium dioxide nanoclusters. Sollar cells made of the mesoporous films (as photoanodes) achieved a better photo-energy conversion efficiency as compared to those prepared from commercially available films.
5. Cubic nano-sized clusters of Ni have been successfully prepared by microwave irradiation. The average size of the clusters can be controlled between 5-8 nm by changing the irradiation condition.
6. High efficiency near-IR emission of Nd (III) has been achieved by ligating it with bis (per fluoromethylsulfonyl)-aminate in cages of a nanocrystalline, large-pore zeolite. The quantum yield for the emission was (9.5±1.0)×10-2 under excitation at 585 nm. This is the highest value ever observed for Nd (III) emission in organic media.
7. Nanoclusters of Si and Ge have been successfully prepared and embedded in the SiO2 matrix by a cosputtering method followed by annealing treatments. An impurity-doping technique to these nanoclusters is also established.

11.Key Words

(1)Atom Cluster、(2)Alloying、(3)Phase Equilibrium
(4)Microwave Irradiation、(5)Sollar Cell、(6)Photoluminescence

12.References

[Reference Articles]
Author Title of Article
H. Yasuda In Situ Observation of Spontaneous Alloying of Antimony into nm-sized Indium Clusters by Optical Absorption Spectroscopy
Journal Volume Year Pages Concerned
Zeitschrift fur Physik D 40 1997 144-146

Author Title of Article
H. Mori Electron Microscopy Study of Spontaneous Alloying in Nanometer-Sized Particles
Journal Volume Year Pages Concerned
Proc. of Int. 7th Beijing Conf. and Exhib. on Instrum. Analysis   1997 A81-A82

Author Title of Article
H. Mori Spontaneous Alloying in Nanometer-Sized Ultra-Fine Particles
Journal Volume Year Pages Concerned
Materials Science Forum Vols.269-272 1998 327-332

Author Title of Article
H. Yasuda Phase Equilibrium in Nanometer-Sized Sb-Au Alloy Clusters
Journal Volume Year Pages Concerned
Materials Science Forum Vols.269-272 1998 333-338

Author Title of Article
H. Mori Spontaneous Alloying in Nanometer-Sized Particles
Journal Volume Year Pages Concerned
Proc. International Symposium on Hybrid Analysis for Functional Nanostructure   1998 41-44

Author Title of Article
H. Yasuda Electron-Irradiation-Induced Chemical Disordering and Crystalline-to-Amorphous Transition in GaSb
Journal Volume Year Pages Concerned
Electron Microscopy 1998 Vol.1 1998 291-292

Author Title of Article
H. Yasuda Alloying Reaction between Nanometer-Sized Gold and Antimony Clusters
Journal Volume Year Pages Concerned
Electron Microscopy 1998 Vol.2 1998 485-486

Author Title of Article
H. Mori Spontaneous Alloying of Antimony into Gold Clusters and Phase Stability of Resultant Alloy Clusters
Journal Volume Year Pages Concerned
Electron Microscopy 1998 Vol.3 1998 485-486

Author Title of Article
M. Kasaya HREM and Optical Absorption Spectroscopy Analysis of AlSb Clusters Formed by Spontaneous Alloying of Antimony Atoms into Indium-Cored Aluminum Clusters
Journal Volume Year Pages Concerned
Electron Microscopy 1998 Vol.3 1998 181-182

Author Title of Article
K. Murakoshi Preparation of Size-controlled Hexagonal CdS Nanocrystallites and Their Microscopic Surface Structure
Journal Volume Year Pages Concerned
J. Chem. Soc., Faraday Trans. Vol.94,No.4 1998 579-586

Author Title of Article
K. Murakoshi Phase Transition of ZnS Nanocrystallites Induced by Surface Modification at Ambient Temperature and Pressure Confirmed by Electron Diffraction
Journal Volume Year Pages Concerned
Chem. Commun.   1998 321-322

Author Title of Article
H. Fujiwara Surface Characteristics of ZnS Nonocrystallites Relating to their Photocatalysis for CO2 Reduction
Journal Volume Year Pages Concerned
Langmuir Vol.14,No.18 1998 5154-5159

Author Title of Article
W. Kubo Fabrication of Quasi-solid-state Dye-Sensitized TiO2 Solar Cells using Low Molecular Weight Gelator
Journal Volume Year Pages Concerned
Chem. Lett.   1998 1241-1242

Author Title of Article
K. Murakoshi Fabrication of Solid State Dye-sensitized TiO2 Solar Cells Combined with Polypyrrole
Journal Volume Year Pages Concerned
Solar Energy Mater. Solar Cells 55 1998 113-125

Author Title of Article
J. Y. Huang Stacking Disordering in Hexagonal BN Induced by Shearing under Ball Milling
Journal Volume Year Pages Concerned
Philosophical Magazine Letters Vol.79,No.5 1999 217-224

Author Title of Article
J. Y. Huang Deformation-Induced Amorphization in Ball-Milled Silicon
Journal Volume Year Pages Concerned
Philosophical Magazine Letters Vol.79,No.6 1999 305-314

Author Title of Article
H. Yasuda Alloying Reaction between Nanometer-Sized Indium and Gold Particles at Reduced Temperatures
Journal Volume Year Pages Concerned
Materials Science Forum Vol.307 1999 167-170

Author Title of Article
H. Mori In Situ TEM Observation of Spontaneous Alloying in Nanometer-Sized Particles
Journal Volume Year Pages Concerned
Bulletin of Materials Science Vol.22,No.3 1999 181-187

Author Title of Article
H. Yasuda Chemical Disordering and Crystalline-to-Amorphous Transition Induced by MeV Electron Irradiation in GaAs
Journal Volume Year Pages Concerned
Journal of Electron Microscopy Vol.48,No.5 1999 581-584

Author Title of Article
H. Mori Phase equilibrium in nanometer-sized particles
Journal Volume Year Pages Concerned
Solid-Solid Phase Transformations   1999 1291-1296

Author Title of Article
H. Yasuda Spontaneous Alloying in Nanoparticles in the Sb-Au System
Journal Volume Year Pages Concerned
Journal of Electron Microscopy Vol.48 1999 1055-1058

Author Title of Article
T. Sumida Photoinduced Deposition of Size-Controlled Gold Nanoclusters onto the Self-Assembled Monolayer of 1, 9-Nonanedithiol
Journal Volume Year Pages Concerned
Chemistry Letters   1999 599-600

Author Title of Article
Y. Wada Preparation of Nano-sized Nickel Metal Particles by Microwave Irradiation
Journal Volume Year Pages Concerned
Chemistry Letters   1999 607-608

Author Title of Article
S. Yanagida Structural Control of Porous Nano-Space in Dye-Sensitized TiO2 Solar Cells
Journal Volume Year Pages Concerned
Zeitschrift fur Physikalische Chemie 212 1999 31-38

Author Title of Article
Y. Inoue Single-Electron Tunneling Through Si Nanocrystals Dispersed in Phosphosilicate Glass Thin Films
Journal Volume Year Pages Concerned
J. Appl. Phys. Vol.86,No.6 1999 3199-3203

Author Title of Article
H. Mori In-situ Observation of Alloying Process in Nm-sized Particles
Journal Volume Year Pages Concerned
Proc. 7th NIRIM International Symposium on Advanced Materials   2000 35-36

Author Title of Article
H. Mori Phase Equilibrium in Nanometer-Sized Particles
Journal Volume Year Pages Concerned
Proc. 5th Intemational Symposium on Advanced Physical Fields   2000 49-52

Author Title of Article
H. Yasuda Spontaneous Atom Mixing and Unmixing in Metallic Nanoparticles
Journal Volume Year Pages Concerned
Philosophical Magazine Letters Vol.80,No.3 2000 181-186

Author Title of Article
H. Mori Anomalous Behavior of Atom Clusters and Materials Design(in Japanese)
Journal Volume Year Pages Concerned
Japanese Scientific Monthly Vol.53,No.3 2000 29-32

Author Title of Article
S. Kambe Mesoporous Electrodes having Tight Agglomeration of Single Phase Anatase TiO2 Nanocrystallites:Application to Dye-sensitized Solar Cells
Journal Volume Year Pages Concerned
Solar Energy Materials and Solar Cells Vol.61 2000 427-441

Author Title of Article
Y. Wada Microwave-assisted Hydrogenation of Chlorinated Phenols for Complete Dechlorination
Journal Volume Year Pages Concerned
Chem. Lett.   2000 632-632

Author Title of Article
M. Matsumoto High Pressure Effects on Fluorescence-Quenching of Coumarin 343 Adsorved on TiO2 Nanocrystallites in Methanol and in N, N-Dimethylformamide
Journal Volume Year Pages Concerned
Chem. Lett.   2000 938-939

Author Title of Article
T. Sumida Electrochemical Preparation of Macroporous Polypyrrole Films with Regular Arrays of Interconnected Spherical Voids
Journal Volume Year Pages Concerned
Chemical Communications   2000 1613-1614

Author Title of Article
Y. Wada High Efficiency Near-IR Emission of Nd (III) Based on Low-Vibrational Environment in Cages of Nanosized Zeolites
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. Vol.122,No.35 2000 8583-8584

Author Title of Article
S. Tomita A New and Simple Method for Thin Graphitic Coating of Magnetic-Metal nanoparticles
Journal Volume Year Pages Concerned
Chem. Phys. Lett. Vol.316 2000 361-364

Author Title of Article
M. Fujii Improvement in Photoluminescence Efficiency of SiO2 Films Containing Si Nanocrystals by P Doping:An Electron Spin Resonance Study
Journal Volume Year Pages Concerned
J. Appl. Phys. Vol.87,No.4 2000 1855-1857

Author Title of Article
S. Takeoka Photoluminescence from Si1-xGex Alloy Nanocrystals
Journal Volume Year Pages Concerned
Phys. Rev. B Vol.61,No.23 2000 15988-15992

Author Title of Article
Y. Inoue Single-electron Tunneling Effects in Thin Nylonll Films Containing Gold Nanoparticles
Journal Volume Year Pages Concerned
Thin Solid Films Vol.372 2000 169-172

Author Title of Article
M. Fujii Effects of Doping to Si-nanocrystals(in Japanese)
Journal Volume Year Pages Concerned
Oyo-Butsuri Vol.69,No.7 2000 820-824

Author Title of Article
Y. Inoue Single-Electron Tunneling through Si Nanocrystals Dispersed in Phosphosilicate glass Thin Films
Journal Volume Year Pages Concerned
Physica E Vol.7 2000 444-447

Author Title of Article
S. Takeoka Control of Photoluminescence Energy of Si Nanocrystals by Ge Doping
Journal Volume Year Pages Concerned
Journal of Luminescence Vol.87-89 2000 350-352

Author Title of Article
A. Mimura Photoluminescence from Si Nanocrystals Dispersed in Phosphosilicate Glass Thin Films
Journal Volume Year Pages Concerned
Journals of Luminescence Vol.87-89 2000 429-431

Author Title of Article
S. Tomita Transformation of Carbon Onions to Diamond by Low-temperature Heat Treatment in Air
Journal Volume Year Pages Concerned
Diamond and Related Materials Vol.9 2000 856-860

Author Title of Article
S. Tomita Formation of Co Filled Carbon Nanocapsules by Metal-template Graphitization of Diamond Nanoparticles
Journal Volume Year Pages Concerned
J. Appl. Phys. Vol.88,No.9 2000 5452-5456

Author Title of Article
A. Mimura Photoluminescence and Free-Electron Absorption in Heavily Phosphorus-doped Si Nanocrystals
Journal Volume Year Pages Concerned
Phys. Rev. B Vol.62,No.19 2000 12625-12627

Author Title of Article
M. Fujii Breakdown of the k-conservation Rule in Si1-xGex Alloy Nanocrystals : Resonant Photoluminescence Study
Journal Volume Year Pages Concerned
J. Appl. Phys. Vol.88,No.10 2000 5772-5776

Author Title of Article
O. Mamezaki Thin Films of Carbon Nanocapsules and Onion-Like Graphitic Particles Prepared by the Cosputtering Method
Journal Volume Year Pages Concerned
Jpn. J. Appl. Phys. Vol.39,Part1,No.12A 2000 6680-6683

Author Title of Article
S. Takeoka Size-dependent Photoluminescence from Surface-oxidized Si Nanocrystals in a Weak Confinement Regime
Journal Volume Year Pages Concerned
Phys. Rev. B Vol.62,No.24 2000 16820-16825

Author Title of Article
O. Mamezaki Current Fluctuation Induced by Visible Light Irradiation on Single-Electron Tunneling via Ge Nanocrystals
Journal Volume Year Pages Concerned
Memoirs of Graduate School of Science and Technology Kobe University 19-A 2000 97-103

Author Title of Article
H. Mori Alloy Phase Formation in Nanometer-sized Particles
Journal Volume Year Pages Concerned
Scripta Materialia   2000 in press

Author Title of Article
H. Mori Alloy Phase Formation in nm-sized Particles
Journal Volume Year Pages Concerned
Mat. Sci. Eng. A   2001 in press

Author Title of Article
J. -G. Lee Gold Atom Implantation into Al Matrix by MeV Electron Irradiation
Journal Volume Year Pages Concerned
J. Electron Microscopy   2001 submitted

Author Title of Article
M. Matsumoto Fabrication of Solid-State Dye-Sensitized TiO2 Solar Cell Using Polymer Electrolyte
Journal Volume Year Pages Concerned
Bulletin of the Chemical Society of Japan Vol.74,No.2 2001 387-393

Author Title of Article
H. Yin Photoreductive Dehalogenation of Halogenated Benzene Derivatives using ZnS or CdS Nanocrystallites as Photocatalysts
Journal Volume Year Pages Concerned
Environmental Science & Technology Vol.35 2001 227-231

Author Title of Article
T. Sumida Macroporous ZnO Films Electrochemically Prepared by Templating of Opal Films
Journal Volume Year Pages Concerned
Chem. Lett.   2001 38-39

Author Title of Article
Y. Wada Microwave-assisted Size Control of CdS Nanocrystallites
Journal Volume Year Pages Concerned
J. Mater. Chem   2001 in press

Author Title of Article
H. Yin Hydrothermal Synthesis of Nanosized Anatase and Rutile TiO2 Using Amorphous Phase
Journal Volume Year Pages Concerned
J. Mater. Chem. Vol.11 2001 1-11

Author Title of Article
H. Yasuda Particle-size Dependence of Phase Stability and Amorphous-like Phase Formation in Nanometer-sized Au-Sn Alloy Particles
Journal Volume Year Pages Concerned
Physical Review B   2001 in press


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