• Proceedings of the Korea Crystallographic Association Conference
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• 2002.11a
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• pp.20-20
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• 2002

Based on experimental and theoretical analyses, we suggested a new possibility that the CVD diamond films grow not by the atomic unit but by the charged clusters containing a few hundreds of carbon atoms, which form spontaneously in the gas phase [J. Crysta] Growth 62 (1996) 55]. These hypothetical negatively-charged clusters were experimentally confirmed under a typical hot-filament diamond CVD process. Thin film growth by charged clusters or gas phase colloids of a few nanometers was also confirmed in Si and ZrO₂ CVD and appears to be general in many other CVD processes. Many puzzling phenomena in the CVD process such as selective deposition and nanowire growth could be explained by the deposition behavior of charged clusters. Charged clusters were shown to generate and contribute at least partially to the film deposition by thermal evaporation. Origin of charging at the relatively low temperature was explained by the surface ionization described by Saha-Langmuir equation. The hot surface with a high work function favors positive charging of clusters while that of a low work function favors negative charging.

• 한국신재생에너지학회:학술대회논문집
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• 2005.11a
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• pp.561-566
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• 2005

Polycrystalline silicon films were deposited using hot wire CVD (HWCVD). The deposition of silicon thin films was approached by the theory of charged clusters (TCC). The TCC states that thin films grow by self-assembly of charged clusters or nanoparticles that have nucleated in the gas phase during the normal thin film process. Negatively charged clusters of a few nanometer in size were captured on a transmission electron microscopy (TEM) grid and observed by TEM. The negatively charged clusters are believed to have been generated by ion-induced nucleation on negative ions, which are produced by negative surface ionization on a tungsten hot wire. The electric current on the substrate carried by the negatively charged clusters during deposition was measured to be approximately $-2{\mu}A/cm^2$. Silicon thin films were deposited at different $SiH_4$ and $H_2$ gas mixtures and filament temperatures. The crystalline volume fraction, grain size and the growth rate of the films were measured by Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The deposit ion behavior of the si1icon thin films was related to properties of the charged clusters, which were in turn controlled by the process conditions. In order to verify the effect of the charged clusters on the growth behavior, three different electric biases of -200 V, 0 V and +25 V were applied to the substrate during the process, The deposition rate at an applied bias of +25 V was greater than that at 0 V and -200 V, which means that the si1icon film deposition was the result of the deposit ion of charged clusters generated in the gas phase. The working pressures had a large effect on the growth rate dependency on the bias appled to the substrate, which indicates that pressure affects the charging ratio of neutral to negatively charged clusters. These results suggest that polycrystalline silicon thin films with high crystalline volume fraction and large grain size can be produced by control1ing the behavior of the charged clusters generated in the gas phase of a normal HWCVD reactor.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 2000.06a
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• pp.87-125
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• 2000

A new paradigm of crystal growth was suggested in a charged cluster model, where charged clusters of nanometer size are suspended in the gas phase in most thin film processes and are a major flux for thin film growth. The existence of these hypothetical clusters was experimentally confirmed in the diamond and silicon CVD processes as well as in gold and tungsten evaporation. These results imply new insights as to the low pressure diamond synthesis without hydrogen, epitaxial growth, selective deposition and fabrication of quantum dots, nanometer-sized powders and nanowires or nanotubes. Based on this concept, we produced such quantum dot structures of carbon, silicon, gold and tungsten. Charged clusters land preferably on conducting substrates over on insulating substrates, resulting in selective deposition. if the behavior of selective deposition is properly controlled, charged clusters can make highly anisotropic growth, leading to nanowires or nanotubes.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 1998.09a
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• pp.33-33
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• 1998

Invisible charged clusters are suggested to form in the gas phase and to become the growth unit in the thin film process. Similar suggestion had been made by Glasner el al. in the crystal growth of KBr and KCL in the solution where the lead ions were added. The charged cluster model, which was suggested in the diamond CVD process by our group, will be extended to the other thin film processes. It will be shown based on both the theoretical analysis and the experimental evidences that the charged clusters are formed in the gas phase and become the growth unit of the crystal in the thin film process.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 1999.06a
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• pp.115-127
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• 1999

The charged clusters or particles, which contain hundreds to thousands of atoms or even more, are suggested to form in the gas phase in the thin film processes such as CVD, thermal evaporation, laser ablation, and flame deposition. All of these processes are also used in the gas phase synthesis of the nanoparticles. Ion-induced or photo-induced nucleation is the main mechanism for the formation of these nanoclusters or nanoparticles inthe gas phase. Charged clusters can make a dense film because of its self-organizing characteristics while neutral ones make a porous skeletal structure because of its Brownian coagulation. The charged cluster model can successfully explain the unusual phenomenon of simultaneous deposition and etching taking place in diamond and silicon CVD processes. It also provides a new interpretation on the selective deposition on a conducting material in the CVDd process. The epitaxial sticking of the charged clusters on the growing surface is gettign difficult as the cluster size increases, resulting in the nanostructure such as cauliflowr or granular structures.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.9 no.3
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• pp.289-294
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• 1999

The charged clusters or particles, which contain hundreds to thousands of atoms or even more, are suggested to from in the gas phase in the thin film processes such as CVD, thermal evaporation, laser ablation, and flame deposition. All of these processes are also phase synthesis of the nanoparticels. Ion-induced or photo-induced nucleation is the main mechanism for the formation of these nanoclusters or nanoparticles in the gas phase. Charge clusters can make a dense film because of its self-organizing characteristics while neutral ones make a porous skeletal structure because of its Brownian coagulation. The charged cluster model can successfully explain the unusual phenomenon of simultaneous deposition and etching taking place in diamond and silicon CVD processes. It also provides a new interpretation on the selective deposition on a conducting material in the CVD process. The epitaxial sticking of the charged clusters on the growing surface is getting difficult as the cluster size increases, resulting in the nanostructure such as cauliflower or granular structures.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 2000.06a
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• pp.127-142
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• 2000

The charged cluster model states that chemical vapor deposition (CVD) begins with gas phase nucleation of charged clusters followed by cluster deposition on a substrate surface to form a thin film. A two-chambered CVD system, separated by a 1-mm orifice, was used to study gold deposition by thermal evaporation in order to determine if the CCM applies in this case. At a filament temperature of 1523 and 1773 K, the presence of nano-meter sized gold clusters was found to be positive and the cluster size and size distribution increased with increasing temperature. Small clusters were found to be amorphous and they combined with clusters already deposited on a substrate surface to form larger amorphous clusters on the surface. This work revealed that gold thin films deposited on a mica surface are the result of the sticking of 4-10 nm clusters. The topography of these films was similar to those reported previously under similar conditions.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.606-612
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• 1991

We have carried out an extended Huckel calculation to rationalize the role of $CuO_3$ chains and the size effect of the charged model clusters for the following charged model culsters : ${{Cu_6}{O_{21}}^{28-},\;{{Cu_6}{O_{22}}^{30-}\;,{{Cu_9}{O_{30}}^{39-}\;,{{Cu_9}{O_{32}}^{43-}\;,{{Cu_{12}{O_{38}}^{48-}\;,{{Cu_{15}{O_{50}}^{65-}\;,{{Cu_{18}{O_{54}}^{66-}\;,{{Cu_{18}{O_{55}}^{68-}\;,{{Cu_{24}{O_{70}}^{84-}\;and\;{{Cu_{27}{O_{78}}^{93-}$ for high-$T_c$ superconductor $YBa_2Cu_3O_7$: ${{Cu_6}{O_{18}}^{22-}\;,{{Cu_9}{O_{26}}^{31-}}\;,{{Cu_{12}{O_{32}}^{36-}\;,{{Cu_{15}{O_{42}}^{49-}\;,{{Cu_{18}{O_{46}}^{50-}\;,{{Cu_{24}{O_{60}}^{64-}\;and\;{{Cu_{27}{O_{66}}^{69-}$ for insulator $YBa_2Cu_3O_6$. The results show that the electronic structures and properties of the charged model clusters relating to high-$T_c$ superconductor are very sensitive to the size change of the clusters with various environmental effects, wherease those of the charged model clusters for insulator $YBa_2Cu_3O_6$ are monotonous to the size change. The $CuO_3$ chains along the b-direction may yield cooperative electronic coupling with the $CuO_2$ layers in determining both conducting and superconducting properties of $YBa_2Cu_3O_{7-x}$ system.

• The Korean Journal of Ceramics
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• v.3 no.1
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• pp.5-12
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• 1997

Charged carbon clusters which are formed by the gas activation are suggested to be responsible for the formation of the metastable diamond film. The number of carbon atoms in the cluster that can reverse the stability between diamond and graphite by the capillary effect increases sensitively with increasing the surface energy ratio of graphite to diamond. The gas activation process produces charges such as electrons and ions, which are energetically the strong heterogeneous nucleation sites for the supersaturated carbon vapor, leading to the formation of the charged clusters. Once the carbon clusters are charged, the surface energy of diamond can be reduced by the electrical double layer while that of graphite cannot because diamond is dielectric and graphite is conducting. The unusual phenomena observed in the chemical vapor deposition diamond process can be successfully approached by the charged cluster model. These phenomena include the diamond deposition with the simultaneous graphite etching, which is known as the thermodynamic paradox and the preferential formation of diamond on the convex edge, which is against the well-established concept of the heterogeneous nucleation.

• 한국정보디스플레이학회:학술대회논문집
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• 2002.08a
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• pp.147-152
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• 2002

A new theory of thin film growth was suggested, where charged clusters of nanometer size are generated in the gas phase and are a major flux for thin films. The existence of these hypothetical clusters was experimentally confirmed in the diamond and silicon CVD processes as well as in metal evaporation. These results imply new insights as to the microstructure control of thin films. Based on this new understanding, the low temperature deposition of crystalline and amorphous silicon can be approached systematically.