Non-Classical Crystallization of Thin Films and Nanostructures in CVD Process

Non-classical crystallization, where crystals grow by the building blocks of nanoparticles, has become a significant issue not only in solution but also in the gas phase synthesis such as chemical vapor deposition (CVD). Recently, non-classical crystallization was observed in solution in-situ by transmission electron microscope (TEM) using a liquid cell technique. In various CVD processes, the generation of charged nanoparticles (CNPs) in the gas phase has been persistently reported. Many evidences supporting these CNPs to be the building blocks of thin films and nanostructures were reported. According to non-classical crystallization, many thin films and nanostructures which had been believed to grow by individual atoms or molecules turned out to grow by the building blocks of CNPs. The purpose of this paper is to review the development and the main results of non-classical crystallization in the CVD process. The concept of non-classical crystallization is briefly described. Further, it will be shown that the puzzling phenomenon of simultaneous diamond deposition and graphite etching, which violates the second law of thermodynamics when approached by classical crystallization, can be approached successfully by non-classical crystallization. Then, various aspects of non-classical crystallization in the growth of thin films and nanostructures by CVD will be described

First-principles study of the effect of charge on the stability of a diamond nanocluster surface

Effects of net charge on the stability of the diamond nanocluster are investigated using the first-principles pseudopotential method with the local density approximation. We find that the charged nanocluster favors the diamond phase over the reconstruction into a fullerene-like structure. Occupying the dangling bond orbitals in the outermost surface, the excess charge can stabilize the bare diamond surface and destabilize the C-H bond on the hydrogenated surface. In combination with recent experimental results, our calculations suggest that negative charging could promote the nucleation and further growth of low-pressure diamond.open8

Non-classical crystallization of thin films and nanostructures in CVD and PVD processes

This book provides a comprehensive introduction to a recently-developed approach to the growth mechanism of thin films and nanostructures via chemical vapour deposition (CVD). Starting from the underlying principles of the low pressure synthesis of diamond films, it is shown that diamond growth occurs not by individual atoms but by charged nanoparticles. This newly-discovered growth mechanism turns out to be general to many CVD and some physical vapor deposition (PVD) processes. This non-classical crystallization is a new paradigm of crystal growth, with active research taking place on growth in solution, especially in biomineralization processes. Established understanding of the growth of thin films and nanostructures is based around processes involving individual atoms or molecules. According to the author’s research over the last two decades, however, the generation of charged gas phase nuclei is shown to be the rule rather than the exception in the CVD process, and charged gas phase nuclei are actively involved in the growth of films or nanostructures. This new understanding is called the theory of charged nanoparticles (TCN). This book describes how the non-classical crystallization mechanism can be applied to the growth of thin films and nanostructures in gas phase synthesis. Based on the author’s graduate lecture course, the book is aimed at senior undergraduate and graduate students and researchers in the field of thin film and nanostructure growth or crystal growth. It is hoped that a new understanding of the growth processes of thin films and nanostructures will reduce trial-and-error in research and in industrial fabrication processes

Yttrium Oxyfluoride Coating Deposited with a Y5O4F7/YF3 Suspension by Suspension Plasma Spraying Under Atmospheric Pressure

To develop the plasma-resistant coating of yttrium oxyfluoride using the suspension plasma spraying (SPS) process, a mixed Y5O4F7/YF3 suspension was developed for fluorine-rich yttrium oxyfluoride coating. The undesired cubic and monoclinic Y2O3 was formed in the yttrium oxyfluoride coating deposited with the Y5O4F7 suspension by the SPS process at atmospheric pressure. To minimize the formation of Y2O3, we inferred and proposed the mechanism of the SPS coating at atmospheric pressure and analyzed the coatings deposited by four suspensions with different mass ratios containing Y5O4F7 and YF3 particles. During the SPS process, the Y5O4F7 particles in the suspension reacted with hydrogen and oxygen through chemical reactions using the remaining thermal energy after the evaporation process, forming YOF and Y2O3 composites near the surface of the coating. Using x-ray diffraction (XRD) and a high-resolution three-dimensional x-ray tomography microscope system (HR-XRM), a relatively large amount of Y2O3 was found to have formed near the surface of the coating deposited with the Y5O4F7 suspension, whereas the formation of Y2O3 was minimized and the formation of yttrium oxyfluoride was maximized in the coating deposited with the mixed Y5O4F7/YF3 suspension at a mass ratio of 7:3. This coating containing a minimum amount of Y2O3 is expected to offer high plasma resistance.N

Non-uniform deposition in the early stage of hot-wire chemical vapor deposition of silicon: The charge effect approach

The deposition behavior in hot-wire chemical vapor deposition (HWCVD) of silicon was investigated, focusing on the thickness uniformity of films deposited on silicon and glass substrates, and based on the previous suggestion that a major depositing flux in HWCVD should be negatively charged nanoparticles. The deposition was performed using a 20%-SiH4-80%-H-2 gas mixture at a 450 degrees C substrate temperature under a working pressure of 66.7 Pa (0.5 Tort). Non-uniform depositions for three hot-wire temperatures, 1590 degrees C, 1670 degrees C, and 1800 degrees C, and on the silicon and glass substrates were compared. The non-uniformity was most pronounced at 1800 degrees C and more pronounced on the glass substrate. On the glass substrate, the deposition rate was highest at the corner and lowest at the center, which was attributed to the fastest charge removal, to a conducting stainless steel substrate holder, at the corner. Once the entire glass substrate was deposited with silicon, the growth rate tended to become uniform, possibly due to the high charge removal rate of silicon. The observed deposition behavior indicated that the major depositing flux is negatively charged.close141

Effect of Crystal Shape on the Grain Growth during Liquid Phase Sintering of Ceramics

he equilibrium or growth shape of ceramic materials is classified largely into two categories according to the thermodynamic conditions imposed. One is a polyhedral shape where the surface free energy is anisotropic, and the other a spherical shape where the surface free energy is isotropic. In the case of grains with a polyhedral shape of anisotropic surface free energy, so- called abnormal grain growth usually takes place due to a significant energy barrier for a growth unit to be attached to the crystal surface. In the case of grains with a spherical shape of isotropic surface free energy, however, normal grain growth with a uniform size distribution takes place. In this contribution, the state-of-the-art of our current understanding of the relationship between the crystal shape and the microstructure evolution during the sintering of ceramic materials in the presence of a liquid phase was discussed.close

Generation of Charged Ti Nanoparticles and Their Deposition Behavior with a Substrate Bias during RF Magnetron Sputtering

This study is based on the film growth by non-classical crystallization, where charged nanoparticles (NPs) are the building block of film deposition. Extensive studies about the generation of charged NPs and their contribution to film deposition have been made in the chemical vapor deposition (CVD) process. However, only a few studies have been made in the physical vapor deposition (PVD) process. Here, the possibility for Ti films to grow by charged Ti NPs was studied during radio frequency (RF) sputtering using Ti target. After the generation of charged Ti NPs was confirmed, their influence on the film quality was investigated. Charged Ti NPs were captured on amorphous carbon membranes with the electric bias of −70 V, 0 V, +5 V, +15 V and +30 V and examined by transmission electron microscopy (TEM). The number density of the Ti NPs decreased with increasing positive bias, which showed that some of Ti NPs were positively charged and repelled by the positively biased TEM membrane. Ti films were deposited on Si substrates with the bias of −70 V, 0 V and +30 V and analyzed by TEM, field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and X-ray reflectivity (XRR). The film deposited at −70 V had the highest thickness of 180 nm, calculated density of 4.974 g/cm3 and crystallinity, whereas the film deposited at +30 V had the lowest thickness of 92 nm, calculated density of 3.499 g/cm3 and crystallinity. This was attributed to the attraction of positively charged Ti NPs to the substrate at −70 V and to the landing of only small-sized neutral Ti NPs on the substrate at +30 V. These results indicate that the control of charged NPs is necessary to obtain a high quality thin film at room temperature

Spontaneous generation of charged atoms or clusters during thermal evaporation of silver

Spontaneous generation of charged atoms or clusters was investigated during thermal evaporation of silver. For this, the effect of the applied electric bias on the film growth rate was examined during evaporation of silver at 1373 K in a tungsten basket. Film growth rates on three silicon substrates biased + 300, 0 and -300 V with respect to the chamber were 300, 420 and 960 nm per hour, respectively. The number density of generated positively-charged atoms or clusters could be measured by the electric current on the Faraday cup in the chamber. From the temperature dependence of the positive current, the activation energy for charging was determined to be similar to 2.2 eV. This value could be best explained by the surface ionization of clusters of a few atoms on the oxidized tungsten surface.N

Plasma Etching Behavior of YOF Coating Deposited by Suspension Plasma Spraying in Inductively Coupled CHF3/Ar Plasma

Dense yttrium oxyfluoride (YOF) coating was successfully deposited by suspension plasma spraying (SPS) with coaxial feeding. After deposition for 6 min at a plasma power of 105 kW, the thickness of the YOF coating was 55 ± 3.2 µm with a porosity of 0.15% ± 0.01% and the coating rate was ~9.2 µm/min. The crystalline structure of trigonal YOF was confirmed by X-ray diffractometry (XRD). The etching behavior of the YOF coating was studied using inductively coupled CHF3/Ar plasma in comparison with those of the Al2O3 bulk and Y2O3 coating. Crater-like erosion sites and cavities were formed on the whole surface of the Al2O3 bulk and Y2O3 coating. In contrast, the surface of the YOF coating showed no noticeable difference before and after exposure to the CHF3/Ar plasma. Such high resistance of the YOF coating to fluorocarbon plasma comes from the strongly fluorinated layer on the surface. The fluorination on the surface of materials was confirmed by X-ray photoelectron spectrum analysis (XPS). Depth profiles of the compositions of Al2O3, Y2O3, and YOF samples by XPS revealed that the fluorination layer of the YOF coating was much thicker than those of Al2O3 and Y2O3. These results indicate that if the inner wall of the semiconductor process chamber is coated by YOF using SPS, the generation of contamination particles would be minimized during the fluorocarbon plasma etching process