Proceedings of the Korea Association of Crystal Growth Conference (한국결정성장학회:학술대회논문집)
The Korea Association of Crystal Growth
- Semi Annual
Domain
- Earth Science(Earth/Atmosphere/Marine/Astronomy) > Geological Science
1999.06a
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Fukuda, T.;Shimamura, K.;Tabata, H.;Takeda, H.;Futagawa, N.;Yoshikawa, A.;Kochurikhin, Vladimir-V. 3
We have successfully grown <111>-oriented (La,Sr)(Al,Ta)$O_3$ (LSAT) mixed-perovskite single crystals and <0001>-oriented$Ca_8La_2(PO_4)_6O_2$ (CLPA) single crystals with the apatite structure by the Czochralski method. The compositional and lattice parameter uniformity of the crystals are discussed in relation to the growth conditions. Since LSAT and CLPA single crystals have excellent lattice matching with GaN, they ar promising as new substrates for the growth of high quality GaN epitaxial layers. -
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When concentration of vacancies in a CZ silicon crystal is defined by molar fraction XB, the degree of super-saturation
$\sigma$ is given by [XB-XBS]/XBS=XB/XBS-1=ln (XB/XBS) because XB/XBS is nearly equal to unity. Here, XBS is the saturated concentration of vacancies in a silicon crystal and XB is a little larger than XBS. According to Bragg-Williams approximation, the chemical potential of the vacancies in the crystal is given by${\mu}$ B=${\mu}$ 0+RT ln XB+RT ln${\gamma}$ , where R is the gas constant, T is temperature,${\mu}$ 0 is an ideal chemical potential of the vacancies and${\gamma}$ is an adjustable parameter similar to the activity of solute in a solution. Thus,$\sigma$ (T) is equal to (${\mu}$ B-${\mu}$ BS)/RT. Driving force of nucleation of the vacancy agglomeration will be proportional to the chemical potential difference (${\mu}$ B-${\mu}$ BS) or$\sigma$ (T), while growth of the vacancy agglomeration is proportional to diffusion of the vacancies and grad${\mu}$ B. -
The growth of crystals with high melting points tfus
$\geq$ 1$600^{\circ}C$ faces the researcher with experimental problems, as the choice of materials that withstand such high t is rather limited. Many metallic construction materials are in this high t range already molten or exhibit at least a drastically reduced mechanical strength. The very few materials with tfus》1$600^{\circ}C$ as e.g. W, Mo, and partially even Ir are more or less sensitive against oxygen upon heating. Whenever possible, high t crystal growth is performed under inert atmosphere (noble gases). Unfortunately, any oxides are not thermodynamically stable under such conditions, as reduction takes place within such atmosphere. A thoroughly search for suitable growth conditions has to be performed, that are on the one side "oxidative enough" to keep the oxides stable and on the other side "reductive enough" to avoid destruction of constructive parts of the crystal growth assembly. The relevant parameters are t and the oxygen partial pressure pO2. The paper discusses quantitatively relevant properties of interesting oxides and construction materials and ways to forecast their behavior under growth conditions.r growth conditions. -
Computer simulations have played a central role in the development of out understanding of the atomic scale processes involved in crystal growth. The assumptions underlying computer modeling will be discussed and out recent work on modeling of the kinetic formation of thermodynamically unstable phases in alloys or mixtures will be reviewed. Our Monte Carlo computer simulations have reproduced the experimental results on the rapid recrystallization of laser-melted doped silicon. An analytical model for this phenomenon has been developed, and its applicability to other materials will be discussed.
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The strain, surface and inerfacial energies of III-V ternary systems were calculated for three kinds of structure modes: the Frank-van der Merwe (FM) mode, the Stranski-Krastanov (SK) mode an the Volmer-Wever (VW) mode. The free energy for each mode was estimated as functions of the thickness and composition or lattice misfit. Through comparison of the free energy of each mode, it was found that the thickness-composition phase diagrams of III-V ternary systems can be determined only by considering the balance of the free energy and three kinds of structure modes appear in the phase diagrams. The SK mode appears only when the lattice misfit is large and/or the lattice layer is thick. The most stable structure of the SK mode is a cluster with four lattice layers or minimum thickness on a wetting layer of increasing lattice layers. The VW mode appears when the lattice misfit is large and the lattice layer is thin and only in the InPSb/InP and GaPSb/GaP systems which have the largest lattice misfit of III-V ternary systems. The stable region of the SK mode in the GaPSb/GaP and InPSb/InP phase diagrams is largest of all because the composition dependence of the strain energy of these systems is stronger than that of the other systems. The critical number of lattice layers below which tow-dimensional (2D) layers precede the three-dimensional (3D) nucleation in the SK mode at x=1.0 depnds on the lattice misfit.
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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.
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Low-dislocation-density large-diameter GaAs single crystals with low-residual-strain have been strongly required. We have developed dislocation-free 3-inch Si-doped GaAs crystals for photonic devices [1], and low-dislocation-density low-residual-strain 4-inch to 6-inch [2, 3] semi-insulating GaAs crystals for electronic devices by Vertical Boat (VB) technique. We confirmed that VB substrates with low-residual-strain have higher resistance against slip-line generation during MBE process. VB-GaAs single crystals show uniform radial profile of resistivity reflecting to the flat solid-liquid interface during the crystal growth. Uniformity of micro-resistivity of VB-GaAs substrate is much better than that of the LEC-GaAs substrate, which is due to the low-dislocation-density of VB-GaAs single crystals.
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In the present paper, KLN crystals have been grown along <001>, <100> and <110> directions by the top seeded solution growth (TSSG) method from Li-richer melts with different compositions. The morphologies of KLN crystals grown along different directions have been studied, and the well-developed facets have been unambiguously indexed using X-ray goniometer and stereographic projection analysis. The growth mechanism and defects such as cracks and inclusions were discussed on the basis of observations of facets on the crystal-melt interfaces. The crystal compositions were determined by chemical analysis method. The structure and lattice constants of KLN crystals were determined and calculated on the basis of XRD data by using TREOR90 and PIRUM programs. The Curie temperature and optical absorption were determined by dielectric constant peak and spectrum measurements, respectively. The blue SHG characteristics of a KLN sample were also investigated using a pulsed dye laser. PACS: 42.70.M;81.10;81.10A;42.65.K.
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The thermal distributions near the growth interface of 150mm CZ crystals were measured by three thermocouples installed at the center, middle (half radius) and edge (10m from surface) of the crystals. The results show that larger growth rates produced smaller thermal gradients. This contradicts the widely used heat flux balance equation. Using this fact, it si confirmed in CZ crystals that the type of point defects created is determined by the value of the thermal gradient (G) near the interface during growth, as already reported for FZ crystals. Although depending on the growth systems the effective lengths of the thermal gradient for defect generation are varied, were defined the effective length as 10mm from the interface in this experiment. If the G is roughly smaller than 20C/cm, vacancy rich CZ crystals are produced. If G is larger than 25C/cm, the species of point defects changes dramatically from vacancies to interstitial. The experimental results which FZ and CZ crystals are detached from the melt show that growth interfaces are filled with vacancy. We propose that large G produces shrunk lattice spacing and in order to relax such lattice excess interstitial are necessary. Such interstitial recombine with vacancies which were generated at the growth interface, next occupy interstitial sites and residuals aggregate themselves to make stacking faults and dislocation loops during cooling. The shape of the growth interface is also determined by the distributions of G across the interface. That is, the small G and the large G in the center induce concave and convex interfaces to the melt, respectively.
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Detailed description of the crystal growth methods permitting one to obtain complicated shape crystals from the melt is given. The variable shaping technique provides the growth of crystals with a discrete altering cross-section configuration during crystallization. The dynamic local shaping technique enables one to grow items with a continuous alteration of the side surface profile by a preset program.
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The reproducibility of successive growth of Bi12TiO20(BTO) single crystals using a top-seeded solution growth (TSSG) pulling method was evaluated by measuring the lattice constants and their standard deviations. A substantial phase diagram in the region close to the stoichiometric BTO was established experimentally for this purpose, and the existence of a retrograde solid solution close to a BTO was clarified. It was emphasize that a starting solution, with a 10.0~10.1 mol% TiO2 concentration, results in large single crystals with a highly homogeneous lattice constant of within
$\pm$ 1x10-4$\AA$ , when the solidified fraction of the grown crystal is less than about 45%. A wavelength dispersion of refractive index was measured for the first time, an it was verified that the refractive index of BTO is larger than that of BSO(Bi12TiO20), allowing the voltage sensitivity of EOS higher than the case with BSO as a probe head. -
The development of telecommunication and information technology requires to develop new piezoelectric materials with small size, low impedance, wide pass band width and high thermal stability of frequency. Langasite (La3Ga5SiO14) single crystal has been researched substitute of quartz and LiNbO3 for the applications of SAW filter, BAW filter and resonator. Its single crystal growth has been carried out by Czochralski Method. So, in order to get single crystal with higher quality, in this study, lnagasite (La3Ga5SiO14) single crystal was grown by using Floating Zone (FZ) method and characterized. For the growth of langasite single crystals, the langasite powder was synthesized at 135
$0^{\circ}C$ for 5hrs and the feed rod was sintered at 135$0^{\circ}C$ for 5hrs. The growing rate was 1.5mm/h and the rotation speed was 15 rpm for an upper rotation and 13 rpm for a lower rotation. In order to prevent the evaporation of gallium oxide, Ar and O2 gas mixture was flowed. The growth direction was analyzed by Laue back-scattered analysis. The composition of grown crystal was analyzed suing XRD and WDS. The electrical properties of grown crystal at various frequencies and temperature were discussed. -
As a semiconductor material for electronic devices operated under extreme environmental conditions, silicon carbides (SiCs) have been intensively studied because of their excellent electrical, thermal and other physical properties. The growth characteristics of single-crystalline 4H-SiC homoepitaxial layers grown by a thermal chemical vapor deposition (CVD) were investigated. Especially, the successful growth condition of 4H-SiC homoepitaxial layers using a SiC-uncoated graphite susceptor that utilized Mo-plates was obtained. The CVD growth was performed in an RF-induction heated atmospheric pressure chamber and carried out using off-oriented substrates prepared by a modified Lely method. In order to investigate the crystallinity of grown epilayers, Nomarski optical microscopy, Raman spectroscopy, photoluminescence(PL), scanning electron microscopy (SEM) and other techniques were utilized. The best quality of 4H-SiC homoepitaxial layers was observed in conditions of growth temperature 1500
$^{\circ}C$ and C/Si flow ratio 2.0 of C3H3 0.2sccm & SiH4 0.3sccm. The growth rate of epilayers was about 1.0$\mu\textrm{m}$ /h in the above growth condition. -
Thin films of hydrogenated amorphous silicon carbide compounds (a-SixC1x:H) of different compositions were deposited on Si substrate by RF plasma-enhanced chemical vapor deposition (PECVD). Experiments were carried out using silane(SiH4) and methane(CH4) as the gas precursors at 1 Torr and at low substrate temperature (25
$0^{\circ}C$ ). The gas flow rate was changed with every other parameters (pressure, temperature, RF power) fixed. The substrate was Si(100) wafer and all of the films obtained were amorphous. The bonding structure of a-SixC1x:H films deposited was investigated by X-ray photoelectron spectroscopy (XPS) for the film compositions. In addition, the surface morphology of films was investigated by atomic force microscopy (AFM). -
It was grown Er2O3 doped LiNbO3 single crystal thin films with high crystal quality by liquid phase epitaxial (LPE) method. Er2O3 was doped with a concentration of 1, 3, and 5 mol% respectively. After the growth of single crystal thin film, we examined the crystallinity and the lattice mismatch along the c-axis between the film and the substrate with the variation of Er2O3 dopant using X-ray double crystal technique. There were no lattice mismatches along the c-axis for the undoped and the films doped with 1 and 3 mol% of Er2O3. For 5 mol% of Er2O3 doped film, there was a lattice mismatch of 7.86x10-4nm along the c-axis.
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Erbium(Er) doped LiNbO3(Er:LiNbO3) single crystal gibers were grown free of cracks along the c-axis by micro-pulling down method. the Er3+ concentration was distributed homogeneously along the growth axis. The samples for optical characterization were cut from as-grown single crystal fibers and polished. When the 980 nm light was incident on the sample, upconversion phenomena were observed at the green range of wavelength 510~570 nm. In addition, the intensity of upconversion was remarkably increased by increasing the concentration of Er2O3 dopant in as-grown Er:LiNbO3 crystals.
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Thick diamond film having ~700
${\mu}{\textrm}{m}$ thickness was deposited on polycrystalline molybdenum (Mo) substrate using high power (4kW) microwave plasma enhanced chemical vapor deposition (MPECVD) system. We could achieve free-standing diamond film via detaching as-deposited diamond film from the substrate by rapid cooling them under vacuum. We investigated the variation of photoconductivity after exposing the film surface to either oxygen or hydrogen plasma. At as-grown state, the growth side (the as-grown surface of the film) showed noticeable photoconductivity. The oxygen plasma treatment of this side led to the insulator. After exposing the film surface to hydrogen plasma, on the other hand, we could observe the reappearing of photoconductivity at the growth side. Based on these results, we suggest that the hydrogen plasma treatment may enhance the photoconductivity of free-standing diamond film. -
Ha, Jong-Pil;Seo, Dong-Nam;Kim, Seong-Yong;Jung, Mi-Jeong;Moon, In-Ho;Cho, Sang-Joon;Park, Hyun-Min;Kim, Ik-Jin 351
A large NaX type zeolite crystal of a uniform particle size of 20${\mu}{\textrm}{m}$ are grown with various H2O content by hydrothermal reaction and added seed crystal (2~3${\mu}{\textrm}{m}$ ) to reactant solution as a function of different adding seed levels from 3 to 15 %. The result that increased purity of NaX zeolite above 95% and homogeneity of crystal size by increasing adding seed levels, also decreased crystallization time. It was explained that adding seed to synthesis solution leaded out increase of surface area of physical contact reaction and directed growth of seed crystal, so more rapid consumption of reaction gel as increase seeding levels. -
New method of control based upon a physical model of the Stepanov growth technique has been developed. The controller keeps the system stable and completely denies operator's interference into the process. The system demonstrates very reliable results under commercial production of shaped sapphire crystals.
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La2-xSrxCuO4 single-crystalline films were prepared on bulk single crystals of Zn-doped La2CuO4 as the substrates by LPE technique using tow deferent methods. When prepared using an alumina crucible in normal electrical furnace, the La2-xSrxCuO4 films were contaminated with less than 3 at% aluminum from the alumina crucibles. Aluminum contamination either reduced or completely destroyed the superconductivity of the La2-xSrxCuO4 films. For LPE growthby modified TSFZ method using an infrared heating furnace without crucibles, the La2-xSrxCuO4 films of x=0.11 showed superconducting with Tconset 36 K, which is 10 K higher than that in the La2-xSrxCuO4 bulk single crystals.
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Single crystal of Li2Cu1-xMxO4 (M=Ni, Zn) are promising as a substrate to realize superconducting electronic devices. The distribution coefficients of Ni and Zn to the Cu site in La2CuO4 (LCO) were estimated by the zone melting technique to grow high quality single crystals of La2Cu1-xMxO4(M=Ni, Zn). The distribution coefficient value of Ni was estimated to be 4.2 and that of Zn was estimated to be 0.66, respectively. Suitable solvent compositions were determined using these values to grow single crystals by he traveling floating zone (TSFZ) method. Single crystal of LCO, La2Cu1-xMxO4(M=Ni(x=0.01, 0.02, 0.03, 0.04), Zn(x=0.01, 0.02, 0.03) of high homogeneity were grown. The behaviors of the magnetization of these as-grown crystals do not indicate superconductivity except LCO. Ni or Zn substitution can make LCO non superconductor. This fact suggest that single crystals substituted by Ni or Zn are useful as substrate crystals.
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Fiber growth of Al2O3/R-Al-O(R=Y, Gd, Dy, Ho, Er) eutectic by the micro-pulling down methods is described. The thermal stability and strength at elevated temperature of each material is evaluated in relation to the microstructure. PACS: 81.05 Mh, 81.10 Fq, 81.30-t.
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InP, III-V binary compound semiconductor, single crystal was grown by VGF (vertical gradient freeze) method using quartz ampoule and its electrical optical properties were investigated. Phosphorous powders were put in the bottom of quartz ampoule and Indium metal changed in conical quartz crucible hat was attached at the upper side position inside the quartz ampoule. It was vacuous under the pressure of 10-5 Torr and sealed up. In metal in the quartz crucible was melted at 1070
$^{\circ}C$ and phophorous sublimated at 450$^{\circ}C$ , there after it was diffused in In melt and so InP composition was formed. By cooling the InP composition melt (2$^{\circ}C$ ∼5$^{\circ}C$ /hr of cooling rate) in range of 1070$^{\circ}C$ ∼900$^{\circ}C$ , InP crystal was grown. the grown InP single crystals were investigated by X-ray analysis and polarized optical microscopy. Electrical properties of them were measured by Van der Pauw method. At the cooling rate of 2$^{\circ}C$ /hr, its direction was (111), quality of the ingot ws better upper side of the ingot than lower. It was found that the InP crystals were n-type semiconductor and the carrier concentration, electron mobility and relative resistivity were 1015∼1016/㎤, 2x103∼3x104$\textrm{cm}^2$ /Vsec and 2x10-1∼2x10-3Ωcm in the range of 150K∼300K, respectively.