Earticle

Metal-semiconductor contact is very important for the operating property of semiconductor detector. Cd0.96Zn0.04Tesemiconductor crystal was grown with Bridgman method, and the crystal was cut and polished. EPMA (Electron ProbeMicro Analyzer) and ICP-MS (Inductively Coupled Plasma Mass Spectrometry) analysis were done to obtain the chemicalcomposition and impurity of the crystal. Metal contact was deposited with thermal evaporator on both sides of the crystal.Detectors with Au/CZT/Au and In/CZT/Au structure were made, and I-V curve and the energy spectrum were measuredwith the detectors. It could be seen that the detector with the In/CZT/Au structure has superior property than the detectorwith Au/CZT/Au structure when the crystal resistivity was low. However, the metal contact structure effect becomes lowwhen the crystal resistivity was high.

Some lead-based crystals show excellent ferroelectric, piezoelectric or scintillation properties and have attracted much attention in recent years. However, the erosion of the high temperature solution on platinum crucible and the evaporation of PbO component are the main problems often encountered during the crystal growth. In this paper, we reported recent progress on the Bridgman growth of lead-based functional crystals, such as novel relaxor ferroelectric crystals (PZNT and PMNT), scintillation crystals $(PbWO_4,\;PbF_2\;and\;PbClF)$ and piezoelectric crystals $(Pb_5Ge_3O_{11}\;and\;Pb_2KNb_5O_{15}),$ in Shanghai Institute of Ceramics, Chinese Academy of Sciences. The vertical Bridgman method has been modified to grow PZNT crystals from high temperature solution and as-grown crystals have been characterized. Large size lead-based scintillators, $PbWO_4\;and\;PbF_2$ crystals, have been mass-produced by the vertical Bridgman method in the multi-crucible fumace. These crystals have been supplied to CERN and other laboratories for high-energy physics experiments. The Bridgman growth of piezoelectric crystals $Pb_5Ge_3O_{11}\;and\;Pb_2KNb_5O_{15}$ are discussed also.

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, and low-dislocation-density low-residual-strain 4-inch to 6-inch semi-insulating GaAs crystals for electronic devices by Vertical Bridgman(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 of the LEC-GaAs substrate, which is due to the low-dislocation-density of VB-GaAs single crystals.

Single crystal of p-$CdIn_{2}Te_{4}$ was grown in a three-stage vertical electric furnace by using Bridgman method. The quality of the grown crystal has been investigated by x-ray diffraction and photoluminescence measurements. From the photoluminescence spectra of the as-grown $CdIn_{2}Te_{4}$ crystal and the various heat-treated crystals, the ($D^{o}$, X) emission was found to be the dominant intensity in the photoluminescence spectrum of the $CdIn_{2}Te_{4}$:Cd, while the ($A^{o}$, X) emission completely disappeared in the $CdIn_{2}Te_{4}$:Cd. However, the ($A^{o}$, X) emission in the photoluminescence spectrum of the $CdIn_{2}Te_{4}$:Te was the dominant intensity like in the as-grown $CdIn_{2}Te_{4}$ crystal. These results indicated that the ($D^{o}$, X) is associated with $V_{Te}$ which acted as donor and that the ($A^{o}$, X) emission is related to $V_{Cd}$ which acted as acceptor, respectively. The p-$CdIn_{2}Te_{4}$ crystal was obviously found to be converted into n-type after annealing in Cd atmosphere. The origin of ($D^{o},{\;}A^{o}$) emission and its to phonon replicas is related to the interaction between donors such as $V_{Te}$ or $Cd_{int}$, and acceptors such as $V_{Cd}$ or $Te_{int}$. Also, the In in the $CdIn_{2}Te_{4}$ was confirmed not to form the native defects because it existed in a stable bonding form.

Slip lines and dislocation structures developed by deformation at 77 K, 292 K and 500 K have been investigated by an optical microscope and a high-voltage electron microscope. Slip patterns after the deformation by 4-5% at 77 K and 500 K are compared. From the slip line geometry, operation of both primary and secondary {111} slips have been confirmed. However, the primary slip lines formed at 77 K appear coarser and more pronounced than those at 500 K. This indicates that a larger number of dislocations have moved on the same plane at 77 K. Another characteristic difference noted here is that the slip lines are straight and pass through the specimen from one end to the other at 77 K. On the contrary, slip lines are rather faint at 500 K. The typical change found at 77 K is the increase in the [$0{\bar{1}}1$] dipole dislocations and generation of the [$10{\bar{1}}$] screw dipoles upon increase in the strain from 1.2% to 5.2%. This is the indication that the straight dipole dislocations were formed by a pinning effect due to jogs generated by mutual cutting between primary and secondary dislocations. Extremely fine slip has been noted after deformation at 500 K indicating that the usual Frank-Read source is not operative at high temperatures due to the strong KW locking.

A colorless and transparent zirconium oxide ($Zr_{0.73}Y_{0.27}O_{1.87}$) crystal has been synthesized by the Bridgman-Stockbager method. The gem-quality material is produced by adding 20${\sim}$25 wt.% $Y_2O_3$ (stabilizer) and 0.04 wt.% $Nd_2O_3$ (decolorising agent) to the $ZrO_2$ powder. It shows a vitreous luster with a slight oily appearance. Under a polarizing microscope, it shows isotropic nature with no appreciable anisotropism. Mohs hardness value and specific gravity is measured to be 8${\sim}$$8{\frac{1}{2}}$ and 5.85, respectively. Under ultraviolet light it shows a faint white glow. The crystal structure of yttria-stabilized zirconia with 0.27 at.% Y has been re-investigated, using single crystal X-ray diffraction, and confirmed to be a cubic symmetry, space group $Fm{\overline{3}}m$ ($O^5_h$) with a=5.1552(5) ${{\AA}}$, V=136.99(5) ${{\AA}}^3$, Z=4. The stabilizer atoms randomly occupy the zirconium sites and there are displacements of oxygen atoms with amplitudes of ${\Delta}/a{\sim}$0.033 and 0.11 along <110> and <111> from the ideal positions of the fluorite structure, respectively.

The p-CIn2Te4 single crystal was grown in the three-stage vertical electric furnace by using Bridgman method. The quality of the grown crystal has been investigated by the x-ray diffraction and the photoluminescence measurements. From the photoluminescence spectra of the as-grown CdIn2Te4 crystal and the various heat-treated crystals, the (Do, X) emission was found to be the dominant intensity in the photoluminescence spectrum of the CdIn2Te4:Cd, while the (Ao, X) emission completely disappeared in the CdIn2Te4:Cd. However, the (Ao, X) emission in the photoluminescence spectrum of the CdIn2Te4:Te was the dominant intensity like an as-grown CdIn2Te4 crystal. These results indicated that the (Do, X) is associated with VTe acted as donor and that the (Ao, X) emission is related to VCd acted as acceptor, respectively. The p-CdIn2Te4 crystal was found to be obviously converted into the n-type after annealing in the Cd atmosphere. The origin of (Do, Ao) emission and its TO phonon replicas is related to the interaction between donors such as VTe or Cdint, and accepters such as VCd or Teint. Also, the In in the CdIn2Te4 was confirmed not to form the native defects because it existed in the stable form of bonds.

The single crystal of CdTe was grown by modified 6 zone Bridgman method under the conditions of excess Te and excess Cd. To prevent the constitutional supercooling, the crystal growth was done under the temperature gradient of $17^{\circ}C/cm$ in front of the solid /liquid interface and the growth rate was 3mm/hr. The grain morphologies and the growth mechanism were investigated in excess Te and excess Cd conditions. The grain size of excess Te crystal was increased with an increase of the distance from the tip but, in the case of excess Cd crystal, single crystal was not obtained because of the cavities due to the excess Cd vapors so that the grain size was not increased with an increase of the distance from the tip. In addition, the growth of single crystal of CdTe was done with repeated necking ampoule. It was found that the necking had no effects on the grain selection because the cavities trapped in the necking portion acted as heterogeneous nucleation sites.

수평 전기로에서 CdIn2Te4 다결정을 용융법으로 합성하고 Bridgman법으로 tetragonal structure의 c축에 평행한 CdIn2Te4 단결정을 성장시켰다. c축에 평행한 시료의 광흡수와 광전류 spectra를 293K에서 10K까지 측정하였다. 광흡수 spectra에 의해 band gap Eg(T)는 varshni공식에 따라 계산한 결과 1.4753eV-(7.78$\times$$10^{-3}$eV/K)T$^2$/(T+2155K)임을 확인하였다. Hall 효과는 van der Pauw 방법에 의해 측정되었으며, 온도에 의존하는 운반자 농도와 이동도는 293K에서 각각 9.01$\times$$10^{16}$ /㎤, 219 $\textrm{cm}^2$/V.S였다. 광전류 스펙트럼으로부터 Hamilton matrix(Hopfield quasicubic mode)법으로 계산한 결과 crystal field splitting $\Delta$cr값이 0.2704 eV이며 spin-orbit $\Delta$so 값은 0,1465 eV임을 확인하였다. 10K일 때 광전류 봉우리들은 n=1일때 Al-, Bl-와 Cl-exciton 봉우리임을 알았다.

Metallurgical-grade polycrystalline silicon was directionally solidified at growth rates of $0.2{\sim}1.0mm/min$ by using split type, reusable graphite molds which were coated with $Si_3N_4$ powder. The resultant grain sizes of the silicon ingots and the shapes of the solid/liquid(S/L) interfaces were investigated. X-ray diffraction was used to determine the preferred orientation in each of the silicon ingots. The impurity content of the silicon was analyzed and the resistivities of the ingots were measured. During the growth of an ingot, the shape of the S/L interface was concave to the silicon melt, and the resistivity decreased. The presence of Al which can be acting as a carrier, is thought to be the main factor causing such a decrease in resistivity. When a growth rate of 0.2㎜/min was used, the preferred orientation was found to be (111).

The undoped-InSe and Sn-doped InSe single crystals were grown by vertical Bridgman method and their properties were invesigated. The orientations and the crystallinites of these crystals were identified by X-ray diffraction(XRD), double crystal rocking curve(DCRC) and etch-pit density(EPD) measurements. From the Raman spectrum at room temperature, TO, LO modes and together with their overtones and combinations were observed. Optical properties were inves ated by PL at 12K and direct band gap of these crystals obtained from optical absorption spectrum. Compared with undo&-InSe, electrical properties of Sn-doped InSe were increased and the electrical conductivity type were n-type. But electrical properties along growth direction of crystals and radial direction of wafer showed nearly uniform distribution. The Zn diffusion mechanism in InSe could be explained by interstitial-substitutional and vacancy complex models and the activation energy of 1.15-3.01eV were needed for diffusion.fusion.

A ternary compound semiconductor $Al_{x}$-Ga/1-x/Sb crystals which have energy gap from 0.7eV to 1.6ev at room temperature with the composition ratio were grown by using the vertical Bridgman method. The characteristics of $Al_{x}$-Ga/1-x/Sb were investigated in this study. The lattice constants of $Al_{x}$-Ga/1-x/Sb crystals with the composition ratio were appeared from 6.096$\AA$ to 6.135$\AA$ with the composition ratio. The electrical properties of the $Al_{x}$-Ga/1-x/Sb crystals measured the Hall effect by van der Pauw method at the magnetic field of 3 kilogauss and at room temperature. The resistivity of Te-doped $Al_{x}$-Ga/1-x/Sb crystals increased from 0.771 $\Omega$-cm to 5 $\Omega$-cm at room temperature with increasing the composition ratio. The mobility of Te-doped $Al_{x}$-Ga/1-x/Sb crystals varied with the composition ratio x, within the following three different regions, such as GaSb-like (0$\leq$x$\leq$0.3), intermediate (0.3$\leq$x$\leq$0.4) and AlSb-like (0.4$\leq$x$\leq$1).eq$</TEX>1).

A p-$CdIn_2Te_4$ single crystal has been grown by the Bridgman method without a seed crystal in a tree-stage vertical electric furnace. From photocurrent measurements, it was found that three peaks, A, B, and C, corresponded to an intrinsic transition due to the band-to-band transition from the valence band states ${\Gamma}_7(A),\;{\Gamma}_6(B),\;and\;{\Gamma}_7(C)$ to the conduction band state ${\Gamma}_6$, respectively. Also, the valence band splitting of the $CdIn_2Te_4$ crystal has been confirmed by photocurrent spectroscopy. The crystal field splitting and the spin orbit splitting were obtained to be 0.2360 and 0.1119 eV, respectively. Also, the temperature dependence of the band gap energy of the $CdIn_2Te_4$ crystal has been driven as the following equation of $E_g(T)\;=E_g(0)\;-\;(9.43\;{\times}\;10^{-3})T^2/(2676\;+\;T)$. In this equation, the Eg(0) was estimated to be 1.4750, 1.7110, and 1.8229 eV at the valence band state A, B, and C, respectively. The band gap energy of the p-$CdIn_2Te_4$ at room temperature was determined to be 1.2023 eV.

석영 boat를 반응용기로 쓰는 수평 Bridgman 법에서, GaAs 단결정에 유입되는 Si 농도를 Ga-As 계의 상평형에 근거한 열역학적 평형을 가정하여 성장방법 별로 계산하였고, Hall 측정에 의한 전자 농도 측정치와 비교하였다. 단일 온도대역 수평 Bridgman(1-T HB) 법의 경우 Si 농도의 계산치가 5.3 ×10 15(atoms/cm3)인데 비해 실험치는 9.8 ×10 15(/cm3) 이었고, 이중 온도대역 수평 Bridgman(2-T HB) 법에서는 계산치가 1.1 ×10 16(atoms/cm3), 측정치가 1.5 ×10 16(/cm3) 인 것으로 각각 나타났다. 한편 1-T나 2-T HB 법에 비하여 성장시간이 절반 정도인 VGF(vertical gradient freeze) 방법의 경우 이론치와 실험치가 비교적 일치 하였고 그 값은 (6∼8) ×10 15 (atoms/cm3)인 것으로 나타났다.

The mechanism of silicon incorporation has been analyzed for the boat-grown GaAs crystals on the basis of phase equilibrium in the Ga and As system. Comparison was made between silicon concentrations calculated from the thermodynamics of incorporation reaction and carrier concentrations measured from van der Pauw method. For the 1-T HB(single temperature zone horizontal Bridgman) crystals, calculated concentrations were 5.3 ×10 15 (atoms/cm3), measured as 9.8 ×10 15(/cm3) at the seed part. They were calculated to be 1.1 ×10 16(atoms/cm3) and measured as 1.5 ×10 16(/cm3) for the 2-T(double temperature zone) HB crystals. On the other hand, it was found to be closer between the calculated and measured silicon concentrations for the VGF(vertical gradient freeze) crystals, which were grown within half the run time compared with 1-T or 2-T HB method.

The undoped-InSe and Sn-doped InSe single crystals were grown by vertical Bridgman method and their properties were invesigated. These crystals were obtained by lowering the quartz ampoule for growth in the furnace and growth rate at optimum condition is 0.4mm/hr. The orientations and the crystallinites of these crystals were identified by X-ray diffraction(XRD), double crystal rocking curve(DCRC) and etch-pit density(EPD) measurements. From the Raman spectrum at room temperature, TO, LO modes together with their overtones and combinations were observed. Optical properties were investigated by photoluminescence at 12K and direct band gap of these crystals obtained from optical absorption spectrum. Compared with undoped-lnSe, electrical properties of Sn-doped InSe were increased and the electrical conductivity type were n-type. But electrical properties along growth direction of crystals and radial direction of wafer showed nearly uniform distribution.

단일 온도대역 수평 Bridgman(1-T HB)법에 의해 2인치 직경의 GaAs 단결정을 성장시키기 위하여 그 장치를 설계·제작하였고, undoped, Si-doped 및 Zn-doped 단결정을 성장하였다. 단결정성의 측면에서 성장횟수별 비로 0.73의 단결정성을 보였고, 격자결함 밀도(etch pit density)는 n-type의 경우 평균 5,000/cm2, p-type의 경우 10,000/cm2, 그리고 undoped의 경우 20,000/cm2 정도를 보였다. 한편 undoped GaAs 단결정의 경우, Hall 측정에 의한 carrier 농도가 ∼1×1016/cm3인 것으로 나타나 기존의 이중 온도대역(2-T : double temperature zone) 또는 삼중 온도대역(3-T : three temperature zone) 수평 Bridgman 방식에 비하여 Si 유입량이 절반 수준인 것으로 측정되었다. 따라서 1-T HB 방식에 의하여 2-T나 3-T HB 방법보다 나은 수율을 갖고 더 순도가 높은 GaAs 단결정을 성장시킬 수 있었다.

The single crystal growth has been carried out with the newly designed 1-T HB(single temperature zone horizontal Bridgman) system for GaAs crystals of 2 inch diameter doped with Si, Zn or undoped. With this method, incidence probability of single crystallinity was shown to be 0.73. Lattice defects evaluated from EPD(etch pit density) measurement were in the range of 5,000-20,000/cm2, dependent upon the doping condition. For the undoped GaAs crystals, carrier concentrations from the Hall measurement were ∼1×1016/cm3 at the seed part, which were less than half the concentrations of double of triple temperature zone(2-T, 3-T) HB grown crystals. By the 1-T HB method, therefore, GaAs crystals can be grown successfully with better yield and higher purity.