Growth and characterization of CdSe single crystals by modified vertical vapor phase method

Good quality, large single crystals of CdSe were grown by the modified growth method (i.e., vertical unseeded vapor phase growth with multi-step purification of the starting material in the same quartz ampoule without any manual transfer between the steps). Lower temperature gradients (8–9°C/cm) at the growth interface were used for the crystal growth. As-grown CdSe crystals was characterized by X-ray diffraction, scanning electron microscopy, energy dispersive analyzer of X-rays, high-resistance instrument measurement, and etch-pit observation. It is found that there are two cleavage faces of (1 0 0) and (1 1 0) orientations on the crystal, the resistivity is about 10⁸ Ω cm, and the density of etch pits is about 10^3–4/cm². The crystal was cut into wafers and was fabricated into detectors. The detectors were tested using an ²⁴¹Am radiation source. γ-ray spectra at 59.5 keV were obtained. The results demonstrated that the quality of the as-grown crystals was good. The crystals were useful for fabrication of room-temperature-operating nuclear radiation detectors. Therefore, the modified growth technique is a promising, convenient, new method for the growth of high-quality CdSe single crystals.     

Crystal growth of Ce: PrF3 by micro-pulling-down method

Micro-pulling-down (μ-PD) growth apparatus was modified for fluoride crystals. PrF₃ was grown with various concentrations of Ce³⁺ from 0–100%. The crystals were transparent and colorless (CeF₃) or greenish and 3 mm in diameter and 15–50 mm in length. Neither visible inclusions nor cracks were observed. Radioluminescence spectra and decay kinetics were measured for the sample set at room temperature. In comparison to the Czochralski or Bridgman method, the μ-PD method allows to produce single crystalline material in a faster thus more economic way. Once it is established for the fluoride crystals, it is an efficient tool for exploring the field of new functional fluorides.     

Evidence of free carrier concentration gradient along the c-axis for undoped GaN single crystals

Results of measurements of infrared reflectivity and micro-Raman scattering on the undoped GaN high pressure grown single crystals are reported. These crystals have usually a high electron concentration due to unintentional doping by oxygen. We show, by the shift of the plasma edge (infrared reflectivity measurements), that the free electron concentration is always higher on the (0 0 0  )N face of the GaN single crystal than on the (0 0 0 1)Ga face. In order to determine the profile of the free carrier concentration, we performed transverse micro-Raman scattering measurements along the (0 0 0 1) c-axis of the crystal with spatial resolution of 1 μm. Micro-Raman experiments give a quantitative information on the free carrier concentration via the longitudinal optical phonon–plasmon (LPP) coupling modes. Thus, by studying the behavior of the LPP mode along the c-axis, we found the presence of a gradient of free electrons. We suppose that this gradient of electrons is due to the gradient of the main electron donor, in undoped GaN single crystals, i.e. oxygen impurity. We propose a growth model which explains qualitatively the incorporation of oxygen during the growth of GaN crystal under high pressure of nitrogen.     

Growth and properties of Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals directly from melt

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by a modified Bridgman method directly from melt using an allomeric Pb[(Mg_1/3Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal as a seed. X-ray diffraction (XRD) measurement confirmed that the as-grown PZNT91/9 single crystals are of pure perovskite structure. Electrical properties and thermal stabilization of PZNT91/9 crystals grown directly from melt exhibit different characters from those of PZNT91/9 crystals grown from flux, although segregation and the variation of chemical composition are not seriously confirmed by X-ray fluorescence analysis (XPS). The [0 0 1]-oriented PZNT91/9 crystals cut from the middle part of the as-grown crystal boules exhibit broad dielectric-response peaks at around 105 °C, accompanied by apparent frequency dispersion. The values of piezoelectric constant d₃₃, remnant polarization P_r, and induced strain are about 1800–2200 pC/N, 38.8 μC/cm², and 0.3%, respectively, indicating that the quality of PZNT crystals grown directly from melt can be comparable to those of PZNT91/9 single crystals grown from flux. However, further work deserves attention to improve the dielectric properties of PZNT crystals grown directly from melt. Such unusual characterizations of dielectric properties of PZNT crystals grown directly from melt are considered as correlating with defects, microinhomogeneities, and polar regions.     

Structural, thermal and dielectric studies on a new solution grown 4-dimethylaminopyridinium dihydrogen phosphate crystal

Single crystals of 4-dimethylaminopyridinium dihydrogen phosphate (DMAPDP) (C₇H₁₃N₂PO₄) were grown by the solvent evaporation method. The three-dimensional structure was solved by the single-crystal X-ray diffraction method which belongs to triclinic crystal system and the molecular arrangements in the crystal were studied. The thermal behaviour was investigated using differential scanning calorimetry (DSC) and no phase transition was identified in the temperature region −150 to 230 °C. The thermal parameters—thermal diffusivity (), thermal effusivity (e), thermal conductivity (K) and heat capacity (C_p) of DMAPDP were measured by an improved photopyroelectric technique at room temperature. Dielectric constant and dielectric loss of the grown crystal were evaluated for the frequency range 1–200 KHz in the temperature region 28–135 °C. The Vicker's hardness was measured as 42.2 for a load of 98.07 mN. The laser induced surface damage threshold of DMAPDP crystal was found to be 4.8 GW/cm² with nanosecond Nd:YAG laser.     

Crystal growth of Co46Ni27Ga27 ferromagnetic shape memory alloys with large single-variant set

The present work proposes a directional solidification method based on liquid melt cooling (LMC) technique to prepare large grain with single-variant set in Co–Ni–Ga alloys. The competitive growth from equaixed grains to steady columnar crystals with 1 1 0 orientation along the axis was observed. The directionally solidified rod has a uniform chemical composition. It can be also found that the unidirectional lamellar martensitic variants were well aligned in a whole grain, forming a single-variant state. Furthermore, the needle-like Ni₃Ga-type γ′ precipitates were formed in alloy with lower growth velocity, and it exhibited the complicated microstructural evolution. At the lowermost part of rod-like crystal, a large number of precipitates were dispersed both in grain interiors and at boundaries but its amount decreased when the columnar crystals were formed and gradually increased again from bottom up to top in the whole rod.     

Growth and characterization of 2-amino-5-chlorobenzophenone (2A-5CB) single crystals

Organic nonlinear optical single crystals of 2-amino-5-chlorobenzophenone (2A-5CB) were grown in ethanol by slow solvent evaporation technique. The grown crystals were characterized by single-crystal XRD, FTIR, FT-Raman and UV–vis–NIR techniques. The UV–vis–NIR spectrum ascertains the cut-off wavelength of the sample as 390 nm. The powder second harmonic generation (SHG) technique reveals that 2A-5CB crystal has its SHG efficiency nearly three times that of KDP. The dielectric response of the sample was studied in the frequency region of 50 Hz–1 MHz at varying temperatures. The photoconductivity studies indicate that the 2A-5CB crystal exhibits negative photoconductivity. TGA–DTA studies confirm the melting point of the sample as 101.5 °C.     

Large-size β-Ga2O3 single crystals and wafers

Large-size single crystals of β-Ga₂O₃ with 1 inc in diameter have been grown by the floating zone technique. The stable growth conditions have been determined by the examination of the crystal structure. Wafers have been cut and fine polished in the (1 0 0), (0 1 0) and (0 0 1) planes. These were highly transparent in the visible and near UV, as well as electrically conductive, indicating the potential use of β-Ga₂O₃ as a substrate for optoelectic devices operating in the visible/near UV and with vertical current flow.     

Photocurrent measurements on GaAs1−xNx epilayers grown by metalorganic chemical vapor deposition

GaAs_1−xN_x epilayers were grown on a GaAs(0 0 1) substrate by metalorganic chemical vapor deposition. Composition was determined by high resolution X-ray diffraction. Band gap was measured from 77 to 400 K by using photocurrent measurements. The photocurrent spectra show clear near-band-edge peak and their peak energies drastically decrease with increasing nitrogen composition due to band gap bowing in the GaAs_1−xN_x epilayers. Those red shifts were particularly notable for low nitrogen compositions. However, the shifts tended to saturate when the nitrogen composition become higher than 0.98%. When the nitrogen composition is in the range 1.68–3.11%, the measured temperature dependence of the energy band gap was nicely fitted. However, the properties for the nitrogen composition range 0.31–0.98% could not be fitted with a single fitting model. This result indicates that the bowing parameter reaches 25.39 eV for low nitrogen incorporation (x=0.31%), and decreases with increasing nitrogen composition.     

Growth, dielectric, ferroelectric and optical properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were grown by the Czochralski method. The effective segregation coefficients of Ca, Ba, Na elements in CBN-28 crystal growth were measured, and the rocking curve from 0 0 2 reflection of CBN-28 wafer was also measured by the high-resolution X-ray diffractometer D5005, and the full-width at half-maximum value was measured to be 70.6″. The measured dependence of dielectric constants on temperature showed the Curie temperature of the CBN-28 crystals is between 246.8 and 260 °C. Typical polarization–electric field (P–E) hysteresis loops were measured at room temperature. Ferroelectric 180° domains were observed by scanning electron microscopy (SEM) on the etched (0 0 1) surface of the CBN-28 crystals. The transmittance of [0 0 1]-oriented CBN-28 crystals was measured and the result shows that optical properties of CBN-28 crystal are almost the same as those of SBN for wavelengths between 2500 and 7500 nm.     

Synthesis, growth of organic nonlinear optical crystal: Semicarbazone of 2-amino-5-chloro-benzophenone (S2A5CB) and its characterisation

A new organic crystal of semicarbazone of 2–amino–5–chloro–benzophenone has been grown as a single crystal by slow evaporation solution growth technique for the first time in the literature. The grown crystal has been characterised by proton nuclear magnetic resonance spectral analysis and single crystal and powder X-ray diffraction studies. Functional groups of the crystallised molecules were confirmed by FT-IR and FT-Raman analyses. Mechanical strength of the crystals was studied by microhardness test. Optical transparency of the grown crystals has been studied by UV-Visible spectra. The second harmonic generation property of the compound was analysed.     

Growth and spectroscopic properties of Er single doped and Er–Yb co-doped YAl3(BO3)4 crystals

Er³⁺-doped and Er³⁺–Yb³⁺ co-doped yttrium aluminum borate (YAB) single crystals have been grown by the top-seeded solution growth method using a new flux system, namely NaF–MoO₃–B₂O₃. The Er³⁺ concentrations were 1.3 mol% for both single doped and co-doped crystals and the Yb³⁺ concentration in the Er³⁺–Yb³⁺ co-doped crystal was 20.0 mol% in the raw materials. The distribution coefficients of Er³⁺ single doped and Er³⁺–Yb³⁺ co-doped crystals were measured. The polarized absorption and fluorescence spectra of Er³⁺–Yb³⁺ co-doped crystal were recorded and compared with those of Er³⁺ single doped crystal. The results demonstrate that Er³⁺–Yb³⁺ co-doped YAB crystal is a potential candidate for 1.55 μm laser materials.     

Growth of large dimension BaWO4 crystal by the Czochralski method

In this paper, polycrystalline materials of BaWO₄ were synthesized by solid-state phase method, and a single crystal of BaWO₄ was successfully grown along a and c-axis direction by using the Czochralski method. Up to 20×22×80 mm³ BaWO₄ crystal was obtained, and X-ray powder diffraction results show that the as-grown BaWO₄ crystal belongs to the scheelite structure. The effective segregation coefficients of Ba and W of the BaWO₄ crystal were measured by the X-ray fluorescence method, and the effective segregation coefficients of Ba and W were near 1. The rocking curve from (2 0 0) diffraction plane of as-grown BaWO₄ single crystal was measured on the High-resolution X-ray diffractometer D5005, and the full-width at half-maximum value was found to be 26.64′′ The density and hardness of the BaWO₄ crystal was measured, the measured density was in agreement with the calculated result, and the Mohs hardness was about 4.     

Single crystal growth of copper phthalocyanine using exaltation–evaporation growth method

A new method of growing single crystal for β-form copper phthalocyanine (CuPc) is presented in this paper. Melted anthracene was used as solvent of CuPc. The method, vaporizing the solvent using an automatic exaltation machine, was employed to grow CuPc single crystals. The needle-like single crystals of CuPc up to 11.6 mm in length were obtained by applying this method. The influences of different temperatures, exaltation speeds and concentrations on the single crystals growth were also discussed. The method was called exaltation–evaporation growth method.     

AlGaN photodetectors grown on Si(1 1 1) by molecular beam epitaxy

The fabrication and characterisation of Al_xGa_1−xN (0x0.35) photodetectors grown on Si(1 1 1) by molecular beam epitaxy are described. For low Al contents (<10%), photoconductors show high responsivities (10A/W), a non-linear dependence on optical power and persistent photoconductivity (PPC). For higher Al contents the PPC decreases and the photocurrent becomes linear with optical power. Schottky photodiodes present zero-bias responsivities from 12 to 5 mA/W (x=0−0.35), a UV/visible contrast higher than 10³, and a time response of 20 ns, in the same order of magnitude as for devices on sapphire substrate. GaN-based p–n ultraviolet photodiodes on Si(1 1 1) are reported for the first time.     

Growth and morphology of ruby crystals with unusual chromium concentration

Single crystals of ruby have been obtained from fluxed melts based on the systems Li₂O–MoO₃, Li₂O–WO₃, Na₂O–WO₃, 2PbO–3V₂O₅, PbO–V₂O₅–WO₃, PbF₂–Bi₂O₃ and Na₃AlF₆ by both the TSSG method and spontaneous crystallization at the temperatures 1330–900 °C. Al₂O₃ solubility has been measured for the flux composition of 2Bi₂O₃–5PbF₂ in the temperature range 1200–1000 °C and dissolution enthalpy has been defined as 29.4 KJ/Mol. The composition of grown crystals was studied by electron microprobe analysis. The synthetic ruby contains from 0.51 to 6.38 at% of chromium admixture depending on the crystal growth conditions. Experimental results on growth conditions, composition and morphology of grown crystals are presented for each flux and temperature interval.     

Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.     

Growth of InAs on GaAs(1 0 0) by low-pressure metalorganic chemical vapor deposition employing in situ generated arsine radicals

InAs was grown by low-pressure metalorganic chemical vapor deposition on vicinal GaAs(1 0 0) substrates misoriented by 2° toward [0 0 1]. We observed InAs crystal growth, at substrate temperatures down to 300°C, employing in situ plasma-generated arsine radicals as the arsenic source. The in situ generated arsine was produced by placing solid arsenic downstream of a microwave driven hydrogen plasma. Trimethylindium (TMIn) feedstock carried by hydrogen gas was used as the indium source. The Arrhenius plot of InAs growth rate vs. reciprocal substrate temperature displayed an activation energy of 46.1 kcal/mol in the temperature range of 300–350°C. This measured activation energy value is very close to the energy necessary to remove the first methyl radical from the TMIn molecule, which has never been reported in prior InAs growth to the best of authors’ knowledge. The film growth mechanism is discussed. The crystallinity, infrared spectrum, electrical properties and impurity levels of grown InAs are also presented.     

The influences of supersaturation on LPE growth of GaN single crystals using the Na flux method

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.     

Growth morphology of perfect and twinned face-centered-cubic crystals by Monte Carlo simulation

The effect of the relative growth rate between {1 1 1} and {1 0 0} faces on the growth morphology of perfect and twinned face-centered-cubic crystals was investigated with a Monte Carlo simulation considering both first-nearest-neighbor (FNN) and second-nearest-neighbor (SNN) interactions. When the bond energy ratio of SNN to FNN interactions is close to zero, the {1 1 1} twin planes make a reentrant edge, which enhances the growth rate on this plane, leading to a tabular growth shape. When the ratio is 0.25, the ridge side face of a tabular shape has the {1 0 0}/{1 0 0}/{1 1 1} structure instead of the {1 1 1}/{1 1 1} reentrant edge. In spite of disappearance of the reentrant edge, the side face has a higher growth rate than the top face because the {1 0 0} face still grows faster than the {1 1 1} face.