Developments in the bulk growth of Cd1−xZnxTe for substrates

Single crystal of CdTe or dilute alloys of Cd_1−yZn_yTe (y < 0.04) and CdTe_1−zSe_z (z < 0.04) with low defect density, high purity, and large single-crystal area (>30 cm²) are required as substances for high-quality epitaxial Hg_1−xCd_xTe thin films in the infrared (IR) detector industry. Bridgman or gradient freeze is the most common technique used for commercial production of these materials because of its success in producing large-area substrates of good quality and reproducibility. For epitaxial growth of Hg_1−xZn_xTe, which has been of considerable interest in recent years as an IR detector material, the substrate of choice has been Cd_0.80Zn_0.20Te, for lattice matching with long-wavelength Hg_1−xZn_xTe epitaxial layers (x = 0.15). The primary focus of this paper is on CdZnTe, which is currently the preffered subtrate material and most widely used for both HgCdTe and HgZnTe epitaxy. This paper reviews the current status of bulk substrate technology for IR detector applications, highlighting critical issues and essential research areas for further improvement of these materials.     

Electronic traps in mixed Si1−xGexO2 films

Thermally stimulated luminescence (TSL) and infrared (IR) spectroscopy were measured in plasma grown Si_1−xGe_xO₂ (x=0, 0.08, 0.15, 0.25, 0.5) with different thicknesses (12–40 nm). A comparison with the TSL properties of thermally grown SiO₂ and GeO₂ was also performed. A main IR absorption structure was detected, due to the superposition of the peaks related to the asymmetric O stretching modes of (i) Si–O–Si (at ≈1060 cm⁻¹) and (ii) Si–O–Ge (at 1001 cm⁻¹). Another peak at ≈860 cm⁻¹ was observed only for Ge concentrations, x>0.15, corresponding to the asymmetric O stretching mode in Ge–O–Ge bonds. A TSL peak was observed at 70°C, and a smaller structure at around 200°C. The 70°C peak was more intense in all Ge rich layers than in plasma grown SiO₂. Based on the thickness dependence of the signal intensity we propose that at Ge concentrations 0.25x0.5 TSL active defects are localised at interfacial regions (oxide/semiconductor, Ge poor/Ge rich internal interface, oxide external surface/atmosphere). Based on similarities between TSL glow curves in plasma grown Si_1−xGe_xO₂, thermally grown GeO₂ and SiO₂ we propose that oxygen vacancy related defects are trapping states in Si_1−xGe_xO₂ and GeO₂.     

Compositional dependence of the optical gap in Ge1−xSx, Ge40−xSbxS60 and (As2S3)x(Sb2S3)1−x non-crystalline systems

An attempt is made to calculate the compositional dependence of the optical gap (E_g) in Ge_1−xS_x, Ge_40−xSb_xS₆₀ and (As₂S₃)_x(Sb₂S₃)_1−x non-crystalline systems in an alloy-like approach. From the comparison of both the experimental dependence of E_g and the calculated ones using the Shimakawa relation [E_{g AB} = YE_{g A} + (1−Y)E_{g B}] it is assumed that this equation is useful for such systems or parts of the systems which behave like almost ideal solutions.     

The lattice constants of ternary and quaternary alloys in the PbTe–SnTe–MnTe system

The study of structural properties of quaternary Pb_1−x−ySn_xMn_yTe alloys revealed that they crystallise in a cubic structure of NaCl-type for a wide region of manganese content (up to y=0.16). It was found from X-ray measurements and microprobe analysis that Vegard's law is obeyed. The dependencies of the lattice constants on composition for Pb_1−x−ySn_xMn_y, Pb_1−yMn_yTe and Sn_1−yMn_yTe were used to extract the lattice parameter of NaCl-type MnTe phase by extrapolation. The experimental data were also used to obtain an improved estimate of the covalent octahedral radius for Mn.     

Growth of Cu(AlxGa1−x)SSe pentenary alloy crystals by iodine chemical vapor transport method

Single crystals of Cu(Al_xGa_1−x)SSe pentenary alloys were successfully grown by the vapor transport technique using iodine as a transport agent. Systematic measurements of the basic crystal properties were carried out using powder X-ray, photoluminescence (PL), photoreflectance (PR), and Van der Pauw methods. Dependence of the lattice constants, exciton transition energies, and PL peak energies on Al composition, x, were examined in detail. The lattice constants obeyed Vegard's law. A quadratic dependence of exciton transition energies on x was found. The broadening parameters in the PR spectrum increase monotonically with increasing x, the results showing that the crystal quality degrades with increasing x. Exciton-related PL peaks were found for 0 ≤ x ≤ 0.77 at 77 K.     

Elastic properties of GexAsySe100−x−y glasses

The elastic properties of Ge_xAs_ySe_100−x−y (0x30; 10y40) glasses have been studied. The results were analyzed in terms of the dependence on the theoretical mean coordination number (mean number of covalent bonds per atom) m (m=2+(2x+y)×0.01). Three ranges of m (2.1m2.51, 2.51<m2.78, 2.78<m3) were revealed, where different dependencies of elastic moduli (Young’s modulus, shear modulus) and Poisson’s ratio of glasses on m were observed.     

Growth, morphological and structural characterization of Pb1−xSnxTe single crystals

Pb_1−xSn_xTe single crystals have been grown by a vertical Bridgman method. They have typical Hall mobilities and carrier concentration values of 10³ cm²/V · s and 10¹⁸ cm^-3, respectively, and change from p- to n-type as the Sn content increases. The ingots were single crystal with a subgrain structure that has a misorientation no higher than 2′. The segregation of Sn has been determined and it suggests that there is a convective flow in the liquid.     

XPS and electroluminescence studies on SrS1−xSex and ZnS1−xSex thin films deposited by atomic layer deposition technique

SrS_1−xSe_x and ZnS_1−xSe_x thin films were deposited by the atomic layer deposition (ALD) technique using elemental selenium as the Se source, thus avoiding use of H₂Se or organometallic selenium compounds. X-ray diffraction (XRD) analysis showed that the films were solid solutions and X-ray photoelectron spectroscopy (XPS) data showed that the surface of both ZnS_1−xSe_x and SrS_1−xSe_x were covered with an oxide and carbon-containing contaminants from exposure to air. The oxidation of SrS_1−xSe_x extended into the film and peak shifts from sulfate were found on the surface. Luminance measurements showed that emission intensity of the ZnS_1−xSe_x:Mn alternating current thin film electroluminescent (ACTFEL) devices at fixed voltage was almost the same as that of the ZnS:Mn device, while emission intensity of the SrS_1−xSe_x:Ce devices decreased markedly as compared to the SrS:Ce device. Emission colors of the devices were altered only slightly due to selenium addition.     

Low-temperature growth of epitaxial layers of ZnSe1−xTex solid solutions

The layers of ZnSe_1−xTe_x (0 < x < 1.0) solid solutions have been grown by liquid-phase epitaxy in a closed tube at 620–680 °C. Zinc chloride served as a solvent. ZnTe and ZnSe crystals were used as sources and substrates with orienting surfaces (110) and (111) for ZnSe and (110) for ZnTe. The composition of the grown layer was specified by the relative content of the ZnSe and the ZnTe in the solution and was controlled by X-ray analysis. The position of the exciton bands in the photoluminescence spectra of ZnSe_1−xTe_x over the interval 0.3 < x < 1.0 is in agreement with the free exciton energies calculated for these compositions. Relatively low-ohmic (of about 10² Ω cm) epitaxial layers of ZnSe_1−xTe_x solid solutions were grown.     

Thermodynamic analysis of the MOVPE growth of InxGa1−xN

A chemical equilibrium model is applied to the growth of the In_xGa_1−xN alloy grown by metalorganic vapor-phase epitaxy (MOVPE). The equilibrium partial pressures and the phase diagram of deposition are calculated for the In_xGa_1−xN alloy. The vapor-solid distribution relationship is discussed in comparison with the experimental data reported in the literature. It is shown that the solid composition of the In_xGa_1−xN alloy grown by MOVPE is thermodynamically controlled and that the incorporation of group III elements into the solid phase deviates from a linear function of the input mole ratio of the group III metalorganic sources under the conditions of high mole fraction of decomposed NH₃ (high value of ), high temperature and low input V/III ratio. The origin of the deviation of the solid composition from the linear relation is also discussed.     

Compositional control of CdxZn1−xSe grown by photoassisted organometallic vapor phase epitaxy

The photoassisted OMVPE growth technique is important for the fabrication of blue/green laser diodes based on Cd_xZn_1−xSe quantum wells. Low temperature growth with photoassistance is key to the fabrication of these devices, however, the compositional control of Cd_xZn_1−xSe becomes increasingly difficult as the growth temperature is reduced. We have studied the compositional control of Cd_xZn_1−xSe using the sources DMCd, DMZn, and DMSe, with irradiation from a Hg arc lamp. We studied the dependence of the composition on the growth temperature, irradiation intensity, and source mass flows. The composition x increases with increasing temperature and decreases with increasing irradiation intensity. The solid-phase composition is a non-linear function of the gas-phase composition X. The slope of this characteristic, dx/dX, should be minimized for good compositional control. At 475°C without photoassistance, dx/dX is 1.75 near a composition of 20%, as determined from the data of Parbrook et al. Decreasing the temperature increases dx/dX. At 370°C with 12 mW/cm², dx/dX ≈ 13 and at 350°C with 58 mW/cm² dx/dX ≈ 60. We have investigated this behavior at 370°C with 12 mW/cm² irradiation by studying both the composition and the growth rate as a function of the gas-phase composition. The growth rate is non-monotonic, and is minimum for a gas-phase composition of 0.20. The behavior is quite complex, and is not fully understood at the present time. Nonetheless, our results indicate that the Cd-bearing precursor is adsorbed much more strongly than the Zn-bearing precursor. In addition to this, the introduction of the DMCd strongly inhibits the growth of ZnSe. We have achieved sufficiently good compositional control at 370°C and 12 mW/cm² to grow ZnSe/Cd_xZn_1−xSe/ZnSe multiple quantum well structures. More work is necessary in order to clarify the roles of irradiation intensity and VI/II ratio so that good compositional control can be achieved at lower growth temperatures.     

Anomalous behavior of excess energy curves of InxGa1−xN grown on GaN and InN

We worked out the excess energies for bulk In_xGa_1−xN and In_xGa_1−xN thin films on GaN and InN in order to investigate their thermodynamic stabilities. It has been found that the excess energy maximum shifted toward x0.80 for InGaN/GaN and x0.10 for InGaN/InN due to the lattice constraint in contrast with x0.50 for bulk. Moreover, it has been revealed that the excess energy for InGaN/GaN is larger than that for bulk at x>0.65. This suggests that In-rich films are less stable on GaN than bulk state. These results indicate that the lattice constraint has a significant influence on thermodynamic stabilities of thin films.     

Structural analysis of AlGaAs quantum wires on vicinal (110)GaAs by transmission electron microscopy and energy dispersive X-ray spectroscopy

Giant step structures consisting of coherently aligned multi-atomic steps were naturally formed during the molecular beam epitaxy growth of Al_0.5Ga_0.5As/GaAs superlattices (SLs) on vicinal (110)GaAs surfaces misoriented 6° toward (111)A. The growth of AlAs/Al_xGa_1−xAs/AlAs quantum wells (QWs) on the giant step structures realized Al_x0Ga_1−x0As (x₀<x) quantum wires (QWRs). We studied the giant step structures and the QWRs by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). TEM observations revealed that the QWRs were formed at the step edges. The cross sections of the QWRs were as small as 10 nm×20 nm and the lateral distances between them were about 0.15 μm. We clarified the roles of the SLs to form the coherent giant step structures. From EDX analysis, it was estimated that the AlAs composition in the Al_0.5Ga_0.5As layers varied from 0.5 (terrace) to 0.41 (step edge). In the AlAs/Al_xGa_1−xAs/AlAs QWs, the AlAs compositional modulation and the confinement by the AlAs barriers led to the embedded Al_x0Ga_1−x0As regions. These results supported the existence of the Al_x0Ga_1−x0As QWRs on the giant step structures.     

Atomic structure of Al55(Cr1−xMnx)15Si30 metallic glasses observed by neutron diffraction

An atomic structure of Al₅₅(Cr_1−xMn_x)₁₅Si₃₀ (x = 0, 0.49,1) metallic glasses was studied by neutron diffraction. An advantage of the neutron diffraction technique was fully exploited by utilizing the negative scattering length of Mn to form a neutron zero scattering ‘alloy’ for the component Cr_0.51Mn_0.49 in this quaternary Al---(Cr, Mn)---Si alloy. This allows the atomic distribution of the resulting quasibinary Al---Si metallic glass to be derived directly. Moreover, the (Al, Si)---TM (TM = Mn, Cr) and TM---TM pair correlations were also extracted by taking appropriate linear combinations of the atomic structures for the Al₅₅(Cr_1−xMn_x)₁₅Si₃₀ (x = 0, 0.49, 1) metallic glasses. A sharp first peak in the (Al,Si) ---TM pair correlations thus obtained led to the conclusion that a strong attractive interaction exists between (Al, Si) and TM atoms and, hence, that the presence of the TM atoms is responsible for the formation of an amorphous phase.     

Indium content determination related with structural and optical properties of InGaN layers

We studied the structural and optical properties of a set of nominally undoped epitaxial single layers of In_xGa_1−xN (0<x0.2) grown by MOCVD on top of GaN/Al₂O₃ substrates. A comparison of composition values obtained for thin (tens of nanometers) and thick (≈0.5 μm) layers by different analytical methods was performed. It is shown that the indium mole fraction determined by X-ray diffraction, measuring only one lattice parameter strongly depend on the assumptions made about strain, usually full relaxation or pseudomorphic growth. The results attained under such approximations are compared with the value of indium content derived from Rutherford backscattering spectrometry (RBS). It is shown that significant inaccuracies may arise when strain in In_xGa_1−xN/GaN heterostructures is not properly taken into account. Interpretation of these findings, together with the different criteria used to define the optical bandgap of In_xGa_1−xN layers, may explain the wide dispersion of bowing parameters found in the literature. Our results indicate a linear, E_g(x)=3.42−3.86x eV (x0.2), “anomalous” dependence of the optical bandgap at room temperature with In content for In_xGa_1−xN single layers.     

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.     

Heavily carbon-doped p-type InGaAs by MOMBE

Carbon-doped In_xGa_1−xAs layers (x=0−0.96) were grown by metalorganic molecular beam epitaxy (MOMBE) using trimethylgallium (TMG), solid arsenic (As₄) and solid indium (In) as sources of Ga, As and In, respectively. The carrier concentration is strongly affected by growth temperature and indium beam flux. Heavy p-type doping is obtained for smaller In compositions. The hole concentration decreases with the indium composition from 0 to 0.8, and then the conductivity type changes from p to n at x=0.8. Hole concentrations of 1.0×10¹⁹ and 1.2×10¹⁸ cm^-3 are obtained for x=0.3 and 0.54, respectively. These values are significantly higher than those reported on carbon-doped In_xGa_1−xAs by MBE. Preliminary results on carbon-doped GaAs/In_xGa_1−xAs strained layer superlattices are also discussed.     

Growth of pyroxene-type MnGeO3 and (Mn,Mg)GeO3 crystals by the floating-zone method

Pyroxene-type solid–solution crystals of (Mn_1−xMg_x)GeO₃ with x=0.06, 0.10 and 0.20 have been grown by the floating-zone method. The end member crystal of MnGeO₃ is broken into small pieces by the orthorhombic-to-monoclonic phase transition during cooling after growth. On the other hand, the solid–solution crystals keep the orthorhombic structure between the melting points and room temperature and no crack is formed. The unit cell volumes are significantly decreased with an increase in Mg content.     

Heavily carbon-doped p-type (In)GaAs grown by gas-source molecular beam epitaxy using diiodomethane

Heavily carbon-doped p-type In_xGa_1−xAs (0≤x<0.49) was successfully grown by gas-source molecular beam epitaxy using diiodomethane (CH₂I₂), triethylindium (TEIn), triethylgallium (TEGa) and AsH₃. Hole concentrations as high as 2.1×10²⁰ cm⁻³ were achieved in GaAs at an electrical activation efficiency of 100%. For In_xGa_1−xAs, both the hole and the atomic carbon concentrations gradually decreased as the InAs mole fraction, x, increased from 0.41 to 0.49. Hole concentrations of 5.1×10¹⁸ and 1.5×10¹⁹ cm⁻³ for x = 0.49 and x = 0.41, respectively, were obtained by a preliminary experiment. After post-growth annealing (500°C, 5 min under As₄ pressure), the hole concentration increased to 6.2×10¹⁸ cm⁻³ for x = 0.49, probably due to the activation of hydrogen-passivated carbon accepters.     

Design and optimisation of AlxGa1−xAs/AlyGa1−yAs multilayer structures for visible wavelength applications

Quantum wells with excitonic features in the visible wavelength range were designed using the Al_xGa_1−xAs/Al_yGa_1−yAs material system, and grown using low pressure metal organic vapour phase epitaxy. Characterisation of these quantum well samples was carried out by using photovoltaic spectroscopy, photoluminescence, differential reflectance or photoreflectance techniques. These measurements showed that excitonic absorption in the 520–630 nm range could be achieved using these AlGaAs quantum wells.