The direct determination of the vacancy concentration andP-T phase diagram of Hg0.8Cd0.2Te and Hg0.6Cd0.4Te by dynamic mass-loss measurements

A modified mass-loss measurement technique is employed, for the direct,in- situ determination of the metal vacancy formation in (Hg_1x2212;itxCd _x )_1−y Te _y (s) withx = 0.2 and 0.4. Forx = 0.2, the metal vacancy concentrations are determined between 336 and 660° C for three different compositions(y) within the homogeneity region and range from 2.4 to6.8 x 10¹⁹cm₋₃. The enthalpy of formation of a singly-ionized metal vacancy is derived to be between 0.17 and 0.45 eV depending upon the deviation from stoichiometry (compositiony). Forx= 0.4, three samples of different y-values give the metal vacancy concentrations from 1.9 to 5.5 x 10¹⁹cm⁻³ between 316 and 649° C, and the enthalpy of vacancy formation between 0.25 and 0.40 eV. Compared to the recent data on HgTe(s), these experimental results show a slight but significant decrease in the enthalpy of vacancy formation from HgTe to Hg_0.8Cd_0.2Te, which supports theoretical predictions of the bond weakening effect of Cd for the latter alloy system. Based on the simultaneously determined equilibrium Hg partial pressures within the homogeneity range, the vacancy concentration-partial pressure isotherms are constructed. The Hg partial pressures are also measured along the three-phase boundaries of the solid solutions of bothx = 0.2 and 0.4, and these are in close agreement with published data obtained by optical absorption measurements.     

The direct determination of the vacancy concentration and P-T phase diagram of Hgin0.8Zn0.2Te by dynamic mass-loss measurements

A modified mass-loss measurement technique is employed, for the first time, for the direct, in-situ determination of the metal vacancy formation in (Hg_0.8Zn_0.2)_1-yTe_y,(s). The metal vacancy concentrations are determined between 350 and 650° C for four different compositions(y) within the homogeneity region and range from 1.7 to 6.6 × 10¹⁹ cm^-3. The enthalpy of formation of a singly-ionized metal vacancy is derived to be between 0.32 and 0.72 eV depending upon the deviation from stoichiometry (compositiony). Com-pared to the recent data on HgTe(s), these experimental results show a slight but sig-nificant increase in the enthalpy of vacancy formation from HgTe to Hg_0.8Zn_0.2Te. These data provide the first, direct experimental evidence, in terms of vacancy formation en-ergy, supporting theoretical predictions of the bond strengthening effect of Zn for the latter alloy system. Based on the simultaneously determined equilibrium Hg partial pressures within the homogeneity range, the vacancy concentration-partial pressure iso-therms are constructed. The Hg partial pressures are also measured along the three-phase boundaries of the solid solutions, and these are in close agreement with published data obtained by optical absorption measurements. A considerable part of the P-T phase diagram is, thus, established in this work.     

Growth and properties of Hg1-x Cdx Te epitaxial layers

The growth of epitaxial layers of mercury-cadmium-telluride (Hg_1-xCd_xTe) with relatively low x (0.2-0.3) from Te-rich solutions in an open tube sliding system is studied. The development of a semiclosed slider system with unique features permits the growth of low x material at atmospheric pressure. The quality of the films is improved by the use of Cd_1-yZ_yTe and Hg_1-xCd_xTe substrates instead of CdTe. The substrate effects and the growth procedure are discussed and a solidus line at a relatively low temperature is reported. The asgrown epitaxial layers are p-type with hole concentration of the order of 1·10¹⁷ cm⁻³, hole mobility of about 300 cm²·V⁻¹ sec⁻¹ and excess minority carrier life-time of 3 nsec, at 77 K.     

Transport properties of undoped Cd0.9Zn0.1Te grown by high pressure bridgman technique

The electron drift mobility of undoped Cd_0.9Zn_0.1Te grown by high-pressure Bridgman method is measured by a time-of-flight technique. The sample shows a room temperature mobility and mobility lifetime product of 950 cm²/Vs and 1.6 × 10⁻⁴cm²/V, respectively. The mobility increases monotonically with decreasing temperature to 3000 cm²/Vs at 100 K. The dominant scattering mechanism for the electron transport is discussed by comparing with the theoretical mobility obtained by iterative solution of the Boltzmann equation.     

Effects of growth conditions on the composition of CVT and PVT grown Hg1-x Cd x Te epitaxial layers

Single crystal epitaxial layers of Hg_1-x Cd _x Te were grown on CdTe substrates employing the chemical and physical vapor transport techniques. Different growth temperatures and various pressures of HgI₂ as a transport agent were used while the source materials had compositions of eitherx = 0.4 orx = 0.6. The epilayers are of nearly uniform composition to a depth of about one-half of the layer thickness. The Hgl₂ pressure and the growth temperature used for the growth experiments have significant effects on the layer composition. The desired epilayer composition ofx = 0.2 can be achieved with either source compositions by properly adjusting the HgI₂ pressure and the growth temperature.     

Transient behavior of Hg1−xCdxTe film growth on 3° off-(100) CdTe substrates by chemical vapor transport

The effects of substrate misorientation on Hg_1−xCd_xTe films, deposited on 3° off-(100) CdTe substrates by chemical vapor transport (CVT), have been studied for the first time using a transient growth technique. The morphological evolution of Hg_1−xCd_xTe films deposited on the vicinal CdTe substrates at 545°C shows a transition from three-dimensional islands to two-dimensional layer growth. The time and thickness required for the above morphological transition is about 0.75 h and 7 μm, respectively, under present experimental conditions. The pronounced long-range-terrace surface morphology of the Hg_1−xCd_xTe films illustrates the strong effects of the misorientation of the CdTe substrates and of the growth kinetics on the CVT growth of this hetero-epitaxial system. The transient behavior of the surface morphology, of the surface composition, and of the growth rate all reveal the influences of the 3° misorientation of the (100) CdTe substrates on the Hg_1−xCd_xTe epitaxy. The experimental mass flux results of the Hg_1−xCd_xTe-HgI₂ CVT system under transient and steady-state conditions can be related to the surface kinetics and to the thermodynamic properties of the system. The combined results show that the interface kinetics are not fixed in the transient regime and that they are coupled to the vapor mass transport.     

Slider LPE of Hg1-xCdxTe using mercury pressure controlled growth solutions

Homogeneous, nearly perfect single crystals of Hg_1-xCd_xTe are extremely difficult to prepare due primarily to the high vapor pressure of mercury. However, epitaxially grown Hg_1-xCd_xTe layers have a high potential for yielding material of a substantially higher quality. Using a new, open-tube, horizontal slider-type liquid phase epitaxial (LPE) growth technique, in which mercury pressure controlled growth solutions are used, a high degree of growth solution compositional control has been demonstrated. LPE layers of Hg_1-xCd_xTe have been grown on CdTe substrates and their high quality has been confirmed by optical, transport and electron microprobe measurements. Layer thicknesses are uniform and have been varied from 5 to 40 μ by changing the degree of supercooling or the growth time. An electron carrier concentration as low as 8.6 × 10¹⁵/cm³ and electron Hall mobilities up to 2.8 × 105 cm²/V-sec at 77K have been measured on in situ annealed samples. This work was sponsored by the Department of the Air Force and the U.S. Army Research Office.     

Compositional dependence of infrared phonon parameters for Hg1-xCdxTe

The full set of Lorentzian oscillator parameters describing the two-mode phonon behavior in Hg_1-x-jCd_xTe is reported. A new analysis of reflectivity spectra combined with existing results gives the most accurate available values for the CdTe-like and HgTe-like transverse optical frequency, strength and (for the first time) damping constant vs CdTe fractionx at room, liquid nitrogen and liquid helium temperatures. Polynomial fits vsx for each parameter are provided for use in characterizing Hg_1-xCd_xTe and the HgTe-CdTe superlattice.     

Structure investigation on Hg1−xCdxTe liquid phase epitaxial films grown by the meltetch technique

Hg_1−xCd_xTe films were grown by a modified meltetch liquid phase epitaxial (LPE) technique which includes both substrate and epilayer etchback steps. The crystal quality of epilayer has been investigated by means of transmission electron microscopy, scanning electron microscopy, and double crystal x-ray diffraction. It has been found that adequate meltetch of the substrate at the beginning of LPE provides a fresh and flat surface for epitaxial growth, while epilayer meltetch at the end of LPE may prevent spurious melt sticking.     

Oxidation of Hg1−xCdxTe studied with surface sensitive techniques

We report the use of surface sensitive electron spectroscopies to monitor the initial steps of formation of a native oxide on atomically clean cleaved Hg_l-xCd_xTe single crystal surfaces in ultrahigh vacuum (UHV). Here the oxide is formed by oxygen excited by the presence of an operating ion gauge. During the reaction, the composition of the surface region of the substrate was found to change, with a net loss of Hg from the surface. Parallel studies of the compositions of thick anodic oxides using sputter profiling techniques showed only small amounts of Hg in the anodic oxides. On leave from Odense University, Denmark.     

Passivation of Hg1−xCdxTe by photochemical native oxidation: Growth characteristics

The growth of photochemical native oxides on x = 0.3 bulk wafers of n-type Hg_1−xCd_xTe has been studied with relation to growth temperature, gas flow rate, oxidizing ambient, and the wavelengths of ultraviolet radiation needed to drive the process. The growth was found to proceed with a relationship of thickness ∝ (time)^1/3 for both O₂ and N₂O ambients. An observed inverse relationship between thickness, and both growth temperature and gas flow rate, indicates a growth process that is either competing with parasitic quenching of the excited oxidizing species produced, or a diffusion controlled process, in which different growth conditions produce oxides with a variety of diffusion characteristics. The physical and optical properties of the photochemical oxides were found to be similar to anodic oxides. Rutherford backscattering spectra have shown the composition of the films to be highly dependent on growth conditions with films grown in O₂ ambients generally showing a higher mercury content than those grown in N₂O. Further, for growths in O₂ atmospheres, those carried out at lower temperatures result in more mercury in the oxide and at the oxide/mercury cadmium telluride interface when compared to those grown at higher temperatures.     

Passivation of Hg1-xCdxTe by photochemical native oxidation: Quantitative analysis of oxide composition

The composition of photochemically grown native oxides on Hg_1-xCd_xTe (x = 0.3) has been analyzed and depth profiled using x-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy. The oxide films were grown in either N₂O or O₂ ambients, and differences in the oxidation process were examined by varying the time and temperature of oxide growth. Under all growth conditions, oxides grown in an O₂ ambient exhibited a higher Hg concentration in the bulk oxide region when compared to N₂O grown oxides. The Hg/Te ratio of all the oxides was found to be less than the starting Hg_1-xCd_xTe substrates and, in some cases, this may be leading to an accumulation of Hg in the oxide/Hg_1-xCd_xTe interface region. For growths at higher temperatures (∼75°C), the excess Hg was seen to move from the oxide/Hg_1-xCd_xTe interface region to the oxide surface. In O₂ ambients, the Hg accumulated at the surface of the oxide whereas for growths in N₂O, it was lost to the ambient. Previous results on photochemical oxidation of Hg_1-xCd_xTe show an inverse relationship between oxide growth rate and temperature. Evidence obtained in this study from oxide compositions, depth profiles and annealing at higher temperatures, suggest that this relationship between oxide growth rate and temperature is primarily due to temperature induced differences in the oxidizing ambient, and not the result of a change in the film growth mechanism due to changing diffusion characteristics with temperature.     

Characterization of CdTe/Hg1−xCdxTe heterostructures by high-resolution x-ray diffraction

CdTe/Hg_1−xCd_xTe heterostructures variously heat-treated and implanted with boron were studied by means of high-resolution x-ray diffraction. A novel procedure for simulating diffraction spectra was developed, which is based on direct summation of scattered waves across a heterostructure. In that routine, short-range variations of structural parameters, including concentration of the components, can be taken into account. The new approach allows precise characterization of II–VI heterostructures, because it correctly treats atomic diffusion effects in diffraction spectra. As a result, subtle spectral modifications induced by boron implantation could be detected and were attributed to the dynamics of post implantation point defects.     

The temperature-composition phase diagram and the miscibility gap of Hg1-xCdxTe solid solutions by dynamic mass-loss measurements

The dynamic mass-loss technique has been employed to measure Hg partial pressures over Te-saturated Hg_1-xCd_xTe solid solutions with x = 0.40, 0.54, and 0.70 in the 10^-1 to 10^-4 atm range. The relative chemical potentials of HgTe in Hg_1-xCd_xTe solid solutions have been calculated using the measured Hg partial pressures at temperatures below 413°C, and fitted into an analytical expression. A Gibbs-Duhem integration yielded the relative chemical potentials of CdTe. By combining the relative chemical potentials of the binary components HgTe and CdTe, an expression for the Gibbs free energy of mixing was derived. The binodal (miscibility gap) and spinodal curves of the Hg_1-xCd_xTe solid solutions have been established with the critical temperature and composition of 221°C and Hg_0.40Cd_0.60Te.     

Growth study of large non-seeded Pb1−x Snx Te single crystals

Large single crystals of Pb_1−xSn_xTe (x∼0.20) were grown by sublimation on the quartz surface of a closed ampoule. Initial undercritical supercooling provided nearly equilibrium conditions for in situ nucleation of a monocrystalline seed from which a high quality single crystal could be grown at a high growth rate. The presence of free elements in untreated charges had a strong influence on the concentration of imperfections, i.e. inclusions, holes, dislocations and low angle grain boundaries. Excess Te (δ∼ 0.01 mole %) in the annealed charge was necessary for the nucleation of a solid monocrystallite through a vapor-solid mechanism, leading, under appropriate thermal conditions, to the growt of a high quality single crystal. The apparent growth rate of the as-grown crystals appeared to be linearly dependent on the undercooling δT in the entire range (0≤δT≤25‡C) studied and it was found to be greatly influenced by deviation of the charge from stoichiometry. No apparent effect of the growth orientation on the overall growth rate was found. The crystal habit and possible driving forces of the crystal growth are qualitatively discussed.     

Electrical activity,mode of incorporation and distribution coefficient of group V elements in Hg1−xCdxTe grown from tellurium rich liquid phase epitxial growth solutions

Hg_1−xCd_xTe films were grown liquid phase epitaxially from tellurium rich solutions containing up to 10 at. % of the group V elements P, As, Sb, and Bi. Chemical analysis of the Te growth solutions and the films was carried out in conjunction with extensive Hall effect measurements on the films subsequent to various annealing treatments under Hg rich and Te rich conditions. Despite the presence of a large concentration of the group V elements in the Te source solution, the maximum concentration of these elements incorporated into the liquid phase epitaxially grown Hg_1-xCd_xTe appears to vary from <10¹⁵cm⁻³ for Bi up to 10¹⁷cm⁻³ for phosphorus and As implying a distribution coefficient varying from <10⁻⁵ for Bi up to 10⁻³ for P at growth temperature of ∼500° C. This low value of the distribution coefficient for group V elements for growths from Te rich solutions contrasts with the moderately high values reported in the literature to date for growth from Hg rich solutions as well as pseudobinary solutions (Bridgman growth). The widely differing distribution coefficients and hence the solubility of the group V elements for Hg rich and Te rich liquid phase epitaxial solutions is explained on the basis that the activity coefficient of the group V elements in Te rich solutions is probably orders of magnitude lower than it is in Hg rich solutions. Finally, the results of the anneals at 200° C under Hg saturated conditions with and without a 500° C Hg saturated preanneal have indicatedn top conversion in many of the films attesting to the amphoteric behavior of the group V elements in LPE grown Hg_1−xCd_xTe(s) similar to the previously reported behavior of P in bulk grown Hg_0.8Cd_0.2Te.     

Observation of phase separation in Hg1−xCdxTe solid solutions by low incident angle x-ray diffraction

The low incident angle (surface analysis) and the conventional wide angle (bulk analysis) x-ray diffraction techniques were employed to investigate the existence of a miscibility gap in the Hg_1−xCd_xTe system. Samples of initial composition Hg_0.46Cd_0.54Te were annealed at 140 and 400°C, respectively, for four weeks. The diffraction planes (531) and (642) have been selected for the x-ray diffraction analysis. The results of this work provide the first, direct experimental evidence for the existence of a miscibility gap at lower temperature in the Hg_1−xCd_xTe system. The phase separation occurs primarily in a thin surface layer at 140°C and is reversible after annealing at 530°C. The compositions of the two compounds at the tie-line at 140°C are Hg_0.22Cd_0.78Te and Hg_0.63Cd_0.37Te.     

Fast vapor growth of cadmium telluride single crystals

Cadmium telluride single crystals were grown at growth rates of 35 mm per day by the physical vapor transport (PVT) method under high temperature gradient conditions. This is believed to be the highest PVT growth rate of CdTe reported to date. Lamellar twins are the only ones present in the CdTe crystals grown under optimal conditions in this work. At growth rates up to 15 mm per day, the crystals have a dislocation density of ∼10⁴ cm⁻². The etch pit density increases to ∼10⁵ cm⁻² with an increase of the growth rate up to 35 mm per day. Based on a uniform thermal field and high interface stability, which are established by large temperature gradients up to 40°C/cm at the growth interface, spurious nucleation and lateral twins were effectively eliminated, and the density of the lamellar twins remained low at crystal growth rates up to 35 mm per day. The major contributions of the high temperature gradients to the single crystalline growth and the apparent origin of polycrystalline grains are also discussed in this paper.     

Temperature dependence of the optical properties of Hg1−xCdxTe

The alloy composition of Hg_1−xCd_xTe should be controlled during growth, so that the desired band gap and the lattice-matched layer may be obtained. In-situ spectroscopic ellipsometry, now commercially available, enables one to acquire spectral data during growth. If one knows the optical dielectric function as a function of alloy composition and temperature, the technique can be fully used to monitor and control temperature, the thickness, and the alloy composition. For this purpose, we first obtained temperature dependent spectral data of Hg_1−xCd_xTe by spectroscopic ellipsometry (SE). The spectral data of Hg_1−xCd_xTe with x = 1,0.235, and 0.344 were obtained from room temperature to 800Kin the photon energy range from 1.3 to 6 eV. The spectral data revealed distinctive critical point structures at E₀, E₀+Δ₀, E₁, E₁+Δ₁, E₂(X), and E₂(Σ). Critical point energies decreased and linewidths increased monotonically as temperature increased. The model for the optical dielectric function enabled (i) the critical point parameters to be determined accurately, and (ii) the spectral data to be expressed as a function of temperature within and outside the experimental range.