Growth Mechanism in Atomic Layer Epitaxy (II). A Model of the Growth Process of CdTe on CdTe (111) Substrates

A realistic model of CdTe growth by atomic layer epitaxy (ALE) has been proposed. This model is based on experimental studies concerning the isothermal re-evaporation rates of elemental Cd and Te deposits on the (lll)A and (lll)B surfaces of CdTe substrates, on a study of surface morphology and crystal structure of CdTe single crystal overlayers grown by ALE on CdTe(lll)B substrates under various crystallization conditions as well as on the existing theories related to the interaction of thermally activated atoms or molecules with hot solid surfaces. This model includes: (i) an existence of transition layers of both Cd and Te₂ species, intermediate between a chemisorbed and a bulk-like film, which create reaction zones 3–4 monolayers thick near the substrate surface, and (ii) partial re-evaporation of the first, chemisorbed monolayer of the deposited constituent elements.     

Growth mechanism in atomic layer epitaxy (III) reevaporation of Cd and Te from CdTe (111) surfaces and thick elemental deposits monitored by quadrupole-mass spectrometry

Quadrupole-mass spectroscopical (QMS) studies on isothermal reevaporation of Cd and Te species from the CdTe (111) surface have been performed in two extreme cases. The first concerns the reevaporation of thick, bulk-like non-crystalline Cd and Te films deposited in high vacuum at room temperature on the (111) surface, whereas in the second case evaporation of the constituent species from the bare single crystalline (111) surface has been investigated. The fluxes of the species desorbing in high vacuum (10⁻⁶ Pa) have been monitored with QMS and the desorption temperatures have been measured with a thermocouple mounted as near as possible to the sample surface. The following values E_a(Cd)_bulk = 1.13 ± 0.12 eV, E_a(Te)_bulk = 1.64 ± 0.18 eV and E_a(Cd)₍₁₁₁₎ = 1.13 ± 0.06 eV, E_a(Te)₍₁₁₁₎ = 1.92 ± 0.13 eV of the activation energies for these two cases have been determined from the slopes of the Arrhenius plots. Using these experimental values, the numbers of atomic bonds N_Cd and N_Te occurring in the atomic aggregates of quasi-gas molecules forming the near surface quasi-gas transition layers have been estimated. For Cd quasi-gas molecules 2 ≤ N_Cd ≤ 5, whereas for Te molecules 3 ≤ N_Te ≤ 10. However, no prediction concerning the number of atoms creating the quasi-gas molecules could be made on the basis of the QMS investigations. It has also been shown that Cd atoms evaporate from the bare single crystalline CdTe (111) surface with an activation energy that is equal (in the limits of the experimental error) to the activation energy for sublimation of Cd atoms from pure, non-crystalline, bulk Cd pieces. The analogous activation energy measured for Te atoms is about 20% larger than that of the relevant sublimation process. This result confirms the fact that Te atoms are bound much stronger in the CdTe crystal lattice than Cd atoms.     

Ultrahigh Vacuum Atomic Layer Epitaxy of Ternary II-VI Semiconductor Compounds

A concise discussion concerning the UHV ALE growth of ternary II-VI compounds is presented in this paper. Simultaneous reflection mass spectrometry (REMS) and reflection high energy electron diffraction (RHEED) measurements of the surface kinetic and structural parameters, respectively, governing the UHV ALE growth of Cd_1-xZn_xTe and Cd_1-xMn_xTe heteroepitaxial films are reported. In addition, a Monte-Carlo-based method for simulation of the UHV ALE process of CdTe (the model-compound for this growth technique) has been used for investigation of the Cd cation's fluxes reflected from the growing epilayer surface in different phases of the ALE process. The Cd⁺ ion-related REMS signals measured during CdTe growth have been compared with the simulation results.     

Comprehensive characterization of CdTe and (Cd,Zn)Te single crystals by a chemical etchant

Using a known chemical etchant low- and high angle boundaries and lamellar twins can be seen on CdTe and (Cd, Zn)Te crystal ingots as a whole as well as on slices with naked eyes. Also the polarity of {111} samples can be determined in this way. Etch pits are produced on cut and polished surfaces independent of their crystallographic orientation. A new modified etchant was used to study the low angle subgrain structure on (111)Te surfaces.     

Se-doped AlGaAs grown on GaAs(111)A by molecular beam epitaxy

The electrical properties of Se-doped Al_0.3Ga_0.7As layers grown by molecular beam epitaxy (MBE) on GaAs(111)A substrates have been investigated by Hall-effect and deep level transient spectroscopy (DLTS) measurements. In Se-doped GaAs layers, the carrier concentration depends on the misorientation angle of the substrates; it decreases drastically on the exact (111)A surface due to the re-evaporation of Se atoms. By contrast, in Se-doped AlGaAs layers, the decrease is not observed even on exact oriented (111)A. This is caused by the suppression of the re-evaporation of Se atoms, by Se---Al bonds formed during the Se-doped AlGaAs growth. An AlGaAs/GaAs high electron mobility transistor (HEMT) structure has been grown. The Hall mobility of the sample on a (111)A 5° off substrate is 5.9×10⁴ cm²/V·s at 77 K. This result shows that using Se as the n-type dopant is effective in fabricating devices on GaAs(111)A.     

CdTe(110)表面原子与电子结构的第一性原理研究

采用基于密度泛函理论的第一性原理计算了CdTe(110)表面的原子和电子性质.结果表明,CdTe(110)理想表面在禁带中出现两个明显的表面态,弛豫后表层Cd原子和Te原子p态电子发生转移,Cd原子趋向于sp2平面杂化构型,Te原子趋向p3杂化的锥形构型.经过表面弛豫大大降低了表面能,增大了表面功函数,表面占据态和表面空态分别被推进价带顶之下和导带底之上,导致弛豫表面没有明显的表面态.     

Phase-field simulations of Te-precipitate morphology and evolution kinetics in Te-rich CdTe crystals

Te precipitates are one of principal defects that form during cooling of melt-grown CdTe or CZT crystals when grown Te-rich. Many factors such as the kinetic properties of intrinsic point defects (vacancy, interstitial, and antisite defects); stresses associated with the lattice mismatch between precipitate and matrix; temperature gradients and extended defects (dislocations, twin and grain boundaries); non-stoichiometric composition; thermal treatment history all affect the formation and growth/dissolution of Te precipitates in CdTe. A good understanding of these effects on Te precipitate evolution kinetics is technically important in order to optimize material processing and obtain high-quality crystals. This research develops a phase-field model capable of investigating the evolution of coherent Te precipitates in a Te-rich CdTe crystal undergoing cooling from the melt. Cd vacancies and Te interstitials are assumed to be the dominant diffusing species in the system, which is in two-phase equilibrium (matrix CdTe and liquid Te inclusion) at high temperatures and three-phase equilibrium (matrix CdTe, Te precipitate, and void) at low temperatures. Using available thermodynamic and kinetic data from experimental phase diagrams and thermodynamic calculations, the effects of Te interstitial and Cd vacancy mobility, cooling rates and stresses on Te precipitate, and void evolution kinetics are investigated.     

Properties of Hg1‐xCdxTe epitaxial films grown on (211)CdTe and (211)CdZnTe

Hg_1‐xCd_xTe (MCT) epitaxial films have been grown employing single crystalline substrates of CdTe and Cd_0.96Zn_0.04Te with (211)Cd and (211)Te crystalline orientations. The Isothermal Vapor Phase Epitaxy (ISOVPE) technique without Hg overpressure has been used for the epitaxial growth. Substrates and films were characterized by optical microscopy, chemical etching and x ray diffraction (Laue technique). The electrical properties were determined by Hall effect measurements. The characterization results allowed to evaluate the crystalline quality of MCT films. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and spectrum stability of high quality CdTe quantum dots capped with stearate groups in N-oleoylmorpholine solvent

The stearate-capped CdTe quantum dots (QDs) have been first prepared via direct reaction of cadmium stearate with Te powder in N-oleoylmorpholine solvent, which was a kind of clean, air-stable and conveniently synthesized acylamide, and can readily dissolve precursors cadmium stearate and Te powder at a relative low temperature. The as-prepared CdTe QDs exhibited size-dependent optical properties, steep absorbance edge and narrow photoluminescence full width at half maximum. The high-resolution transmission electron microscopy images and X-ray diffraction revealed that the highly monodisperse CdTe QDs were of regular spherical morphology with zinc blende crystal structure displaying mean sizes of about 4 nm. The energy dispersed spectrometry measurement indicated the presence of Cd and Te, with the Cd:Te ratio being close to 1:1. Fourier transform infrared transmission spectra confirmed the existence of stearate on the CdTe QDs surfaces. The experimental results also demonstrated that the stearate-capped CdTe QDs had an unexpected good stability.     

Vapor growth of CdTe laser window materials

Vapor deposition of CdTe from elemental cadmium and tellurium sources was studied as a function of the Cd/Te ratio, the supersaturation and the substrate temperature, in order to achieve optimum growth conditions for CdTe windows with low optical absorptivity in the infrared. A multisubstrate arrangement was designed to enable acquisition of growth data simultaneously on up to six specimens, each exposed to different growth conditions. Polycrystalline blanks up to 15 cm² × 2 mm thick were grown at rates of 0.02-1.5 mm/h with the growth rate exhibiting sensitivity to all of the above variables. Our results show that stoichiometry (as well as free carrier concentrations) can be controlled by adjustments in the Cd/Te ratio and/or the substrate temperature. Similarly, microstructural aspects (e.g., grain and void size) are shown to exhibit strong sensitivity to variations in growth conditions.     

A study of the Growth-Temperature-dependent Surface Morphology in InSb Liquid Phase Epitaxy

InSb LPE layers were grown on (111) InSb substrates, their phase diagram and growth rates studied. The InSb activity coefficient α(T), determined by fitting the experimental data, had a value of 2556–11.11 · T cal · mole⁻¹. The terraces on the surface were reduced by increasing the temperature to 350 °C. Hall measurements of InSb/CdTe heterostructure failed due to the high Te segregation. The carrier concentration of these InSb epilayers, however, was determined by C-V measurements with values between 7.5 · 10¹⁴ cm⁻³ and 5 · 10¹⁵ cm⁻³.     

Specific features of the growth of A II B VI films on (0001)Al2O3 substrates

The structure and orientation of CdTe and ZnO films on sapphire have been investigated for different techniques of pregrowth substrate treatment. Polycrystalline CdTe films are found to grow of substrates unannealed or annealed in vacuum at a residual pressure P < 0.13 Pa. Epitaxial CdTe films with the sphalerite cubic structure, oriented parallel to the substrate by the (111) plane, grow on substrates annealed in air at a temperature of 1000°C or more and having a system of smooth terraces and steps on the surface. For ZnO films with a wurtzite hexagonal structure obtained by magnetron sputtering, a similar correlation between the structural quality and the regime of treatment of sapphire substrates is observed. It is shown that thermal annealing of (0001) sapphire plates in air is the optimal way of substrate preparation for growing epitaxial ZnO films with the base orientation. The obtained epitaxial CdTe films contain a certain amount of structural defects (mosaicity and twins), while the epitaixal ZnO films treated in the same way are close to perfect.     

In situ monitoring of CdTe nucleation on GaAs (100) using spectroscopic ellipsometry

In situ spectroscopic ellipsometry was used to monitor the nucleation behavior of CdTe grown on vicinal GaAs (100) substrates by organometallic vapor phase epitaxy. CdTe was grown on GaAs (100) substrates of exact and 2° off towards 110 orientations. A spectroscopic ellipsometer was used to collect in situ data at 44 wavelengths from 4000–7000 Å. The Bruggeman's effective medium approximation was employed to determine the variation of the epilayer volume fraction with thickness, which was an indirect way of monitoring the expected island growth behavior. The Stranski-Krastonov (layer plus island) mode of growth was clearly observed for CdTe growth. The growth on the 2° off substrate was also “denser” than that on exact (100), which implied that coalescence of the islands occurred at lower thickness. This was expected since island nucleation is most favored along the ledges on the surface whose spacing decreases with increasing misorientation. A simple nucleation model, assuming cylinder-like islands, was able to fit the experimental data quite well, lending support to the island growth model.     

AES Investigation of Chemical Treatment Effect on CdTe and CdZnTe Surfaces

{211} polar surfaces of a Cd_0.96Zn_0.04Te chemically treated single crystal were investigated by Auger electron spectroscopy depth profiling. It was found that the use of a discriminatory “black-white” etchant causes the formation of a thick layer with cadmium having been severely depleted at both (211) A and (211) B faces. The thickness of this layer is larger by a factor of 2 for the matt black face then for the bright and reflecting face. AES investigation of chemical treatment influence on (100) CdTe epitaxial layer surface has been performed. It has been established that etching in Br/methanol solution removes S, Cl and O containing contaminants from the surface, but simultaneously forms a Cd-depleted layer.     

Effects of surface reconstruction on CdTe/GaAs(001) interface structure

CdTe/GaAs(001) heterostructures were fabricated by molecular beam epitaxy on chemically etched and thermally deoxidized GaAs(001) substrates, as well as GaAs(001) (3×1) buffer layers grown in situ by molecular beam epitaxy. Different growth protocols were also explored, leading to Te-induced (6×1) or (2×1) surface reconstructions during the early growth stage. High-resolution cross-sectional transmission electron microscopy was used to examine the final interface structure resulting from the different substrate preparations, and surface reconstructions. The (2×1) surface reconstruction led to pure (001) growth, while the (6×1) reconstruction led to an interface which included small (111)-oriented inclusions. In addition, deposition on etched and deoxidized GaAs(001) wafers led to preferential CdTe growth within etch pits and resulted in a macroscopically rough interface region.     

TEM analysis of the container effect of Au‐based catalyst droplets during vapour‐liquid‐solid growth of axial ZnTe/CdTe nanowires

Axial heterostructure nanowires (NWs) of ZnTe/CdTe were grown by vapour‐liquid‐solid growth realized in a molecular beam epitaxial chamber. By alternative supply of Zn or Cd and constant Te the heterostructure was generated. The liquid phase is provided by a Au‐based eutectic droplet which stays at the tip of the NW during the entire growth. For structural and chemical characterization by TEM the NWs were harvested from the substrate and transferred to a holey carbon film. The NWs exhibit an expansion of the diameter correlated with the interface region between ZnTe and CdTe. Idiomorphic growth of the CdTe is evident from electron diffraction experiments. The growth rate of CdTe appears to be smaller compared to that of ZnTe at the same temperature. Both, quantitative high‐resolution TEM and energy dispersive X‐ray spectroscopy line scans reveal a smeared ZnTe/CdTe interface along about 200 nm. The smearing is due to both, the liquid catalyst which buffers the supply of Cd instead of Zn at the liquid/solid interface and to the strain which is induced by the lattice mismatch. It forces the system to consume the remnant Zn for the NW growth in favour of Cd. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High-resolution photoluminescence studies of (211) CdTe grown on (211)B GaAs substrate

Sharp and rich photoluminescence lines accociated with free exciton (FE), excitons bound to neutral acceptors (A⁰X) and donors (D⁰X) in molecular beam epitaxially (MBE) grown (211) CdTe/(211)B GaAs have been reported for the first time. The results show that the (211) CdTe/(211)B GaAs grown under optimized conditions could have as high a crystal perfection as those grown on lattice-matched substrates.     

Melt growth and post‐grown annealing of semiinsulating (CdZn)Te by vertical gradient freeze method

We present results of development of CdZnTe semi‐insulating crystals prepared by Vertical Gradient Freeze method in a 4‐zone furnace. We applied the way of growth of the crystal from the top when the first crystallization seed is created on the surface of the melt. The typical height of the crystals is 5 cm. Resistivity and photoconductivity profiles measured along the growth axis by contactless method are compared and their mutual correlation is explained based on a model of relative shift of the Fermi level and the midgap level present in the material. The influence of the Fermi level on electron trapping and recombination is summarized. We present here results of a two‐step annealing method aimed at reduction of Te inclusions while keeping the resistivity high. We employed CdTe:Cl VGF grown samples to eliminate Te inclusions observed in as grown crystals by two‐step post grown annealing in Cd and Te atmosphere and present a model of the processes leading to high resistivity material after annealing.     

Influence of substrate temperature on nitridation of (0 0 1) GaAs using RF-radical source

The mechanism of nitridation of (0 0 1) GaAs surface using RF-radical source was systematically studied with changing substrate temperature, nitridation time and supplying As molecular beam. It was found from atomic forth microscopy (AFM) measurements that supplying As is very important to suppress the re-evaporation of As atoms and to keep the surface smooth. Reflection high-energy electron diffraction (RHEED) measurements shows that surface lattice constant (SLC) of GaAs of 0.565 nm decreases with increasing the substrate temperature and that it finally relaxes to the value of c-GaN of 0.452 nm, at 570 °C in both [1 1 0] and [1¯ 1 0] directions without concerning with the supply of As molecular beam. But, in the medium temperature range (between 350 and 520 °C), SLC of [1 1 0] direction was smaller than that of [1¯ 1 0] direction. This suggests a relation between the surface structure and the relaxing mechanism of the lattice. The valence band discontinuity between the nitridated layer and the GaAs layer was estimated by using X-ray photoemission spectroscopy (XPS). It was between 1.7 and 2.0 eV, which coincides well with the reported value of c-GaN of 1.84 eV. This suggests that the fabricated GaN layer was in cubic structure.     

Vapour-phase epitaxial growth of ZnS on GaP

Single crystal layers of ZnS about 100 μm thick were grown epitaxially on GaP substrates in an open tube system using source ZnS powder and a flowing hydrogen atmosphere. The growth rate for different substrate temperatures increases with increasing hydrogen flow rate, but the growth rate profiles resemble each other in shape. The profile shifts towards the low temperature side as the source temperature is decreased. The (111)B substrate orientation is found to be preferable to the (111)A or the (100) with respect to surface morphology and crystal quality. X-ray diffraction investigations and luminescent properties show that the (111)B grown layers are of high quality. All ZnS layers grown on GaP substrates are craked on cooling, which may be due to the thermal expansion mismatch between the layer and the substrate. Heat-treatment of the grown layer does not reduce the resistivity, but increases the photoluminescence intensity markedly. Selective vapour-phase epitaxial growth has been successfully applied resulting in crack-free ZnS layers on GaP substrates.