Improved CdTe layers on GaAs and Si using atomic layer epitaxy

In this paper, we report on the atomic layer epitaxy (ALE) of CdTe on GaAs and Si by the organometallic vapor phase epitaxial process at atmospheric pressure. Self-limiting growth at one monolayer was obtained over the temperature range from 250°C to 320°C, under a wide range of reactant pressure conditions. A study of growth mechanism indicates that DMCd decomposes into Cd on the surface and the Te precursors react catalytically on the Cd covered surface. We have used this ALE grown layer to improve the crystal quality and the morphology of conventionally grown CdTe on GaAs. Improvement in the crystal quality was also observed when ALE CdTe nucleation was carried out on Si pretreated with DETe at 420°C. Atomic layer epitaxy grown ZnTe was used to obtain (100) oriented CdTe on (100) silicon.     

Growth of high quality CdTe and ZnTe on Si substrates using organometallic vapor phase epitaxy

Epitaxial (100) CdTe and ZnTe layers with high crystalline quality have been grown on Si substrates by atmospheric pressure organometallic vapor phase epitaxy (OMVPE). A thin Ge interfacial layer grown at low temperature was used as a buffer layer prior to ZnTe and CdTe growth. The layers were characterized by Nomarski optical microscopy and double crystal x-ray diffraction. Double crystal rocking curves with full width at half maximum of about 110 and 250 arc-sec have been obtained for a 7 μm thick ZnTe layer and a 4 μm thick CdTe layer, respectively. The results presented demonstrate a novel method ofin-situ Si cleaning step without a high temperature deoxidation process to grow high quality CdTe and ZnTe on Si in a single OMVPE reactor.     

Reaction kinetics control in preparation of CdTe and HgCdTe by hot wall metalorganic vapor phase epitaxy

The growth rates of CdTe and HgCdTe by hot wall metalorganic vapor phase epitaxy were studied as functions of growth temperatures and partial pressures of precursors. It is suggested that the growth of CdTe and HgCdTe was controlled by reaction kinetics. The relationship between growth processes and epilayer properties was discussed and high quality epilayers were obtained.     

Direct growth of high-quality thick CdTe epilayers on Si (211) substrates by metalorganic vapor phase epitaxy for nuclear radiation detection and imaging

Direct growth of high-quality, thick CdTe (211) epilayers, with thickness up to 100 μm, on Si (211) substrates in a vertical metalorganic vapor phase epitaxy system is reported. In order to obtain homo-orientation growth on Si substrates, pretreatment of the substrates was carried out in a separate chamber by annealing them together with pieces of GaAs at 800–900°C in a hydrogen environment. Grown epilayers had very good substrate adhesion. The full-width at half-maximum (FWHM) value of the x-ray double-crystal rocking curve from the CdTe (422) reflection decreased rapidly with increasing layer thickness and remained between 140–200 arcsec for layers >18 μm. Photoluminescence measurement at 4.2 K showed high-intensity, bound excitonic emission and very small defect-related deep emissions, indicating the high crystalline quality of the grown layers. Furthermore, a CdTe/n⁺-Si heterojunction diode was fabricated that exhibited clear rectifying behavior.     

Nucleation of ZnTe/CdTe epitaxy on high-miller-index Si surfaces

Tellurium-adsorption studies were conducted on {111}-type Si surfaces that are off-cut from the {111} in the range of 0–30° on both nonpassivated-and arsenic-passivated Si surfaces. Relative surface coverages as a function of Te exposure time and Si-surface orientation were obtained with in-situ x-ray photoelectron spectroscopy (XPS). The XPS results indicate that Te coverage on arsenic-passivated Si surfaces increases as the step density of the surface increases. In contrast, Te-adsorption studies conducted on nonpassivated-Si surfaces showed no dependence between Te coverage and the surface-step density. Subsequent ZnTe and CdTe molecular-beam epitaxial growth on these high-Miller-index Si surfaces further validate a step-edge nucleation model. Additionally, it was observed that the CdTe-epilayer orientation did not always reproduce the Si-substrate orientation and was a function of both the initial Si surface and the growth conditions used.     

Metal-organic vapor-phase epitaxy growth and characterization of thick (100) CdTe layers on (100) GaAs and (100) GaAs/Si substrates

The growth characteristics and crystalline quality of thick (100) CdTe-epitaxial layers grown on (100) GaAs and (100) GaAs/Si substrates in a metal-organic vapor-phase epitaxy (MOVPE) system for possible applications in x-ray imaging detectors were investigated. High-crystalline-quality epitaxial layers of thickness greater than 100 μm could be readily obtained on both types of substrates. The full width at half maximum (FWHM) values of the x-ray double-crystal rocking curve (DCRC) decreased rapidly with increasing layer thickness, and remained around 50–70 arcsec for layers thicker than 30 μm on both types of substrates. Photoluminescence (PL) measurement showed high-intensity excitonic emission with very small defect-related peaks from both types of epilayers. Stress analysis carried out by performing PL as a function of layer thickness showed the layers were strained and a small amount of residual stress, compressive in CdTe/GaAs and tensile in CdTe/GaAs/Si, remained even in the thick layers. Furthermore, the resistivity of the layers on the GaAs substrate was found to be lower than that of layers on GaAs/Si possibly because of the difference of the activation of incorporated impurity from the substrates because of the different kinds of stress existing on them. A heterojunction diode was then fabricated by growing a CdTe epilayer on an n⁺-GaAs substrate, which exhibited a good rectification property with a low value of reverse-bias leakage current even at high applied biases.     

Low pressure MOVPE growth of ZnSe,ZnTe, and ZnSe/ZnTe strained-layer superlattices

ZnSe and ZnTe single-crystal layers have been grown onto (100) GaAs substrates by low-pressure metalorganic vapor-phase epitaxy (LP-MOVPE) using the triethylamine-dimethylzinc adduct [DMZn(NEt₃)] as the zinc precursor. The selenium and tellurium precursors were H₂Se (5% in H₂) and di-isopropyltellurium (DiPTe), respectively. These two semiconductors have been grown with different VI/II molar ratios, at different growth temperatures, and with an overall growth pressure ranging from 40 to 400 Torr. Optimal growth parameters have been determined by optical means for the two materials. This information was then used to grow ZnTe/ZnSe strained-layer superlattices. We have studied structures grown on both ZnSe and ZnTe relaxed buffer layers which display a drastic dependence of the Stokes shift between photoluminescence and the optical bandgap on the nature of the buffer layer. Growth interruptions have been used to optimize the optical properties of the superlattices. Theoretical modeling of superlattice band structures has been performed using results of optical and structural characterizations. Observations of zone center transitions as well as excitons associated with the miniband dispersion of the superlattices are reported, in agreement with the theoretical calculation.     

Growth of thick CdTe epilayers on GaAs substrates and evaluation of CdTe/n<Superscript>+</Superscript>-GaAs heterojunction diodes for an X-ray imaging detector

The growth characteristics of thick (100) CdTe epitaxial layers of a thickness up to 200 μm on a (100) GaAs substrate in a metal-organic vapor-phase epitaxy (MOVPE) system and fabrication of CdTe/n⁺-GaAs heterojunction diodes for their possible applications in low-energy x-ray imaging detectors are reported. The grown epilayers were of high structural quality as revealed from the x-ray double-crystal rocking curve (DCRC) analysis, where the full-width at half-maximum (FWHM) values of the (400) diffraction peaks was between 50 arcsec and 70 arcsec. The 4.2-K photoluminescence (PL) showed high-intensity bound-excitonic emission and very small defect-related peaks. The heterojunction diode fabricated had a good rectification property with a low value of reverse-bias current. The x-ray detection capability of the diode was examined by the time-of-flight (TOF) measurement, where good bias-dependent photoresponse was observed, but no carrier transport property could be deduced. It was found that the CdTe layer has a large number of trapping states as attributed to the cadmium-related vacancy and Ga-impurity, diffused from the substrate, related defect complexes.     

Application of spectroscopic ellipsometry for real-time control of CdTe and HgCdTe growth in an OMCVD system

A multi-wavelengthinsitu spectroscopic ellipsometer system is described. The hardware can acquire accurate ellipsometric data at 44 wavelengths in less than one second, is simple and compact, and is well suited forin-situ monitoring of chemical vapor deposition. The software used for data analysis is capable of determining the growth rate and composition of the growing layer in real time. These tools were used to study the organometallic chemical vapor deposition of CdTe, HgTe, and HgCdTe on GaAs. We could obtain the dielectric constants of these materials at the growth temperature and also the growth rate and composition of the layers in real time. Feedback control of CdTe growth was performed by connecting an analog control voltage line from the data acquisition/ analysis computer to the dimethylcadmium mass flow controller. Using dielectric constants of HgCdTe for two different compositions at the growth temperature, composition control of HgCdTe was attempted in a similar manner.     

Metalorganic vapor phase epitaxial growth of GaInAsP/GaAs

Ga_xAs_yP_1−y lattice matched to GaAs has been grown by low pressure metalorganic phase vapor epitaxy over the entire compositional range. At T_G = 670°C broad peaks of low intensity are observed in the 10K photoluminescence for y = 0.2–0.4 due to the predicted miscibility gap in this compositional region. An increase in growth temperature leads to a smaller miscibility gap. The band gap as well as the morphology show a strong dependence on substrate misorientation. The smoothest GalnAsP surfaces are obtained on exact oriented substrates. For the ternary GalnP the surface roughness is correlated to the degree of ordering in the temperature range of 600 to 750°C. The smallest band gap together with the smoothest surface is obtained on (100) 2° off to (111)B. Ordering effects are also observed in the quaternary GalnAsP. Broad-area lasers processed from the grown layers show high slope efficiency (0.9 W/A) and low internal losses (<3 cm⁻¹).     

The role of the V/III ratio in the growth and structural properties of metalorganic vapor phase epitaxy GaAs/Ge heterostructures

GaAs epitaxial layers have been grown on (001) 6† off-oriented toward (110) Ge substrates by metalorganic vapor phase epitaxy. In order to study the influence of V/III ratio on the growth mechanisms and the structural properties of the layers, the input flow of arsine was changed over a wide range of values, while keeping constant all other experimental settings. Optical microscopy in the Nomarski contrast mode, x-ray topography and high resolution diffractometry, transmission electron microscopy and Rutherford backscattering have been used to investigate the epilayers. It has been found that the growth rate increases and the surface morphology worsens with increasing V/III ratio. The abruptness of the layer-substrate interface has also been found to strongly depend on the V/III ratio, the best results being obtained under Ga-rich conditions. The main structural defects within the layers are stacking faults and misfit dislocations. Layers grown under As-rich conditions only contain stacking faults, probably originated by a growth island coalescence mechanism, whereas layers grown under Ga-rich conditions contain both misfit dislocations and stacking faults generated by dissociation of threading segments of interfacial dislocations. In spite of the different defects, the strain relaxation has been found to follow the same trend irrespective of the V/III ratio. Finally, the relaxation has been found to start at a thickness exceeding the theoretical critical value.     

Microstructural and optical characterization of CdTe(211)B/ZnTe/Si(211) grown by molecular beam epitaxy

CdTe layers have been grown by molecular beam epitaxy on 3 inch nominal Si(211) under various conditions to study the effect of growth parameters on the structural quality. The microstructure of several samples was investigated by high resolution transmission electron microscopy (HRTEM). The orientation of the CdTe layers was affected strongly by the ZnTe buffer deposition temperature. Both single domain CdTe(133)B and CdTe(211)B were obtained by selective growth of ZnTe buffer layers at different temperatures. We demonstrated that thin ZnTe buffer layers (<2 nm) are sufficient to maintain the (211) orientation. CdTe deposited at ∼300°C grows with its normal lattice parameter from the onset of growth, demonstrating the effective strain accommodation of the buffer layer. The low tilt angle (<1°) between CdTe[211] and Si[211] indicates that high miscut Si(211) substrates are unnecessary. From low temperature photoluminescence, it is shown that Cd-substituted Li is the main residual impurity in the CdTe layer. In addition, deep emission bands are attributed to the presence of As_Te and Ag_Cd acceptors. There is no evidence that copper plays a role in the impurity contamination of the samples.     

Interdiffusion and relaxation in metalorganic vapor phase epitaxy grown InGaAs/GaAs strained layer quantum wells

Low pressure metalorganic vapor phase epitaxy grown strained InGaAs/GaAs quantum well structures have been characterized by photoluminescence and x-ray diffraction. It is shown that beyond the pseudomorphic limit, these structures show considerable gallium/indium interdiffusion at the interfaces and partial strain relaxation in the quantum well layers.     

Substrate issues for the growth of mercury cadmium telluride

Close lattice matching and lattice compatibility with mercury cadmium telluride (MCT) make CdTe and related alloys ideal substrate materials for growth of MCT layers for the purpose of making high-performance second-generation infrared detectors. However, the limitations in the properties of CdTe and the difficulties in its bulk growth have prompted extensive research in the area of alternative substrates. Some basic relevant characteristics of substrates such as sapphire, GaAs, and silicon are compared and the possibilities and problems associated with each material are analyzed in the light of the most recent results in the field.     

Studies on the growth of CdTe on Si using ge interfacial layer in an organometallic vapor phase epitaxial system

Epitaxial CdTe layers were grown using organometallic vapor phase epitaxy on Si substrates with a Ge buffer layer. Ge layer was grown in the same reactor using germane gas and the reaction of germane gas with the native Si surface is studied in detail at low temperature. It is shown that germane gas can be used to “clean” the Si surface oxide prior to CdTe growth by first reducing the thin native oxide that may be present on Si. When Ge layer was grown on Si using germane gas, an induction period was observed before the continuous layer of Ge growth starts. This induction period is a function of the thickness of the native oxide present on Si and possible reasons for this behavior are outlined. Secondary ion mass spectrometry (SIMS) data show negligible outdiffusion and cross contamination of Ge in CdTe.     

Impact of growth rate on the quality of ZNS-MQW InGaAsP/InP laser structures grown by LP-MOVPE

We investigated the influence of the growth rate on the quality of zero-net-strained InGaAsP/InGaAsP/InP multiquantum well structures for 1.55 μm emission grown by low pressure metalorganic vapor phase epitaxy. The samples consisted of fixed compressive strained wells (ɛ=+1%) and tensile strained barriers (ɛ=−0.5%) grown with different quaternary bandgap wavelengths (λ_B=1.1–1.4 μm). Using higher growth rates, we obtained for the first time high quality zero net strained multi quantum well structures, regardless having constant group V composition in the well and barriers. The samples were analyzed by x-ray diffraction, photoluminescence and atomic force microscopy techniques. The amplitude of surface modulation roughness along [011] direction decreased from 20 nm to 0.53 nm with increasing growth rate and/or quaternary compositions grown outside the miscibility gap. A new deep PL broad emission band strongly correlated with the onset of wavy layer growth is also reported. Broad area and ridge waveguide lasers with 10 wells exhibited low losses (34 cm⁻¹) and low threshold current densities at infinite cavity length (1020 A·cm⁻² and 1190 A·cm⁻², respectively).     

Two-dimensional molecular beam epitaxy of {001} CdTe on Cd and Zn terminated {001} GaAs

Amorphous layers of CdTe deposited on Cd or Zn terminated GaAs {001} surfaces can be recrystallized above ∼200°C. Subsequent molecular beam epitaxy of CdTe proceeds in a two-dimensional mode and leads to layers which are specular and single domain {0011}. Threading dislocation density in these layers was 1–2 x 10⁵ cm⁻². Values of full width at half maximum for x-ray rocking curves were as low as 80 arc-s.     

Crystallographic orientation dependence of the growth rate for GaAs low pressure organometallic vapor phase epitaxy

The complete crystallographic orientation dependence of the growth rate for GaAs low pressure organometallic vapor phase epitaxy (LPOMVPE) is determined using a previously described semi-empirical model. A set of LPOMVPE growth rate polar diagrams is presented for reactor temperatures near 550°C as well as near 700°C. Also, the variation of the growth rate polar diagrams as a function of process variables is given. The experimental data utilized in the semiempirical model was attained using a typical horizontal reactor LPOMVPE system and typical LPOMVPE process parameters.     

Metalorganic vapor phase epitaxial growth and structural characterization of GaAs/InP heterostructures

Highly mismatched GaAs epitaxial layers with thickness ranging from 15 nm to 7 μm have been grown on InP substrates by atomospheric pressure metalorganic vapor phase epitaxy. Layers thinner than 30 nm exhibited 3-D growth mechanism; in the thicker layers, the islands coalesced and then the growth followed the layer by layer mechanism. The elastic strain and the extended defects have been studied by high resolution x-ray diffraction and transmission electron microscopy, respectively. The common observation of planar defects, misfit, and threading dislocations in the layers has been confirmed. The results on the elastic strain release have been discussed on the basis of the equilibrium theory.     

Probing the mechanisms of growth of gallium arsenide by metalorganic vapor phase epitaxy using experimental and theoretical studies of designed precursors

Decomposition of o-CH₃C₆H₄AsD₂ in the gas phase at 600–1000°C produces toluenes with 0-3 D atoms in the methyl group. It is shown that this cannot be accounted for by conventional mechanisms involving initial As-C bond cleavage or reductive elimination, but rather that the first step is As-D bond cleavage and this is followed by reductive elimination of o-CH₃C₆H₄D or H atom transfer to give o-HDAsC₆H₄CH₂· which abstracts D from an intact o-tolylarsine to give o-CH₂DC₆H₄AsHD. Repetition of these steps can lead to multiple D incorporation. The free energies of activation for reductive elimination or multiple D incorporation are found to be very similar. Theoretical studies on the decomposition of^tBuAsH₂ show that the first step for decomposition can be As-H bond cleavage to give^tBuAsH· or loss of H₂ to^tBuAs.^tBuAsH· decomposes to^tBu· which abstracts H· from^tBuAsH₂ to give 2-methylpropane or by β-H abstraction to give 2-methylpropene.^tBuAs, on the other hand only gives 2-methylpropene,via a β-H abstraction mechanism. Measured effects of total reactor pressure on product distribution are modeled qualitatively. Hex-5-enylarsine also decomposesvia initial As-H bond cleavage followed by reductive elimination of 1-hexene. However, it reacts in the liquid or solution phase with Me₃Ga to give the adduct. [Me₃Ga.AsH₂hex]. On heating, this loses methane to give first [Me₂Ga.AsHhex]₃ then [MeGa.Ashex]_n. Finally, GaAs is produced with the formation of methane and methylenecyclopentane. The last product indicates a free radical mechanism involving cleavage of the As-hex bond for the last step. In the gas phase at 600°C, GaAs is again formed but the major C₆ product is 1-hexene. This is interpreted as meaning that the adduct, [Me₃Ga.AsH₂hex] is not formed in the gas phase under growth conditions.