The use of a metalorganic compound for the growth of InP-epitaxial layers

InP epitaxial layers have been grown by the pyro-lysis of a new metalorganic compound, a trimethyl-indium trimethyl-phosphene adduct. The formation of unwanted polymer products during epitaxial growth could be avoided in this way. The layers were grown at 500°C with a growth rate of about 1 μmh_-1. Net carrier concentrations of n≏5-10^l5cm^-3 could be achieved.     

Variation of the thickness and composition of lpe InGaAsP,InGaAs, and InP layers grown from a finite melt by the step-cooling technique

Constant composition InGaAsP and InGaAs epitaxial layers can be grown using the step-cooling technique. However, the requirement of a fixed growth temperature limits the maximum thickness that can be obtained. The thickness of InGaAsP (λ_g = 1.15 μm@#@), InGaAs (λ_g = 1.68 μm), and InP liquid phase epitaxial layers grown on (100) InP sub-strates by the step-cooling technique has been measured as a function of growth time. (λ_g is defined as the wave-length corresponding to the band gap of the epitaxial layer). For long growth times, the effect of the finite growth solution becomes important, and beyond a distinct growth time, constant composition growth can no longer be maintained. The maximum constant composition layer thick-ness obtainable is not severely restricted by the fixed growth temperature, and from the experimental results this maximum thickness can be estimated for any melt size.     

电流控制LPE生长In_（1－x）Ga_xAs_yP_（1－Y）

用电流控制液相外延（ＣＣＬＰＥ）方法首次在（１００）ＩｎＰ衬底上成功地生长出Ｉｎ１－ｘＧａｘＡｓｙＰ１－ｙ（０．３０＜ｘ＜０．４７，０．７０＜ｙ＜０．９６）外延层，并对外延层特性进行了详细研究，提出在ＩｎＰ衬底上生长电外延层的机理，推导出生长动力学的理论模型，该模型与上述实验结果十分吻合。     

Lpe growth of Hgl−xCdxTe using conventional slider boat and effects of annealing on properties of the epilayers

The epitaxial layers of Hg_1−xCd_xTe (0.17≦×≦0.3) were grown by liquid phase epitaxy on CdTe (111)A substrates using a conventional slider boat in the open tube H₂ flow system. The as-grown layers have hole concentrations in the 10¹⁷− 10¹⁸ cm⁻³ range and Hall mobilities in the 100−500 cm²/Vs range for the x=0.2 layers. The surfaces of the layers are mirror-like and EMPA data of the layers show sharp compositional transition at the interface between the epitaxial layer and the substrate. The effects of annealing in Hg over-pressure on the properties of the as-grown layers were also investigated in the temperature range of 250−400 °C. By annealing at the temperature of 400 °C, a compositional change near the interface is observed. Contrary to this, without apparent compositional change, well-behaved n-type layers are obtained by annealing in the 250−300 °C temperature range. Sequential growth of double heterostructure, Hg_l−xCd_xTe/Hg_l−yCd_yTe on a CdTe (111)A substrate was also demonstrated.     

Liquid phase epitaxial growth and characterization of InAsxSb1−;x AND In1−yGaySb ON (111)B InSb substrates

Liquid phase epitaxial growth of InAs_xSb_1−x, for 0<_x<0.27 and In_1−yGa_ySb, for 0<y<0.37, has been successfully accomplished on (111)B InSb substrates between the temperatures of 450 and 520°C. The phase diagrams and the growth conditions for high-quality planar epitaxial layers have been determined. For growth of InAs_xSb_1−x for high values of x, the strong tendency of the ternary melt to dissolve the substrate, even when the liquid is a few degrees below its melting point, was negated by using large supercooling. Small supercooling of zero to 5.6°C were required over the whole range of composition examined for (In.Ga)Sb, whereas, for example, supercooling greater than 30°C was required to grow InAs_o.26Sb_o.74 to avoid substrate dissolution. Lattice mismatch to the substrate was relieved by compositional grading. Etch pit studies in both materials yielded dislocation densities ranging from 5.8 × 10² to 2×10⁶ cm⁻² with most materials in the low 10⁴ range. Hall and resistivity measurements performed at 300K and 77K on most samples showed an impurity contamination of the epitaxial layers. Some samples were n-type (carrier concentration approximately 10¹⁷/cm³), with varying degrees of acceptor compensation and others were n-type (carrier concentration approximately l0¹⁷/cm³) at room temperature due to intrinsic conduction, but exhibited p-type conduction (carrier concentration approximately 5×l0^l6/cm³) at 77K. Hall measurements performed on one of the latter samples ofvery low As content from 77K to 4.2K to examine hole freeze-out yielded an acceptor level ionization energy of 0.0126eV which is close to the effective mass acceptor level ionization energy in InSb. The electron-to-hole mobility ratio was also found to be 65.9. Electron microprobe analysis showed silicon to be the dominant impurity.     

Supercooling studies and LPE growth of Hg1−xCdxTe from Te-Rich solutions

Hg_1-xCd_xTe liquid phase epitaxial (LPE) layers were grown from well-stirred large (100 g) Te-rich Hg-Cd-Te solutions by the dipping method. Supercooling below the liquidus temperature in Te-rich solutions was studied by differential thermal analysis (DTA) and film growth results. Although supercooling of 20 to more than 100° C was routinely measured in small (2 g) sample melts, supercooling in larger melts (>100 g) was erratic and smaller. Factors affecting the degree of supercooling were identified and a Hg-reflux was found to be a major cause of erratic melt behavior. The LPE reactor was modified to correct the Hg-reflux action and a visual technique was developed for in situ determination of the liquidus temperature. A limited amount of supercooling was found in the melt after reactor modification but it was difficult to maintain for extended durations before spontaneous nucleation occurred. Consequently, programmed cooling rather than isothermal LPE was employed to grow many of the films reported here. Hg_1−xCd_xTe epitaxial layers ofx = 0.2 to 0.25 were grown on (111)B oriented CdTe substrates by cooling the melts only 1–2° C below the previously measured crystallization temperature. The small amount of cooling minimized composition variation with film thickness. Excellent surface morphology was obtained when slow cooling rates of 0.02–0.05° C/ min were used. Cooling rates greater than 0.2° C/min created rough, pitted surface. Precise substrate orientation was important in reducing surface terracing. Composition and thickness uniformities of the epitaxial films were excellent as a result of substrate rotation. Run-to-run reproducibility of film composition was ±0.01 inx. Hall measurements showed carrier concentrations in the range 2–20 × 10¹⁴ cm⁻³ with photoconductive lifetimes of 0.5–3.0 dms forx = 0.20 to 0.25.     

Molecular beam epitaxial growth of HgCdTe on CdZnTe(311)B

A series of n-type, indium-doped Hg_1−xCd_xTe (x∼0.225) layers were grown on Cd_0.96Zn_0.04Te(311)B substrates by molecular beam epitaxy (MBE). The Cd_0.96Zn_0.04Te(311)B substrates (2 cm × 3 cm) were prepared in this laboratory by the horizontal Bridgman method using double-zone-refined 6N source materials. The Hg_1−xCd_xTe(311)B epitaxial films were examined by optical microscopy, defect etching, and Hall measurements. Preliminary results indicate that the n-type Hg_1−xCd_xTe(311)B and Hg_1−xCd_xTe(211)B films (x ∼ 0.225) grown by MBE have comparable morphological, structural, and electrical quality, with the best 77 K Hall mobility being 112,000 cm²/V·sec at carrier concentration of 1.9×10⁺¹⁵ cm⁻³.     

Electrical properties of InAlAs/InAsxP1-x/InP composite-channel modulation-doped structures grown by solid source molecular beam epitaxy

We report on the electrical characteristics of the two-dimensional electron gas (2DEG) formed in an InAlAs/InAs_xP_1-x/InP pseudomorphic composite-channel modulation-doped (MD) structure grown by solid source (arsenic and phosphorus) molecular beam epitaxy (SSMBE). The As composition, x, of strained InAs_xP_1-x was determined by x-ray diffraction analysis of InP/InAs_xP_1-x/InP multi-quantum wells (MQWs) with compositions of x=0.14 to x=0.72. As the As composition increases, the room temperature sheet resistance of InAlAs/InAs_xP_1-x/InP composite-channel MD structures grown over a range of As compositions decreased from 510 to 250 Ω/cm², resulting from the greater 2DEG confinement and lower electron effective mass in the InAs_xP_1-x channel as x increases. The influence of growth conditions and epitaxial layer designs on the 2DEG mobility and concentration were investigated using 300 K and 77 K Hall measurements. As the exposure time of the As₄ flux on the growth front of InAs_xP_1-x increased during growth interruptions, the 2DEG mobility, in particular the 77K mobility, was considerably degraded due to increased roughness at the InAlAs/InAs_xP_1-x interface. For the InAlAs/InAs_0.6P_0.4/InP composite-channel MD structure with a spacer thickness of 8 nm, the room temperature 2DEG mobility and density were 7200 cm²/Vs and 2.5 × 10¹² cm⁻², respectively. These results show the great potential of the InAlAs/InAs_xP_1-x/InP pseudomorphic composite-channel MD heterostructure for high frequency, power device applications.     

OMVPE growth of the metastable III/V alloy GaAs0.5Sb0.5

The two crystal growth parameters most likely to affect the occurrence of GaAs_0.5Sb_0.5 spinodal decomposition during organometallic vapor phase epitaxial (OMVPE) growth, substrate temperature and substrate orientation, were investigated in detail. The temperature range studied was the widest over which good morphology layers could be grown, from 550 to 680° C. The InP substrate orientations used were (100), (221) and (311). The growth process was found to be diffusion controlled at high temperatures, but to be controlled by surface kinetics at temperatures below approximately 620° C, depending on substrate orientation. Growth of high quality layers was found to be much easier between 570 and 640° C. In addition, the 77 K PL intensity is much stronger for layers grown in this temperature range. The minimum PL halfwidth at 77 K is 20 meV and at 8 K is 16 meV. The typical room temperature hole mobilities are 100 cm²/Vs with hole concentrations of 2 x 10¹⁷ cm^-3 in undoped material. The temperature dependence of mobility is consistent with enhanced alloy scattering. Surprisingly, the growth temperature has no significant effect on either PL halfwidth or hole mobility between 560 and 660° C. The single Raman line observed for the unannealed alloy is split after annealing into two lines corresponding to the GaAs-rich and GaSb-rich alloys on either side of the range of solid immiscibility. The spinodal decomposition apparently starts at the surface where the coherency strain, which stabilizes the single phase alloy, is smallest.     

The behavior of unintentional impurities in Ga0.47 In0.53As grown by MBE

A number of factors contribute to the high n-type background carrier concentration (high 10¹⁵ to low 10¹⁶ cm⁻³) measured in MBE Ga_0.47In_0.53As lattice-matched to InP. The results of this study indicate that the outdiffusion of impurities from InP substrates into GalnAs epitaxial layers can account for as much as two-thirds of the background carrier concentration and can reduce mobilities by as much as 40%. These impurities and/or defects can be gettered at the surfaces of the InP by heat treatment and then removed by polishing. The GalnAs epitaxial layers grown on the heat-treated substrates have significantly improved electrical properties. Hall and SIMS measurements indicate that both donors and acceptors outdiffuse into the epitaxial layers during growth resulting in heavily compensated layers with reduced mobilities. The dominant donor species was identified by SIMS as Si, and the dominant acceptors as Fe, Cr and Mn.     

Very high purity In0.53Ga0.47As grown by molecular beam epitaxy

Very high purity In0_0.53Ga_0.47As layers were grown by molecular beam epitaxy (MBE). Origins ofn-type impurities in undoped In_0.53Ga_0.47As grown on an InP:Fe substrate were systematically examined. The most possible origins were impurities diffusing from the InP:Fe substrate and those contained in As molecular beam. These impurities were dramatically reduced by using an InAlAs buffer layer and a growth condition of high substrate temperature and low As pressure. The lowest electron concentration of the In0_0.53Ga_0.47As layer wasn = 1.8 × 10¹³ cm_-3 with mobilitiesμ = 15200 cm²/Vs at 300 K andμ = 104000 cm²/Vs at 77 K.     

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.     

Vapor growth of InP for MESFET’S

Epitaxial layers of InP have been grown by the conventional In/PCl₃/H{ion2} technique. With the aim of fabricating FET’s structures, we have studied the growth of low doped buffer layers and the doping by H₂S. It has been shown, that the purity of the layers increases from experiment to experiment and that low doped layers, in the 10¹³ – 10¹⁴ cm^-3 range, are obtained after growth of about 10 layers. Evidence for the purity of these layers have been obtained from Hall, photoluminescence and SIMS measurements. Cr and Fe outdiffusion from the substrate has been studied by SIMS. Fe is found to diffuse from the substrates, even in the case of substrates which are not intentionally doped with Fe. Some FET’s have been fabricated on epitaxial structures with and without buffer layers: the static characteristics of the transistors are encouraging (I_Dss = 24 mA, g_m = 19 mS for a gate of 2 μm and 200 μm in length and width, respectively); the pinch-off is better in devices fabricated from structures with buffer layers.     

Ga1-xinxas - inp abrupt heterostructures grown by MOVPE at atmospheric pressure

High quality InP and Ga_1-x In_xAs layers have been grown on InP substrates using MOVPE growth at atmospheric pressure. Excellent material quality has been obtained using triethylindium and trimethylgallium sources(n = 1.7 10¹⁴ cm^-3, μ = 106 000 cm²V^-1s^-1 at 77 K for InP andn = 1 ? 3 10¹⁵ cm^-3, μ= 75 000 cm²V^-1 s^-1 at 77 K for Ga_1-xIn_xAs). The InP/Ga_1-xIn_xAs interface width obtained is very small (10 Å). The first PIN diodes grown by the process exhibit excellent characteristics.     

Properties of Bi-doped PbTe layers grown by liquid phase epitaxy under controlled Te vapor pressure

Effects of Bi doping in PbTe liquid-phase epitaxial layers grown by the temperature difference method under controlled vapor pressure (TDM-CVP) are investigated. For Bi concentrations in the solution, x_Bi, lower than 0.2 at.%, an excess deep-donor level (activation energy E_d≈0.03–0.04 eV) appears, and Hall mobility is low. In contrast, for x_Bi>0.2 at.%, Hall mobility becomes very high, while carrier concentration is in the range of 10¹⁷ cm⁻³. Inductive coupled plasma (ICP) emission analysis shows that, for x_Bi=1 at.%, Bi concentration in the epitaxial layer is as high as N_Bi=2.3–2.7 × 10¹⁹ cm⁻³. These results indicate that Bi behaves not only as a donor but also as an acceptor, and the nearest neighbor or very near donor-acceptor (D-A) pairs are formed, so that strong self-compensation of Bi takes place. Carrier concentration for highly Bi-doped layers shows a minimum at a Te vapor pressure of 2.2 × 10⁻⁵ torr for growth temperature 470°C, which is coincident with that of the undoped PbTe.     

Structural characterization of thick, high-quality epitaxial Ge on Si substrates grown by low-energy plasma-enhanced chemical vapor deposition

In this paper, we report on the growth of epitaxial Ge on a Si substrate by means of low-energy plasma-enhanced chemical vapor deposition (LEPECVD). A Si_1?xGe_x graded buffer layer is used between the silicon substrate and the epitaxial Ge layer to reduce the threading dislocation density resulting from the lattice mismatch between Si and Ge. An advantage of the LEPECVD technique is the high growth rate achievable (on the order of 40 Å/sec), allowing thick SiGe graded buffer layers to be grown faster than by other epitaxial techniques and thereby increasing throughput in order to make such structures more manufacturable. We have achieved relaxed Ge on a silicon substrate with a threading dislocation density of 1 × 10⁵ cm^?2, which is 4?10x lower than previously reported results.     

Growth and characterization of OMVPE grown (In,Mn)As diluted magnetic semiconductor

In_1−xMn_xAs diluted magnetic semiconductor (DMS) thin films with x 0.14 have been grown using organometallic vapor phase epitaxy. Tricarbonyl-(methylcyclopentadienyl)manganese was successfully used as the Mn source. Single phase, epitaxial films were achieved for compositions as high as x=0.14 using growth temperatures ≥475°C. For lower growth temperatures or x>0.14, nanometer scale MnAs precipitates were observed within the In_1−xMn_xAs matrix. Transport properties were investigated using the Hall effect. All Mn doped films were p-type with single phase films exhibiting hole concentrations 2≤×10¹⁹ cm⁻³. Magnetization was measured as a function of temperature and applied field for a single phase film with x=0.1. Ferromagnetic ordering was observed at 5 K with a saturation magnetization of M_s=68 emu/cm³, a remnant magnetization, M_r=10 emu/cm³, and a coercive field H_c=400 Oe.     

Elastic strains in heteroepitaxial ZnSe1−xTex on InGaAs/InP (001)

Here we report on the elastic strains in ZnSe_1−xTe_x (x<0.9) epitaxial layers grown using photo-assisted metalorganic vapor phase epitaxy on In_0.53Ga_0.47As/InP (001) substrates. High-resolution x-ray diffraction was used to determine their composition and strain. At room temperature, we observed an apparent asymmetry in strains for tensile and compressive layers. However, when we accounted for the difference in thermal expansion between the substrate and epitaxial material, the growth temperature strain relaxation appears symmetric with respect to the sign of mismatch. The growth temperature strains are in agreement with the Matthews and Blakeslee (MB) model [J.W. Matthews and A.E. Blakeslee, J. Cryst. Growth 27, 118 (1974)] for both compressive (x>0.6) and tensile (x<0.4) layers. However, for the layers with composition in the range 0.4<x<0.6, the growth temperature strains exceed the values predicted by the MB theory. Apparently, low-mismatch layers experience a kinetic barrier to relaxation. The overall behavior can be fit by the relaxation model of Dodson and Tsao [B.W. Dodson and J.Y. Tsao, Appl. Phys. Lett. 51, 1325 (1987)] using the values Cμ²=80 s⁻¹ and γ₀=10⁻⁹.     

Green emitting Zn-diffused LPE GaP diodes

The growth of liquid phase epitaxial (LPE) layers of n-type GaP on GaP substrates was investigated using a multi-wafer growth system constructed of fused quartz which had provisions for gas phase saturation and doping of the gallium melt. The effect of growth temperature, substrate orientation, doping level, and repeated use of the same melt on the properties of zinc diffused electroluminescent diodes fabricated from these epitaxial layers were investigated. After an initial increase, the carrier concentration remained relatively constant (1.7 × 10¹⁷/cc) throughout a series of eighteen runs from the same melt. Using conventional commercial techniques, zinc diffused diodes with efficiencies of 0.05% at 30A/cm² and a brightness of 1200 fL at 10A/cm² were produced. These diodes had a limited area n and p-type contact and had an epoxy dome. Layers grown on the 〈 111 〉P orientation had the best surface quality whereas those grown on the 〈 100 〉 plane incorporated less background impurities. The use of relatively low growth starting temperatures (∼ 920°C) was found to minimize the background impurity of the layers and the substrate surface deterioration due to the reaction with ammonia. This work was, in part, sponsored by the Air Force Materials Laboratory under the direction of Mrs. E. H. Tarrants, contract number F33615-71-C-1621     

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.