On the validity of the amphoteric-defect model in gallium arsenide and a criterion for Fermi-level pinning by defects

Using the theoretically calculated point-defect total-energy values of Baraff and Schlüter in GaAs, anamphoteric-defect model has been proposed by Walukiewicz to explain a large number of experimental results. The suggested amphoteric-defect system consists of two point-defect species capable of transforming into each other: the doubly negatively charged Ga vacancyV _Ga ^2– and the triply positively charged defect complex (AS_Ga+V _As)³⁺, with As_Ga being the antisite defect of an As atom occupying a Ga site andV _As being an As vacancy. When present in sufficiently high concentrations, the amphoteric defect systemV _Ga ^2– /(As_Ga+V _As)³⁺ is supposed to be able to pin the GaAs Fermi level at approximately theE _v +0.6 eV level position, which requires that the net free energy of theV _Ga/(As_Ga+V _As) defect system to be minimum at the same Fermi-level position. We have carried out a quantitative study of the net energy of this defect system in accordance with the individual point-defect total-energy results of Baraff and Schlüter, and found that the minimum net defect-system-energy position is located at about theE _v +1.2 eV level position instead of the neededE _v +0.6 eV position. Therefore, the validity of the amphoteric-defect model is in doubt. We have proposed a simple criterion for determining the Fermi-level pinning position in the deeper part of the GaAs band gap due to two oppositely charged point-defect species, which should be useful in the future.     

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V _Ga ^3– , has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V _Ga ^3– concentration, , has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V _Ga ^3– has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.     

Si DX centers in GaAs at large hydrostatic pressures

A number of experimental and theoretical studies indicate that DX centers in GaAs, its alloys and other III–V semiconductors have negative U properties. Using far infrared localized vibrational mode (LVM) spectroscopy of Si donors in GaAs under large hydrostatic pressure in a diamond anvil cell we have discovered an LVM of the Si DX center. From the ratio of the LVM absorption lines of Si_Ga and Si_DX and the compensation in our GaAs samples, we show unambiguously that two electrons are trapped when the ionized shallow Si donors transform into negatively charged DX centers, in full agreement with the negative U model.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

Dopant diffusion and segregation in semiconductor heterostructures: Part III, diffusion of Si into GaAs

We have mentioned previously that in the third part of the present series of papers, a variety of n-doping associated phenomena will be treated. Instead, we have decided that this paper, in which the subject treated is diffusion of Si into GaAs, shall be the third paper of the series. This choice is arrived at because this subject is a most relevent heterostructure problem, and also because of space and timing considerations. The main n-type dopant Si in GaAs is amphoteric which may be incorporated as shallow donor species Si_Ga ⁺ and as shallow acceptor species Si_As ^-. The solubility of Si_As ^- is much lower than that of Si_Ga ⁺ except at very high Si concentration levels. Hence, a severe electrical self-compensation occurs at very high Si concentrations. In this study we have modeled the Si distribution process in GaAs by assuming that the diffusing species is Si_Ga ⁺ which will convert into Si_As ^- in accordance with their solubilities and that the point defect species governing the diffusion of Si_Ga ⁺ are triply-negatively-charged Ga vacancies V_Ga ^3-. The outstanding features of the Si indiffusion profiles near the Si/GaAs interface have been quantitatively explained for the first time. Deposited on the GaAs crystal surface, the Si source material is a polycrystalline Si layer which may be undoped or n⁺-doped using As or P. Without the use of an As vapor phase in the ambient, the As- and P-doped source materials effectively render the GaAs crystals into an As-rich composition, which leads to a much more efficient Si indiffusion process than for the case of using undoped source materials which maintains the GaAs crystals in a relatively As-poor condition. The source material and the GaAs crystal together form a heterostructure with its junction influencing the electron distribution in the region, which, in turn, affects the Si indiffusion process prominently. Received: 19 April 1999 / Accepted: 3 May 1999 / Published online: 4 August 1999     

Photoluminescence of Al x Ga1−x As/GaAs quantum well heterostructures grown by molecular beam epitaxy

Nominally undoped Al_xGa_1–xAs grown by molecular beam epitaxy from As₄ species at elevated substrate temperatures of 670°C exhibits well-resolved excitonic fine structure in the low-temperature photoluminescence spectra, if the effective As-to-(Al+Ga) flux ratio on the growth surface is kept within a rather narrow range of clearly As-stabilized conditions. In contrast to previous results on Al_xGa_1–xAs of composition 0.15not to shift in energy by changing the excitation intensity. This implies a simple freeelectron carbon-acceptor recombination mechanism for the line without any participation of a donor. In Al_xGa_1–xAs of composition close to the direct-to-indirect cross-over point, two distinct LO-phonons separated by 34 and 48 meV from the (D ⁰,C ⁰) peak position at x=0.43 were observed which were before only detectable by Raman scattering experiments. The intensity of the carbon-impurity related luminescence lines in bulk-type Al_xGa_1–xAs and GaAs layers was found to be strongly reduced, as compared to the excitonic recombination lines, if the respective active layer was covered by a very thin confinement layer of either GaAs on top of Al_xGa_1–xAs or vice versa grown in the same growth cycle.     

Dopant diffusion and segregation in semiconductor heterostructures: Part 1. Zn and Be in III-V compound superlattices

chemical effect on the neutral species; and (ii) a Fermi-level effect on the ionized species, because, in addition to the chemical effect, the solubility of the species also has a dependence on the semiconductor Fermi-level position. For Zn and Be in GaAs and related compounds, their diffusion process is governed by the doubly-positively-charged group III element self-interstitials (I²⁺ _III), whose thermal equilibrium concentration, and hence also the diffusivity of Zn and Be, exhibit also a Fermi-level dependence, i.e., in proportion to p². A heterojunction consists of a space-charge region with an electric field, in which the hole concentration is different from those in the bulk of either of the two layers forming the junction. This local hole concentration influences the local concentrations of I²⁺ _III and of Zn^- or Be^-, which in turn influence the distribution of these ionized acceptor atoms. The process involves diffusion and segregation of holes, I²⁺ _III, Zn^-, or Be^-, and an ionized interstitial acceptor species. The junction electric field also changes with time and position. Received: 20 August 1998/Accepted: 23 September 1998     

Study of perfection of layers of AlGaSb(AS) solid solution

Studies have been carried out on the perfection of then-Al_xGa_1–xSb_1–yAs_y (0.12x0.26) layer grown on GaSb substrates under different conditions of lattice matching. During the relaxation of the mechanical stresses at first a system of tilt dislocations with a density of up to 5 · 10⁵ cm^–2 is formed while in thick layers (h 20 m) a network of misfit dislocations parallel to the heteroboundary is formed. The time required to dissolve a weighed amount of GaAs in the melt is shown to be of major importance for obtaining layers of a solid solution that are isoperiodic with the substrate. The entry of arsenic only in the initial portion of the epitaxial layer can reduce the dislocation density in the layer without decreasing the measured value of Aa. Dissolution of a weighed amount of GaAs in a Ga + Sb melt for two hours at T=730–750°C is sufficient to obtain layers of Al_xGa_1–xSb_1–yAs_y solid solution that are isoperiodic with the substrate.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 84–89, January, 1988.In conclusion, we thank L. V. Druzhinina for useful discussions as well as Z. V. Korotchenko, L. S. Khludkova, and F. S. Kim for assistance in the performance of the experiments.     

Hydrogen sulphide doping of GaAs and AlxGa1−xAs grown by molecular beam epitaxy (MBE)

H₂S gas has been used during molecular beam epitaxy (MBE) growth of GaAs and Al _x Ga_1–x As as sulphur vector forn-type doping. Doping efficiencies are less than 10^–3 at usual growth temperatures, and are limited by an incorporation competitive surface process, probably 2Ga+H₂SGa₂S+H₂. In Al_xGa_1–x As forx0.2 the doping efficiency is further reduced by carrier freeze-out at deep levels. Measured thermal activation energies depend on growth conditions and remain relatively low even up to the direct-indirect bandgap crossover for substrate temperatures in the 585–645 C range.     

Study of nuclear quadrupole interactions and quadrupole Raman processes of Ga and Ga in a β-Ga2O3:Cr single crystal

Nuclear magnetic resonance (NMR) data and the spin–lattice relaxation times, T₁, of ⁶⁹Ga and ⁷¹Ga nuclei in a β-Ga₂O₃:Cr³⁺ single crystal were obtained using FT NMR spectrometry. Four sets of NMR spectra for ⁶⁹Ga (I = 3/2) and ⁷¹Ga (I = 3/2) were obtained in the crystallographic planes. The ⁶⁹Ga and ⁷¹Ga nuclei each had two chemically inequivalent Ga_I and Ga_II centers. Each of the ⁶⁹Ga and ⁷¹Ga isotopes yielded two different central NMR resonance lines originating from Ga_I and Ga_II sites. The nuclear quadrupole coupling constants and asymmetry parameters of ⁶⁹Ga_I, ⁶⁹Ga_II, ⁷¹Ga_I, and ⁷¹Ga_II centers in a β-Ga₂O₃:Cr³⁺ crystal were obtained. Analysis of the EFG tensor principal axes (PAs) for Ga nuclei and the ZFS tensor PAs for the Cr³⁺ ion confirmed that the Cr³⁺ paramagnetic impurity ion substitutes for the Ga³⁺ ion in the oxygen octahedron. In addition, the temperature dependencies of the ⁶⁹Ga and ⁷¹Ga relaxation rates were consistent with Raman processes, as T₁⁻¹ ∝ T². Even though the Cr³⁺ impurities are paramagnetic, the relaxations were dominated by electric quadrupole interactions of the nuclear spins in the temperature range investigated.     

Energy distributions and emission coefficients of secondary ions ejected from AIIIBV group semiconductors

The energy distributions of Ga⁺ and Ga₂ ⁺ secondary ions sputtered from the surface of single crystals of GaAs and GaP by Ar⁺ (E = 18 keV, j = 1·10^–6 A/cm²) ions were studied. Integral emission coefficients for secondary ions from four semiconductors (GaAs, GaP, InAs, and A1_0.35Ga_0.65As) bombarded by Ar⁺ ions (E = 2 keV, j₀ = 1·10^–6 A/cm²) were also measured. It is shown that the energy distribution of the Ga⁺ secondary ions are broad and qualitatively similar to distributions of secondary ions sputtered from metal oxide surfaces. Very high integral emission coefficients (up to 20–30%) for secondary ions are also observed, exceeding analogous coefficients for clean metal surfaces. These facts (the significant number of low energy secondary electrons and high secondary ion emission coefficients) are due to the lower density of free electrons in comparison with metals, which ensures a high degree of survival of sputtered ions, and the partially ionic character of the bonds in the semiconductors under study.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 88–92, November, 1990.     

高组份Al值的AlxGa1-x As和AlxGa1-x As/GaAs/AlxGa1-xAs/GaAs多层结构的MOCVD生长

用自制常压MOCVD系统,在半绝缘GaAs衬底上生长高Al组份Al_xGa_1-xAs（其x值达0.83）,和Al_xGa_1-xAs/GaAs/Al_xGa_1-xAs/GaAs多层结构,表面镜面光亮。生长层厚度从几十到十几μm可控,测试表明外延层晶格结构完整,x值调节范围宽,非有意掺杂低,高纯GaAs外延层载流子浓度n_300K=1.7×10¹⁵cm^-3,n_77K=1.4×10¹⁵cm^-3,迁移率μ_300K=5900cmcm²/V.S,μ_77K=55500cm²/V.S。用电子探针,俄歇能谱仪测不出非有意掺杂的杂质,各层间界面清晰平直。 对GaAs,AlGaAs生长层表面缺陷,衬底偏角生长温度及其它生长条件也进行了初步探讨。     

Study of n type porous GaAs by photoluminescence spectroscopy: Effect of the etching time on the deep levels

Photoluminescence (PL) analysis is used to study porous layers elaborated by electrochemical etching of n⁺ Si-doped GaAs substrate with different etching times. Temperature and power dependence photoluminescence (PL) studies were achieved to characterize the effect of the etching time on the deep levels of the n⁺ Si-doped GaAs. The energy emission at about 1.46 eV is attributed to the band-to-band (B-B) (e-h) recombination of a hole gas with electrons in the conduction band. The emission band is composed of four deep levels due to the complex of (V_AsSi_GaV_Ga), a complex of a (Ga vacancy - donor - As vacancy), a (Si_Ga-V_Ga³⁻) defect or Si clustering, and a (gallium antisite double acceptor-effective mass donor pair complex) and which peaked, respectively, at about (0.94, 1, 1.14, and 1.32 eV). The PL intensity behavior as function of the temperature is investigated, and the experimental results are fitted with a rate equation model with double thermal activation energies.     

Raman scattering study of Al/Ga interdiffusion in ion-implanted and annealed GaAsGa1−xAlxAs superlattices

The Al/Ga interdiffusion after annealing has been characterized by Raman scattering on a GaAsGa_1−xAl_xAs superlattice where different densities of damage had been initially induced by implantation of electrically inactive isoelectronic elements, ³¹P⁺, in order to eliminate the impurity charge associated effects. To probe the mixing beyond the damaged zone of the superlattice, complementary Auger and SIMS experiments have implantation induced defects proceeds from the examination of the whole set of results.     

Non-equilibrium point defect phenomena influencing beryllium and zinc diffusion in GaAs and related compounds

Beryllium and zinc are the main p-type dopants used for the fabrication of devices based on GaAs or related III-V materials. Both elements are substitutionally dissolved on the group III sublattice and diffuse via the kick-out mechanism which involves group III self-interstitials. Non-equilibrium concentrations of these self-interstitials have a strong influence on the diffusivities of Be and Zn with often drastic consequences on device behavior especially if Be or Zn is used to realize narrow base regions in heterojunction bipolar transistors (HBTs). Various situations in which non-equilibrium point defects play a role for Be and Zn diffusion are discussed such as: in-diffusion of these dopants from an outside source, diffusion of grown-in dopants, self-interstitial generation by Fermi level surface pinning of highly n ⁺-doped emitter cap or subcollector layers in HBTs, or recom bination-enhanced beryllium diffusion during device operation. Finally, we will comment on the diffusion behavior of carbon, which is dissolved on the group V sublattice in GaAs, is much less sensitive to non-equilibrium point defect, and, therefore, is increasingly used to replace Be and Zn as p-type dopants.On sabbatical leave from Duke University, School of Engineering, Durham, NC 27706, USA     

Photoluminescence of AlxGa1−xAs/GaAs quantum well heterostructures grown by molecular beam epitaxy

Low-temperature photoluminescence measurements on nominally undoped Al_xGa_1–xAs/GaAs quantum well heterostructures (QWHs) grown by molecular beam epitaxy (MBE) exemplified the exclusivelyintrinsic free-exciton nature of the luminescence under moderate excitation conditions. Neither any spectroscopic evidence for alloy clustering in the Al_xGa_1–xAs barriers nor any extrinsic luminescence due to recombination with residual acceptors has been detected in single and double QWHs when grown at 670 °C under optimized MBE growth conditions. Carrier confinement in Al_xGa_1–xAs/GaAs QWHs starts at a well width ofL _z30 nm when x0.25. The minor average well thickness fluctuation ofL _z=4×10^–2nm as determined from the excitonic halfwidth allowed the realization of well widths as low asL _z=1 nm and thus a shift of the free-exciton line as high as 2.01 eV which is close to the conduction band edge of the employed Al_0.43Ga_0.57As confinement layer. The measurements further revealed a strongly enhanced luminescence efficiency of the quantum wells as compared to bulk material which is caused by the modified exciton transition probabilities due to carrier localization.     

Competition of N-passivation and Te-passivation in hydrogenation of Te-doped (Ga,In)(N,As)

(Ga,In)(N,As) lattice matched to GaAs with a band gap of 1 eV is employed as active material in high-efficiency III–V solar cells. Te-doped Ga_0.934In_0.066N_0.023As_0.977 layers were grown by metal-organic vapor-phase epitaxy on (1 0 0) GaAs. The samples were highly doped n-type with carrier concentrations ranging from about 10¹⁷–10¹⁹ cm⁻³. Pieces of the samples were hydrogenated with H-doses of 10¹⁸ ion/cm². The optical and electrical properties of the samples before and after hydrogenation were studied by low-temperature photoluminescence and magnetotransport. In undoped samples hydrogen is known to form N–H complexes which strongly reduce the local perturbation of the lattice due to nitrogen and thus reverse the N-induced global changes of the band structure. Combined analysis of photoluminescence and transport measurements on Te-doped samples, however, indicates a competition between N–H formation and passivation of the Te donor favoring the latter. Hardly any band structure changes due to hydrogenation are observed in these Te-doped samples, instead a strong reduction of the free-carrier concentration is observed after hydrogenation.     

Diffusion studies of Be-implanted GaAs by SIMS and electrical profiling

Secondary ion mass spectrometry (SIMS) has been used with differential resistivity and Hall effect measurements to study the 900°C diffusion of implanted Be in GaAs. Some outdiffusion of Be into the Si₃N₄ encapsulant occurs for surface Be concentrations above 1 × 10¹⁸cm^?3. However, excellent agreement between the electrical and atomic profiles indicates that 85–100% of the Be remaining after annealing is electrically active. The concentration-dependent diffusion observed for implanted Be in GaAs was not significantly altered in experiments using hot substrate implants, two-step anneals, or annealing with Ga and As overpressure.     

Shallow acceptor population and free hole concentration in Si: In and Si:Ga with IR-photoexcitation

Hall measurements at low temperaturesT<50 K have been performed on Si:In (N _In10¹⁷ cm^–3) and Si:Ga (N _Ga10¹⁸ cm^–3) with infrared photoexcitation of holes into the valence band. It is shown in quantitative agreement with a theoretical model that the population of shallow acceptors, e.g. B and Al, which are present as impurities in concentrations ofN _B,Al10¹²-10¹⁴ cm^–3 strongly affects the photoexcited hole concentration. Photo-Hall measurements can, therefore, serve as a tool for the determination of low impurity acceptor concentrations in the case of high In- or Ga-doping. Hole capture coefficientsB _In=6×10^–4 (T/K)^–1,8 cm³ s^–1 andB _Ga=2×10^–4 (T/K)^–1 cm³ s^–1 have been determined.     

XPS data for sputter-cleaned In0.53Ga0.47As,GaAs, and InAs surfaces

Core level binding energies and Auger parameters were determined for In, Ga, and As in the three compounds In_0.53Ga_0.47As, GaAs, and InAs. The surfaces were cleaned by 1.5 keV Ar ion bombardment. Under this condition the radiation-induced defects are small. In the case of GaAs the Ga and As3d levels become comparable with available data for chemically cleaned surfaces. The high Ga deficiency of chemically cleaned In_0.53Ga_0.47As surfaces could not be observed. Sputter cleaned surfaces seem to be closer to the bulk composition.     

Tunable growth of (GaxIn1−x)2O3 nanowires by water vapor

The tunable growth of In-doped Ga₂O₃ (Ga₂O₃:In) and Ga-doped In₂O₃ (In₂O₃:Ga) nanowires (NWs) on Au-coated Si substrates was achieved by modulating the amount of water vapor in flowing Ar at 700–750 °C via carbothermal reduction of Ga₂O₃/In₂O₃ powders with a fixed weight ratio. In Ar, only the Ga₂O₃:In NWs were grown, while in wet Ar the In₂O₃:Ga NWs were synthesized instead. The Ga concentration in In₂O₃ NWs decreased with the increment of water vapor in flowing Ar. The growth of both Ga₂O₃:In and In₂O₃:Ga NWs followed the vapor–liquid–solid process. The In and Ga doping induced a redshift and a blueshift in the optical bandgaps of Ga₂O₃ NWs and In₂O₃ NWs, respectively. The growth mechanisms and optical properties of Ga₂O₃:In and In₂O₃:Ga NWs were discussed.