Growth temperature dependence in molecular beam epitaxy of gallium arsenide

Epitaxial layers of GaAs were grown on GaAs(100) at substrate temperatures ranging from 400° to 600°C by molecular beam epitaxy. Surface structures of the substrate and the epitaxial layers were investigated by means of low-energy electron diffraction. Two new structures of c(4 × 4) and c(8 × 8) were observed from layers grown at the low temperature of 400°C. The electrical and optical properties of layers doped with Si were investigated by measurement of Hall effect and photoluminescence as a function of growth temperature. It is found that a semi-insulating layer is grown below a critical temperature, and the layer is useful as a buffer layer for GaAs FET's. Variation of carrier concentration was observed near the interface between layers grown at different temperatures under a constant Sn beam flux. The effect is attributed to defect-induced segregation of Sn.     

Shallow donors and deep levels in GaAs grown by atomic layer molecular beam epitaxy

We correlate the Si concentration measured by secondary ion mass spectrometry (SIMS) and the net donor concentration in GaAs:Si grown by atomic layer molecular beam epitaxy (ALMBE); Si was supplied during: (a) both the As and the Ga subcycles, (b) the As subcycle, and (c) the Ga subcycle; the layers were grown at temperatures in the 300-530°C range. The results show that Si incorporation and its compensation depend on the Si-supply scheme and that the extent of compensation decreases with the growth temperature. We also study the deep levels in the ALMBE GaAs grown under the above conditions. Our results show the occurrence of M1, M3 and M4 levels with concentrations that are: (i) essentially independent of both the Si supply scheme and the ALMBE growth temperature, (ii) close to those of MBE GaAs grown at 600°C, and (iii) up to 2 orders of magnitude lower than that of GaAs prepared by molecular beam epitaxy (MBE) at similar temperatures.     

Heteroepitaxial growth of GaP on silicon

Epitaxial gallium phosphide layers have been grown on silicon substrates by the metal-organic process. This process involves the reaction between trimethylgallium (CH₃)₃Ga and PH₃ and gives a high density of nucleation sites on the silicon. The influence of the substrate orientation and of the deposition temperature on the crystallinity of the layers has been studied. Best results were obtained on (001) oriented substrate at a deposition temperature of 800°C. X-ray reflection topographs of the layers have revealed the formation of cracks extending along the [110] direction, which are explained by the lattice mismatch and the difference in thermal expansion coefficients. The cracking is asymmetric with the main direction parallel to [110]. The density of cracks can be reduced by a two stage epitaxy. The electrical properties of undoped and n-type doped layers have been assessed by Hall and C(V) measurements. It shows auto-doping with silicon coming from the substrate.     

Growth and characterization of SSD InP crystals used as substrates for infra-red LED's

Bulk indium phosphide crystals have been grown by the synthesis, solute diffusion (SSD) method. Various growth temperatures and temperature gradients in the indium melt were investigated. The growth temperature of about 850–900°C and the temperature gradient of about 10–15°C cm⁻¹ were found as the most suitable growth conditions. All grown crystals were of the n-type either undoped or doped with Te or Sn. Infrared light-emitting junctions were grown by single LPE process. Characteristic surface structures of InP epitaxial layers as a function of the growth temperature and cooling rate were observed. Efficiencies of LED's have been typically 0.8%. Single LPE process on LEC InP substrates has given LED's with substantially lower efficiencies.     

Silicon compensation and scattering mechanisms in two-dimensional electron gases on (110)GaAs

A study of the MBE growth of (001) and (110) (Al,Ga)As is reported, and the efficiency of Si as an n-type dopant in (110)GaAs is accessed. A 40 nm spacer two-dimensional electron gas (2DEG) structure grown on (110)GaAs gives a mobility of 540,000 cm² V⁻¹ s⁻¹ at 4 K after illumination. The dominant scattering mechanisms in 2DEGs on (110) and (001)GaAs grown under the separate optimum growth conditions for the two orientations are compared.     

Spatiotemporal protein crystal growth studies using microfluidic silicon devices

Fundamental investigations of protein crystallization using miniaturized microfluidic silicon devices were presented towards achieving spatiotemporal nucleation and subsequent post-nucleation growth. The developed microfluidic silicon device was typically composed of crystal growth cell, reservoir cell, and optionally of heater elements for supersaturation control. A specific fine pattern area in the growth cell which was fabricated on the silicon substrate with doped p- and n-type silicon layers, served as spatially selective nucleation site of dissolved protein molecules through electrostatic attractive force. In a model material, hen egg white lysozyme, a large number of crystals were grown on the defined nucleation site evenly spaced from each other, whereas parasitic crystal growth positioned around the selective nucleation site, was suppressed by the effects of electrostatic repulsive force between the doped silicon surface and charged protein molecules. A possible crystallization mechanism of describing the heterogeneous nucleation during the initial stage and during the growth of the crystal at the electrolyte–semiconductor silicon surface is proposed and discussed.     

Er doping of Si and Si0.88Ge0.12 using Er2O3 and ErF3 evaporation during molecular beam epitaxy A transmission electron microscopy study

The incorporation behavior of Er into Si and Si_0.88Ge_0.12 using ErF₃ and Er₂O₃ as dopant sources during molecular beam epitaxy has been studied. The Er-compounds were thermally evaporated from a high-temperature source. Dissociation of Er₂O₃ took place and reaction with graphite parts in the high temperature source gave an increased CO background pressure and evaporation of metallic Er. Surface segregation of Er may be strong, but with a high CO or F background pressure, the surface segregation could be reduced and sharp Er concentration profiles were obtained. Transmission electron microscopy analysis shows that it is possible to prepare high crystalline quality structures with Er concentrations up to 4×10¹⁹ cm⁻³ using Er₂O₃ and a high F background pressure. Using ErF₃ compound as source material a F/Er incorporation ratio of approximately three has been measured by secondary ion mass spectrometry. Fluorine incorporation can occur not only from evaporated units of ErF₃ molecules, but also from CF_x (x=1–4) and F background species, which are present due to a reaction between the ErF₃ source material and the graphite crucible in the source. After careful degassing of the source, the partial pressures of these species can be significantly reduced. By producing an Er-doped multilayer structure consisting of alternating doped layers grown at low temperature (350°C) and undoped layers grown at a higher temperature (630°C), a flat surface could be maintained during the growth sequence. In this way it was possible to prepare Er-doped structures with an average Er concentration of 1×10¹⁹ cm⁻³ and without observable defects using ErF₃ as source material. For the case of Er-doping of Si_0.88Ge_0.12 using ErF₃, we observed contrast along lines in the growth direction at an Er concentration of 1×10¹⁹ cm⁻³, which was attributed to Si concentration variations. Intense emission related to Er has been observed by electro- and photoluminescence.     

Photoluminescence characteristics of Mg- and Si-doped GaN thin films grown by MOCVD technique

We have studied the optical, structural and surface morphology of doped and undoped GaN thin films. The p- and n-type thin films have been successfully prepared by low-pressure MOCVD technique by doping with Mg and Si, respectively. The different carrier concentrations were obtained in the GaN thin films by varying dopant concentrations. Photoluminescence (PL) studies were carried to find the defect levels in the doped and undoped GaN thin films at low temperature. In the undoped GaN thin films, a low intensity and broad yellow band peak was observed. The donor–acceptor pair (DAP) emission and its phonon replicas were observed in both the Si or Mg lightly doped GaN thin films. The dominance of the blue and the yellow emissions increased in the PL spectra, as the carrier concentration was increased. The XRD and SEM analyses were employed to study the structural and surface morphology of the films, respectively. Both the doped and the undoped films exhibited hexagonal structure and polycrystalline nature. Mg-doped GaN thin films showed columnar structure whereas Si-doped films exhibited spherical shape grains.     

Influence of arsenic flow on the crystal structure of epitaxial GaAs grown at low temperatures on GaAs (100) and (111)<Emphasis Type="Italic">A</Emphasis> substrates

The influence of arsenic flow in a growth chamber on the crystal structure of GaAs grown by molecular-beam epitaxy at a temperature of 240°C on GaAs (100) and (111)A substrates has been investigated. The flow ratio γ of arsenic As4 and gallium was varied in the range from 16 to 50. GaAs films were either undoped, or homogeneously doped with silicon, or contained three equidistantly spaced silicon δ-layers. The structural quality of the annealed samples has been investigated by transmission electron microscopy. It is established for the first time that silicon δ-layers in “low-temperature” GaAs serve as formation centers of arsenic precipitates. Their average size, concentration, and spatial distribution are estimated. The dependence of the film structural quality on γ is analyzed. Regions 100–150 nm in size have been revealed in some samples and identified (by X-ray microanalysis) as pores. It is found that, in the entire range of γ under consideration, GaAs films on (111)A substrates have a poorer structural quality and become polycrystalline beginning with a thickness of 150–200 nm.     

Etch Pit Density Distributions in Undoped and Doped GaAs Single Crystals

The undoped and doped (Si, N, In) GaAs single crystals are grown by horizontal Bridgman technique. The etch pit density (EPD) profiles were measured in transverse direction for each crystal. It was found that the shape of EPD profiles differs in dependence on the used dopant.     

System of Mathematical Models for the Analysis of Industrial FZ-Si-Crystal Growth Processes

A system of coupled mathematical models and the corresponding program package is developed to study the interface shape, heat transfer, thermal stresses, fluid flow as well as the transient dopant segregation in the floating zone (FZ) growth of large silicon crystals (diameter more than 100mm) grown by the needle-eye technique. The floating zone method with needle-eye technique is used to produce high-purity silicon single crystals for semiconductor devices to overcome the problems resulting from the use of crucibles. The high frequency electric current induced by the pancake induction coil, the temperature gradients and the feed/crystal rotation determine the free surface shape of the molten zone and cause the fluid motion. The quality of the growing crystal depends on the shape of the growth interface, the temperature gradients and corresponding thermal stresses in the single crystal, the fluid flow, and especially on the dopant segregation near the growth interface. From the calculated transient dopant concentration fields in the molten zone the macroscopic and microscopic resistivity distribution in the single crystal is derived. The numerical results of the resistivity distributions are compared with the resistivity distributions measured in the grown crystal.     

LPE growth of DH laser structures with the double source method

For the reproducible processing of double heterojunction injection laser structures to stripe geometry laser diodes, e.g. by proton bombardment, the thickness of the p-Ga_0.7Al_0.3As confining layer and of the p-GaAs top layer are of great importance. It is shown that the thickness control of these layers grown by liquid phase epitaxy can be improved considerably by introducing two source crystals into the growth system. Both source crystals are brought into contact with the solutions consecutively and prior to the seed. If this method is combined with the use of relatively thin melts (about 2 mm), a growth scheme may be chosen such that the growth rates of the p-GaAlAs and of the p-GaAs layers have reached a practically constant value on the seed crystal, independent of the initial degree of supersaturation. This behaviour is found to be in accordance with the diffusion-limited growth model applied for thin solutions, including a temperature dependence for both the diffusion constant and the slope of the liquidus curve. The results indicate that a second solid phase may appear in the p-GaAlAs solutions at a supersaturation as small as 4°C, which reduces the growth rate on the substrates by a factor of about 2. This situation is different from that of GaAs solutions, where a second phase appears only at a much higher degree of supersaturation. For the p-GaAlAs and the p-GaAs layers a thickness control of ⁺_-0.2 μm is thus achieved with this growth method, without the necessity of very precise temperature control and weighing so as to keep the total supersaturation less than 0.2°C.     

Tin and tellurium doping of InAs using SnTe in molecular beam epitaxy (MBE)

Tin telluride (SnTe) was utilized as an n-type dopant in the MBE growth of InAs epitaxial layers on GaAs substrates. The highest carrier concentration obtained was 2.9 × 10¹⁹ cm^-3 and the carrier density could be varied over three orders of magnitude by changing the SnTe source temperature. The highest mobilities obtained were 16,900 and 23,300 cm²/V … s at 300 and 77 K, respectively, for carrier concentration of 5 × 10¹⁶ cm^-3. Both Sn and Te were incorporated in the layers as determined by secondary ion mass spectroscopy (SIMS) analysis and the total concentration of Sn and Te were the same as the carrier density in the layer.     

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.     

Growth of ZnTe layers on (111) GaAs substrates by metalorganic vapor phase epitaxy

ZnTe layers were grown on (111) GaAs substrates by metalorganic vapor phase epitaxy using dimethylzinc and diethyltelluride as the source materials. X-ray diffraction analysis revealed that epitaxial ZnTe layers can be obtained on (111) GaAs substrates. X-ray rocking curves, Raman spectroscopy, and photoluminescence measurements showed that the crystal quality of ZnTe layers depends on the substrate temperature during the growth. A high-crystalline quality (111) ZnTe heteroepitaxial layer with strong near-band-edge emission at 550 nm was obtained at a substrate temperature of 440 °C.     

Epitaxial growth of α-SiC layers by chemical vapor deposition technique

Single crystals of α-SiC were grown on α-SiC substrates at a temperature between 1570 and 1630°C with the standard gas flow rate: H₂ ～ 1 liter/min, SiCl₄ ～ 1.7 ml/min and C₃H₈ ～ 0.1 ml/min. The grown layers were transparent greenish-blue, and surfaces were mirror-like. By an X-ray back-reflection Laue pattern and a reflection electron diffraction method, the grown layer was identified as 6H-SiC, one polytype of α-SiC. Crystal growth was influenced by substrate temperature, flow rates of reaction gases and the surface polarity of the substrate. The growth rate decreased with increase of the substrate temperature in the above temperature region. A lamellar structure was observed on the (0001) Si surface and a mosaic structure was observed on the (000$\text{1}$)C surface. The mole ratios of both SiCl₄ and C₃H₈ to H₂ and that of Si to C had some influence on crystal growth. Undoped layers were n-type due to nitrogen. P-type SiC was grown by doping Al during crystal growth. Doping effects were studied by photoluminescence and electrical measurements.     

利用Al/AlAs中间层调控GaAs在Si(111)上外延生长的研究

为了实现Ⅲ-V器件在硅基平台上单片集成,近年来Ⅲ-V半导体在硅衬底上的异质外延得到了广泛研究。由于Ⅲ-V半导体与Si之间大的晶格失配以及晶格结构不同,在Si上生长的Ⅲ-V半导体中存在较多的失配位错及反相畴,对器件性能造成严重影响。而Si(111)表面的双原子台阶可以避免Ⅲ-V异质外延过程中形成反相畴。本文利用分子束外延技术通过Al/AlAs作为中间层首次在Si(111)衬底上外延生长了GaAs(111)薄膜。通过一系列对比实验验证了Al/AlAs中间层的插入对GaAs薄膜质量的调控作用,并在此基础上通过低温-高温两步法优化了GaAs的生长条件。结果表明Al/AlAs插层可以为GaAs外延生长提供模板,并在一定程度上释放GaAs与Si之间的失配应力,从而使GaAs薄膜的晶体质量得到提高。以上工作为Ⅲ-V半导体在硅上的生长提供了新思路。     

HigHighly strained InGaAs/GaAs quantum wells emitting beyond 1.2 µm

Highly strained In_xGa_1–xAs quantum wells (QWs) with GaAs barriers emitting around 1.2 µm are grown on GaAs substrates by metal organic vapour phase epitaxy (MOVPE) at low growth temperatures using conventional precursors. The effects of growth temperature, V/III ratio and growth rate on QW composition and luminescence properties are studied. The variation of indium incorporation with V/III ratio at a growth temperature of 510 °C is found to be opposite to the results reported for 700 °C. By an appropriate choice of the growth parameters, we could extend the room temperature photoluminescence (PL) wavelength of InGaAs/GaAs QWs up to about 1.24 µm which corresponds to an average indium content of 41% in the QW. The results of the growth study were applied to broad area laser diodes emitting at 1193 nm with low threshold current densities. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ionenstrahlgestäubte GaAs-Schichten auf verschiedenen einkristalline Substraten

Thin GaAs-films have been deposited on spinel, (111)-Si, and (100)-GaAs by ion beam sputtering. The beam system operated with argon ions at a vacuum of 5…︁8 · 10⁻⁶ torr in the chamber. Undoped polycrystalline GaAs was used as target material. The film proporties were investigated by electron optical methods (RHEED respective by C/Pt replica). Substrate temperatures were varied between 180 and 590 °C, and deposition rates were adjusted between 1…︁3 Å/s. Within a relative narrow temperature range epitaxial layers of good quality were obtained; the optimum values being 540 °C in case of GaAs/Si or 400…︁450 °C for GaAs/GaAs. Films deposited at higher temperatures showed extended defects induced by gallium excess because of dissociation.     

Investigations on the HCl gas-phase etching of differently doped and oriented gaas crystals

The influence of the orientation and dopant on the dissolution of GaAs surfaces in H₂–HCl gas mixtures has been investigated. For this purpose the etch rates, temperature regions of different etching behaviour and the corresponding activation energies were determined for temperatures ranging from 540 °C to 945 °C. The etch rate anisotropy is correlated with the three existing temperature regions of different dissolution mechanisms. The orientation-dependent transition temperatures are influenced by the dopant and can be related to the thermodynamic data of the dopant.