CBE growth of GaAs/GaAlAs HBTs using the new DEAlH-NMe3 precursor and all-gaseous dopants

This paper describes the first reported use of diethylaluminium hydride-trimethylamine adduct (DEAlH-NMe₃) for the growth of GaAs/GaAlAs power heterojunction bipolar transistors (HBTs) by chemical beam epitaxy (CBE). This precursor possesses a significantly higher vapour pressure than the more conventionally used triethylaluminium (TEA), and leads to much less stringent requirements for bubbler and gas-line heating, and also much-improved GaAs/GaAlAs heterojunction definition when no carrier gas is employed. The use of all-gaseous n- and p-type dopants offers significant technological advantages in CBE, and the current paper also provides the first report of the use of hydrogen sulphide for n-type doping of CBE-grown GaAlAs HBT emitter regions. In conclusion, DC and RF data obtained from the heterojunction bipolar transistors fabricated to date are described. A DC gain of 40 has already been measured and encouraging early data obtained from RF-probed devices are also presented.     

Reaction kinetics for the CBE growth of GaAs from triethylgallium; computer modelling studies incorporating recent surface spectroscopic data

A new model for the decomposition of triethylgallium on GaAs(100), with kinetic parameters derived from the results of surface science experiments, is presented. Deficiencies of early models are corrected by including surface coverage and site blocking effects, and lateral interactions between absorbed DEG species are included. The model successfully predicts variations in the rate of CBE growth of GaAs with substrate temperature, and addresses effects induced by variations in arsenic overpressure. This dependence of growth rate on the arsenic flux is modelled by computing the steady state concentrations of absorbed arsenic as a function of temperature and As₂ and TEG flux. Excess arsenic is shown to inhibit GaAs growth by blocking sites for TEG absorption.     

CBE growth of GaAs/GaAs, GaAs/Si and AlGaAs/GaAs using TEG, AsH3 and amine-alane precursors

The growth of high quality AlGaAs by CBE has been limited by the high levels of carbon and oxygen contamination. The use of alane based precursors offers a significant reduction in such contamination. We report for the first time the CBE growth of Al_xGa_1−xAs from triethylgallium, dimethylethylamine-alane and arsine, and compare with. growth from triethylgallium, trimethylamine-alane and arsine. Some preliminary results of work on the CBE growth of GaAs on silicon will also be reported.     

p-Type GaAs doped by diiodomethane (CI2H2) in molecular beam epitaxy, metalorganic molecular beam epitaxy, and chemical beam epitaxy

Highly p-type carbon-doped GaAs epitaxial layers were obtained using diiodomethane (CI₂H₂) as a carbon source. In the low 10¹⁹ cm⁻³ range, almost all carbon atoms are electrically activated and at 9×10¹⁹ cm⁻³, 91% are activated. The carbon incorporation efficiency in GaAs layers grown by metalorganic molecular beam epitaxy (MBE) and chemical beam epitaxy (CBE) is lower than that by MBE due to the site-blocking effect of the triethylgallium molecules. In addition, in CBE of GaAs using tris-dimethylaminoarsenic (TDMAAs), the carbon incorporation is further reduced, but it can be increased by cracking TDMAAs. Annealing studies indicate no hydrogenation effect.     

Laser-assisted chemical beam epitaxy for selective growth

A recent exciting development in the growth of compound semiconductors is the use of light to modify the film growth rate in the irradiation area. We report Ar⁺-laser-assisted CBE of GaAs, InP, GaP and InGaAs to generate various patterned films without lithography. A linked-circle pattern is formed by laser beam scanning and a 0.85 μm pitch corrugation pattern formed by a holographic interference technique. Relationships between the growth rate and substrate temperature for the materials are compared. The mechanism of the growth rate enhancement is revealed to be photolytic decomposition of metalorganic molecules. In the case of InGaAs, laser irradiation above 500°C results in new phenomena of growth rate suppression and composition variation.     

Anisotropy in InGaAs/GaAs heterostructures grown by low-pressure MOVPE and CBE

InGaAs/GaAs heterostructures grown on (001) substrates by low-pressure MOVPE exhibit a measurable anisotropy in their structural, optical and electrical properties. This anisotropy occurs in structures which have undergone partial or complete strain relaxation and it can be strongly reduced by using slightly misoriented substrates. A comparison with similar structures grown by CBE indicates that this anisotropy is less important. This study suggests that strain relaxation is achieved by a combination of several mechanisms whose relative importance depends on the orientation of the substrate and on growth temperature which varies with the growth technique.     

Dependence of InP and GaAs chemical beam epitaxy growth rate on substrate orientations; applications to selective area epitaxy

In order to optimize the shape of chemical beam epitaxy (CBE) selective area growth, growth rates on (100), (111)B, (111)A and (110) substrate orientations have been examined for GaAs and InP materials. (111)B GaAs growth rate appears to be drastically enhanced at low V/III ratio, which has been applied to grow selective GaAs patterns limited by vertical sidewalls. Concerning InP, high growth rates were obtained on all orientations. This was used to perfectly fill a rectangular groove by selective embedded InP growth.     

XeCl excimer laser assisted CBE growth of GaAs

The effect of 12 ns, 308 nm (XeCl) excimer laser pulses on the CBE growth rate of GaAs, at temperatures below the maximum non-laser assisted growth rate, G_max, has been studied as a function of laser fluence and repetition frequency. There is a threshold fluence for growth rate enhancement, above which the growth rate is dependent on repetition frequency, being restored to G_max at 20 Hz. The growth rate in the laser spot is measured by dynamic optical reflectivity (DOR).     

RHEED studies of MOMBE growth using TMGa or TEGa with As2

MOMBE and CBE growth has until recently been based on largely empirical studies of the epitaxial process. We have used reflection high energy electron diffraction (RHEED), previously applied to the study of MBE, to study the growth GaAs using TMGa and As₂. In this work we have extended our previous studies to include a detailed study of the effect of As₂ flux on growth rate and to compare data on singular and vicinal plane surfaces cut off orientation in two orthogonal {110} directions. Clear evidence for site blocking mechanisms is observed together with an indication that the concentration of elemental Ga present on the surface during growth is negligible even under conditions where the arrival rate of TMGa exceeds that As₂. We have compared this behaviour with that observed using TEGa and As₂ under identical conditions. Using TEGa a conversion from a (2×4) to (4×2) reconstructed surface is observed under As deficient conditions indicating the presence of elemental Ga on the surface. This is accompanied by an abrupt change in growth rate similar to that secn in MBE.     

Recent progress in multi-wafer CBE systems

We describe the recent progress of multi-wafer CBE systems demonstrating their potential capability of producing III–V semiconductor device structures with excellent uniformity and state-of-the-art performance. Up to three 4 inch wafers can be grown simultaneously with excellent uniformity and extremely small wafer-to-wafer variation (x in Al_xGa_1−x As: 0.2136 ± 0.0014). A specifically designed high-conductance metalorganic gas cell with a tilted aperture without any diffuser gives a high uniformity together with a fast switching at the heterointerfaces. An intrinsic difficulty for obtaining good compositional uniformity of ternary alloys containing indium is overcome by improvement in the design of an In-free substrate holder showing a uniform temperature profile within ± 0.9°C across a whole wafer. To extend the capability of CBE, an in situ cleaning method which combines hydrogen radical cleaning and As-free cleaning was investigated. The n-type GaAs epilayers showed a reduced depletion of electrons at the air-exposed regrown interface. From SIMS analysis, hydrogen radical and As-free cleaning show stronger effects on gettering carbon, and oxygen, respectively. Some C contamination during the 2nd As-free cleaning procedure is expected to be eliminated by decreasing the treatment temperature from the separately optimized one. The successful cleaning of InP substrates using trisdimethylaminophosphorous (TDMAP) would also extend the capability of CBE for the reproducible growth of large area (> 3 × 3 inch) InP-based materials.     

Kinetics and mechanisms of surface reactions in epitaxial growth of Si from SiH4 and Si2H6

Surface science and kinetic modelling studies of the surface chemical mechanisms active during low pressure chemical vapor deposition (CVD) and chemical beam epitaxy (CBE) growth of Si from mono- and disilane are summarized. Time-of-flight direct recoiling (DR) is discussed as an in situ method to analyze the composition of the growth interface. Steady state measurements of surface hydrogen coverage (θ_H) are made by DR in situ during CBE Si growth from Si₂H₆ and SiH₄, and are illustrated here. Key results using other experimental methods are briefly discussed.     

Incorporation of phosphorus during gas phase epitaxy

The PH₃ desorption rate can be reduced and the decomposition rate increased, thereby increasing the P incorporation efficiency by replacing TMIn with InCl created by the pyrolysis of DEIn. InCl generated by cracking DEInCl and uncracked PH₃ could be used for CBE growth of InP provided that H on the PH₃ can be used to remove Cl from the InCl. Evidence is presented that this is possible. Evidence is also provided that P is more readily incorporated during OMVPE growth using TBP than PH₃ because PH₂ is a primary pyrolysis product, and it is less likely to desorb and more likely to decompose than PH₃.     

Extremely flat interfaces in GaAs/AlGaAs quantum wells with high Al content(0.7) grown on GaAs (411)A substrates by molecular beam epitaxy

Effectively atomically flat interfaces over a macroscopic area (200 μm diameter) have been achieved in GaAs/Al_0.7Ga_0.3As quantum wells (QWs) with well widths of 3.6-12 nm grown on (411)A GaAs substrates by molecular beam epitaxy (MBE) for the first time. A single and very narrow photoluminescence peak (FWHM, full width at half maximum, is 6.1 meV) was observed at 717.4 nm for the QW with a well width of 3.6 nm at 4.2 K. The linewidth is comparable to that of growth-interrupted QWs grown on (100)-oriented GaAs substrates by MBE. A 1.5 μm thick Al_0.7Ga_0.3As layer with good surface morphology also could be grown on (411)A GaAs substrates in the entire growth temperature region of 580-700°C, while rough surfaces were observed in Al_0.7Ga_0.3As layers simultaneously grown on (100) GaAs substrates at 640-700°C. These results indicate that the surface of GaAs and Al_0.7Ga_0.3As grown on the (411)A GaAs substrates are extremely flat and stable on the (411)A plane.     

Growth of GaAs/AlGaAs HBTs by MOMBE (CBE)

In this paper, we will discuss how the unique growth chemistry of MOMBE can be used to produce high speed GaAs/AlGaAs heterojunction bipolar transistors (HBTs). The ability to grow heavily doped, well-confined layers with carbon doping from trimethylgallium (TMG) is a significant advantage for this device. However, in addition to high p-type doping, high n-type doping is also required. While elemental Sn can be used to achieve doping levels up to 1.5×10¹⁹ cm^-3, severe segregation limits its use to surface contact layers. With tetraethyltin (TESn), however, segregation does not occur and Sn doping can be used throughout the device. Using these sources along with triethylgallium (TEG), trimethylamine alane (TMAA), and AsH₃, we have fabricated Npn devices with 2 μm×10 μm emitter stripes which show gains of ≥ 20 with either ƒ_t = 55 GHz and ƒ_max = 70 GHz or ƒ_t = 70 GHz and ƒ_max = 50 GHz, depending upon the structure. These are among the best RF values reported for carbon doped HBTs grown by any method, and are the first reported for an all-gas source MOMBE process. In addition, we have fabricated a 70 transistor decision circuit whose performance at 10 Gb/s equals or exceeds that of similar circuits made from other device technologies and growth methods. These are the first integrated circuits reported from MOMBE grown material.     

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。     

A comparative study of GaAs- and InP-based HBT growth by means of LP-MOVPE using conventional and non gaseous sources

Low-pressure metalorganic vapor phase epitaxy (LP-MOVPE) growth of carbon doped (InGa)P/GaAs and InP/(InGa)As heterojunction bipolar transistors (HBT) is presented using a non-gaseous source (ngs-) process. Liquid precursors TBAs/TBP for the group-V and DitBuSi/CBr₄ for the group-IV dopant sources are compared to the conventional hydrides AsH₃/PH₃ and dopant sources Si₂H₆/CCl₄ while using TMIn/TEGa in both cases. The thermal decomposition of the non gaseous sources fits much better to the need of low temperature growth for the application of carbon doped HBT. The doping behavior using DitBuSi/CBr₄ is studied by van der Pauw Hall measurements and will be compared to the results using Si₂H₆/CCl₄. Detailed high resolution X-ray diffraction (HRXRD) analysis based on 004 and 002 reflection measurements supported by simulations using BEDE RADS simulator enable a non-destructive layer stack characterization. InGaP/GaAs HBT structures designed for rf-applications are grown at a constant growth temperature of T_gr=600°C and at a constant V/III-ratio of 10 for all GaAs layers. P-type carbon concentrations up to P = 5·10¹⁹cm⁻³ and n-type doping concentrations up to N = 7·10¹⁸cm⁻³ are achieved. The non self-aligned devices (A_E = 3·10 μm²)_show excellent performance, like a dc-current gain of B_max = 80, a turn on voltage of V_offset = 110 mV (Breakdown Voltage V_CEBr,0 > 10 V), and radio frequency properties of f_T/f_max = 65 GHz/59 GHz.

In the non-gaseous source configuration the strong reduction in the differences of V/III-ratios and temperatures during HBT structure growth enable easier LP-MOVPE process control. This is also found for the growth InP/InGaAs HBT where a high dc-current gain and high transit frequency of f_T= 120 GHz are achieved.     

Effects of pressure and temperature on RD detected growth oscillations

We report on the vacuum chemical epitaxy (VCE) growth of GaAs from triethylgallium and arsine at varying partial pressures of arsine and hydrogen. In situ, monolayer growth oscillations were, for the first time, detected in a hydrogen environment using reflectance difference (RD). These results offer the possibility to link surface mechanisms occuring during chemical beam epitaxy (CBE) with those taking place in metalorganic vapour phase epitaxy (MOVPE) and may lead to the observation of growth oscillations also during MOVPE. Finally, the behaviour of the RD signal as a function of substrate temperature is studied over a wider temperature interval than has previously been reported, giving further information about surface processes.     

Strong enhancement of the optical and electrical properties, and spontaneous formation of an ordered superlattice in(111)B AlGaAs

Strong enhancement in the luminescence intensity is observed in Al_0.22Ga_0.78As epitaxial layers grown on misoriented (111)B GaAs as compared to those simultaneously grown on (100) GaAs. For a 1° misorientation the luminescence intensity is almost 1° to 1000 times that of the (100) layers, depending on the growth temperature. Room temperature electron mobility for 3° misoriented (111)B Al_0.18Ga_0.82As is 19% higher than that for side-by-side grown (100). The strong luminescence associated with a large red shift of 90 meV and the 19% mobility enhancement are related to the long range composition ordering in (111)B AlGaAs, which is observed by cross-sectional transmission electron microscopy in a 280 å Al_0.4GaAs quantum well heterostructure with Al_0.7GaAs barriers grown on (111)B GaAs substrates.     

Surfactant-mediated molecular-beam epitaxy of III-V strained-layer heterostructures

In this review we first present the two classes of non-reactive and reactive surfactants effective during homoepitaxy and heteroepitaxy, respectively. We then describe and analyse the results obtained by "true" surfactant-mediated molecular-beam epitaxy (SM-MBE) of Ga_1−xIn_xAs layers on GaAs substrates. Then, the data obtained by using In as a "virtual" surfactant during SM-MBE of InAs layers on Al_xGa_0.48−xIn_0.52As/InP and GaAs substrates are presented. We finally provide evidence that the growth mode influences the resulting defect microstructure in (partially) relaxed layers.     

The growth and physics of ultra-high-mobility two-dimensional hole gas on (311)A GaAs surface

We report on the molecular beam epitaxy growth of modulation-doped GaAs-(Ga,Al)As heterostructures on the (311)A GaAs surface using silicon as the acceptor. Two-dimensional hole gases (2DHGs) with low-temperature hole mobility exceeding 1.2×10⁶ cm² V⁻¹ s⁻¹ with carrier concentrations as low as 0.8×10¹¹ cm⁻² have been obtained. This hole mobility is the highest ever observed at such low densities by any growth technique. We also report the first observation of persistent photoconductivity in a 2DHG. An analysis of the number density and temperature dependence of the mobility leads us to conclude that the mobility is limited by phonon scattering above 4 K and interface scattering at lower temperatures.