Thermodynamics of GaAs nanowire MBE growth with gold droplets

The thermodynamics of growth conditions of GaAs nanowires using gold droplets is analyzed. Equilibrium conditions for steady-state growth using experimental molecular beam epitaxy (MBE) impinging molecular flows, as previously published, are calculated in the range 793–893 K. These show that: (i) the tie line for Ga liquidus composition in equilibrium with GaAs(s) is in the 0.4–0.6 mole fraction range, close to the GaAu–GaAs pseudo-binary section, (ii) the As content of the droplet is in the 0.2–0.4×10⁻³ mole fraction range and (iii) the growth rate is mainly governed by the contact angle that determines the droplet section. Different cooling conditions are analyzed using the Scheil–Guliver assumptions to compare final phases after solidification, as analyzed by X-ray diffraction (XRD), with our calculations. The agreement is very good and this feature demonstrates that quasi-equilibrium conditions prevail in the growth process of nanowires.     

GaN/GaAs(1 0 0) superlattices grown by metalorganic vapor phase epitaxy using dimethylhydrazine precursor

Superlattices of cubic gallium nitride (GaN) and gallium arsenide (GaAs) were grown on GaAs(1 0 0) substrates using metalorganic vapor phase epitaxy (MOVPE) with dimethylhydrazine (DMHy) as nitrogen source. Structures grown at low temperatures with varying layer thicknesses were characterized using high resolution X-ray diffraction and atomic force microscopy. Several growth modes of GaAs on GaN were observed: step-edge, layer-by-layer 2D, and 3D island growth. A two-temperature growth process was found to yield good crystal quality and atomically flat surfaces. The results suggest that MOVPE-grown thin GaN layers may be applicable to novel GaAs heterostructure devices.     

Atomic Processes during Crystal Growth Studied by Reflection High-Energy Electron Diffraction

After a short retrospect on the development of the electron diffraction techniques it is shown that the atomic-scale morphology of the crystal surface and growth processes on it can be studied in detail during molecular beam epitaxy (MBE) by reflection high-energy electron diffraction (RHEED). This is demonstrated for the evolution of the terrace-step-structure of the singular GaAs (001) surface during growth and after growth interruption and for the attachment of Si atoms at misorientation steps on vicinal GaAs (001) surfaces.     

In-situ and ex-situ characterization of GaAs/AlAs quantum well structures using spectroscopic ellipsometry

Spectroscopic ellipsometer is used to monitor the MBE growth of quantum well structures. Real time monitoring of the growth enabled the measurement of growth rate and correlation with RHEED oscillations. The growth of a single GaAs/AlAs quantum well is also monitored in real time using multiple wavelengths. Interface roughness of the interrupted “inverted” AlAs/GaAs interface was also monitored with SE. Under our growth conditions, we measure approximately a 2 ML interfacial region at the inverted interface. A correlation with photoluminescence is also discussed.     

The influence of the growth rate and V/III ratio on the crystal quality of InGaAs/GaAs QW structures grown by MBE and MOCVD methods

The influence of the growth rate and V/III ratio on the crystal quality of In_0.2GaAs/GaAs quantum well structures was examined. The investigated heterostructures were grown by molecular beam epitaxy (MBE) and metalorganic chemical vapour deposition (MOCVD). Reflection high energy electron diffraction (RHEED), photoluminescence measurements (PL), high-resolution X-ray diffraction (HRXRD) and atomic force microscopy (AFM) were applied for evaluation of the interfaces smoothness and the overall layer quality. Comprehensive characterisation of InGaAs/GaAs structures allowed us to establish optimal values of analysed technological parameters. Moreover, the comparison between the results obtained for samples grown by two different epitaxial techniques allowed us to find, which of the analysed growth parameters has the strongest influence on the quality of MBE and MOCVD grown structures. In contrast with the growth temperature and the interruption time, which in different manner impact on the crystal quality of QWs obtained by different method, the growth rate and the V/III ratio play similar role in both epitaxial techniques.     

The influence of the lattice misfit on the growth of CuGaSe2 Epitaxial Films on {100}-oriented GaAs and GaP Substrates

CuGaSe₂ epitaxial layers were prepared on GaAs and GaP {100}-oriented substrates by flash evaporation technique and characterized by RHEED. Different epitaxial relationships have been found for growth on the different types of substrate material. The orientation is determined by the minimum misfit.     

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.     

Surface morphology of carbon-doped GaAs grown by MOVPE

The development of the surface structures of carbon-doped epitaxial GaAs layers grown by metalorganic vapor phase epitaxy was investigated by atomic force microscopy (AFM). Carbon-doped GaAs layers were grown using trimethyl gallium and a mixture of AsH₃/TMAs. The AFM micrographs were quantitatively analyzed through the determination of the height-height and height-difference correlation functions, which yields both the short and long range surface structures. The incorporation of carbon leads to the progressive roughening of the GaAs surface as well as an increase in surface correlation length. The high concentration of surface-adsorbed methyl radicals are suggested to lead to the diminution of growth rate and change in surface structure.     

GaSb薄膜生长的RHEED研究

采用分子束外延技术,在GaAs衬底上生长GaSb薄膜时,利用反射式高能电子衍射仪(RHEED)对衬底表面清洁状况、外延层厚度等进行在线监控.通过RHEED讨论低温缓冲层对GaSb薄膜表面结构和生长机制的作用,可以估算衬底温度,并能计算出薄膜的生长速率.实验测量GaSb的生长周期为1.96s,每秒沉积0.51单分子层.低温缓冲层提高了在GaAs衬底上外延GaSb薄膜的生长质量.     

Simultaneous reflection high-energy electron diffraction oscillations and mass spectroscopy investigations during molecular beam epitaxy growth of (001) GaAs - smooth surfaces or stoichiometric films?

Film composition and surface morphology of molecular beam epitaxy (MBE)-grown GaAs(001) surfaces were investigated in situ as a function of flux ratio J_Ga/J_As4. The flux of As₄ molecules desorbing from the sample surface was measured with a quadrupole mass spectrometer (QMS) simultaneously with the observation of reflection high energy electron diffraction (RHEED) intensity oscillations. The incorporation ratio, given by the number of incorporated Ga atoms per As atom, was calculated independent of both the QMS data and the decreasing growth rate for growth conditions with As deficiency, as obtained from the RHEED oscillation frequency. Stoichiometric growth was found up to a flux ratio J_Ga/J_As4 ≈ 0.9. At flux ratios of 1.1 to 1.2, a minimum of the damping of the RHEED oscillation amplitude indicates a very smooth growth front profile, but Ga excess appears to be incorporated mainly in As sites without disturbing the crystal lattice. This assumption was confirmed by photoluminescence (PL) spectroscopy of films grown at a flux ratio J_Ga/J_As4 of 1.2. An additional PL peak was observed, which indicates the incorporation of Ga atoms on As sites.     

The influence of the growth temperature and interruption time on the crystal quality of InGaAs/GaAs QW structures grown by MBE and MOCVD methods

The impact of two technological parameters, i.e., the growth temperature and the interface growth interruption, on the crystal quality of strained InGaAs/GaAs quantum well (QW) structures was studied. The investigated heterostructures were grown by molecular beam epitaxy (MBE) and metalorganic chemical vapour deposition (MOCVD) under As-rich conditions. Photoluminescence (PL), reflection high-energy electron diffraction (RHEED) and atomic force microscopy (AFM) were adopted for the evaluation of specified interfaces smoothness and the quality of layers. Comparison between both epitaxial techniques allowed us to find, that the growth temperature plays more significant role in the case of structures grown by MBE technique, whereas the quality of MOCVD grown structures is more sensitive to the growth interruption. Optimum values of the investigated parameters of QW crystallization were obtained for both growth techniques.     

90° double reflection high-energy electron diffraction experiments on vicinal surfaces of GaAs

Reflection high-energy electron diffraction (RHEED) experiments recording the intensity of the specular beam in two azimuths have been carried out simultaneously. The critical temperature for the transition from 2D nucleation to step-flow growth was simultaneously estimated in the [ 10] and [110] directions by observing the disappearance of RHEED intensity oscillations on GaAs(001) substrates 2° misoriented towards GaAs(111)A. It was found that the oscillations disappear at a lower substrate temperature in the [110] azimuth. The difference in the transition temperatures was 25°C.     

AgGaSe2 on {100} and {110} GaAs—Special Features of Epitaxial Growth

AgGaSe₂ thin epitaxial layers onto {100} and {110} oriented GaAs substrates were prepared by flash evaporation technique and investigated by the RHEED method (reflection high energy electron diffraction). Special epitaxial relationships were found and the results will be discussed.     

Interface reconstruction in the Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>/GaAs(100) and In<Subscript>2</Subscript>Se<Subscript>3</Subscript>/InAs(100) nanoheterostructures

The surface of GaAs(100) and InAs(100) substrates thermally treated in selenium vapor has been investigated by transmission electron microscopy (TEM) and reflection high-energy electron diffraction. Transmission electron microscopy and high-energy electron diffraction data on these heterostructures confirms the epitaxial pseudomorphic growth of the gallium selenide Ga₂Se₃(100) and indium selenide In₂Se₃(100) phases with ordered stoichiometric cation vacancies. A model of the atomic structure of the Ga₂Se₃(100) and In₂Se₃(100) surfaces is proposed, and the 2 × 2 reconstruction of the GaAs(100) and InAs(100) surfaces after treatment in selenium vapor is discussed within this model.     

A scanning tunnelling microscopy study of the deposition of Si on GaAs(001); Implications for Si δ-doping

Atomic resolution scanning tunnelling microscopy (STM) has been used to study the adsorption of Si on GaAs(001) surfaces, grown in situ by molecular beam epitaxy (MBE), with a view to understanding the incorporation of Si in δ-doped GaAs structures. Under the low-temperature deposition conditions chosen, the clean GaAs surface is characterized by a well-defined c(4×4) reflection high-energy electron diffraction (RHEED) pattern, a structure involving termination with two layers of As. Filled states STM images of this surface indicate that the basic structural unit, when complete, consists of rectangular blocks of six As atoms with the As-As bond in the surface layer aligned along the [110] direction. Deposition of <0.05 ML of Si at 400°C onto this surface shows significant disruption of the underlying structure. A series of dimer rows are formed on the surface which, with increasing coverage, form anisotropic "needle-like" islands which show no tendency to coalesce even at relatively high coverages (0.5 ML). The formation of these islands accompanies the splitting of the 1/2 order rods in the RHEED pattern along [110]. As the Si is known to occupy only Ga sites, the Si atoms displace the top layer As atoms of the c(4×4) structure, with the displaced As atoms forming dimers in a new top layer. The results are consistent with a recently proposed site exchange model and subsequent island formation for surfactant mediated epitaxial growth.     

Selective growth and other applications of hydrogen-assisted molecular beam epitaxy

The usefulness of atomic hydrogen in molecular beam epitaxy has been demonstrated, centering around selective growth. Atomic hydrogen is effective for low-temperature cleaning of substrates, surfactant effects such as restrain of island growth and suppression of the surface migration of the adatoms and selective growth on masked or V-grooved substrates. These effects are dependent on substrate temperatures. The selective growth of GaAs has been successfully demonstrated at the conventional growth temperature and growth rate with the aid of atomic hydrogen. The main mechanism of the selective growth is the re-evaporation of Ga and As from mask materials such as SiN_x or SiO₂. Selective growth has also been observed on low-index crystal facets. On (111)A and (110) facets, no GaAs was deposited in the presence of atomic hydrogen, the flux of which is approximately the same as that of Ga. GaAs quantum wire structures have been fabricated on the substrates with V-shaped grooves. The efficient capture and confinement of carriers into wire regions have been observed by photolumenescence.     

RHEED Measurements of AgGaSe2 thin films flash evaporated onto {111} a-GaAs

AgGaSe₂ thin films were prepared by flash evaporation on {111} A-oriented GaAs substrates and investigated by reflection high energy electron diffraction (RHEED). Epitaxial growth takes place in the substrate temperature interval of T_s = 845–920 K. The azimuthal orientation of the deposit on the substrate is discussed, supposing a AgGaSe₂ c/a ratio of 1.82. It is shown that detection of twin formation in the films is possible from RHEED measurements in the <211>-azimuths with respect to the substrate.     

Arsenic-free GaAs substrate preparation and direct growth of GaAs/AlGaAs multiple quantum well without buffer layer

High-temperature treatment of GaAs substrate without As flux in a preparation chamber was investigated as a substrate surface cleaning method for molecular beam epitaxial (MBE) growth. Oxide gases such as CO and CO₂ were almost completely desorbed at a temperature above which Ga and As started to evaporate from the substrate. During the cleaning at a temperature as high as 575°C for 30 min, about 100 nm thick GaAs was evaporated from the substrate, but its surface maintained mirror-like smoothness and showed streak pattern with surface reconstruction pattern in the reflection high energy electron diffraction (RHEED) observation. Direct growth of GaAs/Al GaAs quantum well (QW) structures was tried on such surfaces without introducing any buffer layers. The QW structure showed photoluminescence with both intensity and full width at half maximum comparable with those for the QW grown on the substrate cleaned by the conventional method with introducing a GaAs buffer layer.     

MOVPE growth of GaAs on Ge substrates by inserting a thin low temperature buffer layer

High quality GaAs layers have been grown by low pressure MOVPE on Ge(001) and Ge(001) 9° off oriented in [110] direction by using a thin low temperature (LT) GaAs layer. Investigations of the initial growth step were performed at different V/III ratios and temperatures. To show the good buffer layer quality solar cell structures were grown on off oriented n‐Ge(001) and n‐GaAs(001) substrates. The surface morphology was studied by atomic force microscopy which showed the step‐flow growth mode on 1.2 µm thick GaAs/Ge structures. The crystalline qualities of this structures and the smooth surface morphology were investigated by double crystal X‐ray diffraction (XRD) and atomic force microscopy (AFM). (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Compositional effects accompanying near equilibrium vapour growth of solid solution crystals of the types IV‐VI and II‐VI

Near equilibrium evaporation‐condensation in a sealed ampoule leads to almost full compositional reproduction of a solid solution if it consists of components having comparable vapour pressures; this can be qualitatively interpreted by domination of entropy increase. Nevertheless, even vestigial separation requires closer characteristics, since it may prove crucial – particularly for properties of semiconducting solid solutions. Maximum component separation allowed by a small temperature difference is described here in terms of thermodynamics and kinetics of solid‐vapour and vapour‐solid phase transitions. Theoretical models of the determining effects having different character are shortly described, and their applicability areas are determined. Experimental data collected for crystal growth of numerous semiconducting solid solutions of the II‐VI and IV‐VI type support the conclusion drawn from the models that the near equilibrium crystal growth from the vapour in a closed system ensures the highest degree of compositional uniformity. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)