Effects of ultraviolet irradiation during growth of ZnSe epilayers by atmospheric pressure metalorganic vapor-phase epitaxy using dimethyl zinc and H2Se

This work has investigated the effects of ultraviolet irradiation on the epitaxial growth process of undoped ZnSe by atmospheric-pressure metalorganic vapor phase epitaxy. Dimethyl zinc and H₂Se at a [VI]/[II] mole ratio of 20 were the source gases used for growth onto (100)-just oriented semi-insulating GaAs substrates. Hydrogen was used as the carrier gas. A 500 W Hg-Xe lamp irradiated the substrate at 300 nm wavelength during growth. Growth temperature was varied from 210 to 450°C. Epilayers grown in the presence of irradiation experienced a prominent decrease in growth rate, which occurred even at high temperatures. Through a combination of surface and vapor-phase reactions, UV irradiation also affected the photoluminescence properties, crystalline quality, and surface morphology of the epilayers.     

Heavily carbon-doped p-type (In)GaAs grown by gas-source molecular beam epitaxy using diiodomethane

Heavily carbon-doped p-type In_xGa_1−xAs (0≤x<0.49) was successfully grown by gas-source molecular beam epitaxy using diiodomethane (CH₂I₂), triethylindium (TEIn), triethylgallium (TEGa) and AsH₃. Hole concentrations as high as 2.1×10²⁰ cm⁻³ were achieved in GaAs at an electrical activation efficiency of 100%. For In_xGa_1−xAs, both the hole and the atomic carbon concentrations gradually decreased as the InAs mole fraction, x, increased from 0.41 to 0.49. Hole concentrations of 5.1×10¹⁸ and 1.5×10¹⁹ cm⁻³ for x = 0.49 and x = 0.41, respectively, were obtained by a preliminary experiment. After post-growth annealing (500°C, 5 min under As₄ pressure), the hole concentration increased to 6.2×10¹⁸ cm⁻³ for x = 0.49, probably due to the activation of hydrogen-passivated carbon accepters.     

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 growth temperature and V/III ratio on surface structure and ordering in Ga0.5In0.5P

Surface photoabsorption (SPA) measurements were used to clarify the CuPt ordering mechanism in Ga_0.5In_0.5P layers grown by organometallic vapor phase epitaxy. The CuPt ordering is known to be strongly affected by the growth temperature and the input partial pressure of the phosphorus precursor, i.e. the V/III ratio. The SPA peak at 400 nm was found to be a measure of the concentration of [ 10]-oriented phosphorus dimers on the surface, which are characteristic of the (2 × 4) reconstruction. Both ordering, measured using the low temperature photoluminescence peak energy, and the SPA signal difference due to P dimers were studied versus the growth temperature and V/III ratio. The degree of order decreases markedly with increasing growth temperature above 620°C at a constant V/III ratio of 40. This corresponds directly to a decrease of the [ 10]-oriented P dimer concentration on the surface determined using SPA. Below 620°C, the degree of order decreases as the growth temperature decreases, even though the concentration of P dimers increases. The presence of an isotropic “excess P” phase observed in the SPA spectrum at 480 nm might be responsible for the decrease of CuPt ordering, although it has previously been attributed to the slow rearrangement of adatoms. The degree of order is found to decrease monotonically with decreasing V/III ratio in the range from 160 to 8 at 670°C and from 40 to 8 at 620°C. This also corresponds directly to the decrease of the P dimer concentration on the surface measured using SPA. At 620°C and a V/III ratio of 160, the degree of order decreased despite an increase of the P dimer concentration. This may also be due to the formation of the isotropic “excess P” phase on the surface. The direct correlation of the [ 10]-oriented P dimer concentration and the degree of order with changes in temperature ( ≥ 620°C) and V/III ratio (≤ 160 at 670°C and ≤ 40 at 620°C) suggests that, in this range of growth parameters, the (2 × 4) surface reconstruction is necessary to form the CuPt structure, in agreement with published theoretical studies.     

Characteristics of GaSb growth using various gallium and antimony precursors

We report the epitaxial growth of GaSb using trimethylgallium (TMGa) or triethylgallium (TEGa) with trimethylantimony (TMSb), triethylantimony (TESb), or trisdimethylaminoantimony (TDMASb) in a low-pressure vertical rotating-disk reactor. Growth is kinetically limited for TMGa in the temperature range 560 to 640°C, and is mass-transport limited for TEGa in the range 525 to 640°C. A minimum V/III ratio is necessary to obtain stoichiometric GaSb, and is dependent on the pyrolysis temperature of Ga and Sb precursors. Featureless morphology is achieved for layers grown with TMGa or TEGa and TMSb, while surface defects are observed for layers grown with TEGa and TESb or TDMASb. These observations are consistent with Fourier transform infrared measurements, which indicate interactions between TEGa and TESb or TDMASb. All nominally undoped layers are p-type, with overall superior properties being obtained for layers grown with TEGa and TMSb. However, growth conditions that yield layers with the best electrical properties do not necessarily correspond to the same conditions for highest optical quality.     

Structural and electrical properties of GaSb, AlGaSb and their heterostructures grown on GaAs by metalorganic chemical vapor deposition

A systematic study of structural and electrical properties of GaSb and AlGaSb grown on GaAs by metalorganic chemical vapor deposition is reported. In general, the results obtained from surface morphologies, X-ray linewidths and Hall properties are consistent with each other and indicate that the optimal growth conditions for GaSb are at 525°C around V/III = 1. A highest hole mobility of 652 cm²/V · s at RT (3208 cm²/V · s at 77 K) and a lowest concentration of 2.8 × 10¹⁶ cm⁻³ (1.2 × 10¹⁵ cm⁻³ at 77 K) were obtained for GaSb grown under this optimal condition. Compared to the GaSb growth, a smaller V/III ratio is needed for the AlGaSb growth to protect the surface morphology. When Al was incorporated into GaSb growth, mobility decreased and carrier concentration increased sharply. The AlGaSb grown at 600°C had a background concentration about one order of magnitude lower than the AlGaSb grown at 680°C. Room-temperature current-voltage characteristics of GaSb/Al_xGa_{1 − x}Sb/GaSb show a rectifying feature when Al composition x is higher than 0.3, suggesting a valence-band discontinuity at the AlGaSb/GaSb interface. A leakage current much higher than the value predicted by the thermionic emission theory is observed at 77 K, presumably due to a large number of dislocations generated by the huge lattice mismatch between GaSb and GaAs.     

Low temperature growth of AlGaAs by MOMBE (CBE) using trimethylamine alane

In order to gain further insight into the surface chemistry of AlGaAs growth by metalorganic molecular beam epitaxy, we have investigated the deposition behavior and material quality of AlGaAs grown at temperatures from 350 to 500°C using trimethylamine alane (TMAA), triethylgallium (TEG) and arsine (AsH₃). Though the Al incorporation rate decreases with decreasing temperature, Ga-alkyl pyrolysis, and hence Ga incorporation rate, declines more rapidly. Thus the Al content increases from X_AlAs = 0.25 at 500°C to X_AlAs = 0.57 at 350°C. Below 450°C, the Ga incorporation rate appears to be determined by the desorption of diethylgallium species, rather than interaction with adsorbed AlH₃. Similarly, carbon incorporation is enhanced by 2 orders of magnitude over this temperature range due to the increasingly inefficient pyrolysis of the Ga-C bond in TEG. Additionally, active hydrogen from the TMAA1, which normally is thought to getter the surface alkyls, is possibly less kinetically active at lower growth temperatures. Contrary to what has been observed in other growth methods, low growth temperatures produced a slight decrease in oxygen concentration. This effect is likely due to reduced interaction between Ga alkoxides (inherent in the TEG) and the atomic hydrogen blocked Al species on the growth surface. This reduction in oxygen content and increase in carbon concentration causes the room temperature PL intensity to actually increase as the temperature is reduced from 500 to 450°C. Surprisingly, the crystalline perfection as measured by ion channeling analysis is quite good, χ_min≤5%, even at growth temperatures as low as 400°C. At 350°C, the AlGaAs layers exhibit severe disorder. This disorder is indicative of insufficient Group III surface mobility, resulting in lattice site defects. The disorder also supports our conclusions of kinetically limited surface mobility of all active surface components.     

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.     

Transmission electron microscopy observation of GaAs/Al0.3Ga0.7As T-shaped quantum well structure fabricated by glancing angle molecular beam epitaxy on GaAs(100) reverse-mesa etched substrates

GaAs/Al_0.3Ga_0.7As multi-layer structures were grown on GaAs (100) reverse-mesa etched substrates by glancing angle molecular beam epitaxy (GA-MBE). A(111)B facet was formed as a side-facet. Surface migration of Ga and Al atoms from the (100) flat region to the (111)B side-facet region has been investigated to fabricate T-shaped GaAs/AlGaAs quantum wells (QWs) under the condition that Ga and Al atoms impinge only an the (100) flat region and do not impinge on the (111)B side-facet. Observation of T-shaped GaAs/AlGaAs quantum wires (QWRs) by cross-sectional transmission electron microscopy (TEM) revealed that there is no migration of Al atoms from the (100) to the (111)B facet region at a substrate temperature (T_s) as high as 630°C, under a V/III ratio of 28 (in pressure ratio). On the other hand, very thin GaAs epitaxial layers grown on the (111)B side-facet region owing to the Ga migration were observed for substrate temperatures of 600 and 630°C. It was found that the mass flow of Ga atoms from the (100) region to the (111)B side-facet region increases, with the thermal activation energy of 2.0 eV, as the substrate temperature increases from 570 to 630°C. The GA-MBE growth on a reverse-mesa etched GaAs substrate at a low temperature 570°C or lower is desirable to fabricate a nm-scale GaAs/AlGaAs QWR structure with nm-scale precision.     

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.     

Tin as an n-type dopant in the molecular beam epitaxial growth of GaAs(111)A

We have made a systematic study of the tin doping of GaAs layers grown on GaAs(111)A substrates using molecular beam epitaxy (MBE). A series of samples were grown with a range of substrate temperatures (from 460 to 620°C), As:Ga flux ratios (5:1 to 25:1) and tin concentrations (10¹⁶ to 10²⁰ atoms cm⁻³). Layers grown on (111)A surfaces were n-type (in contrast to silicon doping) but with carrier concentrations dependent on growth conditions. We have used secondary ion mass spectrometry (SIMS) measurements to confirm the concentration of tin incorporated and its distribution within the layers.     

Initial growth behavior of GaAs on ZnSe in MOVPE

We have used atomic force microscopy to investigate the initial stages of the growth of GaAs on ZnSe by metalorganic vapor phase epitaxy. Underlying ZnSe with an atomically flat surface is achieved by growth at 450°C and post-growth annealing at the same temperature. The growth modes of GaAs on the ZnSe surface strongly depend on growth temperatures. The growth carried out at 450°C is 2-dimensional, while that at 550°C is highly 3-dimensional (3D), where the 3D islands are elongated in the [110] direction. The growth behavior, unlike homoepitaxy, is well interpreted in terms of low sticking coefficient and anisotropic lateral growth rate in the heterovalent heteroepitaxy.     

The behaviour of copper on gallium arsenide

Cu has been reported to diffuse rapidly in GaAs at low temperatures (2.3×10^-5 cm² s^-1 at 600°C). The rapid diffusion is attributed to the interstitial movement of Cu atoms. The present investigation was undertaken to examine preferential diffusion of Cu⁺ along dislocations and grain boundaries in GaAs. The experiments consisted of depositing ⁶⁴Cu on a GaAs water surface, annealing in vacuum, and observing the Cu distribution by autoradiography. From these observations no preferential diffusion along dislocations or grain boundaries was detected in SI GaAs annealed between 600 and 1000°C. In the sample annealed above 800°C, the deposited Cu reacted with the GaAs forming a liquid on the sample surface, which solidified into complex Cu-Ga-As compounds. The liquid also produced Cu-rich pipes which extended through the GaAs wafer.     

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.     

Effects of growth temperature on the properties of ZnO/GaAs prepared by metalorganic chemical vapor deposition

A series of ZnO films were grown on GaAs(0 0 1) substrates at different growth temperatures in the range 250–720°C by metalorganic chemical vapor depostion. Field emission scanning electron microscopy was utilized to investigate the surface morphology of ZnO films. The crystallinity of ZnO films was investigated by the double-crystal X-ray diffractometry. The optical and electrical properties of ZnO films were also investigated using room-temperature photoluminescence and Hall measurements. Arrhenius plots of the growth rate versus reciprocal temperature revealed the kinetically limited growth behavior depending on the growth temperature. It was found that the surface morphology, structural, optical and electrical properties of the films were improved with increasing growth temperature to 650°C. All the properties of the film grown at 720°C were degraded due to the decomposition of ZnO film.     

A study of growth and morphological features of TiOxNy thin films prepared by MOCVD

The growth and morphological features of MOCVD TiO_xN_y films have been characterized to evaluate the effect of various process parameters on film growth. XRD analysis of the films deposited at 600°C on Si(1 1 1) and mica show a TiN(1 1 1) peak at 2θ=36.6°, but only anatase peaks are detected below 550°C. Above 650°C, both anatase and rutile peaks are detected. The presence of ammonia is not effective below 550°C as the deposited film is mostly TiO₂. Also, ammonia does not play any role in homogeneous nucleation in the gas phase, as evident by the deposition of anatase/rutile particles above 650°C. The following changes in the morphological features are observed by varying process parameters. By increasing the ratio of titanium-isopropoxide to ammonia flow, the cluster shape changes from angular to rounded; dilution of the flow results in larger elongated clusters; increase in flow rate at constant precursor to ammonia ratios, changes the cluster shape from rounded to elongated and the cluster size deceases. Deposition at higher temperatures results in finer clusters with a slower growth rate and eventually results in a very thin film with particle deposition at 650°C and above.     

Surface reconstruction of sulfur-terminated GaAs(001) observed during annealing process by scanning tunneling microscopy

The surface reconstruction of in-situ prepared sulfur-terminated (S-terminated) and sulfur-protected (S-protected) GaAs(001) is studied by scanning tunneling microscopy (STM) at high temperatures of up to 260°C. We demonstrate a new reordering process from the (4×6) Ga-stabilized surface to the (2×6) S-stabilized surface and a novel method of air protection using a S passivation layer. Moreover, the in-situ observation of the annealing process of this S-protection layer is performed by high-temperature STM, avoiding the adsorption from environments and verifying that the (2×6) structure still becomes dominant on the S-terminated GaAs(001) surface without the effects of As atoms.     

Stability and formation of pyrochlore phase in doped Sr0.8Bi2.3Ta2O9 thin films

Ferroelectric thin films of bismuth-containing layered perovskite Sr_0.8Bi_2.3Ta_2−xM_xO₉ (SBTM), where M is V, Ti, W, and Zr, have been prepared on Pt/Ti/SiO₂/Si substrates using the metal-organic decomposition method. The effect of the incorporated B-site cations on pyrochlore phase formation and microstructure evolution of SBTM films was investigated. The pyrochlore phase formation has been identified due to out-diffusion of titanium from underneath platinum layer to participate in the reaction with the films. Furthermore, the formation of pyrochlore phase in the SBTM films has been observed strongly dependent on the characteristics of incorporated M cation. The substitution of both W and V for Ta leads to the formation of pyrochlore phase at lower annealing temperature (750–800 °C). On the other hand, the addition of Zr can retard the formation of pyrochlore phase from 850 to 900 °C. A model based on the binding energy of octahedral structure is used to elucidate the formation and stability of the pyrochlore phase present in the SBT film.     

Growth of InAs on GaAs(1 0 0) by low-pressure metalorganic chemical vapor deposition employing in situ generated arsine radicals

InAs was grown by low-pressure metalorganic chemical vapor deposition on vicinal GaAs(1 0 0) substrates misoriented by 2° toward [0 0 1]. We observed InAs crystal growth, at substrate temperatures down to 300°C, employing in situ plasma-generated arsine radicals as the arsenic source. The in situ generated arsine was produced by placing solid arsenic downstream of a microwave driven hydrogen plasma. Trimethylindium (TMIn) feedstock carried by hydrogen gas was used as the indium source. The Arrhenius plot of InAs growth rate vs. reciprocal substrate temperature displayed an activation energy of 46.1 kcal/mol in the temperature range of 300–350°C. This measured activation energy value is very close to the energy necessary to remove the first methyl radical from the TMIn molecule, which has never been reported in prior InAs growth to the best of authors’ knowledge. The film growth mechanism is discussed. The crystallinity, infrared spectrum, electrical properties and impurity levels of grown InAs are also presented.     

The growth kinetics of (SmY)3(FeGa)5O12 epitaxial layers in the 920–980°C range

The growth kinetics of (SmY)₃(FeGa)₅O₁₂ garnets obtained by liquid phase epitaxy on Gd₃Ga₅O₁₂ substrates are discussed in the 920 to 980°C. range. The experiments have been carried out with the substrates in a horizontal plane and with unidirectional rotation ranging from 30 to 300 rotations per minute (rpm). A sharp increase in the growth velocity at temperatures higher than 960°C is interpreted on the basis of a diffusion-reaction theory. It is found that the diffusion constant increases steeper at higher temperatures and that the linear law of the growth rate as a function of the square root of the rotation rate holds to much higher rotation rates at these temperatures. The influence of the surface incorporation is too small to be detectable. The results are compared with published data concerning other compositions.