Electrical and photo-luminescence properties of ZnSe epitaxial layers grown on GaAs (100) by atmospheric pressure MOVPE: The role of substrate temperature

Epitaxial layers of ZnSe ranging in thickness from 5μm to 30 μm have been grown on GaAs (100) substrates over the temperature range 240° C to 340° C by atmospheric pressure MOVPE employing dimethylzinc and hydrogen selenide. An optimum growth temperature of 280 ± 5° C has been identified and when grown at this temperature the ZnSe epitaxial layers exhibit low resistivity (ρ_{298 K} ≤ 10 ohm · cm), a low compensation ratio (θ_{298 K} = 0.27), a carrier mobility (μ_{298 K}) of 250 ±10 cm²V^-1s^-1) and aren-type (n _{298 K} = 8.0 × 10¹⁴ cm^-3). The ratio of photoluminescence intensity measured at 298K and at 12 K is high (10⁴) and is dominated by a sharp emission due to excitons bound to neutral donors at 2.7956 eV. Mass spectrometric investigations of the chemical reactions occurring inside the reactor in the presence of the GaAs substrate indicate significant surface-controlled reactivity in the region of 280° C.     

Ion-assisted molecular beam epitaxy of GaAs on Si(100)

GaAs was grown by molecular beam epitaxy (MBE) and ion-assisted MBE on Si(100) substrates. Three-dimensional (3D) island nucleation, observed during MBE growth, was eliminated during ion-assisted MBE when the ion energyE was >25 eV and the product ofE and the current densityJ was ≈6-12 eV mA/cm². IncreasingEJ to ≈15 eV mA/ cm² resulted in excessive ion damage. Decreasing the substrate temperature from 280 to 580° C during ion-assisted MBE yielded a slight decrease in surface roughness, and flatter surfaces were obtained for lower As⁴/Ga flux ratios. The suppression of 3D island nucleation led to an improvement in the crystalline perfection of thicker GaAs films. For example, the x-ray diffraction rocking-curve full-width-at-half-maximum values for 0.5 μm thick films grown at 380° C decreased from 1700 arcsec to 1350 arcsec when ion irradiation was used during nucleation. IAMBE allowed nucleation of thin, relatively flat-surfaced GaAs films even at 580° C, resulting in FWHM values of 1850 arcsec for 0.14 /μm thick films.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Magnetron Deposition of In Situ Thermoelectric Mg2Ge Thin Films

Thin films of the semiconducting compound Mg₂Ge were deposited by magnetron cosputtering from source targets of high-purity Mg and Ge onto glass substrates at temperatures T _s = 300°C to 700°C. X-ray diffraction shows that the Mg₂Ge compound begins to form at a substrate temperature T _s ≈ 300°C. Films deposited at T _s = 400°C to 600°C are single-phase Mg₂Ge and have strong x-ray peaks. At higher T _s the films tend to be dominated by a Ge-rich phase primarily due to the loss of magnesium vapor from the condensing film.␣At optimum deposition temperatures, 550°C to 600°C, films have an electrical conductivity σ _600 K = 20 Ω⁻¹ cm⁻¹ to 40 Ω⁻¹ cm⁻¹ and a Seebeck coefficient α = 300 μV K⁻¹ to 450 μV K⁻¹ over a broad temperature range of 200 K to 600 K.     

Comparison of MBE Growth of InSb on Si (001) and GaAs (001)

We describe the epitaxial growth of InSb films on both Si (001) and GaAs (100) substrates using molecular-beam epitaxy and discuss the structural and electrical properties of the resulting films. The complete 2 μm InSb films on GaAs (001) were grown at temperatures between 340°C and 420°C and with an Sb/In flux ratio of approximately 5 and a growth rate of 0.2 nm/s. The films were characterized in terms of background electron concentration, mobility, and x-ray rocking curve width. Our best results were for a growth temperature of 350°C, resulting in room-temperature mobility of 41,000 cm²/V s.  For the growth of InSb on Si, vicinal Si(001) substrates offcut by 4° toward (110) were used. We investigated growth temperatures between 340°C and 430°C for growth on Si(001). In contrast to growth on GaAs, the best results were achieved at the high end of the range of T _S =  C, resulting in a mobility of 26,100 cm²/V s for a 2 μm film. We also studied the growth and properties of InSb:Mn films on GaAs with Mn content below 1%. Our results showed the presence of ferromagnetic ordering in the samples, opening a new direction in the diluted magnetic semiconductors.     

Low temperature grown be-doped InAIP band offset reduction layer to p-type ZnSe

To solve the difficulty of achieving low resistance ohmic contact to p-type ZnSe, the use of an intermediate p-type InAlP layer to p-type ZnSe as a valence band offset reduction layer is studied by gas source molecular beam epitaxy. It is found that hole concentrations as high as 2 × 10¹⁸ cm⁻³ are easily obtained for p-type InAlP layers grown on GaAs even at low temperature of 350°C, although a higher Be cell temperature is required than that for a 500°C grown p-type InAlP due to the decreased electrical activity of Be in InAlP. Despite the very high Be concentrations, the Be precipitation/segregation is not observed. It was difficult to obtain the same hole concentration of InAlP layers grown on ZnSe as that on GaAs. However, the insertion of only several monolayers of GaAs between ZnSe and InAlP makes it possible to avoid faceting growth of InAlP and to improve the electrical properties of Be-doped InAlP grown on ZnSe. These results suggest that the Be-doped InAlP layer can be used as an intermediate layer to form the low resistance ohmic contact to p-type ZnSe.     

Molecular beam epitaxial growth of green light emitting diodes on ZnSe wafers

We have performed a preliminary investigation into the use of ZnSe bulk crystals fabricated by Sumitomo Electric Industries, Ltd. as substrates for the epitaxial1 deposition of ZnSe-based materials and light emitting devices. A low temperature (<380 °C)in- situ cleaning process has been developed for the (100) oriented ZnSe wafers involving the use of a remotely generated atomic hydrogen beam. The process produces a (1 × 1) atomically smooth ZnSe surface which is highly suitable for epitaxy. Hall-effect measurements performed on nitrogen-doped ptype ZnSe/S.I. ZnSe epilayers have revealed free-hole concentrations in the homoepitaxial material as high as 2.1 × 10¹⁷cm⁻³, so far, with room temperature and 77Khole mobility values of 20 and 100 cm²V _su−1 ^ins/su−1 , respectively. Finally, green light emitting diodes have been grown on the ZnSe wafers having Cd_0.2Zn_0.8Se/ ZnSe multiple quantum well active regions which have exhibited electroluminescence peak linewidths around 9.9 nm at room temperature.     

Indium layers in low-temperature gallium arsenide: Structure and how it changes under annealing in the temperature range 500–700 °C

Transmission electron microscopy is used to study the microstructure of indium δ layers in GaAs(001) grown by molecular beam epitaxy at low temperature (200 °C). This material, referred to as LT-GaAs, contains a high concentration (≈10²⁰ cm⁻³) of point defects. It is established that when the material is δ-doped with indium to levels equivalent to 0.5 or 1 monolayer (ML), the roughness of the growth surface leads to the formation of InAs islands with characteristic lateral dimensions <10 nm, which are distributed primarily within four adjacent atomic layers, i.e., the thickness of the indium-containing layer is 1.12 nm. Subsequent annealing, even at relatively low temperatures, leads to significant broadening of the indium-containing layers due to the interdiffusion of In and Ga, which is enhanced by the presence of a high concentration of point defects, particularly V _Ga, in LT-GaAs. By measuring the thickness of indium-containing layers annealed at various temperatures, the interdiffusion coefficient is determined to be D _In-Ga=5.1×10⁻¹² exp(−1.08 eV/kT) cm²/s, which is more than an order of magnitude larger than D _In-Ga for stoichiometric GaAs at 700 °C. Fiz. Tekh. Poluprovodn. 32, 769–774 (July 1998)     

Influence of Substrate Temperature on Structural and Thermoelectric Properties of Antimony Telluride Thin Films Fabricated by RF and DC Cosputtering

Antimony and tellurium were deposited on BK7 glass using direct-current magnetron and radiofrequency magnetron cosputtering. Antimony telluride thermoelectric thin films were synthesized with a heated substrate. The effects of substrate temperature on the structure, surface morphology, and thermoelectric properties of the thin films were investigated. X-ray diffraction patterns revealed that the thin films were well crystallized. c-Axis preferred orientation was observed in thin films deposited above 250°C. Scanning electron microscopy images showed hexagonal crystallites and crystal grains of around 500 nm in thin film fabricated at 250°C. Energy-dispersive spectroscopy indicated that a temperature of 250°C resulted in stoichiometric Sb₂Te₃. Sb₂Te₃ thin film deposited at room temperature exhibited the maximum Seebeck coefficient of 190 μV/K and the lowest power factor (PF), S ² σ, of 8.75 × 10⁻⁵ W/mK². When the substrate temperature was 250°C, the PF increased to its highest value of 3.26 × 10⁻³ W/mK². The electrical conductivity and Seebeck coefficient of the thin film were 2.66 × 10⁵ S/m and 113 μV/K, respectively.     

High temperature MOVPE growth of GaAs/AlGaAs device structures with tertiarybutylarsine

The performance characteristics of epitaxial structures suitable for optoelectronic and electronic devices were investigated. These were fabricated by MOVPE using tertiary-butylarsine, a non-hydride arsenic source. Minority carrier diffusion lengths of 5μm at 3 × 10¹⁸/cm³ and 2μm at 2 × 10¹⁹/cm³ were achieved inp-type GaAs. Recombination velocities at the GaAs/AlGaAs interface are reduced to 1 × 10³ cm/sec by processing under appropriate conditions. Electron mobilities of 4000 cm²/V-sec inn-type (2 × 10¹⁷/cm³) layers resulted in transconductances of 120 mS/mm in 1.5μm gate depletion mode MESFETs. The above values are comparable to those obtained with arsine in this work and others reported in the literature.     

A study of chemical beam epitaxy of GaAs using tris-dimethylaminoarsenic

The growth of GaAs by chemical beam epitaxy using triethylgallium and trisdimethylaminoarsenic has been studied. Reflection high-energy electron diffraction (RHEED) measurements were used to investigate the growth behavior of GaAs over a wide temperature range of 300–550°C. Both group III- and group Vinduced RHEED intensity oscillations were observed, and actual V/III incorporation ratios on the substrate surface were established. Thick GaAs epitaxial layers (2–3 μm) were grown at different substrate temperatures and V/III ratios, and were characterized by the standard van der Pauw-Hall effect measurement and secondary ion mass spectroscopy analysis. The samples grown at substrate temperatures above 490°C showed n-type conduction, while those grown at substrate temperatures below 480°C showed p-type conduction. At a substrate temperature between 490 and 510°C and a V/III ratio of about 1.6, the unintentional doping concentration is n ∼2 × 10¹⁵ cm⁻³ with an electron mobility of 5700 cm²/V·s at 300K and 40000 cm²/V·s at 77K.     

High-efficiency,thin-film InP concentrator solar cells

High-efficiency, thin-film InP solar cells grown heteroepitaxially on GaAs and Si single-crystal bulk substrates are being developed as a means of eliminating the problems associated with using single-crystal InP substrates (e.g., high cost, fragility, high mass density and low thermal conductivity). A novel device structure employing a compositionally graded Ga _x In_1−x As layer (∼8 μm thick) between the bulk substrate and the InP cell layers is used to reduce the dislocation density and improve the minority carrier properties in the InP. The structures are grown in a continuous sequence of steps using computer-controlled atmospheric-pressure metalorganic vapor-phase epitaxy (AP-MOVPE). Dislocation densities as low as 3×10⁷ cm⁻² and minority carrier lifetimes as high as 3.3 ns are achieved in the InP layers with this method using both GaAs or Si substrates. Structures prepared in this fashion are also completely free of microcracks. These results represent a substantial improvement in InP layer quality when compared to heteroepitaxial InP prepared using conventional techniques such as thermally cycled growth and post-growth annealing. The present work is concerned with the fabrication and characterization of thin-film InP solar cells designed for operation at high solar concentration (∼100 suns) which have been prepared from similar device structures grown on GaAs substrates. The cell performance is characterized as a function of the air mass zero (AM0) solar concentration ratio (1–100 suns) and operating temperature (25°–80° C). From these data, the temperature coefficients of the cell performance parameters are derived as a function of the concentration ratio. Under concentration, the cells exhibit a dramatic increase in efficiency and an improved temperature coefficient of efficiency. At 25° C, a peak conversion efficiency of 18.9% (71.8 suns, AM0 spectrum) is reported. At 80° C, the peak AM0 efficiency is 15.7% at 75.6 suns. These are the highest efficiencies yet reported for InP heteroepitaxial cells. Approaches for further improving the cell performance are discussed.     

Solution Growth and Thermoelectric Properties of Single-Phase MnSi<Subscript>1.75−<Emphasis Type="Italic">x</Emphasis></Subscript>

We have investigated the crystal growth of single-phase MnSi_1.75−x by a temperature gradient solution growth (TGSG) method using Ga and Sn as solvents and MnSi_1.7 alloy as the solute, and measured the thermoelectric properties of the resulting crystals. Single-phase Mn₁₁Si₁₉ and Mn₄Si₇ crystals were grown successfully using Ga and Sn as solvents, respectively. The typical size of a grown ingot of Mn₁₁Si₁₉ was 2 mm to 4 mm in thickness and 12 mm in diameter, whereas Mn₄Si₇ had polyhedral shape with dimensions in the range of several millimeters. The single-phase Mn₁₁Si₁₉ has good electrical conduction (ρ = 0.89 × 10⁻³ Ω cm to 1.09 × 10⁻³ Ω cm) compared with melt-grown multiphase higher-manganese silicide (HMS) crystals. The Seebeck coefficient, power factor, and thermal conductivity were 77 μV K⁻¹ to 85 μV K⁻¹, 6.7 μW cm⁻¹ K⁻² to 7.2 μW cm⁻¹ K⁻², and 0.032 W cm⁻¹ K⁻¹, respectively, at 300 K.     

Structural properties of ZnSy Se1−yZnSe/GaAs (001) heterostructures grown by photoassisted metalorganic vapor phase epitaxy

ZnS_ySe_1−yZnSe/GaAs (001) heterostructures have been grown by photoassisted metalorganic vapor phase epitaxy, using the sources dimethylzinc, dimethylselenium, diethylsulfur, and irradiation by a Hg arc lamp. The solid phase composition vs gas phase composition characteristics have been determined for ZnSy_ySe_1−y grown with different mole fractions of dimethylselenium and different temperatures. Although the growth is not mass-transport controlled with respect to the column VI precursors, the solid phase composition vs gas phase composition characteristics are sufficiently gradual so that good compositional control and lattice matching to GaAs substrates can be readily achieved by photoassisted growth in the temperature range 360°C ≤ T ≤ 400°C. ZnSe/GaAs (001) single heterostructures were grown by a two-step process with ZnSe thicknesses in the range from 54 nm to 776 nm. Based on 004 x-ray rocking curve full width at half maximums (FWHMs), we have determined that the critical layer thickness is h_c ≤200 nm. Using the classical method involving strain, lattice relaxation is undetectable in layers thinner than 270 nm for the growth conditions used here. Therefore, the rocking curve FWHM is a more sensitive indicator of lattice relaxation than the residual strain. For ZnS_ySe_1−y layers grown on ZnSe buffers at 400°C, the measured dislocation density-thickness product Dh increases monotonically with the room temperature mismatch. Lower values of the Dh product are obtained for epitaxy on 135 nm buffers compared to the case of 270 nm buffers. This difference is due to the fact that the 135 nm ZnSe buffers are pseudomorphic as deposited. For ZnS_ySe_1−y layers grown on 135 nm ZnSe buffers at 360°C, the minimum dislocation density corresponds approximately to room-temperature lattice matching (y ∼ 5.9%), rather than growth temperature lattice matching (y ∼ 7.6%). Epitaxial layers with lower dislocation densities demonstrated superior optical quality, as judged by the near-band edge/deep level emission peak intensity ratio and the near band edge absolute peak intensity from 300K photoluminescence measurements.     

Thermoelectric Properties of In<Subscript>0.3</Subscript>Ga<Subscript>0.7</Subscript>N Alloys

We report on the experimental investigation of the potential of InGaN alloys as thermoelectric (TE) materials. We have grown undoped and Si-doped In_0.3Ga_0.7N alloys by metalorganic chemical vapor deposition and measured the Seebeck coefficient and electrical conductivity of the grown films with the aim of maximizing the power factor (P). It was found that P decreases as electron concentration (n) increases. The maximum value for P was found to be 7.3 × 10⁻⁴ W/m K² at 750 K in an undoped sample with corresponding values of Seebeck coefficient and electrical conductivity of 280 μV/K and 93␣(Ω cm)⁻¹, respectively. Further enhancement in P is expected by improving the InGaN material quality and conductivity control by reducing background electron concentration.     

Preparation and Characterization of Ultralow-Dielectric-Constant Porous SiCOH Thin Films Using 1,2-Bis(triethoxysilyl)ethane,Triethoxymethylsilane, and a Copolymer Template

Ultralow-dielectric-constant (k) porous SiCOH films have been prepared using 1,2-bis(triethoxysilyl)ethane, triethoxymethylsilane, and a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer template by means of spin-coating. The resulting films were characterized by cross-section scanning electron microscopy, small-angle x-ray diffraction, atomic force microscopy, Fourier-transform infrared spectroscopy, nanomechanical testing, and electrical measurements. Thermal treatment at 350°C for 2 h resulted in the formation of ultralow-k films with k of ∼2.0, leakage current density of 3 × 10⁻⁸ A/cm² at 1 MV/cm, reduced modulus (E _r) of ∼4.05 GPa, and hardness (H) of ∼0.32 GPa. After annealing between 400°C and 500°C for 30 min, the resulting films showed fluctuant k values of 1.85 to 2.22 and leakage current densities of 3.7 × 10⁻⁷ A/cm² to 3 × 10⁻⁸ A/cm² at 0.8 MV/cm, likely due to the change of the film microstructure. Compared with 350°C annealing, higher-temperature annealing can improve the mechanical strength of the ultralow-k film, i.e., E _r ≈ 5 GPa and H ≈ 0.56 GPa after 500°C annealing.     

Low resistance Pd/Zn/Pd Au ohmic contacts to P-type gaas

Many optoelectronic devices require contacts top-doped epitaxial layers. To achieve low contact resistance, the semiconductor has to be doped to high levels. Thep-dopants most commonly used are Be, Mg, and Zn. The contacts were formed by the sequential e-beam evaporation of 10 nm Pd, ≤5 nm Zn, 20 nm Pd and 40 nm Au layers onto a 0.2 μm thick Be-doped (5 × 10¹⁸ cm) GaAs layer grown by MBE. The minimum contact resistance of 0.04Ω-mm (≤1 × 10⁻⁷ Ω-cm²), as measured using the transmission line method, was obtained for contacts annealed at 500° C for 30s. These are the lowest contact resistance values reported to date for alloyed contacts top-GaAs.     

The effect of neutron irradiation and annealing temperature on the electrical properties and lattice constant of epitaxial gallium nitride layers

Effect of irradiation with high reactor-neutron fluences (Φ = 1.5 × 10¹⁷-8 × 10¹⁹ cm⁻²) and subsequent heat treatments in the temperature range 100–1000°C on the electrical properties and lattice constant of epitaxial GaN layers grown on an Al₂O₃ substrate is considered. It is shown that, with the neutron fluence increasing to (1–2) × 10¹⁸ cm⁻², the resistivity of the material grows to values of about 10¹⁰ Ω cm because of the formation of radiation defects, and, with the fluence raised further, the resistivity passes through a maximum and then decreases to 2 × 10⁶ Ω cm at 300 K, which is accounted for by the appearance of a hopping conductivity via deep defects in the overlapping outer parts of disordered regions. With the neutron fluence raised to 8 × 10¹⁹ cm⁻², the lattice constant c increases by 0.38% at a nearly unchanged parameter a. Heat treatment of irradiated samples at temperatures as high as 1000°C does not fully restore the lattice constant and the electrical parameters of the material.     

Growth of (GaAs)1_x(Ge2)x by metalorganic chemical vapor deposition

We report deposition of (GaAs)_{1_x}(Ge₂)_x on GaAs substrates over the entire alloy range. Growth was performed by metalorganic chemical vapor deposition at temperatures of 675 to 750°C, at 50 and 760 Torr, using trimethylgallium, arsine, and germane at rates of 2–10 μ/h. Extrinsic doping was achieved using silane and dimethylzinc in hydrogen. Characterization methods include double-crystal x-ray rocking curve analysis, Auger electron spectroscopy, 5K photoluminescence, optical transmission spectra, Hall-effect, and Polaron profiling. Results achieved include an x-ray rocking curve full-width at half maximum as narrow as 12 arc-s, Auger compositions spanning the alloy range from x = 0.03 to x = 0.94, specular surface morphologies, and 5K photoluminescence to wavelengths as long as 1620 nm. Undoped films are n type, with n ≈ 1 × 10¹⁷ cm⁻³. Extrinsic doping with silane and dimethylzinc have resulted in films which are n type (10¹⁷ to 10¹⁸ cnr⁻³) or p type (5 × 10¹⁸ to 1 × 10²⁰ cm⁻³). Mobilities are generally ≈ 50 cm²/V-s and 500 cm²/V-s, for p and n films, respectively.     

Effects of contact metals on minority carrier diffusion lengths in GaAs

Contact technology for GaAs involves optimizing such factors as contact resistance or Schottky barrier height, alloy cycle conditions, thermal ageing, adhesion, and ease of high resolution processing. Minority carrier properties may be significantly degraded by in-diffusing contact metals. At typical alloying conditions of 10 sec at 500° C, Ni diffuses at least 10 μm and reduces the hole diffusion length (L_p) in vapor phase epitaxial GaAs from 4.4 to 1.7 ym. At 600°C, L_p becomes 1.0 μm. Other metals, such as Fe, Pt, and Cr, significantly improve L_p in VPE GaAs. L_p increases from 3.0 to 5.0 μm for an Fe diffusion of 5 minutes at 500°C. These improvements may be due to interaction of in-diffused Fe with recombination centers, such as Ga vacancy complexes or Ni. Fe causes increases in minority carrier diffusion lengths also in n and p type ingot GaAs, though 800 – 900°C diffusions are required and at these temperatures the doping is significantly changed by Fe acceptors.