Effect of growth temperature on oxygen incorporation in GaP

The temperature dependence of oxygen incorporation in GaP has been studied over the range 900–1000°C using liquid phase epitaxy. The growth solutions were oxygen saturated to provide the maximum oxygen concentration in the solid. The concentration of substitutional (donor) oxygen was determined by electrical compensation measurements in p-type material. It has been found that whereas the oxygen concentration in the liquid increases with increasing growth temperature, the distribu-tion coefficient decreases. This behavior results in a maximum oxygen donor concentration of ∼3×10¹⁷ atoms/cm³ which is realized in the temperature range 970–1060°C. For T > 1100°C, the oxygen donor concen-tration falls below 1×10¹⁷ atoms/cm³, in agreement with prior solution growth results. These results thus suggest an optimum temperature range for oxygen doping and fix an upper limit to the number of Zn-O radiative centers (hence light output) for GaP red emitting diodes .     

High purity and chrome-doped GaAs buffer layers grown by liquid phase epitaxy for mesfet application

High purity GaAs buffer layers of carrier concentration in the low (l-5)×l0^l4/cm³ range with 77K electron mobility over 100,000 cm²/V-sec and 300K mobility around 8000 cm?/ V-sec have been grown by liquid phase epitaxy on Cr-doped GaAs substrates using the graphite sliding boat method. The high purity has been achieved with systematic and concurrent long term bake-outs (24 hrs) of both LPE melt and substrate, both exposed to the H₂ ambient gas stream at 775?C, prior to epitaxial growth at 700?C. Substrate surface degradation was reduced by using Ga:GaAs etch melts that were undersaturated at 700?C by 5? to 40?C. Best buffer layer morphologies with regard to surface planarity were obtained using etch melts that were saturated by near 85% of weight of GaAs at 700°C. The importance of substrate preconditioning in order to achieve the low ( 1 -2)×l0¹⁴ was examined and found to be critical. Melt and substrate bake outs at 800?C, and use of a 40?C undersaturated etch melt prior to epitaxial growth at 800?C resulted in a p-type layer of carrier concentration, 1 .9×l0^l2/cm³ and resistivity 1×10⁵ ohm-cm. Chromium doping at 700?C resulted in buffer layers with sheet resistivities greater than 10 ohms/sq and low pinhole densities.     

High purity LPE InP

Typical LPE InP layers have previously been limited to liquid nitrogen mobilities of 25,000 cm²/ V-sec, which implies a total impurity concentration of 9 × 10¹⁵/cm³. Of the donor impurities identified in InP, Si is reported to have the highest segregation coefficient, with a value of 30 at typical growth temperatures of 650–700°C (1) . Because of this large segregation coefficient, and the fact that commercially available In has typical Si concentrations in the 0.1 ppm range, it is necessary to take additional purification steps on LPE starting materials to reproducibly obtain epitaxial layers with total impurity concentrations below the previously mentioned limit. This paper will discuss a novel approach to the problem by employing a baking scheme to reduce Si contamination. Thermodynamics of the SiO₂ , H₂, Si, H₂O system will be considered which lead to a detailed schedule of time-temperature cycles for the removal of Si from an In based melt. Experimental data are presented which corroborates our thermodynamic, model, and which reproducibly yields epitaxial layers with 77°K mobilities in the range of 50,000–67,000 cm²/V-sec, and total impurity concentration below 2 × 10¹⁵/cm³ . Limiting factors in obtaining higher purity are discussed and suggestions are made for overcoming this problem.     

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.     

Diffusion and solid solubility of Zn in GaP at 850°C

Zinc was diffused at 850°C from ternary sources containing 1–20 atom percent Zn and 0.5–1.0 atom percent P in Ga into n-type GaP grown by liquid phase epitaxy (LPE) and the liquid encapsulated Czochralski (LEC) process. Data on the surface concentration, and thereby the solid solubility of Zn as a function of the source composition, were obtained from⁶⁵Zn radiotracer analysis and electrical measurements. At 850°C these values range from 8×l0¹⁷ cm⁻³ for a 1 atom percent Zn to 5×10¹⁸ cm⁻³ for a 20 atom percent Zn concentration in the Ga/P/Zn ternary solution. These data are self-consistent, although they are somewhat lower than the previously reported values . Qualitatively, the results agree with recent thermodynamic calculations. The diffusion kinetics were found to be non-ideal as indicated by departures from a linear-square-root-of-time model and by reproducible changes in the junction depth following pre-diffusion heat treatments in different ambients.     

Improved oxidation procedures for reduced SiO2/SiC defects

A significant reduction in the effective oxide charge and interface state densities in oxides grown on p-type 6H-SiC has been obtained by lowering the oxidation temperature of SiC to 1050°C. Further improvements are obtained by following the oxidation with an even lower temperature re-oxidation anneal. This anneal dramatically improves the electrical properties of the Si/SiC interface, and substantially lowers the interface state density. The net oxide charge density on p-type 6H-SiC is also lowered significantly, but remains quite high, at 1.0 × 10¹² cm^-2. The interface state densities of 1.0 × 10¹¹ cnr⁻²/eV are approaching acceptable MOS device levels. The breakdown fields of the oxides are also substantially improved by both the lower oxidation temperature and re-oxidation anneal. Using a low temperature oxidation followed by a re-oxidation anneal for MOSFETs results in a room temperature mobility of 72 cm²/V-s, the highest channel mobility reported for SiC MOSFETs to date.     

Thermally stable Ge/Cu/Ti ohmic contacts to n-type GaN

The performance of a novel Ge/Cu/Ti metallization scheme on n-type GaN has been investigated for obtaining thermally and electrically stable low-resistance ohmic contacts. Isochronal (2 min.) anneals in the 600–740°C temperature range and isothermal (690°C) anneals for 2–10 min. duration were performed in inert atmosphere. For the 690°C isothermal schedule, ohmic behavior was observed after annealing for 3 min. or longer with a lowest contact resistivity of 9.1 × 10⁻⁵ Ωcm² after the 10 min. anneal for a net donor doping concentration of 9.2 × 10¹⁷ cm^−Ω3. Mean roughness (R_a) for anneals at 690°C was almost constant at around 5 nm, up to an annealing duration of 10 min., which indicates a good thermal stability of the contact scheme.     

High-Dose Phosphorus-Implanted 4H-SiC: Microwave and Conventional Post-Implantation Annealing at Temperatures ≥1700°C

Semi-insulating 4H-SiC ⟨0001⟩ wafers have been phosphorus ion implanted at 500°C to obtain phosphorus box depth profiles with dopant concentration from 5 × 10¹⁹ cm⁻³ to 8 × 10²⁰ cm⁻³. These samples have been annealed by microwave and conventional inductively heated systems in the temperature range 1700°C to 2050°C. Resistivity, Hall electron density, and Hall mobility of the phosphorus-implanted and annealed 4H-SiC layers have been measured in the temperature range from room temperature to 450°C. The high-resolution x-ray diffraction and rocking curve of both virgin and processed 4H-SiC samples have been analyzed to obtain the sample crystal quality up to about 3 μm depth from the wafer surface. For both increasing implanted phosphorus concentration and increasing post-implantation annealing temperature the implanted material resistivity decreases to an asymptotic value of about 1.5 × 10⁻³ Ω cm. Increasing the implanted phosphorus concentration and post-implantation annealing temperature beyond 4 × 10²⁰ cm⁻³ and 2000°C, respectively, does not bring any apparent benefit with respect to the minimum obtainable resistivity. Sheet resistance and sheet electron density increase with increasing measurement temperature. Electron density saturates at 1.5 × 10²⁰ cm⁻³ for implanted phosphorus plateau values ≥4 × 10²⁰ cm⁻³, irrespective of the post-implantation annealing method. Implantation produces an increase of the lattice parameter in the bulk 4H-SiC underneath the phosphorus-implanted layer. Microwave and conventional annealing produce a further increase of the lattice parameter in such a depth region and an equivalent recovered lattice in the phosphorus-implanted layers.     

Nitrogen implantation into GaP: Damage and nitrogen location studies

Implantations of 80 and 40 keV nitrogen into GaP have been carried out. The implants were performed at temperatures from 25° to 400°C for total doses in the range 10¹⁵ to 10^l6 cm⁻². Backscattering and channeling techniques have been used to determine the associated damage and its annealing characteristics for temperatures up to 800°C . Also determined, has been the lattice location of the implanted nitrogen. This was performed by implanting with the isotope¹⁵N and using the¹⁵N (p,α_o)¹²C nuclear reaction in conjunction with channeling techniques using a l MeV proton beam. Results indicate that the GaP is totally damaged following 25°C implants with 10¹⁵N⁺cm⁻². After annealing to 800°C , 70% of the damage has recovered. For implants above 100°C the initial damage is ~15%. Lattice location studies on samples implanted above 150°C show that following an 8 × 10¹⁴N⁺cm⁻² implant, ~60% of the nitrogen is located substitutionally. The substitutional content is reduced to 33% for an 8 × 10^l5N⁺cm^-2 implant. For anneals above 600°C the nitrogen is found to move off the substitutional sites. The results show that using ion implantation at elevated temperatures it is possible to obtain high concentrations of substitutional nitrogen in relatively damage free space.     

Electrical properties of molecular beam epitaxial GaAs grown at 300–450°C

We use the Hall effect and a new charge-transfer technique to study molecular beam epitaxial GaAs grown at the low substrate temperatures of 300–450°C. Layers grown from 350–450°C are semi-insulating (resistivity greater than 10⁷ Ω-cm), as grown, because of an As_Ga-related donor (not EL2) at E_C-0.65 eV. The donor concentrations are about 2×10¹⁸ cm⁻³ and 2×10¹⁷ cm⁻³ at growth temperatures of 300 and 400°C, respectively, and acceptor concentrations are about an order of magnitude lower. Relatively high mobilities (∼5000 cm²/V s) along with the high resistivities make this material potentially useful for certain device applications.     

P-type doping of GaAs by carbon implantation

The electrical properties of C-implanted <100> GaAs have been studied following rapid thermal annealing at temperatures in the range from 750 to 950°C. This includes dopant profiling using differential Hall measurements. The maximum p-type activation efficiency was found to be a function of C-dose and annealing temperature, with the optimum annealing temperature varying from 900°C for C doses of 5 × 10¹³ cm⁻² to 800°C for doses ≥5 × 10¹⁴cm⁻². For low dose implants, the net p-type activation efficiency was as high as 75%; while for the highest dose implants, it dropped to as low as 0.5%. Moreover, for these high-dose samples, 5 × 10¹⁵ cm⁻², the activation efficiency was found to decrease with increasing annealing temperature, for temperatures above ∼800°C, and the net hole concentration fell below that of samples implanted to lower doses. This issue is discussed in terms of the amphoteric doping behavior of C in GaAs. Hole mobilities showed little dependence on annealing temperature but decreased with increasing implant dose, ranging from ∼100 cm²/V·s for low dose implants, to ∼65 cm²/V·s for high dose samples. These mobility values are the same or higher than those for Be-, Zn-, or Cd-implanted GaAs.     

Exfoliation and blistering of Cd<Subscript>0.96</Subscript>Zn<Subscript>0.04</Subscript>Te substrates by ion implantation

As part of a series of wafer bonding experiments, the exfoliation/blistering of ion-implanted Cd_0.96Zn_0.04Te substrates was investigated as a function of postimplantation annealing conditions. (211) Cd_0.96Zn_0.04Te samples were implanted either with hydrogen (5×10¹⁶ cm⁻²; 40–200 keV) or co-implanted with boron (1×10¹⁵ cm⁻²; 147 keV) and hydrogen (1–5×10¹⁶ cm⁻²; 40 keV) at intended implant temperatures of 253 K or 77 K. Silicon reference samples were simultaneously co-implanted. The change in the implant profile after annealing at low temperatures (<300°C) was monitored using high-resolution x-ray diffraction, atomic force microscopy (AFM), and optical microscopy. The samples implanted at the higher temperature did not show any evidence of blistering after annealing, although there was evidence of sample heating above 253 K during the implant. The samples implanted at 77 K blistered at temperatures ranging from 150°C to 300°C, depending on the hydrogen implant dose and the presence of the boron co-implant. The production of blisters under different implant and annealing conditions is consistent with nucleation of subsurface defects at lower temperature, followed by blistering/exfoliation at higher temperature. The surface roughness remained comparable to that of the as-implanted sample after the lower temperature anneal sequence, so this defect nucleation step is consistent with a wafer bond annealing step prior to exfoliation. Higher temperature anneals lead to exfoliation of all samples implanted at 77 K, although the blistering temperature (150–300°C) was a strong function of the implant conditions. The exfoliated layer thickness was 330 nm, in good agreement with the projected range. The “optimum” conditions based on our experimental data showed that implanting CdZnTe with H⁺ at 77 K and a dose of 5×10¹⁶/cm² is compatible with developing high interfacial energy at the bonded interface during a low-temperature (150°C) anneal followed by layer exfoliation at higher (300°C) temperature.     

Temperature-Dependent Studies of Si-Implanted Al<Subscript>0.33</Subscript>Ga<Subscript>0.67</Subscript>N with Different Annealing Temperatures and Times

Electrical activation studies were carried out on Si-implanted Al_0.33Ga_0.67N as a function of ion dose, annealing temperature, and annealing time. The samples were implanted at room temperature with Si ions at 200 keV in doses ranging from 1 × 10¹⁴ cm⁻² to 1 × 10¹⁵ cm⁻², and subsequently proximity-cap annealed from 1150°C to 1350°C for 20 min to 60 min in a nitrogen environment. One hundred percent electrical activation efficiency was obtained for Al_0.33Ga_0.67N samples implanted with a dose of 1 × 10¹⁵ cm⁻² after annealing at either 1200°C for 40 min or at 1300°C for 20 min. The samples implanted with doses of 1 × 10¹⁴ cm⁻² and 5 × 10¹⁴ cm⁻² exhibited significant activations of 74% and 90% after annealing for 20 min at 1300°C and 1350°C, respectively. The mobility increased as the annealing temperature increased from 1150°C to 1350°C, showing peak mobilities of 80 cm²/V s, 64 cm²/V s, and 61 cm²/V s for doses of 1 × 10¹⁴ cm⁻², 5 × 10¹⁴ cm⁻², and 1 × 10¹⁵ cm⁻², respectively. Temperature-dependent Hall-effect measurements showed that most of the implanted layers were degenerately doped. Cathodoluminescence measurements for all samples exhibited a sharp neutral donor-bound exciton peak at 4.08 eV, indicating excellent recovery of damage caused by ion implantation.     

Characterization of very high purity InAs grown using trimethylindium and tertiarybutylarsine

The growth of high purity InAs by metalorganic chemical vapor deposition is reported using tertiarybutylarsine and trimethylindiμm. Specular surfaces were obtained for bulk 5-10 μm thick InAs growth on GaAs substrates over a wide range of growth conditions by using a two-step growth method involving a low temperature nucleation layer of InAs. Structural characterization was performed using atomic force microscopy and x-ray diffractometry. The transport data are complicated by a competition between bulk conduction and conduction due to a surface accumulation layer with roughly 2–4 × 10¹² cm⁻² carriers. This is clearly demonstrated by the temperature dependent Hall data. Average Hall mobilities as high as 1.2 x 10⁵ cm²/Vs at 50K are observed in a 10 μm sample grown at 540°C. Field-dependent Hall measurements indicate that the fitted bulk mobility is much higher for this sample, approximately 1.8 × 10⁵ cm²/Vs. Samples grown on InAs substrates were measured using high resolution Fourier transform photoluminescence spectroscopy and reveal new excitonic and impurity band emissions in InAs including acceptor bound exciton “two hole transitions.” Two distinct shallow acceptor species of unknown chemical identity have been observed.     

Nearly Perfect Electrical Activation Efficiencies from Silicon-Implanted Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N with High Aluminum Mole Fraction

Electrical activation studies of Al _x Ga_1−x N (x = 0.45 and 0.51) implanted with Si for n-type conductivity have been made as a function of ion dose and anneal temperature. Silicon ions were implanted at 200 keV with doses ranging from 1 × 10¹⁴ cm⁻² to 1 × 10¹⁵ cm⁻² at room temperature. The samples were subsequently annealed from 1150°C to 1350°C for 20 min in a nitrogen environment. Nearly 100% electrical activation efficiency was successfully obtained for the Si-implanted Al_0.45Ga_0.55N samples after annealing at 1350°C for doses of 1 × 10¹⁴ cm⁻² and 5 × 10¹⁴ cm⁻² and at 1200°C for a dose of 1 × 10¹⁵ cm⁻², and for the Al_0.51Ga_0.49N implanted with silicon doses of 1 × 10¹⁴ cm⁻² and 5 × 10¹⁴ cm⁻² after annealing at 1300°C. The highest room-temperature mobility obtained was 61 cm²/V s and 55 cm²/V s for the low-dose implanted Al_0.45Ga_0.55N and Al_0.51Ga_0.49N, respectively, after annealing at 1350°C for 20 min. These results show unprecedented activation efficiencies for Al _x Ga_1−x N with high Al mole fractions and provide suitable annealing conditions for Al _x Ga_1−x N-based device applications.     

Electronic properties and deep traps in electron-irradiated <Emphasis Type="Italic">n</Emphasis>-GaN

The study is concerned with the effect of electron irradiation (with the energies E = 7 and 10 MeV and doses D = 10¹⁶−10¹⁸ cm⁻²) and subsequent heat treatments in the temperature range 100–1000°C on the electrical properties and the spectrum of deep traps of undoped (concentration of electrons n = 1 × 10¹⁴−1 × 10¹⁶ cm⁻³), moderately Si-doped (n = (1.2−2) × 10¹⁷ cm⁻³), and heavily Si-doped (n = (2−3.5) × 10¹⁸ cm⁻³) epitaxial n-GaN layers grown on Al₂O₃ substrates by metal-organic chemical vapor deposition. It is found that, on electron irradiation, the resistivity of n-GaN increases, this is due to a shift of the Fermi level to the limiting position close to E _c −0.91 eV. The spectrum of deep traps is studied for the initial and electron-irradiated n-GaN. It is shown that the initial properties of the irradiated material are restored in the temperature range 100–1000°C, with the main stage of the annealing of radiation defects at about 400°C.     

Lateral schottky GaN rectifiers formed by Si<Superscript>+</Superscript> ion implantation

Type conversion of p-GaN by direct Si⁺ ion implantation and subsequent annealing was demonstrated by the fabrication of lateral Schottky diodes. The Si⁺ activation percentage was measured as a function of annealing time (30–300 sec) and temperature (1,000–1,200°C), reaching a maximum of ∼30% for 1,200°C, 2-min anneals. The resulting n-type carrier concentration was 1.1×10¹⁸ cm⁻³ for a moderate Si⁺ ion dose of ∼2×10¹⁴ cm⁻². The lateral Schottky diodes displayed a negative temperature coefficient of −0.15 V·K for reverse breakdown voltage.     

Redistribution of implanted dopants in GaN

Donor (S, Se, and Te) and acceptor (Mg, Be, and C) dopants have been implanted into GaN at doses of 3–5×10¹⁴ cm⁻² and annealed at tem peratures up to 1450°C. No redistribution of any of the elements is detectable by secondary ion mass spectrometry, except for Be, which displays behavior consistent with damageassisted diffusion at 900°C. At higher temperatures, there is no further movement of the Be, for peak annealing temperature durations of 10 s. Effective diffusivities are ≤2×10⁻¹³ cm²·s⁻¹ at 1450°C for each of the dopants in GaN.     

Optically active layers of silicon doped with erbium during sublimation molecular-beam epitaxy

A study is made of the electrical, optical, and structural properties of Si:Er layers produced by sublimation molecular-beam epitaxy. The Er and O contents in the layers, grown at 400–600°C, were as high as 5×10¹⁸ and 4×10¹⁹ cm⁻³, respectively. The electron concentration at 300 K was ∼10% of the total erbium concentration and the electron mobility was as high as 550 cm²/(V·s). Intense photoluminescence at 1.537 μm was observed from all the structures up to 100–140 K. The structure of the optically active centers associated with Er depended on the conditions under which the layers were grown. Fiz. Tekh. Poluprovodn. 33, 156–160 (February 1999)     

Growth Optimization of an Electron Confining InN/GaN Quantum Well Heterostructure

The molecular beam epitaxy of In-face InN (0001) epilayers with optimized surface morphology, structural quality, and electrical properties was investigated. Namely, compact InN epilayers with atomically flat surfaces, grown in a step-flow mode, were obtained using stoichiometric fluxes of In and N and substrate temperatures in the range from 400°C to 435°C. Typical values for the electron concentration and the Hall mobility at 300 K were 4.3 × 10¹⁸ cm⁻³ and 1210 cm²/Vs, respectively. The growth mode of InN during the very first stage of the nucleation was investigated analytically, and it was found that the growth proceeds through nucleation and fast coalescence of two-dimensional (2-D)–like InN islands. The preceding conditions were used to grow an InN/GaN quantum well (QW) heterostructure, which exhibited well-defined interfaces. Schottky contacts were successfully fabricated using a 15-nm GaN barrier enhancement cap layer. Capacitance-voltage measurements revealed the confinement of electrons within the InN QW and demonstrated the capability to modulate the electron density within an InN channel. The sheet concentration of the confined electrons (1.5 × 10¹³ cm⁻²) is similar to the calculated sheet polarization charge concentration (1.3 × 10¹³ cm⁻²) at the InN/GaN interface. However, electrons may also originate from ionized donors with a density of 8 × 10¹⁸ cm⁻³ within the InN layer.