Growth and characterization of indium arsenide thin films

The growth and characterization of indium arsenide films grown on indium phosphide substrates by the metal organic chemical vapor deposition (MOCVD) process is reported. Either ethyl dimethyl indium or trimethyl indium were found to be suitable in combination with arsine as source compounds. The highest electron mobilities were observed in films nucleated at reduced growth temperature. Scanning electron microscopy studies show that film nucleation at low temperature prevents thermal etch pits from forming on the InP surface before growth proceeds at an elevated temperature. Electron mobilities as high as 21,000 cm²V⁻¹ sec⁻¹ at 300 K were thus obtained for a film only 3.4 μm thick. This mobility is significantly higher than was previously observed in InAs films grown by MOCVD. From the depth dependence of transport properties, we find that in our films electrons are accumulated near the air interface of the film, presumably by positive ions in the native oxide. The mobility is limited by electrons scattering predominantly from ionized impurities at low temperature and from lattice vibrations and dislocations at high temperature. However, scattering from dislocations is greatly reduced in the surface accumulation layer due to screening by a high density of electrons. These dislocations arise from lattice mismatch and interface disorder at the film-substrate interface, preventing these films from obtaining mobility values of bulk indium arsenide.     

InP-on-CdS thin film heterostructures

Thin films of InP were deposited on single crystals and thin films of CdS by the planar reactive deposition technique. Good local epitaxy was observed on single crystals of CdS as well as InP and GaAs. The electrical evaluation of unintentionally doped films on semi-insulating InP substrates show them to be n-type with room temperature electron concentrations ranging from 5 × 1016 cm⁻³ to 5 × 10¹⁷ cm⁻³ and mobilities up to 1350 cm²/Vsec. For films intentionally doped with Mn and Be, p-type films were obtained. For Mn doping (deep acceptor level), room temperature mobilities as high as 140 cm²/Vsec and free carrier concentrations as low as 5 × 10¹⁶ cm⁻³ (with dopant level of 3 × 10¹⁸ cm⁻³) were obtained. For Bedoped films, free carrier concentrations of about 5 × 10¹⁸ cm⁻³ and mobilities of 20 cm²/Vsec were found. Scanning electron microscope and microprobe pictures show appreciable interdiffusion between the InP/CdS thin-film pair for InP deposited at 450°C. The loss of Cd from the CdS and the presence of an indium-cadmium-sulfur phase at the InP/CdS interface were observed. Interdiffusion is alleviated for InP deposition at lower temperatures. Supported in part by ERDA and AFOSR.     

The impact of nitridation and nucleation layer process conditions on morphology and electron transport in GaN epitaxial films

A systematic study has been performed to determine the characteristics of an optimized nucleation layer for GaN growth on sapphire. The films were grown during GaN process development in a vertical close-spaced showerhead metalorganic chemical vapor deposition reactor. The relationship between growth process parameters and the resultant properties of low temperature GaN nucleation layers and high temperature epitaxial GaN films is detailed. In particular, we discuss the combined influence of nitridation conditions, V/III ratio, temperature and pressure on optimized nucleation layer formation required to achieve reproducible high mobility GaN epitaxy in this reactor geometry. Atomic force microscopy and transmission electron microscopy have been used to study improvements in grain size and orientation of initial epitaxial film growth as a function of varied nitridation and nucleation layer process parameters. Improvements in film morphology and structure are directly related to Hall transport measurements of silicon-doped GaN films. Reproducible growth of silicon-doped GaN films having mobilities of 550 cm²/Vs with electron concentrations of 3 × 10¹⁷ cm⁻³, and defect densities less than 10⁸ cm⁻² is reported. These represent the best reported results to date for GaN growth using a standard two-step process in this reactor geometry.     

Study of indium droplets formation on the InxGa1−xN films by single crystal x-ray diffraction

Indium droplet formation during the epitaxial growth of In_xGa_1−xN films is a serious problem for achieving high quality films with high indium mole fraction. In this paper, we studied the formation of indium droplets on the In_xGa_1−xN films grown by metalorganic chemical vapor deposition (MOCVD) using single crystal x-ray diffraction. It is found that the indium (101) peak in the x-ray diffraction spectra can be utilized as a quantitative measure to determine the amounts of indium droplets on the film. It is shown by monitoring the indium diffraction peak that the density of indium droplets increases at lower growth temperature. To suppress these indium droplets, a modulation growth technique is used. Indium droplet formation in the modulation growth is investigated and it is revealed in our study that the indium droplets problem has been partially relieved by the modulation growth technique.     

Characterization of GaxIn1−xAs grown with TMIn

High quality Ga_xIn_1−xAs, lattice matched to InP, has been reproducibly grown by organometallic vapor phase epitaxy using trimethylgallium (TMGa), trimethylindium (TMIn), and AsH₃ in an atmospheric pressure reactor with no observable adduct formation. For the first time, using TMIn, room temperature electron mobilities of 10⁴ cm²/Vs and 77 K mobilities greater than 4 × 10⁴ cm²/Vs have beep obtained. Residual donor doping densities in the low 10¹⁵ cm⁻³ range have been routinely obtained. Material with excellent morphology has been grown from 540 to 670 C with the highest quality material being obtained near 650 C. The 4 K photoluminescence (PL) peak due to carbon is not seen in the material grown at higher temperatures; however, it increases dramatically as the growth temperature is lowered. This increased carbon incorporation leads to a sharp drop in the electron mobility, which exhibits a T^−0.5 behavior between 77 and 300 K. With optimum growth conditions, 4 K PL halfwidths of 4–5 meV are commonly observed. This high quality material is characterized by x-ray diffraction, PL, and Hall mobility measurements. Carbon and other impurity incorporation as a function of the growth parameters will be described.     

Growth and characterization of inTISb for IR-detectors

Epitaxial In_1-xTl_xSb films with compositions up to x = 0.1 have been demonstrated using the metalorganic chemical vapor deposition technique on InSb and GaAs substrates. A specially designed high-temperature source delivery system was used for the low vapor pressure cyclopentadienylthallium source. Tl-compositions in the deposited films were measured by Rutherford backscattering spectroscopy which confirmed the incorporation of up to 10% Tl. Room temperature infrared transmission spectra of InTISb exhibited considerable absorption beyond 7 μm. Photoconductive detectors were fabricated in InTISb films grown on semi-insulating GaAs. Spectral response measurements showed substantial photoresponse at 8.5 to 14 μm. In spite of the large lattice-mismatch (≈14%) between InTISb and GaAs, photoconductive detectors exhibited black-body detectivities (D^* _bb) of 5.0 × 10⁸ cm-Hz^1/2W⁻¹ at 40K.     

Growth of tin-doped indium antimonide for magnetoresistors

Magnetoresistors made from n-type indium antimonide are of interest for magnetic position sensing applications. In this study, tin-doped indium antimonide was grown by the metalorganic chemical vapor deposition technique using trimethylindium, trisdimethylaminoantimony, and tetraethyltin in a hydrogen ambient. Using a growth temperature of 370°C and a pressure of 200 Torr, it was found that the electron density in tin-doped films varied from 3.3×10¹⁶ cm⁻³ to 4.0×10¹⁷ cm⁻³ as the 5/3 ratio was varied from 4.8 to 6.8. From secondary ion mass spectroscopy (SIMS) studies, it was found that this variation is not caused by a change in site occupancy of the tin atoms from antimony to indium lattice sites, but rather to a change in the total tin concentration incorporated into the films. This dependence of tin incorporation on stoichiometry could be used to rapidly vary the doping level during growth. Undoped films grown under similar conditions had electron densities of about 2×10¹⁶ cm⁻³ and electron mobilities near 50,000 cm²V⁻¹s⁻¹ at room temperature for films that were only 1.5 μm thick on a gallium arsenide substrate. Attempts to grow indium antimonide at 280°C resulted in p-type material caused by carbon incorporation. The carbon concentration as measured with SIMS increased rapidly with increasing growth rate, to above 10¹⁹ cm⁻³ at 0.25 μm/h. This is apparently caused by incomplete pyrolysis of a reactant at this low growth temperature. Growth at 420°C resulted in rough surface morphologies. Finally, it was demonstrated that films with excellent electron mobility and an optimized doping profile for magnetoresistors can be grown.     

Investigation of microstructure and V-defect formation in In<Subscript>x</Subscript>Ga<Subscript>1−x</Subscript>N/GaN MQW grown using temperature-gradient metalorganic chemical vapor deposition

Temperature-gradient metalorganic chemical vapor deposition (MOCVD) was used to deposit In_xGa_1−xN/GaN multiple quantum well (MQW) structures with a concentration gradient of indium across the wafer. These MQW structures were deposited on low defect density (2×10⁸ cm⁻²) GaN template layers for investigation of microstructural properties and V-defect (pinhole) formation. Room temperature (RT) photoluminescence (PL) and photomodulated transmission (PT) were used for optical characterization, which show a systematic decrease in emission energy for a decrease in growth temperature. Triple-axis x-ray diffraction (XRD), scanning electron microscopy, and cross-sectional transmission electron microscopy were used to obtain microstructural properties of different regions across the wafer. Results show that there is a decrease in crystal quality and an increase in V-defect formation with increasing indium concentration. A direct correlation was found between V-defect density and growth temperature due to increased strain and indium segregation for increasing indium concentration.     

Indium doping of HgCdTe grown by metalorganic chemical vapor deposition-direct alloy growth using triisopropylindium and diisopropyltellurium triisopropylindium adduct

A new indium source, triisopropylindium, was used to dope HgCdTe layers grown by metalorganic chemical vapor deposition n-type with carrier concentrations, n_H, in the range between low 10¹⁵ and low 10¹⁷ cm⁻³ at 77K. The reproducibility of carrier concentration was found to be excellent for n_H<3×10¹⁵ cm⁻³. High electron mobilities and minority carrier lifetime comparable to published values indicate that indium doping produces high quality n-type HgCdTe material. State-of the-art photodiodes were obtained by growing a p-type HgCdTe layer by liquid phase epitaxy on an indium doped layer. In addition, and adduct compound formed between diisopropyltellurium (DIPTe) and triisopropylindium (TIPIn): DIPTe·InTIP, was also found to be a viable n-type dopant for HgCdTe especially at concentrations in the low 10¹⁵ cm⁻³ or less.     

P- and N-type doping of GaN and AlGaN epitaxial layers grown by metalorganic chemical vapor deposition

Mg- and Si-doped GaN and AlGaN films were grown by metalorganic chemical vapor deposition and characterized by room-temperature photoluminescence and Hall-effect measurements. We show that the p-type carrier concentration resulting from Mg incorporation in GaN:Mg films exhibits a nonlinear dependence both on growth temperature and growth pressure. For GaN and AlGaN, n-type doping due to Si incorporation was found to be a linear function of the silane molar flow. Mg-doped GaN layers with 300K hole concentrations p ∼2×10¹⁸ cm⁻³ and Si-doped GaN films with electron concentrations n∼1×10¹⁹ cm⁻³ have been grown. N-type Al_0.10Ga_0.90N:Si films with resistivities as low as p ∼6.6×10⁻³ Ω-cm have been measured.     

Liquid encapsulated czochralski pulling of InP crystals

The growth of bulk indium phosphide crystals via liquid encapsulated Czochralski pulling from both stoichiometric and nonstoichiometric melts is described. Nominally un-doped crystals with carrier concentration N_D-N_A = 6 × 10¹⁵ cm⁻³ and Hall mobilities of 4510 cm²/Vsec at room temperature were grown. Also, we prepared Zn-or Cd-doped p-type crystals in the range 10¹⁶ ≤ N_A-N_D ≤ 10¹⁸ cm⁻³ with Hall mobilities ≤ 130 cm²/Vsec and Sn-doped n-type crystals in the range 4 × 10¹⁷ ≤ N_A-N_D ≤ 10¹⁸ cm^-3 with Hall mobilities ≤ 2400 cm²/Vsec. The dislocation density of LEC pulled InP crystals is typically ~ 10⁴ cm⁻².     

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.     

Growth of InAs-AlSb quantum wells having both high mobilities and high concentrations

Low-temperature mobilities in InAs-AlSb quantum wells depend sensitively on the buffer layer structures. Reflection high energy electron diffraction and x-ray diffraction show that the highest crystalline quality and best InAs transport properties are obtained by a buffer layer sequence GaAs → AlAs → AlSb → GaSb, with a final GaSb layer thickness of at least 1 μm. Using the improved buffer scheme, mobilities exceeding 600,000 cm²/Vs at 10 K are routinely obtained. Modulation δ-doping with tellurium has yielded electron sheet concentrations up to 8 × 10¹² cm⁻² while maintaining mobilities approaching 100,000 cm²/Vs at low temperatures.     

The effect of a continuous etch on the growth rate and morphology of InP prepared by the vapor phase epitaxial-hydride method

A study of the effect of a continuousin situ etch of HC1 on growth rate and the properties of epitaxial InP layers prepared by the vapor phase epitaxial-hydride technique is reported. Growth rates were determined as a function of the following variables: HC1 flow rates in the mixing and source zones, PH₃ flow rates, and mixing zone temperatures. Epitaxial InP structures with good morphology were obtained when the continuous HC1 etch was varied between 0.8 and 1.5 cc/min. The average values (77K) of the carrier concentrations and mobilities were 1.3 × 10¹⁵ cm^s−3 and 23,000 cm²V^−l Sec⁻¹, respectively. The study indicates that the continuousin situ HCl etch improves the quality of epitaxial InP layers.     

Effect of copper and chlorine on the properties of SiO2 encapsulated polycrystalline CdSe films

The effects of different copper doping concentrations on the properties of SiO₂ encapsulated CdSe films have been investigated. Two methods were used to dope the films with copper: ion implantation and diffusion from a surface layer. The room temperature dark resistivity of films annealed in oxygen at 450°C was found to increase as the copper concentration was increased until a maximum resistivity of 10⁸ ohm cm occurred at a copper concentration of 10²⁰ atoms cm⁻³. The room temperature resistivity in the light was found to be independent of the copper concentration and whether the films were annealed in argon or oxygen. During annealing the grains grew from 0.03 μm to 0.3 μm and this growth was independent of the doping or the annealing ambient. The energy levels, carrier mobilities, and microstructure of the annealed films were dependent on the method of doping. The ion implanted films had an additional energy level at 0.33 eV and their mobility was a factor of 4 smaller than films doped by the surface diffusion method, whose mobilities were 20 to 35 cm²V⁻¹ s⁻¹. The addition of chlorine to copper doped films had no effect on either the resistivity or photosensitivity but slowed the response times of the photocurrent by a factor of 10. No energy levels were observed which could be associated with the copper nor was the copper found to affect the density of the observed intrinsic levels at 0.65 and 1.1 eV.     

Field Emission and Electric Discharge of Nanocrystalline Diamond Films

Nanocrystalline diamond (NCD) films were produced by microwave plasma-enhanced chemical vapor deposition (MPECVD) using gas mixtures of Ar, H₂, and CH₄. The structural properties, electron emission, and electric discharge behaviors of the NCD films varied with H₂ flow rates during MPECVD. The turn-on field for electron emission at a pressure of 2.66 × 10⁻⁴ Pa increased from 4.2 V μm⁻¹ for the NCD films that were deposited using a H₂ flow rate of 10 cm³ min⁻¹ to 7 V μm⁻¹ for films deposited at a H₂ flow rate of 20 cm³ min⁻¹. The NCD film with a low turn-on field also induced low breakdown voltages in N₂. The grain size and roughness of the NCD films may influence both the electron emission and the electric discharge behaviors of the NCD cathodes.     

Pulsed laser deposition and processing of wide band gap semiconductors and related materials

The present work describes the novel, relatively simple, and efficient technique of pulsed laser deposition for rapid prototyping of thin films and multi-layer heterostructures of wide band gap semiconductors and related materials. In this method, a KrF pulsed excimer laser is used for ablation of polycrystalline, stoichiometric targets of wide band gap materials. Upon laser absorption by the target surface, a strong plasm a plume is produced which then condenses onto the substrate, kept at a suitable distance from the target surface. We have optimized the processing parameters such as laser fluence, substrate temperature, background gas pressure, target to substrate distance, and pulse repetition rate for the growth of high quality crstalline thin films and heterostructures. The films have been characterized by x-ray diffraction, Rutherford backscattering and ion channeling spectrometry, high resolution transmission electron microscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy, cathodoluminescence, and electrical transport measurements. We show that high quality AlN and GaN thin films can be grown by pulsed laser deposition at relatively lower substrate temperatures (750–800°C) than those employed in metal organic chemical vapor deposition (MOCVD), (1000–1100°C), an alternative growth method. The pulsed laser deposited GaN films (∼0.5 μm thick), grown on AlN buffered sapphire (0001), shows an x-ray diffraction rocking curve full width at half maximum (FWHM) of 5–7 arc-min. The ion channeling minimum yield in the surface region for AlN and GaN is ∼3%, indicating a high degree of crystallinity. The optical band gap for AlN and GaN is found to be 6.2 and 3.4 eV, respectively. These epitaxial films are shiny, and the surface root mean square roughness is ∼5–15 nm. The electrical resistivity of the GaN films is in the range of 10⁻²–10² Θ-cm with a mobility in excess of 80 cm²V⁻¹s⁻¹ and a carrier concentration of 10¹⁷–10¹⁹ cm⁻³, depending upon the buffer layers and growth conditions. We have also demonstrated the application of the pulsed laser deposition technique for integration of technologically important materials with the III–V nitrides. The examples include pulsed laser deposition of ZnO/GaN heterostructures for UV-blue lasers and epitaxial growth of TiN on GaN and SiC for low resistance ohmic contact metallization. Employing the pulsed laser, we also demonstrate a dry etching process for GaN and AlN films.     

The influence of OMVPE growth pressure on the morphology, compensation, and doping of GaN and related alloys

Growth pressure has a dramatic influence on the grain size, transport characteristics, optical recombination processes, and alloy composition of GaN and AlGaN films. We report on systematic studies which have been performed in a close spaced showerhead reactor and a vertical quartz tube reactor, which demonstrate increased grain size with increased growth pressure. Data suggesting the compensating nature of grain boundaries in GaN films is presented, and the impact of grain size on high mobility silicon-doped GaN and highly resistive unintentionally doped GaN films is discussed. We detail the influence of pressure on AlGaN film growth, and show how AlGaN must be grown at pressures which are lower than those used for the growth of optimized GaN films. By controlling growth pressure, we have grown high electron mobility transistor (HEMT) device structures having highly resistive (10⁵ Ω-cm) isolation layers, room temperature sheet carrier concentrations of 1.2×10¹³ cm⁻² and mobilities of 1500 cm²/Vs, and reduced trapping effects in fabricated devices.     

Electrical properties and compositional distributions of CVT and PVT grown Hg1−xCdxTe epilayers

Epitaxial layers of Hg_1−xCd_x Te were grown on CdTe substrates by the chemical vapor transport technique using Hgl₂ as a transport agent. The epilayers were of nearly uniform composition both laterally and to a depth of about one-half of the layer thickness. By comparison, the composition varied continuously throughout the depth of the layer for epilayers grown by the physical vapor transport technique. Layers were grown both p- and n-type with carrier concentrations on the order of 10¹⁷ cm⁻³. Low-temperature annealing was used to convert the p-type layers into n-type. The room-temperature carrier mobilities of as-grown and converted n-type layers ranged from 10³ to 10⁴ cm²/V-s depending on the composition and are comparable to previous literature values for undoped Hg_1−xCd_xTe crystals.     

Low oxygen and carbon incorporation in AIGaAs using tritertiarybutylaluminum in organometallic vapor phase epitaxy

High-quality AIGaAs epilayers have been grown by low pressure organometallic vapor phase epitaxy with a new aluminum precursor tritertiarybutylaluminum (TTBAl). Layers grown at 650°C have a featureless mirror surface morphology and strong room temperature photoluminescence. Carbon was not detectable in chemical analysis by secondary ion mass spectroscopy, nor in low temperature (4K) photoluminescence spectra. Oxygen concentration in Al_0.25Ga_0.75As is as low as ∼2−3 × 10¹⁷ cm⁻³. Nominally undoped AIGaAs layers exhibit n-type conductiv-ity with electron concentrations at ∼ 1−1.5 × 10¹⁶ cm⁻³. A high degree of compo-sitional uniformity over 5 cm diam substrates (0.268 ±0.001) was obtained. These results indicate the potential for TTBA1 as an aluminum precursor for low temperature growth of Al-containing III-V alloys.