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MBE growth technology for high quality strained III-V layers

The III-V films are grown on large automatically perfect terraces of III-V substrates which have a different lattice constant, with temperature and Group III and V arrival rates chosen to give a Group III element stable surface. The growth is pulsed to inhibit Group III metal accumulation of low temperature, and to permit the film to relax to equilibrium. The method of the invention: (1) minimizes starting step density on sample surface; (2) deposits InAs and GaAs using an interrupted growth mode (0.25 to 2 monolayers at a time); (3) maintains the instantaneous surface stoichiometry during growth (As-stable for GaAs, In-stable for InAs); and (4) uses time-resolved RHEED to achieve aspects (1) through (3).

Grunthaner, Frank J.

MBE growth technology for high quality strained III-V layers

III-V films are grown on large automatically perfect terraces of III-V substrates which have a different lattice constant, with temperature and Group II and V arrival rates chosen to give a Group III element stable surface. The growth is pulsed to inhibit Group III metal accumulation to low temperature, and to permit the film to relax to equilibrium. The method of the invention 1) minimizes starting step density on sample surface; 2) deposits InAs and GaAs using an interrupted growth mode (0.25 to 2 mono-layers at a time); 3) maintains the instantaneous surface stoichiometry during growth (As-stable for GaAs, In-stable for InAs); and 4) uses time-resolved RHEED to achieve aspects (1)-14 (3).

Grunthaner, Frank J.

Use of column V alkyls in organometallic vapor phase epitaxy (OMVPE)

The use of the column V-trialkyls trimethylarsenic (TMAs) and trimethylantimony (TMSb) for the organometallic vapor phase epitaxy (OM-VPE) of III-V compound semiconductors is reviewed. A general discussion of the interaction chemistry of common Group III and Group V reactants is presented. The practical application of TMSb and TMAs for OM-VPE is demonstrated using the growth of GaSb, GaAs(1-y)Sb(y), Al(x)Ga(1-x)Sb, and Ga(1-x)In(x)As as examples.

Ludowise, M. J.

TPSAS-NF1676L-16388-DND

The 60° rotated twin defect on {111} planes is one of the most common crystal structure defects in the cubic semiconductors. This defect has a sigma-3 grain boundary commonly called the sigma-3 twin defect on {111} plane. Sigma-3 twin defects are also frequently found in the group IV semiconductors (Si, Ge, C) in a diamond structure and other cubic zinc blende III-V and II-VI compound semiconductors such as GaP, InP, InGaAs, CdTd and ZnSe.

Yeonjoon Park

III-V aresenide-nitride semiconductor materials and devices

III-V arsenide-nitride semiconductor crystals, methods for producing such crystals and devices employing such crystals. Group III elements are combined with group V elements, including at least nitrogen and arsenic, in concentrations chosen to lattice match commercially available crystalline substrates. Epitaxial growth of these III-V crystals results in direct bandgap materials, which can be used in applications such as light emitting diodes and lasers. Varying the concentrations of the elements in the III-V crystals varies the bandgaps, such that materials emitting light spanning the visible spectra, as well as mid-IR and near-UV emitters, can be created. Conversely, such material can be used to create devices that acquire light and convert the light to electricity, for applications such as full color photodetectors and solar energy collectors. The growth of the III-V crystals can be accomplished by growing thin layers of elements or compounds in sequences that result in the overall lattice match and bandgap desired.

Major, Jo S.

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

Beatriz H. Cardelino

Ballistic transport in II-VI semiconductor compounds and alloys

Realistic band structures are used in calculating the group velocity and scattering rates for electrons with injection energies up to 1 eV in ZnTe, CdTe, and the low-effective-mass alloy Hg(0.7)Cd(0.3)Te. Scattering from longitudinal optical phonons, ionized impurities, and alloy disorder have been included in the full band-structure calculation, which automatically includes both intra- and intervalley scattering. Of the II-VI materials considered, at 77 K HgCdTe is superior for low injection energies (up to 0.25 eV) while CdTe is superior at higher injection energies (1 eV) at room temperature. The attainable mean free paths (equal to or greater than 1000 A) and group velocities (equal to or greater than 10 to the 8th cm/s) for both systems are comparable to values found in III-V systems.

Berding, M. A.

Reductive pathways in molten inorganic salts enable colloidal synthesis of III-V semiconductor nanocrystals

Colloidal quantum dots, with their size-tunable optoelectronic properties and scalable synthesis, enable applications in which inexpensive high-performance semiconductors are needed. Synthesis science breakthroughs have been key to the realization of quantum dot technologies, but important group III-group V semiconductors, including colloidal gallium arsenide (GaAs), still cannot be synthesized with existing approaches. The high-temperature molten salt colloidal synthesis introduced in this work enables the preparation of previously intractable colloidal materials. We directly nucleated and grew colloidal quantum dots in molten inorganic salts by harnessing molten salt redox chemistry and using surfactant additives for nanocrystal shape control. Synthesis temperatures above 425°C are critical for realizing photoluminescent GaAs quantum dots, which emphasizes the importance of high temperatures enabled by molten salt solvents. We generalize the methodology and demonstrate nearly a dozen III-V solid-solution nanocrystal compositions that have not been previously reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

(abstract) Transmission Electron Microscopy of Al(sub x)Ga(sub 1-x)N/SiC Multilayer Structures Grown on Sapphire Substrates

The potential of wide-band-gap III-V nitrides as ultraviolet sensors and light emitters has prompted an increasing amount of work recently, including the fabrication of the first UV sensors from as-deposited single crystal GaN. We have used high resolution transmission electron microscopy (TEM) to study the microstructure of two novel developments of wide-band-gap III-V nitrides: the growth of ultra-short period GaN/AlN superlattices; and the incorporation of SiC layers into Al(sub x)Ga(sub 1-x)N structures. By varying the relative periods in a GaN/AlN superlattice, the band gap of the composite can be tailored to lie between the elemental values of 365 nm for GaN and 200 nm for AlN. The group IV semiconductor, SiC, has a wide band-gap and has a close lattice match (less than 3 %) to Al(sub x)Ga(sub 1-x)N for growth on the basal plane. Demonstration of epitaxial growth for Al(sub x)Ga(sub 1-x)N/SiC multilayers would introduce a wide band-gap analog to the already existing family of III-V and Si(sub 1-x)Ge(sub x) heteroepitaxial growth systems. Although good quality growth of GaN on SiC substrates has been demonstrated, Al(sub x)Ga(sub 1-x)N/SiC multilayer structures have never been grown and the interfacial structure is unknown.

GaN AlN GaN/AlN

(abstract) Transmission Electron Microscopy of Al(sub x)Ga(sub 1-x)N/SiC Multilayer Structures

The potential of wide-band-gap III-V nitrides as solar-blind ultraviolet sensors and light emitters has prompted an increasing amount of work recently, including the fabrication of the first UV sensors from as-deposited single crystal GaN. We have used high resolution transmission electron microscopy (TEM) to study the microstructure of two novel developments of wide-band-gap III-V nitrides: the growth of ultra-short period GaN/AlN super lattices (digital alloys); and the incorporation of SiC layers into Al(sub x)Ga(sub 1-x)N structures. By varying the relative periods in a GaN/AlN superlattice, it should be possible to tailor the band gap of the composite to lie between the elemental values of 365 nm for GaN and 200 nm for AlN. The group IV semiconductor, SiC, has a close lattice match (< 3%) to Al(sub x)Ga(sub 1-x)N for growth on the basal plane. Demonstration of epitaxial growth for Al(sub x)Ga(sub 1-x)N/SiC multilayers could enable an extension of direct band-gap material towards the visible.

microscopy GaN AlN semiconductor SiC

Closing the Accuracy Gap in Tandem Photovoltaic Testing: An Accessible and Efficient Spectral Tuning Method Using LED-Based Simulators for Research Laboratories and Industry

Accurate performance calibration of multijunction (MJ) solar cells is critical for advancing this technology toward large-scale terrestrial application, yet existing testing methods developed by photovoltaics calibration laboratories remain prohibitively complex and resource intensive for most research laboratories. Current approaches rely on expensive multisource simulators and/or intricate spectral tuning algorithms, limiting accessibility and hindering standardized comparisons of emerging MJ technologies such as perovskite-based tandems. This paper introduces a streamlined spectral irradiance adjustment method for light-emitting diode (LED)-based solar simulators, which are increasingly adopted in the photovoltaics community due to their versatility and cost-effectiveness. The method we present bins LED channels into groups based on the number of junctions of the MJ photovoltaic device under test (DUT) and their corresponding band gaps and incorporates an automated tuning algorithm that eliminates the need to adjust each channel’s irradiance individually. This tuning algorithm requires the relative spectral responsivities of both the DUT and a broadband reference cell, as well as a calibrated spectroradiometer. Measurement validation across various MJ devices, including III-V and perovskite/silicon tandems, demonstrates excellent agreement within 1% with well-established xenon-tungsten multisource simulators and associated tuning algorithms. By enabling precise spectral tuning with readily available equipment and a simple tuning algorithm, our approach bridges the measurement accuracy gap between research laboratories and accredited testing facilities, fostering more reliable device comparisons and accelerating the translation of MJ technologies into real-world energy systems.

14 SOLAR ENERGY

Quantum-Dot Laser for Wavelengths of 1.8 to 2.3 micron

The figure depicts a proposed semiconductor laser, based on In(As)Sb quantum dots on a (001) InP substrate, that would operate in the wavelength range between 1.8 and 2.3 m. InSb and InAsSb are the smallest-bandgap conventional III-V semiconductor materials, and the present proposal is an attempt to exploit the small bandgaps by using InSb and InAsSb nanostructures as midinfrared emitters. The most closely related prior III-V semiconductor lasers are based, variously, on strained InGaAs quantum wells and InAs quantum dots on InP substrates. The emission wavelengths of these prior devices are limited to about 2.1 m because of critical quantum-well thickness limitations for these lattice mismatched material systems. The major obstacle to realizing the proposed laser is the difficulty of fabricating InSb quantum dots in sufficient density on an InP substrate. This difficulty arises partly because of the weakness of the bond between In and Sb and partly because of the high temperature needed to crack metalorganic precursor compounds during the vapor-phase epitaxy used to grow quantum dots: The mobility of the weakly bound In at the high growth temperature is so high that In adatoms migrate easily on the growth surface, resulting in the formation of large InSb islands at a density, usually less than 5 x 10(exp 9) cm(exp -2), that is too low for laser operation. The mobility of the In adatoms could be reduced by introducing As atoms to the growth surface because the In-As bond is about 30 percent stronger than is the In-Sb bond. The fabrication of the proposed laser would include a recently demonstrated process that involves the use of alternative supplies of precursors to separate group-III and group-V species to establish local non-equilibrium process conditions, so that In(As)Sb quantum dots assemble themselves on a (001) InP substrate at a density as high as 4 x 10(exp 10) cm(exp -2). Room-temperature photoluminescence spectra of quantum dots formed by this process indicate that they emit at wavelengths from 1.7 to 2.3 microns.

Qiu, Yueming

Correlated X‐Ray and Electron Microscopies of a Single Biphasic GaAs Nanowire

Engineering the properties of semiconductors by changing their crystalline phase is a technologically and economically relevant alternative to doping using foreign elements, with strong potential for photonic and electronic applications. Although major advances have been reported recently for crystal‐phase engineering of III‐V and group IV semiconductor nanowires, interfacing two mismatched crystalline phases in a nanostructure induces several deformation mechanisms, which remain largely unexplored. Here, using state‐of‐the‐art synchrotron X‐ray nanobeam diffraction and transmission electron microscopy, subtle twisting and bending is unveiled within an individual GaAs nanowire containing cubic and hexagonal segments. Their role is discussed in accommodating the inter‐reticular spacing fluctuations, and their variations are correlated to the nanoscale phase distribution and to the effect of the NW support. This study brings direct evidence of a complex combination of deformation mechanisms in biphasic nanowires, which opens a new path to tune the nanowire properties with appealing perspectives for device engineering in nanophotonics and nanomechanics.

III-V semiconductors

Halide Vapor Phase Epitaxy of Ge from an Elemental Source

Halide vapor phase epitaxy shows promise for low-cost photovoltaic device manufacturing because of its high growth rates and lower cost elemental precursors but previously has not been used to deposit epitaxial Ge. Here, we demonstrate Ge deposition by generating GeCl 2 in situ from solid Ge and HCl in a N 2 ambient. To achieve Ge growth, we inject AsH 3 and PH 3 as sources of active hydrogen to the growth surface to create a driving force for growth. We do not observe Ge growth unless a supply of hydrogen is added, consistent with thermodynamic calculations. Furthermore, we show the hydrogen source must crack readily on the substrate surface to enable growth; relatively stable sources such as H 2 do not cause growth. Unintentional group V doping is one drawback of using AsH 3 and PH 3 to drive the Ge reaction. We observed As or P concentrations in the Ge films ranging from 4 x 10 17 to 1 x 10 18 atoms/cm 3 , concentrations that can drastically influence device characteristics. However, we note there are numerous other "helper molecule" options that can provide active hydrogen without doping or etching the material. This work provides a path forward for Ge deposition for optoelectronic devices from an elemental source.

14 SOLAR ENERGY

Electron beam source molecular beam epitaxial growth of analog graded Al(x)Ga(1-x)As ballistic transistors

A new method has been developed for the growth of graded band-gap Al(x)Ga(1-x)As alloys by molecular beam epitaxy which is based upon electron beam evaporation of the group III elements. The metal fluxes are measured and feedback controlled using a modulated ion gauge sensor. The system is computer controlled which allows precise programming of the Ga and Al evaporation rates. The large dynamic response of the metal sources enables growth of variable band-gap III-V alloys with arbitrary composition profiles. This new technique is demonstrated by synthesis of analog graded Al(x)Ga(1-x)As unipolar ballistic electron transistors.

Malik, Roger J.

Lattice-matched heteroepitaxy of wide gap ternary compound semiconductors

A variety of applications are identified for heteroepitaxial structures of wide gap I-III-VI2 and II-IV-V2 semiconductors, and are assessed in comparison with ternary III-V alloys and other wide gap materials. Non-linear optical applications of the I-III-VI2 and II-IV-V2 compound heterostructures are discussed, which require the growth of thick epitaxial layers imposing stringent requirements on the conditions of heteroepitaxy. In particular, recent results concerning the MOCVD growth of ZnSi(x)Ge(1-x)P2 alloys lattice-matching Si or GaP substrates are reviewed. Also, heterostructures of Cu(z)Ag(1-z)GaS2 alloys that lattice-match Si, Ge, GaP or GaAs substrates are considered in the context of optoelectronic devices operating in the blue wavelength regime. Since under the conditions of MOCVD, metastable alloys of the II-IV-V2 compounds and group IV elements are realized, II-IV-V2 alloys may also serve as interlayers in the integration of silicon and germanium with exactly lattice-matched tetrahedrally coordinated compound semiconductors, e.g. ZnSi(x)Ge(1-x)P2.

Bachmann, Klaus J.

Lattice-matched heteroepitaxy of wide gap ternary compound semiconductors

A variety of applications are identified for heteroepitaxial structures of wide gap I-III-VI(sub 2) and II-IV-V(sub 2) semiconductors, and are assessed in comparison with ternary III-V alloys and other wide gap materials. Non-linear optical applications of the I-III-VI(sub 2) and II-IV-V(sub 2) compound heterostructures are discussed, which require the growth of thick epitaxial layers imposing stringent requirements on the conditions of heteroepitaxy. In particular, recent results concerning the MOCVD growth of ZnSi(x)Ge(1-x)P2 alloys lattice matching Si or GaP substrates are reviewed. Also, heterostructures of Cu(z)Ag(1-z)GaS2 alloys that lattice-match Si, Ge, GaP, or GaAs substrates are considered in the context of optoelectronic devices operating in the blue wavelength regime. Since under the conditions of MOCVD, metastable alloys of the II-IV-V(sub 2) compounds and group IV elements are realized, II-IV-V(sub 2) alloys may also serve as interlayers in the integration of silicon and germanium with exactly lattice-matched tetrahedrally coordinated compound semiconductors, e.g. ZnSi(x)Ge(1-x)P2.

Bachmann, Klaus J.

Electrochemical Characterization of Semiconductor Materials and Structures

For a period covering October 1, 1995 through August 12, 1996, the research group at CSU has conducted theoretical and experimental research on "Electrochemical Characterization of Semiconductor Materials and Structures. " The objective of this investigation was to demonstrate the applicability of electrochemical techniques for characterization of complex device structures based on InP and GaAs, Ge, InGaAs, InSb, InAs and InSb, including: (1) accurate EC-V net majority carrier concentration depth profiling, and (2) surface and bulk structural and electrical type defect densities. Our motivation for this R&D effort was as follows: "Advanced space solar cells and ThermoPhotoVoltaic (TPV) cells are fabricated using a large variety of III-V materials based on InP and GaAs for solar cells and low bandgap materials such as Ge, InGaAs, InAs and InSb for TPV applications. At the present time for complex device structures using these materials, however, there is no simple way to assess the quality of these structures prior to device fabrication. Therefore, process optimization is a very time consuming and a costly endeavor". Completion of this R&D effort would have had unquestionable benefits for space solar cell and TPV cells, since electrochemical characterization of the above cell structures, if properly designed can provide many useful structural and electrical material information virtually at any depth inside various layers and at the interfaces. This, could have been applied for step-by-step process optimization, which could have been used for fabrication of new generation high efficiency, low cost space PV and TPV cells.

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