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DOE OSTI2025

Controlling Interfacial Energetics and Charge Transfer Rates in 2D Semiconductors: Fundamental Studies en Route to Photoelectrochemical Energy Conversion Beyond the Shockley-Queisser Limit (Final Scientific/Technical Report)

Current photovoltaic and solar-to-fuel technologies do not fully utilize the energy of sunlight because excess photon energy above the semiconductor band gap is rapidly lost as heat through hot-carrier thermalization. Overcoming this loss mechanism is critical, as hot-carrier-based energy conversion systems are predicted to exceed the conventional efficiency limit of ~33%. This project advanced fundamental understanding of hot-carrier energy conversion in two-dimensional (2D) semiconductors, with a focus on monolayer MoS 2 . Using a combination of electrochemical microscopy and in situ ultrafast spectroscopic measurements, this research directly demonstrated hot-carrier extraction from monolayer MoS 2 photoelectrodes in proof-of-concept liquid junction solar cells. These measurements established that hot-carrier transfer can compete with ultrafast carrier cooling at solid–liquid interfaces, providing unambiguous experimental evidence that hot-carrier extraction is feasible in atomically thin semiconductors under operating photoelectrochemical conditions. Beyond demonstration, the project identified design rules for tuning hot-carrier extraction rates relative to cooling rates in 2D semiconductor photoelectrodes. The outcomes of this research provide foundational thermodynamic and kinetic insights for the rational design of next-generation hot-carrier-enabled solar energy conversion systems. These findings have broad implications for photoelectrochemical solar fuels production, electrocatalysis, and emerging energy conversion architectures that seek to harness nonequilibrium charge carriers for enhanced efficiency.

14 SOLAR ENERGY↗

NASA NTRS1980

Apparatus for measuring semiconductor device resistance

A test structure is described for enabling the accurate measurement of the resistance characteristics of a semiconductor material and includes one or more pairs of electrical terminals disposed on the surface of the material to enable measurements of the resistance encountered by currents passed between the terminals. A pair of terminals includes a first terminal extending in a closed path, such as a circle, around a second terminal, so that all currents flowing between the terminals flow along a region of known width and length. Two or more pairs of concentric terminals can be utilized, wherein the ratio of radii of each pair of terminals is the same as the ratio for all other pairs of terminals, to facilitate the calculation of the contact resistance between each terminal and the semiconductor surface, as well as the calculation of the resistance of the semiconductor material apart from the effect of the terminal to semiconductor contact resistances.

Matzen, W. J.↗

NASA NTRS1984

Effect of barrier height on friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals

Friction experiments were conducted for the semiconductors silicon and gallium arsenide in contact with pure metals. Polycrystalline titanium, tantalum, nickel, palladium, and platinum were made to contact a single crystal silicon (111) surface. Indium, nickel, copper, and silver were made to contact a single crystal gallium arsenide (100) surface. Sliding was conducted both in room air and in a vacuum of 10 to the minus 9th power torr. The friction of semiconductors in contact with metals depended on a Schottky barrier height formed at the metal semiconductor interface. Metals with a higher barrier height on semiconductors gave lower friction. The effect of the barrier height on friction behavior for argon sputtered cleaned surfaces in vacuum was more specific than that for the surfaces containing films in room air. With a silicon surface sliding on titanium, many silicon particles back transferred. In contrast, a large quantity of indium transferred to the gallium arsenide surface.

Mishina, H.↗

NASA NTRS1994

Sensor Detects Semiconductor Escaping From Ampoule

Electrical resistance and temperature change upon exposure to semiconductors. Sensor detects breakage of ampoule containing molten semiconductor. Chemical reaction between hot semiconductor material and wire causes step increase in electrical resistance and temperature of wire. Step increase in temperature and resistance of sensor indicates presence of hot GaAs. Sensor used to shut down furnace automatically if ampoule breaks and prevents further release of molton semiconductor, which could quickly breach surrounding thin wall of cartridge, damage furnace, and/or release toxic vapors into surrounding area.

Watring, Dale A.↗

NASA NTRS1993

Electronic characterization of defects in narrow gap semiconductors

The study of point defects in semiconductors has a long and honorable history. In particular, the detailed understanding of shallow defects in common semiconductors traces back to the classic work of Kohn and Luttinger. However, the study of defects in narrow gap semiconductors represents a much less clear story. Here, both shallow defects (caused by long range potentials) and deep defects (from short range potentials) are far from being completely understood. In this study, all results are calculational and our focus is on the chemical trend of deep levels in narrow gap semiconductors. We study substitutional (including antisite), interstitial and ideal vacancy defects. For substitutional and interstitial impurities, the efects of relaxation are included. For materials like Hg(1-x)Cd(x)Te, we study how the deep levels vary with x, of particular interest is what substitutional and interstitial atoms yield energy levels in the gap i.e. actually produce deep ionized levels. Also, since the main technique utilized is Green's functions, we include some summary of that method.

Patterson, James D.↗

NASA NTRS1994

Monolithic in-based III-V compound semiconductor focal plane array cell with single stage CCD output

A monolithic semiconductor imager includes an indium-based III-V compound semiconductor monolithic active layer of a first conductivity type, an array of plural focal plane cells on the active layer, each of the focal plane cells including a photogate over a top surface of the active layer, a readout circuit dedicated to the focal plane cell including plural transistors formed monolithically with the monolithic active layer and a single-stage charge coupled device formed monolithically with the active layer between the photogate and the readout circuit for transferring photo-generated charge accumulated beneath the photogate during an integration period to the readout circuit. The photogate includes thin epitaxial semiconductor layer of a second conductivity type overlying the active layer and an aperture electrode overlying a peripheral portion of the thin epitaxial semiconductor layer, the aperture electrode being connectable to a photogate bias voltage.

Fossum, Eric R.↗

NASA NTRS1995

Etching Semiconductors With Beams Of Reactive Atoms

Method of etching semiconductors with energetic beams of electrically neutral, but chemically reactive, species undergoing development. Enables etching of straight walls into semiconductor substrates at edges of masks without damage to underlying semiconductor material. In addition to elimination of charge damage, technique reduces substrate bombardment damage because translational energy of neutral species in range 2-12 eV, below damage threshold of many semiconductor materials. Furthermore, low-energy neutrals cause no mask erosion allowing for etching features with very high aspect ratios.

Minton, Timothy K.↗

NASA NTRS1997

A Thermal and Electrical Analysis of Power Semiconductor Devices

The state-of-art power semiconductor devices require a thorough understanding of the thermal behavior for these devices. Traditional thermal analysis have (1) failed to account for the thermo-electrical interaction which is significant for power semiconductor devices operating at high temperature, and (2) failed to account for the thermal interactions among all the levels involved in, from the entire device to the gate micro-structure. Furthermore there is a lack of quantitative studies of the thermal breakdown phenomenon which is one of the major failure mechanisms for power electronics. This research work is directed towards addressing. Using a coupled thermal and electrical simulation, in which the drift-diffusion equations for the semiconductor and the energy equation for temperature are solved simultaneously, the thermo-electrical interactions at the micron scale of various junction structures are thoroughly investigated. The optimization of gate structure designs and doping designs is then addressed. An iterative numerical procedure which incorporates the thermal analysis at the device, chip and junction levels of the power device is proposed for the first time and utilized in a BJT power semiconductor device. In this procedure, interactions of different levels are fully considered. The thermal stability issue is studied both analytically and numerically in this research work in order to understand the mechanism for thermal breakdown.

Vafai, Kambiz↗

NASA NTRS1998

Computational Modeling of Semiconductor Dynamics at Femtosecond Time Scales

The Interchange No. NCC2-5149 deals with the emerging technology of photonic (or optoelectronic) integrated circuits (PICs or OEICs). In PICs, optical and electronic components are grown together on the same chip. To build such devices and subsystems, one needs to model the entire chip. PICs are useful for building components for integrated optical transmitters, integrated optical receivers, optical data storage systems, optical interconnects, and optical computers. For example, the current commercial rate for optical data transmission is 2.5 gigabits per second, whereas the use of shorter pulses to improve optical transmission rates would yield an increase of 400 to 1000 times. The improved optical data transmitters would be used in telecommunications networks and computer local-area networks. Also, these components can be applied to activities in space, such as satellite to satellite communications, when the data transmissions are made at optical frequencies. The research project consisted of developing accurate computer modeling of electromagnetic wave propagation in semiconductors. Such modeling is necessary for the successful development of PICs. More specifically, these computer codes would enable the modeling of such devices, including their subsystems, such as semiconductor lasers and semiconductor amplifiers in which there is femtosecond pulse propagation. Presently, there are no computer codes that could provide this modeling. Current codes do not solve the full vector, nonlinear, Maxwell's equations, which are required for these short pulses and also current codes do not solve the semiconductor Bloch equations, which are required to accurately describe the material's interaction with femtosecond pulses. The research performed under NCC2-5149 solves the combined Maxwell's and Bloch's equations.

Agrawal, Govind P.↗

NASA NTRS1997

An Innovative Method for Preparing Semiconductor Change Used in Crystal Growth and Shear Cell Diffusion Experiments

An innovative technique for machining semiconductors has been developed. This technique was used to prepare semiconductor charges for crystal growth and shear cell diffusion experiments. The technique allows brittle semiconductor materials to be quickly and accurately machined. Lightly doping the semiconductor material increases the conductivity enough to allow the material to be shaped by an electrical discharge machine (EDM).

Anrold, William A.↗

NASA NTRS2002

Static and Dynamic Effects of Lateral Carrier Diffusion in Semiconductor Lasers

Electron and hole diffusions in the plane of semiconductor quantum wells play an important part in the static and dynamic operations of semiconductor lasers. It is well known that the value of diffusion coefficients affects the threshold pumping current of a semiconductor laser. At the same time, the strength of carrier diffusion process is expected to affect the modulation bandwidth of an AC-modulated laser. It is important not only to investigate the combined DC and AC effects due to carrier diffusion, but also to separate the AC effects from that of the combined effects in order to provide design insights for high speed modulation. In this presentation, we apply a hydrodynamic model developed by the present authors recently from the semiconductor Bloch equations. The model allows microscopic calculation of the lateral carrier diffusion coefficient, which is a nonlinear function of the carrier density and plasma temperature. We first studied combined AC and DC effects of lateral carrier diffusion by studying the bandwidth dependence on diffusion coefficient at a given DC current under small signal modulation. The results show an increase of modulation bandwidth with decrease in the diffusion coefficient. We simultaneously studied the effects of nonlinearity in the diffusion coefficient. To clearly identify how much of the bandwidth increase is a result of decrease in the threshold pumping current for smaller diffusion coefficient, thus an effective increase of DC pumping, we study the bandwidth dependence on diffusion coefficient at a given relative pumping. A detailed comparison of the two cases will be presented.

Li, Jian-Zhong↗

NASA NTRS2002

Microscopic Foundation and Simulation of Coupled Carrier-Temperature Diffusions in Semiconductor Lasers

A typical semiconductor-based optoelectronic device, such as a diode laser, consists of three subsystems: an optical field, an electron-hole plasma (EHP), and a host crystal lattice. The physics of such a device involves the interplay of optical, electrical and thermal processes. A proper description of such a device requires that all three processes are treated on equal footing and in a self-consistent fashion. Furthermore, since a semiconductor laser has intrinsic spatial inhomogeneity, such a self-consistency naturally leads to a set of partial differential equations in space and time. There is a significant lacking of research interest and results on the transport aspects of optical devices in the literature with only a few exceptions. Even the most important carrier diffusion coefficient has not been properly derived and studied so far for optically excited plasma, while most of the work adopted results from electronics community where heavily doped semiconductors with mainly one type of carriers are dealt with. The corresponding transport equation for plasma energy or temperature has received even less attention. In this talk we describe our recent results on such a self-consistent derivation of temperature and carrier-density diffusion equations coupled with the lasing process. Starting from the microscopic semiconductor Bloch equations (SBEs) including the Boltzmann transport terms in the distribution function equations for electrons and holes, we derived a closed set of diffusion equations for carrier densities and temperatures with self-consistent coupling to Maxwell's equation and to an effective optical polarization equation. The coherent many-body effects are included within the screened Hartree-Fock approximation, while scatterings are treated within the second Born approximation including both the in- and out-scatterings. Microscopic expressions for electron-hole (e-h) and carrier-LO (c-LO) phonon scatterings are directly used to derive the momentum and energy relaxation rates. These rates expressed as functions of temperatures and densities lead to microscopic expressions for self- and mutual-diffusion coefficients in the coupled density-temperature diffusion equations. Approximations for reducing the general two-component description of the electron-hole plasma (EHP) to a single-component one are discussed. In particular, we show that a special single-component reduction is possible when e-h scattering dominates over c-LO phonon scattering. The ambipolar diffusion approximation is also discussed and we show that the ambipolar diffusion coefficients are independent of e-h scattering, even though the diffusion coefficients of individual components depend sensitively on the e-h scattering rates. Our discussions lead to new perspectives into the roles played in the single-component reduction by the electron-hole correlation in momentum space induced by scatterings and the electron-hole correlation in real space via internal static electrical field. Finally, the theory is completed by coupling the diffusion equations to the lattice temperature equation and to the effective optical polarization which in turn couples to the laser field. The equations derived above are implemented in various limiting cases to a typical diode laser to study the consequences of nonlinear diffusion and the cross diffusion terms on laser behavior, especially the dynamic behavior of a diode laser under modulation. Detailed results will be presented by comparing with the standard rate equation results.

Li, J.↗

NASA NTRS2001

Semiconductor Reference Oscillator Development for Coherent Detection Optical Remote Sensing Applications

The NASA Earth Science Enterprise Advanced Technology Initiatives Program is supporting a program for the development of semiconductor laser reference oscillators for application to coherent optical remote sensing from Earth orbit. Local oscillators provide the frequency reference required for active spaceborne optical remote sensing concepts that involve heterodyne (coherent) detection. Two recent examples of such schemes are Doppler wind lidar and tropospheric carbon dioxide measurement by laser absorption spectrometry, both of which are being proposed at a wavelength of 2.05 microns. Frequency-agile local oscillator technology is important to such applications because of the need to compensate for large platform-induced Doppler components that would otherwise interfere with data interpretation. Development of frequency-agile local oscillator approaches has heretofore utilized the same laser material as the transmitter laser (Tm,Ho:YLF in the case of the 2.05-micron wavelength mentioned above). However, a semiconductor laser-based frequency-agile local oscillator offers considerable scope for reduced mechanical complexity and improved frequency agility over equivalent crystal laser devices, while their potentially faster tuning capability suggest the potential for greater scanning versatility. The program we report on here is specifically tasked with the development of prototype novel architecture semiconductor lasers with the power, tunability, and spectral characteristics required for coherent Doppler lidar. The baseline approach for this work is the distributed feedback (DFB) laser, in which gratings are etched into the semiconductor waveguide structures along the entire length of the laser cavity. However, typical DFB lasers at the wavelength of interest have linewidths that exhibit unacceptable growth when driven at the high currents and powers that are required for the Doppler lidar application. Suppression of this behavior by means of corrugation pitch-modulation (using a detuned central section to prevent intensity peaking in the center of the cavity) is currently under investigation to achieve the required performance goals.

distributed feedback (DFB) laser↗

NASA NTRS1992

Monolithic semiconductor light emitter and amplifier

A semiconductor light emitter comprising a substrate of a semiconductor material having a pair of opposed surfaces and a body of semiconductor material on one of the surfaces. The body includes a pair of clad layers of opposite conductivity types having an intermediate quantum well region therebetween. The clad layers are of a semiconductor material which forms a heterojunction with the material of the quantum well region. The clad layers and the quantum well region form a waveguide which extends along the body. A plurality of gain sections are formed in the body spaced along and optically coupled by the waveguide. Each of the gain sections is adapted to generate light therein when a voltage is placed thereacross. One of the gain section has gratings at each end thereof which are adapted to reflect light back into the one gain section and thereby create a beam of light. The grating between the one gain section and an adjacent gain section is adapted to allow some of the light generated in the one gain section to pass therethrough along the waveguide to the next gain section. Each of the other gain sections have gratings adjacent an end opposite the first gain sections. The periods of the grating are such that no self-oscillation of the light in the waveguide occurs so that each of the other gain sections serve as single pass amplifiers. The gratings also direct the amplified light from the other gain sections out of the body.

Carlson, Nils W.↗

NASA NTRS2000

Monolithic integrated high-T.sub.c superconductor-semiconductor structure

A method for the fabrication of active semiconductor and high-temperature superconducting device of the same substrate to form a monolithically integrated semiconductor-superconductor (MISS) structure is disclosed. A common insulating substrate, preferably sapphire or yttria-stabilized zirconia, is used for deposition of semiconductor and high-temperature superconductor substructures. Both substructures are capable of operation at a common temperature of at least 77 K. The separate semiconductor and superconductive regions may be electrically interconnected by normal metals, refractory metal silicides, or superconductors. Circuits and devices formed in the resulting MISS structures display operating characteristics which are equivalent to those of circuits and devices prepared on separate substrates.

Burns, Michael J.↗

NASA NTRS1995

Monolithic in-based III-V compound semiconductor focal plane array cell with single stage CCD output

Fossum, Eric R.↗

NASA NTRS2000

Method for making a monolithic integrated high-T.sub.c superconductor-semiconductor structure

A method for the fabrication of active semiconductor and high-temperature perconducting devices on the same substrate to form a monolithically integrated semiconductor-superconductor (MISS) structure is disclosed. A common insulating substrate, preferably sapphire or yttria-stabilized zirconia, is used for deposition of semiconductor and high-temperature superconductor substructures. Both substructures are capable of operation at a common temperature of at least 77 K. The separate semiconductor and superconductive regions may be electrically interconnected by normal metals, refractory metal silicides, or superconductors. Circuits and devices formed in the resulting MISS structures display operating characteristics which are equivalent to those of circuits and devices prepared on separate substrates.

Burns, Michael J.↗

NASA NTRS2009

Lattice-Matched Semiconductor Layers on Single Crystalline Sapphire Substrate

SiGe is an important semiconductor alloy for high-speed field effect transistors (FETs), high-temperature thermoelectric devices, photovoltaic solar cells, and photon detectors. The growth of SiGe layer is difficult because SiGe alloys have different lattice constants from those of the common Si wafers, which leads to a high density of defects, including dislocations, micro-twins, cracks, and delaminations. This innovation utilizes newly developed rhombohedral epitaxy of cubic semiconductors on trigonal substrates in order to solve the lattice mismatch problem of SiGe by using trigonal single crystals like sapphire (Al2O3) as substrate to give a unique growth-orientation to the SiGe layer, which is automatically controlled at the interface upon sapphire (0001). This technology is different from previous silicon on insulator (SOI) or SGOI (SiGe on insulator) technologies that use amorphous SiO2 as the growth plane. A cubic semiconductor crystal is a special case of a rhombohedron with the inter-planar angle, alpha = 90 deg. With a mathematical transformation, all rhombohedrons can be described by trigonal crystal lattice structures. Therefore, all cubic lattice constants and crystal planes (hkl) s can be transformed into those of trigonal crystal parameters. These unique alignments enable a new opportunity of perfect lattice matching conditions, which can eliminate misfit dislocations. Previously, these atomic alignments were thought to be impossible or very difficult. With the invention of a new x-ray diffraction measurement method here, growth of cubic semiconductors on trigonal crystals became possible. This epitaxy and lattice-matching condition can be applied not only to SiGe (111)/sapphire (0001) substrate relations, but also to other crystal structures and other materials, including similar crystal structures which have pointgroup rotational symmetries by 120 because the cubic (111) direction has 120 rotational symmetry. The use of slightly miscut (less than plus or minus 10 deg.) sapphire (0001) substrate can be used to improve epitaxial relationships better by providing attractive atomic steps in the epitaxial process.

Choi, Sang↗