Performance assessment of a triple-junction solar cell with 1.0 eV GaAsBi absorber.

Group III-V semiconductor multi-junction solar cells are widely used in concentrated-sun and space photovoltaic applications due to their unsurpassed power conversion efficiency and radiation hardness. To further increase the efficiency, new device architectures rely on better bandgap combinations over the mature GaInP/InGaAs/Ge technology, with Ge preferably replaced by a 1.0 eV subcell. Herein, we present a thin-film triple-junction solar cell AlGaAs/GaAs/GaAsBi with 1.0 eV dilute bismide. A compositionally step-graded InGaAs buffer layer is used to integrate high crystalline quality GaAsBi absorber. The solar cells, grown by molecular-beam epitaxy, achieve 19.1% efficiency at AM1.5G spectrum, 2.51 V open-circuit voltage, and 9.86 mA/cm2 short-circuit current density. Device analysis identifies several routes to significantly improve the performance of the GaAsBi subcell and of the overall solar cell. This study is the first to report on multi-junctions incorporating GaAsBi and is an addition to the research on the use of bismuth-containing III-V alloys in photonic device applications.

Semiconductor Characterization by Terahertz Excitation Spectroscopy.

Surfaces of semiconducting materials excited by femtosecond laser pulses emit electromagnetic waves in the terahertz (THz) frequency range, which by definition is the 0.1-10 THz region. The nature of terahertz radiation pulses is, in the majority of cases, explained by the appearance of ultrafast photocurrents. THz pulse duration is comparable with the photocarrier momentum relaxation time, thus such hot-carrier effects as the velocity overshoot, ballistic carrier motion, and optical carrier alignment must be taken into consideration when explaining experimental observations of terahertz emission. Novel commercially available tools such as optical parametric amplifiers that are capable of generating femtosecond optical pulses within a wide spectral range allow performing new unique experiments. By exciting semiconductor surfaces with various photon energies, it is possible to look into the ultrafast processes taking place at different electron energy levels of the investigated materials. The experimental technique known as the THz excitation spectroscopy (TES) can be used as a contactless method to study the band structure and investigate the ultrafast processes of various technologically important materials. A recent decade of investigations with the THz excitation spectroscopy method is reviewed in this article. TES experiments performed on the common bulk A3B5 compounds such as the wide-gap GaAs, and narrow-gap InAs and InSb, as well as Ge, Te, GaSe and other bulk semiconductors are reviewed. Finally, the results obtained by this non-contact technique on low-dimensional materials such as ultrathin mono-elemental Bi films, InAs, InGaAs, and GaAs nanowires are also presented.

The Crystalline Structure of Thin Bismuth Layers Grown on Silicon (111) Substrates.

Bismuth films with thicknesses between 6 and ∼30 nm were grown on Si (111) substrate by molecular beam epitaxy (MBE). Two main phases of bismuth - α-Bi and ß-Bi - were identified from high-resolution X-ray diffraction (XRD) measurements. The crystal structure dependencies on the layer thicknesses of these films were analyzed. ß-Bi layers were epitaxial and homogenous in lateral regions that are greater than 200 nm despite the layer thickness. Further, an increase in in-plane 2θ values showed the biaxial compressive strain. For comparison, α-Bi layers are misoriented in six in-plane directions and have ß-Bi inserts in thicker layers. That leads to smaller (about 60 nm) lateral crystallites which are compressively strained in all three directions. Raman measurement confirmed the XRD results. The blue-sift of Raman signals compared with bulk Bi crystals occurs due to the phonon confinement effect, which is larger in the thinnest α-Bi layers due to higher compression.

Synthesis and physical characteristics of narrow bandgap chalcogenide SnZrSe 3.

Background: The development of organic/inorganic metal halide perovskites has seen unprecedent growth since their first recognition for applications in optoelectronic devices. However, their thermodynamic stability and toxicity remains a challenge considering wide-scale deployment in the future. This spurred an interest in search of perovskite-inspired materials which are expected to retain the advantageous material characteristics of halide perovskites, but with high thermodynamic stability and composed of earth-abundant and low toxicity elements. ABX 3 chalcogenides (A, B=metals, X=Se, S) have been identified as potential class of materials meeting the aforementioned criteria. Methods: In this work, we focus on studying tin zirconium selenide (SnZrSe 3) relevant physical properties with an aim to evaluate its prospects for application in optoelectronics. SnZrSe 3 powder and monocrystals were synthesized via solid state reaction in 600 - 800 °C temperature range. Crystalline structure was determined using single crystal and powder X-ray diffraction methods. The bandgap was estimated from diffused reflectance measurements on powder samples and electrical properties of crystals were analysed from temperature dependent I-V measurements. Results: We found that SnZrSe 3 crystals have a needle-like structure (space group - Pnma) with following unit cell parameters: a=9.5862(4) Å, b=3.84427(10) Å, c=14.3959(5) Å. The origin of the low symmetry crystalline structure was associated with stereochemical active electron lone pair of Sn cation. Estimated bandgap was around 1.15 eV which was higher than measured previously and predicted theoretically. Additionally, it was found that resistivity and conductivity type depended on the compound chemical composition. Conclusions: Absorption edge in the infrared region and bipolar dopability makes SnZrSe 3 an interesting material candidate for application in earth-abundant and non-toxic single/multi-junction solar cells or other infrared based optoelectronic devices.

Terahertz emission from ultrathin bismuth layers.

Thinner than 10 nm layers of bismuth (Bi) were grown on (111) Si substrates by molecular beam epitaxy. Terahertz (THz) radiation pulses from these layers excited by tunable wavelength femtosecond optical pulses were measured. THz emission sets on when the photon energy exceeds 0.45 eV, which was explained by the semimetal-to-semiconductor transition at this Bi layer thickness. A THz signal has both isotropic and anisotropic components that could be caused by the lack of balance of lateral photocurrent components and the shift currents, respectively.

Terahertz Pulse Emission from Semiconductor Heterostructures Caused by Ballistic Photocurrents.

Terahertz radiation pulses emitted after exciting semiconductor heterostructures by femtosecond optical pulses were used to determine the electron energy band offsets between different constituent materials. It has been shown that when the photon energy is sufficient enough to excite electrons in the narrower bandgap layer with an energy greater than the conduction band offset, the terahertz pulse changes its polarity. Theoretical analysis performed both analytically and by numerical Monte Carlo simulation has shown that the polarity inversion is caused by the electrons that are excited in the narrow bandgap layer with energies sufficient to surmount the band offset with the wide bandgap substrate. This effect is used to evaluate the energy band offsets in GaInAs/InP and GaInAsBi/InP heterostructures.

Terahertz Photoconductivity Spectra of Electrodeposited Thin Bi Films.

Electron dynamics in the polycrystalline bismuth films were investigated by measuring emitted terahertz (THz) radiation pulses after their photoexcitation by tunable wavelength femtosecond duration optical pulses. Bi films were grown on metallic Au, Pt, and Ag substrates by the electrodeposition method with the Triton X-100 electrolyte additive, which allowed us to obtain more uniform films with consistent grain sizes on any substrate. It was shown that THz pulses are generated due to the spatial separation of photoexcited electrons and holes diffusing from the illuminated surface at different rates. The THz photoconductivity spectra analysis has led to a conclusion that the thermalization of more mobile carriers (electrons) is dominated by the carrier-carrier scattering rather than by their interaction with the lattice.

Atomic-Resolution EDX, HAADF, and EELS Study of GaAs1-xBix Alloys.

The distribution of alloyed atoms in semiconductors often deviates from a random distribution which can have significant effects on the properties of the materials. In this study, scanning transmission electron microscopy techniques are employed to analyze the distribution of Bi in several distinctly MBE grown GaAs1-xBix alloys. Statistical quantification of atomic-resolution HAADF images, as well as numerical simulations, are employed to interpret the contrast from Bi-containing columns at atomically abrupt (001) GaAs-GaAsBi interface and the onset of CuPt-type ordering. Using monochromated EELS mapping, bulk plasmon energy red-shifts are examined in a sample exhibiting phase-separated domains. This suggests a simple method to investigate local GaAsBi unit-cell volume expansions and to complement standard X-ray-based lattice-strain measurements. Also, a single-variant CuPt-ordered GaAsBi sample grown on an offcut substrate is characterized with atomic scale compositional EDX mappings, and the order parameter is estimated. Finally, a GaAsBi alloy with a vertical Bi composition modulation is synthesized using a low substrate rotation rate. Atomically, resolved EDX and HAADF imaging shows that the usual CuPt-type ordering is further modulated along the [001] growth axis with a period of three lattice constants. These distinct GaAsBi samples exemplify the variety of Bi distributions that can be achieved in this alloy, shedding light on the incorporation mechanisms of Bi atoms and ways to further develop Bi-containing III-V semiconductors.

GaAs1-xBix growth on Ge: anti-phase domains, ordering, and exciton localization.

The dilute bismide alloy GaAs1-xBix has drawn significant attention from researchers interested in its fundamental properties and the potential for infrared optoelectronics applications. To extend the study of bismides, molecular-beam heteroepitaxy of nominally 1.0 eV bandgap bismide on Ge substrates is comprehensively investigated. Analysis of atomic-resolution anti-phase domain (APD) images in the direct-epitaxy revealed a high-density of Ga vacancies and a reduced Bi content at their boundaries. This likely played a key role in the preferential dissolution of Bi atoms from the APD interiors and Bi spiking in Ge during thermal annealing. Introduction of GaAs buffer on offcut Ge largely suppressed the formation of APDs, producing high-quality bismide with single-variant CuPtB-type ordered domains as large as 200 nm. Atomic-resolution X-ray imaging showed that 2-dimensional Bi-rich (111) planes contain up to x = 9% Bi. The anomalously early onset of localization found in the temperature-dependent photoluminescence suggests enhanced interactions among Bi states, as compared to non-ordered samples. Growth of large-domain single-variant ordered GaAs1-xBix films provides new prospects for detailed analysis of the structural modulation effects and may allow to further tailor properties of this alloy for optoelectronic applications.

Spectral dependence of THz emission from InN and InGaN layers.

Spectral dependence of terahertz emission is a sensitive tool to analyze the structure of conduction band of semiconductors. In this work, we investigate the excitation spectra of THz pulses emitted from MOCVD-grown InN and InGaN epitaxial layers with indium content of 16%, 68%, and 80%. In InN and indium-rich InGaN layers we observe a gradual saturation of THz emission efficiency with increasing photon energy. This is in stark contrast to other III-V semiconductors where an abrupt drop of THz efficiency occurs at certain photon energy due to inter-valley electron scattering. From these results, we set a lower limit of the intervalley energy separation in the conduction band of InN as 2.4 eV. In terms of THz emission efficiency, the largest optical-to-THz energy conversion rate was obtained in 75 nm thick In0.16Ga0.84N layer, while lower THz emission efficiency was observed from InN and indium-rich InGaN layers due to the screening of built-in field by a high-density electron gas in these materials.

Silicon Field Effect Transistor as the Nonlinear Detector for Terahertz Autocorellators.

We demonstrate that the rectifying field effect transistor, biased to the subthreshold regime, in a large signal regime exhibits a super-linear response to the incident terahertz (THz) power. This phenomenon can be exploited in a variety of experiments which exploit a nonlinear response, such as nonlinear autocorrelation measurements, for direct assessment of intrinsic response time using a pump-probe configuration or for indirect calibration of the oscillating voltage amplitude, which is delivered to the device. For these purposes, we employ a broadband bow-tie antenna coupled Si CMOS field-effect-transistor-based THz detector (TeraFET) in a nonlinear autocorrelation experiment performed with picoseconds-scale pulsed THz radiation. We have found that, in a wide range of gate bias (above the threshold voltage V th = 445 mV), the detected signal follows linearly to the emitted THz power. For gate bias below the threshold voltage (at 350 mV and below), the detected signal increases in a super-linear manner. A combination of these response regimes allows for performing nonlinear autocorrelation measurements with a single device and avoiding cryogenic cooling.

Bismuth Quantum Dots in Annealed GaAsBi/AlAs Quantum Wells.

Formation of bismuth nanocrystals in GaAsBi layers grown by molecular beam epitaxy at 330 °C substrate temperature and post-growth annealed at 750 °C is reported. Superlattices containing alternating 10 nm-thick GaAsBi and AlAs layers were grown on semi-insulating GaAs substrate. AlAs layers have served as diffusion barriers for Bi atoms, and the size of the nanoclusters which nucleated after sample annealing was correlating with the thickness of the bismide layers. Energy-dispersive spectroscopy and Raman scattering measurements have evidenced that the nanoparticles predominantly constituted from Bi atoms. Strong photoluminescence signal with photon wavelengths ranging from 1.3 to 1.7 µm was observed after annealing; its amplitude was scaling-up with the increased number of the GaAsBi layers. The observed photoluminescence band can be due to emission from Bi nanocrystals. The carried out theoretical estimates support the assumption. They show that due to the quantum size effect, the Bi nanoparticles experience a transition to the direct-bandgap semiconducting state.

Strong terahertz emission and its origin from catalyst-free InAs nanowire arrays.

The unique features of nanowires (NW), such as the high aspect ratio and extensive surface area, are expected to play a key role in the development of very efficient semiconductor surface emitters in the terahertz (THz) spectral range. Here, we report on optically excited THz emission from catalyst-free grown arrays of intrinsically n-type InAs NWs using THz time-domain spectroscopy. Depending on the aspect ratio, the THz emission efficiency of the n-type InAs NWs is found to be up to ∼3 times stronger than that of bulk p-type InAs, known as currently the most efficient semiconductor-based THz surface emitter. Characteristic differences from bulk p-type InAs are particularly revealed from excitation wavelength-dependent measurements, showing monotonously increasing THz pulse amplitude in the NW arrays with increasing photon energy. Further polarization-dependent and two-color pump-probe experiments elucidate the physical mechanism of the THz emission: In contrast to bulk p-type InAs, where the anisotropic photoconductivity in the surface electric field is the dominant cause for THz pulse generation, the origin of the intrinsic THz emission in the NWs is based on the photo-Dember effect. The strong THz emission from high aspect ratio NW arrays further suggests an improved out-coupling of the radiation, while further enhancements in efficiency using core-shell NW geometries are discussed.