Solar-Driven Sustainability: III-V Semiconductor for Green Energy Production Technologies.

Long-term societal prosperity depends on addressing the world's energy and environmental problems, and photocatalysis has emerged as a viable remedy. Improving the efficiency of photocatalytic processes is fundamentally achieved by optimizing the effective utilization of solar energy and enhancing the efficient separation of photogenerated charges. It has been demonstrated that the fabrication of III-V semiconductor-based photocatalysts is effective in increasing solar light absorption, long-term stability, large-scale production and promoting charge transfer. This focused review explores on the current developments in III-V semiconductor materials for solar-powered photocatalytic systems. The review explores on various subjects, including the advancement of III-V semiconductors, photocatalytic mechanisms, and their uses in H2 conversion, CO2 reduction, environmental remediation, and photocatalytic oxidation and reduction reactions. In order to design heterostructures, the review delves into basic concepts including solar light absorption and effective charge separation. It also highlights significant advancements in green energy systems for water splitting, emphasizing the significance of establishing eco-friendly systems for CO2 reduction and hydrogen production. The main purpose is to produce hydrogen through sustainable and ecologically friendly energy conversion. The review intends to foster the development of greener and more sustainable energy source by encouraging researchers and developers to focus on practical applications and advancements in solar-powered photocatalysis.

Highly Luminescent Shell-Less Indium Phosphide Quantum Dots Enabled by Atomistically Tailored Surface States.

Contrary to the prevailing notion that shell structures arise from the intricate chemistry and surface defects of InP quantum dots (QDs), an innovative strategy that remarkably enhances the luminescence efficiency of core-only InP QDs to over 90% is introduced. This paradigm shift is achieved through the concurrent utilization of group 2 and 3 metal-derived ligands, providing an effective remedy for surface defects and facilitating charge recombination. Specifically, a combination of Zn carboxylate and Ga chloride is employed to address the undercoordination issues associated with In and P atoms, leading to the alleviation of in-gap trap states. The intricate interplay and proportional ratio between Ga- and Zn-containing ligands play pivotal roles in attaining record-high luminescence efficiency in core-only InP QDs, as successfully demonstrated across various sizes and color emissions. Moreover, the fabrication of electroluminescent devices relying solely on InP core emission opens a new direction in optoelectronics, demonstrating the potential of the approach not only in optoelectronic applications but also in catalysis or energy conversion by charge transfer.

Recent progress of group III-V materials-based nanostructures for photodetection.

Due to the suitable bandgap structure, efficient conversion rates of photon to electron, adjustable optical bandgap, high electron mobility/aspect ratio, low defects, and outstanding optical and electrical properties for device design, III-V semiconductors have shown excellent properties for optoelectronic applications, including photodiodes, photodetectors, solar cells, photocatalysis, etc. In particular, III-V nanostructures have attracted considerable interest as a promising photodetector platform, where high-performance photodetectors can be achieved based on the geometry-related light absorption and carrier transport properties of III-V materials. However, the detection ranges from Ultraviolet to Terahertz including broadband photodetectors of III-V semiconductors still have not been more broadly development despite significant efforts to obtain the high performance of III-V semiconductors. Therefore, the recent development of III-V photodetectors in a broad detection range from Ultraviolet to Terahertz, and future requirements are highly desired. In this review, the recent development of photodetectors based on III-V semiconductor with different detection range is discussed. First, the bandgap of III-V materials and synthesis methods of III-V nanostructures are explored, subsequently, the detection mechanism and key figures-of-merit for the photodetectors are introduced, and then the device performance and emerging applications of photodetectors are provided. Lastly, the challenges and future research directions of III-V materials for photodetectors are presented.

Van der Waals Epitaxial Growth of Ultrathin Indium Antimonide on Arbitrary Substrates through Low-Thermal Budget.

III-V semiconductors possess high mobility, high frequency response, and detection sensitivity, making them potentially attractive for beyond-silicon electronics applications. However, the traditional heteroepitaxy of III-V semiconductors is impeded by a significant lattice mismatch and the necessity for extreme vacuum and high temperature conditions, thereby impeding their in situ compatibility with flexible substrates and silicon-based circuits. In this study, a novel approach is presented for fabricating ultrathin InSb single-crystal nanosheets on arbitrary substrates with a thickness as thin as 2.4 nm using low-thermal-budget van der Waals (vdW) epitaxy through chemical vapor deposition (CVD). In particular, in situ growth has been successfully achieved on both silicon-based substrates and flexible polyimide (PI) substrates. Notably, the growth temperature required for InSb nanosheets (240 °C) is significantly lower than that employed in back-end-of-line processes (400 °C). The field effect transistor devices based on fabricated ultrathin InSb nanosheets exhibit ultra-high on-off ratio exceeding 108 and demonstrate minimal gate leakage currents. Furthermore, these ultrathin InSb nanosheets display p-type characteristics with hole mobilities reaching up to 203 cm2 V-1 s-1 at room temperatures. This study paves the way for achieving heterogeneous integration of III-V semiconductors and facilitating their application in flexible electronics.

Design and performance of GaSb-based quantum cascade detectors.

InAs/AlSb quantum cascade detectors (QCDs) grown strain-balanced on GaSb substrates are presented. This material system offers intrinsic performance-improving properties, like a low effective electron mass of the well material of 0.026 m 0, enhancing the optical transition strength, and a high conduction band offset of 2.28 eV, reducing the noise and allowing for high optical transition energies. InAs and AlSb strain balance each other on GaSb with an InAs:AlSb ratio of 0.96:1. To regain the freedom of a lattice-matched material system regarding the optimization of a QCD design, submonolayer InSb layers are introduced. With strain engineering, four different active regions between 3.65 and 5.5 µm were designed with InAs:AlSb thickness ratios of up to 2.8:1, and subsequently grown and characterized. This includes an optimized QCD design at 4.3 µm, with a room-temperature peak responsivity of 26.12 mA/W and a detectivity of 1.41 × 108 Jones. Additionally, all QCD designs exhibit higher-energy interband signals in the mid- to near-infrared, stemming from the InAs/AlSb type-II alignment and the narrow InAs band gap.

Detecting defects that reduce breakdown voltage using machine learning and optical profilometry.

Semiconductor wafer manufacturing relies on the precise control of various performance metrics to ensure the quality and reliability of integrated circuits. In particular, GaN has properties that are advantageous for high voltage and high frequency power devices; however, defects in the substrate growth and manufacturing are preventing vertical devices from performing optimally. This paper explores the application of machine learning techniques utilizing data obtained from optical profilometry as input variables to predict the probability of a wafer meeting performance metrics, specifically the breakdown voltage (Vbk). By incorporating machine learning techniques, it is possible to reliably predict performance metrics that cause devices to fail at low voltage. For diodes that fail at a higher (but still below theoretical) breakdown voltage, alternative inspection methods or a combination of several experimental techniques may be necessary.

Halide-Driven Synthetic Control of InSb Colloidal Quantum Dots Enables Short-Wave Infrared Photodetectors.

In the III-V family of colloidal quantum dot (CQD) semiconductors, InSb promises access to a wider range of infrared wavelengths compared to many light-sensing material candidates. However, achieving the necessary size, size-dispersity, and optical properties has been challenging. Here the synthetic challenges associated with InSb CQDs are investigated and it is found that uncontrolled reduction of the antimony precursor hampers the controlled growth of CQDs. To overcome this, a synthetic strategy that combines nonpyrophoric precursors with zinc halide additives is developed. The experimental and computational studies show that zinc halide additives decelerate the reduction of the antimony precursor, facilitating the growth of more uniformly sized CQDs. It is also found that the halide choice provides additional control over the strength of this effect. The resultant CQDs exhibit well-defined excitonic transitions in spectral range of 1.26-0.98 eV, along with strong photoluminescence. By implementing a postsynthesis ligand exchange, colloidally stable inks enabling the fabrication of high-quality CQD films are achieved. The first demonstration of InSb CQD photodetectors is presented reaching 75% external quantum efficiency (QE) at 1200 nm, to the knowledge the highest short-wave infrared (SWIR) QE reported among heavy-metal-free infrared CQD-based devices.

Three-Dimensional Integration of InAs Nanowires by Template-Assisted Selective Epitaxy on Tungsten.

3D integration of III-V semiconductors with Si CMOS is highly attractive since it allows combining new functions such as photonic and analog devices with digital signal processing circuitry. Thus far, most 3D integration approaches have used epitaxial growth on Si, layer transfer by wafer bonding, or die-to-die packaging. Here we present low-temperature integration of InAs on W using Si3N4 template assisted selective area metal-organic vapor-phase epitaxy (MOVPE). Despite growth nucleation on polycrystalline W, we can obtain a high yield of single-crystalline InAs nanowires, as observed by transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). The nanowires exhibit a mobility of 690 cm2/(V s), a low-resistive, Ohmic electrical contact to the W film, and a resistivity which increases with diameter attributed to increased grain boundary scattering. These results demonstrate the feasibility for single-crystalline III-V back-end-of-line integration with a low thermal budget compatible with Si CMOS.

Strain Relaxation of InAs Quantum Dots on Misoriented InAlAs(111) Metamorphic Substrates.

We investigate in detail the role of strain relaxation and capping overgrowth in the self-assembly of InAs quantum dots by droplet epitaxy. InAs quantum dots were realized on an In0.6Al0.4As metamorphic buffer layer grown on a GaAs(111)A misoriented substrate. The comparison between the quantum electronic calculations of the optical transitions and the emission properties of the quantum dots highlights the presence of a strong quenching of the emission from larger quantum dots. Detailed analysis of the surface morphology during the capping procedure show the presence of a critical size over which the quantum dots are plastically relaxed.

Doped or Quantum-Dot Layers as In Situ Etch-Stop Indicators for III/V Semiconductor Reactive Ion Etching (RIE) Using Reflectance Anisotropy Spectroscopy (RAS).

Reflectance anisotropy spectroscopy (RAS), which was originally invented to monitor epitaxial growth, can-as we have previously shown-also be used to monitor the reactive ion etching of III/V semiconductor samples in situ and in real time, as long as the etching rate is not too high and the abrasion at the etch front is not totally chaotic. Moreover, we have proven that-using RAS equipment and optical Fabry‒Perot oscillations due to the ever-shrinking thickness of the uppermost etched layer-the in situ etch-depth resolution can be as good as ±0.8 nm, employing a Vernier-scale type measurement and evaluation procedure. Nominally, this amounts to ±1.3 lattice constants in our exemplary material system, AlGaAsSb, on a GaAs or GaSb substrate. In this contribution, we show that resolutions of about ±5.6 nm can be reliably achieved without a Vernier scale protocol by employing thin doped layers or sharp interfaces between differently doped layers or quantum-dot (QD) layers as etch-stop indicators. These indicator layers can either be added to the device layer design on purpose or be part of it incidentally due to the functionality of the device. For typical etch rates in the range of 0.7 to 1.3 nm/s (that is, about 40 to 80 nm/min), the RAS spectrum will show a distinct change even for very thin indicator layers, which allows for the precise termination of the etch run.

Characterization of Electrical Traps Formed in Al2O3 under Various ALD Conditions.

Frequency dispersion in the accumulation region seen in multifrequency capacitance-voltage characterization, which is believed to be caused mainly by border traps, is a concerning issue in present-day devices. Because these traps are a fundamental property of oxides, their formation is expected to be affected to some extent by the parameters of oxide growth caused by atomic layer deposition (ALD). In this study, the effects of variation in two ALD conditions, deposition temperature and purge time, on the formation of near-interfacial oxide traps in the Al2O3 dielectric are examined. In addition to the evaluation of these border traps, the most commonly examined electrical traps-i.e., interface traps-are also investigated along with the hysteresis, permittivity, reliability, and leakage current. The results reveal that a higher deposition temperature helps to minimize the formation of border traps and suppress leakage current but adversely affects the oxide/semiconductor interface and the permittivity of the deposited film. In contrast, a longer purge time provides a high-quality atomic-layer-deposited film which has fewer electrical traps and reasonable values of permittivity and breakdown voltage. These findings indicate that a moderate ALD temperature along with a sufficiently long purge time will provide an oxide film with fewer electrical traps, a reasonable permittivity, and a low leakage current.

Shape-controlled single-crystal growth of InP at low temperatures down to 220 °C.

III-V compound semiconductors are widely used for electronic and optoelectronic applications. However, interfacing III-Vs with other materials has been fundamentally limited by the high growth temperatures and lattice-match requirements of traditional deposition processes. Recently, we developed the templated liquid-phase (TLP) crystal growth method for enabling direct growth of shape-controlled single-crystal III-Vs on amorphous substrates. Although in theory, the lowest temperature for TLP growth is that of the melting point of the group III metal (e.g., 156.6 °C for indium), previous experiments required a minimum growth temperature of 500 °C, thus being incompatible with many application-specific substrates. Here, we demonstrate low-temperature TLP (LT-TLP) growth of single-crystalline InP patterns at substrate temperatures down to 220 °C by first activating the precursor, thus enabling the direct growth of InP even on low thermal budget substrates such as plastics and indium-tin-oxide (ITO)-coated glass. Importantly, the material exhibits high electron mobilities and good optoelectronic properties as demonstrated by the fabrication of high-performance transistors and light-emitting devices. Furthermore, this work may enable integration of III-Vs with silicon complementary metal-oxide-semiconductor (CMOS) processing for monolithic 3D integrated circuits and/or back-end electronics.

Composition determination for quaternary III-V semiconductors by aberration-corrected STEM.

Quantitative scanning transmission electron microscopy (STEM) is a powerful tool for the characterization of nano-materials. Absolute composition determination for ternary III-V semiconductors by direct comparison of experiment and simulation is well established. Here, we show a method to determine the composition of quaternary III-V semiconductors with two elements on each sub lattice from the intensities of one STEM image. As an example, this is applied to (GaIn)(AsBi). The feasibility of the method is shown in a simulation study that also explores the influence of detector angles and specimen thickness. Additionally, the method is applied to an experimental STEM image of a (GaIn)(AsBi) quantum well grown by metal organic vapour phase epitaxy. The obtained concentrations are in good agreement with X-ray diffraction and photoluminescence results.

Simultaneous determination of local thickness and composition for ternary III-V semiconductors by aberration-corrected STEM.

Scanning transmission electron microscopy (STEM) is a suitable method for the quantitative characterization of nanomaterials. For an absolute composition determination on an atomic scale, the thickness of the specimen has to be known locally with high accuracy. Here, we propose a method to determine both thickness and composition of ternary III-V semiconductors locally from one STEM image as shown for the example material systems Ga(AsBi) and (GaIn)As. In a simulation study, the feasibility of the method is proven and the influence of specimen thickness and detector angles used is investigated. An application to an experimental STEM image of a Ga(AsBi) quantum well grown by metal organic vapour phase epitaxy yields an excellent agreement with composition results from high resolution X-ray diffraction.

Altering the Optical Properties of GaAsSb-Capped InAs Quantum Dots by Means of InAlAs Interlayers.

In this work, we investigate the optical properties of InAs quantum dots (QDs) capped with composite In0.15Al0.85As/GaAs0.85Sb0.15 strain-reducing layers (SRLs) by means of high-resolution X-ray diffraction (HRXRD) and photoluminescence (PL) spectroscopy at 77 K. Thin In0.15Al0.85As layers with thickness t = 20 Å, 40 Å, and 60 Å were inserted between the QDs and a 60-Å-thick GaAs0.85Sb0.15 layer. The type II emissions observed for GaAs0.85Sb0.15-capped InAs QDs were suppressed by the insertion of the In0.15Al0.85As interlayer. Moreover, the emission wavelength was blueshifted for t = 20 Å and redshifted for t ≥ 40 Å resulting from the increased confinement potential and increased strain, respectively. The ground state and excited state energy separation is increased reaching 106 meV for t = 60 Å compared to 64 meV for the QDs capped with only GaAsSb SRL. In addition, the use of the In0.15Al0.85As layers narrows significantly the QD spectral linewidth from 52 to 35 meV for the samples with 40- and 60-Å-thick In0.15Al0.85As interlayers.

An optical Bragg scattering readout for simultaneous detection of all low-order mechanical modes of gallium nitride nanowires in nanowire arrays.

We report the use of optical Bragg scattering and homodyne interferometry to simultaneously measure all the first order cantilever-mode mechanical resonance frequencies and quality factors (Q) of gallium nitride nanowires (GaN NWs) in 100 NW periodic selected-area growth arrays. Hexagonal 2D arrays of 100 GaN NWs with pitch spacings of 350-1100 nm were designed and prepared to allow optical Bragg scattering. The NWs studied have diameters ranging from 100-300 nm, lengths from 3-10 µm, resonance frequencies between 1-10 MHz, and Q-values near 10,000 at 300 K. The system can passively detect the thermally induced Brownian mechanical motion of the NWs and can study driven NW motion, enabling the simultaneous monitoring of hundreds of mechanical resonators in a 10-100 µm2 area with a single optical beam. The read-out system allows large arrays of NWs to be characterized and applied as e.g. spatially resolved temperature and mass sensors.

Probing and Manipulating the Interfacial Defects of InGaAs Dual-Layer Metal Oxides at the Atomic Scale.

The interface between III-V and metal-oxide-semiconductor materials plays a central role in the operation of high-speed electronic devices, such as transistors and light-emitting diodes. The high-speed property gives the light-emitting diodes a high response speed and low dark current, and they are widely used in communications, infrared remote sensing, optical detection, and other fields. The rational design of high-performance devices requires a detailed understanding of the electronic structure at this interface; however, this understanding remains a challenge, given the complex nature of surface interactions and the dynamic relationship between the morphology evolution and electronic structures. Herein, in situ transmission electron microscopy is used to probe and manipulate the structural and electrical properties of ZrO2 films on Al2 O3 and InGaAs substrate at the atomic scale. Interfacial defects resulting from the spillover of the oxygen-atom conduction-band wavefunctions are resolved. This study unearths the fundamental defect-driven interfacial electric structure of III-V semiconductor materials and paves the way to future high-speed and high-reliability devices.

Metamaterial Waveguide Devices for Integrated Optics.

We show the feasibility of controlling the magnetic permeability of optical semiconductor devices on InP-based photonic integration platforms. We have achieved the permeability control of GaInAsP/InP semiconductor waveguides by combining the waveguide with a metamaterial consisting of gate-controlled split ring resonators. The split-ring resonators interact magnetically with light travelling in the waveguide and move the effective relative permeability of the waveguide away from 1 at optical frequencies. The variation in permeability can be controlled with the gate voltage. Using this variable-permeability waveguide, we have built an optical modulator consisting of a GaInAsP/InP Mach-Zehnder interferometer for use at an optical communication wavelength of 1.55 µm. The device changes the permeability of its waveguide arm with controlling gate voltage, thereby varying the refractive index of the arm to modulate the intensity of light. For the study of variable-permeability waveguide devices, we also propose a method of extracting separately the permittivity and permeability values of devices from the experimental data of light transmission. Adjusting the permeability of optical semiconductors to the needs of device designers will open the promising field of 'permeability engineering'. Permeability engineering will facilitate the manipulation of light and the management of photons, thereby contributing to the development of novel devices with sophisticated functions for photonic integration.

Electron Raman Scattering and Raman Gain in Pyramidal Semiconductor Quantum Dots.

The Raman scattering related with conduction band states in semiconductor pyramidal quantum dots is theoretically investigated. The electron Raman differential cross section and Raman gain coefficient are calculated making use of analytically determined quantum states. The energy spectrum is obtained within the effective mass approximation. The features of the Raman differential cross section are discussed in terms of their dependence on the changes of the quantum dot geometry. The variation of the Raman gain coefficient as a function of the quantum dot size and shape is also analyzed.

Influence of spatial and temporal coherences on atomic resolution high angle annular dark field imaging.

Aberration-corrected (scanning) transmission electron microscopy ((S)TEM) has become a widely used technique when information on the chemical composition is sought on an atomic scale. To extract the desired information, complementary simulations of the scattering process are inevitable. Often the partial spatial and temporal coherences are neglected in the simulations, although they can have a huge influence on the high resolution images. With the example of binary gallium phosphide (GaP) we elucidate the influence of the source size and shape as well as the chromatic aberration on the high angle annular dark field (HAADF) intensity. We achieve a very good quantitative agreement between the frozen phonon simulation and experiment for different sample thicknesses when a Lorentzian source distribution is assumed and the effect of the chromatic aberration is considered. Additionally the influence of amorphous layers introduced by the preparation of the TEM samples is discussed. Taking into account these parameters, the intensity in the whole unit cell of GaP, i.e. at the positions of the different atomic columns and in the region between them, is described correctly. With the knowledge of the decisive parameters, the determination of the chemical composition of more complex, multinary materials becomes feasible.