Ultrawide Bandgap Semiconductors: Influence of Material Properties on Power Device Performance.
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Abstract Remote epitaxy has opened novel opportunities for advanced manufacturing and heterogeneous integration of two-dimensional (2D) materials and conventional (3D) materials. The lattice transparency as the fundamental principle of remote epitaxy has been studied and challenged by recent observations defying the concept. Understanding remote epitaxy requires an integrated approach of theoretical modeling and experimental validation at multi-scales because the phenomenon includes remote interactions of atoms across an atomically thin material and a few van der Waals gaps. The roles of atomically thin 2D material for the nucleation and growth of a 3D material have not been integrated into a framework of remote epitaxy research. Here, we summarize studies of remote epitaxy mechanisms with a comparison to other epitaxy techniques. In the end, we suggest the crucial topics of remote epitaxy research for basic science and applications. Graphical Abstract
Heterogeneous integration techniques allow the coupling of highly lattice-mismatched solid-state membranes, including semiconductors, oxides, and two-dimensional materials, to synergistically fuse the functionalities. The formation of heterostructures generally requires two processes: the combination of crystalline growth and a non-destructive lift-off/transfer process enables the formation of high-quality heterostructures. Although direct atomic interaction between the substrate and the target membrane ensures high-quality growth, the strong atomic bonds at the substrate/epitaxial film interface hinder the non-destructive separation of the target membrane from the substrate. Alternatively, a 2D material-coated compound semiconductor substrate can transfer the weakened (but still effective) surface potential field of the surface through the 2D material, allowing both high-quality epitaxial growth and non-destructive lift-off of the grown film. This Perspective reviews 2D/3D heterogeneous integration techniques, along with applications of III–V compound semiconductors and oxides. Here, the advanced heterogeneous integration methods offer an effective method to produce various freestanding membranes for stackable heterostructures with unique functionalities that can be applied to novel electrical, optoelectronic, neuromorphic, and bioelectronic systems.
Chiral materials are important tools for transducing circularly polarized light within many emerging opto-electronic and spin-based technologies. Here, we demonstrate that thin films of a bismuth iodide-based 0D chiral hybrid organic-inorganic semiconductor (HOIS) exhibit large anisotropy values in circularly polarized light emission (CPLE) that approach 50%, with mirror-image responses from front- and back-side measurements. A comprehensive analysis of light-wave propagation, absorption, emission, and scattering is constructed on the basis of a symmetry-derived exciton fine structure model, which accurately describes the direction and polarization dependence of the observed excitonic circular dichroism and CPLE, including contributions from both photoluminescence and resonant Raman scattering. Our analysis indicates that molecular chirality drives preferential film alignment with respect to the out-of-plane lattice vector direction, producing the observed anisotropies. This first demonstration in an HOIS system provides a unique route for enhancing polarization-dependent emission, and circularly polarized light transduction more broadly, in self-assembled HOIS.
Abstract Silicon carbide (SiC) can be synthesized in a number of different structural forms known as polytypes with a vast array of optically active point defects of interest for quantum information sciences. The ability to control and vary the polytypes during SiC synthesis may offer a powerful methodology for the formation of new material architectures that expand our ability to manipulate these defects, including extending coherence lifetimes and enhancing room temperature operation. Polytypic control during synthesis presents a significant challenge given the extreme conditions under which SiC is typically grown and the number of factors that can influence polytype selection. In situ monitoring of the synthesis process could significantly expand our ability to formulate novel polytype structures. In this perspective, we outline the state of the art and ongoing challenges for precision synthesis in SiC. We discuss available in situ x-ray characterization methods that will be instrumental in understanding the atomic scale growth of SiC and defect formation mechanisms. We highlight optimistic use cases for SiC heterostructures that will become possible with in situ polytypic control and end by discussing extended opportunities for integration of ultrahigh quality SiC materials with other semiconductor and quantum materials.
Magnetic dopants in three-dimensional topological insulators (TIs) offer a promising avenue for realizing the quantum anomalous Hall effect (QAHE) without the necessity for an external magnetic field. Understanding the relationship between site occupancy of magnetic dopant elements and their effect on macroscopic property is crucial for controlling the QAHE. By combining atomic-scale energy-dispersive X-ray spectroscopy (EDS) maps obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM) and novel data processing methodologies, including semi-automatic lattice averaging and frame registration, we have determined the substitutional sites of Mn atoms within the 1.2% Mn-doped Sb 2 Te 3 crystal. More importantly, the methodology developed in this study extends beyond Mn-doped Sb 2 Te 3 to other quantum materials, traditional semiconductors, and even electron irradiation sensitive materials.
Single-crystal compound semiconductors, such as III-N and III-V, are important building blocks for functional devices due to their high electron mobilities, wide range of bandgaps, and excellent optoelectronic properties. However, current methods to produce their freestanding membranes for heterointegration suffer from slow processes or poor material quality. Here, we demonstrate an approach to grow and harvest multiple wafer-scale single-crystal membranes with high throughput by introducing weak van der Waals interfaces between epitaxial layers. This is achieved by directly growing two-dimensional (2D) materials on compound semiconductors in their native deposition systems, which enables alternating growth of 2D material and compound semiconductor epitaxial layers in a single run. Each epilayer in the multi-stack structure is then sequentially harvested by mechanical exfoliation, producing multiple freestanding single-crystal membranes with extremely high throughput from a single wafer, primed for integration in mixed-dimensional heterostructures.
Single-crystal compound semiconductors, such as III-N and III-V, are important building blocks for functional devices due to their high electron mobilities, wide range of bandgaps, and excellent optoelectronic properties. However, current methods to produce their freestanding membranes for heterointegration suffer from slow processes or poor material quality. Here, we demonstrate an approach to grow and harvest multiple wafer-scale single-crystal membranes with high throughput by introducing weak van der Waals interfaces between epitaxial layers. This is achieved by directly growing two-dimensional (2D) materials on compound semiconductors in their native deposition systems, which enables alternating growth of 2D material and compound semiconductor epitaxial layers in a single run. Each epilayer in the multi-stack structure is then sequentially harvested by mechanical exfoliation, producing multiple freestanding single-crystal membranes with extremely high throughput from a single wafer, primed for integration in mixed-dimensional heterostructures.
This article highlights the critical role of window design on short circuit carrier collection in rear-emitter solar cells, as demonstrated through modeling and experiment using metamorphic GaAs y P 1-y . Ultimately, if the window design is not carefully considered, surface depletion caused by Fermi level pinning at the window/air interface can extend into regions of active collection resulting in a large increase in effective window/base interface recombination velocity. This was experimentally shown here to result in a potential AM1.5G photocurrent loss of 8.1 mA/cm 2 , or nearly 50%, based on integrated internal quantum efficiency (IQE). Associated IQE modeling and curve fitting indicate that the effective IRV at the GaAs 0.75 P 0.25 /Al 0.64 In 0.36 P interface is increased by multiple orders of magnitude when the window is not sufficiently thick or doped to fully contain the surface depletion to within the window layer. Calculations of the surface depletion depth as a function of doping and the surface Fermi pinning energy level provides insight into the fundamental limits of window thickness. As a result, this allows the estimation of the Al 0.64 In 0.36 P surface pinning level to be at least 1.25 eV below the conduction band edge, or in the bottom half of the bandgap.
Fluorite-based ferroelectric materials are revolutionizing the application space of polar semiconductors. These materials leverage robust polarization of extremely thin films, compatibility with the silicon chip processing, and decades of manufacturing experience to enable a new generation of ferroelectric memory devices. As a new paradigm for ferroelectrics, understanding of phase transitions and the switching mechanism in fluorites is essential both for advancing applications and for fundamental science. In this article, we outline the recent progress that has been made to understand the relative phase stability, phase transition and order parameter coupling, ferroelectric switching through unique nucleation and growth processes, and how defects affect these phases and processes. The main challenges, opportunities, and next steps for leveraging these materials for next-generation devices are reviewed.
After decades of developments, electron microscopy has become a powerful and irreplaceable tool in understanding the ionic, electrical, mechanical, chemical, and other functional performances of next-generation polymers and soft complexes. The recent progress in electron microscopy of nanostructured polymers and soft assemblies is important for applications in many different fields, including, but not limited to, mesoporous and nanoporous materials, absorbents, membranes, solid electrolytes, battery electrodes, ion- and electron-transporting materials, organic semiconductors, soft robotics, optoelectronic devices, biomass, soft magnetic materials, and pharmaceutical drug design. For synthetic polymers and soft complexes, there are four main characteristics that differentiate them from their inorganic or biomacromolecular counterparts in electron microscopy studies: (1) lower contrast, (2) abundance of light elements, (3) polydispersity or nanomorphological variations, and (4) large changes induced by electron beams. Since 2011, the Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory has been working with numerous facility users on nanostructured polymer composites, block copolymers, polymer brushes, conjugated molecules, organic–inorganic hybrid nanomaterials, organic–inorganic interfaces, organic crystals, and other soft complexes. This review crystalizes some of the essential challenges, successes, failures, and techniques during the process in the past ten years. It also presents some outlooks and future expectations on the basis of these works at the intersection of electron microscopy, soft matter, and artificial intelligence. Machine learning is expected to automate and facilitate image processing and information extraction of polymer and soft hybrid nanostructures in aspects such as dose-controlled imaging and structure analysis.
Diluting small molecule organic semiconductor hole transport materials with Teflon AF (TAF) dramatically increases their thermal/morphological stability while counterintuitively also increasing the current density in hole-only diodes. Here, we explore the origin of this current enhancement in co-evaporated blends of TAF and N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD) and find that it results from improved hole injection and not from a mobility enhancement due to semiconductor dilution effects. Whereas electroabsorption measurements indicate that an interface dipole shift of up to 0.5 eV (depending on TAF concentration) aides hole injection at the indium-tin-oxide anode, time-of-flight and temperature-dependent current-voltage measurements show that the mobility of 25 vol% TAF:NPD blends decreases by roughly an order of magnitude relative to neat NPD despite having slightly lower energetic disorder. For comparison, diluting with 25 vol% high density polyethylene achieves a similar reduction in energetic disorder but only decreases the mobility by a factor of two. Furthermore, these results highlight the tradeoff between reducing energetic disorder and frustrating percolation in diluted organic semiconductors, and represent a step toward thermally-evaporated polymer-small molecule composites that maintain high mobility while offering improved morphological stability and lower refractive index for organic light emitting diodes.
Eliminating photolithography from solar cell processing is a significant opportunity for cost reduction for III-V solar cells. Here, in this work, we explore femtosecond laser ablation as an alternative to contact photolithography and wet chemical etching for mesa isolation. We demonstrate both GaAs and GaInP solar cells mesa-isolated by femtosecond laser ablation with minimal to no loss in solar cell performance. We show the best results with a 400 fs UV pulsed laser and a short clean-up etch that also serves as a contact layer removal etch.
Eliminating photolithography from photovoltaic device processing is a significant opportunity for cost reduction and increased manufacturing throughput. In this work, we test femtosecond laser ablation and scribing as an alternative to contact photolithography and wet chemical etching for mesa isolation of multijunction devices. We demonstrate that upright multijunction devices isolated by using the laser as a scribe to cleave through the substrate had virtually no performance loss when compared to a baseline device processed with photolithography. By contrast, devices isolated by laser ablating through the active layers have performance losses that cannot be fully eliminated with postprocess etching. This demonstration of photolithography-free mesa isolation with no performance losses is promising as a pathway to less expensive and higher throughput III-V device manufacturing.
I 2 -II-IV-VI 4 and I-III-VI 2 semiconductor nanocrystals have found applications in photovoltaics and other optoelectronic technologies because of their low toxicity and efficient light absorption into the near-infrared. Herein, we report the discovery of a metastable wurtzite-like polymorph of Cu 2 FeSnSe 4 , a member of the I 2 -II-IV-VI 4 family of semi-conductors containing only Earth-abundant metals. Density functional theory calculations on this metastable poly-morph of Cu 2 FeSnSe 4 indicate that it may be a superior semiconductor for solar energy and optoelectronics applications compared to the thermodynamically preferred stannite polymorph, since the former displays a sharper dispersion of energy levels near the conduction band minimum that can enhance electron mobility and suppress hot electron cooling. The experimental optical band gap was measured by the inverse logarithmic derivative method to be direct, in agreement with theory, and in the range of 1.48-1.59 eV. Mechanistic studies reveal that this metastable phase de-rives from intermediate Cu 3 Se 2 nanocrystals that serve as a structural template for the final hexagonal wurtzite-like product. We compare the chemistry of wurtzite-like Cu 2 FeSnSe 4 to the related CuFeSe 2 material system. Our experimental and computational comparisons between Cu 2 FeSnSe 4 and CuFeSe 2 help explain both the crystal chemistry of CuFeSe 2 that prevents it from forming wurtzite-like polymorphs and the essential role of Sn in stabilizing the metastable structure of Cu 2 FeSnSe 4 . Furthermore, this work provides insight into the importance of elemental composition when designing syntheses for metastable materials.
Scattering of energetic charge carriers and their coupling to lattice vibrations (phonons) in dielectric materials and semiconductors are crucial processes that determine the functional limits of optoelectronics, photovoltaics, and photocatalysts. The strength of these energy exchanges is often described by the electron-phonon coupling coefficient, which is difficult to measure due to the microscopic time- and length-scales involved. In the present study, we propose an alternate means to quantify the coupling parameter along with thermal boundary resistance and electron conductivity by performing a high angular-resolution time-resolved X-ray diffraction measurement of propagating lattice deformation following laser excitation of a nanoscale, polycrystalline metal film on a semiconductor substrate. Our data present direct experimental evidence for identifying the ballistic and diffusive transport components occurring at the interface, where only the latter participates in thermal diffusion. This approach provides a robust measurement that can be applied to investigate microscopic energy transport in various solid-state materials.