Epitaxial Growth Research Articles

Effect of seawater and dissolved cations on scorodite synthesis via iron coprecipitation

In recent years, one of the more effective developments in the fixation of arsenic from nonferrous waste has been the synthesis of scorodite via the co-precipitation of arsenic with iron during Fe(II) oxidation. This work examines the impact of cation impurities on the process with the aim of widening the application of this approach to incorporate the use of seawater and the treatment of ferrous metallurgy waste. Scorodite formation was promoted by the presence of cations in the order of Cu2+ >> Zn2+ > Al3+ > Ca2+ ∼ Mg2+, with differences in precipitation behaviour, yield and kinetics due to specific cation effects on iron oxidation. A grain size increase was observed with Cu, while the opposite was found with Al, attributed to crystallisation from solution over epitaxial growth. The use of seawater decreased As precipitation by <4 % without affecting grain size, showing the potential to be utilised as reaction medium. While the presence of Na+ hinders As precipitation, the impact appears less pronounced with seawater due to competing effects from other cations. Since scorodite precipitation is slowed down by high Fe(III) in the feed, a pre-reduction approach with Al, Cu and Zn base metals was examined for conversion of Fe(III) in metallurgical waste to Fe(II) prior to co-precipitation with As. While this produced stable scorodite precipitates, the yield and presence of unstable by-products were impacted by the method of reductant addition.

Analysis of large-scale high-quality graphene production and applications

Graphene, a single-atom-thick layer of carbon atoms arranged in a hexagonal lattice, is the thinnest and strongest material known to mankind. It has excellent electrical, thermal, and mechanical properties, making it a promising material for a wide range of applications in electronics, optoelectronics, energy storage, and more. With the increasing demand for graphene in various applications, large-scale and high-quality graphene production has become a significant challenge. While early methods of graphene production involved mechanical exfoliation, this method is limited in terms of scalability and yield. To meet the increasing demand for large-scale production of graphene, various methods have been developed in recent years, including chemical vapor precipitation, epitaxial crystal growth, graphene oxide reduction and solvent exfoliation and so on. This study aims to introduce several existing methods for the mass production of graphene with high quality and analyzes the advantages and disadvantage involve thereof. The findings in this paper may provide a valuable reference for the industrial-scale production of graphene.

480 nm InGaN-based cyan laser diode grown on Si by interface engineering of active region

InGaN-based long wavelength laser diodes (LDs) grown on Si are highly desirable for expanding the applications in laser display and lighting. Proper interface engineering of high In-content InGaN multi-quantum wells (MQWs) is urgently required for the epitaxial growth of InGaN-based long wavelength LD on Si, because the deteriorated interfaces and crystalline quality of InGaN MQWs can severely increase the photon scattering and further exacerbate the internal absorption loss of LDs, which prevents the lasing wavelength of InGaN-based LDs from extending. In this work, a significantly improved morphology and sharp interface of the InGaN active region are obtained by using a graded-compositional InGaN lower waveguide (LWG) capped with a 10-nm-thick Al0.1Ga0.9N layer. The V-pits density of the InGaN LWG was one order of magnitude reduction from 4.8 × 108 to 3.6 × 107 cm-2 along with the root-mean-square surface roughness decreasing from 0.3 to 0.1 nm. Therefore, a room-temperature electrically injected 480 nm InGaN-based cyan LD grown on Si under pulsed current operation was successfully achieved with a threshold current density of 18.3 kA/cm2.

Eight In. Wafer-Scale Epitaxial Monolayer MoS2.

Large-scale, high-quality, and uniform monolayer molybdenum disulfide(MoS2) films are crucial for their applications in next-generation electronics and optoelectronics. Epitaxy is a mainstream technique for achieving high-quality MoS2 films and is demonstrated at a wafer scale up to 4-in. In this study, the epitaxial growth of 8-in. wafer-scale highly oriented monolayer MoS2 on sapphire is reported as with excellent spatial homogeneity, using a specially designed vertical chemical vapor deposition (VCVD) system. Field effect transistors (FETs) based on the as-grown 8-in. wafer-scale monolayer MoS2 film are fabricated and exhibit high performances, with an average mobility and an on/off ratio of 53.5 cm2 V-1 s-1 and 107, respectively. In addition, batch fabrication of logic devices and 11-stage ring oscillators are also demonstrated, showcasing excellent electrical functions. This work may pave the way of MoS2 in practical industry-scale applications.

CsZnPbBr3/ZnS core/shell perovskite nanocrystals for stable and efficient white light-emitting diodes.

The widespread applicability of perovskite nanocrystals (PeNCs) is impeded by their intrinsic instability. A promising solution is utilizing robust chalcogenides as a protective shell to shield the sensitive luminescent cores from the external environment. However, the inferior structural stability and surface lability of PeNCs usually lead to perovskite phase transition during shell growth. Herein, we introduced smaller Zn ions to partially replace Pb ions in perovskites, which reduces the Pb-X bond length and enhances the Pb-X bond energy for inner lattice stabilization. Simultaneously, extra oleylammonium bromide (OAmBr) was added to protect the labile surface of PeNCs by compensating for the detachment of ligands and the loss of surface Br ions. As a result, the dual strategies enable the epitaxial growth of a ZnS shell and significantly enhance the chemical stability of CsZnPbBr3/ZnS core/shell PeNCs. After three thermal cycles ranging from 300 to 450 K, the core/shell PeNCs retained 70% of their initial photoluminescence (PL) intensity. In stark contrast, the pristine CsPbBr3 PeNCs exhibit complete PL quenching after just the first temperature cycle. For practical applications, the green core/shell PeNCs were integrated with commercially available red-emitting phosphors on a blue-emitting InGaN chip to fabricate a white light-emitting diode (WLED), which demonstrates a high luminous efficacy (LE) of 61.3 lm W-1 and nearly constant Commission Internationale de l'Eclairage (CIE) coordinates under varying operating currents.

Growth of Single Crystalline 2D Materials beyond Graphene on Non-metallic Substrates.

The advent of 2D materials has ushered in the exploration of their synthesis, characterization and application. While plenty of 2D materials have been synthesized on various metallic substrates, interfacial interaction significantly affects their intrinsic electronic properties. Additionally, the complex transfer process presents further challenges. In this context, experimental efforts are devoted to the direct growth on technologically important semiconductor/insulator substrates. This review aims to uncover the effects of substrate on the growth of 2D materials. The focus is on non-metallic substrate used for epitaxial growth and how this highlights the necessity for phase engineering and advanced characterization at atomic scale. Special attention is paid to monoelemental 2D structures with topological properties. The conclusion is drawn through a discussion of the requirements for integrating 2D materials with current semiconductor-based technology and the unique properties of heterostructures based on 2D materials. Overall, this review describes how 2D materials can be fabricated directly on non-metallic substrates and the exploration of growth mechanism at atomic scale.

Lattice Mismatch at the Heterojunction of Perovskite Solar Cells.

Lattice mismatch significantly influences microscopic transport in semiconducting devices, affecting interfacial charge behavior and device efficacy. This atomic-level disordering, often overlooked in previous research, is crucial for device efficiency and lifetime. Recent studies have highlighted emerging challenges related to lattice mismatch in perovskite solar cells, especially at heterojunctions, revealing issues like severe tensile stress, increased ion migration, and reduced carrier mobility. This review systematically discusses the effects of lattice mismatch on strain, material stability, and carrier dynamics. It also includes detailed characterizations of these phenomena and summarizes the current strategies including epitaxial growth and buffer layer, as well as explores future solutions to mitigate mismatch-induced issues. We also provide the challenges and prospects for lattice mismatch, aiming to enhance the efficiency and stability of perovskite solar cells, and contribute to renewable energy technology advancements.

Lattice Mismatch at the Heterojunction of Perovskite Solar Cells

Lattice mismatch significantly influences microscopic transport in semiconducting devices, affecting interfacial charge behavior and device efficacy. This atomic‐level disordering, often overlooked in previous research, is crucial for device efficiency and lifetime. Recent studies have highlighted emerging challenges related to lattice mismatch in perovskite solar cells, especially at heterojunctions, revealing issues like severe tensile stress, increased ion migration, and reduced carrier mobility. This review systematically discusses the effects of lattice mismatch on strain, material stability, and carrier dynamics. It also includes detailed characterizations of these phenomena and summarizes the current strategies including epitaxial growth and buffer layer, as well as explores future solutions to mitigate mismatch‐induced issues. We also provide the challenges and prospects for lattice mismatch, aiming to enhance the efficiency and stability of perovskite solar cells, and contribute to renewable energy technology advancements.

Epitaxial growth and characterization of GaAs (111) on 4H-SiC

SiC is an indirect bandgap semiconductor with material properties ideal for power electronics but not so much as an optical emitter. Meanwhile, gallium arsenide (GaAs) is a material known for high-performance optical devices due to its direct bandgap and carrier lifetime. Integrating GaAs with silicon carbide (SiC) can result in the best of both materials. However, integrating the two presents a significant challenge due to the large lattice mismatch between the two materials. In this paper, we investigate the growth of high-quality GaAs directly on 4H-SiC and on AlAs/4H-SiC substrates. The thin films were characterized using key techniques for structural and optical analyses, such as x-ray diffraction, atomic force microscopy, and photoluminescence (PL) spectroscopy. The 3D-island nature of growth of GaAs directly on SiC results in weak in-plane correlation with the substrate but high photoluminescence. This was demonstrated with an observed PL intensity comparable to the PL observed from a GaAs substrate with a similar buffer layer. Introduction of a thin AlAs nucleation layer results in improved wetting of the substrate, better in-plane correlation with substrate, and overall improved crystalline quality and is now under further study.

Liquid-Metal-Based Spin-Coating Exfoliation for Atomically Thin Metal Oxide Synthesis.

Two-dimensional (2D) semiconductors possess exceptional electronic, optical, and magnetic properties, making them highly desirable for widespread applications. However, conventional mechanical exfoliation and epitaxial growth methods are insufficient in meeting the demand for atomically thin films covering large areas while maintaining high quality. Herein, leveraging liquid metal oxidation reaction, we propose a motorized spin-coating exfoliation strategy to efficiently produce large-area 2D metal oxide (2DMO) semiconductors with high crystallinity, atomically thin thickness, and flat surfaces on diverse substrates. Moreover, we realized a 2D gallium oxide-based deep ultraviolet solar-blind photodetector featuring a metal-semiconductor-metal structure, showcasing high responsivity (8.24 A W-1) at 254 nm and excellent sensitivity (4.3 × 1012 cm Hz1/2 W-1). This novel liquid-metal-based spin-coating exfoliation strategy offers great potential for synthesizing atomically thin 2D semiconductors, opening new avenues for future functional electronic and optical applications.

Toughness enhancement in TiN/Zr0.37Al0.63N1.09 multilayer films

The hardness and fracture toughness of high-temperature wear-resistant transition metal aluminum nitride multilayer films depend largely on the constituting layer's structure, compositional modulation, morphology, and interface coherency. We present a study on 1-micron thick multilayered films consisting of stacked layers of TiN and Zr0.37Al0.63N1.09, each layer being 10 nm thick. The films were grown using ion-assisted reactive magnetron sputtering on MgO(001) and Si(001) at substrate temperatures ranging from ambient to 900°C. By increasing growth temperature, we found that the ZrAlN layers transition from near amorphous to nanocrystalline wurtzite to decomposed c-ZrN and w-AlN domains. Concurrently, the TiN layers exhibit strong fiber texture, polycrystallinity, and epitaxial growth carried by the ZrN domains. Both hardness and fracture stress, evaluated by nanoindentation and micromechanical tests, increase with temperature from H=24 GPaMgO, 23 GPaSi to 36 GPaMgO, 30 GPaSi, and σFSi= 6.1-7.7 GPa, respectively. An improved fracture toughness of KIC=2.4-2.8 MPa√m is related to different toughening mechanisms for the various microstructures. The difference in hardness between the substrates is related to compressive stress due to the deposition conditions and thermal contraction. The superior fracture stress is attributed to dense multilayers, free from macroscopic defects due to ion-assisted growth. After being deposited at 200°C, the multilayers remained thermally stable when vacuum annealed for 15 hours at 900°C, with no significant change in phase composition or hardness. The improved hardness, toughness, and temperature stability of the otherwise brittle nitrides are promising for industrial applications.

Van der Waals Epitaxially Grown Molecular Crystal Dielectric Sb2O3 for 2D Electronics.

Two-dimensional (2D) semiconducting materials have attracted significant interest as promising candidates for channel materials owing to their high mobility and gate tunability at atomic-layer thickness. However, the development of 2D electronics is impeded due to the difficulty in formation of high-quality dielectrics with a clean and nondestructive interface. Here, we report the direct van der Waals epitaxial growth of a molecular crystal dielectric, Sb2O3, on 2D materials by physical vapor deposition. The grown Sb2O3 nanosheets showed epitaxial relations of 0 and 180° with the 2D template, maintaining high crystallinity and an ultrasharp vdW interface with the 2D materials. As a result, the Sb2O3 nanosheets exhibited a high breakdown field of 18.6 MV/cm for 2L Sb2O3 with a thickness of 1.3 nm and a very low leakage current of 2.47 × 10-7 A/cm2 for 3L Sb2O3 with a thickness of 1.96 nm. We also observed two types of grain boundaries (GBs) with misorientation angles of 0 and 60°. The 0°-GB with a well-stitched boundary showed higher electrical and thermal stabilities than those of the 60°-GB with a disordered boundary. Our work demonstrates a method to epitaxially grow molecular crystal dielectrics on 2D materials without causing any damage, a requirement for high-performance 2D electronics.

Oriented‐Electrochemical Etching of Zn Crystal Edges in Deep Eutectic Solvent for Enhancing Stability and Reversibility of Zn Anodes

AbstractMetal Zn anode encounters uncontrolled dendrite growth, resulting in poor cycling stability and low coulombic efficiency (CE). Herein, a novel approach for oriented‐electrochemical etching of Zn (ECE‐Zn) in deep eutectic solvent (DES) is presented to adjust the interface concentration and electric fields, effectively mitigating intractable issues. The oriented etches off the crystal edges between the (002), (100), and (101) principal crystal planes of commercial Zn foil, subsequently etches the (100) and (101) crystal planes, resulting in the formation well‐organized Zn columns. Comprehensive experimental investigations and theoretical analyses reveal that Zn ions directionally nucleate and grow between Zn columns, enabling epitaxial growth at the (002) crystal plane. The ECE‐Zn‐2 anodes demonstrate remarkable stability, along with low nucleation and polarization voltages. Specifically, the symmetric ECE‐Zn‐2 cells show sustained operation for 5400 h, and long‐term 10 000 cycles at 40 mA cm−2. More significantly, the asymmetric cells exhibit an average CE as high as 99.92% over 6000 cycles at 5.0 mA cm−2. When assembled with a V2O5 cathode, a high retention of 81.5% can be maintained even under severe condition (N/P ratio of 7.35). This strategy of oriented‐electrochemical etching for commercial Zn opens up a new pathway for dendrite‐free Zn metal anode.

Status of h-BN quasi-bulk crystals and high efficiency neutron detectors

III-nitrides have fomented a revolution in the lighting industry and are poised to make a huge impact in the field of power electronics. In the III-nitride family, the crystal growth and use of hexagonal BN (h-BN) as an ultrawide bandgap (UWBG) semiconductor are much less developed. Bulk crystals of h-BN produced by the high-temperature/high-pressure and the metal flux solution methods possess very high crystalline and optical qualities but are impractical to serve as substrates or for device implementation as their sizes are typically in millimeters. The development of crystal growth technologies for producing thick epitaxial films (or quasi-bulk or semi-bulk crystals) in large wafer sizes with high crystalline quality is a prerequisite for utilizing h-BN as an UWBG electronic material. Compared to traditional III-nitrides, BN has another unique application as solid-state neutron detectors, which however, also require the development of quasi-bulk crystals to provide high detection efficiencies because the theoretical efficiency (ηi) relates to the detector thickness (d) by ηi=1−e−dλ, where λ denotes the thermal neutron absorption length which is 47 μm (237 μm) for 10B-enriched (natural) h-BN. We provide an overview and recent progress toward the development of h-BN quasi-bulk crystals via hydride vapor phase epitaxy (HVPE) growth and the attainment of thermal neutron detectors based on 100 μm thick 10B-enriched h-BN with a record efficiency of 60%. The thermal neutron detection efficiency was shown to enhance at elevated temperatures. Benchmarking the crystalline and optical qualities of h-BN quasi-bulk crystals with the state-of-the-art mm-sized bulk crystal flakes and 0.5 μm thick epitaxial films identified that reducing the density of native defects such as vacancies remains the most critical task for h-BN quasi-bulk crystal growth by HVPE.

Approaching the Ideal Linearity in Epitaxial Crystalline-type Memristor by Controlling Filament Growth.

Brain-inspired neuromorphic computing has attracted widespread attention owing to its ability to perform parallel and energy-efficient computation. However, the synaptic weight of amorphous/polycrystalline oxide based memristor usually exhibits large nonlinear behaviour with high asymmetry, which aggravates the complexity of peripheral circuit system.[6-10] Controllable growth of conductiv filaments is highly demanded for achieving the highly-linear conductance modulat ion. However, the stochastic behaviour of the filament growth in commonly used amorphous/polycrystalline oxide memristor makes it very challenging. Here, we report the epitaxially grown Hf0.5Zr0.5O2-based memristor with the linearity and symmetry approaching ideal case. A layer of Cu nanoparticles is inserted into epitaxially grown Hf0.5Zr0.5O2 film to form the grain boundaries due to the breaking of the epitaxial growth. By combining with the local electric field enhancement, the growth of filament is confined in the grain boundaries due to the fact that the diffusion of oxygen vacancy in crystalline lattice is more difficult than that in the grain boundaries. Furthermore, the decimal operation and high-accuracy neural network are demonstrated by utilizing the highly-linear and multi-level conductance modulation capacity. Our method opens an avenue to control the filament growth for the application of resistance random access memory (RRAM) and neuromorphic computing. This article is protected by copyright. All rights reserved.

On the control of epitaxial growth and stray grains during laser-directed energy deposited Ni-based single crystal superalloy

Laser-directed energy deposition (L-DED) is considered as an effective repair method for damaged single-crystal (SX) superalloy turbine blades. However, controlling stray grains (SGs) and epitaxial growth is still the major problem. This study investigated the influences of pre-solution treatment and intrinsic heat treatment (IHT) on the formation of SGs and epitaxial growth of L-DED René N5 SX superalloy. The γ/γ’ eutectics and coarse γ’ precipitates at the inter-dendrite region can be eliminated after pre-solution treatment procedures before the L-DED experiment. A lower temperature in pre-solution treatment resulted in the retention of residual γ/γ’ eutectics and coarse γ’ precipitates. Thus, the aggravated element segregation within the local melt pool and interface collapse during the L-DED process can result in stray grains (SGs) formation. Improved pre-solution treatment procedures can help reduce SGs caused by the residual carbides at the bottom of the molten pool. Besides, the SG formation in the deposited layers can be attributed to the recrystallization as a result of high thermal stress during the IHT in thermal cycles. The optimized pre-solution treatment procedure reduced the elemental segregation of the substrates, resulting in a larger primary dendrite arm spacing (PDAS) from the bottom of the deposited layers. Due to IHT during thermal cycles in the deposited layers, the partial aging treatment promoted the re-precipitation and growth of γ’ phase. Meanwhile, the optimized pre-solution treatment procedure decreased the size of the heat-affected zone (HAZ) caused by thermal cycles. In summary, by optimizing the substrates' pre-solution treatment procedures to eliminate the γ/γ’ eutectics, the formation of SGs resulting from substrate segregation can be controlled. This work provides the potential guidance of substrate pre-treatment for L-DED repair of SX superalloys.

Effect of Si addition on epitaxial growth and gas sensing properties of tungsten oxide films

Effect of Si addition on epitaxial growth and gas sensing properties of tungsten oxide films

Investigation of electronic, ferroelectric and local electrical conduction behavior of RF sputtered BiFeO3 thin films

Most of the applied research on BiFeO3 (BFO) focuses on magnetoelectric and spintronic applications. This calls for a detailed grasp of multiferroic and conduction properties. BFO thin films with (100) epitaxial growth has been deposited on a LaNiO3 (LNO) buffered Pt/Ti/SiO2/Si(100) substrate using RF magnetron sputtering. The film formed at 15 mTorr, 570 °C, and with Ar/O2 4:1 had a reasonably high degree of (100)-preferential orientation, the least surface roughness, and a densely packed structure. We obtained ferroelectric loops with strong polarization (150 μC cm−2). The leakage current density is as low as 10–2 A cm−2 at 100 kV cm−1, implying that space-charge-limited bulk conduction (SCLC) was the primary conduction channel for carriers within BFO films. Local electrical conduction behavior demonstrates that at lower voltages, the grain boundary dominates electrical conduction and is linked to the displacement of oxygen vacancies in the grain boundary under external electric fields. We hope that a deeper understanding of the conduction mechanism will help integrate BFO into viable technologies.

Epitaxial growth of gehlenite in CaO-MgO-Al2O3-SiO2 based glass ceramic induced by Nb2O5 addition

In this study, the crystallization behavior of a CaO-MgO-Al2O3-SiO2 based glass ceramics with Nb2O5 addition was investigated by using DSC, XRD and TEM techniques. It was found that three crystalline phases, namely, CaNb2O6, diopside and Gehlenite (Ca2Al2SiO7), were formed from the glass matrix during the crystallization heat treatment. The CaNb2O6 phase was the first to precipitate from the glass matrix at around 850°C, acting as a nucleating agent that facilitated the formation of Gehlenite (Ca2Al2SiO7) at 900-950°C. The TEM observation revealed a consistent orientation relationship between the CaNb2O6 and the Gehlenite (Ca2Al2SiO7) phases, indicating that CaNb2O6 could induce the epitaxial growth of Gehlenite (Ca2Al2SiO7). This result provides a new insight into the preparation of Gehlenite epitaxial films and glass ceramics.

Molecular beam epitaxy growth and characterization of GePb alloys

Pb based group-IV alloys such as GePb have been gaining interest as a potential alternative for infrared detectors, quantum materials, and high-speed electronic devices. Challenges remain in their growth due to the extremely low solid solubility of Pb in the Ge–Pb system. This paper reports molecular beam epitaxy growth of GePb alloy thin films on Ge(100) substrates. Effusion cells of Ge and Pb are used to control the flux ratio independently. The optimal substrate temperature is found to be near the thermocouple temperature of 300 °C based on the characterization of the grown films using high-resolution x-ray diffraction. A large change in the Ge:Pb beam equivalent pressure ratio from 10:1 to 1:1 results in only a minimal increase of the Pb composition from 0.74% to 2.84% as estimated from Raman spectroscopy and Rutherford backscattering spectrometry. Scanning electron microscopy images show a large volume of Pb islands on the surface that form into either long trapezoidal rods or uniform droplets, with increasing Pb flux and growth time the density of Pb islands increased.