High Growth Temperature Research Articles

Shortwave Infrared Photodetection with oCVD Polythiophene.

Shortwave infrared (SWIR, λ = 1-3µm) photodetectors typically use compound semiconductors that are fabricated using high-temperature epitaxial growth and require active cooling. New technologies that overcome these constraints are the focus of intensive current research. Herein, oxidative chemical vapor deposition (oCVD) is used for the first time to create a room temperature, vapor-phase deposited SWIR photoconductive detector with a unique tangled wire film morphology that detects nW-level photons emitted from a 500°C cavity blackbody radiator-a rarity for polymer systems. A new, window-based process that greatly simplifies device fabrication is used to construct doped polythiophene-based SWIR sensors. The detectors feature an 8.97 kΩ dark resistance and are limited by 1/f noise. They feature an external quantum efficiency (gain-external quantum efficiency) product of 395% and have a measured specific detectivity (D*) of 106 Jones, with the potential to reach D* = 1010 Jones after 1/f noise is minimized. Still, the measured D* is only a factor of 102 lower than a typical microbolometer and after optimization, the newly described oCVD polymer-based IR detectors will be in a category competitive with commercially available, room temperature lead salt photoconductors and within reach of room temperature photodiodes.

Controllable nitrogen doping of MOCVD Ga2O3 using NH3

We report on the controllable nitrogen doping of β-Ga2O3 as a deep acceptor dopant using ammonia diluted in nitrogen (NH3/N2) as a source of active nitrogen in the metal organic chemical vapor deposition epitaxy. The effects of the NH3/N2 flow rate and substrate temperature on the incorporation efficiency, reproducibility, and controllability of N doping into Ga2O3 were studied using secondary ion mass spectrometry measurements. With the increase in the NH3/N2 molar flow rate from ∼2 × 10−8 to ∼2 × 10−6 mol/min, the N impurities incorporated into the β-Ga2O3 increased linearly from ∼1 × 1018 to ∼2 × 1020 cm−3. At low substrate temperatures (<800 °C), hydrogen was incorporated into the film accompanying nitrogen with comparable concentrations. Despite this, the current–voltage measurements showed that the N and H co-doped films were resistive with a measured resistance of >70 MΩ for a film grown with [N] ≈ [H] of ∼8 × 1018 cm−3. X-ray on-axis (020) and off-axis (111) rocking curve ω-scans and atomic force microscopy measurements show no influence of NH3/N2 dopant on the structural and surface quality of the films. However, the presence of H promoted the growth of (110) and (1¯10) facets elongated along the [001] direction. At high growth temperatures (≥950 °C), the H concentration in the films was reduced by nearly ∼10×, but with a slight increase in the concentration of N. The results show that controllable and repeatable nitrogen doping into β-Ga2O3 can be achieved using ammonia to obtain deep acceptor doping or compensation needed for device engineering in β-Ga2O3-based power electronic devices.

Selective Growth of Graphene-Confined Inkjet-Printed Sn Nanoparticles on Plastic Using Intense Pulsed Light Annealing.

Printing graphene-based nanomaterials on flexible substrates has become a burgeoning platform for next-generation technologies. Combining graphene and nanoparticles to create hybrid nanomaterials has been proven to boost device performance, thanks to their complementary physical and chemical properties. However, high growth temperatures and long processing times are often required to produce high-quality graphene-based nanocomposites. For the first time, we report a novel scalable approach for additive manufacturing of Sn patterns on polymer foil and their selective conversion into nanocomposite films under atmospheric conditions. A combination of inkjet printing and intense flashlight irradiation techniques is studied. Light pulses that are selectively absorbed by the printed Sn patterns cause a temperature of over 1000 °C to be reached locally in a split second without damaging the underlying polymer foil. The top surface of the polymer foil at the interface with printed Sn becomes locally graphitized and acts as a carbon source, transforming printed Sn into Sn@graphene (Sn@G) core-shell patterns. Our results revealed a decrease in electrical sheet resistance, with an optimal value (Rs = 72 ± 2 Ω/sq) reached when light pulses with an energy density of 12.8 J/cm2 were applied. These graphene-protected Sn nanoparticle patterns exhibit excellent resistance against air oxidation for months. Finally, we demonstrate the implementation of Sn@G patterns as electrodes for Li-ion microbatteries (LIBs) and triboelectric nanogenerators (TENGs), showing remarkable performance. This work offers new insight into the development of a versatile, eco-friendly, and cost-effective technique for producing well-defined patterns of graphene-based nanomaterials directly on a flexible substrate using different light-absorbing nanoparticles and carbon sources.

Fast synthesis of large-area bilayer graphene film on Cu

Bilayer graphene (BLG) is intriguing for its unique properties and potential applications in electronics, photonics, and mechanics. However, the chemical vapor deposition synthesis of large-area high-quality bilayer graphene on Cu is suffering from a low growth rate and limited bilayer coverage. Herein, we demonstrate the fast synthesis of meter-sized bilayer graphene film on commercial polycrystalline Cu foils by introducing trace CO2 during high-temperature growth. Continuous bilayer graphene with a high ratio of AB-stacking structure can be obtained within 20 min, which exhibits enhanced mechanical strength, uniform transmittance, and low sheet resistance in large area. Moreover, 96 and 100% AB-stacking structures were achieved in bilayer graphene grown on single-crystal Cu(111) foil and ultraflat single-crystal Cu(111)/sapphire substrates, respectively. The AB-stacking bilayer graphene exhibits tunable bandgap and performs well in photodetection. This work provides important insights into the growth mechanism and the mass production of large-area high-quality BLG on Cu.

Global Transcriptome-Guided Identification of Neutral Sites for Engineering Synechococcus elongatus PCC 11801.

Engineered cyanobacteria are attractive hosts for the phototrophic conversion of CO2 to chemicals. Synechococcus elongatus PCC11801, a novel, fast-growing, and stress-tolerant cyanobacterium, has the potential to be a platform cell factory, and hence, it necessitates the development of a synthetic biology toolbox. Considering the widely followed cyanobacterial engineering strategy of chromosomal integration of heterologous DNA, it is of interest to discover and validate new chromosomal neutral sites (NSs) in this strain. To that end, global transcriptome analysis was performed using RNA Seq under the conditions of high temperature (HT), carbon (HC), and salt (HS) and ambient growth conditions. We found upregulation of 445, 138, and 87 genes and downregulation of 333, 125, and 132 genes, under HC, HT, and HS, respectively. Following nonhierarchical clustering, gene enrichment, and bioinformatics analysis, 27 putative NSs were predicted. Six of them were experimentally tested, and five showed confirmed neutrality, based on unaltered cell growth. Thus, global transcriptomic analysis was effectively exploited for NS annotation and would be advantageous for multiplexed genome editing.

Investigation of the Nucleation Process during the Initial Stage of PVT Growth of 4H-SiC

Due to high growth temperatures during the physical vapor transport (PVT) it is still almost impossible to gain proper insight into the actual growth conditions. Therefore, computer tomography (CT) is used as an in-situ monitoring during the crystal growth process. With the help of this technique, it is possible to observe the nucleation centers during the initial stage of growth (CT after 0h) of a 4H-SiC single crystal. These growth islands are likely built before the actual growth conditions are reached. Raman investigations of the area around a growth island located directly on the interface between seed and grown crystal is used to support this assumption. In addition, optical analysis after KOH etching were made to reveal the defects around the growth island. The island exhibits a rough doping concentration in comparison to the surrounding grown crystal.

Improvement of optical properties of InGaN-based red multiple quantum wells.

The realization of red-emitting InGaN quantum well (QW) is a hot issue in current nitride semiconductor research. It has been shown that using a low-Indium (In)-content pre-well layer is an effective method to improve the crystal quality of red QWs. On the other hand, keeping uniform composition distribution at higher In content in red QWs is an urgent problem to be solved. In this work, the optical properties of blue pre-QW and red QWs with different well width and growth conditions are investigated by photoluminescence (PL). The results prove that the higher-In-content blue pre-QW is beneficial to effectively relieve the residual stress. Meanwhile, higher growth temperature and growth rate can improve the uniformity of In content and the crystal quality of red QWs, enhancing the PL emission intensity. Possible physical process of stress evolution and the model of In fluctuation in the subsequent red QW are discussed. This study provides a useful reference for the development of InGaN-based red emission materials and devices.

Influence of HCl concentration in source solution and growth temperature on formation of α-Ga2O3 film via mist-CVD process

We have examined the effect of synthesis conditions on α-Ga2O3 film, one of the ultra-wide bandgap semiconductors, on c-plane sapphire substrate via mist CVD process. The resultant film is dominantly composed of α-Ga2O3 phase, but a small amount of κ-Ga2O3 phase coexists when the growth temperature is higher. The source solution containing higher concentration of HCl expands the range of temperatures at which single-phase α-Ga2O3 is grown and suppresses the inclusion of κ-Ga2O3 at higher growth temperatures. Moreover, the growth with higher concentration of HCl up to 0.66 mol l−1 increases the growth rate and improves the surface roughness. Thus, HCl has a crucial role in the selective growth of α-Ga2O3 and the quality of the film. Also, some pits are observed at the surface of α-Ga2O3 and κ-Ga2O3 is precipitated inside the pit defect when the concentration of HCl is low and the growth temperature is high.

Effects of growth temperature on structural and electrical properties of in-rich InAlN–GaN heterostructures by radio-frequency metal–organic molecular beam epitaxy

In-rich InAlN is a promising nitride semiconductor alloy for high-efficiency solar cells and wide-range light-emitting diodes due to its tunable bandgap from 0.7 to 6.2 eV. However, incomplete characterization has led to inconsistent fundamental properties in some studies. The aim of this study was to comprehensively investigate the structural, optical, and electrical properties of In-rich InAlN films grown on GaN/Al2O3 templates by RF-MOMBE at various temperatures. The methodology involved state-of-the-art metrology techniques, such as high-resolution x-ray diffraction (HRXRD), scanning electron microscopy (FE-SEM), Hall effect measurements, and transmission electron microscopy (TEM). The results showed that all InxAl1-xN films were epitaxially grown on the GaN/Al2O3 template, with the indium composition (x) decreasing with increasing growth temperature. Furthermore, phase separation of the In-rich InAlN films occurred at high growth temperatures(>550 °C), resulting in a relatively smooth surface. The optical absorption method measured the band-gap of the InxAl1-xN films, which ranged from 1.7 to 1.9 eV for x values between 0.77 and 0.91. The mobility and carrier concentrations of all In-rich InAlN films were measured at ∼60−277 cm2 V−1-s−1 and 2–7 × 1019 cm3 in the growth temperature of range 450 °C–610 °C, respectively. In conclusion, our comprehensive characterization using advanced metrology methods provides valuable insights into the properties of In-rich InAlN films, which can inform future optimization of these materials for various applications.

Robust temperature–strain coupling in phase and shape evolution of MoTe2 nanosheets

Molybdenum ditelluride (MoTe2) has a stable semiconducting hexagonal (2H) phase and a metastable metallic distorted octahedral (1T′) phase at the same time, which attracts much attention due to its attractive properties. However, the mechanism of phase and shape evolution in the preparation of MoTe2 is still unclear, which limits the controllable preparation and the wider device application of MoTe2. Here, we prepare few-layer MoTe2 with controllable phase and shape by using MoO3 and Te powders as precursors. With this method, triangle and hexagon 2H MoTe2 can be prepared, and long-strip and irregular 1T′ MoTe2 can be obtained. The phase and shape of as-prepared MoTe2 are determined by the coupling effect in the growth temperature and the lattice strain between 2H and 1T′ MoTe2. Low growth temperature combined with low Te concentration could induce small growth strain potential, leading to the growth of triangle and hexagon 2H MoTe2. While high growth temperature combined with high Te concentration could induce large strain potential, which is conducive to the preparation of long-strip and irregular 1T′ MoTe2. This study deeply investigates the evolution mechanism of phase and shape in MoTe2 growth, which has important guiding significance for the controllable preparation of phase and shape of other two-dimensional materials.

Superconductivity and magnetic and transport properties of single-crystalline CaK(Fe1−xCrx)4As4

Members of the CaK(Fe$_{1-x}$Cr$_{x}$)$_{4}$As$_{4}$ series have been synthesized by high-temperature solution growth in single crystalline form and characterized by X-ray diffraction, elemental analysis, magnetic and transport measurements. The effects of Cr substitution on the superconducting and magnetic ground states of CaKFe$_4$As$_4$ ($T_c$ = 35 K) have been studied. These measurements show that the superconducting transition temperature decreases monotonically and is finally suppressed below 1.8 K as $x$ is increased from 0 to 0.038. The magnetic transition temperature increases in a roughly linear manner as Cr substitution increases. A temperature-composition (\textit{T}-\textit{x}) phase diagram is constructed, revealing a half-dome of superconductivity with the magnetic transition temperature, $T^*$, appearing near 22~K for $x$ $\sim$ 0.017 and rising slowly up to 60~K for $x$ $\sim$ 0.077. The $T$-$x$ phase diagrams for CaK(Fe$_{1-x}$$T$$_{x}$)$_4$As$_4$ for $T$ = Cr and Mn are essentially the same despite the nominally different band filling; this is in marked contrast to $T$ = Co and Ni series for which the $T$-$x$ diagrams scale by a factor of two, consistent with the different changes in band filling Co and Ni would produce when replacing Fe. Superconductivity of CaK(Fe$_{1-x}$Cr$_{x}$)$_{4}$As$_{4}$ is also studied as a function of magnetic field. A clear change in $H^\prime_{c2}$($T$)/$T_c$, where $H^\prime_{c2}$($T$) is d$H_{c2}$($T$)/d$T$, at $x$ $\sim$ 0.012 is observed and probably is related to change of the Fermi surface due to magnetic order. Coherence length and the London penetration depths are also calculated based on $H_{c1}$ and $H_{c2}$ data. Coherence lengths as the function of $x$ also shows changes near $x$ = 0.012, again consistent with Fermi surfaces changes associated with the magnetic ordering seen for higher $x$-values.

In Situ Growth of Graphene on Polyimide for High-Responsivity Flexible PbS-Graphene Photodetectors.

Graphene is an ideal material for flexible optoelectronic devices due to its excellent electrical and optical properties. However, the extremely high growth temperature of graphene has greatly limited the direct fabrication of graphene-based devices on flexible substrates. Here, we have realized in situ growth of graphene on a flexible polyimide substrate. Based on the multi-temperature-zone chemical vapor deposition cooperated with bonding a Cu-foil catalyst onto the substrate, the growth temperature of graphene was controlled at only 300 °C, enabling the structural stability of polyimide during growth. Thus, large-area high-quality monolayer graphene film was successfully in situ grown on polyimide. Furthermore, a PbS-graphene flexible photodetector was fabricated using the graphene. The responsivity of the device reached 105 A/W with 792 nm laser illumination. The in-situ growth ensures good contact between graphene and substrate; therefore, the device performance can remain stable after multiple bending. Our results provide a highly reliable and mass-producible path for graphene-based flexible devices.

Intrinsic resistive switching in ultrathin SiOx memristors for neuromorphic inference accelerators

Two-dimensional (2D) materials are promising memristive materials owing to their outstanding physical properties, electrical tunability and fast switching capability. However, 2D layered materials generally require sophisticated deposition techniques at the expense of limited large-scale homogeneity and high growth temperatures. Furthermore, the variability and reliability of the 2D materials based memristor should be further improved. Here, we report an intrinsic memristor based on ultrathin 2D-like nonlayered amorphous SiOx which is derived from a native oxidation process at ambient temperature. Such 2D-like memristors demonstrate low switching variability (3.7 %), nanosecond switching speed (15 ns), good endurance (>106 cycles) and high retention (>103 s at 85 °C). We verified the resistive switching mechanism via in-depth X-ray photoemission spectroscopy (XPS) analysis at different resistance states and confirmed the oxygen vacancies movement under the electric field between the SnOx reservoir layer and the SiOx layer. Moreover, Simulation results for an MNIST image classifier based on the ultrathin SiOx memristor show a high recognition accuracy of ∼ 98 %, manifesting its potential for the practical implementation of nonlayered 2D-like materials based neural network inference accelerator.

Study on three-dimensional critical nucleation on a planar substrate of 3C-SiC crystal

The growth quality of 3C-SiC crystal is affected by the three-dimensional critical nucleation. A three-dimensional kinetic Monte Carlo model for 3C-SiC crystal growth on a planar substrate has been established. The effects of growth conditions on three-dimensional critical nucleation characteristics are studied. The results show that three-dimensional critical nucleation time is earlier, surface roughness is smaller, and the ratio of average spacing and average size of two-dimensional clusters are greater at a higher growth temperature or a lower deposition rate. In addition, the three-dimensional critical nucleation time is affected by the Ehrlich-Schwoebel barrier. There is a critical Ehrlich-Schwoebel barrier, and the three-dimensional critical nucleation time changes little with the Ehrlich-Schwoebel barrier when the value of Ehrlich-Schwoebel barrier is greater than the critical value.

Deformation Prediction Theory of Thermal Barrier Coatings near Cooling Holes under Thermal Cycling.

Thermal barrier coating (TBC) systems are widely adopted in gas turbine blades to improve the thermal efficiency of gas turbine engines. However, TBC failure will happen due to the thermal stress between the different layers of the TBC systems. The traditional two-layer theoretical model only considers TGO (thermally grown oxide) and a substrate in the inner cooling hole with the surface uncoated, which results in poor prediction of the deformations of the TBC systems. It should be mentioned that the effect of TBC is very important because the thickness of TBC is much larger than the TGO thickness. In this study, a new three-layer theoretical model was derived, which is composed of the cylindrical TGO and TBC mounted in the substrate with a circular hole, and the stress and strain of TGO near the cooling hole under the condition of the thermal cycles were calculated. The high temperature characteristics of TGO and the substrate including the high temperature strength and growth ratio were from the experiments. The results show that the strain of the developed three-layer model is irrelevant with increasing number of cycles, which indicates that TBC in the cooling hole significantly inhibits the deformation of TGO near the cooling hole. Therefore, aimed at confirming the feasibility of the three-layer theoretical model, the finite element analysis with coating in the cooling hole and on the surface was carried out with a three-layer axisymmetric model, which proves that the 3-layer theoretical model can predict the deformation trend near the cooling hole.

Preparation and Physical Properties of Stretchable FeRh Films with Periodic Wrinkle Structure

AbstractStretchable magnetic materials are highly desirable for developing flexible high‐performance magnetoelectronic devices. However, it is still challenge to fabricate stretchable magnetic films with high growth temperature. In this work, metamagnetic FeRh films are grown on mica substrates at high temperature and then transferred onto the prestrained polydimethylsiloxane (PDMS). Due to the large modulus mismatch between FeRh films and PDMS, FeRh films with periodic wrinkle pattern is formed after releasing the prestrain, enabling a controllable stretchability up to a few tens of percent. Moreover, the meta‐magnetic phase transition temperature can be effectively controlled by the prestrain, with an increase of ≈4 K for every 10% increase in the prestrain. In case of the applied tensile strain less than the prestrain, the obtained flexible FeRh films can maintain stable performance after thousands of stretches, making it promising for applications in flexible magnetoelectronic devices.

Climate Change and Inequality: Evidence from the United States

This paper examines the effects of climate change on income inequality in the United States. Computing impulse response functions (IRFs) from the local projections’ method, we empirically show that there is an immediate temporary positive response in income inequality from rising temperatures within the first year. We also observe differences in the effects of temperature growth on inequality across different classifications, mainly states with high inequality and low temperature growth are more susceptible to changes in temperature growth than states with already high temperature growth and high inequality growth. States with low inequality growth exhibit similar positive effects on income inequality across low- and high-temperature-growth classifications. We find that the initial positive effect on income inequality is not permanent. However, if the effects of rising temperatures are unabated in the earlier periods, income inequality starts to rise in the later periods. Our results highlight an important pathway, that climate change can negatively affect sustainable development through increased income inequality.

Single Crystal Growth of Synthetic Sulfide- and Phosphide-Based Minerals for Physical Measurements

In this work, we review recent advances in the use of high-temperature solution growth that allow for the growth of single crystalline samples of synthetic minerals. We outline how low-melting binary or ternary solutions are attractive solvents for solution growth and provide examples of the growth of bismuthinite (Bi2S3), galena (PbS) and parkerite (Ni3Bi2S2). We then focus on the Rh-S, Pd-S and Ni-P phase spaces to discuss how the low-melting regions near transition metal-main group eutectic compositions make excellent solvents for crystal growth of several binary and ternary minerals containing both high melting and volatile elements as well as for the discovery of new materials. We end by discussing the growth of synthetic canfieldite (Ag8SnS6) and argyrodite (Ag8GeS6) from Ag2S–Sn-S-based solutions.

Millimeter-Sized Monoisotopic Cubic 10Boron Phosphide

Boron isotope-containing semiconductors with many novel physical properties have attracted extensive research interest in the areas such as device thermal management, optical components, and neutron detection. However, the existence of strong intrinsic covalent bonding leads to the high-temperature and high-pressure growth conditions of the single crystals of B-compound semiconductors, which has been a great bottleneck limiting their development. Here, high-quality monoisotopic cubic 10BP single crystals at a millimeter scale of approximately 1 mm were grown by a multistep ripening method based on the gas–liquid–solid principle for crystal growth. Structural and morphological analyses have shown that the 10BP single crystals prepared by this method possess a single cubic phase and high crystalline quality. The isotopic effect gives rise to the shift of characteristic peaks in the Raman spectrum. Besides, results obtained through reflection spectrum, photoluminescence (PL), and theoretical calculations demonstrate that 10BP is a semiconductor with an indirect band gap beyond 2 eV. All of these findings can prove that the multipart maturation method is a feasible way to synthesize high-quality 10BP single crystals, which provides a novel and competitive route for the study of isotopic c-BP and the growth of large-sized crystals.

Synthesis and characterization of metal carbides for nanoindentation tip applications

Instrumented indentation experiments at elevated temperatures require careful attention to a myriad of experimental details. Not the least of these is the choice of the indenter tip material. Traditional room-temperature indenters, e.g., diamond and sapphire, can break down, react, and wear excessively at elevated temperatures. In this work, rf-induction heating float-zone and high-temperature solution single-crystal growth techniques have been used to prepare a suite of bulk refractory carbide specimens (i.e., ZrC, VC0.86, NbC, TiC0.95, WC). These potential indenter tip materials were subsequently characterized using nanoindentation testing techniques to determine their single-crystal elastic modulus, hardness, and fracture toughness in order to evaluate their potential for use as elevated-temperature nanoindentation tips. Additionally, subject carbide crystal characteristics were compared to those of single-crystal sapphire and polycrystalline WC-Co. The cumulative results show that single-crystal WC is a promising candidate for indenter tip material based on a combination of its high elastic modulus, hardness, and resistance to cracking—in addition to being crystallographically favorable for fabrication in the frequently used three-sided pyramidal indenter tip geometries.