No Arabic abstract
Cubic boron arsenide (BAs) is attracting greater attention due to the recent experimental demonstration of ultrahigh thermal conductivity k{appa} above 1000 W/mK. However, its bandgap has not been settled and a simple yet effective method to probe its crystal quality is missing. Furthermore, traditional k{appa} measurement methods are destructive and time consuming, thus they cannot meet the urgent demand for fast screening of high k{appa} materials. After we experimentally established 1.82 eV as the indirect bandgap of BAs and observed room-temperature band-edge photoluminescence, we developed two new optical techniques that can provide rapid and non-destructive characterization of k{appa} with little sample preparation: photoluminescence mapping (PL-mapping) and time-domain thermo-photoluminescence (TDTP). PL-mapping provides nearly real-time image of crystal quality and k{appa} over mm-sized crystal surfaces; while TDTP allows us to pick up any spot on the sample surface and measure its k{appa} using nanosecond laser pulses. These new techniques reveal that the apparent single crystals are not only non-uniform in k{appa}, but also are made of domains of very distinct k{appa}. Because PL-mapping and TDTP are based on the band-edge PL and its dependence on temperature, they can be applied to other semiconductors, thus paving the way for rapid identification and development of high-k{appa} semiconducting materials.
Extensive photochemical and spectroscopic properties of the $V_B^-$ defect in hexagonal boron nitride are calculated, concluding that the observed photoemission associated with recently observed optically-detected magnetic resonance is most likely of (1)3E to (1)3A2 origin. Rapid intersystem crossing from the defects triplet to singlet manifolds explains the observed short excited-state lifetime and very low quantum yield. New experimental results reveal smaller intrinsic spectral bandwidths than previously recognized, interpreted in terms spectral narrowing and zero-phonon-line shifting induced by the Jahn-Teller effect. Different types of computational methods are applied to map out the complex triplet and singlet defect manifolds, including the doubly ionised formulation of the equation-of-motion coupled-cluster theory that is designed to deal with the open-shell nature of defect states, and mixed quantum-mechanics/molecular-mechanics schemes enabling 5763-atom simulations. Two other energetically feasible spectral assignments from amongst the singlet and triplet manifolds are considered, but ruled out based on inappropriate photochemical properties.
Recent measurements of an unusual high thermal conductivity of around 1000 W m-1 K-1 at room temperature in cubic boron arsenide (BAs) confirm predictions from theory and suggest potential applications of this semiconductor compound for thermal management applications. Knowledge of the thermal expansion coefficient and Gruneisen parameter of a material contributes both to the fundamental understanding of its lattice anharmonicity and to assessing its utility as a thermal-management material. However, previous theoretical calculations of the thermal expansion coefficient and Gruneisen parameter of BAs yield inconsistent results. Here we report the linear thermal expansion coefficient of BAs obtained from the X-ray diffraction measurements from 300 K to 773 K. The measurement results are in good agreement with our ab initio calculations that account for atomic interactions up to fifth nearest neighbours. With the measured thermal expansion coefficient and specific heat, a Gruneisen parameter of BAs of 0.84 +/- 0.09 is obtained at 300 K, in excellent agreement with the value of 0.82 calculated from first principles and much lower than prior theoretical results. Our results confirm that BAs exhibits a better thermal expansion coefficient match with commonly used semiconductors than other high-thermal conductivity materials such as diamond and cubic boron nitride.
Atomically thin two-dimensional molybdenum disulfide (MoS2) sheets have attracted much attention due to their potential for future electronic applications. They not only present the best planar electrostatic control in a device, but also lend themselves readily for dielectric engineering. In this work, we experimentally investigated the dielectric effect on the Raman and photoluminescence (PL) spectra of monolayer MoS2 by comparing samples with and without HfO2 on top by atomic layer deposition (ALD). Based on considerations of the thermal, doping, strain and dielectric screening influences, it is found that the red shift in the Raman spectrum largely stems from modulation doping of MoS2 by the ALD HfO2, and the red shift in the PL spectrum is most likely due to strain imparted on MoS2 by HfO2. Our work also suggests that due to the intricate dependence of band structure of monolayer MoS2 on strain, one must be cautious to interpret its Raman and PL spectroscopy.
Reducing thermal conductivity ($kappa$) is an efficient way to boost the thermoelectric performance to achieve direct solid-state conversion to electrical power from thermal energy, which has lots of valuable applications in reusing waste resources. In this study, we propose an effective approach for realizing low $kappa$ by introducing lone-pair electrons or making the lone-pair electrons stereochemically active through bond nanodesigning. As a case study, by cutting at the (111) cross section of the three-dimensional cubic boron arsenide (c-BAs), the $kappa$ is lowered by more than one order of magnitude in the resultant two-dimensional system of graphene-like BAs (g-BAs) due to the stereochemically activated lone-pair electrons. Similar concept can be also extended to other systems with lone-pair electrons beyond BAs, such as group III-V compounds, where a strong correlation between $kappa$ modulation and electronegativity difference for binary compounds is found. Thus, the lone-pair electrons combined with a small electronegativity difference could be the indicator of lowering $kappa$ through bond nanodesigning to change the coordination environment. The proposed approach for realizing low $kappa$ and the underlying mechanism uncovered in this study would largely benefit the design of thermoelectric devices with improved performance, especially in future researches involving novel materials for energy applications.
Silicon carbide silicon carbide (SiC SiC) composites are often used in oxidizing environments at high temperatures. Measurements of the thermal conductance of the oxide layer provide a way to better understand the oxidation process with high spatial resolution. We use time domain thermoreflectance (TDTR) to map the thermal conductance of the oxide layer and the thermal conductivity of the SiC SiC composite with a spatial resolution of 3 {mu}m. Heterodyne detection using a 50 kHz modulated probe beam and a 10 MHz modulated pump suppresses the coherent pick-up and enables faster data acquisition than what has previously been possible using sequential demodulation. By analyzing the noise of the measured signals, we find that in the limit of small integration time constants or low laser powers, the dominant source of noise is the input noise of the preamplifier. The thermal conductance of the oxide that forms on the fiber region is lower than the oxide on the matrix due to small differences in thickness and thermal conductivity.