Drastically enhanced cation incorporation in the epitaxy of oxides due to formation and evaporation of suboxides from elemental sources

In the molecular beam epitaxy of oxide films, the cation (Sn, Ga) or dopant (Sn) incorporation does not follow the vapor pressure of the elemental metal sources, but is enhanced by several orders of magnitude for low source temperatures. Using line-of-sight quadrupole mass spectrometry, we identify the dominant contribution to the total flux emanating from Sn and Ga sources at these temperatures to be due to the unintentional formation and evaporation of the respective suboxides SnO and Ga$_{2}$O. We quantitatively describe this phenomenon by a rate-equation model that takes into account the O background pressure, the resulting formation of the suboxides via oxidation of the metal source, and their subsequent thermally activated evaporation. As a result, the total flux composed of the metal and the suboxide fluxes exhibit an textsf{S}-shape temperature dependence instead of the expected linear one in an Arrhenius plot, in excellent agreement with the available experimental data. Our model reveals that the thermally activated regimes at low and high temperatures are almost exclusively due to suboxide and metal evaporation, respectively, joined by an intermediate plateau-like regime in which the flux is limited by the available amount of O. An important suboxide contribution is expected for all elemental sources whose suboxide exhibits a higher vapor pressure than the element, such as B, Ga, In, La, Si, Ge, Sn, Sb, Mo, Nb, Ru, Ta, V, and W. This contribution can play a decisive role in the molecular beam epitaxy of oxides, including multicomponent or complex oxides, from elemental sources. Finally, our model predicts suboxide-dominated growth in low-pressure chemical vapor deposition of Ga$_{2}$O$_{3}$ and In$_{2}$O$_{3}$.

Direct Observation of Reversible Heat Absorption in Li-ion Battery Enabled by Ultra-Sensitive Thermometry

The reversible heat in lithium-ion batteries (LIBs) due to entropy change is fundamentally important for understanding the chemical reactions in LIBs and developing proper thermal management strategies. However, the direct measurements of reversible heat are challenging due to the limited temperature resolution of applied thermometry. In this work, by developing an ultra-sensitive thermometry with a differential AC bridge using two thermistors, the noise-equivalent temperature resolution we achieve (10 uK) is several orders of magnitude higher than previous thermometry applied on LIBs. We directly observe reversible heat absorption of a LIR2032 coin cell during charging with negligible irreversible heat generation and a linear relation between heat generations and discharging currents. The cell entropy changes determined from the reversible heat agree excellently with those measured from temperature dependent open circuit voltage. Moreover, it is found that the large reversible entropy change can cancel out the irreversible entropy generation at a charging rate as large as C/3.7 and produce a zero-heat-dissipation LIB during charging. Our work significantly contributes to fundamental understanding of the entropy changes and heat generations of the chemical reactions in LIBs, and reveals that reversible heat absorption can be an effective way to cool LIBs during charging.

Experimental Observation of Localized Interfacial Phonon Modes

Interfaces impede heat flow in micro/nanostructured systems. Conventional theories for interfacial thermal transport were derived based on bulk phonon properties of the materials making up the interface without explicitly considering the atomistic interfacial details, which are found critical to correctly describing thermal boundary conductance (TBC). Recent theoretical studies predicted the existence of localized phonon modes at the interface which can play an important role in understanding interfacial thermal transport. However, experimental validation is still lacking. Through a combination of Raman spectroscopy and high-energy resolution electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope, we report the first experimental observation of localized interfacial phonon modes at ~12 THz at a high-quality epitaxial Si-Ge interface. These modes are further confirmed using molecular dynamics simulations with a high-fidelity neural network interatomic potential, which also yield TBC agreeing well with that measured from time-domain thermoreflectance (TDTR) experiments. Simulations find that the interfacial phonon modes have obvious contribution to the total TBC. Our findings may significantly contribute to the understanding of interfacial thermal transport physics and have impact on engineering TBC at interfaces in applications such as electronics thermal management and thermoelectric energy conversion.

Data-Efficient Language-Supervised Zero-Shot Learning with Self-Distillation

Traditional computer vision models are trained to predict a fixed set of predefined categories. Recently, natural language has been shown to be a broader and richer source of supervision that provides finer descriptions to visual concepts than supervised gold labels. Previous works, such as CLIP, use a simple pretraining task of predicting the pairings between images and text captions. CLIP, however, is data hungry and requires more than 400M image text pairs for training. We propose a data-efficient contrastive distillation method that uses soft labels to learn from noisy image-text pairs. Our model transfers knowledge from pretrained image and sentence encoders and achieves strong performance with only 3M image text pairs, 133x smaller than CLIP. Our method exceeds the previous SoTA of general zero-shot learning on ImageNet 21k+1k by 73% relatively with a ResNet50 image encoder and DeCLUTR text encoder. We also beat CLIP by 10.5% relatively on zero-shot evaluation on Google Open Images (19,958 classes).

Good Solid-State Electrolytes Have Low, Glass-like Thermal Conductivity

Management of heat during charging and discharging of Li-ion batteries is critical for their safety, reliability, and performance. Understanding the thermal conductivity of the materials comprising batteries is crucial for controlling the temperature and temperature distribution in batteries. This work provides systemic quantitative measurements of the thermal conductivity of three important classes of solid electrolytes (oxides, sulfides, and halides) over the temperature range 150-350 K. Studies include the oxides Li1.5Al0.5Ge1.5(PO4)3 and Li6.4La3Zr1.4Ta0.6O12, sulfides Li2S-P2S5, Li6PS5Cl, and Na3PS4, and halides Li3InCl6 and Li3YCl6. Thermal conductivities of sulfide and halide solid electrolytes are in the range 0.45-0.70 W m-1 K-1; thermal conductivities of Li6.4La3Zr1.4Ta0.6O12 and Li1.5Al0.5Ge1.5(PO4)3 are 1.4 W m-1 K-1 and 2.2 W m-1 K-1, respectively. For most of the solid electrolytes studied in this work, the thermal conductivity increases with increasing temperature; i.e., the thermal conductivity has a glass-like temperature dependence. The measured room-temperature thermal conductivities agree well with the calculated minimum thermal conductivities indicating the phonon mean-free-paths in these solid electrolytes are close to an atomic spacing. We attribute the low, glass-like thermal conductivity of the solid electrolytes investigated to the combination of their complex crystal structures and the atomic-scale disorder induced by the materials processing methods that are typically needed to produce high ionic conductivities.

Thermal Visualization of Buried Interfaces by Transient and Steady-State Responses of Time-Domain Thermoreflectance

Thermal resistances from interfaces impede heat dissipation in micro/nanoscale electronics, especially for high-power electronics. Despite the growing importance of understanding interfacial thermal transport, advanced thermal characterization techniques which can visualize thermal conductance across buried interfaces, especially for nonmetal-nonmetal interfaces, are still under development. This work reports a dual-modulation-frequency TDTR mapping technique to visualize the thermal conduction across buried semiconductor interfaces for beta-Ga2O3-SiC samples. Both the beta-Ga2O3 thermal conductivity and the buried beta-Ga2O3-SiC thermal boundary conductance (TBC) are visualized for an area of 200 um x 200 um. Areas with low TBC values ( smaller than 20 MW/m2-K) are successfully identified on the TBC map, which correspond to weakly bonded interfaces caused by high-temperature annealing. The steady-state temperature rise (detector voltage), usually ignored in TDTR measurements, is found to be able to probe TBC variations of the buried interfaces without the limit of thermal penetration depth. This technique can be applied to detect defects/voids in deeply buried heterogeneous interfaces non-destructively, and also opens a door for the visualization of thermal conductance in nanoscale nonhomogeneous structures.

Quasi-Ballistic Thermal Conduction in 6H-SiC

The minimization of electronics makes heat dissipation of related devices an increasing challenge. When the size of materials is smaller than the phonon mean free paths, phonons transport without internal scatterings and laws of diffusive thermal conduction fail, resulting in significant reduction in the effective thermal conductivity. This work reports, for the first time, the temperature dependent thermal conductivity of doped epitaxial 6H-SiC and monocrystalline porous 6H-SiC below room temperature probed by time-domain thermoreflectance. Strong quasi-ballistic thermal transport was observed in these samples, especially at low temperatures. Doping and structural boundaries were applied to tune the quasi-ballistic thermal transport since dopants selectively scatter high-frequency phonons while boundaries scatter phonons with long mean free paths. Exceptionally strong phonon scattering by boron dopants are observed, compared to nitrogen dopants. Furthermore, orders of magnitude reduction in the measured thermal conductivity was observed at low temperatures for the porous 6H-SiC compared to the epitaxial 6H-SiC. Finally, first principles calculations and a simple Callaway model are built to understand the measured thermal conductivities. Our work sheds light on the fundamental understanding of thermal conduction in technologically-important wide bandgap semiconductors such as 6H-SiC and will impact applications such as thermal management of 6H-SiC-related electronics and devices.

Thermal Conductivity Mapping of Oxidized SiC SiC Composites by Time Domain Thermoreflectance with Heterodyne Detection

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.

Simultaneous Evaluation of Heat Capacity and In-plane Thermal Conductivity of Nanocrystalline Diamond Thin Films

As wide bandgap electronic devices have continued to advance in both size reduction and power handling capabilities, heat dissipation has become a significant concern. To mitigate this, chemical vapor deposited (CVD) diamond has been demonstrated as an effective solution for thermal management of these devices by directly growing onto the transistor substrate. A key aspect of power and radio frequency (RF) electronic devices involves transient switching behavior, which highlights the importance of understanding the temperature dependence of the heat capacity and thermal conductivity when modeling and predicting device electrothermal response. Due to the complicated microstructure near the interface between CVD diamond and electronics, it is difficult to measure both properties simultaneously. In this work, we use time domain thermoreflectance (TDTR) to simultaneously measure the in plane thermal conductivity and heat capacity of a 1 um thick CVD diamond film, and also use the pump as an effective heater to perform temperature dependent measurements. The results show that the in plane thermal conductivity varied slightly with an average of 103 W per meter per K over a temperature range of 302 to 327 K, while the specific heat capacity has a strong temperature dependence over the same range and matches with heat capacity data of natural diamond in literature.

Wafer-scale Heterogeneous Integration of Monocrystalline b{eta}-Ga2O3 Thin Films on SiC for Thermal Management by Ion-Cutting Technique

The ultra-wide bandgap, high breakdown electric field, and large-area affordable substrates make b{eta}-Ga2O3 promising for applications of next-generation power electronics while its thermal conductivity is at least one order of magnitude lower than other wide/ultrawide bandgap semiconductors. To avoid the degradation of device performance and reliability induced by the localized Joule-heating, aggressive thermal management strategies are essential, especially for high-power high-frequency applications. This work reports a scalable thermal management strategy to heterogeneously integrate wafer-scale monocrystalline b{eta}-Ga2O3 thin films on high thermal conductivity SiC substrates by ion-cutting technique. The thermal boundary conductance (TBC) of the b{eta}-Ga2O3-SiC interfaces and thermal conductivity of the b{eta}-Ga2O3 thin films were measured by Time-domain Thermoreflectance (TDTR) to evaluate the effects of interlayer thickness and thermal annealing. Materials characterizations were performed to understand the mechanisms of thermal transport in these structures. The results show that the b{eta}-Ga2O3-SiC TBC values increase with decreasing interlayer thickness and the b{eta}-Ga2O3 thermal conductivity increases more than twice after annealing at 800 oC due to the removal of implantation-induced strain in the films. A Callaway model is built to understand the measured thermal conductivity. Small spot-to-spot variations of both TBC and Ga2O3 thermal conductivity confirm the uniformity and high-quality of the bonding and exfoliation. Our work paves the way for thermal management of power electronics and b{eta}-Ga2O3 related semiconductor devices.