Time-domain Thermoreflectance Measurements Research Articles

Thermal Characterization of Ultrathin MgO Tunnel Barriers.

Magnetic tunnel junctions (MTJs) with ultrathin MgO tunnel barriers are at the heart of magnetic random-access memory (MRAM) and exhibit potential for spin caloritronics applications due to the tunnel magneto-Seebeck effect. However, the high programming current in MRAM can cause substantial heating which degrades the endurance and reliability of MTJs. Here, we report the thermal characterization of ultrathin CoFeB/MgO multilayers with total thicknesses of 4.4, 8.8, 22, and 44 nm, and with varying MgO thicknesses (1.0, 1.3, and 1.6 nm). Through time-domain thermoreflectance (TDTR) measurements and thermal modeling, we extract the intrinsic (∼3.6 W m-1 K-1) and effective (∼0.85 W m-1 K-1) thermal conductivities of annealed 1.0 nm thick MgO at room temperature. Our study reveals the thermal properties of ultrathin MgO tunnel barriers, especially the role of thermal boundary resistance, and contributes to a more precise thermal analysis of MTJs to improve the design and reliability of MRAM technologies.

(Invited) Electrochemical Tuning of Thermoelectric Performance of Carbon Nanotubes

One-dimensional materials have potential for high performance thermoelectric energy conversion. To experimentally understand how one-dimensional electronic structures can enhance thermoelectric performance, we have investigated the thermoelectric properties of single walled carbon nanotubes (SWCNTs) such as the relationships among electronic structures, the location of Fermi-level, Seebeck coefficients, and Power factor by combining thermoelectric measurements and electrolyte gating techniques. Through the studies, we have revealed unique properties such as violation of thermoelectric trade-off, isotropic Seebeck coefficient, and gigantic power factor [1]. However, in addition to that, it is important to understand how the carrier density also affects the thermal conductivity of the carbon nanotube thin films for correct evaluation of ZT value. Therefore, we have developed a measurement system which can evaluate thermal conductivity by tuning the location of Fermi-level through electrochemical gating techniques. Time-domain thermoreflectance (TDTR) measurement is one of methods which can evaluate the thin film thermal conductivity. In conventional TDTR system, Al is used as metal transducer, but Al is electrochemical reactive, and thus it is very difficult to combine the TDTR measurements with electrochemical techniques. To solve this problem, we developed a TDTR system using Au as a metal transducer [2]. By using Au as a metal transducer, we can evaluate both the electrical and thermal properties at the same time. By using system, we can evaluate thermal properties of thin films during electrolyte gating, and have evaluated how the change of charrier density affects the thermal conductivity of carbon nanotube thin films [3]. By preparing the aligned single-walled carbon nanotube thin film, we evaluated the ZT value in the perpendicular direction to the nanotube axis as a function of carrier density. The ZT value in this direction can be maximized to be 0.1 by tuning the Femi-level around 1st van hove singularity [4].

Thermal conductance of interfaces between titanium nitride and group IV semiconductors at high temperatures

Measuring the temperature dependence of material properties is a standard method for better understanding the microscopic origins for that property. Surprisingly, only a few experimental studies of thermal boundary conductance at high temperatures exist. This lack of high temperature data makes it difficult to evaluate competing theories for how inelastic processes contribute to thermal conductance. To address this, we report time domain thermoreflectance measurements of the thermal boundary conductance for TiN on diamond, silicon-carbide, silicon, and germanium between 120 and 1000 K. In all systems, the interface conductance increases monotonically without stagnating at higher temperatures. For TiN/SiC interfaces, G ranges from 330 to 1000 MW/m2-K, with a room temperature conductance of 750 MW/m2-K. The interface conductance for TiN/diamond ranges from 140 to 950 MW/m2-K. Notably, for all four interfacial systems, the conductance continues to increase with temperature even after all phonon modes in the vibrationally soft material are thermally excited. This observation suggests that inelastic processes are significant contributors to the thermal conductance in all four interfacial systems, regardless of whether the materials forming the interface are vibrationally similar or dissimilar. Our study fills a notable gap in the literature for how interfacial conductance evolves at high temperatures and tests burgeoning theories for the role of inelastic processes in interfacial thermal transport.

Multiscale phonon thermal transport in nano-porous silicon

We performed a comprehensive multi-scale phonon-mediated thermal transport study of nano-porous silicon (np-Si) films with average porosities in the range of φ = 30%–70%. This depth-resolved thermal characterization involves a combination of optical methods, including femtosecond laser-based time-domain thermo-reflectance (TDTR) with MHz modulation rates, opto-thermal micro-Raman spectroscopy, and continuum laser wave-based frequency domain thermo-reflectance (FDTR) with kHz modulation rates probing depths of studied samples over 0.5–1.2, 2–3.2, and 23–34 μm, respectively. We revealed a systematic decrease in thermal conductivity (k) with the rise of φ, i.e., with the lowering of the Si crystalline phase volumetric fraction. These data were used to validate our semi-classical phonon Monte Carlo and finite element mesh simulations of heat conduction, taking into account disordered geometry configurations with various φ and pore size, as well as laser-induced temperature distributions, respectively. At high φ, the decrease in k is additionally influenced by the disordering of the crystal structure, as evidenced by the near-surface sensitive TDTR and Rutherford backscattering spectroscopy measurements. Importantly, the k values measured by FDTR over larger depths inside np-Si were found to be anisotropic and lower than those detected by the near-surface sensitive TDTR and Raman thermal probes. This finding is supported by the cross-sectional scanning electron microscopy image indicating enhanced φ distribution over these micrometer-scale probed depths. Our study opens an avenue for nano-to-micrometer scale thermal depth profiling of porous semiconducting media with inhomogeneous porosity distributions applicable for efficient thermoelectric and thermal management.

Propagon boundary scattering relaxed via crystalline host on multiphase germanium telluride

The movement of heat through amorphous solids on an atomic level remains an outstanding question. Recent studies suggest that the primary thermal carrier in amorphous materials, propagons, essentially behaves like phonons. In this work, we provide experimental evidence that shows the interaction between propagons and phonons by utilizing the phase change chalcogenide germanium telluride. A series of ultra-long time-delay time-domain thermoreflectance measurements are used to analyze the scattering of vibrational thermal carriers at the boundaries of amorphous GeTe thin films relative to scattering across a crystalline-amorphous bilayer. We find that amorphous long wavelength propagons that would otherwise scatter can instead be hosted by a crystalline underlayer and its phonon population. This experimental evidence directly demonstrates propagon–phonon interactions in a clear experimental manner.

Quasi-ballistic thermal transport in silicon carbide nanowires

Silicon carbide (SiC) is an important industrial material that enables the thermal stability of power electronics. However, the nanoscale phenomenon of ballistic thermal conduction, which may further improve the thermal performance, remains unexplored in SiC. Here, we reveal the length and temperature scales at which SiC exhibits quasi-ballistic thermal conduction. Our time-domain thermoreflectance measurements probe the thermal conductivity of SiC nanowires as a function of their length and temperature. The deviation of the thermal conductivity from the diffusive limit in nanowires shorter than a few micrometers indicates the transition into a quasi-ballistic thermal conduction regime. Naturally, the deviation is greater at lower temperatures, yet the effect persists even above room temperature. Our Monte Carlo simulations of phonon transport support our experimental results and show how phonons with long mean free paths carry a substantial amount of heat, causing quasi-ballistic conduction. These findings show that quasi-ballistic heat conduction can persist at the microscale at operating temperatures of power devices, and thus may help improve the thermal design in electronics based on SiC.

Time-domain thermoreflectance measurement of the thermal diffusivity of Nb thin films

Nb-coated Cu superconducting radiofrequency (SRF) cavities are of interest as a possible alternative to bulk Nb cavities for particle accelerators due to the high thermal conductivity of Cu and its lower cost than Nb. Studying the thermal diffusion properties in Nb thin films on Cu is important for developing Nb-coated Cu SRF cavities. In the present study, the thermal diffusivity of 100‒800 nm Nb films on Cu is measured by time-domain thermoreflectance (TDTR). The thermal diffusivity is obtained from a curve fit of the TDTR signal to a one-dimensional Fourier heat diffusion model over a time extending from 25 to 985 ps after laser-surface interaction. The film was examined by atomic force microscopy and scanning electron microscopy. The grain size and thermal diffusivity increase with film thickness. The thermal diffusivity reaches a value similar to that reported for bulk Nb for the 400 and 800 nm films, for which the average grain size is 47 ± 13 nm and 68 ± 18 nm, respectively. TDTR measurement for the 400-nm film taken over the temperature range of 293 to 40 K showed that the thermal diffusivity increases as the temperature is reduced. The results indicate that grain boundaries reduce the thermal diffusivity of the Nb film and, therefore, must be considered in Nb-coated Cu SRF cavities.

Accurate Thermal Conductivity Measurements of Porous Thin Films by Time-Domain Thermoreflectance.

Accurate measurements of the thermal conductivity (κ) of porous thin films are still limited due to challenges to deposit flat and continuous metal transducers on porous samples, a necessity for many thermal measurement techniques for nanostructures. In this paper, we introduce an approach based on time-domain thermoreflectance (TDTR) to accurately and conveniently measure κ of porous thin films by transferring a flat and smooth metal film unto porous samples as the transducer for TDTR measurements. We demonstrate our approach by measuring κ of a series of microscale holey SiO2 films with diameters of 1-3.5 μm and porosity of 13-50%. To achieve a measurement uncertainty of <12%, we ensure that the metal transducer films are sufficiently stiff and establish good thermal contact with the holey SiO2 samples. Our κ measurements agree well with calculations of κ from effective medium theory. Our approach could provide a convenient way to further investigate the thermal transport properties of porous films.

Investigation of gallium oxide thin film hetero-integrated with bulk diamond via atomic layer deposition

In this work, the characteristics of the gallium oxide (Ga2O3)/diamond heterostructure were thoroughly examined after the preparation of Ga2O3 thin film on bulk diamond via atomic layer deposition. The X-ray diffraction (XRD) analysis revealed the Ga2O3 film amorphous and diamond polycrystalline. The atomic force microscopy (AFM) mapping displayed remarkably smooth surfaces of the Ga2O3 film and diamond substrate (RMS of 0.184 and 0.508 nm, respectively). The scanning electron microscopy (SEM) images showed conspicuous grains formed on the diamond, and small crystallites on the surface of the film. The optical characteristics were investigated via spectroscopic ellipsometry (SE) and UV/Vis/NIR spectrophotometer. Raman spectroscopy suggested a sharp diamond-related (sp3) peak and an extremely weak bulge band around 1350–1620 cm−1. X-ray photoelectron spectroscopy (XPS) analysis indicated Ga2O3/diamond heterojunction to be staggered (type II) band alignment with valence band and conduction band offsets of around 1.18 eV and 2.09 eV, respectively. Moreover, according to time-domain thermoreflectance (TDTR) measurements, the thermal conductivity of Ga2O3 and the thermal boundary conductivity of the heterointerface were 5.13 W/(m·K) and 19.22 MW/(m2·K), respectively. These findings not only demonstrate the feasibility of Ga2O3-on-diamond hetero-integration but open up new prospects for the design and physical analysis of Ga2O3/diamond-based devices in the future.

Origins of heat transport anisotropy in MoTe2 and other bulk van der Waals materials

Knowledge of how heat flows anisotropically in van der Waals (vdW) materials is crucial for thermal management of emerging 2D materials devices and design of novel anisotropic thermoelectric materials. Despite the importance, anisotropic heat transport in vdW materials is yet to be systematically studied and is often presumably attributed to anisotropic speeds of sound in vdW materials due to soft interlayer bonding relative to covalent in-plane networks of atoms. In this work, we investigate the origins of the anisotropic heat transport in vdW materials, through time-domain thermoreflectance (TDTR) measurements and first-principles calculations of anisotropic thermal conductivity of three different phases of MoTe2. MoTe2 is ideal for the study due to its weak anisotropy in the speeds of sound. We find that even when the speeds of sound are roughly isotropic, the measured thermal conductivity of MoTe2 along the c-axis is 5–8 times lower than that along the in-plane axes. We derive meaningful characteristic heat capacity, phonon group velocity, and relaxation times from our first principles calculations for selected vdW materials (MoTe2, BP, h-BN, and MoS2), to assess the contributions of these factors to the anisotropic heat transport. Interestingly, we find that the main contributor to the heat transport anisotropy in vdW materials is anisotropy in heat capacity of the dominant heat-carrying phonon modes in different directions, which originates from anisotropic optical phonon dispersion and disparity in the frequency of heat-carrying phonons in different directions. The discrepancy in frequency of the heat-carrying phonons also leads to ∼2 times larger average relaxation times in the cross-plane direction, and partially explains the apparent dependence of the anisotropic heat transport on the anisotropic speeds of sound. This work provides insight into understanding of the anisotropic heat transport in vdW materials.

Wide-range continuous tuning of the thermal conductivity of La0.5Sr0.5CoO3-δ films via room-temperature ion-gel gating

Solid-state control of the thermal conductivity of materials is of exceptional interest for novel devices such as thermal diodes and switches. Here, we demonstrate the ability to continuously tune the thermal conductivity of nanoscale films of La0.5Sr0.5CoO3-δ (LSCO) by a factor of over 5, via a room-temperature electrolyte-gate-induced non-volatile topotactic phase transformation from perovskite (with δ ≈ 0.1) to an oxygen-vacancy-ordered brownmillerite phase (with δ = 0.5), accompanied by a metal-insulator transition. Combining time-domain thermoreflectance and electronic transport measurements, model analyses based on molecular dynamics and Boltzmann transport equation, and structural characterization by X-ray diffraction, we uncover and deconvolve the effects of these transitions on heat carriers, including electrons and lattice vibrations. The wide-range continuous tunability of LSCO thermal conductivity enabled by low-voltage (below 4 V) room-temperature electrolyte gating opens the door to non-volatile dynamic control of thermal transport in perovskite-based functional materials, for thermal regulation and management in device applications.

Spin-phonon interactions induced anomalous thermal conductivity in nickel (II) oxide

Nickel (II) oxide is a prominent candidate for spintronic and spin-caloritronic applications operating at room temperature. Although there are extensive studies on nickel oxide, the roles of magnon- and spin-phonon interactions on thermal transport are not well understood. In the present work, the relationship between spin-phonon interactions and thermal transport is investigated by performing inelastic neutron scattering, time-domain thermoreflectance thermal conductivity measurements, and atomistic thermal transport calculations. Inelastic neutron scattering measurements of the magnon lifetime imply that magnon thermal conductivity is trivial, and so heat is conducted only by phonons. Time-domain thermoreflectance measurements of the thermal conductivity vs. temperature follow T−1.5 in the antiferromagnetic phase. This temperature dependence cannot be explained by phonon-isotope and phonon-defect scattering or phonon softening. Instead, we attribute this to magnon-phonon scattering and spin-induced dynamic symmetry breaking. The spin-phonon interactions are saturated in the paramagnetic phase and lead to a weaker temperature dependence of T−1.0 at 550–700 K. These results reveal the importance of spin-phonon interactions on lattice thermal transport, shedding light on the engineering of functional antiferromagnetic spintronic and spin-caloritronic materials through these interactions.

Kinetically-decoupled electrical and structural phase transitions in VO2

Vanadium dioxide (VO2) has drawn significant attention for its near room temperature insulator to metal transition and associated structural phase transition. The underlying Physics behind the temperature induced insulator to metal and concomitant structural phase transition in VO2 is yet to be fully understood. We have investigated the kinetics of the above phase transition behaviors of VO2 with the help of resistivity measurements and Raman spectroscopy. Resistance thermal hysteresis scaling and relaxation measurements across the temperature induced insulator to metal transition reveal the unusual behaviour of this first-order phase transition, whereas Raman relaxation measurements show that the temperature induced structural phase transition in VO2 follows usual behaviour and is consistent with mean field prediction. At higher temperature sweeping rates decoupling of insulator to metal transition and structural phase transition have been confirmed. The observed anomalous first order phase transition behavior in VO2 is attributed to the unconventional quasi particle dynamics, i.e. significantly lowered electronic thermal conductivity across insulator to metal transition, which is confirmed by ultrafast optical pump-probe time domain thermoreflectance measurements.

Incoherent-to-coherent crossover in thermal transport through III–V alloy superlattices

We report on time-domain thermoreflectance measurements of cross-plane thermal conductivity of In0.63Ga0.37As/In0.37Al0.63As superlattices with interface densities ranging from 0.0374 to 2.19 nm−1 in the temperature range 80–295 K. The measurements are complemented by a three-dimensional finite-difference time-domain solution to the elastic wave equation, in which the rms roughness and correlation length at heterointerfaces are varied, and the parameters yielding best agreement with experiment are determined using machine learning. Both experimental measurements and simulations demonstrate the existence of a minimum in the cross-plane thermal conductivity as a function of interface density, which is evidence of a crossover from incoherent to coherent phonon transport as the interface density increases. This minimum persists with increasing temperature, indicating the continued dominance of the temperature-independent interface and alloy-disorder scattering over the temperature-dependent three-phonon scattering in thermal transport through III–V alloy superlattices.

Properties for Thermally Conductive Interfaces with Wide Band Gap Materials.

The goal of this study is to determine how bulk vibrational properties and interfacial structure affect thermal transport at interfaces in wide band gap semiconductor systems. Time-domain thermoreflectance measurements of thermal conductance G are reported for interfaces between nitride metals and group IV (diamond, SiC, Si, and Ge) and group III–V (AlN, GaN, and cubic BN) materials. Group IV and group III–V semiconductors have systematic differences in vibrational properties. Similarly, HfN and TiN are also vibrationally distinct from each other. Therefore, comparing G of interfaces formed from these materials provides a systematic test of how vibrational similarity between two materials affects interfacial transport. For HfN interfaces, we observe conductances between 140 and 300 MW m–2 K–1, whereas conductances between 200 and 800 MW m–2 K–1 are observed for TiN interfaces. TiN forms exceptionally conductive interfaces with GaN, AlN, and diamond, that is, G > 400 MW m–2 K–1. Surprisingly, interfaces formed between vibrationally similar and dissimilar materials are similarly conductive. Thus, vibrational similarity between two materials is not a necessary requirement for high G. Instead, the time-domain thermoreflectance experiment (TDTR) data, an analysis of bulk vibrational properties, and transmission electron microscopy (TEM) suggest that G depends on two other material properties, namely, the bulk phonon properties of the vibrationally softer of the two materials and the interfacial structure. To determine how G depends on interfacial structure, TDTR and TEM measurements were conducted on a series of TiN/AlN samples prepared in different ways. Interfacial disorder at a TiN/AlN interface adds a thermal resistance equivalent to ∼1 nm of amorphous material. Our findings improve fundamental understanding of what material properties are most important for thermally conductive interfaces. They also provide benchmarks for the thermal conductance of interfaces with wide band gap semiconductors.

Graphene Layer Number-Dependent Heat Transport across Nickel/Graphene/Nickel Interfaces.

As a typical two-dimensional material, graphene (Gr) has shown great potential to be used in thermal management applications due to its ultrahigh in-plane thermal conductivity (k). However, low interface thermal conductance (ITC) between Gr and metals to a large extent limits the effective heat dissipation in Gr-based devices. Therefore, having a deep understanding on heat transport at Gr-metal interfaces is essential. Because of the semimetallic nature of Gr, electrons would possibly play a role in the heat transport across Gr-metal interfaces as heat carriers, whereas, However, how much the electron can participate in this process and how to optimize the total ITC considering both electron and phonon transportations have not yet been revealed yet. Therefore, in this work, hydrogenation-treated Gr (H-Gr) was sandwiched by nickel (Ni) nanofilms to compare with the samples containing pure Gr for investigating the interfacial electron behaviors. Moreover, both Gr and H-Gr sets of the samples were prepared with different layer numbers (N) ranging from 1 to 7, and the corresponding ITC was systematically studied based on both time-domain thermoreflectance measurements and theoretical calculations. We found that a larger ITC can be obtained when N is low, and the ITC may reach a peak value when N is 2 in certain circumstances. The present findings not only provide a comprehensive understanding on heat transport across Gr-metal interfaces byconsidering a combined effect of the interfacial interaction strength, phonon mode mismatch, and electron contributions, but also shed new lights on interface strucure optimiazations of Gr-based devices.

Anisotropic thermal and electrical conductivities of individual polyacrylonitrile-based carbon fibers

Understanding the anisotropy of thermal and electrical properties of carbon fibers is important for many applications, but transverse transport properties are difficult to measure. We apply time-domain thermoreflectance (TDTR) mapping to determine spatial variations in the transverse thermal conductivity for different radial positions for two polyacrylonitrile (PAN)-based carbon fibers, the IM7 and AS4 fibers. Single-point TDTR measurements determine the longitudinal and transverse thermal conductivities of the carbon fibers. The transverse and longitudinal electrical resistivities of the AS4 fibers are determined by the van der Pauw method and four-point method, respectively. The transverse thermal conductivity of IM7 fibers is approximately uniform (2.0 W/m-K) at different radial positions. In contrast, the transverse thermal conductivity of the core (3.0 W/m-K) in AS4 fibers is higher than the shell (2.4 W/m-K). The longitudinal thermal conductivity of IM7 fibers is 7.5 W/m-K and the value of AS4 fibers is 6.9 W/m-K. The transverse electrical resistivity of AS4 fibers is 6.3 × 10−5 Ωm and the longitudinal electrical resistivity is 1.5 × 10−5 Ωm; the electrical resistivities of IM7 fibers were reported previously. Both the thermal and electrical measurements indicate a larger anisotropy of the IM7 fiber than the AS4 fiber.

The Effect of Interlayer Microstructure on the Thermal Boundary Resistance of GaN-on-Diamond Substrate

Diamond has the highest thermal conductivity of any natural material. It can be used to integrate with GaN to dissipate heat from AlGaN/GaN high electron mobility transistor (HEMT) channels. Much past work has investigated the thermal properties of GaN-on-diamond devices, especially the thermal boundary resistance between the diamond and GaN (TBReff,Dia/GaN). However, the effect of SiNx interlayer structure on the thermal resistance of GaN-on-diamond devices is less investigated. In this work, we explore the role of different interfaces in contributing to the thermal boundary resistance of the GaN-on-diamond layers, specifically using 100 nm layer of SiNx, 80 nm layer of SiNx, 100 nm layer of SiNx with a 20 nm × 20 nm periodic structure. Through combination with time-domain thermoreflectance measurement and microstructural analysis, we were able to determine that a patterning SiNx interlayer provided the lower thermal boundary resistance (32.2 ± 1.8 m2KGW−1) because of the diamond growth seeding and the diamond nucleation surface. In addition, the patterning of the SiNx interlayer can effectively improve the interface bonding force and diamond nucleation density and reduce the thermal boundary resistance of the GaN-on-diamond. This enables significant improvement in heat dissipation capability of GaN-on-diamond with respect to GaN wafers.

An accurate method to determine nano-film thickness in diamond anvil cells for time domain thermoreflectance measurements.

The thickness of the metal-transducer nano-film is an essential parameter for high-pressure time-domain-thermoreflectance (TDTR) measurements. In this article, an accurate method was proposed to determine the transducer thickness in high-pressure conditions using the pressure-volume equation of state combined with an image processing method. Both the elastic and plastic deformation of the sample squeezed in diamond anvil cells were considered in this method. High-pressure TDTR measurements on thermal conductivity of MgO and mica were further taken for comparing the influence from different thickness-characterization methods up to ∼18 GPa, and the proposed method accurately captured the effect of plastic deformation on thermal conductivity for the first time. This work can not only help achieve more accurate TDTR measurements under high-pressure but also provide valuable guidance for the diamond anvil cell application in nanoscale research.

Systematic investigations on doping dependent thermal transport properties of single crystal silicon by time-domain thermoreflectance measurements

Doped silicon (Si) is the key material in semiconductor industries. It is important to fully understand the doping effect on thermal transport properties of single-crystal Si, especially for the thermal management of Si-based electronic devices. In this work, we used a femtosecond-laser time-domain thermoreflectance method to characterize the thermal transport properties of Si with different doping concentrations (1013-1019 cm−3) and doping elements, boron (B) and phosphorus (P). Results show that the thermal conductivity of heavy doped Si (about 2 × 1019 cm−3) by both B and P decreases by about 22% compared with their pure counterparts. Theoretical calculations based on the Boltzmann transport equation were also carried out for comparison with measurement results, and different scattering terms were discussed to find out the main factors for suppressing the thermal transport in doped Si within different doping concentration ranges. Combining with a cryogenic system, the thermal conductivity of doped Si samples and interfacial thermal conductance between Si and aluminum thin films were also measured under low-temperature conditions (down to 160 K). Our systematic studies on the doping effect in the thermal transport of single-crystal semiconductors not only facilitate the understanding of the microscale thermal transport, but also provide references in industrial applications of doped semiconductors.