Time-domain Thermoreflectance Method Research Articles

Evaluation of Thermal Transport Characteristics of Three-Dimensional Self-Ordered Multilayered Silicon-Germanium Nanodots

1. Background and purpose Silicon-germanium (SiGe) alloys have much lower thermal conductivity than Si and Ge single crystals and are expected to be candidates for next-generation thermoelectric device materials of internet of things society. It is important to achieve both high carrier mobility and low thermal conductivity on the basis of the dimensionless figure of merit [1]. There are several studies on the thermoelectric properties of SiGe with low-dimensional structures such as superlattice and nanodots [2,3] to dramatically decrease thermal conductivity. However, the relationship between the nanoscale thermal properties and the phonon scattering mechanism of self-ordered multilayer SiGe nanodots with high uniformity grown by Stranski-Krastanov [4] mode is unclear. In this study, we demonstrated the thermal transport characteristics of the self-ordered multilayer SiGe nanodots. 2. Experiments Si/SiGe superlattice and nanodots samples were fabricated by reduced pressure chemical vapor deposition. We set to 20 cycles of Si0.65Ge0.35 / Si superlattice, the staggered Si0.65Ge0.35 nanodots (alternately stacked) and the dot-on-dot Si0.65Ge0.35 nanodots (vertically stacked) by changing growth temperature and precursors for Si spacer growth [4], as shown in Fig. 1. Thermal properties were evaluated by the Time Domain Thermoreflectance (TDTR) method. The strain states and Ge fraction were evaluated by Raman spectroscopy. The focal length and wavenumber resolution of the Raman spectrometer were 2,000 mm and 0.1 cm-1, respectively. The excitation light source was a green laser (wavelength: 532 nm). We obtained the Raman spectra of Si-Si, Si-Ge, and Ge-Ge vibrational modes derived from the SiGe regions. 3. Results and discussion Figure 2 shows the thermal conductivity for the SiGe region of the superlattice and nanodots (dot-on-dot and staggered structures) obtained by TDTR method. We found that the SiGe nanodots with the dot-on-dot structure have the highest thermal conductivity, while the SiGe nanodots with the staggered structure and SiGe superlattice have almost the same thermal conductivity. We consider that the heat flow easily penetrates from the top (surface) to the bottom (Si substrate interface) in the dot-on-dot structures. On the other hand, it is possible that the staggered SiGe nanodots can play a sufficient role as a phonon scatterer compared to the dot-on-dot structures since the superlattice structure and the staggered SiGe nanodots have almost the same thermal properties. In conclusion, we demonstrated the possibility of controlling phonon scattering by changing the arrangement of the self-ordered multilayer SiGe nanodots. Acknowledgement This work was supported by JSPS KAKENHI Grant Number 21K14201, Japan.

Seeking non-Fourier heat transfer with ultrabroad band thermoreflectance spectroscopy

Studying superdiffusive thermal transport is crucial for advanced thermal management in electronics and nanotechnology, ensuring devices run efficiently and reliably. Such study also contributes to the design of high-performance thermoelectric materials and devices, thereby improving energy efficiency. This work leads to a better understanding of fundamental physics and non-equilibrium phenomena, fostering innovations in numerous scientific and engineering fields. We are showing, from a one shot experiment, that clear deviations from classical Fourier behavior are observed in a semiconductor alloy such as InGaAs. These deviations are a signature of the competition that takes place between ballistic and diffusive heat transfers. Thermal propagation is modelled by a truncated Lévy model. This approach is used to analyze this ballistic-diffusive transition and to determine the thermal properties of InGaAs. The experimental part of this work is based on a combination of time-domain and frequency-domain thermoreflectance methods with an extended bandwidth ranging from a few kHz to 100 GHz. This unique wide-bandwidth configuration allows a clear distinction between Fourier diffusive and non-Fourier superdiffusive heat propagation in semiconductor materials. For diffusive processes, we also demonstrate our ability to simultaneously measure the thermal conductivity, heat capacity and interface thermal resistance of several materials over 3 decades of thermal conductivity.

Enhanced through-plane thermal conductivity of graphene membranes by the interlayer microstructure manipulation: Multiscale numerical simulations and experimental verifications

Graphene, with ultrahigh in-plane thermal conductivity (IPTC), has been widely applied in the thermal dissipation of integrated circuits. However, the extremely low through-plane thermal conductivity (TPTC) of graphene limits its further application. In this work, a novel strategy was proposed to enhance the TPTC of graphene membranes (GNMs) by improving the interlayer bonding state through interlayer decoration with metal elements. Molecular dynamics simulations demonstrated that decoration with interlayer elements (Al, Ti, and Ni) enhanced the interfacial thermal conductance. This was attributed to interfacial chemical bonding through strong interfacial interactions (intensive electron localization) formed at the interface between metal and GN sheets as implied by the first principles calculations. Furthermore, the composite GNMs decorated with interlayer metal nanoparticles (Al, Ni, and Co) were prepared through co-reduction using thermal decomposition method. The corresponding TPTC was tested using time-domain thermoreflectance (TDTR) method which was much higher for the composite GNMs (175–400 W/m·K) than for pure GNM (∼140 W/m·K), and this was in consistent with the simulation results. Interlayer decoration, which enhanced the TPTC of GNMs, provides a novel and effective strategy for enhancing the overall thermal management performance of graphene-based materials in both vertical and horizontal directions.

Using transducerless time-domain thermoreflectance technique to measure in- and cross-plane thermal conductivity of nanofilms

Time-domain thermoreflectance (TDTR) and frequency-domain thermoreflectance techniques have been widely used to measure thermal properties. However, the existence of the metal sensor brings some limitations to the experimental measurement, such as temperature limits, disability to measure low in-plane thermal conductivity, in situ measurement cannot be achieved, etc. This paper proposes a transducerless time-domain thermoreflectance method to measure in- and cross-plane thermal conductivity of nanofilms, in which the optical absorption depth and thermal conductivity tensor are considered to establish a new differential equation that can describe the heat conduction process in multilayer structures. This thermal model can also calculate the effects of spot ellipticity and spot offset distance. Then, the analytical solution and relative deviation of this new model and the surface heat flow boundary model used in conventional TDTR are compared by calculating the phase signals. In terms of experimental measurement, this model is successfully used to derive cross- and in-plane thermal conductivity of PdSi and IrNiTa amorphous alloy nanofilms without a metal sensor.

The effect of binding energy on optimizing the interfacial thermal transport in metal-MoS2-dielectric nanostructures

The development of MoS2-based devices presents a significant challenge due to the poor interfacial thermal transport of metal-MoS2-dielectric structures, which results in severe thermal dissipation issues. This work aims to investigate the effects of various strategies, including modifying metal electrodes, adjusting the number of MoS2 layers, and incorporating van der Waals heterostructures, on the enhancement of interface thermal conductance (ITC) of metal-MoS2-dielectric structures. The time-domain thermoreflectance method was applied to characterize the ITC and experimental results demonstrate that the effect of regulating metal electrodes depends on the binding energy between the metal-MoS2 interfaces, which is a matter of controversy due to the large dispersion of published results. Furthermore, the increase in the number of MoS2 layers does not necessarily lead to the enhancement of the ITC of metal-MoS2-dielectric structures, as this is a comprehensive reflection of the number of layers' influence on both thermal conductance of MoS2 itself and the ITC between MoS2 and the surrounding materials. The results from the heterostructures of hBN-MoS2 and Gr-MoS2 were then systematically compared, and the results indicate the potential of Gr-MoS2 heterostructures in augmenting ITC. In addition, the nonequilibrium molecular dynamics simulation was effectively employed to gain deeper insights into the effect of binding energy on optimizing the ITC of metal-heterostructures-dielectric nanostructures. Finally, the effectiveness of these strategies in enhancing thermal properties was discussed through an analysis of interfacial binding energy. This finding provides a valuable direction for enhancing the thermal management of MoS2-based devices.

(Invited, Digital Presentation) Ultra-Low Thermal Conductance across Hetero-Structured Four-Layered Van Der Waals Materials

Tuning the thermal properties of materials and exploring their heat transport mechanisms are of critical significance for optimizing the performance of current electronic and thermoelectric devices. Regarding flexible thermoelectric, recently, gigantic power factor is achieved in carbon nanotube fibers with tuned Fermi energy level [1]. Thus, control of heat transport across van der Waals (vdW) interfaces, which are the origins of flexibility, is very important for improvement of thermoelectric conversion efficiency. Considering that thermal transport is mainly affected by phonon-boundary scattering, development a route to tune such scattering at vdW interfaces is important. Ultrathin two-dimensional (2D) materials have been widely studied in electronic and photonic fields due to the distinctly unique geometrical and electronic structures of such materials. Regarding thermal transport properties, they have a lot of degrees of freedom in their integration, and the layered vdW integrated structure of these materials, in which building blocks are physically assembled together through weak vdW interactions, provides a strategy to reduce thermal conductance. The rich interfacial lattice mismatch in layered vdW structures is promising for enhancing phonon-boundary scattering at interfaces. For instance, Vaziri et al. studied the thermal boundary resistance of various heterointerfaces via the stacking of exfoliated several-micron-sized graphene, MoS2, and WSe2 monolayers using Raman thermometry, suggesting great potential for controlling heat flow by using the interfaces of vdW heterostructures [2]. However, there has been no systematic study on how homo- and hetero-interfaces with or without lattice matches influence heat flow. Therefore, a systematic study on the thermal conductance (G) of vdW structures with various comparable interfaces is urgently required to understand how homo- and heterointerfaces and the coupling effect influence thermal transport. Here we demonstrate the thermal conductance across four layered (4L) homo- and hetero-structured MoS2 and MoSe2 using time-domain thermo-reflectance method. Compared with the thermal conductance of homo-structured sample, the thermal conductance across hetero-structured 4L sample was significantly reduced, indicating that hetero-interface is an efficient way to reduce thermal conductance [3]. In addition, we have combined electrochemical gating method and TDTR measurements, and employed our technique on the 4L sample and investigated how the intercalation can influence the thermal conductance on the 4L sample. In this presentation, I would like to discuss our recent results.

Revealing an elusive metastable wurtzite CuFeS2 and the phase switching between wurtzite and chalcopyrite for thermoelectric thin films

As the alternative for the high-performance thermoelectric semiconductors such as GeTe, PbTe, and other compounds with rare and expensive elements, the cost-effective and abundant sulfides have been considered as one of the promising materials and garnered intensive interest. In this study, a rarely reported metastable wurtzite-type phase of CuFeS2 has been successfully obtained as thin film grown on quartz substrates via magnetron sputtering. Subsequent temperature-dependent depositions were performed to establish a phase transition between the metastable wurtzite and the chalcopyrite phase in the temperature range between room temperature and 473 K while maintaining the nominal composition ratio of CuFeS2. The wurtzite metastable analogue can be recovered and stabilized when the temperature reached 573 K and above. Thermoelectric properties were evaluated and constituted the first experimental result of the inorganic CuFeS2 thin film for thermoelectrics. The phase change between the wurtzite and chalcopyrite structure induced a significant effect on the thermoelectric properties associated with the lattice disorder and carrier scattering. The reduced thermal conductivity compared with bulk was demonstrated by the picosecond time-domain thermoreflectance method, which was found to be well correlated with the polycrystal sizes. The work provides new insight into synthesizing and manipulating the metastable wurtzite phase of the ternary I-III-VI for future applications in thermoelectrics, solar cells, and other electronic applications.

Growth and Thermal Conductivity Study of CuCr2Se4-CuCrSe2 Hetero-Composite Crystals

The CuCrSe2 shows attractive physical properties, such as thermoelectric and multiferroic properties, but pure-phase CuCrSe2 crystal is still quite challenging to obtain because CuCr2Se4 can be easily precipitated from a CuCrSe2 matrix. Here, taking the advantage of this precipitation reaction, we grew a series of CuCrSe2-CuCr2Se4 hetero-composites by adjusting growth parameters and explored their thermal conductivity property. Determined by electron-diffraction, the orientation relationship between these two compounds is [001] (100) CuCrSe2‖[111] (220) CuCr2Se4. The out-of-plane thermal conductivity κ of these hetero-composites was measured by a time-domain thermo-reflectance method. Fitting experimental κ by the Boltzmann-Callaway model, we verify that interface scattering plays significant role to κ in CuCrSe2-CuCr2Se4 hetero-composites, while in a CuCrSe2-dominated hetero-composite, both interface scattering and anharmonic three-phonon interaction lead to the lowest κ therein. Our results reveal the thermal conductivity evolution in CuCr2Se4-CuCrSe2 hetero-composites.

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.

Measuring thermal properties of thin layers with rough surfaces by using the bidirectional heat flow approach

Abstract Thermophysical properties of materials and the optimization of the heat transfer are becoming more and more important for industrial applications of micro- and nanoelectronic devices. Thin layers in the micrometer to nanometer range are used to give specific functions to the devices. Since the thermophysical properties of thin layers differ from bulk material, this data is required for precise predictions of thermal management. One way to obtain the thermal properties of thin layers is the optical-based Time Domain Thermoreflectance (TDTR) method. To carry out TDTR measurements with a low level of uncertainty, the samples under study must meet requirements related to the surface roughness and a low level of optical scattering. The range of samples analysable by TDTR can be extended by applying the so-called bidirectional heat flow approach. This approach opens the possibility to assess thermal properties of materials with rough surfaces as well. The validity of the implemented model was shown by the characterisation of a test sample with well-known thermal properties fabricated for this purpose out of poly(methyl methacrylate) (PMMA) roughened with acetone:ethanol. The results obtained by TDTR measurements were compared to literature values, demonstrating the applicability of the bidirectional heat flow approach for this setup.

Pore-Confined Polymers Enhance the Thermal Conductivity of Polymer Nanocomposites.

Molecularly confined polymer fillers in nanopores were found to give superior mechanical properties of polymer nanocomposites. In this work, we study the thermal conductivity of such nanocomposites and unveil the effect of polymer confinement on thermal conductivity. Using the time-domain thermoreflectance method, we measure the cross-plane thermal conductivity of polymer nanocomposites that consist of polystyrene fillers confined within a nanoporous organosilicate matrix. Compared to unconfined bulk polystyrene fillers, we find that pore-confined polystyrene fillers enhance the thermal conductivity of the polymer nanocomposites. This enhancement is attributed to the better aligned and less entangled chains in the confined phase, where chain-chain phonon scatterings are reduced. Our work provides essential insights into the thermal conductivity of polymer nanocomposites for multifunctional thermal and mechanical applications.

Capacitor-type thin-film heat flow switching device

We developed a capacitor-type heat flow switching device, in which electron thermal conductivity of the electrodes is actively controlled through the carrier concentration varied by an applied bias voltage. The device consisted of an amorphous p-type Si–Ge–Au alloy layer, an amorphous SiO2 as the dielectric layer, and an n-type Si substrate. Both amorphous materials are characterized by very low lattice thermal conductivity, ≤1 W m–1 K–1. The Si–Ge–Au amorphous layer with 40 nm in thickness was deposited by means of molecular beam deposition technique on the 100 nm thick SiO2 layer formed at the top surface of Si substrate. Bias voltage-dependent heat flow density through the fabricated device was evaluated by a time-domain thermoreflectance method at room temperature. Consequently, we observed a 55% increase in the heat flow density at the maximum.

Thermal Conductance of Epoxy/Alumina Interfaces

The interfacial thermal conductance (ITC) between filler and polymer matrix is considered as one of the important factors that limits the thermal conductivity of thermally conductive polymer composites. The effect of two different surface treatments (piranha solution and plasma) on ITC of epoxy/alumina was investigated using Time-domain thermoreflectance method (TDTR). The TDTR results show that compared with non-treated samples, the ITC of samples treated by piranha solution and plasma increased 2.9 times and 3.4 times, respectively. This study provides guidance for improving the thermal conductivity of thermally conductive polymer composites.

Interfacial Thermal Conductance between Alumina and Epoxy

Interfacial thermal conductance (ITC) of inorganic/epoxy interface is regarded as one of the most significant factors in determining thermal transport performance of epoxy composite. Here, ITC between alumina and epoxy was experimentally investigated by time-domain thermoreflectance (TDTR) method. The results show that the ITC is effectively increased from 9.0 MW m-2 K-1 for non-treated alumina/epoxy interfaces to 26.3 MW m-2 K-1 for plasma treated interfaces. This work sheds some light on design and application for thermally conductive composites.

Control of Thermal Conductance across Vertically Stacked Two-Dimensional van der Waals Materials via Interfacial Engineering.

A comprehensive understanding of the roles of various nanointerfaces in thermal transport is of critical significance but remains challenging. A two-dimensional van der Waals (vdW) heterostructure with tunable interface lattice mismatch provides an ideal platform to explore the correlation between thermal properties and nanointerfaces and achieve controllable tuning of heat flow. Here, we demonstrate that interfacial engineering is an efficient strategy to tune thermal transport via systematic investigation of the thermal conductance (G) across a series of large-area four-layer stacked vdW materials using an improved polyethylene glycol-assisted time-domain thermoreflectance method. Owing to its rich interfacial mismatch and weak interfacial coupling, the vertically stacked MoSe2-MoS2-MoSe2-MoS2 heterostructure demonstrates the lowest G of 1.5 MW m-2 K-1 among all vdW structures. A roadmap to tune G via homointerfacial mismatch, interfacial coupling, and heterointerfacial mismatch is further demonstrated for thermal tuning. Our work reveals the roles of various interfacial effects on heat flow and highlights the importance of the interfacial mismatch and coupling effects in thermal transport. The design principle is also promising for application in other areas, such as the electrical tuning of energy storage and conversion and the thermoelectricity tuning of thermoelectronics.

(Invited) Thermoelectric Performance of Fermi-Level Tuned and Aligned Single Walled Carbon Nanotubes

Thermoelectric power generation is one of important technologies for realization of highly efficient energy uses. Improvement of performance of thermoelectric materials is required, and theoretical studies suggest one-dimensional materials have potentials for the realization of the highest performance [1]. However, how 1D materials can really improve the thermoelectric performance has not been experimentally verified yet. In this context, thermoelectric properties of single walled carbon nanotubes attract a lot of attention because of their one-dimensional structure and electronic structures (See a review by Blackburn et al. [2]). Thermoelectric properties significantly depend on the electronic structures of SWCNTs, and relationships among Seebeck coefficient (S), electrical conductivity (σ), power factor, doping levels and their electronic structures have been revealed through various studies [3-5]. As a result, a very unique characteristics on thermoelectric properties of SWCNTs has been clarified [5]. In conventional materials, there is a trade-off between Seebeck coefficient and electrical conductivity, but in the metallic SWCNTs, the trade-off is broken because of the presence of 1D electronic structures, indicating the uniqueness of SWCNTs [5]. For the correct understanding of the thermoelectric performance, zT, in SWCNT thin films, clarification of the relationships among S, σ, and thermal conductivity κ is very important. Although the relationships between S and σ have been well understood, the relationships among those parameters and κ have not yet. Avery et al. clarified κ is almost constant by the change of σ, and they estimated the zT value is approximately 0.01-0,05 [3]. Recently we developed a technique to clarify the cross-plane thermal conductivity κ ⊥ in SWCNT thin films with tuned Fermi level by a combination of time-domain thermoreflectance method and electrolyte gating technique [6], and then clarified that the κ ⊥ is almost constant even when in-plane σ is changed three order of magnitude from ~10 Sm-1 to 104 Sm-1 [5]. Such constant behavior of κ by the change of σ in SWCNT thin films is interesting in both basic science and application perspectives. Now we can prepare Fermi-level tuned and microscopically aligned SWCNT thin films [7], and the relationships between S and σ in the aligned directions have been clarified [8]. In this talk, I would like to discuss the recent results in our group and the estimated zT values of Fermi-level tuned and aligned SWCNTs.

Improving the local thermal conductivity of flexible films by microchannels filled with graphene

Low thermal conductivity is an outstanding problem that hinders the application of polymer substrates in flexible devices. Incorporating high thermal conductivity fillers into polymer to enhance its thermal conductivity usually requires a large mass fraction of fillers at the expense of the flexibility and the insulation capabilities of polymer substrates. The non-uniform heat distribution in flexible devices allows for improving the local thermal conductivity of the core areas via microchannels, a strategy which is an effective method in thermal engineering and can be well designed to adapt to large deformation of flexible devices. Here, we report the fabrication of microchannels in polyimide (PI) composite film by oxygen plasma etching and subsequent filling the microchannels with graphene. Utilizing the time-domain thermoreflectance method and the finite element method, we confirmed that the local thermal conductivity of graphene-filled region is about 10 times larger than that of the unfilled region, which is comparable to that of the PI composite filled heavily with traditional high thermal conductive fillers. In addition, it was also found that stretching the film did not lower the thermal conductivity of the same region.

Probing thermal properties of vanadium dioxide thin films by time-domain thermoreflectance without metal film* *Project supported by the National Natural Science Foundation of China (Grant Nos. 61825102, 51872038, and 52021001) and the “111” Project, China (Grant No. B18011).

Vanadium dioxide (VO2) is a strongly correlated material, and it has become known due to its sharp metal-insulator transition (MIT) near room temperature. Understanding the thermal properties and their change across MIT of VO2 thin film is important for the applications of this material in various devices. Here, the changes in thermal conductivity of epitaxial and polycrystalline VO2 thin film across MIT are probed by the time-domain thermoreflectance (TDTR) method. The measurements are performed in a direct way devoid of deposition of any metal thermoreflectance layer on the VO2 film to attenuate the impact from extra thermal interfaces. It is demonstrated that the method is feasible for the VO2 films with thickness values larger than 100 nm and beyond the phase transition region. The observed reasonable thermal conductivity change rates across MIT of VO2 thin films with different crystal qualities are found to be correlated with the electrical conductivity change rate, which is different from the reported behavior of single crystal VO2 nanowires. The recovery of the relationship between thermal conductivity and electrical conductivity in VO2 film may be attributed to the increasing elastic electron scattering weight, caused by the defects in the film. This work demonstrates the possibility and limitation of investigating the thermal properties of VO2 thin films by the TDTR method without depositing any metal thermoreflectance layer.

In situ time-domain thermoreflectance measurements using Au as the transducer during electrolyte gating

Understanding the relationships between the thermal conductivity and carrier density in thin films is of great importance for the thermal management of flexible thin film electronics. Here, we report a robust measurement technique to tune the carrier density in thin films and to evaluate their cross-plane thermal conductivities simultaneously. We employed the time-domain thermoreflectance method using an Au transducer and evaluated the thin film thermal conductivity in situ using electrolyte gating with an ionic gel. The robust measurement technique proposed in this study elucidated the relationships among the above-mentioned parameters in semiconducting single-walled carbon nanotubes.

Experimental measurement of thermal conductivity along different crystallographic planes in graphite

In this work, the time-domain thermoreflectance (TDTR) method is used to measure the thermal conductivity of graphite along different crystallographic planes at room temperature for the first time and the thermal conductivities along the non-principal axes of graphite are obtained. A focused ion beam is used to cut graphite samples along different crystallographic planes for the TDTR measurement. Then, a thermal model is developed to extract the thermal conductivity of graphite along different crystallographic planes from the measured signals of the TDTR method. The measured thermal conductivities along different crystallographic planes in graphite agree well with the anisotropy model, revealing that the traditional TDTR method can be used to measure the non-principal axis thermal conductivity of anisotropic layered materials. Moreover, the experimental results demonstrate that once the crystallographic plane deviates from the cross-plane direction, the in-plane phonon modes will dominate the heat transfer in graphite.