Yanan Yue

Thermal Transport in Graphene Nanostructures: Experiments and Simulations

a Birck Nanotechnology Center, Purdue University, West Lafayette, IN 47907 b School of Electrical and Computer Engineering, Purdue University, West Lafayette, IN 47907 c Department of Mechanical Engineering, Iowa State University, Ames, IA 50011 d School of Physics, Georgia Institute of Technology, Atlanta, GA 30332 e Department of Electrical and Computer Engineering, University of Houston, Houston, Texas 77204 f Department of Physics, Purdue University, West Lafayette, IN 47907 g School of Mechanical Engineering, Purdue University, West Lafayette, IN 47907

Micro/nanoscale spatial resolution temperature probing for the interfacial thermal characterization of epitaxial graphene on 4H-SiC.

Limited internal phonon coupling and transfer within graphene in the out-of-plane direction significantly affects graphene-substrate interfacial phonon coupling and scattering, and leads to unique interfacial thermal transport phenomena. Through the simultaneous characterization of graphene and SiC Raman peaks, it is possible, for the first time, to distinguish the temperature of a graphene layer and its adjacent 4H-SiC substrate. The thermal probing resolution reaches the nanometer scale with the graphene (≈1.12 nm) and is on the micrometer scale (≈12 μm) within SiC next to the interface. A very high thermal resistance at the interface of 5.30 (-0.46) (+0.46) x 10(-5) Km2 W(-1) is observed by using a Raman frequency method under surface Joule heating. This value is much higher than those from molecular dynamics predictions of 7.01(-1.05) (+1.05) x 10(-1) and 8.47(-0.75) (+0.75) x 10(-10) Km2 w(-1) for surface heat fluxes of 3 × 10(9) and 1 × 10(9) and 1 x 10(10) W m(-2) , respectively. This analysis shows that the measured anomalous thermal contact resistance stems from the thermal expansion mismatch between graphene and SiC under Joule heating. This mismatch leads to interface delamination/separation and significantly enhances local phonon scattering. An independent laser-heating experiment conducted under the same conditions yielded a higher interfacial thermal resistance of 1.01(-0.59) (+1.23) x 10(-4) Km2 W(-1). Furthermore, the peak width method of Raman thermometry is also employed to evaluate the interfacial thermal resistance. The results are 3.52 × 10(-5) and 8.57 × 10(-5) K m2 W(-1) for Joule-heating and laser-heating experiments, respectively, confirming the anomalous thermal resistance between graphene and SiC. The difference in the results from the frequency and peak-width methods is caused by the thermal stress generated in the heating processes.

Nanoscale thermal probing

Nanoscale novel devices have raised the demand for nanoscale thermal characterization that is critical for evaluating the device performance and durability. Achieving nanoscale spatial resolution and high accuracy in temperature measurement is very challenging due to the limitation of measurement pathways. In this review, we discuss four methodologies currently developed in nanoscale surface imaging and temperature measurement. To overcome the restriction of the conventional methods, the scanning thermal microscopy technique is widely used. From the perspective of measuring target, the optical feature size method can be applied by using either Raman or fluorescence thermometry. The near-field optical method that measures nanoscale temperature by focusing the optical field to a nano-sized region provides a non-contact and non-destructive way for nanoscale thermal probing. Although the resistance thermometry based on nano-sized thermal sensors is possible for nanoscale thermal probing, significant effort is still needed to reduce the size of the current sensors by using advanced fabrication techniques. At the same time, the development of nanoscale imaging techniques, such as fluorescence imaging, provides a great potential solution to resolve the nanoscale thermal probing problem.

Thermal transport across graphene and single layer hexagonal boron nitride

As the dimensions of nanocircuits and nanoelectronics shrink, thermal energies are being generated in more confined spaces, making it extremely important and urgent to explore for efficient heat dissipation pathways. In this work, the phonon energy transport across graphene and hexagonal boron-nitride (h-BN) interface is studied using classic molecular dynamics simulations. Effects of temperature, interatomic bond strength, heat flux direction, and functionalization on interfacial thermal transport are investigated. It is found out that by hydrogenating graphene in the hybrid structure, the interfacial thermal resistance (R) between graphene and h-BN can be reduced by 76.3%, indicating an effective approach to manipulate the interfacial thermal transport. Improved in-plane/out-of-plane phonon couplings and broadened phonon channels are observed in the hydrogenated graphene system by analyzing its phonon power spectra. The reported R results monotonically decrease with temperature and interatomic bond strengths. No thermal rectification phenomenon is observed in this interfacial thermal transport. Results reported in this work give the fundamental knowledge on graphene and h-BN thermal transport and provide rational guidelines for next generation thermal interface material designs.

Investigation of sulfur forms and transformation during the co-combustion of sewage sludge and coal using X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy was used to investigate the characteristics and evolution of sulfur (S) in mixtures of bituminous coal and sewage sludge (SS) and their chars during isothermal combustion. Five groups of mixtures with SS content of 0%, 10%, 20%, 30% and 100%, were examined at different burn-off ratios (beta) of 0, 30%, 50%, 70% and 100%. The S in the coal mainly exist as the forms of mercaptan (S1), sulfide (S2), thiophene (S3), sulfoxide (S4), sulfone (S5) and sulfate (S6). During the coal combustion process, the content of S1 and S2 decreased, while that of S3 and S5 increased in the early stage and decreased in the late stage. The S4 content increased throughout the entire process of combustion. Small amount of S6 was detected, showing a fluctuated pattern. The trend of S1, S2, S5 and S6 in SS was alike with that in coal, whereas S4 decreased at the end of combustion. The changing process of S3 in SS was opposite to that of coal, while the composition of S in the mixtures resulted from the mixing of coal and SS. The transformation of each functional group during co-combustion were correlated with their transformation characteristics during the mono-combustion of coal and SS, and no obvious interaction was observed, which demonstrated that the coal-origin and SS-origin sulfur in mixtures kept their own characteristics in the combustion. SS may accumulate on the solid surface as alpha increase, resulting its significant influence on the evolution of each form of S. When alpha was low, most of the S-contained functional groups presented the characteristics of coal. The percentage of coal-origin functional groups declined as alpha increased. The transforming trends of most functional groups were similar with that of SS when alpha reached 30%.

Noncontact sub-10 nm temperature measurement in near-field laser heating.

An extremely focused optical field down to sub-10 nm in an apertureless near-field scanning optical microscope has been used widely in surface nanostructuring and structure characterization. The involved sub-10 nm near-field heating has not been characterized quantitatively due to the extremely small heating region. In this work, we present the first noncontact thermal probing of silicon under nanotip focused laser heating at a sub-10 nm scale. A more than 200 °C temperature rise is observed under an incident laser of 1.2 × 10(7) W/m(2), while the laser polarization is well aligned with the tip axis. To explore the mechanism of heating and thermal transport at sub-10 nm scale, a simulation is conducted on the enhanced optical field by the AFM tip. The high intensity of the optical field generated in this region results in nonlinear photon absorption. The optical field intensity under low polarization angles (∼10(14) W/m(2) within 1 nm region for 15° and 30°) exceeds the threshold for avalanche breakdown in silicon. The measured high-temperature rise is a combined effect of the low thermal conductivity due to ballistic thermal transport and the nonlinear photon absorption in the enhanced optical field. Quantitative analysis reveals that under the experimental conditions the temperature rise can be about 235 and 105 °C for 15° and 30° laser polarization angles, agreeing well with the measurement result. Evaluation of the thermal resistances of the tip-substrate system concludes that little heat in the substrate can be transferred to the tip because of the very large thermal contact resistance between them.

High temperature dependence of thermal transport in graphene foam.

In contrast to the decreased thermal property of carbon materials with temperature according to the Umklapp phonon scattering theory, highly porous free-standing graphene foam (GF) exhibits an abnormal characteristic that its thermal property increases with temperature above room temperature. In this work, the temperature dependence of thermal properties of free-standing GF is investigated by using the transient electro-thermal technique. Significant increase for thermal conductivity and thermal diffusivity from ∼0.3 to 1.5 W m(-1) K(-1) and ∼4 × 10(-5) to ∼2 × 10(-4) m(2) s(-1) respectively is observed with temperature from 310 K to 440 K for three GF samples. The quantitative analysis based on a physical model for porous media of Schuetz confirms that the thermal conductance across graphene contacts rather than the heat conductance inside graphene dominates thermal transport of our GFs. The thermal expansion effect at an elevated temperature makes the highly porous structure much tighter is responsible for the reduction in thermal contact resistance. Besides, the radiation heat exchange inside the pores of GFs improves the thermal transport at high temperatures. Since free-standing GF has great potential for being used as supercapacitor and battery electrode where the working temperature is always above room temperature, this finding is beneficial for thermal design of GF-based energy applications.

Fluorescence spectroscopy of graphene quantum dots: temperature effect at different excitation wavelengths

This paper reports a comprehensive study of temperature dependence of fluorescence spectroscopy of graphene quantum dots at different excitation wavelengths. Very significant (more than 50%) and similar decrease of normalized spectrum intensity is observed within temperature range less than 80 °C for excitation wavelengths of 310 nm, 340 nm and 365 nm. Besides, the temperature dependence of the red-shift of spectrum peak shows different wavelength dependence characteristic with coefficient as high as 0.062 nm K(-1) for the same temperature range, which gives us a hint about selecting the right excitation wavelength by compromising the excitation efficiency for fluorescence intensity and the temperature coefficient for peak shift in thermal applications. Temperature dependence of peak width is in a weakly linear relationship with a coefficient of 0.026 nm K(-1). Regarding the excellent stability and reversibility during thermal measurement, graphene quantum dot is a good candidate for the implementation in the nanoscale thermometry, especially in the bio-thermal field considering its superior biocompatibility and low cytotoxicity.

Sub-wavelength temperature probing in near-field laser heating by particles

This work reports on the first time experimental investigation of temperature field inside silicon substrates under particle-induced near-field focusing at a sub-wavelength resolution. The noncontact Raman thermometry technique employing both Raman shift and full width at half maximum (FWHM) methods is employed to investigate the temperature rise in silicon beneath silica particles. Silica particles of three diameters (400, 800 and 1210 nm), each under four laser energy fluxes of 2.5 × 10(8), 3.8 ×10(8), 6.9 ×10(8) and 8.6 ×10(8) W/m(2), are used to investigate the effects of particle size and laser energy flux. The experimental results indicate that as the particle size or the laser energy flux increases, the temperature rise inside the substrate goes higher. Maximum temperature rises of 55.8 K (based on Raman FWHM method) and 29.3K (based on Raman shift method) are observed inside the silicon under particles of 1210 nm diameter with an incident laser of 8.6 × 10(8) W/m(2). The difference is largely due to the stress inside the silicon caused by the laser heating. To explore the mechanism of heating at the sub-wavelength scale, high-fidelity simulations are conducted on the enhanced electric and temperature fields. Modeling results agree with experiment qualitatively, and discussions are provided about the reasons for their discrepancy.

Thermal transport across atomic-layer material interfaces

Abstract Emergence of two-dimensional (2D) materials with atomic-layer structures, such as graphene and MoS2, which have excellent physical properties, provides the opportunity of substituting silicon-based micro/nanoelectronics. An important issue before large-scale applications is the heat dissipation performance of these materials, especially when they are supported on a substrate, as in most scenarios. Thermal transport across the atomic-layer interface is essential to the heat dissipation of 2D materials due to the extremely large contact area with the substrate, when compared with their atomic-scale cross-sections. Therefore, the understanding of the interfacial thermal transport is important, but the characterization is very challenging due to the limitations for temperature/thermal probing of these atomic-layer structures. In this review, widely used characterization techniques for experimental characterization as well as their results are presented. Emphasis is placed on the Raman-based technology for nm and sub-nm temperature differential characterization. Then, we present physical understanding through theoretical analysis and molecular dynamics. A few representative works about the molecular dynamics studies, including our studies on the size effect and rectification phenomenon of the graphene-Si interfaces are presented. Challenges as well as opportunities in the thermal transport study of atomic-layer structures are discussed. Though many works have been reported, there is still much room in both the development of experimental techniques as well as atomic-scale simulations for a clearer understanding of the physical fundamentals of thermal transport across the atomic-layer interfaces, considering the remarkable complexity of physical/chemical conditions at the interface.