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.     

Electrical and thermal conductivity of low temperature CVD graphene: the effect of disorder

In this paper we present a study of graphene produced by chemical vapor deposition (CVD) under different conditions with the main emphasis on correlating the thermal and electrical properties with the degree of disorder. Graphene grown by CVD on Cu and Ni catalysts demonstrates the increasing extent of disorder at low deposition temperatures as revealed by the Raman peak ratio, IG/ID. We relate this ratio to the characteristic domain size, La, and investigate the electrical and thermal conductivity of graphene as a function of La. The electrical resistivity, ρ, measured on graphene samples transferred onto SiO2/Si substrates shows linear correlation with La(-1). The thermal conductivity, K, measured on the same graphene samples suspended on silicon pillars, on the other hand, appears to have a much weaker dependence on La, close to K～La1/3. It results in an apparent ρ～K3 correlation between them. Despite the progressively increasing structural disorder in graphene grown at lower temperatures, it shows remarkably high thermal conductivity (10(2)-10(3) W K(-1) m(-1)) and low electrical (10(3)-3×10(5) Ω) resistivities suitable for various applications.     

Negative thermal expansion coefficient of graphene measured by Raman spectroscopy

The thermal expansion coefficient (TEC) of single-layer graphene is estimated with temperature-dependent Raman spectroscopy in the temperature range between 200 and 400 K. It is found to be strongly dependent on temperature but remains negative in the whole temperature range with a room temperature value of (-8.0 ± 0.7) × 10(-6) K(-1). The strain caused by the TEC mismatch between graphene and the substrate plays a crucial role in determining the physical properties of graphene, and hence its effect must be accounted for in the interpretation of experimental data taken at cryogenic or elevated temperatures.     

Graphene-multilayer graphene nanocomposites as highly efficient thermal interface materials

We found that the optimized mixture of graphene and multilayer graphene, produced by the high-yield inexpensive liquid-phase-exfoliation technique, can lead to an extremely strong enhancement of the cross-plane thermal conductivity K of the composite. The "laser flash" measurements revealed a record-high enhancement of K by 2300% in the graphene-based polymer at the filler loading fraction f = 10 vol %. It was determined that the relatively high concentration of the single-layer and bilayer graphene flakes (~10-15%) present simultaneously with the thicker multilayers of large lateral size (~1 μm) were essential for the observed unusual K enhancement. The thermal conductivity of the commercial thermal grease was increased from an initial value of ~5.8 W/mK to K = 14 W/mK at the small loading f = 2%, which preserved all mechanical properties of the hybrid. Our modeling results suggest that graphene-multilayer graphene nanocomposite used as the thermal interface material outperforms those with carbon nanotubes or metal nanoparticles owing to graphene's aspect ratio and lower Kapitza resistance at the graphene-matrix interface.     

SnP2O7中温固体电解质的制备和导电性能

用固相反应法制备了不同P/Sn物质的量比的SnP2O7,并研究了该电解质在120～260℃范围内的导电性能。XRD分析表明SnP2O7为立方结构。热重分析了电解质在中温范围内的稳定性。用交流阻抗谱测量了电解质电导率,电导率随着HPO3在电解质中的残余量的提高而提高。测试结果表明电解质中起导电作用的主要是HPO3,而SnP2O7主要起支撑作用。最大电导率是在200℃,P/Sn物质的量比为3.0时,干空气条件下为5.1×10-2S/cm,湿空气条件下为6.6×10-2S/cm。     

Single-layer and bilayer graphene superlattices: collimation, additional Dirac points and Dirac lines

We review the energy spectrum and transport properties of several types of one-dimensional superlattices (SLs) on single-layer and bilayer graphene. In single-layer graphene, for certain SL parameters an electron beam incident on an SL is highly collimated. On the other hand, there are extra Dirac points generated for other SL parameters. Using rectangular barriers allows us to find analytical expressions for the location of new Dirac points in the spectrum and for the renormalization of the electron velocities. The influence of these extra Dirac points on the conductivity is investigated. In the limit of δ-function barriers, the transmission T through and conductance G of a finite number of barriers as well as the energy spectra of SLs are periodic functions of the dimensionless strength P of the barriers, Pδ(x) = V(x)/?v(F), with v(F) the Fermi velocity. For a Kronig-Penney SL with alternating sign of the height of the barriers, the Dirac point becomes a Dirac line for P = π/2+nπ with n an integer. In bilayer graphene, with an appropriate bias applied to the barriers and wells, we show that several new types of SLs are produced and two of them are similar to type I and type II semiconductor SLs. Similar to single-layer graphene SLs, extra 'Dirac' points are found in bilayer graphene SLs. Non-ballistic transport is also considered.     

OH concentration and temperature measurements by use of near-resonant holographic interferometry

Near-resonant holographic interferometry is demonstrated to measure temperature and species concentration in a two-dimensional steady premixed air-acetylene flame. A peak temperature of (2600 +/- 100) K and a peak OH number density of (9.6 +/- 0.3) x 10(22) m(-3) are obtained, consistent with the expected values for such a flame. These values are determined by recording interferograms with a laser assumed sufficiently detuned from line center so that pressure and temperature broadening can be ignored. The results are thus obtained without making prior assumptions on the temperature or pressure of the flame beyond the existence of thermal equilibrium.     

Terahertz and infrared spectroscopy of gated large-area graphene

We have fabricated a centimeter-size single-layer graphene device with a gate electrode, which can modulate the transmission of terahertz and infrared waves. Using time-domain terahertz spectroscopy and Fourier-transform infrared spectroscopy in a wide frequency range (10-10?000 cm(-1)), we measured the dynamic conductivity change induced by electrical gating and thermal annealing. Both methods were able to effectively tune the Fermi energy, E(F), which in turn modified the Drude-like intraband absorption in the terahertz as well as the "2E(F) onset" for interband absorption in the mid-infrared. These results not only provide fundamental insight into the electromagnetic response of Dirac fermions in graphene but also demonstrate the key functionalities of large-area graphene devices that are desired for components in terahertz and infrared optoelectronics.     

Graphene bimetallic-like cantilevers: probing graphene/substrate interactions

The remarkable mechanical properties of graphene, the thinnest, lightest, and strongest material in existence, are desirable in applications ranging from composite materials to sensors and actuators. Here, we demonstrate that these mechanical properties are strongly affected by the interaction with the substrate onto which graphene is deposited. By measuring the temperature-dependent deflection of graphene/substrate "bimetallic" cantilevers we determine strain, thermal expansion coefficient, and the adhesion force acting on graphene films attached to a substrate. Graphene deposited on silicon nitride (SiN(x)) is under much larger strain, ε(g) ～ 1.5 × 10(-2), compared to graphene on gold (Au), ε(g) < 10(-3). The thermal expansion coefficient α(g) of graphene attached to SiN(x) is found to be negative, in the range from (- 5... - 1) × 10(-6)K(-1) and smaller in magnitude than α(g) of suspended graphene. We also estimate the interfacial shear strength of the graphene/SiN(x) interface to be ～1 GPa at room temperature.     

Heat conduction across monolayer and few-layer graphenes

We report the thermal conductance G of Au/Ti/graphene/SiO(2) interfaces (graphene layers 1 ≤ n ≤ 10) typical of graphene transistor contacts. We find G ≈ 25 MW m(-2) K(-1) at room temperature, four times smaller than the thermal conductance of a Au/Ti/SiO(2) interface, even when n = 1. We attribute this reduction to the thermal resistance of Au/Ti/graphene and graphene/SiO(2) interfaces acting in series. The temperature dependence of G from 50 ≤ T ≤ 500 K also indicates that heat is predominantly carried by phonons through these interfaces. Our findings suggest that metal contacts can limit not only electrical transport but also thermal dissipation from submicrometer graphene devices.     

石墨烯改性相变聚氨酯发泡材料传热特性研究及仿真

目的 提升无源冷链物流中保温容器的保温性能,减少或取消短途冷链运输中蓄冷剂的使用量.方法 将石墨烯改性相变大胶囊与聚氨酯发泡材料共混,制备石墨烯改性相变聚氨酯发泡材料,研究石墨烯的添加对其导热系数和保温性能的影响,并基于COMSOL Multiphysics对石墨烯改性相变大胶囊和石墨烯改性相变聚氨酯发泡材料的传热过程进行有限元模拟.结果 在常温状态下,石墨烯的添加会增加石墨烯改性相变聚氨酯发泡材料的导热系数;在冷藏工况下,石墨烯改性相变聚氨酯发泡材料的导热系数随石墨烯添加量的增加而降低,石墨烯改性相变聚氨酯发泡材料制备的保温容器的系统热阻随石墨烯的增加而升高.通过有限元模拟可发现,石墨烯的加入能够提升相变大胶囊的导热系数,同时能够减缓升温平台阶段的升温速率;在跨越平台区后,即内部相变大胶囊完全融化后,石墨烯会提升保温材料的导热系数,从而降低保温容器的保温效果.结论 制备的石墨烯改性相变聚氨酯发泡材料能够在设计使用时间内提升保温容器的保温性能,该材料在需要冷藏的生鲜果蔬短途无源冷链物流领域具有广阔的应用前景.     

Magnetically-functionalized self-aligning graphene fillers for high-efficiency thermal management applications

We report on heat conduction properties of thermal interface materials with self-aligning “magnetic graphene” fillers. Graphene enhanced nano-composites were synthesized by an inexpensive and scalable technique based on liquid-phase exfoliation. Functionalization of graphene and few-layer-graphene flakes with Fe₃O₄ nanoparticles allowed us to align the fillers in an external magnetic field during dispersion of the thermal paste to the connecting surfaces. The filler alignment results in a strong increase of the apparent thermal conductivity and thermal diffusivity through the layer of nano-composite inserted between two metallic surfaces. The self-aligning “magnetic graphene” fillers improve heat conduction in composites with both curing and non-curing matrix materials. The thermal conductivity enhancement with the oriented fillers is a factor of two larger than that with the random fillers even at the low ~ 1 wt.% of graphene loading. The real-life testing with computer chips demonstrated the temperature rise decrease by as much as 10 °C with use of the non-curing thermal interface material with ~ 1 wt.% of the oriented fillers. Our proof-of-concept experiments suggest that the thermal interface materials with functionalized graphene and few-layer-graphene fillers, which can be oriented during the composite application to the surfaces, can lead to a new method of thermal management of advanced electronics.     

聚酰亚胺/羰基铁粉吸波包装材料性能分析

目的 制备聚酰亚胺(PI)/羰基铁粉(CI)复合膜并探究其性能,以改变微波加热过程中的加热方式.方法 主要通过红外光谱、扫描电镜、力学性能、透氧透湿和微波转热测试分析其性能.结果 聚酰亚胺与羰基铁粉是物理结合;当羰基铁粉质量分数超过25％时,开始发生团聚;当羰基铁粉质量分数为20％时,弹性模量最小;当羰基铁粉质量分数为15％时,透氧透湿系数最低;随着羰基铁粉含量的增加,复合膜在微波加热下升温和常温下降温的速率增加.结论 PI/CI复合膜能够吸收部分微波转热能,是一种新型的吸波包装材料,为微波加热用包装材料的设计提供了新思路.     

电器封装用高效导热/阻燃环氧复合材料的制备

目的为了提高电器封装材料的安全性,制备出一种具有高效导热/阻燃的环氧复合材料。方法通过原位聚合法,采用三聚氰胺-甲醛树脂预聚体(MF)修饰石墨烯(G)/磷烯(BP)合成纳米填料,辅以环氧树脂(E51)制备高导热/阻燃的环氧复合材料。通过TGA、热线法和锥形量热法分别测试复合材料的热稳定性、导热性和阻燃性。结果研究结果表明,当MF@BP/G的质量分数为3%时,环氧复合材料的残碳量高达22.19%,相较于纯的环氧复合材料提升了76.77%;导热系数提升至0.257 W/(m∙K),提升率为27.86%;峰值热释放率、总的热释放量、峰值烟雾释放率和总的烟雾释放量分别下降了43.76%,27.72%,46.81%和28.83%。结论以MF@BP/G为功能填料,可以有效提高环氧复合材料的导热性和阻燃性,有利于提升环氧复合材料的使用安全性。     

Gate-induced insulating state in bilayer graphene devices

The potential of graphene-based materials consisting of one or a few layers of graphite for integrated electronics originates from the large room-temperature carrier mobility in these systems (approximately 10,000 cm2 V(-1) s(-1)). However, the realization of electronic devices such as field-effect transistors will require controlling and even switching off the electrical conductivity by means of gate electrodes, which is made difficult by the absence of a bandgap in the intrinsic material. Here, we demonstrate the controlled induction of an insulating state--with large suppression of the conductivity--in bilayer graphene, by using a double-gate device configuration that enables an electric field to be applied perpendicular to the plane. The dependence of the resistance on temperature and electric field, and the absence of any effect in a single-layer device, strongly suggest that the gate-induced insulating state originates from the recently predicted opening of a bandgap between valence and conduction bands.     

Optoelectronic properties of graphene thin films prepared by thermal reduction of graphene oxide

Graphene thin films have been prepared by thermal reduction of graphene oxide. Raising the reduction temperature results in a red-shift of the G peak in Raman spectra. The reduction temperature turns out to strongly affect the morphology of the prepared graphene film. Photoluminescence (PL) results show that the band gap of graphene can be tuned by varying the reduction temperature. The thermal reduction process has been optimized in an effort to minimize the formation of wrinkles/folds on the graphene surface leading to enhanced PL and Raman peak intensities and reduced electrical sheet resistance.     

不同填料复配对尼龙6/石墨烯复合材料导热性能的影响

高分子材料的绝热特性极大地限制了其作为导热材料在工业中的应用。选用多层石墨烯作为导热填料,并分别与导热填料氧化铝(Al_2O_3)和碳化硅(SiC)复配,探究导热填料的复配对尼龙6(PA6)复合材料导热性能的影响。加入质量分数为3%石墨烯时,PA6复合材料的热导率为0.548W·m^-1·K^-1,相比PA6基体提高161%。通过调节石墨烯与Al_2O_3和SiC复配的比例以及复合填料量,PA6复合材料的热导率可控在0.653~4.307W·m^-1·K^-1之间,最高是PA6基体的20倍。为拓展石墨烯在导热材料方面的应用及PA6导热材料在工业上应用提供了有价值的实验依据。     

Composite infrared bolometers with Si3N4 micromesh absorbers

We report the design and performance of 300-mK composite bolometers that use micromesh absorbers and support structures patterned from thin films of low-stress silicon nitride. The small geometrical filling factor of the micromesh absorber provides 20x reduction in heat capacity and cosmic ray cross section relative to a solid absorber with no loss in IR-absorption efficiency. The support structure is mechanically robust and has a thermal conductance, G < 2 x 10(-11) W/K, which is four times smaller than previously achieved at 300 mK. The temperature rise of the bolometer is measured with a neutron transmutation doped germanium thermistor attached to the absorbing mesh. The dispersion in electrical and thermal parameters of a sample of 12 bolometers optimized for the Sunyaev-Zel'dovich Infrared Experiment is +/-7% in R (T), +/-5% in optical efficiency, and +/-4% in G.     

温度对堆叠双层石墨烯层间耦合的影响

将不同层数堆叠和化学气相沉积法（CVD）生长的石墨烯在室温下进行拉曼光谱表征分析其层间耦合状态,并分析了不同温度下堆叠和CVD生长的双层石墨烯温度对其层间耦合的影响。研究结果表明:室温下CVD生长双层石墨烯和堆叠双层石墨烯的层间耦合状态截然不同;在25～250 ℃范围内,层间没有耦合作用或存在弱耦合作用的堆叠双层石墨烯的G峰峰位温度系数小于存在电子耦合的CVD生长双层石墨烯;超过250 ℃后,堆叠双层石墨烯G峰峰位温度系数变为正值,层与层之间可能产生了耦合,性质发生改变;在25～400 ℃ 范围内两种材料的2D峰半峰宽和G峰/2D峰强度比变化趋势几乎相同,但堆叠双层石墨烯波动大,对温度更敏感。     

Wet-resilient graphene aerogel for thermal conductivity enhancement in polymer nanocomposites

Three-dimensional(3D)graphene-based aerogels have significant potential for adsorption,sensors,and thermal management applications.However,their practical applications are limited by their disorganized structure and ultra-low resilience after compression.Some methods can realize a well-aligned structure,however,they involve high costs and complex technology.Herein,a 3D graphene hybrid aerogel with an anisotropic open-cell and well-oriented structure is realized by unidirectional freeze casting,which com-bines the'soft'(e.g.graphene oxide,Tween-80)and'hard'(e.g.graphene assembly)components to realize full recovery after flattening.A graphene aerogel annealed at a moderate temperature(～200℃)can pos-sess superhydrophilicity and outstanding wet-resilience properties,including after being pressed under 40 MPa.Furthermore,the graphene aerogel annealed at a high temperature of～1500℃exhibits excellent thermal conductivity enhancement efficiency in polydimethylsiloxane(PDMS).The resultant nanocom-posites clearly demonstrate anisotropic thermal conductivity and promising applications as thermal interface materials.This strategy offers new insights into the design and fabrication of 3D multifunctional graphene aerogels.