薄膜热导率测试方法研究进展

薄膜材料的热导率一般与其相应的块体材料有较大的差异.由于其厚度较小,对块体材料热导率的测试方法一般不适用于薄膜材料,因此近几十年来,研究工作者们发明了很多新的用于薄膜热导率的测试方法.综述了薄膜热导率的一些常用测试方法,着重介绍了薄膜热导率的最新测试方法的特点及其适用范围,并针对广泛使用的3ω法进行了详细介绍.     

Thermal and Electrical Properties of a Suspended Nanoscale Thin Film

This paper reports on measurements of in-plane thermal conductivities, electrical conductivities, and Lorentz number of two microfabricated, suspended, nanosized thin films with a thickness of 28 nm. The effect of the film thickness on the in-plane thermal conductivity is examined by measuring other nanofilm samples with a thickness of 40 nm. The experimental results show that the electrical conductivity, resistance–temperature coefficient, and in-plane thermal conductivity of the nanofilms are much smaller than the corresponding bulk values from 77 to 330 K. However, the Lorentz number of the nanofilms is about two times that of the bulk value at room temperature, and even up to three times that of the bulk value at 77 K. These results indicate that the relation between the thermal conductivity and electrical conductivity of the nanofilms does not follow the Wiedemann–Franz law for bulk metallic materials.     

Thermal Conductivity of AlN and SiC Thin Films

The thermal conductivity of AlN and SiC thin films sputtered on silicon substrates is measured employing the 3ω method. The thickness of the AlN sample is varied in the range from 200 to 2000 nm to analyze the size effect. The SiC thin films are prepared at two different temperatures, 20 and 500°C, and the effect of deposition temperature on thermal conductivity is examined. The results reveal that the thermal conductivity of the thin films is significantly smaller than that of the same material in bulk form. The thermal conductivity of the AlN thin film is strongly dependent on the film thickness. For the case of SiC thin films, however, increased deposition temperature results in negligible change in the thermal conductivity as the temperature is below the critical temperature for crystallization. To explain the thermal conduction in the thin films, the thermal conductivity and microstructure are compared using x-ray diffraction patterns.     

Thermal conductivity of copper films

The thermal conductivity of thin films of copper (400–8000 Å) has been measured in the temperature range 100–500 K. It decreases with decreasing film thickness. An electrical-thermal transport analogy has been used to calculate the size-dependent thermal conductivity of the thin copper films. The decrease of the thermal conductivity with thickness is attributed partly to the scattering of the conduction electrons from the film surfaces and partly to the scattering by lattice impurities and frozen-in structural defects in the films. The variation of the thermal conductivity with temperature agrees with the variation for bulk copper. The Lorentz ratio has been determined and is found to vary from 2.4 × 10^-8 to $\text{2.0 × 10}{}^{-8}\text{W}\text{Ω/}\text{deg}{}^2$ for film thicknesses ranging from 400 to 8000 Å.     

Thermal Conductivity Measurement of Submicron-Thick Films Deposited on Substrates by Modified ac Calorimetry (Laser-Heating Ångstrom Method)

Technological development, especially in microelectronics, necessitates the development of new and improved methods for measuring the thermal properties of materials, especially in the form of ultrathin films. Previously, modified ac calorimetry (laser-heating Ångstrom method) using a scanning laser as the energy source was developed and shown to provide accurate values of thermal diffusivity and derived thermal conductivity for a broad range of materials in the form of free-standing thin sheets or films, wires including fiber bundles, and some films on substrates. This paper describes further applications of the modified ac-calorimetry technique for measurements of the thermal conductivity of thin films deposited on substrates. It was used to measure successfully the thermal conductivities of 1000- to 3000-Å-thick aluminum nitride films, aluminum oxide films, etc., which were deposited on a glass substrate. It was also shown to be suitable for developmental measurements on submicron-thick chromatic films deposited on a PET substrate, which are photothermal recording layers, used in the media of CD-R drives of computer systems.     

Nanocrystalline ZnO thin films: optoelectronic and gas sensing properties

Nanocrystalline Zinc oxide thin films have been deposited by sol–gel spin coating technique and then have been analyzed before and after a suitable thermal annealing in order to test their applications in various reducing and oxidizing gases. ZnO thin films were highly sensitive and selective for NH₃ gas. The spectrophotometric and conductivity measurements have been performed in order to determine the optical and electrical properties of zinc oxide thin films. The structure and the morphology of such material have been investigated by high resolution electron microscopy and small area electron diffraction. The average particle size is in 60–70 nm.     

Conductivity and nanoscale morphology of thin films prepared from indolo[2,3-a]carbazole and 11,12-dioctylindolo[2,3-a]carbazole

A systematic study on the thin film morphology of heteroacenic derivatives such as indolo[2,3-a]carbazole and 11,12-dioctylindolo[2,3-a]carbazole has been carried out using scanning force microscopy and optical microscopy techniques. The investigation has comprised the preparation of a series of thin films by combining different solvents (dimethylformamide and tetrahydrofurane), substrates (glass, gold, silicon and aluminium) and deposition techniques (spin coating and thermal evaporation) we found a wide variety of self-assembled structures. In addition, conductivity measurements have been performed, showing a very large spread in conductivity values. Some of the samples give quite high conductivity while others conduct very poorly, even in the case of samples prepared with essentially the same conditions. These results indicate that morphology is very critical for the final conductivity of the thin films. In addition we conclude that for some of the films prepared the homogeneous thin film approximation must be revised otherwise obtained conductivity measurements lead to significant error.     

Thermal Diffusivity of Metallic Thin Films: Au, Sn, Mo, and Al/Ti Alloy

The thermal diffusivity of Au, Sn, Mo, and Al_0.97Ti_0.03 alloy thin films, which are commonly used in microelectromechanical (MEMs) system applications, is measured by two independent methods — the ac calorimetric and photothermal mirage methods. Both methods yield similar results of the thin-film thermal conductivity, but the uncertainty of the mirage technique is found to be relatively large because of the large temperature increase during the measurement. The measured thermal diffusivities of the thin films are generally lower than those of the same bulk material. Especially, the Al_0.97Ti_0.03 thin film shows a pronounced thermal conductivity drop compared with bulk Al, which is believed to be mainly due to impurity scattering. Comparison of the thermal conductivity with the electrical conductivity measured by the standard four-probe technique indicates that the relation of thermal and electrical conductivities follows the Wiedemann–Franz law for the case of Au and Sn thin films. However, the Lorentz number is significantly larger than the theoretical prediction for the case of Al_0.97Ti_0.03 and Mo thin films.     

Photoacoustic measurement of thermal properties of TiN thin films

Titanium nitride (TiN) thin films were prepared by reactive DC magnetron sputtering under different nitrogen flow rates and at constant substrate temperature as well as at constant nitrogen flow rate and at different substrate temperatures. Photoacoustic measurement of the thermal properties of the films revealed that the thermal diffusivity and thermal conductivity of the TiN thin films are significantly lower than the bulk values and that the grain size of the films has substantial influence on the thermal properties of TiN thin films. The thermal conductivity of the films decreases with increasing nitrogen flow rates and increases with increasing substrate temperature. The above opposing behaviour in the thermal properties is found to be related to the microstructure, especially, the grain size of the films.     

Phase transition behaviors and thermal conductivity measurements of nitrogen-doped Sb2Te3 thin films

Crystallization temperature of nitrogen-doped Sb₂Te₃ (ST) thin films increased with increasing nitrogen doping concentration, which indicates that the long-term stability of the metastable amorphous state can be improved by nitrogen doping. The root-mean-square (rms) roughness values of the films showed a significant decrease with nitrogen doping. Thermal conductivity of nitrogen-doped ST thin films was measured using a transient thermoreflectance (TTR) technique. It was found that the thermal conductivity decreased with increasing nitrogen doping concentration and increased with increasing annealing temperature. Nitrogen-doped ST thin films are suitable phase-change materials for low programming power consumption applications of phase-change random access memory (PCRAM).     

Improved thermoelectric performance of highly-oriented nanocrystalline bismuth antimony telluride thin films

Improved thermoelectric performance of highly-oriented nanocrystalline bismuth antimony telluride thin films is described. The thin films are deposited by a flash evaporation method, followed by annealing in hydrogen. By optimizing the annealing conditions, the resulting thin films exhibit almost perfect orientation with the c-axis normal to the substrate, and are composed of nano-sized grains with an average grain size of 150 nm. The in-plane electrical conductivity and Seebeck coefficient were measured at room temperature. The cross-plane thermal conductivity of the thin films was measured by a 3ω method, and the in-plane thermal conductivity was evaluated by using an anisotropic factor of thermal conductivity based on a single crystal bulk alloy with almost the same composition and carrier concentration. The measured cross-plane thermal conductivity is 0.56 W/(m K), and the in-plane thermal conductivity is evaluated to be 1.05 W/(m K). Finally, the in-plane power factor and figure-of-merit, ZT, of the thin films are 35.6 μW/(cm K²) and 1.0 at 300 K, respectively.     

On the optical and electrical properties of rf and a.c. plasma polymerized aniline thin films

Polyaniline is a widely studied conducting polymer and is a useful material in its bulk and thin film form for many applications, because of its excellent optical and electrical properties. Pristine and iodine doped polyaniline thin films were prepared by a.c. and rf plasma polymerization techniques separately for the comparison of their optical and electrical properties. Doping of iodine was effectedin situ. The structural properties of these films were evaluated by FTIR spectroscopy and the optical band gap was estimated from UV-vis-NIR measurements. Comparative studies on the structural, optical and electrical properties of a.c. and rf polymerization are presented here. It has been found that the optical band gap of the polyaniline thin films prepared by rf and a.c. plasma polymerization techniques differ considerably and the band gap is further reduced byin situ doping of iodine. The electrical conductivity measurements on these films show a higher value of electrical conductivity in the case of rf plasma polymerized thin films when compared to the a.c. plasma polymerized films. Also, it is found that the iodine doping enhanced conductivity of the polymer thin films considerably. The results are compared and correlated and have been explained with respect to the different structures adopted under these two preparation techniques.     

Properties of niobium nitride-based Josephson tunnel junctions

High T_c (16.8 K) niobium nitride thin films have been prepared by rf diode sputtering in N₂/Ar atmosphere and subsequent high temperature annealing. Josephson tunnel junctions have been made by thermal oxidation of the films. The geometry is defined by high resolution photolithography. The Josephson junctions have been characterized by magnetic field diffraction measurements and other techniques and are shown to be particularly suitable for applications especially in superconducting microwave integrated devices.     

Thermal Characterization of SiC Amorphous Thin Films

The cross-plane thermal conductivity of SiC amorphous films was measured employing the transient thermoreflectance technique. The SiC films were deposited on silicon substrates by RF magnetron sputtering at room temperature. The thickness of the films was varied in the range from 100?nm to 2500?nm to analyze the size effect. The results found that the thermal conductivity of the SiC thin films is significantly smaller than that of the SiC material in bulk form. The small thermal conductivity stems from the structural disorder of the films, which was confirmed by high-resolution transmission electron microscopy and X-ray diffraction. In addition, the contribution of the thermal boundary resistance to the thermal conductivity of the films is discussed.     

四氯苯醌/三苯磷可控掺杂四取代酞菁铜薄膜材料的导电性能研究

本文通过电化学沉积方法制备了一种四氯苯醌/三苯磷可控掺杂四取代酞菁铜薄膜材料体系,研究了该可控掺杂有机薄膜材料的导电性能.研究结果表明,四取代酞菁铜可控掺杂薄膜材料的电导率,随着温度的升高或掺杂剂浓度的增加而显著增加,其原因是酞菁铜给体与四氯苯醌和三苯基磷等小分子电子受体之间发生了较强的氧化还原作用.     

Estimation of thermal properties of composite materials without instrumentation inside the samples

Recent contributions of parameter estimation in the measurement of thermal properties are of great importance. In comparison with other techniques such as steady state (hot guarded plate, etc.) or transient (line source method, flash method, etc.), the use of parameter estimation provides more information and, in most cases, produces faster results. With this technique the thermal conductivity and the volumetric specific heat are estimated simultaneously and as a function of time, temperature, or position. This method requires experimental data, such as transient temperature and heat flux measurements. Previously, the temperature measurements came from thermocouples embedded in the sample. These thermocouples are introduced in the sample either by drilling holes or by molding the material around a series of thermocouples. Both operations are time-consuming and costly and are needed for each sample. In this study, temperature measurements are made only on the two sides of the samples with thin resistance thermometers. Since the sensors are not inside the material, the effect of the thermal contact conductance between sensor and sample was first investigated. The value of this thermal contact conductance was estimated by using samples of high-conductivity material. Using these values, the estimated thermal properties obtained with surface temperature measurements are compared with values provided by other methods for several low-thermal conductivity materials; agreement has been very good.     

Structural and electrical studies of thermally evaporated nanostructured CdTe thin films

CdTe thin films were deposited on KCl and glass substrates using thermal evaporation technique under high vacuum conditions. CdTe bulk compound grown by vertical directional solidification (VDS) technique was used as the source material to deposit thin films. Powder X-ray diffraction technique was employed to identify the phase of the as grown bulk CdTe compound as well as its thin films. Surface morphology and the stoichiometry of the bulk compound and thin films was carried out by using scanning electron microscope (SEM) with an attachment of energy dispersive spectrometer(EDS). Microstructural features associated with the as deposited CdTe thin films were studied by using transmission electron microscope (TEM). The films deposited on to glass substrates at different temperatures have been used to study the I-V characteristics of the films. These parameters have been studied in detail in order to prepare good quality nanostructured thin films of CdTe compound. CdTe bulk compound grown by VDS method and its thin films prepared by thermal evaporation method found to have single phase with cubic structure. Size of the particles in the as deposited films vary between 5 and 40 nm In the present study efforts have been made to correlate the electrical and optical properties of the CdTe thin films with the corresponding microstructural features associated with them.     

Radiative heat transfer in transient hot-wire measurements of thermal conductivity

New measurements of the thermal conductivity of liquid toluene between 300 and 550 K have been used to study the importance of radiative heat transfer when using the transient hot-wire technique. The experimental data were used to obtain the radiation correction to the hot-wire temperature rises. Radiationcorrected values of thermal conductivity are reported. This study shows that the transient hot-wire method is much less affected by radiation than steady-state techniques.     

Thermal Effusivity Determination of Metallic Films of Nanometric Thickness by the Electrical Micropulse Method

The thermal effusivity of gold, aluminum, and copper thin films of nanometric thickness (20 nm to 200 nm) was investigated in terms of the films’ thickness. The metallic thin films were deposited onto glass substrates by thermal evaporation, and the thermal effusivity was estimated by using experimental parameters such as the specific heat, thermal conductivity, and thermal diffusivity values obtained at room conditions. The specific heat, thermal conductivity, and thermal diffusivity values of the metallic thin films are determined with a methodology based on the behavior of the thermal profiles of the films when electrical pulses of few microseconds are applied at room conditions. For all the investigated materials, the thermal effusivity decreases with decreased thickness. The thermal effusivity values estimated by the presented methodology are consistent with other reported values obtained under vacuum conditions and more elaborated methodologies.     

Synthesis and Characterization of Thermally Oxidized ZnO Films

Metallic zinc thin films were deposited onto glass substrates using vacuum thermal evaporation method. By thermal oxidation of as-deposited Zn films, in ambient conditions, at different temperatures (570, 670 and 770 K, respectively, for 1 h) zinc oxide thin films were obtained. The structural characteristics of the obtained films were investigated by X-ray diffraction technique and atomic force microscopy. Characteristic XRD patterns of oxidized films show small and narrow peaks superimposed on the large broad background of the amorphous component of the substrate. Optical transmittance spectra were recorded and it was observed that the transmittances of the studied films increased with increasing oxidation temperature. The values of the optical bandgap, E _g, evaluated from Tauc plots, were found to be ranged between 3·22 and 3·27 eV. Electrical conductivity measurements were performed and it was observed that, after performing a heat treatment, the electrical conductivity of analysed samples decreased with one or two orders of magnitude. The gas sensitivity was investigated for some reducing gases such as acetone, methane and liquefied petroleum gas and it was observed that the films studied were selective to acetone.