Photoacoustic spectroscopy of diamond powders and polycrystalline films

Photoacoustic spectroscopy is used to study optical absorption in diamond powders and polycrystalline films. The photoacoustic spectra of diamond powders with crystallite sizes in the range from ∼100 μm to 4 nm and diamond films grown by chemical vapor deposition (CVD) had a number of general characteristic features corresponding to the fundamental absorption edge for light with photon energies exceeding the width of the diamond band gap (∼5.4 eV) and to absorption in the visible and infrared by crystal-structure defects and the presence of non-diamond carbon. For samples of thin (∼10 μm) diamond films on silicon, the photoacoustic spectra revealed peculiarities associated with absorption in the silicon substrate of light transmitted by the diamond film. The shape of the spectral dependence of the amplitude of the photoacoustic signal in the ultraviolet indicates considerable scattering of light specularly reflected from the randomly distributed faces of the diamond crystallites both in the polycrystalline films and in the powders. The dependence of the shape of the photoacoustic spectra on the light modulation frequency allows one to estimate the thermal conductivity of the diamond films, which turns out to be significantly lower than the thermal conductivity of single-crystal diamond. Fiz. Tverd. Tela (St. Petersburg) 39, 1787–1791 (October 1997)     

Thermal conductivity enhancement in Cu/diamond composites with surface-roughened diamonds

Cu/diamond composites have potential as a heat spreading material in small-scale devices. In this study, we show that the use of surface-roughened diamonds obtained by heat treatment under N₂ atmosphere and subsequently coated with a thin layer of Ti coating is a feasible method to effectively improve the interfacial bonding and thermal conductivity of Cu/diamond composites. The diamond surface state and prepared composites were investigated by the combination of X-ray diffraction, Raman spectroscopy and microstructure analysis. It is found that the surface-roughened diamonds are in favor of the formation of effective chemical bonds between diamonds and Ti coating through the formation of thin TiC layer and simultaneously provide increased Cu/diamond contact area, which are beneficial to largely decrease the interfacial thermal resistance and thus to greatly enhance the thermal conductivity of Cu/diamond composites.     

Thermal conductive performance of deposited amorphous carbon materials by molecular dynamics simulation

A series of diamond-like carbon (DLC) films with different microstructure were prepared by depositing carbon atoms on diamond surface with incident energy ranging from 1 to 100 eV. The thermal conductivity of the deposited films and the Kapitza resistance between the film and the diamond substrate were investigated. Results show that the average density, the average fraction of sp³ bonding and the thermal conductivity of the DLC films increase first, reaching a maximum around 20–40 eV before decreasing, while the Kapitza resistance decreases gradually with increased deposition energy. The analysis suggests that the thermal resistance of the interface layer is in the order of 10^?10 m²K/W, which is not ignorable when measuring the thermal conductivity of the deposited film especially when the thickness of the DLC film is not large enough. The fraction of sp³ bonding in the DLC film decreases gradually normal to the diamond surface. However, the thermal conductivity of the film in normal direction is not affected obviously by this kind of structural variation but depends linearly on the average fraction of sp³ bonding in the entire film. The dependence of the thermal conductivity on the fraction of sp³ bonding was analysed by the phonon theory.     

Thermal parameters of layers and interfaces in silicon-on-diamond structures

The heat propagation at room temperature was studied in a heterostructure consisting of a polycrystalline diamond film deposited from a hydrocarbon plasma on an oriented silicon substrate. The dynamics of cooling of a thin-film indium thermometer evaporated atop the diamond film was measured following its heating by nanosecond nitrogen laser pulses. The experimental data were compared with the values calculated in the framework of the theory of thermal conductivity for multilayer systems. This analysis permitted the determination of both the thermal conductivity of the diamond film and the thermal resistance of the diamond/Si and In/diamond interfaces.     

吸收辐射复合金刚石膜的制备及光学研究

采用微波等离子体化学气相沉积（MW-PCVD）和直流热阴极辉光放电等离子体化学气相沉积（DC-PCVD）两种方法相结合,制备出一种吸收辐射的复合金刚石膜,它对宽光谱范围的光辐射具有99%—99.2%的吸收率,同时具有较低的反射率和透过率.随着黑色吸收辐射金刚石层厚度的增加,复合金刚石膜的热导率将小幅度降低,但黑色金刚石膜层厚度小于15 μm时,复合金刚石膜的热导率都在16 W·cm^-1·K^-1以上,这满足吸收辐射复合金刚石膜的高导热需求.用热阴极DC-PCVD方 关键词： 吸收辐射 光学材料 金刚石 热导率     

Conductivity drop and crystallites redistribution in gold film

Electrical conductivity of Au film deposited on Si(100), Si(111) and BK7 glass substrates, ranging from 20 nm to 1000 nm, was measured. Conductivity drop and a decrease of averaged crystallite size are observed around film thickness of 200 nm. Investigation of the conductivity drop led to the discovery that a redistribution of crystallites of {111} and {220} occurs in the conductivity drop region. By analyzing the relationship of distribution of crystallites, averaged crystallite size and conductivity ratios and together with the atomic force microscope pictures, leads to the conclusion that the thermal conductivity drop region is caused by the presence of many small crystallites. These small crystallites are responsible for yielding a lower averaged crystallite size and causing a higher grain boundary scattering. PACS 73.50; 68.47.De; 68.55.Jk     

Hopping conductivity in polycrystalline diamond films

The results of the experimental study of the conductivity of a polycrystalline diamond film by dielectric spectroscopy are presented. A diamond film about 200 μm thick was grown by microwave plasma-assisted chemical vapor deposition for 180 h. Two pronounced local peaks in the frequency dependence of the conductivity were observed. The relevant frequencies were temperature-dependent. These data permit us to hypothesize that the hopping mechanism of conductivity occurs in the polycrystalline diamond film. Two types of electrically active centers with different activation energies and relaxation times are involved in the conductivity.     

类金刚石薄膜在硅基底上的沉积及其热导率

采用分子动力学方法模拟了碳在晶体硅基底上的沉积过程, 并分析计算了所沉积的类金刚石薄膜的面向及法向热导率. 对沉积过程的模拟表明, 薄膜密度及sp³杂化类型的碳原子所占比例均随沉积高度的增加而减小, 在碳原子以1 eV能量垂直入射的情况下, 在硅基底上沉积的薄膜密度约为2.8 g/cm³, sp³杂化类型的碳原子所占比例约为22%, 均低于碳在金刚石基底上沉积的情况. 采用Green-Kubo方法, 计算了所沉积类金刚石薄膜的热导率, 其面向热导率可以达到相同尺寸规则金刚石晶体的50%左右, 并且随着薄膜密度与sp³杂化类型碳原子所占比例的升高而升高.     

Low-temperature anisotropy of the thermal conductivity of single-crystal nanofilms and nanowires

The effect of phonon focusing on the phonon transport in single-crystal nanofilms and nanowires is studied in the boundary scattering regime. The dependences of the thermal conductivity and the free path of phonons on the geometric parameters of nanostructures with various elastic energy anisotropies are analyzed for diffuse phonon scattering by boundaries. It is shown that the anisotropies of thermal conductivity for nanostructures made of cubic crystals with positive (LiF, GaAs, Ge, Si, diamond, YAG) and negative (CaF₂, NaCl, YIG) anisotropies of the second-order elastic moduli are qualitatively different for both nanofilms and nanowires. The single-crystal film plane orientations and the heat flow directions that ensure the maximum or minimum thermal conductivity in a film plane are determined for the crystals of both types. The thermal conductivity of nanowires with a square cross section mainly depends on a heat flow direction, and the thermal conductivity of sufficiently wide nanofilms is substantially determined by a film plane orientation.     

Finite element analysis of three-dimensional laser-induced transient thermal grating in diamond/ZnSe system

This paper uses finite element method to obtain the three-dimensional temperature field of laser-induced transient thermal grating （TTG） for two-layered structure of diamond film on ZnSe substrate. The numerical results indicate that unique two-times heating process is gradually experienced in the area between two adjacent grating stripes. However, there is a little change for the temperature field along the depth direction for the diamond film due to its great thermal conductivity. It further finds that the thickness of the diamond film has a significant influence on the temperature field in diamond/ZnSe system. The results are useful for the application of laser-induced TTG technique in film/substrate system.     

Heat resistance of the interface in the silicon-on-diamond structure at a temperature of 80 K

Heat propagation at liquid nitrogen temperature in a heterostructure consisting of a polycrystalline diamond film deposited from hydrocarbon plasma on an oriented silicon substrate is studied. A technique for measuring the cooling kinetics of a thin-film indium thermometer deposited on a diamond film after heating by nanosecond pulses of a nitrogen laser is used. The experimental data are compared with the results calculated within the theory of heat conduction for multilayer systems. The analysis performedmade it possible to simultaneously determine the thermal conductivity of the diamond film and the interfacial heat resistance of diamond/Si and In/diamond interfaces at liquid nitrogen temperature.     

Investigation of the thermal conductivity of diamond film on aluminum nitride ceramic

Diamond films were successfully synthesized on aluminum nitride(AlN) ceramic substrates by hot-filament chemical vapor deposition (HFCVD) method. The thermal conductivity of the diamond film/aluminum nitride ceramic (DF/AlN) composites was studied by photothermal deflection (PTD) technique. It has reached 2.04 W/cm K, 73% greater than that of AlN ceramic. Compared with the measurement of scanning electron microscopy (SEM) and Raman spectroscopy, the influence of diamond films on the thermal conductivity of the composites was pointed out. The adhesion and the stresses were also studied. The unusual stability and very good adhesion of the diamond film on AlN ceramic substrate obtained is attributed to the formation of aluminum carbide. Received: 24 March 1998 / Accepted: 8 March 1999 / Published online: 5 May 1999     

金属与金刚石薄膜接触的电学特性研究

用热丝辅助化学汽相沉积技术在Si衬底上合成了含少量受主型杂质的近于本征的金刚石薄膜，并研究了三种金属（Cu，Ag和Al）与它接触的电学特性，以及退火对接触特性的影响．结果表明Cu，Ag与金刚石薄膜接触的电学特性比较类似，而Al则明显不同；而且退火对它们的接触特性影响很大 关键词：     

Particle size effect on thermal conductivity of AlN films with embedded diamond particles

Fabricating composite thin films is an effective and economic solution to improve the thermal performance of the films. The diamond particles of different sizes were successfully embedded in AlN thin films by a chemical solution approach, which was confirmed by scanning electron microscope, x-ray diffraction analysis and x-ray photoelectron spectroscopy. The thermal properties of the films embedded with different diamond particles were studied by using a 3-omega method, which was observed to be strongly dependent on the particle size. A 19 % enhancement in thermal conductivity can be achieved by embedding diamond particles of 1-μm radius in AlN thin films. However, the thermal conductivity decreases after embedding with 10-nm radius diamond particles. The results are discussed with high volume model, which confirms that the interface thermal resistance between the embedded materials and the films plays an important role in determining the thermal conductivity of the as-grown carbon material embedded AlN films.     

氮化硅纳米薄膜非平衡热导率实验研究

3ω实验方法是一种可以对薄膜热导率进行瞬时测量的方法。根据3ω方法测试原理,搭建了薄膜导热系数测试平台,并且分别测试低频率段和高频段薄膜与基底的温升以及薄膜热导率。测试结果表明:Si3N4薄膜的热导率随温度的升高而增大;高频段下,热导率受频率影响大,误差大;在低频段下薄膜热导率与频率变化基本无关;基于电子与声子的局部热平衡运输方程假设,S i3N4薄膜的热导率具有极度非平衡性;通过比较电阻、热导率与温度的关系可以看出加热器的尺寸大小会影响薄膜的热导率,最佳加热器的宽度选用20μm左右。     

Experimental and numerical study of the effect of conjugate heat transfer on film cooling

Combined convection heat transfer and thermal conduction for film cooling of a flat plate with 45° ribs on one wall was investigated experimentally and numerically. The flat plate surface temperature was measured using thermochromic liquid crystals. The results show that the film cooling is the main mechanism for the local cooling with a very low thermal conductivity while the convection heat transfer of the coolant in the coolant channel is the dominant heat transfer mechanism for the high thermal conductivity plate, with both film cooling and convection heat transfer by the coolant being important with medium thermal conductivity walls.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

Thermal conductivity of polycrystalline CVD diamond: Experiment and theory

The temperature dependences of thermal conductivity κ of polycrystalline CVD diamond are measured in the temperature range from 5 to 410 K. The diamond sample is annealed at temperatures sequentially increasing from 1550 to 1690°C to modify the properties of the intercrystallite contacts in it. As a result of annealing, the thermal conductivity decreases strongly at temperatures below 45 K, and its temperature dependence changes from approximately quadratic to cubic. At T > 45 K, the thermal conductivity remains almost unchanged upon annealing at temperatures up to 1650°C and decreases substantially at higher annealing temperatures. The experimental data are analyzed in terms of the Callaway theory of thermal conductivity [9], which takes into account the specific role of normal phonon-phonon scattering processes. The thermal conductivity is calculated with allowance for three-phonon scattering processes, the diffuse scattering by sample boundaries, the scattering by point and extended defects, the specular scattering by crystallite boundaries, and the scattering by intercrystallite contacts. A model that reproduces the main specific features of the thermal conductivity of CVD diamond is proposed. The phonon scattering by intercrystallite contacts plays a key role in this model.     

Influence of structural characteristics on the thermal conductivity of polycrystalline diamond films

By analyzing the signal formed by the photoacoustic effect as a function of the light modulation frequency, it is shown that this effect may be used to determine the thermal conductivity of diamond materials. The method is checked experimentally for two types of polycrystalline diamond films grown by chemical vapor deposition with the gaseous medium activated by a dc discharge and a microwave discharge. The data obtained on the thermal conductivity of the films are discussed with reference to the results of an investigation of the optical absorption, Raman light scattering, and cathodoluminescence of similar films. It is shown that the thermal conductivity of polycrystalline diamond films depends on the structural characteristics, which are determined by the deposition conditions. Fiz. Tverd. Tela (St. Petersburg) 40, 1221–1225 (July 1998)     

Considerable increase in thermal conductivity of a polycrystalline CVD diamond upon isotope enrichment

We measured the temperature dependence of thermal conductivity of a polycrystalline CVD diamond with natural isotope composition and an isotope enriched (99.96% ¹²C) sample at temperatures from 5 to 420 K. The isotope enriched diamond demonstrates a considerable growth of thermal conductivity at temperatures above 80 K compared to the diamond with natural composition of isotopes. At room temperature the thermal conductivity reaches 24.3 W·cm^?1K^?1, and the isotope effect makes up not less than 34%.