Synthesis and characterization of p-type boron-doped IIb diamond large single crystals

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K.The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively.The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique.The electrical properties including resistivities,Hall coefficients,Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method.The results show that large p-type boron-doped diamond single crystals with few nitrogen impurities have been synthesized.With the increase of quantity of additive boron,some high-index crystal faces such as {113} gradually disappear,and some stripes and triangle pits occur on the crystal surface.This work is helpful for the further research and application of boron-doped semiconductor diamond.     

Two-dimensional phonon transport in graphene

Properties of phonons-quanta of the crystal lattice vibrations-in graphene have recently attracted significant attention from the physics and engineering communities. Acoustic phonons are the main heat carriers in graphene near room temperature, while optical phonons are used for counting the number of atomic planes in Raman experiments with few-layer graphene. It was shown both theoretically and experimentally that transport properties of phonons, i.e. energy dispersion and scattering rates, are substantially different in a quasi-two-dimensional system such as graphene compared to the basal planes in graphite or three-dimensional bulk crystals. The unique nature of two-dimensional phonon transport translates into unusual heat conduction in graphene and related materials. In this review, we outline different theoretical approaches developed for phonon transport in graphene, discuss contributions of the in-plane and cross-plane phonon modes, and provide comparison with available experimental thermal conductivity data. Particular attention is given to analysis of recent results for the phonon thermal conductivity of single-layer graphene and few-layer graphene, and the effects of the strain, defects, and isotopes on phonon transport in these systems.     

Thermal conductivity reduction and thermoelectric figure of merit increase by embedding nanoparticles in crystalline semiconductors

Atomic substitution in alloys can efficiently scatter phonons, thereby reducing the thermal conductivity in crystalline solids to the "alloy limit." Using In0.53Ga0.47As containing ErAs nanoparticles, we demonstrate thermal conductivity reduction by almost a factor of 2 below the alloy limit and a corresponding increase in the thermoelectric figure of merit by a factor of 2. A theoretical model suggests that while point defects in alloys efficiently scatter short-wavelength phonons, the ErAs nanoparticles provide an additional scattering mechanism for the mid-to-long-wavelength phonons.     

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.     

Hetero-Epitaxial Diamond Single Crystal Growth on Surface of cBN Single Crystals at High Pressure and High Temperature

We report a new diamond synthesis process in which cubic boron nitride single crystals are used as seeds, FesoNi20 alloy powder is used as catalyst/solvent and natural flake-like graphite is used as the carbon source. The samples are investigated using laser Raman spectra and x-ray diffraction （XRD）. Morphology of the sample is observed by a scanning electron microscope （SEM）. Based on the measurement results, we conclude that diamond single crystals have grown on the cBN crystal seeds under the conditions of high temperature 1230℃ and high pressure 4.8 GPa. This work provides an original method for synthesis of high quality hereto-semiconductor with cBN and diamond single crystals, and paves the way for future development.     

Heat transfer in solid HD at low temperatures

The lattice thermal conductivity of solid HD has been calculated in the temperature range 0.2–4°K. The important scatterers of phonons are found to be boundary walls of the crystal, isotopic impurities, phonons and molecules of ortho hydrogen and para deuterium. The presence of molecules of ortho hydrogen and para deuterium in solid HD which act as rotational impurities, are responsible for one and two phonon scattering processes in the system. The entire study is based on the Callaway model of the lattice thermal conductivity of an insulator. Excellent agreement is found between calculated and experimental values of phonon conductivity. The extra lattice thermal resistivity due to the presence of the ortho hydrogen and para deuterium is also calculated.     

籽晶尺寸对宝石级金刚石单晶生长的影响

本文在国产六面顶压机上,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用边长0.8, 1.5和2.2 mm三种尺寸的籽晶,系统开展了Ib型宝石级金刚石单晶的生长研究.文中系统考察了籽晶尺寸对宝石级金刚石单晶生长的影响.首先,考察了籽晶尺寸变化对宝石级金刚石单晶裂晶问题带来的影响.研究得到了籽晶尺寸变大,裂晶出现概率增加的晶体生长规律.其次,在25 h的生长时间内,考察了上述三种尺寸籽晶生长金刚石单晶时,生长时间与单晶极限生长速度的关系.得到了选用大尺寸籽晶,可以提高优质单晶合成效率、降低合成成本的研究结论.借助扫描电子显微镜和光学显微镜,对三种尺寸籽晶生长金刚石单晶的表面形貌进行了标定.最后,傅里叶微区红外测试,对三种尺寸籽晶生长宝石级金刚石单晶的N杂质含量进行了表征.研究得到了选用大尺寸籽晶实现快速生长金刚石的同时,晶体的N杂质含量会随之升高的晶体生长规律.     

The mechanism of Landau-Rumer relaxation of thermal and high-frequency phonons in cubic crystals of germanium,silicon, and diamond

Transverse phonon relaxation according to the Landau-Rumer mechanism is considered for an isotropic medium and crystals of germanium, silicon, and diamond possessing a cubic symmetry. The energy of elastic deformation caused by the anharmonicity of vibrations of the cubic crystal lattice is expressed via the second-and third-order moduli of elasticity. Using the known values of these elastic moduli, parameters determining the frequencies of the transverse phonon relaxation in the Landau-Rumer mechanism are evaluated for the germanium, silicon, and diamond crystals. It is shown that the dependence of the relaxation frequency on the wavevector of thermal and high-frequency phonons sharply differs from the classical Landau-Rumer relationship both in the isotropic medium and in the cubic crystals. It is established that the observed peculiarities in the relaxation frequency are related to the angular dependence of the probability of anharmonic scattering and the anisotropy of elastic properties of the germanium, silicon, and diamond crystals. A new method is proposed for the experimental determination of the relaxation frequency of high-frequency phonons as a function of the wavevector using the temperature dependence of the coefficient of absorption of high-frequency ultrasound.     

硼掺入量对含硼金刚石单晶热稳定性的影响

 在铁基触媒原材料中添加不同含量的六方氮化硼,采用粉末冶金方法制备片状触媒,在六面顶压机上合成出含硼金刚石单晶。用体视显微镜对金刚石单晶的结构、形貌进行观察,并用电子探针（EPMA）和波谱仪（WDS）分析了金刚石（111）晶面的硼含量,发现金刚石表面有硼元素存在,且其含量随着触媒中掺硼量的增加而变化。在测定了含硼金刚石单晶的静压强度的基础上,采用冲击韧性测定仪和差热分析仪对不同掺硼量触媒合成出的金刚石单晶在空气中的热稳定性进行了系统的对比研究。结果表明,触媒掺硼量对金刚石的机械强度和热稳定性有重要影响,随着掺硼量的变化,其机械强度和热稳定性均存在一个最佳值。     

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     

Synergistic influences of titanium,boron, and oxygen on large-size single-crystal diamond growth at high pressure and high temperature

The synergistic influences of boron, oxygen, and titanium on growing large single-crystal diamonds are studied using different concentrations of B₂O₃ in a solvent-carbon system under 5.5 GPa-5.7 GPa and 1300 ℃-1500 ℃. It is found that the boron atoms are difficult to enter into the crystal when boron and oxygen impurities are doped using B₂O₃ without the addition of Ti atoms. However, high boron content is achieved in the doped diamonds that were synthesized with the addition of Ti. Additionally, boron-oxygen complexes are found on the surface of the crystal, and oxygen-related impurities appear in the crystal interior when Ti atoms are added into the FeNi-C system. The results show that the introduction of Ti atoms into the synthesis cavity can effectively control the number of boron atoms and the number of oxygen atoms in the crystal. This has important scientific significance not only for understanding the synergistic influence of boron, oxygen, and titanium atoms on the growth of diamond in the earth, but also for preparing the high-concentration boron or oxygen containing semiconductor diamond technologies.     

透明硼皮金刚石的高压合成研究

 本文根据硼皮金刚石的理论模型，采用石墨中掺微量硼的方法，控制人造金刚石中的硼含量与分布，用高压合成出一种含微量硼元素的淡黄色透明的硼皮金刚石。这种新型金刚石具有强度高，耐热性好的特性，其抗氧化性能比一般黄金刚石约高200 ℃，其耐热性与强度也比一般含硼量高的黑金刚石高。     

A low frequency Raman-active vibration of hexagonal boron nitride

Raman spectra of single crystals and powder of hexagonal boron nitride have been measured at room temperature. Two Raman lines due to phonons of 52.5 and 1366 cm^-1 were observed. The 52.5 cm^-1 line, observed for the first time, has been attributed to the shear-type rigid layer mode of the crystal. The force constants related with the vibrations of these modes and their anisotropy are compared with those of graphite.     

On the role played by bending vibrations in heat transfer in layered crystals

The temperature dependences of the thermal conductivity of layered crystals (LCs) of graphite, boron nitride, gallium sulfide, etc., are analyzed. It is shown that the bending branch of vibrations typical of LCs determines the behavior of the thermal conductivity only in the region of its increase. The decrease in thermal conductivity upon heating cannot be explained by taking into account the bending vibrations only, and phonon-phonon interaction processes become effective only in the case of excitation of other branches in the acoustic spectrum.     

高温高压下掺硼宝石级金刚石单晶生长特性的研究

本文在5.1—5.6 GPa,1230—1600℃的压力、温度条件下,以FeNiMnCo作为触媒,进行单质硼添加宝石级金刚石单晶的生长研究.借助于有限元法,对触媒内的温度场进行模拟.研究得到了FeNiMnCo-C-B体系下,金刚石单晶生长的P-T相图.该体系下合成金刚石单晶的最低压力、温度条件分别为5.1 GPa,1230℃左右.研究发现,在单晶同一{111}扇区内部,硼元素呈内多外少的分布规律.有限元模拟结果给出,该分布规律是由在晶体生长过程中,{111}扇区的增长速度逐渐减小所致.{111}晶向的晶体生长实验结果表明,硼元素优先从{111}次扇区进入晶体.研究发现,这是该扇区增长速度相对较快,硼元素扩散逃离可用时间短导致的.另外,同磨料级掺硼金刚石单晶生长相比,对于温度梯度法生长掺硼宝石级金刚石单晶,由于晶体的增厚速度较慢,即使硼添加量相对较高,也可以实现表面无凹坑缺陷的优质金刚石单晶的生长.     

降温工艺对宝石级金刚石单晶品质的影响

在国产六面顶压机上,采用温度梯度法,在5.6 GPa,1200—1400?C的高压高温条件下,裂晶问题频繁出现的合成周期内,围绕裂晶现象开展了Ib型宝石级金刚石单晶的生长研究,系统考察了降温工艺对宝石级金刚石单晶品质的影响.针对宝石级金刚石单晶常见的裂纹缺陷,借助于扫描电子显微镜,分别对优质金刚石单晶和存在裂纹金刚石单晶的表面形貌进行了表征;利用微区傅里叶转换红外光谱测试手段,对上述两类晶体的N杂质含量分别进行了测试,依据测试结果,对裂晶出现的原因进行了分析;分别采用传统断电降温和缓慢降温工艺,考察了晶体生长结束后的降温工艺对宝石级金刚石单晶品质的影响.结果表明,缓慢降温工艺在很大程度上可以有效抑制裂晶问题出现.另外,从宝石级金刚石单晶品质和单晶受到的外应力两个方面着手,分别对裂晶出现的机理和采用缓慢降温工艺有效解决裂晶问题的机理进行了讨论.     

Effect of dispersion on the phonon focusing and anisotropy of thermal conductivity of silicon single crystals in the boundary scattering regime

The effect of dispersion on the focusing of thermal phonons and on the thermal conductivity of silicon single crystals in the boundary scattering regime has been investigated. Analysis of the spectra of acoustic modes obtained for silicon single crystals from inelastic neutron scattering data has demonstrated that, upon transition from long-wavelength phonons to short-wavelength phonons, the directions of their focusing change. With an increase in temperature, this leads to a change in the anisotropy of thermal conductivity of phonons with different polarizations and, consequently, to a change in the anisotropy of the total thermal conductivity. Analysis of the temperature dependence of the thermal conductivity has revealed that the presence of extended flattened sections in the spectrum of short-wavelength transverse phonons indicates anomalously low values of the group velocity and, accordingly, a significant decrease in the contribution from these phonons to the thermal conductivity with increasing temperature. The contribution from longitudinal phonons to the thermal conductivity also significantly increases even at temperatures higher than 110 K and becomes dominant.     

Isotopic phonon effects in β-rhombohedral boron--non-statistical isotope distribution

On the basis of the spectra of IR- and Raman-active phonons, the isotopic phonon effects in β-rhombohedral boron are analysed for polycrystalline (10)B- and (11)B-enriched samples of different origin and high-purity (nat)B single crystals. Intra- and inter-icosahedral B-B vibrations are harmonic, hence meeting the virtual crystal approximation (VCA) requirements. Deviations from the phonon shift expected according to the VCA are attributed to the anharmonic share of the lattice vibrations. In the case of icosahedral vibrations, the agreement with calculations on α-rhombohedral boron by Shirai and Katayama-Yoshida is quite satisfactory. Phonon shifts due to isotopic disorder in (nat)B are separated and determined. Some phonon frequencies are sensitive to impurities. The isotopic phonon effects yield valuable specific information on the nature of the different phonon modes. The occupation of regular boron sites by isotopes deviates significantly from the random distribution.     

高能氮离子注入人造金刚石的热稳定性

 叙述了在GLZ-100E工业离子注入机上采用20~60 keV氮离子及氮分子离子注入人造金刚石晶体的实验研究。XPS分析表明，注入离子在人造金刚石颗粒表面形成了一层较为稳定的含氮混合物层。高温差热分析（DTA）的实验表明，经氮离子束处理的金刚石，其氧化起始温度T（onset）由原来的730 ℃左右提高到800 ℃以上，且随着氮注入剂量的增加而增加，氧化速度也随之变缓；差热分析还表明，随着温度的升高，金刚石首先转化为石墨（DTA曲线上表现为吸热），然后氧化燃烧生成CO₂（放热），而注入离子能量的增加，氧化温度的提高幅度略有下降。离子注入还使其高温石墨化性能显著改善。