退火温度对硼掺杂纳米金刚石薄膜微结构和p型导电性能的影响

采用热丝化学气相沉积法制备硼掺杂纳米金刚石 (BDND) 薄膜, 并对薄膜进行真空退火处理, 系统研究退火温度对BDND薄膜微结构和电学性能的影响. Hall效应测试结果表明掺B浓度为5000 ppm (NHB) 的样品的电阻率较掺B浓度为500 ppm (NLB) 的样品的低, 载流子浓度高, Hall迁移率下降. 1000 ℃退火后, NLB和NHB 样品的迁移率分别为53.3和39.3 cm²·V^-1·s^-1, 薄膜的迁移率较未退火样品提高, 电阻率降低. 高分辨透射电镜、紫外和可见光拉曼光谱测试结果表明, NLB样品的金刚石相含量较NHB样品高, 高的硼掺杂浓度使薄膜中的金刚石晶粒产生较大的晶格畸变. 经1000 ℃退火后, NLB和NHB薄膜中纳米金刚石相含量较未退火时增大, 说明薄膜中部分非晶碳转变为金刚石相, 为晶界上B扩散到纳米金刚石晶粒中提供了机会, 使得纳米金刚石晶粒中B浓度提高, 增强纳米金刚石晶粒的导电能力, 提高薄膜电学性能. 1000 ℃退火能够恢复纳米金刚石晶粒的晶格完整性, 减小由掺杂引起的内应力, 从而提高薄膜的电学性能. 可见光Raman光谱测试结果表明, 1000℃退火后, Raman谱图中反式聚乙炔 (TPA) 的1140 cm^-1峰消失, 此时薄膜电学性能较好, 说明TPA减少有利于提高薄膜的电学性能. 退火后金刚石相含量的增大、金刚石晶粒的完整性提高及TPA含量的大量减少有利于提高薄膜的电学性能. 关键词： 硼掺杂纳米金刚石薄膜 退火 微结构 电学性能     

热灯丝CVD金刚石膜硼掺杂效应研究

利用Ｒａｍａｎ谱和Ｘ射线衍射微分析研究了金刚石膜硼掺杂效应．研究发现，在硼浓度较低时，金刚石膜中非晶碳（Ｓｐ²键合）含量减少，而随着硼浓度增加，金刚石膜的Ｒａｍａｎ特征峰（Ｓｐ^３）向低频方向漂移，并且展宽和出现不对称．这是由于硼掺杂引起晶格变化及Ｆａｎｏ互作用所致 关键词：     

Electron-phonon interaction via electronic and lattice Wannier functions: superconductivity in boron-doped diamond reexamined

We present a first-principles technique for investigating the electron-phonon interaction with millions of k points in the Brillouin zone, which exploits the spatial localization of electronic and lattice Wannier functions. We demonstrate the effectiveness of our technique by elucidating the phonon mechanism responsible for superconductivity in boron-doped diamond. Our calculated phonon self-energy and Eliashberg spectral function show that superconductivity cannot be explained without taking into account the finite-wave-vector Fourier components of the vibrational modes introduced by boron, as well as the breaking of the diamond crystal periodicity induced by doping.     

Synthesis and characterizations of boron and nitrogen co-doped high pressure and high temperature large single-crystal diamonds with increased mobility

We synthesized and investigated the boron-doped and boron/nitrogen co-doped large single-crystal diamonds grown under high pressure and high temperature (HPHT) conditions (5.9 GPa and 1290℃). The optical and electrical properties and surface characterization of the synthetic diamonds were observed and studied. Incorporation of nitrogen significantly changed the growth trace on surface of boron-containing diamonds. X-ray photoelectron spectroscopy (XPS) measurements showed good evident that nitrogen atoms successfully incorporate into the boron-rich diamond lattice and bond with carbon atoms. Raman spectra showed differences on the as-grown surfaces and interior between boron-doped and boron/nitrogen co-doped diamonds. Fourier transform infrared spectroscopy (FTIR) measurements indicated that the nitrogen incorporation significantly decreases the boron acceptor concentration in diamonds. Hall measurements at room temperature showed that the carriers concentration of the co-doped diamonds decreases, and the mobility increases obviously. The highest hole mobility of sample BNDD-1 reached 980 cm²·V^-1·s^-1, possible reasons were discussed in the paper.     

Boron distribution in the subsurface region of heavily doped IIb type diamond

For the first time investigations of the boron distribution in the subsurface region of HPHT boron-doped diamond that is promising for applications in electronics were carried out by X-ray photoelectron (XPS) and Raman spectroscopy. It was found from XPS data that the boron content decreased gradually more than one order of magnitude in depth of surface. The first-principle calculations have shown that the Raman polarizability in the crossed polarization configuration should increase considerably with boron doping. The Raman spectra from as-grown and polished surfaces of heavily boron-doped diamond are discussed in the context of theoretical results.     

Ohmic and Schottky contacts of hydrogenated and oxygenated boron-doped single-crystal diamond with hill-like polycrystalline grains

Hill-like polycrystalline diamond grains(HPDGs) randomly emerged on a heavy boron-doped p~+ single-crystal diamond(SCD) film by prolonging the growth duration of the chemical vapor deposition process.The Raman spectral results confirm that a relatively higher boron concentration(～1.1 × 10~(21) cm~(-3)) is detected on the HPDG with respect to the SCD region(～5.4 × 10~(20) cm~(-3)).It demonstrates that the Au/SCD interface can be modulated from ohmic to Schottky contact by varying the surface from hydrogen to oxygen termination.The current-voltage curve between two HPDGs is nearly linear with either oxygen or hydrogen termination,which means that the HPDGs provide a leakage path to form an ohmic contact.There are obvious rectification characteristics between oxygen-terminated HPDGs and SCD based on the difference in boron doping levels in those regions.The results reveal that the highly boron-doped HPDGs grown in SCD can be adopted as ohmic electrodes for Hall measurement and electronic devices.     

Dependence of reaction pressure on deposition and properties of boron-doped freestanding diamond films

In this paper, we investigate the reaction pressure-dependent growth and properties of boron-doped freestanding diamond films, synthesized by hot filament chemical vapor deposition (HFCVD) at different boron-doping levels. With the decrease in pressure, the growth feature of the films varies from mixed [1 1 1] and [1 1 0] to dominated [1 1 1] texture. The low reaction pressure, as well as high boron-doping level, results in the increase (decrease) of carrier concentration (resistivity). The high concentration of atomic hydrogen in the ambient and preferable [1 1 1] growth, due to the low reaction pressure, is available for the enhancement of boron doping. The estimated residual stress increases with increase in the introducing boron level.     

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。     

Study of polycrystalline boron-doped diamond films by Raman spectroscopy and optical absorption spectroscopy

The effect of the degree of doping polycrystalline diamond films by boron on their Raman and absorption spectra has been studied in the visible region (from 200 to 1000 nm). As the boron concentration increases in a polycrystalline diamond film, its Raman spectrum exhibits a number of new specific features caused by the effect of boron atoms on the diamond lattice. The dependences that relate these features to the boron concentration in the films are given. Moreover, the absorption spectra of the films have revealed a peak whose maximum corresponds to photons with an energy near 2 eV.     

A molecular dynamics study of boron and nitrogen in diamond

Based upon molecular dynamics simulation via the Tersoff many-body potential, we proposed the co-doping method for fabricating n-type diamond. We calculated the optimal co-doping configurations of n-type (nitrogen) and p-type (boron) dopants, the stable structure of a boron atom in diamond is associated with four nitrogen atoms placed at the nearest neighbour positions, the total energy of the system with the stable structure is 136 MeV lower than that of the system with the nitrogen atoms placed in others positions. The results indicated that the co-dopants of nitrogen and boron were the perfect candidates to make n-type diamond, and additional boron would increase the solubility limit of nitrogen in diamond, reduce the lattice-relaxation energy of crystal and improve its doping efficiency in diamond.     

Effect of pressure on the Raman spectra of synthetic diamonds with boron impurity

The raman scattering technique is used for studying diamonds with a 0.04–0.1 at % boron impurity under a pressure up to 3 GPa in a chamber with sapphire anvils. The Raman frequency increases linearly with pressure for all samples with pressure coefficients of 2.947 cm^?1/GPa for pure diamond and 3.01 cm^?1/GPa for boron-doped samples. The Raman linewidths remain unchanged for pure diamond and for diamond with a boron concentration of about 0.04 at % and decrease linearly upon an increase in pressure for samples with a boron concentration of about 0.1 at %. The Raman spectra with a line profile corresponding to the Fano resonance do not change qualitatively up to a pressure of 3 GPa. In diamond samples with a boron impurity exceeding 0.1 at %, the boron concentration in the surface layer can be substantially higher than at the center of the sample.     

Influence of boron carbide on properties of CVD-diamond thin films at various deposition pressures

Microcrystalline boron-doped diamond (BDD) films are synthesized on the silicon substrate by the hot-filament chemical vapor deposition method under the gas mixture of hydrogen and methane in the presence of boron carbide (B₄C) placed in front of filaments. The observed results of scanning electron microscopy, Raman spectroscopy and X-ray diffraction show the morphologies. Microstructures for various deposition pressures of as-grown diamond films are found to be dependent on the change of deposition pressure. These results reveal that with the increase of deposition pressure, resistivity decreases and increase in the grain size is noted in the presence of B₄C. Resistivity shows a sudden fall of about three orders of magnitude by the addition of boron in the diamond films. This is due to the crystal integrity induced by B-atoms in the structure of diamond in the presence of B₄C. These results are also significant for the conventional applications of BDD materials. The effects of deposition pressure on the overall films morphology and the doping level dependence of the diamond films have also been discussed.     

葡萄糖掺杂MgB_2块材超导电性研究

本文采用化学溶液法制备了在不同热处理条件下葡萄糖掺杂的MgB2块材样品.并对样品的晶体结构及超导电性进行了系统分析.X射线衍射结果表明掺杂样品a轴方向上的晶格参数减小,说明MgB2晶格中部分硼原子被葡萄糖分解后的活性碳原子所替代.此外,在两种不同烧结温度下,5wt%C6H12O6掺杂量对Tc都有较小的抑制,但不可逆场和高场下的载流能力得到了提高.在10K,5T下,掺杂样品的临界电流密度可达104A/cm2,比纯样Jc值大2～3倍,这表明掺杂样品的磁通钉扎性能得到了有效改善.     

Variable range hopping conduction and percolation networks in the pellets formed from pristine and boron-doped carbon nanohorn particles

Resistivity of pelletized carbon nanohorn particles (CNHs) decreased immediately as the pressure for making the pellet increased. This behavior can be fitted by a power scaling relation with quasi-2-dimensional percolating conducting channels. Similarly, the resistivity of a pelletized boron-doped CNHs (B-CNHs) also decreased rapidly as a function of boron concentration in the region of low boron contents (<∼0.5%). On the other hand, the characteristic temperature for variable range hopping (VRH) conduction indicated different behavior, showing almost constant values for pristine CNHs and drastic changes for B-CNHs. By analyzing these experimental results using VRH theory it was found that the resistivity drop for B-CNHs can be explained by the increase of the electronic density of states at the Fermi level of nanohorns due to substitutional doping of boron in the sp² bonded carbon network which is unlike the percolation for pristine CNHs.     

Molecular dynamics simulation on boron diffusion in diamond

The atomic-scale diffusion mechanism of boron in diamond is investigated by molecular dynamics simulation. A substitutional boron atom diffuses to the self-interstitial site when there exists a self-interstitial carbon atom in its nearest tetrahedral center and the system temperature is high. More important, the bond between boron and the self-interstitial carbon atom is never broken during the diffusion process, indicating that B_s-C_i pairs diffuse in the lattice by the interstitial mechanism. The results suggest that boron diffusion is mediated by carbon self-interstitial and not by the vacancy mechanism. In addition, the estimated activation energy and the diffusion exponential prefactor of boron diffusion in diamond are found to be 0.23 eV and 1.123×10⁻⁶cm²/s, respectively.     

Electrical properties of boron-doped diamond-like carbon thin films deposited by femtosecond pulsed laser ablation

We report on electrical measurements and structural characterization performed on boron-doped diamond-like carbon thin films deposited by femtosecond pulsed laser deposition. The resistance has been measured between 77 and 300 K using four probe technique on platinum contacts for different boron doping. Different behaviours of the resistance versus temperature have been evidenced between pure DLC and boron-doped DLC. The a-C:B thin film resistances exhibit Mott variable range hopping signature with temperature. Potential applications of DLC thin films to highly sensitive resistive thermometry is going to be discussed.     

掺杂CVD金刚石薄膜的应力分析

在不同实验条件下，用微波等离子体化学气相沉积(MPCVD)技术在Si基体上制备了S掺杂和B-S共掺杂CVD金刚石薄膜，利用X射线衍射仪和拉曼光谱仪研究掺杂对CVD金刚石薄膜的应力影响.研究结果发现，随着S掺杂浓度的增加，薄膜中sp²杂化碳含量和缺陷增多，CVD金刚石薄膜压应力增加；小尺寸的B原子与大尺寸的S原子共掺杂时，微量B的加入改变了CVD金刚石薄膜的应力状态，共掺杂形成B-S复合体进入金刚石晶体后降低金刚石晶体的晶格畸变程度，减少S原子在晶界上偏聚数量和晶体中非金刚石结构相含量，降低由于杂质、缺陷及sp²杂化碳含量产生的晶格畸变和薄膜压应力，提高晶格完整性. 关键词： 金刚石薄膜 掺杂 应力     

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.     

Substitution Effects on MgB2 Superconductivity

With the help of supercell method, the first-principle calculations were performed for the study of doping crystal Mg_1-xAl_xB₂ and Mg(B_1-yC_y)₂. Analyzing the variations of the charge distribution and the partial densities of states, we found that the compounds with doping Al to MgB₂ compound and/or replacing boron by carbon exhibit new covalent bond effects and unexpected electronic properties, related to superconductivity. The study of the density of states indicates that superconductivity decreases with the increase of Al fraction and carbon concentration. There exists a transition of superconductor to non-superconductor with the change of Al doping fraction. The substitution of boron by carbon results in the decrease of the transition temperature since the decrease of the electron concentration and the lattice constant. The theoretical predictions agree with experimental observations.     

Effect of oxygen on regulation of properties of moderately boron-doped diamond films

Regulation of oxygen on properties of moderately boron-doped diamond films is fully investigated. Results show that, with adding a small amount of oxygen (oxygen-to-carbon ratio < 5.0%), the crystal quality of diamond is improved, and a suppression effect of residual nitrogen is observed. With increasing ratio of O/C from 2.5% to 20.0%, the hole concentration is firstly increased then reduced. This change of hole concentration is also explained. Moreover, the results of Hall effect measurement with temperatures from 300 K to 825 K show that, with adding a small amount of oxygen, boron and oxygen complex structures (especially B₃O and B₄O) are formed and exhibit as shallow donor in diamond, which results in increase of donor concentration. With further increase of ratio of O/C, the inhibitory behaviors of oxygen on boron leads to decrease of acceptor concentration (the optical emission spectroscopy has shown that it is decreased with ratio of O/C more than 10.0%). This work demonstrates that oxygen-doping induced increasement of the crystalline and surface quality could be restored by the co-doping with oxygen. The technique could achieve boron-doped diamond films with both high quality and acceptable hole concentration, which is applicable to electronic level of usage.