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.     

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     

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.     

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.     

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。     

考虑Stefan影响的单颗粒硼着火过程研究

针对含硼推进剂固体火箭冲压发动机内单颗粒硼的着火过程展开了系统研究. 考虑硼颗粒周围气相流动以及硼颗粒与周围环境间的传热传质过程, 建立了考虑Stefan流作用的一维硼颗粒着火模型, 研究了硼颗粒实现着火和未能实现着火两种典型情形下硼颗粒及周围气相的参数变化规律, 对两种情形下Stefan流的变化规律及其成因展开了详细分析. 研究表明, 在硼颗粒实现着火的过程中, 液态B₂O₃的蒸发及硼的 氧化均能在硼颗粒的反应自加热作用下急剧加速, 硼颗粒表面附近的氧气和气相B₂O₃分布变化剧烈; 在未能实现着火的过程中, 液态B₂O₃的蒸发和氧气消耗的质量流率相对较小, 并逐渐趋于稳定, 硼颗粒表面附近的氧气和气相B₂O₃分布相对变化很小.在两种典型情形下, 硼颗粒外表面的Stefan流都会经历先由周围空间流向颗粒表面, 而后变为由颗粒表面流向周围空间的过程. 关键词： 固体火箭冲压发动机 硼颗粒 着火过程 Stefan流     

The effect of boron ion implantation and annealing on the microstructure and electrical characteristics of the diamond films

Diamond films were doped by boron ion-implantation with the energy of 120 keV. The implantation dose ranged from 10¹⁴ to 10¹⁷ cm⁻². After the implantation, the diamond films were annealed at different temperatures (600–750°C) for different times (2–15 min). Scanning Electronic Microscope, Raman and Secondary Ion Mass-spectrum were used to investigate the effect of boron ion implantation and annealing on the microstructure of the diamond films. The electrical resistivities of the diamond films were also measured. It was found that the best dose of boron ion-implantation into the diamond film was around 10¹⁶ cm⁻². The appropriate annealing temperature and time was 700°C and 2–5 min, respectively. After implantation, the resistivities were reduced to 0.1 Ω cm (almost nine orders lower than the unimplanted diamond films). These results show that boron ion implantation can be an effective way to fabricate P-type diamond films.     

高气压MPCVD沉积金刚石的光谱研究

采用微波等离子体化学气相沉积方法(microwave plasma chemical vapor deposition, MPCVD)在高沉积气压(34.5 kPa)下制备多晶金刚石,利用发射光谱(optical emission spectroscopy, OES)在线诊断了CH₄/H₂/O₂等离子体内基团的谱线强度及其空间分布,并利用拉曼(Raman)光谱评价了不同O₂体积分数下沉积出的金刚石膜质量,研究了金刚石膜质量的均匀性分布问题。结果表明：随着O₂体积分数的增加,C₂, CH及H_α基团的谱线强度均呈下降的趋势,而C₂,CH与H_α谱线强度比值也随之下降,表明增加O₂体积分数不仅导致等离子体中碳源基团的绝对浓度下降,而且碳源基团相对于氢原子的相对浓度也降低,使得金刚石的沉积速率下降而沉积质量提高。此外,具有刻蚀作用的OH基团的谱线强度却随着O₂体积分数的增加而上升,这也有利于降低金刚石膜中非晶碳的含量。光谱空间诊断发现高沉积气压下等离子体内基团分布不均匀,特别是中心区域C₂基团聚集造成该区域内非晶碳含量增加,最终导致金刚石膜质量分布的不均匀。     

铁基触媒中碳化硼含量对含硼金刚石单晶表观活化能的影响

通过在铁基触媒中添加适量的碳化硼,制备出了具有不同硼含量的含硼金刚石单晶。利用差热分析仪,测量了含硼金刚石单晶的差热和热重。采用Kissinger方法,计算了含硼金刚石单晶在加热过程中发生氧化反应的表观活化能,对比分析掺硼量对含硼金刚石单晶热稳定性的影响。结果表明:差热和热重测量值与表观活化能计算值的变化规律基本一致;随着掺硼量的增加,含硼金刚石单晶的热稳定性先提高后降低,剧烈氧化时表观活化能随着掺硼量的增加而减小。     

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.     

Graphite–boron composite heater in a Kawai-type apparatus: the inhibitory effect of boron oxide and countermeasures

We have investigated the performance of a graphite–boron composite (GBC) with 3?wt % boron as a precursor for a boron-doped diamond heater in a Kawai-type apparatus at 15?GPa. We first tested a machinable cylinder of GBC sintered at 1000°C in Ar/H₂ gas (99:1 molar ratio). Boron oxide (B₂O₃) formed during sintering frequently hindered the GBC heater from stable operation at temperatures higher than 1400°C by producing melt throughout the heater together with oxide and/or silicates. We then rinsed the GBC heater in hydrochloric acid to remove B₂O₃. After rinsing, we succeeded in stably generating temperatures higher than 2000°C. We also improved a molding process of different-sized GBC tubes for convenient use and tested the molded GBC heater. It was free from the B₂O₃ problem. The electromotive force of the W/Re thermocouple was successfully monitored up to 2400°C.     

Ground-state properties of boron-doped diamond

Boron-doped diamond undergoes an insulator-metal or even a superconducting transition at some critical value of the dopant concentration. We study the equilibrium lattice parameter and bulk modulus of boron-doped diamond experimentally and in the framework of the density functional method for different levels of boron doping. We theoretically consider the possibility for the boron atoms to occupy both substitutional and interstitial positions and investigate their influence on the electronic structure of the material. The data suggest that boron softens the lattice, but softening due to substitutions of carbon with boron is much weaker than due to incorporation of boron into interstitial positions. Theoretical results obtained for substitution of carbon are in very good agreement with our experiment. We present a concentration dependence of the lattice parameter in boron-doped diamond, which can be used for to identify the levels of boron doping in future experiments. The text was submitted by the authors in English.     

Photoemission from diamond and fullerene films for advancedaccelerator applications

The photoemission properties of thin diamond and fullerene films were investigated for advanced accelerator applications, using subpicosecond laser pulses at three different wavelengths (650, 325, and 217 nm). The quantum efficiency (QE) obtained at 217 nm with a boron-doped, p-type, (111) polycrystalline diamond film (2.6·10 ^-4) was only five times smaller than the QE obtained with a mirror polished copper sample (1.3·10^-3) but more than nine times larger than the QE obtained with a pure diamond film or with natural diamond monocrystals. Similar results were obtained for the two-photon electron yields at 325 mm. The electron yields obtained with pure fullerene films were small and comparable to the ones observed with the pure diamond samples. With 650 mn pulses, the damage threshold of the (110) Type IIa natural diamond monocrystal (9.38·10⁴ μJ cm^-2), defined here as the fluence leading to an onset of ion emission, was 25 times larger than the damage threshold for a copper sample (3.75·10³ μJ cm^-2). The damage threshold of the boron-doped sample at the same wavelength was two times larger than that of copper. Damage thresholds with 325 nm pulses were lower, and with 217 mn pulses ion emission was observed at all fluences probably attributed to ablation of surface hydrocarbon contaminants. Results show that high-quality high-boron concentration diamond films could be a good candidate for high-RF electron guns     

铝基碳化硼材料中子屏蔽性能的蒙特卡罗模拟

采用蒙特卡罗方法, 运用MCNP4C程序研究了碳化硼含量20%–40%、中子能量200 eV–15 keV、材料厚度0.3–2 cm对B₄C/Al复合材料中子屏蔽性能的影响. 结果表明: 碳化硼含量与中子透射系数呈一次线性下降关系; 同含量的碳化硼, B₄C/Al材料的中子屏蔽效果要大大优于聚乙烯碳化硼材料; 在等厚度条件下, 模拟试样B20等的中子屏蔽效果要优于水、铜、混凝土等常规屏蔽材料; 材料厚度与中子透射系数呈指数下降关系, 且单位厚度的增加对中子透射系数改变很大; 含硼量对热中子透射系数影响很大; 在热中子能区, 中子每单位能量的变化对中子透射系数改变较大; 在慢中子能区, 中子每单位能量的变化对中子透射系数改变很小. 关键词： 中子透射系数 蒙特卡罗 铝基复合材料 碳化硼     

Electrical and structural properties of diamond films implanted by various doses of oxygen ions

Oxygen-doped diamond films are prepared by implanting various dose oxygen ions into the diamond films synthesized by hot filament chemical vapour deposition, and their electrical and structural properties are investigated. Hall effect measurements show that lower dose oxygen ion implantation is beneficial to preparing n-type diamonds. The carrier concentration increases with the dose increasing, indicating that oxygen ions supply electrons to the diamonds. The results of AES spectrum indicate that oxygen ions are doped into the diamond films, and the O-implanted depth is around 0.1μm. Raman spectrum measurements indicate that the lower dose oxygen ion implantation at 10¹⁴cm^-2 or 10¹⁵cm^-2 is favourable for producing less damaged O-doped diamond films.     

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：     

N2流量对N掺杂MgZnO薄膜结构和性能的影响

利用射频磁控溅射方法,使用Mg_{0. 04}Zn_0.96O 陶瓷靶材,选用不同流量比的氮气和氩气混和气体作为溅射气体,在石英基片上生长N掺杂Mg_xZn_1-xO合金薄膜。研究了氮流量比对薄膜组分、结构、形貌、电学性质和拉曼光谱的影响。结果显示：随着溅射气氛中氮流量比的增加,薄膜中Mg含量增加,薄膜表面颗粒尺寸减小,结晶质量变差,电阻率逐渐增大,导电类型发生转变。在氮流量比为20%时,获得了最好的p型导电薄膜。另外,随着氮流量比的增加,拉曼光谱中与N_O相关的位于272 cm^-1、642 cm^-1左右的振动峰逐渐增强,表明N_O的浓度随着氮流量比的加大而有所增加。     

B2O3添加宝石级金刚石单晶的生长特性

利用温度梯度法, 在5.3-5.7 GPa压力、1200-1600 ℃的温度条件下, 将B₂O₃粉添加到FeNiMnCo+C合成体系内, 进行B₂O₃添加宝石级金刚石单晶的合成. 研究得到了FeNiMnCo触媒生长B₂O₃添加宝石级金刚石单晶的相图分布规律. 结果表明B₂O₃添加会使晶体生长的“V”形区上移和低温六面体单晶生长区间变宽. 通过晶体生长实验, 研究合成了不同形貌的B₂O₃添加宝石级金刚石单晶. 研究同时证实, B₂O₃的过量添加会对宝石级金刚石单晶生长带来不利影响. 当B₂O₃的添加量高于约3 wt‰、生长时间超过20 h时, 很难实现优质B₂O₃添加宝石级金刚石单晶的生长. 但B₂O₃的适量添加(不超过1 wt‰), 有助于提高低温板状六面体宝石级金刚石单晶的成品率. 通过对晶体生长速度的研究发现, B₂O₃的添加使得优质晶体的生长速度明显降低, 随着晶体生长时间的延长, B₂O₃添加剂对晶体生长的抑制作用会越发明显. 扫描电镜测试结果表明, 合成体系内B₂O₃添加剂的引入, 导致晶体表面的平整度明显下降.     

TiO_2薄膜的硼掺杂对TiO_2/p~+-Si异质结器件电致发光的增强

利用磁控溅射在重掺硼硅(p+-Si)衬底上分别沉积TiO2薄膜和掺硼的TiO2(Ti O2∶B)薄膜,并经过氧气氛下600℃热处理,由此形成相应的TiO2/p+-Si和TiO2∶B/p+-Si异质结。与Ti O2/p+-Si异质结器件相比,TiO2∶B/p+-Si异质结器件的电致发光有明显的增强。分析认为:TiO2∶B薄膜经过热处理后,B原子进入TiO2晶格的间隙位,引入了额外的氧空位,而氧空位是TiO2/p+-Si异质结器件电致发光的发光中心,所以上述由B掺杂引起的氧空位浓度的增加是TiO2∶B/p+-Si异质结器件电致发光增强的原因。