Deep levels of nitrogen vacancy complexes in graphite-like boron nitride

This paper presents the results of a theoretical study of deep nitrogen vacancy levels and of small clusters of nitrogen di-and trivacancies, including the nearest neighbor defects in one layer of graphite-like boron nitride, made using the model-pseudopotential and supercell methods. The calculated spectra and oscillator strengths were used to interpret the local bands of optical absorption, luminescence, and photoconductivity in pyrolytic boron nitride before and after irradiation by fast neutrons, protons, and carbon ions (50–150 keV). The shallow activation levels of thermally stimulated luminescence and conductivity existing before and arising after irradiation were identified.     

高温高压下立方氮化硼和六方氮化硼的结构、力学、热力学、电学以及光学性质的第一性原理研究

本文采用基于密度泛函理论的第一性原理平面波赝势和局域密度近似方法,优化了立方和六方氮化硼的几何结构,系统地研究了零温高压下立方和六方氮化硼的几何结构、力学、电学以及光学性质.结构与力学性质研究表明:立方氮化硼的结构更加稳定,两种结构的氮化硼均表现出一定的脆性,而六方氮化硼的热稳定性则相对较差;电学性质研究表明:立方氮化硼和六方氮化硼均为间接带隙半导体,且立方氮化硼比六方氮化硼局域性更强;光学性质结果显示:立方氮化硼和六方氮化硼对入射光的通过性都很好,在高能区立方氮化硼对入射光的表现更加敏感.此外,还研究了高温高压下立方氮化硼的热力学性质,并得到其热膨胀系数、热容、德拜温度和格林艾森系数随温度和压力的变化关系.本文的理论研究阐述了高压下立方氮化硼和六方氮化硼的相关性质,为今后的实验研究提供了比较可靠的理论依据.     

Optical transitions in single-wall boron nitride nanotubes

Optical transitions in single-wall boron nitride nanotubes are investigated by means of optical absorption spectroscopy. Three absorption lines are observed. Two of them (at 4.45 and 5.5 eV) result from the quantification involved by the rolling up of the hexagonal boron nitride (h-BN) sheet. The nature of these lines is discussed, and two interpretations are proposed. A comparison with single-wall carbon nanotubes leads one to interpret these lines as transitions between pairs of van Hove singularities in the one-dimensional density of states of boron nitride single-wall nanotubes. But the confinement energy due to the rolling up of the h-BN sheet cannot explain a gap width of the boron nitride nanotubes below the h-BN gap. The low energy line is then attributed to the existence of a Frenkel exciton with a binding energy in the 1 eV range.     

Pulsed laser deposition of hexagonal and cubic boron nitride films

Hexagonal and cubic boron nitride films are deposited by pulsed laser ablation from a boron nitride and a boron target using a KrF excimer laser. Hexagonal films are deposited in nitrogen as background gas or with nitrogen/argon ion bombardment at ion-to-arriving-target-atom (I/A) ratios at the substrate below 0.5. Nucleation of the cubic phase takes place exclusively with ion bombardment at I/A ratios above 1.0, which may be reduced down to 0.6 after the completion of the nucleation process. The influence of the parameters of the laser and ion beams on the properties of the hexagonal films are presented. The Vickers microhardness and the intrinsic stress of those films vary in wide ranges of 5 to 25 GPa and 1 to 16 GPa, respectively. Pulsed laser deposited hexagonal boron nitride films show good adhesion to silicon and stainless steel if they are deposited at I/A ratios below 0.5, and can be used as intermediate layers for improving the adhesion of cubic boron nitride films. So far, 0.5 7m thick, nearly phase-pure cubic boron nitride films with good adhesion have been deposited. The microstructural, mechanical, and optical properties of those layer systems are presented and discussed.     

无序双层六角氮化硼量子薄膜的电子性质

基于安德森紧束缚模型,本文研究了无序双层六角氮化硼量子薄膜的电子性质. 数值计算结果表明在双层都无序掺杂的情况下,六角氮化硼量子薄膜的电子是局域的, 其表现为绝缘体性质;而对于单层掺杂(无论是氮原子还是硼原子)的双层六角氮化硼量子薄膜, 在能谱的带尾出现了持续的迁移率边.这就说明在单层掺杂的双层六角氮化硼量子薄膜中产生了 金属绝缘体转变.这一结果证实了有序-无序分区掺杂的理论模型,为理解及调控双层六角氮化硼量子薄膜 的电子性质提供了有益的理论指导.     

Excitons in boron nitride nanotubes: dimensionality effects

We show that the optical absorption spectra of boron nitride (BN) nanotubes are dominated by strongly bound excitons. Our first-principles calculations indicate that the binding energy for the first and dominant excitonic peak depends sensitively on the dimensionality of the system, varying from 0.7 eV in bulk hexagonal BN via 2.1 eV in the single sheet of BN to more than 3 eV in the hypothetical (2, 2) tube. The strongly localized nature of this exciton dictates the fast convergence of its binding energy with increasing tube diameter towards the sheet value. The absolute position of the first excitonic peak is almost independent of the tube radius and system dimensionality. This provides an explanation for the observed "optical gap" constancy for different tubes and bulk hexagonal BN.     

Faraday rotations,ellipticity, and circular dichroism in magneto-optical spectrum of moiré superlattices

We study the magneto-optical conductivity of a number of van der Waals heterostructures, namely, twisted bilayer graphene, AB-AB and AB-BA stacked twisted double bilayer graphene and monolayer graphene and AB-stacked bilayer graphene on hexagonal boron nitride. As the magnetic field increases, the absorption spectrum exhibits a self-similar recursive pattern reflecting the fractal nature of the energy spectrum. Whilst twisted bilayer graphene displays only weak circular dichroism, the other four structures display strong circular dichroism with monolayer graphene and AB-stacked bilayer graphene on hexagonal boron nitride being particularly pronounced owing to strong inversion symmetry breaking properties of the hexagonal boron nitride layer. As the left and right circularly polarized light interact with these structures differently, plane-polarized incident light undergoes a Faraday rotation and gains an ellipticity when transmitted. The size of the respective angles is on the order of a degree.     

含六方氮化硼的一维光子晶体的光学特性

从麦克斯韦方程组出发,结合电磁场边界条件推导出在倾斜光轴条件下的传输矩阵。利用该传输矩阵研究了光轴方向对基于六方氮化硼的光子晶体光学特性的影响。研究表明,当Ф=0~°时,此结构会在六方氮化硼Ⅱ型双曲区域出现全方位禁带。随着Ф的不断增大,TE波和TM波在Ⅱ型双曲区域内的光子禁带逐渐错开,对于TM波,Ⅰ型双曲区域开始产生禁带,且朝着低频方向移动;Ⅱ型双曲区域内的禁带不断变窄,并往高频方向移动。利用这些特性,可实现偏振光分离和禁带加宽。     

Charge distribution of a potassium-doped combined system of graphene and hexagonal boron nitride

By using first-principles density functional theory, we investigate the charge distribution of a potassium-doped layered combined system of graphene and hexagonal boron nitride. Two configurations of potassium-doped hexagonal boron nitride layers on graphenes and the reverse geometry of graphenes on hexagonal boron nitride layers are considered. We find that the charge distribution exhibits different features in these two situations. In the former case, the outmost hexagonal boron nitride layer cannot screen the external charges offered by potassium atom completely and most of the transferred charges reside on the two bounding layers. In contrary, the outmost graphene layer near the potassium atom can accept almost all of the transferred charges and only a few of them stay at interior layers in the latter case. A more amazing result is that the characteristics of charge transfer are independent of the number of hexagonal boron nitride layers and graphenes.     

Optical absorption and electron energy loss spectra of carbon and boron nitride nanotubes: a first-principles approach

We present results for the optical absorption spectra of small-diameter single-walled carbon and boron nitride nanotubes obtained by ab initio calculations in the framework of time-dependent density-functional theory. We compare the results with those obtained for the corresponding layered structures, i.e. the graphene and hexagonal boron nitride sheets. In particular, we focus on the role of depolarization effects, anisotropies, and interactions in the excited states. We show that the random phase approximation reproduces well the main features of the spectra when crystal local field effects are correctly included, and discuss to what extent the calculations can be further simplified by extrapolating results obtained for the layered systems to results expected for the tubes. The present results are relevant for the interpretation of data obtained by recent experimental tools for nanotube characterization, such as optical and fluorescence spectroscopies, as well as polarized resonant Raman scattering spectroscopy. We also address electron energy loss spectra in the small-q momentum-transfer limit. In this case, the interlayer and intertube interactions play an enhanced role with respect to optical spectroscopy. PACS 71.45.Gm; 77.22.Ej; 78.20.Bh; 78.67.Ch     

Optical properties of hexagonal boron nitride thin films deposited by radio frequency bias magnetron sputtering

The optical properties of hexagonal boron nitride (h-BN) thin films were studied in this paper. The films were characterized by Fourier transform infrared spectroscopy, UV--visible transmittance and reflection spectra. h-BN thin films with a wide optical band gap E_g (5.86 eV for the as-deposited film and 5.97 eV for the annealed film) approaching h-BN single crystal were successfully prepared by radio frequency (RF) bias magnetron sputtering and post-deposition annealing at 970~K. The optical absorption behaviour of h-BN films accords with the typical optical absorption characteristics of amorphous materials when fitting is made by the Urbach tail model. The annealed film shows satisfactory structure stability. However, high temperature still has a significant effect on the optical absorption properties, refractive index n, and optical conductivity σ of h-BN thin films. The blue-shift of the optical absorption edge and the increase of E_g probably result from stress relaxation in the film under high temperatures. In addition, it is found that the refractive index clearly exhibits different trends in the visible and ultraviolet regions. Previous calculational results of optical conductivity of h-BN films are confirmed in our experimental results.     

Structure and luminescence of gadolinium-doped cubic boron nitride powder

The structural characteristics and chemical, morphological, and optical properties of cBN and cBN:Gd micropowders are studied by x-ray diffraction, energy-dispersive electron probe microanalysis (x-ray spectral microanalysis), and photoluminescence techniques. Cubic boron nitride (cBN) micropowders were synthesized at high pressures and temperatures from hexagonal boron nitride (hBN) micropowder and Li₃N catalyst. cBN:Gd micropowders were synthesized from mixtures of hBN, Li₃N, and GdF₃ micropowders. A lattice parameter of a~3.615 ? is calculated for both types of powder (cBN and cBN:Gd). The photoluminescence spectra of the cBN:Gd powder are found to contain emission lines attributable to intracenter optical transitions of Gd³⁺ ions.     

GROWTH OF PREFERENTIALLY ORIENTED CUBIC BORON NITRIDE FILMS BY CHEMICAL VAPOR DEPOSITION

Preferentially oriented cubic boron nitride films on nickel substrates have been grown using hot-filament-assisted rf plasma chemical vapor deposition method. X-ray photoelectron spectroscopy shows that the cubic boron nitride films are stoichiometric. Scanning electron microscopy and X-ray diffraction show that the films are of high quality with well-faceted and (220) preferentially oriented grains, without X-ray diffraction detectable hexagonal boron nitride phase. The nucleation and growth process has been investigated. After 40min deposition, well aligned, well faceted cubic boron nitride nuclei can be seen on the substrnies, and after 2 h deposition, the rectangular grains can be seen on the substrate with their corresponding edges parallel to each other in scanning electron microscopic images. The ratio of the diffraction peak height of (220) face to that of (111) face is about 5.2 in the X-ray diffraction pattern, but the corresponding value of the random cubic boron nitride crystallites is only 0.06.     

六方氮化硼单层中一种(CN)3VB缺陷的第一性原理计算

二维六方氮化硼(hBN)的点缺陷最近被发现可以实现室温下的单光子发射,而成为近年的研究热点.尽管其具有重要的基础和应用研究意义,hBN中发光缺陷的原子结构起源仍然存在争议.本文采用基于密度泛函理论的第一性原理计算,研究hBN单层中一种B空位附近3个N原子被C替代的缺陷(CN)3VB.在hBN的B空位处,3个N原子各自带一个在平面内的悬挂键及相应的未配对电子,而通过C替换可以消除未配对的电子.系统研究了(CN)3VB缺陷的几何结构、电子结构以及光学性质,结果表明,缺陷可以由一个对称的亚稳态经过原子结构弛豫变成1个非对称的、3个C原子连在一起的基态结构.缺陷的形成在hBN中引入了一些由缺陷悬挂σ键及重构的π键贡献的局域缺陷态.这些缺陷态可以导致能量阈值在2.58 eV附近的可见光内部跃迁.本文的工作有助于进一步理解hBN中点缺陷的构成及光学性质,为实验上探讨发光点缺陷的原子结构起源及其性质提供理论依据.     

石墨-六角氮化硼微晶混合物与水高压反应产物分析

 利用球磨法制备石墨-六角氮化硼微晶混合物，并在6.1 GPa、800~1 500 ℃条件下与水进行高压反应，以便研究用水作触媒合成B-C-N三元化合物的可能性。通过对反应产物的XRD、XPS谱分析发现：高压下随着温度的升高，反应产物中出现再结晶石墨，其晶化程度逐渐提高；但没有出现再结晶六角氮化硼，也未出现立方氮化硼。在球磨不充分条件下，石墨-六角氮化硼混合物的XRD谱没有完全弥散，它们与水高压反应时，能观察到石墨与立方氮化硼分别结晶的现象，但都没有形成B-C-N晶化结构。     

Electronic band structure and x-ray spectra of boron nitride polytypes

The electronic band structures of boron nitride crystal modifications of the graphite (h-BN), wurtzite (w-BN), and sphalerite (c-BN) types are calculated using the local coherent potential method in the cluster muffin-tin approximation within the framework of the multiple scattering theory. The specific features of the electronic band structure of 2H, 4H, and 3C boron nitride polytypes are compared with those of experimental x-ray photoelectron, x-ray emission, and K x-ray absorption spectra of boron and nitrogen. The features of the experimental x-ray spectra of boron nitride in different crystal modifications are interpreted. It is demonstrated that the short-wavelength peak revealed in the total densities of states (TDOS) in the boron nitride polytypes under consideration can be assigned to the so-called outer collective band formed by 2p electrons of boron and nitrogen atoms. The inference is made that the decrease observed in the band gap when changing over from wurtzite and sphalerite to hexagonal boron nitride is associated with the change in the coordination number of the components, which, in turn, leads to a change in the energy location of the conduction band bottom in the crystal.     

Tuning infrared absorption in hyperbolic polaritons coated silk fibril composite

Advanced textiles for thermal management give rise to many functional applications and unveil a new frontier for the study of human thermal comfort. Manipulating the coated quasi-particles between the composite components offers a platform to study the advanced thermoregulatory textiles. Here, we propose that coating the hyperbolic polariton can be an effective tool to tune infrared absorption in hexagonal boron nitride-coated silk composite. Remarkably, we achieve significant tuning of the infrared absorption efficiency of silk fibrils through the designed hexagonal boron nitride film. The underlying mechanism is related to resonance coupling between hyperbolic phonon polaritons. We find a notably high infrared absorption efficiency, nearly 3 orders larger than that without hBN coating, which can be achieved in our composite system. Our results indicate the promising future of advanced polariton-coated textiles and open a pathway to guide the artificial-intelligence design of advanced functional textiles.     

Spectroscopic in situ diagnostics of boron nitride film growth in plasma-enhanced deposition

The development of in situ diagnostics of the most important species and reactions in the plasma and/or on the surface during thin-film growth is one of the current topics in plasma-enhanced vapor deposition. In situ thin film diagnostic methods which could be used in plasma processing are restricted due to the presence of electrons and ions. The advantages and disadvantages of different applicable methods will be discussed. The spectroscopic in situ control of boron nitride film growth is presented as an example of surface modification in low-temperature, low-pressure plasma processing. The growth of cubic and hexagonal boron nitride is observed by polarized infrared reflection spectroscopy in absorption and ellipsometric configurations as well as by single-wavelength ellipsometry in the visible spectral range. Modeling of the experimental results gives detailed information on growth conditions and internal stress of the films. Received: 8 August 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Residual compressive stress and intensity of infrared absorption of cubic BN films prepared by plasma enhanced chemical vapor deposition

Theoretical and experimental investigations on the dependence of the intensity of infrared （IR） absorption of poly- crystalline cubic boron nitride thin films under the residual compressive stress conditions have been performed. Our results indicate that the intensity of the IR absorption is proportional to the total degree of freedom of all the ions in the ordered regions. The reduction of interstitial Ar atom concentration, which causes the increase in the ordered regions of cubic boron nitride （cBN） crystallites, could be one cause for the increase in the intensity of IR absorption after residual compressive stress relaxation. Theoretical derivation is in good agreement with the experimental results concerning the IR absorption intensity and the Ar interstitial atom concentration in cubic boron nitride films measured by energy dispersion X-ray spec- troscopy. Our results also suggest that the interstitial Ar is the origin of residual compressive stress accumulation in plasma enhanced cBN film deposition.     

Analysis of Transition Mechanism of Cubic Boron Nitride Single Crystals under High Pressure-High Temperature with Valence Electron Structure Calculation

The possibilities of hexagonal boron nitride(hBN) and lithium boron nitride(Li_3BN_2) transition into cubic boron nitride(cBN) under synthetic pressure 5.0 GPa and synthetic temperature 1700 K are analyzed with the use of the empirical electron theory of solids and molecules. The relative differences in electron density are calculated for dozens of bi-phase interfaces hBN/cBN, Li_3BN_2/cBN. These relative differences of hBN/cBN are in good agreement with the first order of approximation(10%), while those of Li_3BN_2/cBN are much greater than 10%.This analysis suggests that Li_3BN_2 is impossible to be intermediate phase but is a catalyst and cBN should be directly transformed by hBN.