Structural Stability, Electronic, Magnetic and Optical Properties of Rectangular Graphene and Boron-Nitride Quantum Dots: Effects of Size, Substitution and Electric Field
Sharma SRKC Yamijala, Arkamita Bandyopadhyay, Swapan K Pati
备注：
32 pages (20 main article, 12 SI), 15 figures (5 main article, 10 SI), Journal Article
发表信息：
Journal of Phyiscal Chemistry C, 117 (44) , 2013, 23295-23304
Using density functional theory calculations, we have examined the structural stability, electronic, magnetic and optical properties of rectangular shaped quantum dots (QDs) of graphene (G), Boron Nitride (BN) and their hybrids. Different hybrid QDs have been considered by substituting a GQD (BNQD) with BN-pairs (carbon atoms) at different positions. Several parameters like size, amount of substitution etc. have been varied for all these QDs (GQDs, BNQDs, hybrid-QDs) to monitor the corresponding changes in their properties. Among the considered parameters, we find that substitution can act as a powerful tool to attain interesting properties with these QDs, for example, broad range of absorption (~2000 nm) in the near infrared (NIR) region, spin-polarized HOMO-LUMO gaps without the application of any external-bias etc., which are highly required in the preparation of opto-electronic, electronic/spintronic devices etc. Explanations have been given in details by varying different factors, like, changing the position and amount of substitution, application of external electric-field etc., to ensure the reliability of our results.
The effect of doping of cubic boron nitride with beryllium, silicon, sulfur and magnesium on the lattice parameters, electrical conductivity and EPR spectra has been studied. It is established that the degree of doping increases significantly in the case of crystallization of cubic boron nitride from BN solutions in supercritical ammonia at 3.9-4.2 GPa and 1100°C in comparison with the conventional synthesis from melts of the Mg-B-N system at 4.2 GPa and 1400°C. Doping with silicon and beryllium results in semiconductor properties of cubic boron nitride.
Nanostructure and mechanical properties of bulk nanocristalline cubic boron nitride have been studied by transmission electron microscopy, and micro- and nanoindentation. The obtained data on hardness, elastic properties and fracture toughness clearly indicate that nano-cBN belongs to a family of advanced ultra-hard materials.
Graphene nanoribbons are prepared inside boron nitride nanotubes by liquid phase encapsulation and subsequent annealing of 1,2,4-trichlorobenzene. The product is imaged with high resolution transmission electron microscopy, and characterized by optical absorption and Raman spectroscopy. Carbon-containing material is detected inside the boron nitride nanotubes with energy-dispersive x-ray spectroscopy (EDS) and scanning transmission electron microscopy (STEM). The observed structures twist under the electron beam and the characteristic features of nanoribbons appear in the Raman spectra.
Uniaxial tensile properties of hexagonal boron nitride nanoribbons and dependence of these properties on temperature, strain rate, and the inclusion of vacancy defects have been explored with molecular dynamics simulations using Tersoff potential. The ultimate tensile strength of pristine hexagonal boron nitride nanoribbon of 26 nm x 5 nm with armchair chirality is found to be 100.5 GPa. The ultimate tensile strength and strain have been found decreasing with increasing the temperature while an opposite trend has been observed for increasing the strain rate. Furthermore, the vacancy defects re…
Using combination of Density Functional Theory and Monte Carlo simulation, we study the phase stability and electronic properties of two dimensional hexagonal composites of boron nitride and graphene, with a goal to uncover the role of the interface geometry formed between the two. Our study highlights that preferential creation of extended armchair interfaces may facilitate formation of solid solution of boron nitride and graphene within a certain temperature range. We further find that for band-gap engineering, armchair interfaces or patchy interfaces with mixed geometry are most suitable. E…
The defect-mediated hexagonal boron nitride (hBN) supercell display the visible optical spectra and electronic characteristics. The defects in the hBN supercell include the atomic vacancy, antisite, antisite vacancy, and substitution of a foreign atom for boron or nitrogen. The hBN supercell with VB, CB, and NB-VN has the high electron density of states across the Fermi level which indicates the high conductive electronic characteristics. The hBN with defects including atomic vacancy, antisite vacancy, and substitution of a foreign atom for boron or nitride exhibit the distinct spin-resolved o…
The phonon dispersion, density of states, Grüneisen parameters, and the lattice thermal conductivity of single- and multi-layered boron nitride were calculated using first-principles methods. For the bulk {\it h}-BN we also report the two-phonon density of states. We also present simple analytical solutions to the acoustic vibrational mode-dependent lattice thermal conductivity. Moreover, computations based on the elaborate Callaway-Klemens and the real space super cell methods are presented to calculate the sample length and temperature dependent lattice thermal conductivity of single- and mu…
The dispersion of nitride and carbide ceramic particles in water is difficult, due to the absence of hydroxyl groups on their surface. Boron nitride is not an exception and despite its numerous applications, no effective dispersant has been identified so far. We demonstrate here the dispersion properties of two cellulose derivatives for hexagonal boron nitride powders, hydroxyl ethyl cellulose and methyl cellulose. The effect of particle sizes and cellulose concentration was investigated. The adsorption of cellulose onto the surface of the BN particles was confirmed by isotherm adsorption. Zet…
Covalent functionalization is a way to tune the electrochemical properties of hexagonal boron nitride (h-BN) monolayers. The wide band gap insulator h-BN may become metallic conductor upon functionalization with strong oxidants, such as fluorosulfonyl radicals ($\cdot$OSO$_2$F), as known since 1978 [N. Bartlett et al., J. Chem. Soc. Chem. Comm. {\bf 5}, 200 (1978)], with electrical conductivity of 1.5 S/cm [C. Shen et al., J. Solid State Chem. {\bf 147}, 74 (1999)] that greatly surpasses commercial cathode material Li$_{x}$CoO$_{2}$ while retaining excellent ionic conductivity. Functionalized …
Topological insulators hold great potential for efficient information processing and storage. Using density functional theory calculations, we predict that a honeycomb lead monolayer can be stabilized on the Al2O3 (0001) substrate and becomes topologically non-trivial with a sizeable band gap (~0.27 eV). Furthermore, we propose to use hexagonal boron-nitride (h-BN) monolayer as a protection for the topological states of Pb/Al2O3 and Sn/Al2O3. Our findings suggest new possibilities for designing and protecting two-dimensional TIs for practical applications.
The current rechargeable battery technologies have a failure in their performance at high pressure and temperature. In this article, we have brought theoretical insights on using boron nitride flakes as a protecting layer for a lithium-ion battery device and extended its application for a spin-dependent photon emission device. Hence, the electronic properties of pristine and lithium-doped hydrogen-edged boron nitride flakes have been studied by the first principle density functional theory calculations. In this study, we have discussed the stability, adsorption energies, bond lengths, electron…
We present an ab-initio study of boron nitride as well as carbon allotropes. Their relative thermodynamic stabilities and structural phase transitions from low- to high-density phases are investigated. Pressure-temperature phase diagrams are calculated and compared to experimental findings. The calculations are performed using quantum chemical wavefunction based as well as density functional theories. Our findings reveal that predicted energy differences often depend significantly on the choice of the employed method. Comparison between calculated and experimental results allows for benchmarki…
Stacking and Registry Effects in Layered Materials: The Case of Hexagonal Boron Nitride
采用van der Waals修正的密度泛函理论方法研究了六方氮化硼（h-BN）的层间滑移能谱.结果表明，范德华力的主要作用是将层间固定在一个固定的距离上，而静电力则决定了最佳的堆积模式和层间滑动能。一个几乎自由滑动的路径被确定，沿着该路径获得~0.6 eV的带隙调制。我们提出了一个简单的几何模型，量化层之间的注册表匹配，并捕捉波纹h-BN层间能量景观的本质。这种现象学模型的简单性为复杂的层状结构（如碳和氮化硼纳米管）的建模开辟了道路。
Quantum emitters in layered hexagonal boron nitride (hBN) have recently attracted a great attention as promising single photon sources. In this work, we demonstrate resonant excitation of a single defect center in hBN, one of the most important prerequisites for employment of optical sources in quantum information application. We observe spectral linewidths of hBN emitter narrower than 1 GHz while the emitter experiences spectral diffusion. Temporal photoluminescence measurements reveals an average spectral diffusion time of around 100 ms. On-resonance photon antibunching measurement is also r…
Spin defects in foils of hexagonal boron nitride are an attractive platform for magnetic field imaging, since the probe can be placed in close proximity to the target. However, as a III-V material the electron spin coherence is limited by the nuclear spin environment, with spin echo coherence time of $\sim100~\mathrm{ns}$ at room temperature accessible magnetic fields. We use a strong continuous microwave drive with a modulation in order to stabilize a Rabi oscillation, extending the coherence time up to $\sim4~\mathrm{μs}$, which is close to the 10-$\mathrm{μs}$ electron spin lifetime in our …
The possibility of modification of the local properties of hexagonal boron nitride (h-BN) by laser irradiation is investigated. Investigations conducted using both Raman spectroscopy and electrostatic force microscopy were performed. Laser light induced modifications are found to cause no structural changes. However, they have impact on Raman spectra and local charge state of the material. They are also shown to be stable in time and during electrical grounding of the sample. The mechanism of photoionization of deep defects present in h-BN is proposed to explain the observed phenomenon. The di…
Single layer hexagonal boron nitride is produced on 2 inch Pt(111)/sapphire wafers. The growth with borazine vapour deposition at process temperatures between 1000 and 1300 K is in-situ investigated by photoelectron yield measurements. The growth kinetics is slower at higher temperatures and follows a tanh$^2$ law which better fits for higher temperatures. The crystal-quality of h-BN/Pt(111) is inferred from scanning low energy electron diffraction (x-y LEED). The data indicate a strong dependence of the epitaxy on the growth temperature. The dominant structure is an aligned coincidence lattic…
In this work, sintered polycrystalline cubic boron nitride (cBN) compacts, with titanium carbonitride (TiC0.7N0.3) and titanium nitride (TiN), respectively, as binders, were prepared at temperature of 1450°C and pressure of 5.5 GPa during 3 minutes, and the influence of binders on the plastic deformation of cBN powder due to the sintering process was experimentally investigated by X-ray diffraction (XRD) analysis. It was shown that the sintered compact with titanium carbonitride as a binder displays more intense plastic deformation of cBN grains than that with titanium nitride binder. This res…
Hexagonal boron nitride (hBN) has been grown on sapphire substrates by ultra-high temperature molecular beam epitaxy (MBE). A wide range of substrate temperatures and boron fluxes have been explored, revealing that high crystalline quality hBN layers are grown at high substrate temperatures, $>$1600$^\circ$C, and low boron fluxes, $\sim1\times10^{-8}$ Torr beam equivalent pressure. \emph{In-situ} reflection high energy electron diffraction (RHEED) revealed the growth of hBN layers with $60^\circ$ rotational symmetry and the $[11\bar20]$ axis of hBN parallel to the $[1\bar100]$ axis of the sapp…
We present a first-principles computational study of the thermodynamics of carbon defects in hexagonal boron nitride (hBN). The defects considered are carbon monomers, dimers, trimers, and larger carbon clusters, as well as complexes of carbon with vacancies, antisites, and substitutional oxygen. Our calculations show that monomers ($\text{C}_{\text{B}}$, $\text{C}_{\text{B}}$), dimers, trimers, and $\text{C}_{\text{N}}\text{O}_{\text{N}}$ pairs are the most prevalent species under most growth conditions. Compared to these defects, larger carbon clusters, as well as complexes of carbon with va…
In this paper, structural and electronic properties and stability of (10, 0) born nitride nanotube (BNNT) are considered within density functional theory by doping group IV elements of the periodic table. The HOMO-LUMO gap has been strongly modified and treated a dual manner by choosing B or N sites for dopant atoms. Formation energy calculation shows that B site doping is more stable than N site doping. Results also show that all dopants turn the pristine BNNT into a p-type semiconductor except for carbon-doped BNNT at B site.
Two dimensional van der Waals crystals and their heterostructures provide an exciting alternative to bulk wide bandgap semiconductors as hosts of single photon emitters. Amongst different layered materials, bright and robust defect-based single photon emitters have been observed within hexagonal boron nitride, a layered wide-bandgap semiconductor. Despite research efforts to date, the identities of the deep defects responsible for quantum emissions in hexagonal boron nitride remain unknown. In this theoretical work, I demonstrate that the strain-induced changes in emission frequencies depend o…
