Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.     

Electronic properties of single-walled V2O5 nanotubes

Atomistic models of quasi-one-dimensional vanadium pentoxide nanostructures—single-walled nanotubes formed by rolling (010) layers of V₂O₅ are constructed and their electronic properties and bond indices are studied using the tight-binding band method. We show that all zigzag (n,0)- and armchair (n,n)-like nanotubes are uniformly semiconducting, and the band gap trends to vanish as the tube diameters decrease. The V-O covalent bonds were found to be the strongest interactions in V₂O₅ tubes, whereas V-V bonds proved to be much weaker.     

First-principles study on the structural and electronic properties of LiB and its hydrides (Li2BnHn, n=5, 8, 12, LiBH4)

Structural, electronic and vibrating properties of LiB and its hydrides (Li₂B_nH_n, n=5, 8, 12, LiBH₄) were calculated by the first-principles using density functional theory in its generalized gradient approximation. The calculated results are in good agreement with experimental studies. The deviation between theory and experimental results are also discussed. With the increasing of H atoms in range of 5-12, the band gap energy increases and the width of the conduction band decreases. Comparing with LiB, the band gap of LiBH₄ is broadened, which indicates the enhancement of Li-B and Li-H bond strength. Valence electrons mainly transfer from Li atoms to B and H atoms. As a result, Li atoms are thought to be partially ionized as Li⁺ cations. There is little contribution of Li orbital to the occupied states, resulting in Li-H and Li-B bond exhibiting an ionic nature, and B-H bond showing a covalent nature.     

Effects of native defects on the electronic structure and photocatalytic activity in anatase TiO2 by first principles calculations

The crystal structure, electronic structure, optical properties and photocatalytic activity of the native defects in anatase TiO₂ were investigated based on the density-functional theory (DFT). The results show that oxygen vacancies (V_O) have the lowest formation energy, and thus are easiest to form in the bulk structure. The conduction and valence band moves to the high or low energy region, and the energy gap becomes narrower for the native point defect models. In particular, oxygen interstitials (O_i) have a direct band gap, and new gap states appear in the band gap, which can be responsible for the high photocatalytic efficiency in anatase TiO₂. The phenomenon of “impurity compensation” takes place for the oxygen and titanium interstitials. Ti vacancy (V_Ti) can promote the utilization of solar light by analyzing the absorption spectra. All the calculated results show that O_i and V_Ti are beneficial in improving the photocatalytic activity of TiO₂ in the UV–visible light range.     

Conversion of covalent to ionic character of V2O5–CeO2–PbO–B2O3 glasses for solid state ionic devices

xV₂O₅–xCeO₂–(30−x)PbO–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. The number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.20 to 1.78 eV and density increases from 3.49 to 4.25 g/cm³. FTIR spectroscopy reveals that incorporation of V₂O₅ in glass network helps to convert the structural units of [BO₃] into [BO₄]. At higher concentration of vanadium, VO vibration of [VO₅] structural units and V–O–V vibration are present. The bond ionicity of glasses increases with incorporation of V₂O₅ contents.     

Investigation of structural,physical and optical properties of CeO2–Bi2O3–B2O3 glasses

xCeO₂–30Bi₂O₃–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. A number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.15 to 1.61 eV, refractive index increases from 2.67 to 2.93 and density increases from 4.151 to 4.633 g/cm³. The decrease in band gap with CeO₂ doping approaches the semiconductor behavior. FTIR spectroscopy reveals that incorporation of CeO₂ into glass network helps to convert the structural units of [BO₃] into [BO₄] and results in Bi–O bond vibration of [BiO₆].     

Transparent nano composite PVA–TiO2 and PMMA–TiO2 thin films: Optical and dielectric properties

Transparent nano composite PVA–TiO₂ and PMMA–TiO₂ thin films were prepared by an easy and cost effective dip coating method. Al/PVA–TiO₂/Al and Al/PMMA–TiO₂/Al sandwich structures were prepared to study the dielectric behavior. The presence of metal–oxide (Ti–O) bond in the prepared films was confirmed by Fourier transform infrared spectroscopy. X-ray diffraction pattern indicated that the prepared films were predominantly amorphous in nature. Scanning electron micrographs showed cluster of TiO₂ nanoparticles distributed over the film surface and also there were no cracks and pin holes on the surface. The transmittance of the films was above 80% in the visible region and the optical band gap was estimated to be about 3.77 eV and 3.78 eV respectively for PVA–TiO₂ and PMMA–TiO₂ films by using Tauc's plot. The determined refractive index (n) values were between 1.6 and 2.3. High value of dielectric constant (?′ = 24.6 and ?′ = 26.8) was obtained for the prepared composite films. The conduction in the composite films was found to be due to electrons. The observed amorphous structure, good optical properties and dielectric behavior of the prepared nano composite thin films indicated that these films could be used in opto-electronic devices and in thin film transistors.     

Adsorption of oxygen molecular on pristine and defected SiC nanotubes

The structural and electronic properties of oxygen molecular adsorbed on the exterior surface of pristine and N_C or B_C defected (10,0) or (6,6) SiCNT have been investigated systematically using the first-principles projector-augmented wave potential within the density-functional theory under the generalized-gradient approximation. We find that for both pristine tubes the preferred adsorption sites of the O₂ molecule are above and nearly parallel to armchair Si-C bond whether physisorption or chemisorption. The strong chemical interaction between O₂ molecule and tube leads to not only a vanishing in magnetism of the O₂ molecule but also an outward relaxation of the underlying Si-C bond. The C atom substituted by N or B atom assists O₂ molecule adsorption above and nearly parallel to zigzag Si-N or Si-B bond as well as imparts a metallic character on the SiCNTs with higher concentration of the defects or a magnetism on the SiCNTs with lower concentration of the defects. Therefore, a combination of N or B doping followed by exposure to air may be an effective way to tune the electronic properties of the semiconducting SiCNTs. Furthermore, the lower binding energies for the pair of oxygen interstitials chemisorbed on N_C or B_C defected (10,0) or (6,6) SiCNT show that the oxygen molecule will dissociate to the pair of oxygen interstitials at the sidewall of N_C or B_C defected SiCNTs.     

Structural feature and electronic property of an (8, 0) carbon--silicon carbide nanotube heterojunction

A supercell of a nanotube heterojunction formed by an (8, 0) carbon nanotube (CNT) and an (8, 0) silicon carbide nanotube (SiCNT) is established, in which 96 C atoms and 32 Si atoms are included. The geometry optimization and the electronic property of the heterojunction are implemented through the first-principles calculation based on the density functional theory (DFT). The results indicate that the structural rearrangement takes place mainly on the interface and the energy gap of the heterojunction is 0.31eV, which is narrower than those of the isolated CNT and the isolated SiCNT. By using the average bond energy method, the valence band offset and the conduction band offset are obtained as 0.71 and --0.03eV, respectively.     

Magnetic field effect on the pairing state competition in quasi-one-dimensional organic superconductors (TMTSF)2X

We study the effect of the magnetic field on the pairing state competition in organic conductors (TMTSF)₂X by applying random phase approximation to a quasi-one-dimensional extended Hubbard model. We show that the singlet pairing, triplet pairing and the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) superconducting states may compete when charge fluctuations coexist with spin fluctuations. This rises a possibility of a consecutive transition from singlet pairing to FFLO state and further to S_z = 1 triplet pairing upon increasing the magnetic field. We also show that the singlet and S_z = 0 triplet components of the gap function in the FFLO state have “d-wave” and “f-wave” forms, respectively, which are strongly mixed.     

Rare-earth gate oxides for GaAs MOSFET application

Rare-earth oxide films for gate dielectric on n-GaAs have been investigated. The oxide films were e-beam evaporated on S-passivated GaAs, considering interfacial chemical bonding state and energy band structure. Rare-earth oxides such as Gd₂O₃, (Gd_xLa_1−x)₂O₃, and Gd-silicate were employed due to high resistivity and no chemical reaction with GaAs. Structural and bonding properties were characterized by X-ray photoemission, absorption, and diffraction. The electrical characteristics of metal-oxide-semiconductor (MOS) diodes were correlated with material properties and energy band structures to guarantee the feasibility for MOS field effect transistor (FET) application.Gd₂O₃ films were grown epitaxially on S-passivated GaAs (0 0 1) at 400 °C. The passivation induced a lowering of crystallization temperature with an epitaxial relationship of Gd₂O₃ (4 4 0) and GaAs (0 0 1). A better lattice matching relation between Gd₂O₃ and GaAs substrate was accomplished by the substitution of Gd with La, which has larger ionic radius. The in-plane relationship of (Gd_xLa_1−x)₂O₃ (4 4 0) with GaAs (0 0 1) was found and the epitaxial films showed an improved crystalline quality. Amorphous Gd-silicate film was synthesized by the incorporation of SiO₂ into Gd₂O₃. These amorphous Gd-silicate films excluded defect traps or current flow path due to grain boundaries and showed a relatively larger energy band gap dependent on the contents of SiO₂. Energy band parameters such as ΔE_C, ΔE_V, and E_g were effectively controlled by the film composition.     

第一原理研究Sn(O1-xNx)2材料的光电磁性质

基于第一原理的密度泛函理论, 以量子化学从头计算软件 为平台研究了Sn(O_1-xN_x)₂材料的光电磁性能, 分析了体系的态密度、 能带结构、 磁性、 介电虚部及折射率. 计算结果表明, N替代O后, 随着掺杂浓度的增加, 体系的带隙先减小后增大, 掺杂量为12.50%时带隙最窄. 由于N 2p轨道电子的贡献, 在0.55-1.05 eV范围内产生了浅受主能级, 价带和导带处的能级均出现了劈裂及轨道的重叠现象, Sn-O键的键强大于N-O键的键强. 从磁性来看, N原子决定了磁矩的大小. 从介电虚部可知, 掺杂后体系的光学吸收边增宽, 主跃迁峰发生红移, 反射率和介电谱相对应, 各峰值与电子的跃迁吸收有关.     

Investigation of the optoelectronic properties of columbite ZnNb2O6 crystal

A high-quality ZnNb₂O₆ single-crystal grown by optical floating zone method has been used as a research prototype to analyze the optoelectronic parameters by measuring the absorption coefficient and transmittance spectra along the b-axis from 200 nm to 1000 nm at room temperature. The optical interband transitions of ZnNb₂O₆ have been determined as a direct transition with a band gap of 3.84 eV. The refractive index, extinction coefficient, and real and imaginary parts of the complex dielectric constants as functions of the wavelength for ZnNb₂O₆ crystal are obtained from the measured absorption coefficients and transmittance spectra. In the Urbach tail of 3.16–3.60 eV, the validity of the Cauchy–Sellmeier equation has also been evaluated. Using the single effective oscillator model, the oscillator energy E_o is found to be 4.77 eV. The dispersion energy E_d is 26.88 eV and ZnNb₂O₆ crystal takes an ionic value.     

On the existence of a homologous series of BamCum+nOy oxides with the cubic structure of the BaCuO2 oxide

Phase relations have been studied in the BaO–CuO_x system in the range of 42.0–83.0 mol.% CuO at P(O₂) = 21 kPa (air) by visual polythermal analysis (VPA), powder X-ray diffraction (XRD), differential thermal analysis (DTA), thermogravimetric analysis (TGA), chemical analysis (CA), and electron diffraction (ED) with simultaneous elemental analysis (EA) in a transmission electron microscope (TEM). The existence of discrete crystallization fields of barium–copper oxides of cation compositions Ba₄Cu₅O_y, Ba₅Cu₆O_y, Ba₇Cu₈O_y, Ba₁₂Cu₁₃O_y, and Ba₂₄Cu₂₅O_y, which have the cubic structure of the BaCuO₂ oxide, is revealed in the studied region of the system. The oxides may be represented as members of a Ba_mCu_m+nO_y homologous series. The BaCuO₂ oxide does not exist in the subsolidus region and does not have its own crystallization field. The oxygen-deficient oxide BaCuO_1.78 of the cation composition (Ba:Cu) 1:1 with the BaCuO₂ cubic structure is found in melted samples of the 50.0 mol.% CuO composition quenched at 1020–1060 °С.     

Fabrication, characterization and photoelectrochemical properties of Fe2O3 modified TiO2 nanotube arrays

TiO₂ nanotube (NT) arrays modified by Fe₂O₃ with high sensibility in the visible spectrum were first prepared by annealing anodic titania NTs pre-loaded with Fe(OH)₃ which was uniformly clung to the titania NTs using sequential chemical bath deposition (S-CBD). The photoelectrochemical performances of the as-prepared composite nanotubes were determined by measuring the photo-generated currents and voltages under illumination of UV-vis light. The titania NTs modified by Fe₂O₃ showed higher photopotential and photocurrent values than those of unmodified titania NTs. The enhanced photoelectrochemical behaviors can be attributed to the modified Fe₂O₃ which increases the probability of charge-carrier separation and extends the range of the TiO₂ photoresponse from ultraviolet (UV) to visible region due to the low band gap of 2.2 eV of Fe₂O₃.     

First-principle study of electronic structure and stability of Sn0.5Sb0.5O2

A theoretical study on Sb-doped SnO₂ has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA) level. Stability and conductivity analyses were performed based on the formation energy and electronic structures. The results show that Sn_0.5Sb_0.5O₂ solid solution is stable because the formation energy of Sn_0.5Sb_0.5O₂ is −0.06 eV. The calculated energy band structure and density of states showed that the band gap of SnO₂ narrowed due to the presence of the Sb impurity energy levels in the bottom of the conduction band, namely there is Sb 5s distribution of electronic states from the Fermi level to the bottom of conduction band after the doping of antimony. The studies provide a theoretical basis to the development and application of Sn_1−xSb_xO₂ solid solution electrode.     

Structural,electronic, and optical absorption properties of TiO2 nanotube adsorbed with Cu n clusters

The structural,electronic,and optical absorption properties of TiO2 nanotube(TiO2NT)with Cun clusters(n=1–4)adsorbed on its surface have been investigated based on density functional theory calculations.The TiO2NT is constructed by rolling up a(101)sheet of anatase TiO2 around the[1 01]direction;the ground states of Cun/TiO2NT systems are determined by analyzing the average adsorption energies.Calculation results show that odd-even oscillations occur for the average adsorption energy,the Cu–O bond length,and the amount of transferred electrons,with the increase in Cun cluster size;and the Cun/TiO2NTs with odd n’s demonstrate stronger interaction between the Cun cluster and the TiO2NT.Also,the impurity states introduced by the Cun cluster to the band gap of TiO2NT cause an obvious redshift of the optical absorption spectrum toward the visible light region,especially for the even n cases.     

Physical properties of NxTiO2 prepared by sol–gel route

The compounds N_xTiO₂(x=0, 0.05, 0.1, 0.2) with the anatase structure have been synthesized by Sol–Gel method using Tri-ethyl Amine as nitrogen source and their optical, electrical and electrochemical properties are investigated. The electrical conductivity and thermoelectric power are measured in the temperature rang 300–600 K. The samples exhibit p-type behavior in contrast to TiO₂. The doped-samples exhibit two optical transitions (2.35≤E_h−Vis(eV)≤2.55; 1.97≤E_l−Vis (eV)≤2.06) directly allowed in the visible region, while only one transition is observed in UV region (E_UV∼3.00 eV). Pure TiO₂ shows direct band gap transition of 3.17 eV. The results confirm experimentally the calculations of Di. Valentin et al. [42]. The transitions E_h−Vis and E_l−Vis are attributed respectively to the promotion of electrons from the localized N 2p and π^? N–O bond to the conduction band. In all cases, E_UV is associated to the forbidden band energy. Though that the conductivity is generally improved by doping process, only N_0.05TiO₂ and N_0.1TiO₂ shows an enhanced mobility. The mechanism of conduction takes place by small polaron hopping. The band edge positions of N_xTiO₂ (x=0, 0.05, 0.1, 0.2) at room temperature is predicted from the obtained physical properties. This study proves experimentally the principal role of nitrogen in doping process and permits the electronic states localization associated with N-impurities in TiO₂ anatase.     

Oxidation of carbon nanotubes by singlet O2

Chemisorption of singlet (1)Delta(g) O2 on single-walled carbon nanotubes is reexamined by first principles calculations, and the reaction barrier is substantially lower than previously reported when the spin on O2 is correctly treated. The process is initiated by the cycloaddition of a singlet O2 on top of a C-C bond and ended with an epoxy structure with each of the two oxygen atoms occupying a bridge position. The overall process is exothermic, with an activation barrier as low as 0.61 eV for the (8, 0) tube. Our results raise the possibility that carbon nanotubes with small diameters could be degraded after exposure to air and sunlight, similar to the degradation of natural rubber and synthetic plastics.     

DFT study of structural, electronic and vibrational properties of pure (Al2O3)n (n = 9, 10, 12, 15) and Ni-doped (Al2O3)n (n = 9, 10) clusters

The geometrical, electronic and vibrational properties of pure (Al₂O₃)_n (n = 9, 10, 12, 15) clusters and Ni-doped (Al₂O₃)_9-10 clusters are investigated by density functional theory. There are four different Ni-doped (Al₂O₃)₉ clusters and one Ni-doped (Al₂O₃)₁₀ cluster taken into account. Compared with the pure clusters, the Ni-doped (Al₂O₃)_9-10 clusters have narrower HOMO-LUMO energy gaps. The results indicate that the impurity of Ni atom is mainly responsible for the reduction of the HOMO-LUMO energy gap. One characteristic vibration band at about 1030 cm⁻¹ is found in the vibrational frequencies of the Ni-doped (Al₂O₃)_9-10 clusters, which is caused by the asymmetric Al-O-Al stretching vibration. Another band at around 826 cm⁻¹ involving the characteristic vibration of Ni-O bond is in good agreement with experimental results.