CrSi2能带结构和光学性质的第一性原理研究

采用基于第一性原理的密度泛函理论（DFT）赝势平面波方法，对CrSi2的能带结构、态密度和光学性质进行了理论计算，能带结构计算表明CrSi2属于一种间接带隙半导体，禁带宽度为0．353eV,其能态密度主要由Cr的3d层电子和Si的3p层电子的能态密度决定；计算了CrSi2的介电函数、反射率、折射率及吸收系数等。经比较，计算结果与已有的实验数据符合较好。     

γ-B28光学性质的第一性原理研究

利用基于密度泛函第一性原理的GGA方法,计算研究了硼的高压相γ-B28的能带结构、态密度、分态密度和光学性质.计算结果表明,γ-B28具有半导体能带结构的特征,其带隙达1.619eV,且整个带结构由杂化的硼2p态和2s态组成,且2p态占主导地位.γ-B28的静态介电常数为11.0733,静态的折射率为3.328,介电函数虚部的吸收边位于1.7eV左右,同时,在2.693eV和5.232eV处有2个明显的特征峰.γ-B28的反射系数在0～16eV范围内随着能量的升高而逐渐增大,但在19.4eV时反射系数急剧下降,而吸收系数的数量级达105cm-1,其电子能量损失谱(EELS)的共振峰在19.4eV处,与反射系数的陡降相对应.     

Ta2N3电子结构与光学性质的第一性原理研究

基于密度泛函第一性原理的GGA方法计算研究了Ta2N3的能带结构、态密度、分态密度和光学性质.计算结果表明,Ta2N3具有明显的金属能带结构特征,且在费米能级附近,Ta的5d态与N的2p态杂化,Ta-N以共价键相互作用.Ta2N3的静态介电常数为77.428,静态的折射率n0为8.88,而介电函数的虚部随能量的增加而减小.Ta2N3多晶体的反射系数在0～1.65eV区域随能量的增加而逐渐减小,在1.65eV附近达极小值,此后随能量的增加而增大,但在15eV时发生陡降.Ta2N3多晶体的吸收系数数量级达105 cm-1,且在高能区对光子的吸收较少,其电子能量损失谱(EELS)的共振峰在15eV处,与此能量时反射系数的陡降相对应.     

Fe-Al-La电子结构及耐腐蚀性第一性原理研究

材料的电子态密度、能量、能带结构、差分电荷密度以及局域态密度对材料的抗腐蚀性有重要影响。本文基于第一性原理密度泛函平面波赝势法,优化了Fe、Fe-Al、Fe₈Al₈La电子结构,并从态密度、峰值分析了Fe-Al合金耐腐蚀性机理。结果表明,在Fe-Al合金中加入La, Fe与La之间存在明显的电荷转移并形成了离子键,使Fe-Al的能带宽度降低到30.8 eV,表明La减弱Fe-Al原子轨道的扩展性,La使Fe-Al态密度的峰值增大到30.26 electron/eV,成键的电子数逐渐增加,提高了Fe-Al的稳定性和抗耐腐蚀性能,为提高Fe-Al合金的性能奠定一定理论基础。     

Mg2Si电子结构及光学性质的研究

采用基于第一性原理的赝势平面波方法系统地计算了Mg2Si基态的电子结构、态密度和光学性质。计算结果表明Mg2Si属于间接带隙半导体，禁带宽度为0．2994eV；其价带主要由Si的3p以及Mg的3s、3p态电子构成，导带主要由Mg的3s、3p以及Si的3p态电子构成；静态介电常数ε1（0）=18．89；折射率n0=4．3460；吸收系数最大峰值为356474．5cm^-1；并利用计算的能带结构和态密度分析了Mg2Si的介电函数、折射率、反射率、吸收系数、光电导率和能量损失函数的计算结果，为Mg2Si的设计与应用提供了理论依据。     

第一性原理研究α-Al2O3的电子结构、力学性质和德拜温度

采用基于密度泛函理论的平面波超软赝势的第一性原理方法,利用CASTEP软件计算了α-Al_2O_3的电子结构、力学性质和德拜温度。计算结果显示优化后的晶格常数与实验数据基本一致。能带结构图表明α-Al_2O_3具有典型的离子化合物特征,禁带宽度为5.964eV。计算的态密度表明α-Al_2O_3的下价带在-19.426~-15.370eV之间,态密度主要由O的2s轨道电子贡献;上价带在-7.178~0.711eV之间,态密度主要由O的2p轨道电子贡献;导带在5.698~14.977eV之间,态密度主要由Al的3s和3p轨道电子贡献。差分电荷密度分布表明α-Al_2O_3中存在离子键和共价键。力学性质的计算结果表明α-Al_2O_3的体积模量为224.885GPa,剪切模量为144.687GPa,弹性模量为357.411GPa,泊松比为0.235,各向异性指数为0.220;α-Al_2O_3剪切模量与体积模量的比值为0.643,表明α-Al_2O_3具有脆性。α-Al_2O_3的德拜温度为974.834K。     

Ti3SnC2电子结构的第一性原理研究

采用密度泛函数理论框架下的第一性原理研究了Ti3SnC2的电子结构,利用GGA-PW91基组对Ti3SnC2晶体结构进行了优化,并计算了Ti3SnC2的能带结构、总态密度和各原子的分态密度.对能带和总态密度的计算结果表明,Ti3SnC2在费米能级处电子态密度较高,材料表现出较强的金属性,同时材料的导电性为各向异性.Ti3SnC2各原子的分态密度图的计算结果表明,其导电性主要由Ti2的3d电子决定,Ti1的3d态电子、Sn的5p态电子和C的2p态电子也有少量贡献.决定材料电学性质的主要是Ti的3d、Sn的5p和C的2p态电子的p-d电子轨道杂化,而p-d电子轨道杂化成键则使材料具有比较稳定的结构.     

ZnO氧化物的电子结构与热学性能的研究

采用密度泛函理论基础上的平面波超软赝势第一性原理计算的方法研究了纤锌矿结构热电氧化物ZnO的电子结构和热学性能。电子结构计算结果表明,纤锌矿结构的ZnO存在着约1.0eV的直接带隙,价带中的载流子有效质量较大,导带中的载流子有效质量较小;靠近价带顶的能带中的电子主要为p态电子,靠近导带底的能带中的电子主要为p,d态电子。体系分态密度计算结果表明,费米能级附近的能带主要由Znp,Znd和Op态电子构成,且Znp和Op态电子之间存在着很强的杂化作用。声子态密度及分布计算结果表明,体系晶格振动频率主要集中在3～10THz和10～12THz范围之内,其中振动频率约为11THz的振动模式在体系中数量较多,主要为光学波声子。热电性能理论分析结果表明,ZnO基热电氧化物应该具有较高的Seebeck系数和热电性能。     

氧和硒掺杂对单层二硫化钼电子结构与光电性质的影响

基于密度泛函理论的第一性原理计算,研究了氧和硒掺杂对单层二硫化钼电子结构与光电性质的影响.结果表明,单层二硫化钼属于直接带隙半导体,其带隙宽度为1.64 eV.单层二硫化钼的价带顶主要由S-3p态电子和Mo-4d态电子构成,而其导带底则主要由Mo-4d态电子和S-3p态电子共同决定;同时通过氧和硒掺杂,使单层二硫化钼的禁带宽度变窄,光吸收特性增强,研究结果为二硫化钼在光电器件方面的应用提供了理论基础.     

OsSi2电子结构及介电性能的第一性原理研究

采用基于密度泛函理论的第一性原理,研究了硅基异质外延的OsSi_2的电子结构和介电性能。结果表明,在1.010nm≤a≤1.030nm范围内,OsSi_2始终为间接带隙的能带结构,且带隙值随晶格常数a的增大而逐渐减小;当晶格常数a为1.020nm时,体系处于稳定平衡态,此时OsSi_2具有0.625eV的间接带隙能量值;OsSi_2的价带主要由Os的5d、5p和Si的3s、3p态电子构成,导带主要由Si的3s、3p和Os的5d、6s态电子构成;OsSi_2在外延稳定平衡态及其附近的介电函数实部和虚部变化趋近一致,与块体OsSi_2相比,OsSi_2在外延稳定平衡态下的介电函数曲线相对往低能区飘移,OsSi_2的介电峰减少且介电峰强度明显增强。     

The use of ZrO2 mixed TiO2 nanostructures as efficient dye-sensitized solar cells' electrodes

The mixed oxide of zirconium (ZrO₂) and titanium (TiO₂) nanostructures have been synthesized and used as electrodes for dye-sensitized solar cells (DSC). The TiO₂–ZrO₂ mixed oxide powder has a larger surface area than the pure component of TiO₂. For the UV action spectra of unsensitized photochemical cell, the TiO₂–ZrO₂ mixed oxide electrode band gap (E_g) around 3.27 eV, which is higher than that of pure component of titania (E_g = 3.2 eV). The increases in both of BET surface area and band gap contributed to the improvement on short-circuit photocurrent and open-circuit voltage, respectively. The DSC fabricated by TiO₂–ZrO₂ mixed oxide electrode significantly improved solar energy conversion efficiency when compared to a cell that was fabricated only by pure component of TiO₂.     

Synthesis of dispersed ZrO2 nano-laminae composed of ZrO2 nanocrystals

Dispersed ZrO₂ nano-laminae were synthesized at low temperature using zirconium oxynitrate and polyvinyl pyrrolidone (PVP) as reaction materials. High-resolution transmission electron microscopy (HRTEM) of individual ZrO₂ nano-laminae showed that each piece of ZrO₂ nano-laminae was assembled by large numbers of ZrO₂ nanocrystals. The bulk dispersed ZrO₂ nano-laminae could be observed in situ from scanning electron microscopy (SEM) images. The results of X-ray diffraction (XRD) showed that the crystallographic phase of ZrO₂ nano-laminae was cubic ZrO₂. Experiments indicated that the morphologies and phase composition of ZrO₂ nano-laminae were affected by the calcined temperature. PVP plays an important role in the formation process of dispersed ZrO₂ nano-laminae.     

Characterization and optical properties of m-Li2ZrO3 prepared by optimized solid-state reaction

m-Li₂ZrO₃ powders were successfully prepared by solid-state reaction method using Li₂CO₃ and ZrO₂ as raw materials. The synthesis was optimized by varying the ball-milling time (0–96 h); Li₂CO₃ excess (0 or 5 wt%), reaction temperature (700, 800, 900 or 1000 °C), and reaction time (3, 6, 9 or 12 h). The structural, morphological and optical properties of m-Li₂ZrO₃ powders were examined by X-Ray Diffraction, Thermogravimetric and Differential-Thermal analysis, Scanning Electron Microscopy, High-Resolution Transmission Electron Microscopy, Laser Diffraction, Dynamic Light Scattering and UV–Vis Diffuse Reflectance Spectroscopy. The results show that precursors suitable for the synthesis of fine powders require ball-milling times longer than or equal to 6 h. Highly crystalline m-Li₂ZrO₃ was synthesized under two distinctive calcination conditions as follows: 900 °C/6h without Li₂CO₃ excess or 1000 °C/12 h using 5 wt% of Li₂CO₃ excess. Particle size of as-synthesized powders was found to be in the range from 200 nm to 1 µm. m-Li₂ZrO₃ was found to be a wide band gap material with apparent optical band gap of 5.5 eV (direct) and 5.1 eV (indirect), which can be used in UV-C applications.     

Colloidal synthesis of Gd<Superscript>3+</Superscript> doped ZrO<Subscript>2</Subscript> based dielectrics and their structural and electrochemical property studies

Solution processed wide band gap dielectrics have nowadays started to receive renewed interest for practical application in semiconductor electronics. In this regard, undoped and gadolinium (Gd) doped zirconia (ZrO₂) nanocrystallites were colloidally processed and their potential for dielectric applications has been demonstrated. X-ray diffraction measurements revealed the effective crystallization of nanostructures and the successful substitution of Gd ions into the cubic ZrO₂ matrix. The particulate-like characteristics of undoped and Gd doped ZrO₂ nanostructures were examined through the electron microscopes, which hardly revealed any difference among them. The optical band gap of ZrO₂ nanostructures was determined to be around 4.64–4.80 eV from the absorbance measurements. The potential of Gd doped ZrO₂ nanostructures for dielectric functions were evaluated through electrochemical impedance spectroscopic measurements. The improved capacitance values estimated from the Nyquist plots suggests the potential of the investigated materials for low power and low voltage electronic applications.     

Samarium-decorated ZrO2@SnO2 nanostructures,their electrical,optical and enhanced photoluminescence properties

In the present work, pure ZrO₂@SnO₂ and Samarium (Sm_x) (x?=?1%, 8% and 12%)-doped ZrO₂@SnO₂ nanoparticles (NPs) successfully synthesized by facile low-cost co-precipitation technique. As-synthesized nanostructures (NS) were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV–visible, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) spectroscopic investigation. The tetragonal crystal phase of the as-synthesized Sm_x:ZrO₂@SnO₂ NS confirmed by XRD analysis. The observed peak shift in the XRD patterns confirmed incorporation of dopant into host lattice. The Sm_x:ZrO₂@SnO₂ NS present irregular spherical morphology and high agglomeration confirmed by FESEM microscope analysis. The presence of functional groups, chemical bonding, chemical constituents and valence state of the NS confirmed by FT-IR and XPS analysis. The Sm_x:ZrO₂@SnO₂ NS showed higher surface area and smaller optical band gap (454 cm²/g and 2.12 eV) than the pure ZrO₂@SnO₂ NS (189–196 cm²/g and 2.84 eV). Photoluminescence (PL) spectra of undoped ZrO₂@SnO₂ and Sm_x:ZrO₂@SnO₂ NS exhibited oxygen vacancies. Undoped ZrO₂@SnO₂ NS exhibited emission intensity at 370.6 nm (λ_excitation?=?300 nm) whereas, Sm_x:ZrO₂@SnO₂ NS showed emission intensities at 453.4 nm, 476.3 nm, 601.3 nm (λ_excitation?=?300 nm). Electrical property studies of Sm_x:ZrO₂:SnO₂ (1%, 8% and 12%) NS showed large variation in Hall constant (0.125?×?10⁶ cm²/coulomb to 0.647?×?10⁶ cm²/coulomb) with proportionately large variation in the resistivity (147.8 Ω-cm to 456.8 Ω-cm) for all the doped samples as compared with pure ZrO₂@SnO₂ NS. The Sm³⁺-doped ZrO₂@SnO₂ NS showed higher stability, intense PL emission and enhanced electrical properties.

     

Effects of atomic oxygen exposure on the tribological performance of ZrO2-reinforced polyimide nanocomposites for low earth orbit space applications

The effects of atomic oxygen exposure on pure polyimide and nano-ZrO₂ reinforced polyimide composites were investigated in a ground-based simulation facility. The experimental results indicated that the surface structure of both pure polyimide and ZrO₂/polyimide composites were destroyed by atomic oxygen attack, but the addition of nano-ZrO₂ particles in polyimide could obviously decrease the mass loss, which showed that ZrO₂ could enhance the atomic oxygen resistance. The results of ZrO₂/polyimide composites before and after atomic oxygen exposure showed that atomic oxygen irradiation aggravated the friction and wear of the ZrO₂/polyimide composites. The wear mechanism was mainly abrasive particles wear arising from the ZrO₂-rich layer on the surface of composites. The ZrO₂/polyimide composites with 1 wt% nano-ZrO₂ owns the lowest varying rate of the friction coefficient and wear rate before and after atomic oxygen exposure, which showed stable friction and wear properties and was expected to become a kind of potential tribological materials for practical spacecraft designation.     

Synthesis,optoelectronic and thermal characterization of PMMA-MWCNTs nanocomposite thin films incorporated by ZrO2 NPs

PMMA polymer doped by multi-walled carbon nanotubes (MWCNTs) has attracted much attention as promising materials for photovoltaic and optoelectronic applications. The undoped poly(methyl methacrylate) (PMMA) and PMMA/MWCNTs nanocomposite films doped with varying concentrations of Zirconium dioxide nanoparticles (ZrO₂ NPs) are synthesized using the casting method. It is found that the transmittance (\(T\%\)) decreases significantly as wt%?=?5% of MWCNTs is injected into PMMA matrix. In addition, increasing the concentration of ZrO₂ NPs into PMMA- MWCNTs nanocomposite thin films results in a further reduction of the transmittance and a further increase of the reflectance (\(R\%\)). The optical band gap energy (E_g) of PMMA-MWCNTs/ZrO₂ NPs decreases from 4.063 \(eV\) to 3.845 \(eV\) upon injection of 5% of MWCNTs and gradually increasing the ZrO₂ concentration in PMMA matrix. Furthermore, other essential optical parameters are estimated using different classical models such as Drude, Spitzer-Fan, Sellmeier, and Wemple–DiDomenico (WDD). Interestingly, thermal stability of PMMA-MWCNTs nanocomposite films is enhanced dramatically upon increasing the content of ZrO₂ NPs. The synthesized nanocomposite thin films could be potential candidates for fabrication realistic scaled optoelectronic devices.

     

A novel method for producing open-cell Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> ceramic foams with controlled cell structure

A novel method was introduced to prepare open-cell Al₂O₃–ZrO₂ ceramic foams with controlled cell structure. This method used epispastic polystyrene (EPS) spheres to array ordered templates and centrifugal slip casting in the interstitial spaces of the EPS template to obtain cell struts with high packing density. Aqueous Al₂O₃–ZrO₂ slurries with up to 50 vol.% solid contents were prepared and centrifuged at acceleration of 2,860g. The effect of the solid contents of slurries on segregation phenomena of different particles and green compact uniformity were investigated. In multiphase system, the settling velocities of Al₂O₃ and ZrO₂ particles were calculated. Theory analysis and calculated results both indicated segregation phenomenon was hindered for slurries with 50 vol.% solid content. The cell struts of sintered products had high green density (61.5%TD), sintered density (99.1%TD) and homogeneous microstructures after sintered at 1,550 °C for 2 h. The cell size and porosity of Al₂O₃–ZrO₂ ceramic foams can be adjusted by changing the size of EPS spheres and the load applied on them during packing, respectively. When the porosity increased from 75.3% to 83.1%, the compressive strength decreases from 3.82 to 2.07 MPa.     

Effect of annealing temperature on optical and electrical properties of ZrO2–SnO2 nanocomposite thin films

ZrO₂–SnO₂ nanocomposite thin films were deposited onto quartz substrate by sol–gel dip-coating technique. Films were annealed at 500, 800 and 1,200 °C respectively. X-ray diffraction pattern showed a mixture of three phases: tetragonal ZrO₂ and SnO₂ and orthorhombic ZrSnO₄. ZrSnO₄ phase and grain size increased with annealing temperature. Fourier transform infra-red spectroscopy spectra indicated the reduction of –OH groups and increase in ZrO₂–SnO₂, by increasing the treatment temperature. Scanning electron microscopy observations showed nucleation and particle growth on the films. The electrical conductivity decreased with increase in annealing temperature. An average transmittance greater than 80 % (in UV–visible region) was observed for all the films. The optical constants of the films were calculated. A decrease in optical band gap from 4.79 to 4.59 eV was observed with increase in annealing temperature. Photoluminescence (PL) spectra revealed an emission peak at 424 nm which indicates the presence of oxygen vacancy in ZrSnO₄. PL spectra of the films exhibited an increase in the emission intensity with increase in temperature which substantiates enhancement of ZrSnO₄ phase and reduction in the non-radiative defects in the films. The nanocomposite modifies the structure of the individual metal oxides, accompanied by the crystallite size change and makes it ideal for gas sensor and optical applications.     

Reflux synthesis and hydrothermal processing of ZrO2 nanopowders at low temperature

In this paper, we report on the reflux synthesis at 90 °C and hydrothermal processing at 120 °C for obtention of zirconium oxide (ZrO₂) nanopowders under several conditions. These nanopowders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman) spectroscopy, adsorption–desorption N₂-isotherms, Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and field-emission scanning electron microscopy (FE-SEM). XRD patterns and Raman spectra indicated that ZrO₂ nanopowders present a monoclinic structure. In addition, the hydrothermal processing promoted an increase in crystallinity of ZrO₂ nanopowders. FT-IR spectra revealed a small shoulder on the ν (Zr–O) bands in transmittance spectra of the ZrO₂ nanopowders. The decomposition of precursor was accompanied by evolution of TGA curves. The morphology of ZrO₂ nanopowders was observed by FEG-SEM. Also, the FEG-SEM micrographs revealed that the presence of H₂O₂ in systems reduced the particle size, while the absence of promoted an increase in particle size.