Oxygen vacancy-induced room-temperature ferromagnetism in D-D neutron irradiated single-crystal TiO2 （001） rutile

Remarkable room temperature ferromagnetism in pure single-crystal rutile TiO2 （001） samples irradiated by D-D neutron has been investigated. By combining X-ray diffraction and positron annihilation lifetime, the contracted lattice has been clearly identified in irradiated TiO2, where Ti4＋ ions can be easily reduced to the state of Ti3＋. As there were no magnetic impurities that could contaminate the samples during the whole procedure, some Ti3＋ ions reside on interstitial or substituted sites accompanied by oxygen vacancies should be responsible for the ferromagnetism.     

First-principles study on with nitrogen and anatase TiO2 codoped praseodymium

<正>The crystal structures,electronic structures and optical properties of nitrogen or/and praseodymium doped anatase TiO₂ were calculated by first principles with the plane-wave ultrasoft pseudopotential method based on density functional theory.Highly efficient visible-light-induced nitrogen or/and praseodymium doped anatase TiO₂ nanocrystal photocatalyst were synthesized by a microwave chemical method.The calculated results show that the photocatalytic activity of TiO₂ can be enhanced by N doping or Pr doping,and can be further enhanced by N+Pr codoping.The band gap change of the codoping TiO₂ is more obvious than that of the single ion doping,which results in the red shift of the optical absorption edges.The results are of great significance for the understanding and further development of visible-light response high activity modified TiO₂ photocatalyst.The photocatalytic activity of the samples for methyl blue degradation was investigated under the irradiation of fluorescent light.The experimental results show that the codoping TiO₂ photocatalytic activity is obviously higher than that of the single ion doping.The experimental results accord with the calculated results.     

Structure, room-temperature magnetic and optical properties of Mn-doped TiO2 nano powders prepared by the sol-gel process

TiO 2 nano powders with Mn concentration of 0 at%-12 at% were synthesized by the sol-gel process,and were annealed at 500 C and 800 C in air for 2 hrs.X-ray diffraction (XRD) measurements indicate that the Mn-TiO 2 nano powders with Mn concentration of 1 at% and 2 at% annealed at 500 and 800 C are of pure anatase and rutile,respectively.The scanning electron microscope (SEM) observations reveal that the crystal grain size increases with the annealing temperature,and the high resolution transmission electron microscopy (HRTEM) investigations further indicate that the samples are well crystallized,confirming that Mn has doped into the TiO 2 crystal lattice effectively.The room temperature ferromagnetism,which could be explained within the scope of the bound magnetic polaron (BMP) theory,is detected in the Mn-TiO 2 samples with Mn concentration of 2 at%,and the magnetization of the powders annealed at 500 C is stronger than that of the sample treated at 800 C.The UV-VIS diffuse reflectance spectra results demonstrate that the absorption of the TiO 2 powders could be enlarged by the enhanced trapped electron absorption caused by Mn doping.     

Analysis of optoelectronic properties of TiO_2 nanowiers/Si heterojunction arrays

The optoelectronic properties of n-TiO2NW/p-Si heterojunction fabricated by depositing TiO2 nanowires on a p-Si substrate are studied. Under excitation at a wavelength of 370 nm, the TiO2 nanowires produce a light emission at 435 nm due to the emission of free excitons. The I-V characteristics are measured to investigate the heterojunction effects under the dark environment and ultraviolet （UV） illumination, n-TiOzNW/p-Si has a p-n junction formed in the n-TiOz/p-Si beterojunction. TiO2NW/Si photodiode produces a pbotocurrent larger than dark current under UV illumination. It is observed that UV photons are absorbed in TiO2 and the heterojunction shows a 0.034-A/W responsivity at 4-V reverse bias.     

Direct growth of graphene on gallium nitride by using chemical vapor deposition without extra catalyst

Graphene on gallium nitride(GaN) will be quite useful when the graphene is used as transparent electrodes to improve the performance of gallium nitride devices. In this work, we report the direct synthesis of graphene on GaN without an extra catalyst by chemical vapor deposition. Raman spectra indicate that the graphene films are uniform and about 5–6 layers in thickness. Meanwhile, the effects of growth temperatures on the growth of graphene films are systematically studied, of which 950℃ is found to be the optimum growth temperature. The sheet resistance of the grown graphene is 41.1Ω/square,which is close to the lowest sheet resistance of transferred graphene reported. The mechanism of graphene growth on GaN is proposed and discussed in detail. XRD spectra and photoluminescence spectra indicate that the quality of GaN epi-layers will not be affected after the growth of graphene.     

Growth of monodisperse nanospheres of MnFe_2O_4 with enhanced magnetic and optical properties

Highly dispersive nanospheres of MnFe204 are prepared by template free hydrothermal method. The nanospheres have 47.3-nm average diameter, narrow size distribution, and good crystallinity with average crystallite size about 22 nm. The reaction temperature strongly affects the morphology, and high temperature is found to be responsible for growth of uniform nanospheres. Raman spectroscopy reveals high purity of prepared nanospheres. High saturation magnetization （78.3 emu/g）, low coercivity （45 Oe, 10e = 79.5775 A.cm-1）, low remanence （5.32 emu/g）, and high anisotropy constant 2.84 × 10^4 J/m3 （10 times larger than bulk） are observed at room temperatures. The nearly snperparamagnetic behavior is ~ spin due to comparable size of nanospheres with superparamagnetic critical thameter Dcr spm The high value of Keff may be due to coupling between the pinned moment in the amorphous shell and the magnetic moment in the core of the nanospheres. The nanospheres show prominent optical absorption in the visible region, and the indirect band gap is estimated to be 0.98 eV from the transmission spectrum. The prepared Mn ferrite has potential applications in biomedicine and photocatalysis.     

Effects of shape and dopant on structural,optical absorption,Raman, and vibrational properties of silver and copper quantum clusters: A density functional theory study

We investigate the effects of shape and single-atom doping on the structural, optical absorption, Raman, and vibra- tional properties of Ag13, Ag12CUl, CUl3, and Cul2Agl clusters by using the （time-dependent） density functional the- ory. The results show that the most stable structures are cuboctahedron （COh） for Ag13 and icosahedron （Ih） for CUl3, Agl2CUlcore, and Cul2Aglsur. In the visible-near infrared optical absorption, the transitions consist of the interband and the intraband transitions. Moreover, red shifts are observed as follows： 1） clusters change from Agl2CUlcore to Ag13 to Ag12Culsur with the same motifs, 2） the shapes of pure Agl3 and Agl2CUlcore clusters change from COh to Ih to decahe- dron （Dh）, 3） the shape of Agl2CUlsur clusters changes from Ih to COh to Dh, and 4） the shapes of pure CU13 and Cu12Agl clusters change from Ih to Dh to COb. All of the Raman and vibrational spectra exhibit many significant vibrational modes related to the shapes and the compositions of the clusters. The ranges of vibrational spectra of Ag13, Agl2CUl or CU13, and Cu12Agl clusters become narrower and the vibrational intensities increase as the shape of the clusters changes from Ih to Dh to COh.     

Improved Ligand-Field Theoretical Calculations of R-Line Thermal Broadenings of NIgO：Cr^3＋ and MgO：V^2＋

With the values of parameters obtained from improved ligand-field theory, by taking into account all the irreducible representations and their components in EPI as well as all the levels and the admixtures of basic wavefunctions within d^3 electronic configuration, the R-line thermal broadenings （TB） of both MgO：Cr^3＋ and MgO：V^2＋ have microscopic-theoretically been calculated, The results are in very good agreement with the experimental data. It is found that the R-line TB of MgO：Cr^3＋ or MgO：V^2＋ comes from the first-order term of EPI. The elastic Raman scattering of acoustic phonons plays a dominant role in R-line TB of MgO：Cr^3＋ or MgO：V^2＋.     

Epitaxial growth of Ge1-xSnx films with x up to 0.14 grown on Ge （001） at low temperature

We characterize the structures of Ge1-xSnx films with x up to 0.14 grown on Ge （001） by molecular-beam epitaxy at low temperature. The results show that Ge1-xSnx films are fully strained even at high Sn composition. The in-plane lattice parameters remain exactly the same as that of the substrate. Depth sensitivity analysis of the lattice parameters indicates that the strains of the epitaxial films are all in homogeneity. The films are fully strained. Poisson ratios, the force constants for the bonds between Ge and Sn are estimated and discussed in the present paper. Raman results show Ge-Ge, Ge-Sn, Sn-Sn vibrational modes. The Sn-Sn bond aggregation may respond to the high quality of our films. The fully strained epitaxy films with high content of Sn may be useful in designing the high quality GeSn films.     

Characterization of deep acceptor level in as-grown ZnO thin film by molecular beam epitaxy

We report deep level transient spectroscopy results from ZnO layers grown on silicon by molecular beam epitaxy(MBE). The hot probe measurements reveal mixed conductivity in the as-grown ZnO layers, and the current–voltage(I–V)measurements demonstrate a good quality p-type Schottky device. A new deep acceptor level is observed in the ZnO layer having activation energy of 0.49±0.03 eV and capture cross-section of 8.57×10-18cm2. Based on the results from Raman spectroscopy, photoluminescence, and secondary ion mass spectroscopy(SIMS) of the ZnO layer, the observed acceptor trap level is tentatively attributed to a nitrogen–zinc vacancy complex in ZnO.     

Structural and optical properties of a NaCl single crystal doped with CuO nanocrystals

A cupric oxide (CuO) nanocrystal-doped NaCl single crystal and a pure NaCl single crystal are grown by using the Czochralski (Cz) method. A number of techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, optical absorption in the UV-visible range, and photoluminescence (PL) spectroscopy are used to characterize the obtained NaCl and NaCl:CuO crystals. It is observed that the average radius of CuO crystallites in NaCl:CuO crystal is about 29.87 nm, as derived from the XRD data analysis. Moreover, FT-IR and Raman spectroscopy results confirm the existence of the monoclinic CuO phase in NaCl crystal. UV-visible absorption measurements indicate that the band gap of the NaCl:CuO crystal is 434 nm (2.85 eV), and it shows a significant amount of blue-shift (△Eg = 1 eV ) in the band gap energy of CuO, which is due to the quantum confinement effect exerted by the CuO nanocrystals. The PL spectrum of the NaCl:CuO shows a broad emission band centred at around 438 nm, which is consistent with the absorption measurement.     

Improved crystal quality of GaN film with the in-plane lattice-matched Ino.17Alo.s3N interlayer grown on sapphire substrate using pulsed metal-organic chemical vapor deposition

We report on an improvement in the crystal quality of GaN film with an Ino.17Alo.83N interlayer grown by pulsed metal-organic chemical vapor deposition, which is in-plane lattice-matched to GaN films. The indium composition of about 17% and the reductions of both screw and edge threading dislocations （TDs） in GaN film with the InA1N interlayer are estimated by high resolution X-ray diffraction. Transmission electron microscopy （TEM） measurements are employed to understand the mechanism of reduction in TD density. Raman and photoluminescence measurements indicate that the InA1N interlayer can improve the crystal quality of GaN film, and verify that there is no additional residual stress induced into the GaN film with InA1N interlayer. Atomic force microscopy measurement shows that the InA1N interlayer brings in a smooth surface morphology of GaN film. All the results show that the insertion of the InA1N interlayer is a convenient method to achieve excellent crystal quality in GaN epitaxy.     

Study on lattice vibrational properties and Raman spectra of Bi_2Te_3 based on density-functional perturbation theory

We present a variational density-functional perturbation theory(DFPT) to investigate the lattice dynamics and vibrational properties of single crystal bismuth telluride material. The phonon dispersion curves and phonon density of states(DOS) of the material were obtained. The phonon dispersions are divided into two fields by a phonon gap. In the lower field,atomic vibrations of both Bi and Te contribute to the DOS. In the higher field, most contributions come from Te atoms. The calculated Born effective charges and dielectric constants reveal a great anisotropy in the crystal. The largest Born effective charge generates a significant dynamic charge transferring along the c axis. By DFPT calculation, the greatest LO–TO splitting takes place in the infrared phonon modes and reaches 1.7 THz in the Brillouin zone center. The Raman spectra and peaks corresponding to respective atomic vibration modes were found to be in good agreement with the experimental data.     

Influence of reaction parameters on synthesis of high-quality single-layer graphene on Cu using chemical vapor deposition

Large-area monolayer graphene samples grown on polycrystalline copper foil by thermal chemical vapor deposition with differing CH4 flux and growth time are investigated by Raman spectra, scanning electron microscopy, atomic force microscopy, and scanning tunneling microscopy. The defects, number of layers, and quality of graphene are shown to be controllable through tuning the reaction conditions: ideally to 2–3 sccm CH4 for 30 minutes.     

Analysis of detection limit to time-resolved coherent anti-Stokes Raman scattering nanoscopy

In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume can be detected. Here reported is a theoretical analysis of detection limit （DL） to time-resolved CARS （T-CARS） nanoscopy based on our proposed additional probe-beam-induced phonon depletion （APIPD） method for the low concentration samples. In order to acquire a detailed shot-noise limited signal-to-noise （SNR） and the involved parameters to evaluate DL, the T-CARS process is described with full quantum theory to estimate the extreme power density levels of the pump and Stokes beams determined by saturation behavior of coherent phonons, which are both actually on the order of ~ 109 W/cm2. When the pump and Stokes intensities reach such values and the total intensity of the excitation beams arrives at a maximum tolerable by most biological samples in a certain suppressed focal volume （40-nm suppressed focal scale in APIPD method）, the DL correspondingly varies with exposure time, for example, DL values are 103 and 102 when exposure times are 20 ms and 200 ms respectively.     

The effect of an anti-hydrogen bond on Fermi resonance： A Raman spectroscopic study of the Fermi doublet v1-v12 of liquid pyridine

The effects of an anti-hydrogen bond on the v1 v12 Fermi resonance （FR） of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode v1 and triangle mode v12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the v1-v12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the v1-v12 FR of pyridine. According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the v1 - v12 FR of pyridine is given.     

Enormous enhancement of electric field in active gold nanoshells

The electric field enhancement properties of an active gold nanoshell with gain material inside have been investigated by using Mie theory. As the gain coefficient of the inner core increases to a critical value, a super-resonance appears in the active gold nanoshell, and enormous enhancements of the electric fields can be found near the surface of the particle. With increasing shell thickness, the critical value of the gain coefficient for the super-resonance of the active gold nanoshell first decreases and then increases, and the corresponding surface enhanced Raman scattering （SERS） enhancement factor （G factor） also first increases and then decreases. The optimized active gold nanoshell can be obtained with an extremely high SERS G factor of the order of 1019-1020. Such an optimized active gold nanoshell possesses a high-efficiency SERS effect and may be useful for single-molecule detection.     

Phase transition and thermal expansion property of Cr_(2-x)Zr_(0.5x)Mg_(0.5x)Mo_3O_(12) solid solution

Compounds with the formula Cr2-xZr0.5xMg0.5xMo3O12（x = 0.0, 0.3, 0.5, 0.9, 1.3, 1.5, 1.7, 1.9） are synthesized, and the effects of Zr4＋ and Mg2＋ co-incorporation on the phase transition, thermal expansion, and Raman mode are investigated. It is found that Cr2-xZr0.5xMg0.5xMo3O12 crystallize into monoclinic structures for x 〈 1.3 and orthorhombic structures for x _〉 1.5 at room temperature. The phase transition temperature from a monoclinic to an orthorhombic structure of Cr2Mo3O12 can be reduced by the partial substitution of （ZrMg）6＋ for Cr3＋. The overall linear thermal expansion coefficient decreases with the increase of the （ZrMg）6＋ content in an orthorhombic structure sample. The co-incorporation of Zr4＋ and Mg2＋ in the lattice results in the occurrence of new Raman modes and the hardening of the symmetric vibrational modes, which are attributed to the MoO4 tetrahedra sharing comers with ZrO6/MgO6 octahedra and to the strengthening of Mo-O bonds due to less electronegativities of Zr4＋ and Mg2＋ than Cr3＋, respectively.     

掺磷TiO_2优化TiO_2/MBA/Ag三明治结构的SERS性能

本文以磷酸为磷源,通过溶胶水热法制备磷掺杂TiO_2,利用Lee和Meisel的方法制备银溶胶,以4-巯基苯甲酸(MBA)为探针分子,通过构建TiO_2/MBA/Ag三明治结构,研究磷掺杂二氧化钛对该基底表面增强拉曼(SERS)性能的提升。通过TEM、XRD、XPS、DRS和拉曼光谱图表征二氧化钛的形貌结构、化学组成、光学和拉曼性能,结果表明,制备出的磷掺杂二氧化钛为锐钛矿型纳米颗粒,粒径范围6~12nm,XPS显示磷以P~(5+)替代了Ti~(4+),形成O-P-O键掺入TiO_2的晶格中,当磷的掺杂量在1.77%时,TiO_2/MBA/Ag三明治体系具有最佳的SERS信号,这是因为适量的磷掺杂降低了TiO_2的能带间隙,丰富TiO_2的表面态,这能促进TiO_2向MBA分子的电荷转移。     

Vibrational properties of cagelike diamondoid nitrogen at high pressure

Under high pressure, a cagelike diamondoid nitrogen structure was lately discovered by first-principles structure researches. This newly proposed structure is very unique and has not been observed in any other element. Using density-functional calculations, we study the pressure effect on its vibrational properties. The Born effective charges are calculated, and the resulting LO-TO splittings of certain infrared active modes are beyond 20 cm 1 . We depict the Γ -point vibrational modes and find the breathing mode, rotational mode, and shearing mode. Frequencies of all the optical modes increase with pressure increasing. Moreover, the relation between the breathing mode frequency and the nitrogen cage diameter is discussed in detail. Our calculation results give a deeper insight into the vibrational properties of the cagelike diamondoid nitrogen.