Optical transmission larger than 1 (T > 1) through ZnS-SiO2/AgOx/ZnS-SiO2 sandwiched thin films

Optical transmission through flat media should be smaller than 1. However, we have observed optical transmission up to T=1.18. The samples were ZnS-SiO2/AgOx/ZnS-SiO2 sandwiched thin films on glass substrate. The supertransmission could only be observed in the near field. We attribute the supertransmission to the lateral propagation relayed by the laser activated and decomposed Ag nanoparticles. (c) 2006 American Institute of Physics.

倾斜角沉积技术制备ZnS双折射雕塑薄膜

使用倾斜角沉积（GLAD）的电子束蒸发技术，制备了倾斜角度在60°～85°之间的ZnS双折射雕塑薄膜（STF）。使用X射线衍射（XRD）和扫描电镜（SEM）检测了ZnS薄膜的结晶状态和断面形貌，使用Lamda-900分光光度计测量了薄膜在不同的偏振光入射时的透过率。研究发现，室温下倾斜沉积ZnS薄膜断面为倾斜柱状结构，且薄膜的结晶程度不高。在相同的监控厚度时，随倾斜角度增大，沉积到基片上的薄膜厚度逐渐变小，但仍然大于余弦曲线显示的理论厚度。根据偏振光垂直入射时薄膜的透过光谱计算了不同角度沉积的薄膜的折射率

Structure and optical properties of ZnS thin films grown by glancing angle deposition

The glancing angle deposition (GLAD) technique was used to deposit ZnS films by electron beam evaporation method. The cross sectional scanning electron microscopy (SEM) image illustrated a highly orientated microstructure composed of slanted column. The atomic force microscopy (APM) analysis indicated that incident flux angle had significant effects on the nodule size and surface roughness. Under identical nominal thickness, the actual thickness of the GLAD films is related to the incident flux angle. The refractive index and in-plane birefringence of the GLAD ZnS films were discussed, and the maximum bireffingence Delta n = 0.036 was obtained at incident flux angle of alpha = 80 degrees. Therefore, the glancing angle deposition technique is a promising way to create a columnar structure with enhanced birefringent property. (c) 2005 Elsevier B.V. All rights reserved.

Structure and UV emission of nanocrystal ZnO films by thermal oxidation of ZnS films

ZnO films prepared by the thermal oxidation of the ZnS films through thermal evaporation are reported. The as-deposited ZnS films have transformed to ZnO films completely at 400 degrees C. The 400-700 degrees C annealed films with a preferential c-axis (002) orientation have a hexagonal wurtzite structure. The band gap of ZnO films shifts towards longer wavelength with the increase of the annealing temperature. The relationship between the band gap energy of ZnO films and the grain size is discussed. The shift of the band gap energy can be ascribed to the quantum confinement effect in nanocrystal ZnO films. The photoluminescence spectra of ZnO films show a dominant ultraviolet emission and no deep level or trap state defect emission in the green region. It confirms the absence of interstitial zinc or oxygen vacancies in ZnO films. These results indicate that ZnO film prepared by this simple thermal oxidation method is a promising candidate for optoelectronic devices and UV laser. (c) 2005 Elsevier BN. All rights reserved.

Influence of ZnS and MgO Shell on the Photoluminescence Properties of ZnO Core/Shell Nanowire

Chinese Academy of Sciences；National Science Fund for Distinguished Young Scholar 60925016；National High Technology Research and Development program of China 2009AA034101；Postdoctoral Foundation 0971050000

Synthesis and photoluminescence, field emission properties of stalactite-like ZnS-ZnO composite nanostructures

Wurtzite stalactite-like quasi-one-dimensional ZnS nanoarrays with ZnO protuberances were synthesized through a thermal evaporation route. The structure and morphology of the samples are studied and the growth mechanism is discussed. X-ray diffraction (XRD) results show both the ZnS stem and the ZnO protuberances have wurtzite structure and show preferred [001] oriented growth. The photoluminescence and field emission properties have also been investigated. Room temperature photoluminescence result shows it has a strong green light emission, which has potential application for green light emitter. Experimental results also show that the stalactite arrays have a good field emission property, with turn-on field of 11.4 V/mu m, and threshold field of 16 V/mu m. The ZnO protuberances on the ZnS stem might enhance the field emission notably.

The bipolar doping of ZnS via native defects and external dopants

By employing first-principle total-energy calculations, a systematic study of the dopability of ZnS to be both n- and p-types compared with that of ZnO is carried out. We find that all the attempted acceptor dopants, group V substituting on the S lattice site and group I and IB on the Zn sites in ZnS, have lower ionization energies than the corresponding ones in ZnO. This can be accounted for by the fact that ZnS has relative higher valence band maximum than ZnO. Native ZnS is weak p-type under S-rich condition, as the abundant acceptor V-Zn has rather large ionization energy. Self-compensations by the formation of interstitial donors in group I and IB-doped p-type ZnS can be avoided when sample is prepared under S-rich condition. In terms of ionization energies, Li-Zn and N-S are the preferred acceptors in ZnS. Native n- type doping of ZnS is limited by the spontaneous formation of intrinsic V-Zn(2-); high efficient n-type doping with dopants is harder to achieve than in ZnO because of the readiness of forming native compensating centers and higher ionization energy of donors in ZnS. (C) 2009 American Institute of Physics. [DOI 10.1063/1.3103585]

Photoluminescence of Te isoelectronic centers in ZnS : Te under hydrostatic pressure

The photoluminescence of four epitaxial ZnS: Te samples with Te concentration from 0.5% to 3.1% was investigated at different temperature and ambient pressure. Two well-known emission bands related to the isolated Te-1 and Te-2 pair isoelectronic centers were observed for the samples with Te concentrations of 0.5% and 0.65%. For the samples with Te concentrations of 1.4% and 3.1%, only was the Te-2-related peak observed. The pressure behaviors of these emission bands, were studied at 15 K. The Te-1 -related band has faster pressure shift to higher energy than ZnS band gap. On the other hand, the pressure coefficient of Te-2 -related bands is smaller than that of the ZnS band gap. According to a Koster-Slater model, we found that the increase of the density bandwidth of the valence band with pressure is the main reason for the faster shift of the Te-1 centers, while the relatively large difference in the pressure behavior of the Te-1 and Te-2 centers is mainly due to the difference in the pressure-induced enhancement of the impurity potential on Te-1 and Te-2 centers.

Structural phase transformations of ZnS nanocrystalline under high pressure

In-situ energy dispersive x-ray diffraction on ZnS nanocrystalline was carried out under high pressure by using a diamond anvil cell. Phase transition of wurtzite of 10 nm ZnS to rocksalt occurred at 16.0 GPa, which was higher than that of the bulk materials. The structures of ZnS nanocrystalline at different pressures were built by using materials studio and the bulk modulus, and the pressure derivative of ZnS nanocrystalline were derived by fitting the equation of Birch-Murnaghan. The resulting modulus was higher than that of the corresponding bulk material, which indicates that the nanomaterial has higher hardness than its bulk materials.

Synthesis and optical properties of europium-doped ZnS: Long-lasting phosphorescence from aligned nanowires

Quasi-aligned Eu2+-doped wurtzite ZnS nanowires on Au-coated Si wafers have been successfully synthesized by a vapor deposition method under a weakly reducing atmosphere. Compared with the undoped counterpart, incorporation of the dopant gives a modulated composition and crystal structure, which leads to a preferred growth of the nanowires along the [0110] direction and a high density of defects in the nanowire hosts. The ion doping causes intense fluorescence and persistent phosphorescence in ZnS nanowires. The dopant Eu2+ ions form an isoelectronic acceptor level and yield a high density of bound excitions, which contribute to the appearance of the radiative recombination emission of the bound excitons and resonant Raman scattering at higher pumping intensity. Co-dopant Cl- ions can serve not only as donors, producing a donor-acceptor pair transition with the Eu2+ acceptor level, but can also form trap levels together with other defects, capture the photoionization electrons of Eu2+, and yield long-lasting (about 4 min), green phosphorescence. With decreasing synthesis time, the existence of more surface states in the nanowires forms a higher density of trap centers and changes the crystal-field strength around Eu2+. As a result, not only have an enhanced Eu2+ -4f(6)5d(1)-4f(7) intra-ion transition and a prolonged afterglow time been more effectively observed (by decreasing the nanowires' diameters), but also the Eu2+ related emissions are shifted to shorter wavelengths.

Optical and magnetic properties of ZnS nanoparticles doped with Mn2+

ZnS:Mn nanoparticles of the cubic zinc blende structure with the average sizes of about 3 nm were synthesized using a coprecipitation method and their optical and magnetic properties were investigated. Two emission bands were observed in doped nanoparitcles and attributed to the defect-related emission of ZnS and the Mn2+ emission, respectively. With the increase of Mn2+ concentration, the luminescence intensities of these two emission bands increased and the ZnS emission band shifted to lower energy. Based on the luminescence excitation spectra of Mn2+, the 3d(5) level structure of Mn2+ in ZnS nanoparticles is similar to that in bulk ZnS:Mn, regardless of Mn2+ concentration. Magnetic measurements showed that all the samples exhibit paramagnetic behavior and no antiferromagnetic interaction between Mn2+ ions exists, which are in contrast to bulk ZnS:Mn. (c) 2005 Elsevier B.V. All rights reserved.

Concentration effect of Mn2+ on the photoluminescence of ZnS : Mn nanocrystals

Mn-doped ZnS nanocrystals of about 3 nm diameter were synthesized by a wet chemical method. X-ray diffraction (XRD) measurements showed that the nanocrystals have the structure of cubic zinc blende. The broadening of the XRD lines is indicative of nanomaterials. Room temperature photoluminescence (PL) spectrum of the undoped sample only exhibited a defected-related blue emission band. But for the doped samples, an orange emission from the Mn2+ T-4(1)-(6)A(1) transition was also observed, apart from the blue emission. The peak position (600 nm) of the Mn2+ emission was shifted to longer wavelength compared to that (584 nm) of bulk ZnS:Mn. With the increase of the Mn2+ concentration, the PL of ZnS:Mn was significantly enhanced. The concentration quenching effect was not observed in our experiments. Such PL phenomena were attributed to the absence of Mn2+ pairs in a single ZnS:Mn nanocrystal, considering the nonradiative energy transfer between Mn2+ ions based on the Poisson approximation. (c) 2005 Elsevier B.V. All rights reserved.

Structural and optical investigation of Mn-doped ZnS nanocrystals

Using a solution-based chemical method, we have prepared ZnS nanocrystals doped with high concentration of Mn2+. The X-ray diffraction analysis confirmed a zinc blende structure. The average size was about 3 nm. Photoluminescence spectrum showed room temperature emission in the visible spectrum, which consisted of the defect-related emission and the T-4(1)-(6)A(1) emission of Mn2+ ions. Compared with the undoped sample, the luminescence of the ZnS:Mn sample is enhanced by more than an order of magnitude, which indicated that the Mn2+ ions can efficiently boost the luminescence of ZnS nanocrystals.

Investigation of phtoluminesecence under hydrostatic pressure in different sized ZnS : Mn nanoparticles

The PL spectra for the 10, 4. 5, 3. 5, 3, 1 nm sized ZnS:Mn2+ nanoparticles and corresponding bulk material under different pressures were investigated. The orange emission band originated from the T-4(1)-(6)A(1) transition of Mn2+ ions showed obvious red shift with the increasing of pressures. The pressure coefficients of Mn-related emissions measured from bulk, 10, 4. 5, 3.5 and 3 nm samples are -29.4 +/- 0.3, -30.1 +/- 0.3, -33.3 +/- 0.6, -34.6 +/- 0.8 and -39 +/- 1 meV/GPa, respectively. The absolute value of the pressure coefficient increases with the decrease of the size of particles. The size dependence of crystal field strength Dq and Racah parameter B accounts for the size behavior of the Mn-related emission in ZnS:Mn nanoparticles. The pressure behavior of Mn-related emission in the 1 nm sized sample is somewhat different from that of other nanoparticles. It may be due to smaller size of 1 nm sample and the special surface condition since ZnS nanoparticles are formed in the cavities of ziolite-Y for the 1 nm sample.