Effect of magnetic pulsed field on luminescence of zinc sulfide doped with CuCl,In, and MnS

The effect of a magnetic pulsed field (MPF) of induction B = 1 T on photoluminescence, electroluminescence, and luminescence excitation spectra of powdered ZnS doped with CuCl, In, and MnS is investigated. It is shown that MPF treatment of these materials changes the photoluminescence spectra only in the case of luminophor ZnS:In whereas only the luminescence excitation spectra change for ZnS:CuCl and ZnS:Mn. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 367–372, May–June, 2007.     

Influences of capping molecules on optical properties of nanocrystalline ZnS:Cu

ZnS:Cu nanocrystals capped with different capping molecules have been successfully synthesized by a simple aqueous method. The prepared nanocrystals were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive analysis by X-rays (EDAX). The surface characterization of the nanocrystals was done by FTIR spectroscopy. The effect of capping agents on absorption and photoluminescence (PL) spectra of the ZnS:Cu nanocrystals was studied. A blue shift of the absorption peaks was observed and attributed to a quantum confinement effect, which increases the band gap energy. The photoluminescence spectra of the capped ZnS:Cu nanocrystals showed a broad peak in the range of 460–480 nm. The intensity of the PL spectra strongly depended on the capping agents.     

Mechanism of photoluminescence excitation of Mn<Superscript>2+</Superscript> ions in ZnS crystals

The mechanisms of photoluminescence excitation of Mn²⁺ ions in ZnS crystals have been investigated on the basis of complex analysis of the temperature dependences of the photoluminescence and photoluminescence-excitation spectra of ZnS:Mn crystals. The activation energy of a manganese luminescence center was estimated at E_a = 0.17 ± 0.05 eV. It is shown that E_a represents an energy band with a width ΔE_a = 0.1 eV, within which a manganese luminescence center can experience radiationless recombination. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 788–793, November–December, 2005.     

Photoluminescence of ZnS:Cu crystals at various concentrations of copper

Doping of ZnS crystals with background impurities and ZnS:Al crystals by various concentrations of copper from a bismuth melt has been carried out. The photoluminescence spectra of the starting ZnS crystals annealed in the bismuth melt and doped by copper have been investigated. Interpretation of the experimental results according to the model in which the associates (Cu _Zn ^′ Cu _i ^● ) are responsible for the B-Cu band (≈460 nm) and the donor—receptor pairs [Cu _i ^● -(Cu _Zn ^′ Cu _i ^● )] are responsible for the G-Cu band (≈505 nm) is given. It is assumed that doping by copper from a bismuth melt is accompanied by the separation of a Cu_xS-type phase. It has been shown that heat treatment of ZnS crystals in the Bi melt does not lead to the appearance of luminescence centers based on Bi_Zn, Bi_S, and Bi_i. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 794–798, November–December, 2005.     

147Pm激发的ZnS：Cu,Cl发光粉的研究

以高纯ZnS粉末为基质,采用高温转相、扩散,以及表面涂敷工艺,制得了¹⁴⁷Pm激发的ZnS:Cu,Cl发光粉。分析了ZnS:Cu,Cl的晶体结构,测量了ZnS:Cu,Cl的激发光谱、发射光谱、发光亮度。其晶体结构主要是六方纤锌矿型结构,激发光谱峰值波长为341nm,发射光谱峰值波长为513nm,初始发光亮度达到312mcd/m₂。由激发光谱的峰值波长341nm推算得到六方ZnS晶体的禁带宽度为3.64eV。分析了¹⁴⁷Pm激发的ZnS:Cu,Cl发光粉的发光寿命,其发光寿命达到5年以上。还探讨了该放射性发光粉的发光机理。¹⁴⁷Pm激发的ZnS:Cu,Cl的稳定发光,实际上是激发过程与复合过程的准平衡。ZnS:Cu,Cl的绿色发光来源于深施主-深受主对的复合发射。实验结果的分析表明,ZnS:Cu,Cl中深施主-深受主之间的能级间隔约为2.42eV。     

The influence of doping element on structural and luminescent characteristics of ZnS thin films

For the fabrication of green and blue emitting ZnS structures the elements of I, III, and VII groups (Cu, Al, Ga, Cl) are used as dopants. The influence of type of impurity, doping technique, and type of substrate on crystalline structure and surface morphology together with luminescent properties was investigated. The doping of thin films was realized during the growth process and/or post-deposition thermal treatment. ZnS thin films were deposited by physical (EBE) and chemical (MOCVD) methods onto glass or ceramic (BaTiO₃) substrates. Closed spaced evaporation and thermodiffusion methods were used for the post-deposition doping of ZnS films. X-ray diffraction (XRD) techniques, atomic force microscopy (AFM), and measurements of photoluminescent (PL) spectra were used for the investigations. It was shown that the doping by the elements of I (Cu) and III (Al, Ga) groups does not change the crystal structure during the thermal treatment up to 1000 C, whereas simultaneous use of the elements of I (Cu) and VII (Cl) groups leads to decrease of the phase transition temperature to 800 C. The presence of impurities in the growth process leads to a grain size increase. At post-deposition treatment Ga and Cl act as activators of recrystallization process. The transition of ZnS sphalerite lattice to wurtzite one leads to the displacement of the blue emission band position towards the short-wavelength range by 10 nm.     

Photoluminescent properties of ZnS nanoparticles prepared by electro-explosion of Zn wires

We study the photoluminescent properties of ZnS nanoparticles without the influence of dopants or magnetic impurities. The ZnS nanoparticles reported in this case were synthesized by a novel method of electro-explosion of wire (EEW). The nanoparticles were prepared employing electro-explosion of pure zinc wires in a cell filled with sulfide ions to produce a free-standing compound ZnS semiconductor. To investigate the structural and optical properties, these nanoparticles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), UV–visible and photoluminescence (PL) spectroscopy. Consistent with the enhancement of the PL intensity of the 443 nm peak due to deep blue emission of ZnS particles, the XRD of the nanoparticles reveals a hexagonal phase of ZnS nanocrystallites prepared by our novel synthesis technique.      

ZnO–ZnS heterostructures with enhanced optical and photocatalytic properties

ZnO–ZnS heterostructures were fabricated via using ZnO rods as template in different Na₂S aqueous solutions. These heterostructures are 5–6 μm in length and formed by coating ZnO rod with a layer of porous ZnS shell comprising primary crystals about 10 nm in diameter. Subsequently, intact ZnS polycrystalline tubes were obtained by removing the ZnO cores with 25% (wt) ammonia. The as-prepared products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDX), Fourier transform infrared (FT-IR), and electrochemical impedance spectroscopy (EIS). It was found that the electron transfer between ZnS shell and ZnO core strongly affect the photoluminescence and photocatalytic performances of these heterostructures. The rapid transfer of photo-induced electrons from the ZnS shell to the ZnO core leads to enhanced ultraviolet emission. However, if this correlation was destroyed, then the corresponding heterostructure exhibits improved photocatalytic efficiency due to the reduced volume recombination of the charge carries and the multiple reflection effect. Finally, a model based on band-gap alignment was proposed to elucidate the underlying mechanism of the enhanced UV emission and photocatalytic activity of these unique heterostructures.     

Photoluminescence characteristics of ZnS nanocrystallites doped with Ti3+and Ti4+

Direct synthesis of ZnS nanocrystallites doped with Ti³⁺ or Ti⁴⁺ by precipitation has led to novel photoluminescence properties. Detailed X-ray diffraction (XRD), fluorescence spectrophotometry, UV–vis spectrophotometry and X-ray photoelectron spectroscopy (XPS) analysis reveal the crystal lattice structure, average size, emission spectra, absorption spectra and composition. The average crystallite size doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2.6±0.2 nm. The nanoparticles can be doped with Ti³⁺ and Ti⁴⁺ during the synthesis without the X-ray diffraction pattern being altered. The strong and stable visible-light emission has been observed from ZnS nanocrystallites doped with Ti³⁺ (its maximum fluorescence intensity is about twice that of undoped ZnS nanoparticles). However, the fluorescence intensity of the ZnS nanocrystallites doped with Ti⁴⁺ is almost the same as that of the undoped ZnS nanoparticles. The emission peak of the undoped sample is at 440–450 nm. The emission spectrum of the doped sample consists of two emission peaks, one at 420–430 nm and the other at 510 nm. Received: 27 April 2001 / Accepted: 16 August 2001 / Published online: 17 October 2001     

Change of the luminescence decay time for Lu<Subscript>2</Subscript>O<Subscript>3</Subscript>: Eu nanocrystals embedded in synthetic opal

The opal-Lu_1.86Eu_0.14O₃ composites have been prepared using the developed technique for synthesizing luminophor nanocrystals in pores of synthetic opal through coprecipitation from a solution. It has been demonstrated that the position of the photonic stop band in the reflection spectrum of the infiltrated opal depends on the diameter of its spheres, the volume fraction of the embedded luminophor, and the angle of detection of the signal. The excitation and photoluminescence spectra of the composites have been analyzed, and the lifetime of the ⁵ D ₀ excited state of Eu³⁺ ions has been examined. It has been revealed that the luminescence decay time for the luminophor increases by almost one order of magnitude with an increase in its content in opal pores. This effect has been attributed to the change in the nanocrystal size and to the decrease in the contribution from the surface nonradiative recombination in luminophor nanolayers of the composites.     

Polarized emission of doped ZnS crystals

Polarization of light emitted in various spectral ranges was studied in two single crystals ZnS:Cu, Cl and ZnS:Ag, Cu, Al. The G-Cu, B-Cu and a small amount of S-A centers have been identified in the ZnS:Cu, Cl crystal by the spectral and polarization methods. The B-Ag band was found in the spectrum of the ZnS:Ag, Cu, Al crystal and its polarization properties investigated. This emission appears to be always polarized perpendicular to the [111]_c axis of the stacking faults independently of the polarization of the exciting light. The symmetry of the B-Ag center is not lower than that of the host lattice. Analogy with G-Cu centers suggests a model for the B-Ag center in which the polarization comes from the symmetry properties of the Ag²⁺ orbitals in the trigonal field of stacking faults.     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Heteroannihilation of the excited states of associates and monomers of fluorescein dyes on the silica surface at low temperatures

The processes of homo-and hetero-triplet—triplet annihilation (TTA) of Bengali rose on the spongy silicon surface have been investigated. It has been found that upon pulse photoexcitation on the silica surface photophysical processes involving the triplet states of monomers and their associates can develop. It has been shown that the processes of hetero-TTA are inhibited due to the decomposition of associates under the influence of hexane molecules in the molecular clusters of the dye adsorbates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 734–737, November–December, 2005.     

核-壳结构的ZnS:Cu/ZnS纳米粒子的制备及发光性质研究

制备了核-壳结构的ZnS:Cu/ZnS纳米粒子以及普通的没有壳的Cu2 掺杂的ZnS纳米粒子,研究了ZnS无机壳层对ZnS:Cu纳米粒子发光性质的影响.透射电子显微镜、激发光谱和发射光谱的研究表明,后加入的Zn2 离子在已经形成的ZnS核表面生长,形成ZnS壳层;而适当厚度的ZnS壳层可以钝化粒子表面,减少无辐射复合中心的数目,抑制表面态对发光的不利影响,提高ZnS:Cu纳米粒子中Cu2 离子在450 nm左右的发光强度.     

Photoelectric Characteristics of Composite Carbazole Polymerfilms Containing 1,8-Naphthoylene-1′,2′-Benzimidazole

The electric conduction and photoconduction of sandwich-type poly-N-epoxypropylcarbazole (PEPC) and 3,6-di-Br-poly-N-epoxypropylcarbazole (3,6-di-Br-PEPC) films containing 33 wt.% of the dye 1,8-naphthoylene-1′, 2′-benzimidazole (NBI) have been investigated. It has been established that the PEPC films, as compared to the 3,6-di-Br-PEPC films, have a higher electric conduction and a lower photosensitivity and an electric field exerts a stronger quenching effect on the photoluminescence of the first-mentioned films. Analysis of the voltampere and lux-ampere characteristics and the kinetics of electric conduction of these films has shown that the space charge and recombination via dye molecules in them influence their electric conduction and photoconduction. The volume recombination of charges is radiative in character. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 627–631, September–October, 2005.     

Electro- and photoluminescence of compounds based on doped zinc sulfide in the 500–750-nm range

The influence of atmospheric passivation on the electro- and photoluminescent properties of ZnS powders doped with In and/or CuCl is investigated. The processes proceeding in the material during thermal doping with In and/or CuCl as well as participation of oxygen in forming the electro- and photoluminescent radiation centers are discussed. The possibility of creating electro- and photoluminophors based on ZnS that have a continuous spectrum in the visible range with the same spectral density is shown. An electroluminophor based on ZnS:In,Cu,Cl that emits radiation with practically the same spectral density in the 550–750-nm range has been created as well as a photoluminophor based on ZnS:In that emits similarly within the range 500 < < 700 nm.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 90–93, January–February, 2005.     

Influence of successive electron and laser irradiation on the photoluminescence of porous silicon

The influence of electron irradiation on the light-emitting properties of p-and n-type porous silicon prepared by electrochemical etching is investigated. The dose and energy dependences of the electron-stimulated quenching of the photoluminescence (PL) are determined. It is shown that electron treatment of a porous silicon surface followed by prolonged storage in air can be used to stabilize the PL. The excitation of photoluminescence by a UV laser acting on sections of porous silicon samples subjected to preliminary electron treatment is discovered for the first time. The influence of the electron energy and the power of the laser beam on this process is investigated. The results presented are attributed to variation in the number of radiative recombination centers as a result of the dissociation and restoration of hydrogen-containing groups on the pore surface. Zh. Tekh. Fiz. 68, 58–63 (March 1998)     

Photoluminescence properties of core-shell SiO2/Lu2O3: Eu monodisperse heteronanoparticles

Core-shell monodisperse heteroparticles of the composition SiO₂/Lu_1.86Eu_0.14O₃ have been synthesized using the developed technique for preparing spherical colloidal silicon dioxide particles with the size dispersion in the range 2.0–2.5% and the procedure for producing nanocoatings on the surface of spheres by codeposition. The structure of heteroparticles has been investigated, their excitation and photoluminescence spectra have been analyzed, and the lifetime of the ⁵ D ₀ excited state of Eu³⁺ ions has been examined. It has been revealed that the luminescence decay time for heteroparticles increases by a factor of approximately two compared to that for a powdered luminophor Lu₂O₃: Eu (7 at %) prepared and treated under the same temperature conditions as the SiO₂/Lu₂O₃: Eu (7 at %) heteroparticles. This effect has been attributed to the change in the effective refractive index and the local density of photon states in luminophor nanolayers of heteroparticles.     

温度对CdSe/ZnS量子点吸收光谱和光致发光谱的影响

测量了分散于正己烷溶液和甲苯溶液中的CdSe/ZnS量子点在室温到近溶液沸点温度间的吸收与光致发光光谱,比较了两种不同的CdSe/ZnS量子点的光谱特性,讨论了温度对吸收和光致发光光谱峰值波长以及相对强度的影响。结果表明:在25~100℃范围内,CdSe/ZnS量子点激子吸收峰波长有微小红移,最大约为4nm;光致发光光谱峰值波长略有红移,但最大不超过6nm。根据光致发光光谱测量的结果,确定了Varshni定律中关于CdSe/ZnS量子点禁带宽度的两个经验参数:α=(2.0±0.2)×10^-4eV/K和β=(200±30)K。温度对CdSe/ZnS量子点吸收强度影响不大,荧光发射强度与温度呈线性关系增强。     

核壳型ZnS∶Cu/ZnS量子点的制备及发光性质

本文采用水相合成方法制备了ZnS∶Cu量子点并进行了ZnS壳层修饰,研究了壳层厚度对ZnS∶Cu量子点光学性质的影响,采用TEM、XRD、PL、PLE和UV-Vis等测试方法对其进行了表征。实验结果表明,合成的ZnS∶Cu/ZnS量子点为立方闪锌矿,尺寸分布均匀呈球形,分散性良好,经过壳层修饰平均粒径由2 nm增加到3.2 nm。随着ZnS壳与ZnS核量的比的增加,量子点的PLE激发峰位置和UV-Vis吸收谱线出现红移,也说明了量子点的尺寸增大,证明ZnS在ZnS∶Cu量子点的表面生长,形成了核壳结构的ZnS∶Cu/ZnS量子点。随着壳层增厚,量子点与铜离子发光中心相关的发射峰强度先增大后减小,当壳核比n_s/n_c=2.5时,发光强度达到最大。