An investigation on the pressure-induced phase transition of nanocrystalline ZnS

An in situ energy dispersive x-ray diffraction study on nanocrystalline ZnS was carried out under high pressure up to 30.8 GPa by using a diamond anvil cell. The phase transition from the wurtzite to the zinc-blende structure occurred at 11.5 GPa, and another obvious transition to a new phase with rock-salt structure also appeared at 16.0 GPa-which was higher than the value for the bulk material. The bulk modulus and the pressure derivative of nanocrystalline ZnS were derived by fitting the Birch-Murnaghan equation. The resulting modulus was higher than that of the corresponding bulk material, indicating that the nanomaterial has higher hardness than the bulk material.

Pressure behavior of Te isoelectronic centers in ZnS : Te

ZnS:Te epilayers with Te concentration from 0.5% to 3.1% were studied by photoluminescence under hydrostatic pressure at 15 K. Two emission bands related to the isolated Te-1 and Te-2 pair isoelectronic centers were observed in the samples with Te concentrations of 0.5% and 0.65%. For the samples with Te concentrations of 1.4% and 3.1%, only the Te-2-related peak was observed. The pressure coefficients of all the Te-1-related bands were found to be unexpectedly much larger than that of the ZnS band gap. The pressure coefficients for all the Te-2-related bands are, however, rather smaller than that of ZnS band gap as usually observed. Analysis based on a Koster-Slater model indicates that an increase of the valence bandwidth with pressure is the main reason for the faster pressure shift of the Te-1 centers, and the huge difference in the pressure behavior of the Te-1 and Te-2 centers is due mainly to the difference in the pressure-induced enhancement of the impurity potential on the Te-1 and Te-2 centers. (C) 2002 American Institute of Physics.

Temperature and pressure dependences of the Mn2+ and donor-acceptor emissions in ZnS : Mn2+ nanoparticles

Temperature and pressure dependent measurements have been performed on 3.5 nm ZnS:Mn2+ nanoparticles. As temperature increases, the donor-acceptor (DA) emission of ZnS:Mn2+ nanoparticles at 440 nm shifts to longer wavelengths while the Mn2+ emission (T-4(1)-(6)A(1)) shifts to shorter wavelengths. Both the DA and Mn2+ emission intensities decrease with temperature with the intensity decrease of the DA emission being much more pronounced. The intensity decreases are fit well with the theory of thermal quenching. As pressure increases, the Mn2+ emission shifts to longer wavelengths while the DA emission wavelength remains almost constant. The pressure coefficient of the DA emission in ZnS:Mn2+ nanoparticles is approximately -3.2 meV/GPa, which is significantly smaller than that measured for bulk materials. The relatively weak pressure dependence of the DA emission is attributed to the increase of the binding energies and the localization of the defect wave functions in nanoparticles. The pressure coefficient of Mn2+ emission in ZnS:Mn2+ nanoparticles is roughly -34.3 meV/GPa, consistent with crystal field theory. The results indicate that the energy transfer from the ZnS host to Mn2+ ions is mainly from the recombination of carriers localized at Mn2+ ions. (C) 2002 American Institute of Physics.

Photoluminescence properties of Eu3+-doped ZnS nanocrystals prepared in a water/methanol solution

Monodispersed ZnS and Eu3+-doped ZnS nanocrystals have been prepared through the co-precipitation reaction of inorganic precursors ZnCl2, EuCl3, and Na2S in a water/methanol binary solution. The mean particle sizes are about 3-5 nm. The structures of the as-prepared ZnS nanoparticles are cubic (zinc blende) as demonstrated by an x-ray powder diffraction. Photoluminescence studies showed a stable room temperature emission in the visible spectrum region for all the samples, with a broadening in the emission band and, in particular, a partially overlapped twin peak in the Eu3+-doped ZnS nanocrystals. The experimental results also indicated that Eu3+-doped ZnS nanocrystals, prepared by controlling synthetic conditions, were stable. (C) 2002 American Institute of Physics.

Pressure dependence of Mn2+ fluorescence in ZnS : Mn2+ nanoparticles

The photoluminescence of Mn2+ in ZnS:Mn2+ nanoparticles with an average size of 4.5 nm has been measured under hydrostatic pressure from 0 to 6 GPa. The emission position is red-shifted at a rate of -33.3+/-0.6meV/GPa, which is in good agreement with the calculated value of -30.4meV/GPa using the crystal field theory. (C) 2000 Elsevier Science B.V. All rights reserved.

Photoluminescence of Eu2+ doped ZnS nanocrystals

Eu2+ doped ZnS nanocrystals exhibit new luminescence properties because of the enlarged energy gap of nanocrystalline ZnS host due to quantum confinement effects. Photoluminescence emission at about 520 nm from Eu2+ doped ZnS nanocrystals at room temperature is investigated by using photoluminescence emission and excitation spectroscopy. Such green emission with long lifetime (ms) is proposed to be a result of excitation, ionization, carriers recapture and recombination via Eu2+ centers in nanocrystalline ZnS host.

Energy structure and fluorescence of Eu2+ in ZnS : Eu nanoparticles

Eu2+-doped ZnS nanoparticles with an average size of around 3 nm were prepared, and an emission band around 530 nm was observed. By heating in air at 150 degrees C, this emission decreased, while the typical sharp line emission of Eu3+ increased. This suggests that the emission around 530 nm is from intraion transition of Eu2+: In bulk ZnS:Eu2+, no intraion transition of Eu2+ was observed because the excited states of Eu2+ are degenerate with the continuum of the ZnS conduction band. We show that the band gap in ZnS:Eu2+ nanoparticles opens up due to quantum confinement, such that the conduction band of ZnS is higher than the first excited state of Eu2+, thus enabling the intraion transition of Eu2+ to occur.

Synthesis and luminescence of CdS/ZnS core/shell nanocrystals

CdS/ZnS core/shell nanocrystals were prepared from an aqueous/alcohol medium. A red shift of the absorption spectrum and an increase of the room temperature photoluminescence intensity accompanied shell growth.

Photoluminescence of ZnS clusters in zeolite-Y

Two obvious emissions are observed from the ZnS clusters encapsulated in zeolite-Y. The emission around 355 nm is sharp and weak, locating at the onset of the absorption edge. The band around 535 nm is broad, strong and Stokes-shifted. Both the two emissions shift to blue and their intensities firstly increase then decrease as the loading of ZnS in zeolite-Y or clusters size decreases. Through investigation, the former is attributed to the excitonic fluorescence, and the latter to the trapped luminescence from surface states. The cluster size-dependence of the luminescence may be explained qualitatively by considering both the carrier recombination and the nonradiative recombination rates. Four peaks appearing in the excitation spectra are assigned to the transitions of 1S-1S, 1S-1P, 1S-1D and surface state, respectively. The excitation spectra of the clusters do not coincide with their absorption spectra. The states splitted by quantum-size confinement are detected in the excitation spectra, but could not be differentiated in the optical absorption spectra due to inhomogeneous broadening. The size-dependence of the excitation spectra is similar to that of the absorption spectra. Both the excitation spectra of excitonic and of trapped emissions are similar, but change in relative intensity and shift in position are observed.

Absorption and luminescence of the surface states in ZnS nanoparticles

A broad absorption band around 500 nm is observed in ZnS nanoparticles. The absorption becomes more intensive and shifts to the blue as the particle size is decreased. The absorption energy is lower than the band gap of the particles and is considered to be caused by the surface states. This assignment is supported by the results of the fluorescence and of the thermoluminescence of the surface states. Both the absorption and the fluorescence reveal that the surface states are size dependent. The glow peak of the semiconductor particles is not varied as much upon decreasing size, indicating the trap depth of the surface states is not sensitive to the particle size. Considering these results, a new model on the size dependence of the surface states is proposed, which may explain our observations reasonably. (C) 1997 American Institute of Physics.

Thermoluminescence of ZnS nanoparticles

The thermoluminescence (TL) of ZnS nanoparticles is reported. The TL intensity increases as the particle size is decreased. The consistency of the size dependence of the TL with that of the surface fluorescence indicates that the TL may be related to the surface states. TL may be caused by the recombination of carriers released from the surface states or defect sites by heating. Smaller particles have higher surface/volume ratio and more surface states, therefore contain more accessible carriers for TL. Besides, the carrier recombination rate increases upon decreasing size due to the increase of the overlap between the electron and hole wave functions. These two effects may make the TL increase upon decreasing size of the particles. The appearance of TL prior to any radiation reveals that trapped carriers have pre-existed. The investigation of TL may provide some useful information about the surface states that may explain the size dependence of the surface fluorescence. (C) 1997 American Institute of Physics.

ZnS中Te等电子中心的时间分辨光谱研究

用时间分辨光谱研究了很大的Te组分范围内的ZnS1-xTex(x=0.005-0.85)合金的发光动力学特性,结果表明:不同形态的Te等电子中心具有不同的辐射复合寿命,从几个ns到几十个ns的范围内变化,当x=0.15左右时,寿命达到最大值(约40 ns).其物理机理源于不同的Te等电子中心具有不同的局域化特性.当Te组分较小时,等电子中心从Te1逐渐演变到Te2,Te3或Te4时,相应发光寿命增加,表现出不断增强的激子发光局域化特性;而当Te组分较大时,Te原子团变得较大,其局域势与基体原子势的相互作用增强,等电子中心的局域化特性减弱,而基体价带扩展态特征变得明显起来,相应发光寿命逐渐减小.还研究了激子束缚能随Te组分的变化以及发光强度随温度的变化关系,所得结果进一步支持了时间分辨光谱研究所得到的结论.

不同尺寸ZnS:Mn纳米粒子的静压光致发光研究

测量了ZnS:Mn纳米粒子以及相应体材料在不同压力下的光致发光谱.随压力增大,来源于Mn2+离子的4T1-6A1跃迁的桔黄色发光明显红移.体材料和10,4.5,3.5,3 nm的ZnS:Mn纳米粒子中Mn2+发光的压力系数分别是-29.4±0.3和-30.1±0.3,-33.3±0.6,-34.6±0.8,-39±1 meV/GPa,压力系数的绝对值随粒子尺寸减小而增大,该种尺寸关系由晶体场场强Dq和Racah参数B值的尺寸依赖性引起.1nm样品的Mn2+发光的特殊压力行为是因为样品的粒子尺寸比较小,另外,分布在Y型沸石中的纳米粒子的表面状况也不同于其它样品.

静压下ZnS∶Te中Te等电子陷阱的发光

研究了4块ZnS∶Te薄膜样品(Te组分从0.5%到3.1%)的光致发光谱在常压下的温度特性.对于Te组分较小的2块样品观察到2个发光峰,分别来自Te1和Te2等电子陷阱;而对Te组分较大的2块样品则只观察到1个来自Te2等电子陷阱的发光.我们还研究了这些发光峰在低温15K下的流体静压压力行为.观察到与Te1有关的发光峰压力系数比ZnS带边的要大很多,而与Te2有关的发光峰压力系数则比带边小.根据Koster-Slater模型,价带态密度半宽随压力的增加是Te1中心有较大压力系数的主要原因,而Te1和Te2中心的不同压力行为则是由于压力对两者缺陷势增强的不同效果引起的.