变色的ZnS：Mn/SrS：Ce/ZnS：Mn薄膜电致发光的研究

利用ZnS:Mn/SrS:Ce/ZnS:Mn多层结构,得到了一种可变颜色的薄膜电致发光器件。研究了这一器件的发射光谱随电压和频率的变化,并讨论了随电压的增加,发射光谱中蓝带和黄带的不同增长的原因,以及在不同电压下,发射光谱中蓝带和黄带随频率变化的不同趋势的原因。观察到随驱动频率的增加,发射光谱出现黄-蓝色位移。     

Mn注入的ZnS薄膜场致发光元件

日本J.Appl.phys.11(10)72,发表一篇短文,介绍Mn注入的ZnS薄膜场致发光元件,内容如下: 利用离子注入技术制造薄膜场致发光元件是卓有成效的。我们研究了Mn注入的ZnS薄膜的场致发光性能及有关特性。这种技术有如下一些引入注目的优点:(1)通过反复交替地注入激活剂(Mn,Cu,Al,     

ZnS:Mn交流薄膜电致发光的存贮效应

ZnS:Mn交流薄膜电致发光(ACTEL)中存在固有存贮效应和很长的使用寿命大大大推动了对这种器件的研究。 我们最近进行了ZnS:Mn薄膜存贮器件的场致发光实验,所用的薄膜结构是～5000厚的ZnS:Mn两边分别夹以～2500厚的非晶BaTiO_3绝缘层,再用InSnOx和Al电极完成装置。图1是我们在ZnS:Mn/a—BaTiO_3ACTEL器件上观察到的亮度—电压特性曲线。 我们观察到在这种器件的电致发光中包含两种成分,一种是空间均匀的发光,即本底发光;另一种是来自直经小于～1微米的定域亮区之发光。在存贮器件的正常工作电压范围内光辐射主要来自定域亮区[图2(a)]。当外加方波电压振幅增加时,这     

Zn1-xMnxS(001)稀磁半导体薄膜的能量稳定性、磁性和电子结构

通过基于广义梯度近似的总能密度泛函理论研究不同Mn掺杂浓度的ZnS(001)薄膜的电学和磁学特性. 计算单个Mn原子和两个Mn原子处于各种掺杂位置及不同的磁耦合状态时的能量稳定性.计算了单个Mn原子掺杂和两个Mn原子掺杂的ZnS(001)薄膜的态密度. 不同掺杂组态的p-d杂化的程度不同. 不同掺杂组态,Mn原子所处的晶场环境不同,所以不同掺杂组态的Mn的3d分波态密度峰的劈裂有很大的不同. 掺杂两个Mn原子时,得到三种稳定组态的基态都是反铁磁态. 分析了以上三种能量稳定的组态中,两个Mn原子在不同磁耦合状态下的3d态密度图. 当两原子为铁磁耦合时,由于d-d电子相互作用,使反键态的态密度峰明显加宽. 随着Mn掺杂浓度的增加,Mn原子有相互靠近,并围绕S原子形成団簇的趋势. 对于这样的组态,Mn原子之间为反铁磁耦合能量更低.     

Mn2+和RE3+在ZnS和ZnSe中的Auger猝灭

在改变MS结势垒区宽度的同时,我们测量了在ZnSe:Mn2+晶体、ZnS:Er3+和ZnS:Sm3+薄膜中的Mn2+、RE3+特征谱的电致发光衰减.测量了高阻和低阻ZnS:Mn2+在变化温度(77K—500K)时,Mn2+发光强度的改变.认为在室温以下,Mn2+和RE3+在低阻ZnS和ZnSe中的辐射跃迁均受到Auger猝灭的影响.     

Mn掺杂的ZnS(001)表面的电子态特性

利用第一性原理计算Mn在ZnS(001)表面上几种掺杂位置的形成能、局域分波态密度和磁矩.对Mn在ZnS(001)表面上的三种位置的形成能进行比较,得到两种填隙位置是非常稳定的掺杂位置.分析ZnS(001):Mn各种再构表面的电子态密度和电荷密度分布.结果表明,三种表面模型中,自旋向上的Mn原子的3d态和近邻S原子的3p态都有一定的杂化,并且替代掺杂的Mn和邻近S原子的p-d杂化最明显,形成的共价键最强.而自旋向下的Mn原子的3d态比较局域,受S原子的3p态影响较小.计算了三种掺杂表面的磁矩,并分析计算结果.     

ZnS:Mn摩擦发光特性的研究

本文报道了ZnS:Mn具有良好摩擦发光性能。研究了ZnS:Mn发光中心Mn^2 及其含量以及样品的灼烧温度、灼烧时间等条件对样品发光特性的影响。优化浓度配比和制备条件制备出了较高摩抢擦发光效率的ZnS:Mn摩擦发光材料。摩擦发光机理可能是由于机械能使ZnS:Mn的电子从基态激发到激发态所致,而具有较高的摩擦发光效率可能来源于ZnS:Mn具有较宽的激发能量范围。     

场致发光薄膜ZnS:Mn,Er内Mn中心和Er中心的相互作用

首次提出了场致发光中Mn及稀土离子的能量传递问题.研究了同时掺有Mn和Er的ZnS:Mn,Er薄膜在脉冲激发下场致发光的衰减常数与杂质浓度的关系.证实了由Mn到Er的能量传递.估计了传递系数及传递效率.     

ZnS:Mn2+,Sm3+中Mn2+、Sm3+中心之间能量传递的分时光谱研究

前一阶段我们比较系统地研究了ZnS:Mn2+,Sm3+材料中Mn2+中心和Sm3+中心之间的能量传递。通过测量ZnS:Mn2+、ZnS:Sm3+和ZnS:Mn2+,Sm3+三种材料的发射光谱、激发光谱、选择激发发光光谱,证实了Mn2+中心和Sm3+中心之间存在偶极—偶极相互作用的无辐射能量传递。为了进一步研究Mn2+中心和Sm3+中心之间的相互作用及其物理特点,我们又仔细测量了上述三种不同类型材料的分时光谱,这不仅可以更清楚地了解激发停止后Mn2+中心和Sm3+中心之间的相互作用,而且有效地解决了Mn2+中心发射光谱和Sm3+中心某些特征光谱线交叠引起的测量发光衰减的困难。     

ZnS掺Mn的电子结构研究

 用自旋极化的LSD-LMTO（Local-Spin-Density Linear Muffin-Tin-Orbital Method）方法，对ZnS掺入Mn发光中心的电子结构进行了大型超原胞模拟计算。在自洽收敛的条件下，先对纯ZnS调节计算参数（原子球、空球占空比），使计算的带隙E_g=3.23 eV；然后用原子球替代方式自洽计算杂质密度在E_g中的相对位置，模拟计算了在六角结构ZnS中掺入不同浓度的Mn杂质后有关的杂质能级在E_g中的相对位置。计算结果表明：（1）单个缺陷的杂质能级性质与配位场理论结果相符合，直接用杂质态密度来表示；（2）掺入杂质的浓度对杂质能级位置的影响不大，这与实验结果相一致。     

Green route fast synthesis and characterization of chemical bath deposited nanocrystalline ZnS buffer layers

Zinc sulphide (ZnS) thin films are deposited using chemical bath deposition method on the glass substrates in an aqueous alkaline reaction bath of zinc acetate and thiourea along with non-toxic complexing agent tri-sodium citrate at 95 °C. The results show noteworthy improvement in the growth rate of the deposited ZnS thin films and thickness of the film increases with the deposition time. From X-ray diffraction patterns, it is found that the ZnS thin films exhibit hexagonal polycrystalline phase reflecting from (101) and (0016) planes. The high resolution transmission electron microscopy studies confirmed the formation of hexagonal phase from the d-value calculation which was 0.3108 nm. X-ray photoelectron spectroscopy reveals that the Zn–S bonding energy is at 1022.5 and 162.1 eV for Zn 2p_3/2 and S 2p_1/2 states, respectively. Field emission scanning electron microscopy study shows that deposited thin films are highly uniform, with thin thickness and completely free from large ZnS clusters which usually form in aqueous solutions. Atomic force microscopy investigates that root mean square values of the ZnS thin films are from 3 to 4.5 nm and all the films are morphologically smooth. Energy dispersive spectroscopy shows that the ZnS thin films are relatively stoichiometric having Zn:S atomic ratio of 55:45. It is shown by ultraviolet–visible spectroscopy that ～90% transmittance and ～10% absorbance for the ZnS films in the visible region, which is significantly higher than that reported elsewhere and the band gap energy of the ZnS films is found to be 3.76, 3.74, and 3.71 eV, respectively.     

ZnS:Mn交流电致发光的效率与Mn浓度的关系和浓度猝灭

从实验上确定了交流电致发光薄膜Y2O3-ZnS:Mn-Y2O3的发光效率与Mn浓度的关系:在低浓度下(10-5～10-4g/g),发光效率随Mn浓度线性增加,在10-3g/g附近发光效率达到最大值,当Mn浓度继续增加时,发光效率开始下降.在ZnS:Mn薄膜中存在两种发光中心—单个Mn中心和Mn对,它们的衰减都是指数形式,它们激发态的寿命随Mn浓度增加而减.Mn对发光中心与单个Mn中心之比随Mn浓度增加而增加.从而减少了有效的发光中心数目,这是浓度猝灭的原因之一.发光效率在高Mn浓度时下降的另外原因是由于电隅极子之间共振能量传递引起浓度猝灭.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Zn1−xMnxO : A typical member of the II-VI:Mn DMS family

ZnO:Mn thin films are grown by MOCVD technique. Mn(x) varies in 0<x<0.44 range. Vegrad’s law has been verified for the lattice parameters. EPR measurements prove the substitution incorporation of Mn²⁺ on zinc sites. The behavior of EPR line-width regarding temperature is discussed. All ZnO:Mn layers show antiferromagnetic interaction and a effective exchange constant. Observation of excitons, giant Zeeman effect, and trace of the Brillouin function is evidence for high quality of the crystal lattice and of substitutional incorporation of manganese ions in place of Zn, as Mn²⁺.     

HCl气氛制备的ZnS:Mn粉末DCEL材料

本文首次较系统报导了HCl气氛中制备的ZnS:Mn粉末DCEL材料的特性。指出HCl气氛的主要作用,一是使材料结晶更好,二是引进Cl施主能级,使得PL和DCEL亮度提高。本实验还研究了ZnS粉在HCl气氛中灼烧时的相转换特点,以及晶相比对抗老化性能的影响。讨论了晶相比与颗粒表面CuxS导电相性质的关系,认为这是晶相比影响老化的原因。     

基于电子回旋共振-等离子体增强金属有机物化学气相沉积技术生长GaMnN稀磁半导体的研究

利用电子回旋共振-等离子体增强金属有机物化学气相沉积 (ECR-PEMOCVD)方法,采用二茂锰(Cp₂Mn)作为Mn源,高纯氮气作为氮源,三乙基镓(TEGa)作为Ga源,在蓝宝石(α-Al₂O₃)(0001)衬底上外延生长GaMnN稀磁半导体薄膜.反射高能电子衍射(RHEED)、X射线衍射(XRD)、原子力显微镜(AFM)表征了GaMnN薄膜的晶体结构和表面形貌.GaMnN薄膜均表现出良好的(0002)择优取向,表明制备的薄膜倾向于 关键词： GaMnN薄膜 稀磁半导体 铁磁性 居里温度     

Improved photoluminescence of ZnS:Mn nanocrystals by microwave assisted growth of ZnS shell

The photoluminescence (PL) of ZnS:Mn nanocrystals was improved greatly by microwave assisted growth of ZnS shell. Under optimized conditions, the luminescence quantum yield of ZnS:Mn nanocrystals increased from 2.8% to 12.1% after the growth of the ZnS shell. Time-resolved fluorescence spectroscopic and electron paramagnetic resonance measurements indicate that the improvement of the dispersivity of the doped Mn ions is responsible for the PL enhancement. Growth of the ZnS shell not only facilitated the diffusion of Mn ions during microwave irradiation but also prohibited the segregation of Mn ions on the particle surface. As a result, more isolated Mn²⁺ ions were produced after the growth of the ZnS shell, and thus the orange luminescence of ZnS:Mn nanocrystals was enhanced greatly.     

Valency and solubility limit of Cu ions in cubic and hexagonal phases of ZnS:Cu:Mn:Dy(Cl) phosphors

Polycrystalline ZnS:Cu:Mn:Dy (Cl) phosphors with varying concentration of Cu and fixed concentrations of Mn and Dy have been prepared, XRD studies showed that the cubic — hexagonal phase transformation in the phosphors is a sensitive function of Cu concentration so that cubic phase dominates at higher Cu concentrations. It has also been found that Cu enters into the cubic ZnS phase as Cu⁺ while in hexagonal ZnS phase as Cu²⁺ and their solubility limits are around 0.1 wt.% and 0.25 wt.% respectively. Attempt has been made to confirm the existence of Cu⁺ in cubic phase and Cu²⁺ in hexagonal phase from EL emission spectra of the phosphors.     

Luminescence enhancement of Mn doped ZnS nanocrystals passivated with zinc hydroxide

Mn-doped ZnS nanocrystals prepared by solvothermal method have been successfully coated with different thicknesses of Zn(OH)₂ shells through precipitation reaction. The impact of Zn(OH)₂ shells on luminescent properties of the ZnS:Mn nanocrystals was investigated. X-ray diffraction (XRD) measurements showed that the ZnS:Mn nanocrystals have cubic zinc blende structure. The morphology of nanocrystals is spherical shape measured by transmission electron microscopy (TEM). ZnS:Mn/Zn(OH)₂ core/shell nanocrystals exhibited much improved luminescent properties than those of unpassivated ZnS:Mn nanocrystals. The luminescence enhancement was observed with the Zn(OH)₂ shell thickening by photoluminescence (PL) spectra at room temperature and the luminescence lifetime of transition from ⁴T₁ to ⁶A₁ of Mn²⁺ ions was also prolonged. This result was led by the effective, robust passivation of ZnS surface states by the Zn(OH)₂ shells, which consequently suppressed nonradiative recombination transitions.