钨酸铅晶体中与氧空位缺陷有关的光学偏振特性

本文利用完全势缀加平面波局域密度泛函近似，计算了含氧空位的PbWO4（PWO）晶体的电子结构，模拟计算了复数折射率及光学参数的偏振特性。比较含氧空位的PWO晶体与完整的PWO晶体的吸收光谱及其偏振特性，得到与氧空位相关的光学偏振特性。结果表明：完整的PWO晶体在可见和近紫外区域内无吸收，而含氧空位的PWO晶体在可见和近紫外区域出现吸收，该吸收谱有2个峰值分别位于370nm和420nm吸收带，它们的峰值位置与实验测得的350nm和420nm吸收带十分接近，由此可见PWO晶体中350nm和420nm吸收带与氧空位的存在有关。     

含铅空位的PbWO4晶体光学性质及其偏振特性的研究

利用完全势缀加平面波局域密度泛函近似，计算了含铅空位的PbWO₄（PWO）晶 体的电 子结构，模拟计算了复数折射率、介电函数及吸收光谱的偏振特性. 比较含铅空位的PWO晶 体与完整的PWO晶体的吸收光谱及其偏振特性，得到与铅空位相关的吸收光谱及其偏振特性 ，计算结果与实验结果基本相符. 计算得到的含铅空位的PWO晶体的光学偏振特性反映了PWO 晶体的结构对称性. 计算结果表明PWO晶体中350，420，550和680 nm的吸收带的出现与PWO 晶体中铅空位的存在直接相关. 关键词： 4晶体')" href="#">PbWO₄晶体 电子结构 光学性质 铅空位     

含铅空位的PbWO4晶体光学性质及其偏振特性的研究

利用完全势缀加平面波局域密度泛函近似,计算了含铅空位的PbWO4(PWO)晶体的电子结构,模拟计算了复数折射率、介电函数及吸收光谱的偏振特性.比较含铅空位的PWO晶体与完整的PWO晶体的吸收光谱及其偏振特性,得到与铅空位相关的吸收光谱及其偏振特性,计算结果与实验结果基本相符.计算得到的含铅空位的PWO晶体的光学偏振特性反映了PWO晶体的结构对称性.计算结果表明PWO晶体中350,420,550和680 nm的吸收带的出现与PWO晶体中铅空位的存在直接相关.     

钨酸铅晶体的本征色心和辐照诱导色心

根据钨酸铅晶体(PbWO4,简称PWO)的缺陷化学和晶体结构特点,用光吸收谱、广延X射线吸收精细结构(EXAFS)和精密X射线衍射(XRD)方法对高温退火后PWO晶体进行微结构研究,获得了其退火前后缺陷变化的情况,据此提出生成态(asgrown)晶体中350nm本征色心吸收带起源于V-F空穴心,并指出PWO中紫外区色心吸收带的强度取决于晶体中铅空位和氧空位浓度之差:[VPb]-[VO];然后,结合晶体在紫外光(UV)辐照过程中色心的转化规律和偏振吸收谱的实验结果,提高420nm辐照诱导色心吸收带起源于V0F双空穴心.并对所提出的PWO晶体色心模型的合理性进行了讨论. 关键词： 钨酸铅 本征色心 辐照诱导色心 色心模型     

F,Y双掺钨酸铅晶体的发光性能和微观缺陷

通过透射光谱、光产额(LY)和光致发光等发光性能测试，研究了F,Y双掺钨酸铅(PbWO₄ ，简称PWO)晶体的发光性能，并利用热释光曲线和正电子湮没寿命谱对F,Y双掺PWO晶 体中的缺陷种类和变化进行了分析. 结果表明：与未掺杂晶体相比，双掺样品在350nm附近 的透过率大大提高，吸收边向短波方向移动约30nm，光致发光谱中出现位于350nm的发光峰 ，双掺样品的LY(100ns内)为未掺杂PWO的2.7倍左右.晶体中主要存在的缺陷为(WO_{3)^{-关键词： F Y双掺钨酸铅闪烁晶体 高光产额 热释光 正电子湮没寿命谱}}     

PbWO4闪烁晶体的辐照损伤机理研究

完成了640—1040℃温度范围内钨酸铅［PbWO₄(PWO)］晶体的退火实验,观察到较低温退火时晶体中本征色心吸收带(350nm)先是增加,其后随退火温度的升高而逐渐降低直至消除的全过程．分析了PWO晶体的本征缺陷和电荷补偿机制．讨论了退火过程中氧进入晶体后色心的产生和转化规律,并提出可能发生Pb³⁺→Pb⁴⁺的进一步氧化过程,从而导致Pb³⁺空穴中心的湮没．测量并比较了不同退火温度处理后PWO晶体的紫外辐照诱导色心     

PbWO4晶体空位型缺陷电子结构的研究

采用基于密度泛函理论的相对论性离散变分和嵌入团簇方法计算了PbWO4晶体中与氧空位和铅空位相关缺陷的态密度分布,并运用过渡态方法计算了其激发能.结果表明:PbWO4晶体中WO3+VO缺陷的O2p→W5d跃迁可引起350nm和420nm附近的吸收,并且发现VPb的存在可以使WO42基团的禁带宽度明显变小 关键词： PbWO4晶体 密度泛函 氧空位和铅空位 态密度分布     

“黑青”“黑碧”的谱学鉴别特征探究

“黑青”指颜色近黑色,主要成分为透闪石的青玉。“黑碧”指颜色近黑色,主要成分为阳起石的碧玉。采用电子探针、激光剥蚀电感耦合等离子体质谱仪和红外光谱测试分析手段,确定“黑青”“黑碧”的矿物种属。采用拉曼光谱、显微紫外-可见分光光度计、红外光谱对“黑青”“黑碧”的谱学鉴别特征进行探究。“黑青”为标准透闪石拉曼谱峰,“黑碧”的谱峰位置与“黑青”存在几个波数的偏差,向波数小的方向移动。可见-近红外波段,“黑青”出现445 nm吸收峰,680和940 nm宽吸收带,为Fe2+和Fe3+作用;“黑碧”出现445 nm吸收峰,660和690 nm双吸收峰以及970 nm吸收峰,为Fe2+,Fe3+,Cr3+作用。显微紫外-可见光谱可分析到样品的近红外区,“黑青”在1 397,2 310,2 387和2 466 nm出现强吸收峰,1 915和2 120 nm出现弱吸收峰;“黑碧”在1 400,2 313和2 394 nm出现吸收峰。红外光谱分析“黑青”在5 225,4 738,4 692,5 349,4 317,4 190和4 064 cm-1存在吸收峰;“黑碧”在4 708,4 307,4 178和4 031 cm-1存在吸收峰。显微紫外-可见光谱与红外光谱分析结果虽然存在小的差异,但基本保持一致,以红外光谱分析结果为准。将透闪石质的“黑青”、阳起石质的“黑碧”、广西大化阳起石质玉进行对比,综合红外光谱和显微紫外-可见光谱分析结果得出“黑青”（透闪石）与“黑碧”（阳起石）近红外光谱的鉴别特征：“黑青”（透闪石）在4 800～4 600 cm-1存在两个吸收峰,4 350～4 300 cm-1存在分裂双吸收峰;“黑碧”（阳起石）在4 800～4 600 cm-1存在一个弱吸收峰,4 350～4 300 cm-1存在一个吸收单峰。且“黑碧”（阳起石）的近红外吸收峰相较于“黑青”（透闪石）整体向低波数方向移动。     

钨酸铅晶体中的偶极缺陷

在用阻抗谱研究PbWO₄（PWO）晶体的介电特性时发现，掺La³⁺的PW O晶体中存在典型的介电弛豫现象，它被归因于La³⁺进入Pb位并与铅空位V_Pb缔合 成偶极缺陷.这一结果不仅清楚地证明了PWO晶体中铅空位的存在，而且表明阻抗谱测试可以成为PWO晶体微结构研究的有力工具.以阻抗谱测试为主要工具，结合光吸收谱（包括红外谱）和x射线光电子能谱，阐明了在异价掺杂离子（3+，4+，5+以及3+和5+双掺）掺杂的PWO晶体中 关键词： 钨酸铅 偶极缺陷 异价掺杂 退火效应     

无缺陷PbWO4晶体光学性质的模拟计算

利用完全势缀加平面波局域密度泛函近似研究PbWO4（PWO）晶体的光学性质.计算了完整的PWO晶体的电子结构、复数折射率、介电函数、光电导谱和吸收光谱.介电函数的虚部、吸收光谱、折射率等的峰值位置存在一一对应关系,这与电子从价带到导带的跃迁吸收有关.完整的PWO晶体在可见光范围内没有吸收,所以完整的PWO晶体是无色透明的晶体.     

斜钨矿结构钨酸铅晶体电子结构和光学的偏振性质研究

利用完全势缀加平面波局域密度泛函近似,计算了完整的白钨矿结构和斜钨矿结构的钨酸铅（PbWO4）晶体的电子结构;模拟计算了复数折射率、介电函数及吸收光谱的偏振特性。分析了各个吸收光谱的峰值所对应的可能的电子跃迁以及钨酸铅晶体的偏振特性。钨酸铅晶体的光学性质的各向异性反映了钨酸铅晶体的品格结构的各向异性。计算结果表明：斜钨矿结构的钨酸铅晶体的光学性质与白钨矿结构的钨酸铅的光学性质之间存在明显的差异。这说明钨酸铅晶体是一种结构敏感的晶体;计算结果为研究钨酸铅晶体的光学性质与晶体结构之间的关系提供理论基础。     

Studies on the origins of the absorption spectra in PbWO4 crystal

The electronic structures and absorption spectra for both the perfect PbWO₄ (PWO) crystal and the three types of PWO crystals, containing V_Pb²⁻, V_O²⁺ and a pair of V_Pb²⁻-V_O²⁺, respectively, have been calculated using CASTEP codes with the lattice structure optimized. The calculated absorption spectra indicate that the perfect PWO crystal does not occur absorption band in the visible and near-ultraviolet region. The absorption spectra of the PWO crystal containing V_Pb²⁻ exhibit seven peaks located at 1.72 eV (720 nm), 2.16 eV (570 nm), 2.81 eV (440 nm), 3.01 eV (410 nm), 3.36 eV (365 nm), 3.70 eV (335 nm) and 4.0 eV (310 nm), respectively. The absorption spectra of the PWO crystal containing V_O²⁺ occur two peaks located at 370 nm and 420 nm. The PWO crystal containing a pair of V_Pb²⁻-V_O²⁺ does not occur absorption band in the visible and near-ultraviolet region. This leads to the conclusions that the 370 and 420 nm absorption bands are related to the existence of both V_Pb²⁻ and V_O²⁺ in the PWO crystal and the other absorption bands are related to the existence of the V_Pb²⁻ in the PWO crystal. The existence of the pair of V_Pb²⁻-V_O²⁺ has no visible effects on the optical properties. The calculated polarized optical properties are well consistent with the experimental results.     

Electronic structure and optical properties of CdWO4 with oxygen vacancy studied from first principles

The electronic structures, dielectric functions and absorption coefficient of both perfect CdWO₄ crystal (CWO) and the CWO crystal containing oxygen vacancy (CWO: V _O) have been studied using the CASTEP code with the lattice structure optimized. The calculated total density of states (TDOS) of CWO: V _O indicates that the oxygen vacancy would introduce a new electronic state within the band gap compared with that of perfect CWO. The dielectric functions are calculated since the imaginary part of the dielectric function can reduce the optical absorption of a certain crystal, and then the absorption coefficient is calculated. The calculated absorption spectra show that CWO: V _O exhibits two absorption bands in the ultraviolet and visible region, peaking at about 3.0 eV (413 nm) and 3.5 eV (354 nm), respectively, which are in agreement with the experimental results showing that the yellow CWO has two optical absorption bands in this region peaking at around 350 nm and 400 nm respectively. It can be concluded that oxygen vacancy causes these two absorption bands. The calculations also indicate that the optical properties of CWO exhibit anisotropy, and can be explained by the anisotropy of the crystal lattice.     

First-Principles Studies on Electronic Structures and Absorption Spectra of PbWO4 Crystals with Defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-c

Electronic structures and absorption spectra for perfect PbW04 （PWO） crystals and the crystal containing aggregated defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-have been calculated using density functional theory code CASTEP with the lattice structure optimized. The calculated absorption spectra of the PWO crystal containing the aggregated defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-exhibit two absorption bands peaking at 1.90eV （65Onto） and 3.02eV （41Onto）. It is predicted that the 420 and fiSOnm absorption bands are related to the existence of the aggregated defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-in the PWO crystal.     

First-principles study on the electronic structures and absorption spectra for the PbWO4 crystal with lead vacancy

The electronic structures and absorption spectra for the perfect PbWO₄ (PWO) crystal and the crystal containing lead vacancy have been calculated using density functional theory code CASTEP with the lattice structure optimized. The calculated absorption spectra of the PWO crystal containing exhibit seven absorption bands peaking at 1.72 eV (720 nm), 2.16 eV (570 nm), 2.81 eV (440 nm), 3.01 eV (410 nm), 3.36 eV (365 nm), 3.70 eV (335 nm) and 4.0 eV (310 nm), which are very close to the experimental values. It predicts that the 330, 360, 420, 500-750 nm absorption bands are related to the existence of in the PWO crystal.     

First-principles study on the effect of the interstitial oxygen ion on the spectral properties of PWO crystal and the origin of the green luminescence band

The electronic structures and absorption spectra of PWO crystals containing interstitial oxygen ions have been calculated using density functional theory code CASTEP with lattice structure optimized. It is shown by calculation that: (1) the interstitial oxygen ion in the perfect PWO crystal doesn’t bring any obvious absorption in the visible region; (2) the green emission of lead tungstate origin is closely related to the interstitial oxygen ion, and probably originates from the center of “ WO₄+O_i”.