Crystal growth,structure and optical properties of Pr~(3+) -doped yttria-stabilized zirconia single crystals

The development of blue semiconductor light-emitting diodes(LEDs) has produced potential applications for Prdoped materials that can absorb blue light, especially crystals, and we now report structure and optical properties for high-quality Pr-doped single crystals of yttria-stabilized zirconia(YSZ) grown by the optical floating zone(FZ) method.X-ray diffraction(XRD) and Raman spectroscopy showed that all of the single crystal samples were in the cubic phase,whereas the corresponding ceramic samples contained a mixture of monoclinic and cubic phases. X-ray photoelectron spectroscopy(XPS) and electron paramagnetic resonance(EPR) spectroscopy showed that Pr was present as the Pr~(3+) ion in ceramic rods and single crystals after heating to high temperatures. The absorption and photoluminescence excitation(PLE) spectra of the Pr-doped YSZ crystals measured at room temperature showed strong absorption of blue light, while their photoluminescence(PL) spectra showed five emission peaks at 565 nm, 588 nm, 614 nm, 638 nm, and 716 nm under450 nm excitation. The optimum luminescence properties were obtained with the crystal prepared using 0.15 mol% Pr_6O_(11),and those with higher concentrations showed evidence of quenching of the luminescence properties. In addition, the color purity of Pr-doped YSZ single crystal reached 98.9% in the orange–red region.     

Temperature-dependent photoluminescence on organic-inorganic metal halide perovskite CH_3NH_3PbI_(3-x)Cl_x prepared on ZnO/FTO substrates using a two-step method

Temperature-dependent photoluminescence characteristics of organic-inorganic halide perovskite CH_3NH_3Pb I_(3-x)Cl_x films prepared using a two-step method on ZnO/FTO substrates were investigated. Surface morphology and absorption characteristics of the films were also studied. Scanning electron microscopy revealed large crystals and substrate coverage. The orthorhombic-to-tetragonal phase transition temperature was~140 K. The films' exciton binding energy was 77.6 ± 10.9 meV and the energy of optical phonons was 38.8 ± 2.5 meV. These results suggest that perovskite CH_3NH_3Pb I_(3-x)Cl_x films have excellent optoelectronic characteristics which further suggests their potential usage in perovskitebased optoelectronic devices.     

CH3NH3I在制备CH3NH3PbI(3-x)Clx钙钛矿太阳能电池中的作用

利用具有钙钛矿结构的有机-无机杂化卤化物制备的太阳能电池, 由于具有溶液可加工性和高光电转换效率, 受到了广泛关注. 在目前报道的最高光电转换效率的器件中, 采用了CH₃NH₃PbI_(3-x)Cl_x碘氯混合钙钛矿作为吸光层, 据报道在这种材料中光电子的扩散长度可以超过1 μm. 本文综述了在CH₃NH₃PbI_(3-x)Cl_x方面现有的研究工作, 指出了薄膜制备条件的重要性, 并研究了CH₃NH₃I在PbCl₂/CH₃NH₃I热解法制备CH₃NH₃PbI_(3-x)Cl_x吸光层中的作用. 扫描电子显微镜研究表明CH₃NH₃I加入量为PbCl₂的2倍到2.75倍时, CH₃NH₃I加入量的增加可以提高CH₃NH₃PbI_(3-x)Cl_x吸光层的覆盖度和结晶度, CH₃NH₃I加入量进一步增加到3倍时, 形貌变化不大. X射线光电子能谱的数据证实了CH₃NH₃I加入量对覆盖度的影响, 并显示在CH₃NH₃I加入量大于PbCl₂的2.5倍以后, CH₃NH₃PbI_(3-x)Cl_x中氯的掺入量急剧下降. 光电测试表明器件性能随CH₃NH₃I加入量增加而增加, 在CH₃NH₃I/PbCl₂为3/1时达到最高, 加入量略小于3/1对性能影响不大.     

钙钛矿(C6H5CH2NH3)2PbBr4拉曼光谱研究

运用激光拉曼光谱实验和密度泛函理论计算研究了450～1 700 cm-1光谱范围内有机-无机杂化钙钛矿材料(C₆H₅CH₂NH₃)₂PbBr₄的振动模式特性。对比实验所得拉曼光谱和理论计算所得拉曼光谱,发现密度泛函理论计算可以很好的模拟(C₆H₅CH₂NH₃)₂PbBr₄有机部分的分子振动模式。同时通过比较分析密度泛函理论计算和参考文献,对450～1 700 cm-1光谱范围内的拉曼峰的分子振动模式进行了初步的归属,并发现该光谱范围内的拉曼峰主要是由(C₆H₅CH₂NH₃)₂PbBr₄分子中有机部分振动所产生的。     

有机阳离子对卤素钙钛矿太阳能电池性能的影响

采用第一性原理计算了CH_3NH_3PbI_3中有机部分CH_3NH_3~+和CH_3NH_3的静电特性.结果表明:CH_3NH_3~+具有强的亲电特性,CH_3NH_3的CH_3~-端具有弱亲电性,而NH_3~-端具有弱亲核性.发现在CH_3NH_3PbI_3中CH_3NH_3~+之间强静电排斥作用在相变中起着重要的作用,且在室温条件下CH_3NH_3~+在无机笼中具备活性和无序的特性,使得TiO_2/CH_3NH_3PbI_3异质结中n型TiO_2的电子通过界面扩散到CH_3NH_3PbI_3材料,并与CH_3NH_3~+结合形成CH_3NH_3,CH_3NH_3的静电特性导致在内建电场作用下更容易取向,取向的CH_3NH_3周围形成的静电场会变得更弱和更加均匀.这对无机框架上载流子的产生和传输更加有利,这样的异质结比传统的pn结具有更大优势.这是CH_3NH_3PbI_3太阳能电池高的光电转换效率的重要原因.     

掺杂的Bi4Ge3O12晶体的近红外发光性能

生长了Mg、Ca离子掺杂(提拉法)和Cl离子掺杂(坩埚下降法)的Bi₄Ge₃O₁₂(BGO)晶体,测试了晶体样品的吸收谱、光致发光谱和发光衰减时间等。这些掺杂的BGO晶体的可见光发光比纯BGO有所减弱,但在808 nm和980 nm激光二极管(LD)激发下出现了纯BGO几乎没有的近红外发光,归因于改变了能级的Bi离子或可能出现的低价态Bi离子。掺杂对近红外发光的影响跟掺杂离子价态有关,同价态的掺杂离子对近红外发光的影响相差不大。     

有机无机杂化固态太阳能电池的研究进展

近年来, 由于钙钛矿材料优良的光学吸收和电荷传导特性, 有机无机杂化固态太阳能电池取得了突破性的进展. 自2009年首次报道了光电转换效率为3.8%的钙钛矿太阳能电池以来, 该类电池的效率不断突破. 基于介孔薄膜的电池已取得了超过16.7%的认证光电转换效率, 基于平板异质结结构电池光电转换效率达到19.3%, 已接近传统硅基太阳能电池的光电转换效率. 本文将介绍有机无机杂化钙钛矿作为光电材料的光学物理结构特性, 以及在固态太阳能电池中的应用. 基于固态钙钛矿太阳能电池结构上的差异, 分别介绍其在多孔结构、平板异质结结构、柔性结构以及无空穴传导材料结构电池工作特性和各自优势, 以及影响电池特性的主要影响因素, 特别是钙钛矿成膜控制等. 并阐述对钙钛矿电池的理解和进一步提高固态钙钛矿电池光电转换效率需要关注的重点以及展望.     

Growth behaviors and emission properties of Co-deposited MAPbI3 ultrathin films on MoS2

Hybrid organic-inorganic perovskite thin films have attracted much attention in optoelectronic and information fields because of their intriguing properties. Due to quantum confinement effects, ultrathin films in nm scale usually show special properties. Here, we report on the growth of methylammonium lead iodide (MAPbI₃) ultrathin films via co-deposition of PbI₂ and CH₃NH₃I (MAI) on chemical-vapor-deposition-grown monolayer MoS₂ as well as the corresponding photoluminescence (PL) properties at different growing stages. Atomic force microscopy and scanning electron microscopy measurements reveal the MoS₂ tuned growth of MAPbI₃ in a Stranski-Krastanov mode. PL and Kelvin probe force microscopy results confirm that MAPbI₃/MoS₂ heterostructures have a type-II energy level alignment at the interface. Temperaturedependent PL measurements on layered MAPbI₃ (at the initial stage) and on MAPbI₃ crystals in averaged size of 500 nm (at the later stage) show rather different temperature dependence as well as the phase transitions from tetragonal to orthorhombic at 120 and 150 K, respectively. Our findings are useful in fabricating MAPbI₃/transition-metal dichalcogenide based innovative devices for wider optoelectronic applications.     

Electron excitations in LiB3O5 crystals with defects: Low-temperature time-resolved luminescence VUV spectroscopy

The dynamics of electron excitations and luminescence of LiB₃O₅ (LBO) single crystals was studied using low-temperature luminescence vacuum ultraviolet spectroscopy with a subnanosecond time resolution under photoexcitation with synchrotron radiation. The kinetics of the photoluminescence (PL) decay, the time-resolved PL emission spectra, and the time-resolved PL excitation spectra of LBO were measured at 7 and 290 K, respectively. The PL emission bands peaking at 2.7 eV and 3.3 eV were attributed to the radiative transitions of electronic excitations connected with lattice defects of LBO. The intrinsic PL emission bands at 3.6 and 4.2 eV were associated with the radiative annihilation of two kinds of self-trapped electron excitations in LBO. The processes responsible for the formation of localized electron excitations in LBO were discussed and compared with those taking place in wide-gap oxides.     

Enhancing the photo-luminescence stability of CH3NH3PbI3 film with ionic liquids

The methylammonium lead triiodide (CH₃NH₃PbI₃)-based perovskite shows a great alluring prospect in areas of solar cells, lasers, photodetectors, and light emitting diodes owing to their excellent optical and electrical advantages. However, it is very sensitive to the surrounding oxygen and moisture, which limits its development seriously. It is urgent to spare no effort to enhance its optical and electrical stability for further application. In this paper, we synthesize the MAPbI₃ perovskite film on the glass substrate with/without the ionic liquid (IL) of 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄) by a simple two-step sequential solution method. The additive of BMIMBF₄ can improve the quality of crystal structure. Moreover, the photo-luminescence (PL) intensity of MAPbI₃ film with BMIMBF₄ is much stronger than the pure MAPbI₃ film after a week in the air, which is almost ten-fold of the pure one. Meanwhile, under the illumination of 405-nm continuous wave (CW) laser, the fluorescent duration of the MAPbI₃ film with BMIMBF₄ is approximately 2.75 min, while the pure MAPbI₃ film is only about 6 s. In fact, ionic liquid of BMIMBF₄ in the perovskite film plays a role of passivation, which prevents the dissolution of MAPbI₃ into CH₃NH₃ and PbI₂ and thus enhances the stability of environment. In addition, the ionic liquid of BMIMBF₄ possesses high ionic conductivity, which accelerates the electron transport, so it is beneficial for the perovskite film in the areas of solar cells, photodetectors, and lasers. This interesting experiment provides a promising way to develop the perovskite's further application.     

Device simulation of lead-free CH_3NH_3SnI_3 perovskite solar cells with high efficiency

The lead-free perovskite solar cells(PSCs) have drawn a great deal of research interest due to the Pb toxicity of the lead halide perovskite.CH_3NH_3SnI_3 is a viable alternative to CH_3NH_3PbX_3,because it has a narrower band gap of 1.3 eV and a wider visible absorption spectrum than the lead halide perovskite.The progress of fabricating tin iodide PSCs with good stability has stimulated the studies of these CH_3NH_3SnI_3 based cells greatly.In the paper,we study the influences of various parameters on the solar cell performance through theoretical analysis and device simulation.It is found in the simulation that the solar cell performance can be improved to some extent by adjusting the doping concentration of the perovskite absorption layer and the electron affinity of the buffer and HTM,while the reduction of the defect density of the perovskite absorption layer significantly improves the cell performance.By further optimizing the parameters of the doping concentration(1.3 × 10~(16) cm~3) and the defect density(1 × 10~(15) cm~3) of perovskite absorption layer,and the electron affinity of buffer(4.0 eV) and HTM(2.6 eV),we finally obtain some encouraging results of the J_(sc) of 31.59 mA/cm~2,V_(oc) of 0.92 V,FF of 79.99%,and PCE of 23.36%.The results show that the lead-free CH_3NH_3SnI_3 PSC is a potential environmentally friendly solar cell with high efficiency.Improving the Sn~(2+) stability and reducing the defect density of CH_3NH_3SnI_3 are key issues for the future research,which can be solved by improving the fabrication and encapsulation process of the cell.     

Electronegativity explanation on the efficiency-enhancing mechanism of the hybrid inorganic–organic perovskite ABX_3 from first-principles study

Organic–inorganic hybrid perovskites play an important role in improving the efficiency of solid-state dye-sensitized solar cells. In this paper, we systematically explore the efficiency-enhancing mechanism of ABX_3(A = CH_3NH_3; B = Sn,Pb; X = Cl, Br, I) and provide the best absorber among ABX_3 when the organic framework A is CH_3NH_3 by first-principles calculations. The results reveal that the valence band maximum(VBM) of the ABX_3 is mainly composed of anion X p states and that conduction band minimum(CBM) of the ABX_3 is primarily composed of cation B p states. The bandgap of the ABX_3 decreases and the absorptive capacities of different wavelengths of light expand when reducing the size of the organic framework A, changing the B atom from Pb to Sn, and changing the X atom from Cl to Br to I. Finally, based on our calculations, it is discovered that CH_3NH_3 Sn I_3has the best optical properties and its light-adsorption range is the widest among all the ABX_3 compounds when A is CH_3NH_3. All these results indicate that the electronegativity difference between X and B plays a fundamental role in changing the energy gap and optical properties among ABX_3 compounds when A remains the same and that CH_3NH_3 Sn I_3 is a promising perovskite absorber in the high efficiency solar batteries among all the CH_3NH_3BX_3 compounds.     

NMR study of monomethylammonium cation in (CH3NH3)5Bi2Cl11 ferroelectric polycrystal

Spin-lattice relaxation times T₁ and T_1ρ are determined for protons in three polycrystals (CH₃NH₃)₅Bi₂Cl₁₁, (CD₃NH₃)₅Bi₂Cl₁₁ and (CH₃ND₃)₅Bi₂Cl₁₁. The temperature dependencies of the relaxation times obtained for (CH₃NH₃)₅Bi₂Cl₁₁ and (CD₃NH₃)₅Bi₂Cl₁₁ are interpreted as a result of correlated motions of the three-proton groups of the monomethylammonium cation. The minimum of the T_1ρ relaxation time is explained as a result of the oscillations of the symmetry axis of the whole cation.     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Thermally and optically stimulated radiative processes in LiBaF3 crystals

In LiBaF₃ crystals both valence–core transitions (5.4–6.5 eV) and so-called self-trapped exciton luminescence (about 4.3 eV) are important for practical application. Here, we present a study of 4.3 eV luminescence under photo- and thermostimulation after X-irradiation of undoped LiBaF₃ crystals at various temperatures. Optically stimulated luminescence as a result of electron recombination with both self-trapped holes and holes localized at some defects, were observed after X-irradiation below 130 K and that of electron recombination with defect-localized holes was observed after X-irradiation above 130 K. The spectra of thermo-stimulated luminescence (TSL) contain a broad band about 4 eV related to the electron (high-energy side) or hole (low-energy side) recombination depending on TSL peak temperature.     

液晶-氧化锌纳米复合材料的可调发光

采用超声波分散技术,选用氧化锌纳米晶体和液晶（N-（4-methoxybenzylidene）-4-ethoxybenzenamine）,制成液晶质量分数分别为10%、20%、30%、40%、50%、60%、70%、80%的液晶-氧化锌纳米复合材料。通过X射线衍射仪、透射电子显微镜、光致发光光谱仪对样品进行表征。实验结果表明：当液晶MB₂BA在氧化锌纳米晶体的质量分数从0增加到80%时,氧化锌纳米复合材料的PL光谱峰值最终移到了418 nm的蓝光区域。随着氧化锌纳米晶体中液晶分子的增加,氧化锌纳米晶体的表面缺陷减少、其深层发光明显削弱,氧化锌纳米晶体的光致发光可以由最初的黄绿色转变为蓝色。因此,可以在氧化锌纳米晶体中通过添加适量的液晶MB₂BA来实现蓝光发射。     

First-principles hybrid functional study of the electronic structure and charge carrier mobility in perovskite CH_3NH_3SnI_3

We calculate the electronic properties and carrier mobility of perovskite CH_3NH_3SnI_3 as a solar cell absorber by using the hybrid functional method. The calculated result shows that the electron and hole mobilities have anisotropies with a large magnitude of 1.4 × 10~4cm~2·V~(-1)·s~(-1) along the y direction. In view of the huge difference between hole and electron mobilities, the perovskite CH3NH3 Sn I3can be considered as a p-type semiconductor. We also discover a relationship between the effective mass anisotropy and electronic occupation anisotropy. The above results can provide reliable guidance for its experimental applications in electronics and optoelectronics.     

场发射显示器用蓝色YVO_4∶Tm~(3+)纳米荧光粉的制备及性能研究

采用溶剂热法成功地制备出了YVO4∶Tm3+纳米荧光粉,并用X射线衍射仪(XRD)、透射电子显微镜(TEM)、紫外分析仪、紫外可见(UV-Vis)吸收光谱和光致发光(PL)光谱对YVO4∶Tm3+纳米荧光粉进行测试和表征。实验结果表明,YVO4∶Tm3+纳米荧光粉可发出明亮的蓝光,色纯度和发光强度都很高,而且具有良好的热稳定性。因此,YVO4∶Tm3+纳米荧光粉是一种十分适用于场发射显示器的荧光粉。     

退火处理对W:Bi4Ge3O12和Bi12GeO20晶体发光性能的影响

通过提拉法制备了W:Bi4 Ge3 O12和Bi12GeO20晶体,测试了晶体的吸收光谱、光致发光谱和发光衰减时间等.W:Bi4 Ge3 O12的可见光发光强度比纯Bi4 Ge3 O12有所增强,而且N2中退火处理对W:Bi4Ge3O12发光有进一步增强作用.Bi12GeO20在N2中退火处理后在745 nm附近有发光...     

Spectral investigation of R,Ce:YAG(R: Pr~(3+), Eu~(3+), Gd~(3+)) single crystals and their applications in white LEDs

Eu3+, Pr3+, or Gd3+codoped Ce:YAG single crystals were grown by using the Czochralski method. The photoluminescence(PL) emission and excitation spectra and transmittance were measured and investigated. The additional red-emitting bands were observed in the PL emission spectra of Eu,Ce:YAG and Pr,Ce:YAG single crystals and the formation of noticeable peaks was studied with reference to the schematic energy level diagrams. A red-shifted phenomenon was observed in the PL emission spectrum of Gd,Ce:YAG. With codoped Eu3+, Pr3+, or Gd3+ions, warmer white light was achieved for the white light emitting diodes and the color rendering index became higher.