Cs2ZnCl4∶Ce3+,Mn2+的合成及其多模发光性能

近年来,低维无铅金属卤化物由于其独特的光学性质、低毒性和优异的环境稳定性等优点受到了广泛关注。采用水热法成功制备Cs₂ZnCl₄∶Ce³⁺、Cs₂ZnCl₄∶Mn²⁺以及Cs₂ZnCl₄∶Ce³⁺,Mn²⁺等微米晶,并利用X射线衍射仪、荧光光谱仪等表征手段对其物相和发光特性进行了系统性研究。研究结果表明,Cs₂ZnCl₄微米晶为正交相零维结构,其发射光谱依赖于掺杂离子的激发波长,例如,Ce³⁺离子掺杂的Cs₂ZnCl₄微米晶在254nm的激发条件下,其发射光谱峰位位于350nm,对应于Ce³⁺离子4f-5d的跃迁;Mn²⁺离子掺杂的Cs₂ZnCl₄微米晶在361nm的激发条件...     

超声辅助制备Cs2AgBiBr6/Bi2WO6 S型异质结用于可见光光催化CO2还原(英文)

光催化因其可以利用太阳能进行光解水产氢、CO₂还原、降解有机污染物及有机物转化而被认为是解决当前能源危机和环境问题的一种有效手段.由于光催化反应是由光激发光催化材料生成光生载流子引发的,因此理想的光催化剂应当具有宽的光响应范围、低的光生载流子复合率和足够的氧化还原能力来进行表面反应.然而单一组分的半导体材料难以同时满足宽光谱响应(即窄带隙)和强氧化还原能力(即价带更正和导带更负).通过耦合两个具有可见光响应且交错能带排布的半导体来构建S型异质结,不仅能拓宽光催化剂的光吸收范围、促进电荷分离,还同时保留了两种半导体的强氧化还原能力,是发展高效光催化材料的一种有效途径.Cs₂AgBiBr₆的导带和价带分别位于-0.65 V vs.NHE和1.60 V vs.NHE,而Bi₂WO₆.的导带和价带分别为-0.4 V vs.NHE和2.4 V vs.NHE,两者能带位置匹配.因此,本文选择Cs₂AgBiBr₆和Bi₂WO<...     

甲脒基铅卤钙钛矿结构及光电特性的第一性原理研究

甲脒基铅卤钙钛矿作为光电转换材料,引起了人们的广泛关注. 采用第一性原理对甲脒基铅卤钙钛矿FAPbI_xCl_3-x（FA=NH₂CH=NH₂⁺,x=0～3）的结构及光电特性进行了理论研究. 计算结果表明,FA在三方晶系的FAPbX₃（X=Cl,Br,I）中沿[001]方向排布,而在混合FAPbI_xCl_3-x中,八面体PbX₆（X=Cl,I）的扭转导致FA朝向发生了微小的偏移. FA对于平衡晶体结构起着重要的作用,并作为电荷供体为PbI₃骨架贡献约0.76 e的电荷. FAPbI_xCl_3-x属于直接带隙半导体,其价带顶（VBM）主要由I 5p（Cl 3p）和少量Pb 6s轨道杂化的反键轨道组成,而导带底主要由Pb 6p轨道组成. 随着I/Cl比例的增大,FAPbI_xCl_3-x的晶格常数和体积逐渐增大,禁带宽度逐渐减小,吸收光谱发生红移. FAPbI₃的禁带宽度为1.53 eV,表现出最佳的吸收光谱特性,是一类极具潜力的光电转换材料.     

稀土Yb3+/Tm3+掺杂NaGd(MO4)2荧光粉的制备及其光致发光

近年来稀土掺杂的上转换发光材料在太阳能电池、工业照明和医学等领域的应用越来越受到重视,目前的研究主要集中于新型高效稀土上转换发光材料的开发。对于发光材料的制备,基质的选择尤为重要,钼酸盐因具有稳定的物理化学性能、低的声子能量而从众多基质中脱颖而出。本文选择钼酸盐为稀土离子掺杂的基质材料,采用水热法制备了Tm、Yb离子掺杂的NaGd(MoO₄)₂样品。通过改变离子掺杂的浓度,探究了NaGd(MoO₄)₂荧光粉的发光特性。研究表明,在980 nm激光照射下,NaGd(MO₄)₂∶Yb³⁺/Tm³⁺在477 nm处发射蓝色荧光,在648 nm处发射红色荧光。固定Yb³⁺的掺杂摩尔分数为6%,改变Tm³⁺的掺杂摩尔分数分别为0、0.5%、1%和2%时,发现随着Tm³⁺掺杂摩尔分数的增加,477 nm处的发射峰的强度先升高后降低,当Tm³⁺     

C3N5光催化制氢性能的系统研究

基于半导体的光催化制氢是解决当前日益增长的能源危机与环境污染等问题的有效选择之一.长期以来,设计具有不同结构与吸光特性的有机及无机半导体材料,开发廉价高效的助催化剂,构筑半导体异质结体系,探索实用研究装置等均受到广泛研究.其中氮化碳材料在过去十年中吸引了较大关注,但其光催化性能受到带隙较宽(代表材料C3N4的带隙为~2.7 e V)的限制.近年来,富氮型氮化碳(C₃N₅)材料因带隙更窄,在光催化污染物去除、光电能源转化和气体传感等领域被广泛研究,但其光催化制氢性能的系统研究尚未见报道.本文以3-氨基-1,2,4-三唑为原料,通过热处理制备C₃N₅,并对其光催化制氢性能进行了系统研究.X射线粉末衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、CHNS元素分析及红外光谱等表征结果确认成功制备了C₃N₅材料.同时,采用化学还原法(Na BH4为还原剂)负载Pt助催化剂并未对C₃N₅的结构及形貌造成影响;XRD,TEM及XPS结果表明,Pt以单质形态分散在C₃N₅材料上.紫外可见漫反射光谱(DRS)分析表明,C₃N₅在400~600 nm范围的可见光区具有强吸收,对600~800 nm范围的近红外光区也有一定的吸收能力.对Pt-C₃N₅材料的光催化制氢反应条件进行优化,以获得较好的催化活性.循环测试及光照后样品的XRD及DRS表明,C₃N₅具有良好的光催化稳定性.对比实验结果表明,负载1.0wt%Pt助催化剂时,C₃N₅的制氢速率约为C3N4的2.2倍.分析结果表明,比表面积及导带位置不是造成两种氮化碳材料光催化性能差异的主要因素.DRS、荧光光谱及光电流行为实验结果表明,C₃N₅具备更宽的可见光吸收范围,更窄的带隙及更快的光生e-/h+分离效率.采用包括原位红外在内的系列表征手段对水分子在材料表面的吸附性能进行研究,发现C₃N₅表面可以吸附更多的水分子,有利于表面水还原反应的进行.综上,本文为富氮型氮化碳材料的开发及其较高光催化活性的内在机制研究提供了新的见解.     

钙钛矿基近红外光电探测器

近年来,具有ABX₃晶体结构的金属卤化物钙钛矿材料因其可调带隙、高吸收系数、长载流子传输距离等光电学特性而在光电探测领域表现出良好应用前景,尤其是基于纯Sn或者Sn/Pb混合阳离子制备的杂化钙钛矿在760～1050nm范围的近红外光电响应性能非常优异,展现出高灵敏度、低暗电流和高探测率等多方面优势。为进一步拓宽钙钛矿的近红外以及红外响应波长范围,研究人员探索了将有机材料、晶体硅/锗、Ⅲ-Ⅴ族化合物、Ⅳ-Ⅵ族化合物、上转换荧光材料等作为互补光吸收层与钙钛矿结合制备异质结来构筑出宽谱响应的近红外光电探测器。基于以上研究,本文总结了当前拓宽钙钛矿光电探测器的光谱范围的有效途径。同时,对钙钛矿材料的近红外光电探测器的未来发展前景作出了展望。     

稀土莫来石型复合氧化物REMn2O5的结构与甲烷催化氧化性能研究

采用溶胶凝胶法制备了4种稀土莫来石型复合氧化物REMn₂O₅ (RE=Pr, Sm, Eu, Y)并负载贵金属Pd,对比了其结构特点和甲烷催化氧化性能。结果表明,Pd/SmMn₂O₅和Pd/YMn₂O₅具有优异的甲烷催化氧化性能,其T₅₀分别为328和308℃,优于目前有报道的贵金属类甲烷氧化催化剂。XRD分析和DFT计算结果表明,稀土元素的离子半径对莫来石结构有明显影响,只有半径合适的离子(Sm, r=0.1079 nm; Eu, r=0.1066 nm)才容易形成莫来石相。Pr³⁺离子半径较大(r=0.1126 nm), PrMn₂O₅样品出现较多的钙钛矿型氧化物;Y³⁺离子半径较小(r=0.1019nm), YMn₂O₅样品中除莫来石相外同时还存在钙钛矿型氧化物和锰氧化物。稀土莫来石型复合氧化物中含...     

一种高效窄带蓝色荧光粉Ba3Y2B6O15:Bi3+及其应用研究

目前,高效窄带荧光粉的研发对于白光发光二极管(WLED)向高性能液晶显示器背光源的应用至关重要.本工作采用高温固相法制备了一种高效窄带蓝色荧光粉Ba₃Y₂B₆O₁₅:Bi³⁺,并对其结构和性能进行了表征和计算.计算表明,Ba₃Y₂B₆O₁₅的带隙较宽,为4.67 eV,宽的带隙为高效率荧光粉提供了保障. Ba₃Y₂B₆O₁₅:0.5%Bi³⁺(0.5%为摩尔分数)的发射光谱峰值在409nm,半峰宽仅为2168cm^-1 (36.2nm),属于窄带蓝光发射.Ba₃Y₂B₆O₁₅:0.5%Bi³⁺的内量子效率高达93.8%,色纯度也高达98.9%,其热稳定性能...     

第一性原理研究HC(NH2)2PbI3钙钛矿(三方相VS六方相)的结构及光电特性

采用第一性原理,研究三方及六方相FAPbI₃（FA=HC（NH₂）₂⁺）钙钛矿的结构及光电特性.结果表明,FAPbI₃钙钛矿由三方到六方的形变能够扭转PbI₃骨架,改变Pb-I键合特性,进而改变其禁带宽度值.两种晶体均属于直接带隙半导体,三方相FAPbI₃的直接带隙点位于布里渊区Z（0,0,0.5）对称点,具有较为理想的约1.50 eV的禁带宽度;六方相FAPbI₃的直接带隙点位于Γ（0,0,0）对称点,具有约2.50 eV的禁带宽度.FA离子不直接参与电子跃迁过程,仅仅充当电荷供体为PbI₃骨架提供超过0.7 e的电荷.相比于六方相晶体,三方相FAPbI₃具有更小的载流子有效质量,吸收光谱发生了显著的红移,并且其吸收特性优于六方相FAPbI₃和四方相MAPbI₃（MA=CH₃NH₃⁺）钙钛矿.六方相FAPbI₃比三方相晶系更稳定,FA和PbI₃骨架之间的结合作用力强于MA和PbI₃骨架之间的作用力.     

银簇化合物Ag3B6O10I的合成、晶体结构和双折射性质

通过高温固相合成技术,成功合成了一种新型含银簇卤化硼酸盐Ag₃B₆O₁₀I。该晶体属正交晶系,空间群为Pnma (No. 62)。结构分析表明,该晶体结构中BO₄四面体和BO₃三角形连接形成[B₆O₁₀]^2-并最终相互连接形成三维孔洞结构,Ag₃I三角锥位于孔洞中。这种基于B₆O₁₀基元的含银簇三维孔洞结构为首次报道。热稳定性分析表明Ag₃B₆O₁₀I为非同成分熔融化合物,熔融分解温度为963 K。紫外-可见-近红外漫反射光谱分析显示该晶体光学带隙约为3.1 eV。值得关注的是,Ag₃B₆O₁₀I晶体具有较大的双折射率(0.031@550 nm)。第一性原理理论计算揭示了该晶体的光学特性来源。     

K+掺杂双钙钛矿Cs2AgInCl6的发光性质

采用固相球磨法制备了K⁺掺杂双钙钛矿Cs₂AgInCl₆纳米材料,该方法无需配体辅助,绿色环保。通过X射线衍射谱和拉曼光谱对晶体结构进行研究,通过激发光谱、发射光谱和时间分辨光谱对其发光性能进行研究。结果表明,Cs₂AgInCl₆为立方晶体,属于Fm3m空间群,由于宇称禁戒跃迁,其荧光量子产率(PLQY)低,小于0.1%。低于60%的K⁺掺杂主要取代Ag⁺的位置,引起Cs₂AgInCl₆的晶格膨胀,消除了晶格结构的反演对称性,打破了宇称禁戒跃迁,掺杂后Cs₂AgInCl₆的光致发光强度显著增强。K⁺的最佳掺杂比例为40%,Cs₂Ag_0.6K_0.4InCl₆发出中心波长为640 nm,半高宽为180 nm,平均荧光寿命达到29.2 ns,PLQY达到10.5%。当K⁺掺杂比例超过60%,K⁺开始取代Cs⁺的位置,产物发生相变,出现立方相的Cs_2-xK_1+x-yAg_yInCl₆和单斜相的Cs_2-xK_1+xInCl₆产物,这些产物由于强电子-声子耦合,非辐射复合占据主导地位。     

K+掺杂双钙钛矿Cs2AgInCl6的发光性质

采用固相球磨法制备了K⁺掺杂双钙钛矿Cs₂AgInCl₆纳米材料,该方法无需配体辅助,绿色环保。通过X射线衍射和拉曼光谱对晶体结构进行研究,通过激发光谱、发射光谱和时间分辨光谱对其发光性能进行研究。结果表明,Cs₂AgInCl₆为立方晶体,属于Fm3m空间群,由于宇称禁戒跃迁,其荧光量子产率(PLQY)低,小于0.1%。低于60%的K⁺掺杂主要取代Ag⁺的位置,引起Cs₂AgInCl₆的晶格膨胀,消除了晶格结构的反演对称性,打破了宇称禁戒跃迁,掺杂后Cs₂AgInCl₆的光致发光强度显著增强。K⁺的最佳掺杂比例为40%,Cs₂Ag_0.6K_0.4InCl₆材料发射中心波长为640 nm,半高宽为180 nm,平均荧光寿命达到29.2 ns,PLQY达到10.5%。当K⁺掺杂比例超过60%,K⁺开始取代Cs⁺的位置,产物发生相变,出现立方相的Cs_2-xK_1+x-yAg_yInCl₆和单斜相的Cs_2-xK_1+xInCl₆产物,这些产物由于强电子-声子耦合,非辐射复合占据主导地位。     

Experimental and Theoretical Investigation of the Structural and Opto-electronic Properties of Fe-Doped Lead-Free Cs2AgBiCl6 Double Perovskite

Lead-free double perovskites have emerged as stable and non-toxic alternatives to Pb-halide perovskites. Herein, the synthesis of Fe-doped Cs₂AgBiCl₆ lead-free double perovskites are reported that display blue emission using an antisolvent method. The crystal structure, morphology, optical properties, band structure, and stability of the Fe-doped double perovskites were investigated systematically. Formation of the Fe-doped Cs₂AgBiCl₆ double perovskite is confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. XRD and thermo-gravimetric analysis (TGA) shows that the Cs₂AgBiCl₆ double perovskite has high structural and thermal stability, respectively. Field emission scanning electron microscopy (FE-SEM) analysis revealed the formation of dipyramidal shape Cs₂AgBiCl₆ crystals. Furthermore, energy-dispersive X-ray spectroscopy (EDS) mapping shows the overlapping of Cs, Bi, Ag, Fe, and Cl elements and homogenous incorporation of Fe in Cs₂AgBiCl₆ double perovskite. The Fe-doped Cs₂AgBiCl₆ double perovskite shows a strong absorption at 380 nm. It extends up to 700 nm, suggesting that sub-band gap states transition may originate from the surface defect of the doped perovskite material. The radiative kinetics of the crystals was studied using the time-correlated single-photon counting (TCSPC) technique. Lattice parameters and band gap value of the Fe-doped Cs₂AgBiCl₆ double perovskites predicted by the density functional theory (DFT) calculations are confirmed by XRD and UV/Visible spectroscopy analysis. Time-dependent photo-response characteristics of the Fe-doped Cs₂AgBiCl₆ double perovskite show fast response and recovery time of charge carriers. We believe that the successful incorporation of Fe in lead-free, environmentally friendly Cs₂AgBiCl₆ double perovskite can open a new class of doped double perovskites with significant potential optoelectronics devices fabrication and photocatalytic applications.     

Single Crystals of Mixed-Cation Copper-Based Perovskite with Trimodal Bandgap Behavior

Two-dimensional (2D) hybrid perovskites with novel functionalities and structural diversity are a perfect platform for emerging optoelectronic devices such as photodetectors, light-emitting diodes, and solar cells. Here, we demonstrate that excess concentration of Cesium bromide (CsBr) is key to the formation of easily exfoliated 2D Cs₂Cu(Cl/Br)₄ perovskite crystal. Furthermore, by employing this trick to 2D perovskite MA₂Cu(Cl/Br)₄ (MA=methylammonium), we achieve a phase-pure easily exfoliated 2D mixed-cation (MA/Cs)₂Cu(Cl/Br)₄ perovskite crystal, which exhibits reduced bandgap (1.53 eV) with ferromagnetic behavior and photovoltaic property. The resultant mixed-cation structured device reveals enhanced efficiency compared to all MA and all Cs counterparts. These findings demonstrate the importance of cation-engineering in developing innovative materials with novel properties.     

Luminescence and crystal growth of Cs2NaYCl6Bi

The crystal growth of Cs₂NaYCl₆ doped with Bi³⁺ is described and its luminescence properties reported and discussed.     

Incorporating Rare‐Earth Terbium(III) Ions into Cs2AgInCl6:Bi Nanocrystals toward Tunable Photoluminescence

The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs₂AgInCl₆ NCs to impart and tune the optical performances in the visible light region. Tb³⁺ ions were incorporated into Cs₂AgInCl₆ NCs and occupied In³⁺ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (⁵D₄→⁷F_6‐3) of Tb³⁺ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb³⁺. By controlling Tb³⁺ ions concentration, the emission colors of Bi‐doped Cs₂Ag(In_1?xTb_x)Cl₆ NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb³⁺ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.     

Lead‐Free Sodium–Indium Double Perovskite Nanocrystals through Doping Silver Cations for Bright Yellow Emission

Lead‐free halide perovskite nanocrystals (NCs) have drawn wide attention for solving the problem of lead perovskites toxicity and instability. Herein, we synthesize the direct band gap double perovskites undoped and Ag‐doped Cs₂NaInCl₆ NCs by variable temperature hot injection. The Cs₂NaInCl₆ NCs have little photoluminescence because of dark self‐trapped excitons (STEs). The dark STEs can be converted into bright STEs by doping with Ag⁺ to produce a bright yellow emission, with the highest photoluminescence quantum efficiency of 31.1 %. The dark STEs has been directly detected experimentally by ultrafast transient absorption (TA) techniques. The dynamics mechanism is further studied. In addition, the Ag‐doped NCs show better stability than the undoped ones. This result provides a new way to enhance the optical properties of lead‐free perovskites NCs for high‐performance light emitters.     

Preparation and Dielectric Properties of Mn-Doped Ba0.6Sr0.4TiO3-MgTiO3 Composite Ceramics

Barium strontium titanate (Ba_0.6Sr_0.4TiO₃, BST) nano-powders were prepared using Ba(NO₃)₂, Sr(NO₃)₂, oxalic acid dehydrate, and tetrabutyl titanate (Ti(OC4H9)4) as precursors by the chemical co-precipitation method. The product was characterized by thermogravimetry-differential scanning calorimetry (TG-DSC) thermal analyses, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The experimental results indicated that the resulting Ba_0.6Sr_0.4TiO₃ nano-powders were homogeneous with agglomerated nature. The Ba_0.6Sr_0.4TiO₃-MgTiO₃ (BST-MT) bulk composite ceramics doped by Mn were obtained by the traditional solid phase method. The XRD patterns demonstrated that Mn-doped BST was unable to change the perovskite crystalline structure of BST materials. SEM photographs revealed that the crystalline grains became larger with increasing the content of doping Mn (<1.5% (x, molar fraction)) and then the size of grains decreased after the Mn content exceeded 1.5% in the BST ceramics, suggesting the effect of Mn doping on the morphologies of BST-MT composites. The dielectric properties of BST-MT composite ceramics doped with 0.1%-2.0% (x) Mn were investigated systematically. Two effects of Mn doping on the dielectric properties of the BST-MT composite ceramics were observed. At low Mn doping concentrations (<1.5%), Mn mainly acted as an acceptor dopant to replace Ti at the B site of ABO3 perovskite structure, leading to a diffused phase transition. It was also observed that the grain size increased drastically as the Mn content increased and thus caused the decrease of dielectric loss. At higher Mn doping concentrations (>1.5%), the grain size decreased and the suppression of permittivity and the drastic increase of the dielectric losses were observed, which indicated a “composite” mixing effect.     

La、Ce、Yb掺杂对LiNi0.5Mn1.5O4高电压正极材料性能的影响

采用低温燃烧法制备出不同稀土元素掺杂的高电压镍锰酸锂(LiNi_(0.5)Mn_(1.5)O_4)正极材料,探究了不同掺杂比例(物质的量分数0.5%、1%、2%)和不同掺杂稀土元素(La、Ce、Yb)对样品性能的影响,并通过X射线衍射、拉曼光谱、电子顺磁共振和恒电流间歇滴定等技术探究了其影响机理。从X射线衍射图可以看出,稀土掺杂可以抑制Li_xNi_(1-x)O杂质相的产生;电感耦合等离子谱结果表明,掺杂进入的稀土元素与设计比例基本相符;从拉曼光谱图可以看出,稀土元素可以使样品的有序相增多,其中Ce掺杂样品的有序相最多;结合电子顺磁共振波谱氧空位测试,发现Ce掺杂诱导了样品中有序相比例增加,从而使样品的稳定性提高;经恒电流间歇滴定技术测试发现,Ce掺杂镍锰酸锂样品的扩散系数比未掺杂样品高了约15倍;在不同掺杂比例上,1%掺杂量时样品性能最佳。在3种最佳掺杂量的稀土元素样品中,Ce掺杂的样品性能最优,首次放电比容量可以达到133.3mAh·g~(-1),比未掺杂样品放电比容量高且首次效率提高了 18%,在1C下循环200次后,容量保持率为102%,比未掺杂样品提高了 8%。     

Effect of transition element doping on crystal structure of rare earth borosilicides REB44Si2

On a previous study on samples of doped-YB₄₄Si₂, an improvement of thermoelectric properties has been achieved. Regarding the interesting effect of the doping of transition elements on the thermoelectric properties, a single crystal study has been carried out on Zn doped, Rh doped and Ni doped samples to assess how the transition element doping affects the crystal structure. Refinements were carried out based on the structural model solution of YB₄₄Si₂ reported in a previous study. Variations in the silicon contents were found in the doped single crystals. Splitting of partially occupied sites has also been detected for some of the doped samples. In this paper we present differences in the partial occupations of boron and silicon sites. Possibility of transition elements insertions based on the differences in crystal structures will be presented.