金属离子掺杂提高全无机钙钛矿纳米晶发光性质的研究进展

金属卤化物钙钛矿纳米晶由于其卓越的光电子性能,在发光二极管、激光器、X射线成像、太阳能电池及光电探测等领域中受到了极大的关注.与有机-无机杂化钙钛矿纳米晶相比,全无机钙钛矿CsPbX₃ (X=Cl, Br, I)纳米晶具有更优异的光电性能和更高的稳定性.为进一步提高CsPbX₃纳米晶的光致发光量子效率和稳定性,有研究已经着手调控纳米晶的微观结构,减少作为非辐射复合中心的缺陷.近年来,在金属离子掺杂CsPb X₃纳米晶过程中,发现不同种类和不同掺杂浓度的金属离子对其电子能带结构和光致发光性能有着巨大的影响,基于金属离子掺杂取得了光致发光量子效率接近100%的CsPb X₃纳米晶.本文综述了近年来在CsPbCl₃, CsPbBr₃, CsPbI₃和Mn²⁺掺杂CsPbX₃ (Mn²⁺:CsPbX₃)四种体系中通过金属离子掺杂提高全无机钙钛矿纳米晶光学性...     

利用脉冲激光沉积外延制备CsSnBr3/Si异质结高性能光电探测器

钙钛矿半导体具有光吸收系数高、载流子扩散长度大和荧光量子效率高等优异物理特性,已在光电探测器、太阳能电池等领域展现出重要的应用潜力.但卤化铅钙钛矿的环境毒性和稳定性大大限制了该类器件的应用范围.因此,寻找低毒、稳定的非铅钙钛矿半导体尤为重要.利用锡元素替代铅元素并生长高质量的锡基钙钛矿薄膜是实现其光电器件应用的可行方案.本文采用脉冲激光沉积方法,在N型单晶硅(100)衬底上外延生长了一层(100)取向的CsSnBr₃钙钛矿薄膜.霍尔效应及电学测试结果表明,基于CsSnBr₃/Si半导体异质结在暗态下具有明显的异质PN结电流整流特征,在光照下具有显著的光响应行为,并具有可自驱动、高开关比(10⁴)以及毫秒量级响应/恢复时间等优良光电探测器件性能.本文研究结果表明利用脉冲激光沉积方法在制备新型钙钛矿薄膜异质结、实现快速灵敏的光电探测方面具有重要应用前景.     

静水压对立方钙钛矿CsSnX3(X=I, Br, Cl)光电性质的第一性原理探究

全无机无铅卤化物钙钛矿已经成为重要的新一代太阳能电池材料.采用密度泛函理论的第一性原理研究了不同静水压下CsSnX₃(X=I, Br, Cl)材料的晶体结构,电子结构和光学性能,并分析了其内在联系.结果表明施加静水压可使材料中Sn-X键长减小,使原子之间的耦合增强,带隙值减小,且随着卤族元素半径的增大,压力效应越明显;随着压力的增加,材料的吸收系数和复折射率增大,吸收光谱出现红移现象,在可见光区和近红外光区吸收增强.相比CsSnBr₃和CsSnCl₃,CsSnI₃在可见光区吸收最佳且受压力作用影响最小,更适用于钙钛矿太阳能电池材料.     

双壳层包覆Mn∶CsPbCl3纳米晶制备及潜指纹识别应用

全无机卤化铅铯钙钛矿纳米晶CsPbX₃(X=Cl,Br,I)因具有独特的光电特性,近年来在固体照明及显示、太阳能电池、阻变存储器等领域成为研究的热门之选。Mn²⁺是一种比Pb²⁺半径小的过渡金属离子,利用Mn²⁺掺杂CsPbCl₃钙钛矿纳米晶能够实现波长位于600 nm左右可见光区域的橘黄色发射,且能够部分替代钙钛矿纳米晶中的Pb²⁺,降低钙钛矿纳米晶的毒性。然而,Mn²⁺掺杂的卤化物钙钛矿纳米晶仍易受环境中水分子等的侵蚀而导致其荧光特性严重退化。本文采用一种利用四甲氧基硅烷(Tetramethoxysilane,TMOS)和聚甲基丙烯酸甲酯(Polymethyl methacrylate,PMMA)对Mn²⁺掺杂CsPbCl₃钙钛矿纳米晶进行双壳层的包覆方法,并分析了双壳层包覆法对钙钛矿纳米晶稳定性提升的机理。此外,还对比了双壳层包覆的Mn²⁺掺杂CsPbCl     

超小晶粒锡掺杂CsPbBr3蓝光量子点的合成及其光学性能研究

近年来,铅卤钙钛矿CsPbX₃ (X=Cl,Br或I)因其具有荧光波段可调、荧光量子产率高(Photoluminescence quantum yield,PLQY)以及荧光半峰宽窄等优点而被广泛应用于光电器件领域.然而,与PLQY接近于100%的绿光和红光相比,蓝光卤素钙钛矿的PLQY仍比较低.在此,采用过饱和结晶的方法在室温下合成了粒径低于4 nm的超小晶粒锡(Sn)掺杂CsPbBr₃量子点,并对其结构特性和光学特性进行了研究.结果表明:随着SnBr₂添加量的增大,量子点晶粒的粒径略微减小,荧光发射峰发生蓝移,粒径由3.33 nm (SnBr₂为0.03 mmol)减小到2.23 nm(SnBr₂为0.06 mmol时),对应的荧光发射峰由490 nm蓝移至472 nm.当SnBr₂添加量为0.05 mmol时合成的超小晶粒锡掺杂CsPbBr₃量子点显示出最优的光学性能,其粒径约为2.91 nm,对应的XRD各晶面衍射峰强度最强,...     

应力调控BlueP/XTe2(X=Mo,W)范德瓦耳斯异质结电子结构及光学性质理论研究

通过第一性原理计算探讨了蓝磷烯与过渡金属硫化物MoTe₂/WTe₂形成范德瓦耳斯异质结的电子结构和光学性质,以及施加双轴应力对相关性质的影响.计算结果表明,形成BlueP/XTe₂(X=Mo,W)异质结,二者能带排列为间接带隙type-Ⅱ并有较强的红外光吸收,同时屏蔽特性增强.随压缩应力增加,BlueP/XTe₂转变为直接带隙type-Ⅱ能带排列最后转变为金属性;随拉伸应力增加,异质结转变为间接带隙type-Ⅰ能带排列.外加应力也能有效调控异质结的光吸收性质,随压缩应力增加吸收边红移,光吸收响应拓展至中红外光谱区且吸收系数增大;BlueP/MoTe₂较BlueP/WTe₂在中红外至红外光区间表现出更强的光吸收响应;静态介电常数ε1(0)大幅增加.结果表明,压缩应力对BlueP/MoTe₂和BlueP/WTe₂能带排列、光吸收特性均有显著的调控作用,其中BlueP/MoTe₂对调控更敏感,这些特性也使BlueP/XTe₂异质结在窄禁带中红外半导体材料及光电器件具有令人期待的应用价值.     

Ge/Si异质键合半/绝接触界面态对异质结光电输运特性的影响研究

Ge/Si异质键合技术作为一种新型的通用材料制备工艺,在制备高质量Si基Ge薄膜方面展现出巨大的潜力,是研制高性能Ge/Si光电器件的备选方案之一。现阶段主流的直接键合和等离子体键合方法在制备Ge/Si薄膜时都容易在Ge/Si键合界面处引入纳米氧化锗层(GeO₂),导致Ge/GeO₂及GeO₂/Si半/绝接触界面存在界面态,从而器件性能受影响。基于载流子三大输运方程、非局域隧穿模型及半经典量子解法,构建了低温Ge/Si异质键合界面,研究了键合界面的界面态密度(ISD)对Ge/Si异质结的载流子电学输运、光吸收、复合及高频响应等性能的影响。结果表明,随着ISD的增加,Ge/Si异质结的暗电流增大,同时界面态对载流子的俘获能力加强,导致总电流减小,光谱响应减弱。另外,ISD的增加导致Ge层内的电场减小,高频特性变差。为获得性能良好的键合Ge/Si异质结,ISD必须低于1×10¹² cm^-2。该研究结果为高质量Si基Ge薄膜及高性能Ge/Si光电器件的制备提供了理论指导。     

钡作为掺杂元素调控铅基钙钛矿材料的毒性和光电特性

近年来,有机-无机杂化卤化物钙钛矿材料(ABX_3)由于具有优异的光电性质,受到了材料、能源等领域的广泛关注.但是,卤化物钙钛矿存在两个明显阻碍其商业化应用的问题:热稳定性差和含有有毒的铅(Pb)元素.相比于有机-无机杂化卤化物钙钛矿,全无机卤化物钙钛矿通常拥有更好的热稳定性.同时,采用一些无毒的元素部分替代B位的Pb,可以在保持优异光电特性的同时减小材料的毒性.本文结合无序合金结构搜索方法和第一性原理计算,系统研究了Ba掺杂CsPbX_3 (X=Cl, Br, I)钙钛矿体系的热稳定性和光电特性.计算结果显示,只有在高Ba浓度时,可以在室温下形成无序固溶体.由于Ba和Pb的离子半径和电负性等物理化学性质存在显著差异,随着Ba掺杂浓度的增加,带隙和载流子有效质量都呈现上升趋势,且带隙具有很宽的调节范围.因此,我们预测高Ba掺杂浓度的CsPbX_3 (X=Cl, Br, I)钙钛矿体系在短波段(如紫外或近紫外光)发光二极管或辐射探测器等领域具有潜在的应用价值.     

顺磁性La2/3Sr1/3MnO3层对Bi0.8Ba0.2FeO3薄膜多铁性能的影响

界面效应在提升异质结构材料的多铁性能方面有着重要的作用. 本文采用脉冲激光沉积技术在SrTiO₃(STO)基片上制备了Bi_0.8Ba_0.2FeO₃(BBFO)/La_2/3Sr_1/3MnO₃(LSMO)异质结. X-射线衍射图谱表明异质结呈现单相外延生长, 利用高分辨透射电镜进一步证实了BBFO为四方相结构. X-射线光电子能谱证实异质结中只存在Fe³⁺ 离子, 没有产生价态的变化, 揭示了异质结铁电和铁磁性的增强与BBFO/LSMO的界面有关. 同时, 测试了磁电阻(MR)和磁介电(MD), 当磁场强度为0.8 T, 温度为70 K时, MR约为-42.2%, MD约为21.2%. 并且发现在180 K时出现磁相的转变. 实验结果揭示出异质界面效应在提升材料的多铁性和磁电耦合效应方面具有超常的优点, 是加快多铁材料实际应用的有效途径.     

BaTiO3/p-Si异质结的整流特性和光诱导特性的研究

利用脉冲激光沉积法成功制备了BaTiO₃/p-Si异质结, 该异质结在80–300 K 显示出了良好的整流特性和光诱导特性. 开启电压随着温度的升高而逐渐降低. 利用不同频率的光子辐照样品, 观察到明显的光电导效应. 且随着照射光子能量的增大, 结电流也相应变大, 光诱导效应越明显. BaTiO₃薄膜电阻-温度(R-T) 曲线显示氧缺陷条件下BaTiO₃薄膜具有良好的半导体特性. 关键词： 异质结 光诱导效应 3薄膜')" href="#">BaTiO₃薄膜     

Stability,electronic structure,and optical properties of lead-free perovskite monolayer Cs3B2X9(B=Sb,Bi;X=Cl,Br,I)and bilayer vertical heterostructure Cs3B2X9/Cs3B’2X9(B,B’=Sb,Bi;X=Cl,Br,I)

The lead-free perovskites Cs₃B₂X₉(B=Sb,Bi;X=Cl,Br,I)as the popular photoelectric materials have excellent optical properties with lower toxicity.In this study,we systematically investigate the stable monolayer Cs₃B₂X₉and bilayer vertical heterostructure Cs₃B₂X₉/Cs3B02X9(B,B0=Sb,Bi;X=Cl,Br,I)via first-principles simulations.By exploring the electrical structures and band edge positions,we find the band gap reduction and the band type transition in the heterostructure Cs₃B₂X₉/Cs3B02X9 due to the charge transfer between layers.Furthermore,the results of optical properties reveal light absorption from the visible light to UV region,especially monolayer Cs3Sb2I9 and heterostructure Cs3Sb2I9/Cs3Bi2I9,which have absorption peaks in the visible light region,leading to the possibility of photocatalytic water splitting.These results provide insights for more two-dimensional semiconductors applied in the optoelectronic and photocatalytic fields.     

Ba2+离子掺杂CsPbBr3蓝光量子点合成及其光学性能

近年来,全无机卤素钙钛矿CsPbX3(X=Cl,Br,I)因其荧光带宽窄、带隙可调、合成工艺简单以及荧光量子产率(Photoluminescence quantum yield,PLQY)高等优点而被应用于光电器件领域.但相比于PLQY接近于100％的红光与绿光CsPbX3量子点,PLQY低于10％的蓝光量子点光学性能...     

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.     

Electronic and optical properties of 3N-doped graphdiyne/MoS2 heterostructures tuned by biaxial strain and external electric field

The construction of van der Waals (vdW) heterostructures by stacking different two-dimensional layered materials have been recognised as an effective strategy to obtain the desired properties. The 3N-doped graphdiyne (N-GY) has been successfully synthesized in the laboratory. It could be assembled into a supercapacitor and can be used for tensile energy storage. However, the flat band and wide forbidden bands could hinder its application of N-GY layer in optoelectronic and nanoelectronic devices. In order to extend the application of N-GY layer in electronic devices, MoS₂ was selected to construct an N-GY/MoS₂ heterostructure due to its good electronic and optical properties. The N-GY/MoS₂ heterostructure has an optical absorption range from the visible to ultraviolet with a absorption coefficient of 10⁵ cm^-1. The N-GY/MoS₂ heterostructure exhibits a type-Ⅱ band alignment allows the electron-hole to be located on N-GY and MoS₂ respectively, which can further reduce the electron-hole complexation to increase exciton lifetime. The power conversion efficiency of N-GY/MoS₂ heterostructure is up to 17.77%, indicating it is a promising candidate material for solar cells. In addition, the external electric field and biaxial strain could effectively tune the electronic structure. Our results provide a theoretical support for the design and application of N-GY/MoS₂ vdW heterostructures in semiconductor sensors and photovoltaic devices.     

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.     

Impeding anion exchange to improve composition stability of CsPbX_3(X= Cl,Br) nanocrystals through facilely fabricated Cs_4Pb_6 shell

Inorganic lead halide perovskite nanocrystals(NCs) with superior photoelectric properties are expected to have excellent performance in many fields. However, the anion exchange changes their features and is unfavorable for their applications in many fields. Hence, impeding anion exchange is important for improving the composition stability of inorganic lead halide perovskite NCs. Herein, CsPb X_3(X = Cl, Br) NCs are coated with Cs_4PbX_6 shell to impede anion exchange and reduce anion mobility. The Cs_4PbX_6 shell is facily fabricated on CsPbX_3 NCs through high temperature injection method.Anion exchange experiments demonstrate that the Cs_4 PbX_6 shell completely encapsulates CsPbX_3 NCs and greatly improves the composition stability of CsPbX_3 NCs. Moreover, our work also sheds light on the potential design approaches of various heterostructures to expand the application of CsPbM_3(M = Cl, Br, I) NCs.     

有机金属卤化物钙钛矿薄膜中的光诱导载流子动力学和动态带重整效应

近年来有机-无机金属卤化物钙钛矿太阳能电池因具有光电能量转换效率高、制备工艺简单等优点,引起了学术界和产业界的广泛关注,其优异的光电特性逐渐在能源领域展现出独特的优越特性.在短短几年内,有机-无机混合物钙钛矿太阳能电池的能量转换效率已经高达23%,发展速度逐步赶上甚至超越了成熟的硅太阳能电池.本文利用飞秒瞬态吸收光谱,对二步法制备的(5-AVA)_(0.05)(MA)_(0.95)PbI_3和(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD有机-无机卤化物钙钛矿薄膜材料的激发态动力学进行了对比研究,详细讨论了两种薄膜样品中的电荷载流子产生与复合机制.通过紫外-可见吸收光谱测得钙钛矿薄膜(5-AVA)_(0.05)(MA)_(0.95)PbI_3和(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD的吸收光谱与CH_3NH_3PbI_3钙钛矿薄膜材料的双价带结构相对应.从瞬态吸收光谱中,观察到760 nm附近的光致漂白信号,此时的载流子复合过程符合二阶动力学过程,而在约550—700 nm光谱范围内则是光诱导激发态吸收信号.实验结果表明,(5-AVA)_(0.05)(MA)_(0.95)PbI_3钙钛矿薄膜样品中光生载流子主要的弛豫途径是自由电子和空穴的复合.抽运光激发样品使价带中的电子跃迁到导带,随着延迟时间的增加,电子和空穴复合,光谱发生红移现象.所观察到的带重整效应可以根据Moss-Burstein效应解释.相比较而言,(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD钙钛矿薄膜样品在光激发后电子和空穴分离,空穴迅速转移到空穴传输层,这将导致样品吸收度增加,漂白信号快速恢复,电子-空穴的复合不再对漂白信号的弛豫动力学起主导作用,同时也削弱了带重整现象.本文的实验结果对半导体有机-无机金属卤化物钙钛矿薄膜在光伏领域的应用具有重要意义,为今后高效、稳定的钙钛矿太阳电池的研究提供了参考.     

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.