采用PEABr添加剂获得高效且稳定的碳基CsPbBr3太阳能电池

全无机CsPbBr₃钙钛矿材料因其本征稳定性好、成本低廉从而在光伏领域展现出巨大的应用潜力,但目前CsPbBr₃太阳能电池的光电转换效率仍远低于其他体系的钙钛矿太阳能电池.本文以无空穴传输层结构的碳基CsPbBr₃全无机钙钛矿电池作为研究对象,以多步旋涂法为基础,通过在PbBr₂(DMF)溶液中添加2-苯乙胺溴盐(PEABr)来调控CsPbBr₃薄膜的结晶质量,降低薄膜缺陷态密度,钝化晶粒间界,并对其中的关键工艺参数包括CsBr的用量(旋涂次数)、旋涂PbBr₂薄膜时的衬底预热温度以及退火温度进行了优化.最终在大气环境下获得了兼具稳定和高效的无空穴传输层结构的碳基CsPbBr₃太阳能电池,器件的光电转换效率达到8.25%,并在无封装条件下保存1500 h仍可保持90%以上的效率,对于进一步拓展CsPbBr₃钙钛矿电池的优化设计思路具有重要意义.     

聚偏氟乙烯添加剂提高CsPbBr3钙钛矿太阳能电池性能

全无机CsPbBr₃钙钛矿太阳能电池因其优良的特性而受到广泛关注,但是钙钛矿层具有带隙宽、结晶性较差、表面缺陷较多和水分稳定性差等缺点,严重制约了全无机CsPbBr₃钙钛矿太阳能电池性能的提高和商业化发展.本文以无空穴传输层的碳基CsPbBr₃钙钛矿太阳能电池作为控制组,在PbBr₂前躯液中引入具有丰富疏水F离子的聚偏氟乙烯(polyvinylideine fluoride,PVDF)作为添加剂,调节CsPbBr₃钙钛矿薄膜的生长过程,改善晶体结构和薄膜形态,降低缺陷密度及非辐射复合几率.结果表明,PVDF处理后钙钛矿器件的光伏性能得到了显著改善,光电转换效率提高至8.17%.并且在无封装条件下保存1400 h后,光电转换效率仍可保持90%以上.这表明适量添加PVDF可以有效提高CsPbBr₃薄膜质量及器件性能.本工作对进一步拓展CsPbBr₃钙钛矿太阳能电池的优化设计思路具有重要意义.     

高效稳定的CsPbBr3-Cs4PbBr6混合相钙钛矿纳米晶的制备及形成过程

通过配体后处理法向CsPbBr₃钙钛矿纳米晶中加入油胺-十四烷基膦酸(OLA-TDPA)的混合配体获得了CsPbBr₃-Cs₄PbBr₆混合材料.在最佳比例下(CsPbBr₃, TDPA与OLA的物质的量的比为1∶1∶15)制备的CsPbBr₃-Cs₄PbBr₆钙钛矿纳米晶混合相的光致发光量子产率可达78%,荧光寿命长达476 ns,且其在室温环境下保持稳定性至少25 d,在293 K和328 K之间的5个加热-冷却循环中具有良好的热稳定性.混合纳米晶的形成经历了表面钝化/溶解和重结晶两个阶段:在第1阶段(t≤1 h), OLA-TDPA混合配体形成了(RNH₃)₂PO₃X型配体与纳米晶表面发生配体交换,交换后的新配体能与纳米晶表面的Pb²⁺紧密的结合且含量较高,降低了纳米晶表面的缺陷态密度,提高了CsPbBr₃     

室温合成具有超纯绿光发射的准二维CsPbBr3钙钛矿纳米片

通过配体辅助溶液相法,在室温下成功合成出一种具有超纯绿光发射的准二维CsPbBr₃钙钛矿纳米片。该制备方法可以实现低成本、高质量CsPbBr₃纳米片的合成。实验结果表明,合成出的CsPbBr₃纳米片荧光发射峰位于526 nm,发射峰半高宽(FWHM)能够达到16 nm,纳米片的荧光量子效率(PLQY)高达87%。将CsPbBr₃纳米片应用于背光显示,实现了(0.145, 0.793)的绿光坐标,该色坐标覆盖近91%的Rec.2020绿光色域,色域范围优于目前报道的绿色荧光粉材料。此外,基于上述CsPbBr₃荧光纳米片,我们还成功构筑出一种白光LED器件,并测得该器件在20 mA驱动电流下的发光效率为39 lm/W。     

2018年2期电子期刊

光诱导功能退化是胶体量子点在应用中面临的主要挑战之一,本文针对这一问题研究了使用磁控溅射沉积SiO₂薄膜形成钝化层来提高CdSe/ZnS量子点发光稳定性的方法。首先,通过三正辛基膦辅助连续离子层吸附反应方法合成了615 nm发光的红色CdSe/ZnS量子点。然后将量子点旋涂在SiO₂/Si基片上,再通过磁控溅射方法在量子点上沉积了厚度为20 nm的SiO₂薄膜作为钝化层。使用连续波激光光源分别在空气气氛和真空条件下照射样品,研究了经过不同照射时间后钝化和未钝化量子点的稳态光致发光光谱。结果表明,随着照射时间的延长,没有SiO₂钝化的量子点的PL强度显著降低、PL峰值发生蓝移、FWHM不断增大。对比研究发现,由于SiO₂薄膜能够阻挡空气中的水和氧,减缓了量子点表面的光诱导氧化现象,因此显著提高了CdSe/ZnS量子点的稳定性。     

多步旋涂过程中CsPbBr3无机钙钛矿成膜机理

在无机钙钛矿太阳能电池的研究中,薄膜制备工艺是影响钙钛矿太阳能电池光电转换效率(PCE)的重要因素之一. CsPbBr₃钙钛矿作为稳定性极好的无机钙钛矿之一,因其前驱体盐(PbBr₂, CsBr)溶解度差异过大,通常采用多步法进行制备.而由于对成膜机理的认识不充分,导致制备的薄膜存在薄膜形貌差、前驱体反应不完全等问题.本文通过旋涂不同次数的CsBr溶液,探究了CsPbBr₃钙钛矿的成膜机理.成膜过程中CsBr扩散进入预先沉积的PbBr₂薄膜完成反应,短暂反应时间使薄膜深层反应不充分而薄膜表面过度反应,CsPb₂Br₅和Cs₄PbBr₆等相伴随CsPbBr₃钙钛矿出现,反复退火形成的薄膜阻挡CsBr扩散加剧了这一现象.适当地延长前驱体的反应时间,能为CsBr扩散及反应提供更充分的空间.基于优化反应时间, CsPbBr₃钙钛矿薄膜形貌得到改善、其晶粒尺寸得到提升,钙钛矿薄膜...     

基于声化学法合成的CsPbBr3钙钛矿微晶双光子发光特性

全无机金属卤化物钙钛矿材料的非线性光学效应对构建新型微纳光子器件具有重要意义。本文重点研究了微米尺度CsPbBr₃钙钛矿单晶颗粒的双光子发射特性,实验中基于声化学合成法制备了不同尺寸的CsPbBr₃微晶颗粒,通过对激发光能量密度、波长、偏振的调整,研究了其对双光子发光特性的影响。实验结果表明在室温下CsPbBr₃微晶即具有较强的双光子发光。波长相关的光致发光光谱表明,同一吸收带隙下,其发光峰位相对于单光子发射变化不大,且随着激发波长的增大双光子发射强度逐渐降低。此外,CsPbBr₃微晶颗粒双光子发射具有偏振依赖性行为,偏振角度在0°～360°范围内呈现四重对称性。上述CsPbBr₃微晶的双光子发光特性使其有望用于非线性集成器件。     

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.     

包含硅量子点的富硅SiNx 薄膜结构与发光特性

采用等离子体增强化学气相沉积法, 以NH₃与SiH₄为反应气体, n型单晶硅为衬底, 低温(220 ℃)沉积了富硅氮化硅(SiN_x)薄膜. 在N₂氛围中, 于500–1100 ℃ 范围内对样品进行了热退火处理. 采用Raman 光谱技术分析了薄膜内硅量子点的结晶情况, 结果表明, 当退火温度低于950 ℃时, 样品的晶化率低于18%, 而当退火温度升为1100 ℃, 晶化率增加至53%, 说明大部分硅量子点都由非晶态转变为晶态. 实验通过Fourier 变换红外吸收(FTIR)光谱检测了样品中各键的键合结构演变, 发现Si–N键和Si–H键随退火温度升高向高波数方向移动, 说明了薄膜内近化学计量比的氮化硅逐渐形成. 实验还通过光致发光(PL)光谱分析了各样品的发光特性, 发现各样品中均有5个发光峰, 讨论了它们的发光来源, 结合Raman光谱与FTIR光谱表明波长位于500–560 nm的绿光来源于硅量子点, 其他峰则来源于薄膜内的缺陷态. 研究了硅量子点的分布和尺寸对发光带移动的影响, 并根据PL峰位计算了硅量子点的尺寸, 其大小为1.6–3 nm, 具有良好的限域效应. 这些结果有助于制备尺寸不同的硅量子点和基于硅量子点光电器件的实现. 关键词： 硅量子点 氮化硅薄膜 光致发光 Fourier 变换红外吸收     

CsPbxSn1-xBr3/a-ZrP复合材料的光学性能及其在白色发光二极管中的应用

钙钛矿量子点(PQDs)由于具有高量子效率、可调节带隙、高色纯度及低成本等优点,在光电领域具有良好的应用前景。然而,其较差的稳定性阻碍了钙钛矿量子点的应用。本文在室温条件下合成了CsPb_xSn_1-xBr₃/a-ZrPPQDs,与传统CsPbBr₃PQDs对比,具有更好的光学性能及稳定性。由于a-ZrP对于Pb²⁺选择吸附性的固有特性以及与Cs⁺离子交换的能力,促进了量子点在a-ZrP表面的吸附锚定。因此,合成的CsPb_xSn_1-xBr₃/a-ZrPPQDs具有更高的激子结合能和更强的环境稳定性。该复合材料为生产稳定高效的钙钛矿量子点提供了一种可行的方法,并表明CsPb_xSn_1-xBr₃/a-ZrPPQDs是一种高效的下转换荧光材料,可用于高效发光二极管的制备。     

Stability and luminescence properties of CsPbBr3/CdSe/Al core-shell quantum dots

To improve the stability and luminescence properties of CsPbBr₃ QDs, we proposed a new core-shell structure for CsPbBr₃/CdSe/Al quantum dots (QDs). By using a simple method of ion layer adsorption and a reaction method, CdSe and Al were respectively packaged on the surface of CsPbBr₃ QDs to form the core-shell CsPbBr₃/CdSe/Al QDs. After one week in a natural environment, the photoluminescence quantum yields of CsPbBr₃/CdSe/Al QDs were greater than 80%, and the PL intensity remained at 71% of the original intensity. Furthermore, the CsPbBr₃/CdSe/Al QDs were used as green emitters for white light-emitting diodes (LEDs), with the LEDs spectrum covering 129% of the national television system committee (NTSC) standard color gamut. The core-shell structure of QDs can effectively improve the stability of CsPbBr₃ QDs, which has promising prospects in optoelectronic devices.     

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,...     

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.     

Insights into the adsorption of water and oxygen on the cubic CsPbBr3 surfaces: A first-principles study

The degradation mechanism of the all-inorganic perovskite solar cells in the ambient environment remains unclear. In this paper, water and oxygen molecule adsorptions on the all-inorganic perovskite (CsPbBr₃) surface are studied by density-functional theory calculations. In terms of the adsorption energy, the water molecules are more susceptible than the oxygen molecules to be adsorbed on the CsPbBr₃ surface. The water molecules can be adsorbed on both the CsBr- and PbBr-terminated surfaces, but the oxygen molecules tend to be selectively adsorbed on the CsBr-terminated surface instead of the PbBr-terminated one due to the significant adsorption energy difference. While the adsorbed water molecules only contribute deep states, the oxygen molecules introduce interfacial states inside the bandgap of the perovskite, which would significantly impact the chemical and transport properties of the perovskite. Therefore, special attention should be paid to reduce the oxygen concentration in the environment during the device fabrication process so as to improve the stability and performance of the CsPbBr₃-based devices.     

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...     

微通道反应器合成高质量的无机钙钛矿量子点及其LED应用

提出一种快速、高效合成高质量无机钙钛矿量子点（CsPbBr₃）的微通道反应器,通过调节前驱体的浓度和流速,可实现荧光光谱绿色至蓝色的转变,波长范围为515~464 nm。利用合成的绿色CsPbBr₃量子点和红色荧光粉制备薄膜,覆盖在蓝色LED芯片表面上,在20 mA的驱动电流下获得流明效率最高可达62.93 lm/W的白光。这种高效的白光LED展示出钙钛矿量子点在低成本显示、照明和光通信等应用领域中巨大的潜力。     

2018年5期 电子期刊

研究了不同Mn/Pb量比的Mn掺杂CsPbCl₃（Mn：CsPbCl₃）钙钛矿量子点的发光性质。Mn/Pb的量比增加引起的Mn²⁺发光峰的红移,被认为是来源于高浓度Mn²⁺掺杂下的Mn²⁺-Mn²⁺对。进一步研究了Mn：CsPbCl₃量子点的发光效率与Mn/Pb的量比之间的关系,发现随着量比达到5：1时,其发光效率明显下降。这种发光效率下降是由于Mn掺杂浓度引起的发光猝灭。Mn：CsPbCl₃量子点的变温发光光谱证实,随着温度的升高,Mn离子发光峰蓝移,线宽加宽,但其发光强度明显增加。     

Quantum emission efficiency of nanocrystalline and amorphous Si quantum dots

The paper presents the comparison of emission efficiencies for crystalline Si quantum dots (QDs) and amorphous Si nanoclusters (QDs) embedded in hydrogenated amorphous (a-Si:H) films grown by the hot wire-CVD method (HW-CVD) at the variation of technological parameters. The correlations between the intensities of different PL bands and the volumes of Si nanocrystals (nc-Si:H) and/or an amorphous (a-Si:H) phase have been revealed using X-ray diffraction (XRD) and photoluminescence (PL) methods. These correlations permit to discuss the PL mechanisms in a-Si:H films with embedded nc-Si QDs. The QD parameters of nc-Si:H and a-Si:H QDs have been estimated from PL results and have been compared (for nc-Si QDs) with the parameters obtained by the XRD method. Using PL and XRD results the relations between quantum emission efficiencies for crystalline (η_cr) and amorphous (η_am) QDs have been estimated and discussed for all studied QD samples. It is revealed that a-Si:H films prepared by HW-CVD with the variation of wire temperatures are characterized by better passivation of nonradiative recombination centers in comparison with the films prepared at the variation of substrate temperatures or oxygen flows.     

Gated photoluminescence study of oxide-free InP MIS structure having an ultrathin silicon interface control layer

In order to investigate the effectiveness of a novel oxide-free surface passivation approach for InP, using an ultrathin silicon interface control layer (Si ICL), gated photoluminescence characteristics of the Si₃N₄/Si ICL/n-InP metal–semiconductor–insulator (MIS) structure were studied at room temperature. As compared with gated PL spectra of Si₃N₄/n-InP MIS without Si ICL, PL intensities of the sample with Si ICL were much more strongly modulated by the gate voltage. The interface state density distribution was estimated by an optical analog of the Terman’s C–V analysis and a good agreement with the C–V analysis was obtained. The result indicates complete removal of Fermi level pinning over the entire bandgap in the novel oxide-free MIS structure.