Dimethylamine oxalate manipulating CsPbI_(3) perovskite film crystallization process for high efficiency carbon electrode based perovskite solar cells

Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells(PSCs).Dimethylamine oxalate has been proven as a multifunctional modulator,and is explored as an efficient additive in manipulating the crystallization process of CsPbI_(3) perovskite films.On one hand,oxalate serves as the precipitator that facilitates the nucleation process of intermediate.The larger size of intermediate is conductive to the larger size and smaller grain boundaries of resultant perovskite.On the other hand,in subsequent annealing process,the phase conversion and growth process of transient perovskite can be decelerated due to the strong interactions of oxalate with both dimethylamine cation(DMA^(+))and Pb^(2+).Due to the optimized crystallization kinetics,the morphology and quality of CsPbI_(3) perovskite films are comprehensively improved with lower defect concentrations,and charge recombination loss is effectively suppressed.Benefiting from the optimized crystal quality of perovskite films,the carbon electrode-based CsPbI_(3) PSCs exhibit a champion efficiency of 18.48%.This represents one of the highest levels among all hole transport layer-free inorganic perovskite solar cells.

基于有机胺盐表面修饰的CsPbI_(3)全无机钙钛矿太阳能电池性能的提升

有机胺盐表面修饰是钙钛矿太阳能电池中钝化钙钛矿表面缺陷和提升电池稳定性的有效方法。旋涂苯乙基碘化铵(phenylethylammonium iodide,PEAI)和四丁基碘化铵(tetrabutylammonium iodide,TBAI)溶液在CsPbI_(3)钙钛矿薄膜表面并进行热处理,修饰钙钛矿表面,采用X射线衍射仪、扫描电镜、稳态-瞬态荧光寿命光谱仪对薄膜的结构形貌和光电性能进行表征分析,通过电流密度-电压测试、电化学阻抗测试和暗态电流密度-电压测试对比两种表面修饰剂对CsPbI_(3)钙钛矿薄膜和器件性能的影响。结果表明:PEAI不能与CsPbI_(3)发生离子交换生成低维钙钛矿,仅通过吸附在表面钝化缺陷并阻碍水汽侵入,提升薄膜的稳定性;而TBAI可有效进入无机CsPbI_(3)钙钛矿晶格,形成低维钙钛矿相,进而改善薄膜形貌、钝化缺陷并提升薄膜的稳定性;TBAI修饰的电池器件光电转换效率相较于PEAI修饰的器件提升了8.5%,同时器件的稳定性也得到了增强。该研究为开发适用于全无机CsPbI_(3)钙钛矿的新型表面修饰剂提供了指导和方向。

Proton‑Prompted Ligand Exchange to Achieve High‑Efficiency CsPbI_(3) Quantum Dot Light‑Emitting Diodes

CsPbI_(3)perovskite quantum dots(QDs)are ideal materials for the next generation of red light-emitting diodes.However,the low phase stability of CsPbI_(3)QDs and long-chain insulating capping ligands hinder the improvement of device performance.Traditional in-situ ligand replacement and ligand exchange after synthesis were often difficult to control.Here,we proposed a new ligand exchange strategy using a proton-prompted insitu exchange of short 5-aminopentanoic acid ligands with long-chain oleic acid and oleylamine ligands to obtain stable small-size CsPbI_(3)QDs.This exchange strategy maintained the size and morphology of CsPbI_(3)QDs and improved the optical properties and the conductivity of CsPbI_(3)QDs films.As a result,high-efficiency red QD-based light-emitting diodes with an emission wavelength of 645 nm demonstrated a record maximum external quantum efficiency of 24.45%and an operational half-life of 10.79 h.

In Situ Iodide Passivation Toward Efficient CsPbI_(3) Perovskite Quantum Dot Solar Cells

All-inorganic CsPbI_3 quantum dots(QDs) have demonstrated promising potential in photovoltaic(PV) applications. However, these colloidal perovskites are vulnerable to the deterioration of surface trap states, leading to a degradation in efficiency and stability. To address these issues, a facile yet effective strategy of introducing hydroiodic acid(HI) into the synthesis procedure is established to achieve high-quality QDs and devices. Through an in-depth experimental analysis, the introduction of HI was found to convert PbI_2 into highly coordinated [PbI_m]~(2-m), enabling control of the nucleation numbers and growth kinetics. Combined optical and structural investigations illustrate that such a synthesis technique is beneficial for achieving enhanced crystallinity and a reduced density of crystallographic defects. Finally, the effect of HI is further reflected on the PV performance. The optimal device demonstrated a significantly improved power conversion efficiency of 15.72% along with enhanced storage stability. This technique illuminates a novel and simple methodology to regulate the formed species during synthesis, shedding light on ofurther understanding solar cell performance, and aiding the design of future novel synthesis protocols for high-performance optoelectronic devices.

Crystallization management of CsPbI_(2)Br perovskites by PbAc_(2)-incorporated twice spin-coating process for efficient and stable CsPbI_(2)Br perovskite solar cells

CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization rate of CsPbI_(2)Br films,resulting in small grain size and high defect density.Additionally,CsPbI_(2)Br demonstrates poor light absorption due to its wide bandgap.Therefore,it is crucial to control the crystallization rate and increase the film thickness to reduce defect density,enhance light absorption,and improve photovoltaic performance.In this study,we utilized a PbAc_(2)-incorporated twice spincoating(PTS) process to address these issues.Initially,PbAc_(2) was added to the CsPbI_(2)Br precursor solution to form a CsPbI_(2)Br film,which was then coated with the CsPbI_(2)Br precursor solution to produce the PTS film,Ac^(-)can delay the perovskite crystallization,leading to the formation of thicker and denser CsPbI_(2)Br films.Moreover,lone-pair electrons of the oxygen atom provided by Ac^(-)formed coordination bonds with under-coordinated Pb~(2+) ions to fill halogen ion vacancies,thereby reducing the defect density.Ultimately,the PTS CsPbI_(2)Br device achieved a peak power conversion efficiency(PCE) of 16.19% and maintained 96.7% of its initial PCE over 1500 h at room temperature under 25% relative humidity without any encapsulation.

Structure,ferroelectric,and enhanced fatigue properties of sol–gel-processed new Bi-based perovskite thin films of Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)

Bi-based perovskite ferroelectric thin films have wide applications in electronic devices due to their excellent ferroelectric properties.New Bi-based perovskite thin films Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)(BCT–PT) are deposited on Pt(111)/Ti/SiO_(2)/Si substrates in the present study by the traditional sol–gel method.Their structures and related ferroelectric and fatigue characteristics are studied in-depth.The BCT–PT thin films exhibit good crystallization within the phase-pure perovskite structure,besides,they have a predominant(100) orientation together with a dense and homogeneous microstructure.The remnant polarization(2P_(r)) values at 30 μC/cm^(2) and 16 μC/cm^(2) are observed in 0.1BCT–0.9PT and 0.2BCT–0.8PT thin films,respectively.More intriguingly,although the polarization values are not so high,0.2BCT–0.8PT thin films show outstanding polarization fatigue properties,with a high switchable polarization of 93.6% of the starting values after 10^(8) cycles,indicating promising applications in ferroelectric memories.

Highly ordered crystallization of α-FAPbl_(3) films via homogeneous seeds for efficient perovskite solar cells

Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition,and lattice defects are still the key challenges limiting the quality of FAPbI_(3) films.Previous studies show that the introduction or adding of seeds in the precursor is effective to promote the nucleation and crystallization of perovskite films.Nevertheless,the seed-assisted approach focuses on heterogeneous seeds or hetero-composites,which inevitably induce a lattice-mismatch,the genera-tion of strain or defects,and the phase segregation in the perovskite films.Herein,we first demonstrate that high-quality perovskite films are controllably prepared using α-and δ-phases mixed FAPbI_(3) micro-crystal as the homogeneous seeds with the one-step antisolvent method.The partially dissolved seeds with suitable sizes improve the crystallinity of the perovskite flm with preferable orientation,improved carrier lifetime,and increased carrier mobility.More importantly,the α-phase-containing seeds promote the formation of α-phase FAPbI_(3) films,leading to the reduction of residual lattice strain and the suppres-sion of I-ion migration.Besides,the adding of dimethyl 2,6-pyridine dicarboxylate(DPD)into the pre-cursor further suppresses the generation of defects,contributing to the PCE of devices prepared in air ambient being significantly improved to 23.75%,among the highest PCEs for fully air-processed FAPbI_(3) solar cells.The unpackaged target devices possess a high stability,maintaining 80%of the initial PCE under simulated solar illumination exceeding 800 h.

Inkjet-Printing Controlled Phase Evolution Boosts the Efficiency of Hole Transport Material Free and Carbon-Based CsPbBr_(3) Perovskite Solar Cells Exceeding 9%

Hole transport material free carbon-based all-inorganic CsPbBr_(3)perovskite solar cells(PSCs)are promising for commercialization due to its low-cost,high open-circuit voltage(V_(oc))and superior stability.Due to the different solubility of PbBr_(2)and CsBr in conventional solvents,CsPbBr_(3)films are mainly obtained by multi-step spin-coating through the phase evolution from PbBr_(2)to CsPb_(2)Br_(5)and then to CsPbBr_(3).The scalable fabrication of high-quality CsPbBr_(3)films has been rarely studied.Herein,an inkjet-printing method is developed to prepare high-quality CsPbBr_(3)films.The formation of long-range crystalline CsPb_(2)Br_(5)phase can effectively improve phase purity and promote regular crystal stacking of CsPbBr_(3).Consequently,the inkjet-printed CsPbBr_(3)C-PSCs realized PCEs up to 9.09%,8.59%and 7.81%with active areas of 0.09,0.25,and 1 cm^(2),respectively,demonstrating the upscaling potential of our fabrication method and devices.This high performance is mainly ascribed to the high purity,strong crystal orientation,reduced surface roughness and lower trap states density of the as-printed CsPbBr_(3)films.This work provides insights into the relationship between the phase evolution mechanisms and crystal growth dynamics of cesium lead bromide halide films.

Comparison of Perovskite Systems Based on AFeO_(3)(A=Ce,La,Y)in CO_(2) Hydrogenation to CO

CO_(2) is the most cost-eff ective and abundant carbon resource,while the reverse water-gas reaction(rWGS)is one of the most eff ective methods of CO_(2) utilization.This work presents a comparative study of rWGS activity for perovskite systems based on AFeO_(3)(where A=Ce,La,Y).These systems were synthesized by solution combustion synthesis(SCS)with diff erent ratios of fuel(glycine)and oxidizer(φ),diff erent amounts of NH 4 NO_(3),and the addition of alumina or silica as supports.Various techniques,including X-ray diff raction analysis,thermogravimetric analysis,Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy,energy-dispersive X-ray spectroscopy,N 2-physisorption,H_(2) temper-ature-programmed reduction,temperature-programmed desorption of H_(2) and CO_(2),Raman spectroscopy,and in situ FTIR,were used to relate the physicochemical properties with the catalytic performance of the obtained composites.Each specifi c perovskite-containing system(either bulk or supported)has its own optimalφand NH_(4) NO_(3) amount to achieve the highest yield and dispersion of the perovskite phase.Among all synthesized systems,bulk SCS-derived La-Fe-O systems showed the highest resistance to reducing environments and the easiest hydrogen desorption,outperforming La-Fe-O produced by solgel combustion(SGC).CO_(2) conversion into CO at 600°C for bulk ferrite systems,depending on the A-cation type and preparation method,follows the order La(SGC)<Y<Ce<La(SCS).The diff erences in properties between La-Fe-O obtained by the SCS and SGC methods can be attributed to diff erent ratios of oxygen and lanthanum vacancy contributions,hydroxyl coverage,morphology,and free iron oxide presence.In situ FTIR data revealed that CO_(2) hydrogenation occurs through formates generated under reaction conditions on the bulk system based on La-Fe-O,obtained by the SCS method.γ-Al_(2)O_(3) improves the dispersion of CeFeO_(3) and LaFeO_(3) phases,the specifi c surface area,and the quantity of adsorbed H_(2) and CO_(2).This led to a signifi cant increase in CO_(2) conversion for supported CeFeO_(3) but not for the La-based system compared to bulk and SiO_(2)-supported perovskite catalysts.However,adding alumina increased the activity per mass for both Ce-and La-based perovskite systems,reducing the amount of rare-earth components in the catalyst and thereby lowering the cost without substantially compromising stability.

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

Treating CsPbI_(3) Perovskite with Pyrrolidinium Iodide to Improve the Performance of Perovskite Solar Cells

All-inorganic CsPbI_(3) perovskite has attracted wide attention due to its desirable optical bandgap(Eg:∼1.7 eV)as well as high chemical stability.Nevertheless,the photovoltaic performance of CsPbI_(3) perovskite solar cells(PSCs)was limited by severe nonradiative charge recombination due to high defect density at the grain boundary and surface of perovskitefilms.To address this issue,a pyrrolidinium iodide(PyI)molecule was introduced to modify the surface and grain boundary of CsPbI_(3) perovskitefilms to passivate defects,which improves the quality of CsPbI_(3) perovskitefilms as well as induces the generation of a quasi-2D Py_(2)CsPb_(2)I_(7) capping layer between per-ovskite layer and hole transport layer.Such quasi-2D Py_(2)CsPb_(2)I_(7) capping layer optimizes interface contact between CsPbI_(3) perovskite layer and hole transport layer and blocks the electron transfer from CsPbI_(3) perovskite photoactive layer to the hole transport layer.As a result,the performance of CsPbI_(3) PSCs is well improved to 17.87%for power conversion efficiency(PCE)with an ultra-high fill factor(FF)of 0.84.In addition,the PyI mole-cule modified CsPbI_(3) perovskite devices exhibit excellent stability,which remains its initial PCE almost unchanged after aging for 35 days under the dry air atmosphere(temperature:20℃–30℃,control relative humid-ity(RH):<10%).

基于FASnI_(3)的钙钛矿太阳电池仿真研究

为提高电池的效率、减少环境污染,提出一种结构为FTO/Zn(O_(0.3),S_(0.7))/FASnI_(3)/NiO/Au的无铅钙钛矿太阳电池。该电池以FASnI_(3)为光活性层,Zn(O_(0.3),S_(0.7))和NiO分别为电子传输层和空穴传输层,FTO和Au为接触电极。在太阳电池电容模拟器(SCAPS)中构建模型并设置材料参数,通过控制变量法进行参数优化。结果表明,当FASnI_(3)厚度为500 nm时,器件对光子的吸收较充分,输出最高的功率转换效率(PCE);随着FASnI_(3)缺陷态密度的升高,器件内部载流子复合中心增多,提高了载流子复合率,控制FASnI_(3)缺陷态密度不超过10^(14) cm^(-3)可确保电池输出性能较佳;当Zn(O_(0.3),S_(0.7))的厚度和电子亲和势优化为30 nm和3.5 eV时,载流子运输更为有效,电池输出最高的PCE;增大Zn(O_(0.3),S_(0.7))与FASnI_(3)界面缺陷态密度,导致光生载流子在界面更容易被捕获,控制Zn(O_(0.3),S_(0.7))与FASnI_(3)界面缺陷态密度不超过10^(13) cm^(-3)有利于提高电池性能。

甲胺基金属卤化物MAPbX_(3)铁电半导体研究进展

为了研究甲胺基金属卤化物MAPbX_(3)铁电半导体的铁电性对光伏性能的影响,文中梳理了近几年MAPbX_(3)的相关研究文献,分析了MAPbX_(3)晶体的光学吸收和载流子输运性能的影响因素,阐述了MAPbX_(3)铁电性的验证方法及铁电体中载流子的分离机制,介绍了铁电半导体的应用,重点分析了MAPbX_(3)晶体结构方面的研究争议,讨论了MAPbX_(3)铁电性与铁弹性的关系,并对光伏器件的设计以及应用提出了新的研究思路。

Ecofriendly Hydroxyalkyl Cellulose Additives for Efficient and Stable MAPbI_(3)-Based Inverted Perovskite Solar Cells

Perovskite solar cells(PSCs)have been demonstrated to be one of the most promising technologies in the field of renewable energy.However,the presence of the defects in the perovskite films greatly limits the efficiency and the stability of the PSCs.The additive engineering is one of the most effective approaches to overcome this problem.Most of the successful additives are extracted from the petroleum-based materials,while the research on the biomass-based additives is still lagging behind.In this paper,two ecofriendly hydroxyalkyl cellulose additives,i.e.,hydroxyethyl cellulose(HEC)and hydroxylpropyl cellulose(HPC),are investigated on the performance of the MAPbl_(3)-based inverted PSCs.Due to the strong interaction between the hydroxyl groups of the cellulose and the divalent cations of the perovskite,these additives enhance the crystal grain orientation and significantly repair the defects of the perovskite films.Working as the additives,these two cellulose derivatives show a strong passivation ability,which significantly reduces the trap density and improves the optoelectronic feature of the PSCs.Compared with the average power conversion efficiency(PCE)of the control device(19.19%),an enhancement of~10%is achieved after the addition of HEC.The optimized device(PCE=21.25%)with a long-term stability(10:80 h,PCE=20.93%)is achieved by the incorporation of the HEC additives into the precursor solution.It is the best performance among the PSCs with the cellulose additives up to now.This research provides a novel choice to develop a cost-effective and renewable additive for the PSCs with high efficiency and excellent long-term stability.

CsPbX_(3)钙钛矿纳米晶中Mn(Ⅱ)离子的可控掺杂及其发光性能研究

Mn离子掺杂策略被广泛用于提高CsPbX3钙钛矿纳米晶(Nanocrystals,NCs)的稳定性和调控Pb的含量,但离子掺杂反应速率极快,不易控制。本文分别采用一步和两步热注射法对Mn^(2+)的掺杂含量进行大范围和精确调控,制备出具有不同Mn^(2+)掺杂含量的CsPbCl_(3)∶Mn^(2+)NCs。通过对其结构及发光性能的研究,将其区分为合金结构和掺杂结构,并进一步揭示了一步法和两步法进行Mn^(2+)调控时的不同机制,明确了在相同Pb∶Mn投料比的情况下,一步法合成的合金结构纳米晶具有更高的Mn^(2+)掺杂量,使得纳米晶在610nm左右与Mn相关的发射峰更为强烈,最高光致发光量子产为77%,而两步法合成的掺杂结构纳米晶在较少的Mn^(2+)情况下同样具有较高的光致发光量子产率。同时,Mn^(2+)的可控掺杂使得钙钛矿纳米晶的稳定性有效提升,放置四周后形貌和发光性能仍稳定。值得注意的是,合金结构对于本征激子发光稳定性的提升比掺杂结构更加有利。此外,还合成了具有优异发光性能的CsPb(Cl_(x)Br_(3-x))∶Mn^(2+)钙钛矿纳米晶,其荧光光谱可在404~640nm之间调控;但当Br-含量较高时,与Mn相关的发射峰消失,这是由于CsPbBr_(3)的能带与Mn^(2+)的^(4)T_(1-)^(6)A_(1)能级不匹配所致。本文强调了在CsPbCl_(3)∶Mn^(2+)钙钛矿制备过程中Mn^(2+)可控掺杂的重要性,对于实现纳米晶的可控合成具有重要意义。

Surface Treatment of Inorganic CsPbI_(3) Nanocrystals with Guanidinium Iodide for Efficient Perovskite Light-Emitting Diodes with High Brightness

The remarkable evolution of metal halide perovskites in the past decade makes them promise for next-generation optoelectronic material.In particular,nanocrystals(NCs)of inorganic perovskites have demonstrated excellent performance for light-emitting and display applications.However,the presence of surface defects on the NCs negatively impacts their performance in devices.Herein,we report a compatible facial post-treatment of CsPbI_(3) nanocrystals using guanidinium iodide(GuI).It is found that the GuI treatment effectively passivated the halide vacancy defects on the surface of the NCs while offering effective surface protection and exciton confinement thanks to the beneficial contribution of iodide and guanidinium cation.As a consequence,the film of treated CsPbI_(3) nanocrystals exhibited significantly enhanced luminescence and charge transport properties,leading to high-performance light-emitting diode with maximum external quantum efficiency of 13.8%with high brightness(peak luminance of 7039 cd m^(−2) and a peak current density of 10.8 cd A^(−1)).The EQE is over threefold higher than performance of untreated device(EQE:3.8%).The operational half-lifetime of the treated devices also was significantly improved with T50 of 20 min(at current density of 25 mA cm^(−2)),outperforming the untreated devices(T50~6 min).

LaCoO_(3)纳米粒子的制备、掺杂及丙酮敏感性能研究

为了开发新型的钙钛矿钴氧化物气敏材料,探究不同掺杂离子及掺杂量对LaCoO_(3)气敏性能的影响,以La(NO_(3))3·6H_(2)O、Co(NO_(3))3·6H_(2)O、丙烯酰胺、柠檬酸为主要原料,采用溶胶-凝胶法制备了钙钛矿结构的LaCoO_(3)及A位Ca^(2+)、Sr^(2+)掺杂的纳米粒子。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、红外光谱(IR)对样品的结构、形貌、半导体性质进行了表征,研究了不同掺杂量对LaCoO_(3)纳米粒子晶粒大小、活化能等的影响。结果表明,A位Ca^(2+)、Sr^(2+)掺杂可以增大LaCoO_(3)晶粒的生长活化能、抑制晶粒生长;对制得样品进行丙酮敏感性能测试后发现,Ca^(2+)、Sr^(2+)掺杂均可提高LaCoO_(3)对丙酮的响应能力,尤其是Ca^(2+)掺杂量为15%时,样品对2%体积分数丙酮的灵敏度可达97.83%。

离子液体界面修饰的高效稳定FAPbI_(3)钙钛矿太阳能电池

碘铅甲眯(FAPbI_(3))钙钛矿太阳能电池因其优异的光伏性能而受到广泛关注,但器件的长期稳定性仍然是FAPbI_(3)太阳能电池的关键问题。FAPbI_(3)黑色钙钛矿相在室温下会相变为黄色非钙钛矿相,且水分会加速这一相变。界面工程是提高钙钛矿太阳能电池稳定性的常用方法之一。作为绿色溶剂,离子液体被认为是有毒界面修饰剂的潜在替代品,这也提高了它们的商业可行性,并加速了它们在可再生能源市场的应用。本研究利用具有低挥发性、低毒性、高导电性和高热稳定性的离子液体1-乙基-3-甲基咪唑四氟硼酸盐(EMIM[BF_(4)])来修饰钙钛矿太阳能电池的电子传输层和钙钛矿层之间的界面。离子液体的引入不仅减少了界面缺陷,而且提高了钙钛矿薄膜的质量。密度泛函理论计算表明,离子液体与钙钛矿表面之间存在较强的界面相互作用,有利于降低钙钛矿表面缺陷态密度,稳定钙钛矿晶格。除钙钛矿薄膜缺陷外,溶液处理的SnO_(2)也存在表面缺陷。在SnO_(2)表面的缺陷产生缺陷态,也会导致能带对准问题和稳定性问题。密度泛函理论计算表明,有离子液体的表面间隙态比没有离子液体的表面间隙态小,这种减弱的表面间隙态表明表面区域载流子复合减少,有利于提高器件性能。因此,我们实现了功率转换效率大于22%的离子液体修饰的FAPbI_(3)钙钛矿太阳能电池(对照21%)。在相对湿度~20%的干箱中存放1800h以上后,冠军器件保留了初始状态的~90%,而控制器件降解为非钙钛矿黄色六方相(δ-FAPbI_(3))。

CsPbBr_(3)@MIL-53纳米复合荧光粉的合成、性能及其白光LEDs应用

全无机钙钛矿(CsPbX3,X=Cl,Br,I)纳米晶因其卓越的光电性能被广泛应用于光电子器件领域,但稳定性问题仍然是制约其商业化发展的主要因素之一。基于此,本研究以提高CsPbBr_(3)纳米晶的稳定性和固态发光性能为研究目标,选用具有优异疏水性能的多孔MIL-53(Al)金属有机框架(MOFs)作为封装基质,通过热注射工艺在MIL-53(Al)孔道内原位限域生长CsPbBr_(3)纳米晶,成功制备了优异发光性能和稳定性的CsPbBr_(3)@MIL-53纳米复合荧光粉。MIL-53通过包含的苯环和有机配体与CsPbBr_(3)纳米晶螯合,将其稳固地锚定在孔道内,既保护了CsPbBr_(3)纳米晶免受外界环境的影响,又有效防止了纳米晶之间的聚集,从而避免了固态荧光猝灭。此外,MIL-53中的COO-官能团与CsPbBr_(3)纳米晶表面未配对的Pb2+结合,钝化了其表面的缺陷,抑制了载流子的非辐射复合。MIL-53包含的苯环及有机长链又赋予了纳米复合荧光粉出色的疏水性能。这些因素的协同作用显著提升了CsPbBr_(3)@MIL-53纳米复合荧光粉的光学性能和水稳定性,其荧光量子产率(Photoluminescence Quantum Yield,PLQY)为75.4%,是固态CsPbBr_(3)纳米晶粉体(33.2%)的2.3倍。将CsPbBr_(3)@MIL-53纳米复合荧光粉完全浸泡在水中10h,其荧光强度仍能维持初始值的75.6%。最后,将绿光发射的CsPbBr_(3)@MIL-53纳米复合荧光粉应用于白光发光二极管(LightEmittingDiodes,LEDs)器件,实现了126%NTSC和85%Rec.2020的宽色域覆盖面积,表明其在显示器件领域具有优异的应用前景。

不同核壳结构的CsPbBr_(3)纳米晶体的稳定性、生物相容性能

CsPbBr_(3)钙钛矿纳米晶体(PNC)由于出色的光学性能使其在生物领域具有广泛的应用前景,但CsPbBr_(3)PNC的低稳定性及高毒性大大限制了其实际应用。因此,通过壳层包裹,采用室温重结晶法分别将环糊精(CD)和SiO_(2)包覆在CsPbBr_(3)PNC表面合成核壳结构的CsPbBr_(3)@CD和CsPbBr_(3)@SiO_(2)。不同的包覆材料使PNC具有不同的光学特性、稳定性及生物相容性。其中,CsPbBr_(3)@SiO_(2)的荧光量子产率(36.16%)约为CsPbBr_(3)@CD(14.39%)的2.5倍。CsPbBr_(3)@SiO_(2)的平均荧光衰减寿命(101.43 ns)约为CsPbBr_(3)@CD(68.73 ns)的1.5倍。在30℃、湿度为60%的空气中放置10天后,CsPbBr_(3)@SiO_(2)荧光强度约为CsPbBr_(3)@CD的3.9倍。将CsPbBr_(3)@CD和CsPbBr_(3)@SiO_(2)与细胞共培养,细胞存活率分别为51.27%和88.57%。结果表明,相较于CsPbBr_(3)@CD,CsPbBr_(3)@SiO_(2)具有更好的光学特性、稳定性以及生物相容性,更有利于在生物医学领域应用。