Efficient energy transfer from self-trapped excitons to Mn^(2+) dopants in CsCdCl_(3):Mn^(2+) perovskite nanocrystals

Mn^(2+)doping has been adopted as an efficient approach to regulating the luminescence properties of halide perovskite nano-crystals(NCs).However,it is still difficult to understand the interplay of Mn^(2+)luminescence and the matrix self-trapped exciton(STE)emission therein.In this study,Mn^(2+)-doped CsCdCl_(3) NCs are prepared by hot injection,in which CsCdCl_(3) is selected because of its unique crystal structure suitable for STE emission.The blue emission at 441 nm of undoped CsCdCl_(3) NCs originates from the defect states in the NCs.Mn^(2+)doping promotes lattice distortion of CsCdCl_(3) and generates bright orange-red light emission at 656 nm.The en-ergy transfer from the STEs of CsCdCl_(3) to the excited levels of the Mn^(2+)ion is confirmed to be a significant factor in achieving efficient luminescence in CsCdCl_(3):Mn^(2+)NCs.This work highlights the crucial role of energy transfer from STEs to Mn^(2+)dopants in Mn^(2+)-doped halide NCs and lays the groundwork for modifying the luminescence of other metal halide perovskite NCs.

Effect of electron-electron interaction on polarization process of exciton and biexciton in conjugated polymer

By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene.The dynamical simulation is performed by adopting the non-adiabatic evolution approach.The results show that under the effect of moderate electric field,when the strength of electron-electron interaction is weak,the singlet exciton is stable but its polarization presents obvious oscillation.With the enhancement of interaction,it is dissociated into polaron pairs,the spin-flip of which can be observed through modulating the interaction strength.For the triplet exciton,the strong electron-electron interaction restrains its normal polarization,but it is still stable.In the case of biexciton,the strong electron-electron interaction not only dissociate it,but also flip its charge distribution.The yield of the possible states formed after the dissociation of exciton and biexciton is also calculated.

Strain tunable excitonic optical properties in monolayer Ga_(2)O_(3)

Two-dimensional(2D)Ga_(2)O_(3)has been confirmed to be a stable structure with five atomic layer thickness configuration.In this work,we study the quasi-particle electronic band structures and then access the excitonic optical properties through solving the Bethe-Salpeter equation(BSE).The results reveal that the exciton dominates the optical absorption in the visible light region with the binding energy as large as~1.0 eV,which is highly stable at room temperature.Importantly,both the dominant absorption P_(1)and P_(2)peaks are optically bright without dark exciton between them,and thus is favorable for luminescence process.The calculated radiative lifetime of the lowest-energy exciton is 2.0×10^(-11)s at 0 K.Furthermore,the radiative lifetime under+4%tensile strain is one order of magnitude shorter than that of the strainfree case,while it is less insensitive under the compressive strain.Our findings set the stage for future theoretical and experimental investigation on monolayer Ga_(2)O_(3).

Excitonic optical properties in monolayer SnP_(2)S_(6)

Quantum confinement effect and reduced dielectric screening in two-dimensional(2D)dramatically enhance theelectron-hole interactions.In this work,we use many-body perturbation theory and Bethe-Salpeter equation(BSE)toinvestigate the electronic and excitonic optical properties of monolayer SnP_(2)S_(6).Our findings reveal that the excitoniceffect dominates the optical absorption spectra in the visible light range,and the lowest-energy exciton X0 in monolayerSnP_(2)S_(6)is optically bright with the binding energy of 0.87 eV and the radiative lifetime of~10^(-11)s,which is highly advantageousto the photo-luminescence.Most importantly,the absence of optically forbidden states below the bright statesX0 would give rise to a high quantum efficiency of 2D SnP_(2)S_(6).We also find that applied biaxial strain can further shortenthe radiative lifetime of the bright states.These results imply that 2D SnP_(2)S_(6)is a promising candidate for the optoelectronicdevices.

Behavior of exciton in direct−indirect band gap Al_(x)Ga_(1−x)As crystal lattice quantum wells

Excitons have significant impacts on the properties of semiconductors.They exhibit significantly different properties when a direct semiconductor turns in to an indirect one by doping.Huybrecht variational method is also found to influence the study of exciton ground state energy and ground state binding energy in Al_(x)Ga_(1−x)As semiconductor spherical quantum dots.The Al_(x)Ga_(1−x)As is considered to be a direct semiconductor at AI concentration below 0.45,and an indirect one at the concentration above 0.45.With regards to the former,the ground state binding energy increases and decreases with AI concentration and eigenfrequency,respectively;however,while the ground state energy increases with AI concentration,it is marginally influenced by eigenfrequency.On the other hand,considering the latter,while the ground state binding energy increases with AI concentration,it decreases with eigenfrequency;nevertheless,the ground state energy increases both with AI concentration and eigenfrequency.Hence,for the better practical performance of the semiconductors,the properties of the excitons are suggested to vary by adjusting AI concentration and eigenfrequency.

Thickness-dependent exciton relaxation dynamics of few-layer rhenium diselenide

Rhenium diselenide(ReSe_(2))has gathered much attention due to its low symmetry of lattice structure,which makes it possess in-plane anisotropic optical,electrical as well as excitonic properties and further enables ReSe_(2)have an important application in optoelectronic devices.Here,we report the thickness-dependent exciton relaxation dynamics of mechanically exfoliated few-layer ReSe_(2)flakes by using time-resolved pump–probe transient transmission spectroscopies.The results reveal two thickness-dependent relaxation processes of the excitons.The fast one correlates with the exciton formation(i.e.,the conversion of hot carriers to excitons),while the slow one is attributed to the exciton recombination dominated by defect-assisted exciton trapping besides photon emission channel.The decrease of scattering probability caused by defects leads to the increase of fast lifetime with thickness,and the increase of slow lifetime with thickness is related to the trap-mediated exciton depopulation induced by surface defects.Polarization-dependent transient spectroscopy indicates the isotropic exciton dynamics in the two-dimensional(2D)plane.These results are insightful for better understanding of excitonic dynamics of ReSe_(2)materials and its application in future optoelectronic and electronic devices.

Interaction of moiréexcitons with cavity photons in two-dimensional semiconductor hetero-bilayers

Moirématerials,composed of two single-layer two-dimensional semiconductors,are important because they are good platforms for studying strongly correlated physics.Among them,moirématerials based on transition metal dichalcogenides(TMDs)have been intensively studied.The hetero-bilayer can support moiréinterlayer excitons if there is a small twist angle or small lattice constant difference between the TMDs in the hetero-bilayer and form a type-Ⅱ band alignment.The coupling of moiréinterlayer excitons to cavity modes can induce exotic phenomena.Here,we review recent advances in the coupling of moiréinterlayer excitons to cavities,and comment on the current difficulties and possible future research directions in this field.

Efficient transfer of metallophosphor excitons via confined polaritons in organic nanocrystals

We investigate the transfer of phosphorescent energy between co-assembled metallophosphors in crystalline nanostructures [Angew. Chem. Int. Ed. 57 7820(2018) and J. Am. Chem. Soc. 140 4269(2018)]. Neither Dexter's nor Forster's mechanism of resonance energy transfer(RET) could account fully for the observed rates, which exceed 85% with significant temperature dependence. But there exists an alternative pathway on RET mediated by intermediate states of resonantly confined exciton–polaritons. Such a mechanism was used to analyze artificial photosynthesis in organic fluorescents [Phys.Rev. Lett. 122 257402(2019)]. For metallophosphors, the confined modes act as extended states lying between the molecular S_(1) and T_(1) states, offering a bridge for the long-lived T_(1) excitons to migrate from donors to acceptors. Population dynamics with parameters taken entirely based on experiments fits the observed lifetimes of phosphorescence across a broad range of doping and temperature.

Melting of electronic/excitonic crystals in 2D semiconductor moirépatterns:A perspective from the Lindemann criterion

Using the Lindemann criterion,we analyzed the quantum and thermal melting of electronic/excitonic crystals recently discovered in two-dimensional(2D)semiconductor moirépatterns.We show that the finite 2D screening of the atomically thin material can suppress(enhance)the inter-site Coulomb(dipolar)interaction strength,thus inhibits(facilitates)the formation of the electronic(excitonic)crystal.Meanwhile,a strong enough moiréconfinement is found to be essential for realizing the crystal phase with a wavelength near 10 nm or shorter.From the calculated Lindemann ratio which quantifies the fluctuation of the site displacement,we estimate that the crystal will melt into a liquid above a critical temperature ranging from several tens Kelvin to above 100 K(depending on the system parameters).

Exciton radiative lifetime in CdSe quantum dots

Colloidal CdSe quantum dots(QDs)are promising materials for solar cells because of their simple preparation pro-cess and compatibility with flexible substrates.The QD radiative recombination lifetime has attracted enormous attention as it affects the probability of photogenerated charges leaving the QDs and being collected at the battery electrodes.However,the scaling law for the exciton radiative lifetime in CdSe QDs is still a puzzle.This article presents a novel explanation that recon-ciles this controversy.Our calculations agree with the experimental measurements of all three divergent trends in a broadened energy window.Further,we proved that the exciton radiative lifetime is a consequence of the thermal average of decays for all thermally accessible exciton states.Each of the contradictory size-dependent patterns reflects this trend in a specific size range.As the optical band gap increases,the radiative lifetime decreases in larger QDs,increases in smaller QDs,and is weakly depend-ent on size in the intermediate energy region.This study addresses the inconsistencies in the scaling law of the exciton life-time and gives a unified interpretation over a widened framework.Moreover,it provides valuable guidance for carrier separa-tion in the thin film solar cell of CdSe QDs.

共轭高聚物双分子结构中激子电致解离的动力学研究

通过绝热动力学方法,研究了共轭高聚物双分子结构中激子对外加电场的响应.当外电场强度超过某个临界值时,激子会被解离成一对自由的电子与空穴.对于双分子结构中的激子,其临界解离电场除了受电子与电子相互作用以及电声相互作用影响之外,还受分子间相互作用的影响.由动力学演化的计算得到,激子临界解离电场强度随分子间相互作用强度的增大而呈非线性降低;随电子与电子相互作用强度的增大呈非线性减小的变化;但是,随电声耦合强度的增大却呈现出线性增大的变化.

自旋-轨道耦合作用下极化激元凝聚中的调制不稳定性

利用线性稳定性分析方法,对存在自旋-轨道耦合(SOS)作用的二维极化激元玻色-爱因斯坦凝聚(BEC)系统中的调制不稳定性(MI)进行了研究.分析了组分内部,组分之间以及SOC相互作用对系统调制不稳定性的影响.结果显示,当系统内部不存在SOC作用,组分之间的相互作用为0,组分内部存在排斥作用时,不会出现调制不稳定性,组分内部存在吸引作用时,会出现调制不稳定性,并且调制不稳定性区间长度随吸引作用的增强而增加;组分之间相互作用不为0时,组分之间的相互作用以平方形式出现,其正负不会对调制不稳定性产生实质性影响.存在SOC相互作用时,SOC相互作用会引起增益谱曲线的不规则振荡,破坏原来的调制不稳定性区间.

Strong coupling and catenary field enhancement in the hybrid plasmonic metamaterial cavity and TMDC monolayers

Strong coupling between resonantly matched surface plasmons of metals and excitons of quantum emitters results in the formation of new plasmon-exciton hybridized energy states.In plasmon-exciton strong coupling,plasmonic nanocavities play a significant role due to their ability to confine light in an ultrasmall volume.Additionally,two-dimensional transition metal dichalcogenides(TMDCs) have a significant exciton binding energy and remain stable at ambient conditions,making them an excellent alternative for investigating light-matter interactions.As a result,strong plasmon-exciton coupling has been reported by introducing a single metallic cavity.However,single nanoparticles have lower spatial confinement of electromagnetic fields and limited tunability to match the excitonic resonance.Here,we introduce the concept of catenary-shaped optical fields induced by plasmonic metamaterial cavities to scale the strength of plasmon-exciton coupling.The demonstrated plasmon modes of metallic metamaterial cavities offer high confinement and tunability and can match with the excitons of TMDCs to exhibit a strong coupling regime by tuning either the size of the cavity gap or thickness.The calculated Rabi splitting of Au-MoSe_2 and Au-WSe_2 heterostructures strongly depends on the catenary-like field enhancement induced by the Au cavity,resulting in room-temperature Rabi splitting ranging between 77.86 and 320 me V.These plasmonic metamaterial cavities can pave the way for manipulating excitons in TMDCs and operating active nanophotonic devices at ambient temperature.

Binding Energies of Screened Excitons in a Strained(111)-Oriented Zinc-Blende GaN/AlGaN Quantum Well Under Hydrostatic Pressure

We investigate the binding energies of excitons in a strained （111）-oriented zinc-blende GaN/Al0.3 Ga0.7 N quantum well screened by the electron-hole （e-h） gas under hydrostatic pressure by combining a variational method and a selfconsistent procedure. A built-in electric field produced by the strain-induced piezoelectric polarization is considered in our calculations. The result indicates that the binding energies of excitons increase nearly linearly with pressure,even though the modification of strain with hydrostatic pressure is considered, and the influence of pressure is more apparent under higher e-h densities. It is also found that as the density of an e-h gas increases,the binding energies first increase slowly to a maximum and then decrease rapidly when the e-h density is larger than about 1 ×10^11 cm^-2. The excitonic binding energies increase obviously as the barrier thickness decreases due to the decrease of the built-in electric field.

噻吩基二维共价有机框架中的拓扑结构诱导局部电荷极化促进光催化制氢

共价有机框架(COFs)是近年来新兴的一类多孔聚合物,在气体吸附、传感器、能源转换和光/电催化等领域表现出较大的应用潜力.然而,欲实现多样化的应用需求常需要对其结构进行合成后改性,这在单一步骤中难以实现.二维亚化学计量共价有机框架(2D-SSCOFs)因其独特的周期性官能团和保持结晶性及孔隙率的能力,成为COFs功能化的新途径.然而,已报道的2D-SSCOFs多具有相同的拓扑结构以及弱电荷极化等问题,限制了其应用潜力.因此,开发具有新颖拓扑结构的2D-SSCOFs对于实现更前沿的功能至关重要.窄带隙噻吩是有机半导体材料的常见单元,它们可以显著地调控共价聚合物骨架的电子和化学环境.本文通过5,5',5''-(苯-1,3,5-三基)三(噻吩-2-甲醛)(TT-3CHO)与4,4',4'',4''-(芘-1,3,6,8-四基)四苯胺(PY-4HN2)的席夫碱缩合反应合成具有大表面积和高结晶度的亚胺连接的新型2D-SSCOF(PTT-COF).噻吩环中2,5位之间的键的弯曲角度使得PTT-COF具有新型的2D亚化学计量拓扑结构,并呈现出非中心对称的优势极化结构.在使用有机空穴传输配体(二茂铁甲醛,FC)精确修饰和Pt作为助催化剂时,PTT-COF-FC体系在可见光照明下表现出较高的析氢产率(79.610 mmol g^(-1) h^(-1)).同时,在420 nm波长的光照下,2 mg的光催化剂表观量子效率达到1.72%.此外,经过24 h循环稳定性测试,PTT-COF-FC体系的活性没有明显下降.为了深入研究PTT-COF-FC体系的高效的产氢机制,通过X射线衍射、红外和固体碳谱等对PTT-COF-FC体系的组成和结构进行分析,确定了PTT-COF-FC的成功合成.通过瞬态吸收、变温荧光和理论计算等研究了材料的激子解离和载流子转移行为.结果表明,得益于独特的富含噻吩的结构设计以及有机空穴传输配体的修饰作用,PTT-COF-FC展现出高效的激子解离和丰富的自由电荷载流子特性.综上所述,本文设计和合成了一种新型PTT-COF光催化材料,其独特的二维亚化学计量拓扑结构和显著的局部电荷极化特性赋予了材料良好的光催化性能.实验和理论研究表明,PTT-COF中的非中心对称拓扑结构和噻吩单元的引入,有效扩展了π离域,进而诱导了局部极化并抑制了激子效应,从而大幅提高了光催化效率.此外,通过二茂铁甲醛的后修饰,结合这些独特的结构特性,PTT-COF在光催化析氢反应中表现出高活性和出色的长期耐久性.本文的研究不仅为设计和构建具有独特结构的新型2D-SSCOF提供新思路,也为构建具有丰富光催化功能的材料开辟了新途径.

二维激子-极化子凝聚体中冲击波的产生与调控

由于半导体微腔中形成的激子-极化子凝聚体能在室温实现,且具有非平衡、强相互作用等特性,其成为研究非平衡量子系统非线性特性的一个理想平台.本文采用谱方法与四阶龙格库塔法,探究二维极化子凝聚体中产生和调控冲击波的方案.发现,若在高凝聚率时淬火凝聚体与热库之间的交叉相互作用,可将初始制备的亮孤子调制成两种波速不同的旋转对称型冲击波,而初始的类暗孤子只能转变成单一波速的旋转对称型冲击波;若淬火外势,则可将类暗孤子转化成各向异性的超声速冲击波,并给出冲击波对外势宽度的依赖关系.若在低凝聚率时调控外势和非相干泵浦,可在均匀凝聚体中激发出多种各向异性冲击波,还可通过它们的振幅调控冲击波的波数和振幅,并展示了激发冲击波所需外势或非相干泵浦的宽度范围.文中方案不仅为激子-极化子凝聚体中产生和调控冲击波提供理论指导,找到了与实验相似的对称型冲击波,而且为非平衡或不可积系统中激发冲击波开辟了一条普适捷径,可能成为调控孤子向冲击波转变的一种范式.

有机体系中激子极化激元研究进展

激子极化激元(EPs)是一种准粒子,是由光子与半导体材料激子强耦合形成。EPs具备光子速度快、相干性好和激子易调控等特点,并且由于其玻色子性质,可形成玻色-爱因斯坦凝聚(BEC)。相较于无机体系,有机体系更有利于实现室温下的凝聚,引起学术界的广泛兴趣。本文回顾了EPs的发展历程,深入介绍了基于有机体系EPs的机理、BEC、超流、涡旋形成和能量传递等的研究进展。

色坐标可调的单发光体热激子OLED

色域可调的高效有机发光二极管(OLED)器件由于可实现广泛的色彩表现范围,为显示、照明和光电应用带来了新的可能性。本工作以热激子材料C3为唯一发光客体,通过改变主体及客体浓度,制备了系列色坐标可调的OLED器件。在2.5%低掺杂浓度下,器件中C3分子的三个激发态都呈现较显著的发光,单主体与双主体器件L1、L3可分别实现暖白光与冷白光发射,在17 V工作电压下对应的CIE坐标分别为(0.298,0.381)、(0.241,0.329)。在较高掺杂浓度(10%)下,第二单重态的发射占主导地位,单主体与双主体器件L2和L4分别呈现黄绿光及绿光。其中,双主体器件由于具有更好的载流子平衡,相比单主体器件启动电压降低、器件效率提升且效率衰减减少。由于存在高能级反向系间窜越的热激子机制,器件L4的最大EQE为5.36%,突破了传统荧光EQE的理论上限(5%)。本工作为设计基于单发光组分的色域可调及白光OLED器件提供了新的思路。

金属卤化物零维钙钛矿材料及其应用研究进展

金属卤化物零维钙钛矿因其大激子结合能、出色的稳定性、高发光效率以及大Stokes位移等优点,受到广泛的关注。首先,探讨了金属卤化物零维钙钛矿的电子结构与发光机理。其次,分析了离子掺杂对金属卤化物零维钙钛矿光学特性的影响。在此基础上,阐述了金属卤化物零维钙钛矿的合成方法,并详细介绍了金属卤化物零维钙钛矿在发光二极管、防伪、X射线成像和传感等领域的应用。最后,对目前金属卤化物零维钙钛矿面对的挑战和潜在解决方案进行了总结与展望。

基于双给体三元体异质结的高性能倍增型有机光电探测器

为了拓展光谱响应范围至近红外,采用双给体单受体的三元体异质结策略,基于溶液法制备了以ITO/PEDOT∶PSS/活性层/Al为基本结构的倍增型有机光电探测器,活性层由P3HT∶PTB7-Th∶IEICO-4F(100-x∶x∶1,wt/wt/wt)组成,研究了不同质量比的PTB7-Th对器件光电特性的影响。优化后的三元倍增型有机光电探测器以P3HT∶PTB7-Th∶IEICO-4F(60∶40∶1,wt/wt/wt)为活性层,在-15 V偏压下,在450、520、655和850 nm处的外量子效率分别为2 666.40%、1 752.11%、1 894.26%和938.22%,响应度分别为965.80、733.35、998.68和641.91 A/W,比探测率均超过10^(13)Jones,在850 nm处的响应度与比探测率分别是相同条件下二元器件P3HT∶IEICO-4F(100∶1,wt/wt)的2.23倍和7.08倍。结果表明,在二元体系P3HT∶IEICO-4F中掺入适量的PTB7-Th,不仅能拓展光谱响应范围至近红外,还能改变活性层中激子解离界面、电子陷阱类型和空穴注入势垒高度,优化器件的电学性能。