Exciton Formation Dynamics and Band-Like Free Charge-Carrier Transport in 2D Metal Halide Perovskite Semiconductors

Metal halide perovskite (MHP) semiconductors have driven a revolution in optoelectronic technologies over the last decade, in particular for high-efficiency photovoltaic applications. Low-dimensional MHPs presenting electronic confinement have promising additional prospects in light emission and quantum technologies. However, the optimisation of such applications requires a comprehensive understanding of the nature of charge carriers and their transport mechanisms. This study employs a combination of ultrafast optical and terahertz spectroscopy to investigate phonon energies, charge-carrier mobilities, and exciton formation in 2D (PEA)₂PbI₄ and (BA)₂PbI₄ (where PEA is phenylethylammonium and BA is butylammonium). Temperature-dependent measurements of free charge-carrier mobilities reveal band transport in these strongly confined semiconductors, with surprisingly high in-plane mobilities. Enhanced charge-phonon coupling is shown to reduce charge-carrier mobilities in (BA)₂PbI₄ with respect to (PEA)₂PbI₄. Exciton and free charge-carrier dynamics are disentangled by simultaneous monitoring of transient absorption and THz photoconductivity. A sustained free charge-carrier population is observed, surpassing the Saha equation predictions even at low temperature. These findings provide new insights into the temperature-dependent interplay of exciton and free-carrier populations in 2D MHPs. Furthermore, such sustained free charge-carrier population and high mobilities demonstrate the potential of these semiconductors for applications such as solar cells, transistors, and electrically driven light sources.     

超晶格电子垂直输运的激子势垒穿透

激子的势垒穿透在超晶格的光电性质研究中有着十分重要的意义。文章在Fowler-Nordheim理论基础上,引入权重因子描述了激子库仑场和外场之间的竞争,并对不同的权重因子进行了仿真分析。结果表明,激子效应使势垒高度降低。用爱里函数和椭圆积分严格地给出了激子的势垒穿透几率,为超晶格光电性质和垂直输运提供了基础分析。     

超晶格电子垂直输运的激子势垒穿透

激子的势垒穿透在超晶格的光电性质研究中有着十分重要的意义。文章在Fowler-Nordheim理论基础上, 引入权重因子描述了激子库仑场和外场之间的竞争, 并对不同的权重因子进行了仿真分析。结果表明, 激子效应使势垒高度降低。用爱里函数和椭圆积分严格地给出了激子的势垒穿透几率, 为超晶格光电性质和垂直输运提供了基础分析。     

Band‐Edge Exciton Fine Structure and Exciton Recombination Dynamics in Single Crystals of Layered Hybrid Perovskites

2D perovskite materials have recently reattracted intense research interest for applications in photovoltaics and optoelectronics. As a consequence of the dielectric and quantum confinement effect, they show strongly bound and stable excitons at room temperature. Here, the band‐edge exciton fine structure and in particular its exciton and biexciton dynamics in high quality crystals of (PEA)₂PbI₄ are investigated. A comparison of bulk and surface exciton lifetimes yields a room temperature surface recombination velocity of 2 × 10³ cm s^?1 and an intrinsic lifetime of 185 ns. Biexciton emission is evidenced at room temperature, with a binding energy of ≈45 meV and a lifetime of 80 ps. At low temperature, exciton state splitting is observed, which is caused by the electron–hole exchange interaction. Transient photoluminescence resolves the low‐lying dark exciton state, with a bright/dark splitting energy estimated to be 10 meV. This work contributes to the understanding of the complex scenario of the elementary photoexcitations in 2D perovskites.     

Photo- and Nanoelectronics Based on Two-Dimensional Materials. Part I. Two-Dimensional Materials: Properties and Synthesis

Journal of Communications Technology and Electronics - We review the synthesis methods, crystal parameters, and band structure of two-dimensional and quasi-two-dimensional materials, including...     

Triplet Exciton and Polaron Dynamics in Phosphorescent Dye Blended Polymer Photovoltaic Devices

The triplet exciton and polaron dynamics in phosphorescent dye (PtOEP) blended polymer (MEH‐PPV) photovoltaic devices are investigated by quasi‐steady‐state photo‐induced absorption (PIA) spectroscopy. According to the low‐temperature PIA and photoluminescence (PL) results, the increase in strength of the triplet‐triplet (T₁‐T_n) absorption of MEH‐PPV in the blend system originates from the triplet‐triplet energy transfer from PtOEP to MEH‐PPV. The PtOEP blended MEH‐PPV/C₆₀ bilayer photovoltaic device shows a roughly 30%–40% enhancement in photocurrent and power‐conversion efficiency compared to the device without PtOEP. However, in contrast to the bilayer device results, the bulk heterojunction photovoltaic devices do not show a noticeable change in photocurrent and power‐conversion efficiency in the presence of PtOEP. The PIA intensity, originating from the polaron state, is only slightly higher (within the experimental error), indicating that carrier generation in the bulk heterojunction is not enhanced in the presence of PtOEP. The rate and probability of the exciton dissociation between PtOEP and PCBM is much faster and higher than that of the triplet‐triplet energy transfer between PtOEP and MEH‐PPV.     

Magnetically Controllable Two-Dimensional Spin Transport in a 3D Crystal

2D phases of matter have become a new paradigm in condensed matter physics, bringing in an abundance of novel quantum phenomena with promising device applications. However, realizing such quantum phases has its own challenges, stimulating research into non-traditional methods to create them. One such attempt is presented here, where the intrinsic crystal anisotropy in a “fractional” perovskite, Eu_xTaO₃ (x = 1/3 − 1/2), leads to the formation of stacked layers of quasi-2D electron gases, despite being a 3D bulk system. These carriers possess topologically non-trivial spin textures, indirectly controlled by an external magnetic field via proximity effect, making it an ideal system for spintronics, for which several possible applications are proposed. An anomalous Hall effect with a non-monotonic dependence on carrier density is shown to exist, signifying a shift in band topology with carrier doping. Furthermore, quantum oscillations in charge conductivity and oscillating thermoelectric properties are examined and proposed as routes to experimentally demonstrate the quasi-2D behavior.     

Two-Dimensional Antimony-Based Perovskite-Inspired Materials for High-Performance Self-Powered Photodetectors

The ongoing Internet of Things revolution has led to strong demand for low-cost, ubiquitous light sensing based on easy-to-fabricate, self-powered photodetectors. While solution-processable lead-halide perovskites have raised significant hopes in this regard, toxicity concerns have prompted the search for safer, lead-free perovskite-inspired materials (PIMs) with similar optoelectronic potential. Antimony- and bismuth-based PIMs are found particularly promising; however, their self-powered photodetector performance to date has lagged behind the lead-based counterparts. Aiming to realize the full potential of antimony-based PIMs, this study examines, for the first time, the impact of their structural dimensionality on their self-powered photodetection capabilities, with a focus on 2D Cs₃Sb₂I_9−xCl_x and Rb₃Sb₂I₉ and 0D Cs₃Sb₂I₉. The 2D absorbers deliver cutting-edge self-powered photodetector performance, with a more-than-tenfold increase in external quantum efficiency (up to 55%), speed of response (>5 kHz), and linear dynamic range (>four orders of magnitude) compared to prior self-powered A₃M₂X₉ implementations (A⁺: monovalent cation; M³⁺: Sb³⁺/Bi³⁺; X⁻: halide anion). Detailed characterization reveals that such a performance boost originates from the superior carrier lifetimes and reduced exciton self-trapping enabled by the 2D structure. By delivering cutting-edge performance and mechanistic insight, this study represents an important step in lead-free perovskite-inspired optoelectronics toward self-powered, ubiquitous light sensing.     

Photovoltaic Function and Exciton/Charge Transfer Dynamics in a Highly Efficient Semiconducting Copolymer

Exciton dissociation is a key step for the light energy conversion to electricity in organic photovoltaic (OPV) devices. Here, excitonic dissociation pathways in the high‐performance, low bandgap “in‐chain donor–acceptor” polymer PTB7 by transient optical absorption (TA) spectroscopy in solutions, neat films, and bulk heterojunction (BHJ) PTB7:PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) films are investigated. The dynamics and energetics of the exciton and intra‐/intermolecular charge separated states are characterized. A distinct, dynamic, spectral red‐shift of the polymer cation is observed in the BHJ films in TA spectra following electron transfer from the polymer to PC₇₁BM, which can be attributed to the time evolution of the hole–electron spatial separation after exciton splitting. Effects of film morphology are also investigated and compared to those of conjugated homopolymers. The enhanced charge separation along the PTB7 alternating donor–acceptor backbone is understood by intramolecular charge separation through polarized, delocalized excitons that lower the exciton binding energy. Consequently, ultrafast charge separation and transport along these polymer backbones reduce carrier recombination in these largely amorphous films. This charge separation mechanism explains why higher degrees of PCBM intercalation within BHJ matrices enhances exciton splitting and charge transport, and thus increase OPV performance. This study proposes new guidelines for OPV materials development.     

Exciton Dynamics and Optically Pumped Lasing in 1-Naphthylmethylamine-Based Quasi-2D Perovskite Films

Films of the quasi-2D perovskite based on 1-naphthylmethylamine (NMA) are promising as the gain medium for optically pumped lasing and future electrically pumped lasing because of its low lasing threshold and small electroluminescence efficiency rolloff. However, reasons for the low threshold and small efficiency rolloff are still unclear. Therefore, exciton dynamics are investigated in NMA-based quasi-2D perovskite films. It is found that quenching of bright excitons by other excitons or charge carriers is unlikely in NMA-based quasi-2D perovskite films, which is one reason for the low lasing threshold and small efficiency rolloff. Moreover, thermally stimulated current measurements reveal that the defect levels inside the band gap of the NMA-based quasi-2D perovskite are shallow, with a depth of ≈0.3 eV, causing a decrease in nonradiative exciton recombination through the defects. Therefore, population inversion can be easily achieved, leading to the low lasing threshold as well. For fabrication of NMA-based quasi-2D perovskite laser devices with even lower lasing thresholds, a circular-shaped optical resonator, and small-molecule-based defect passivation are used. Optically pumped lasing can be obtained from these devices, with a threshold of ≈1 µJ cm⁻², which is one of the lowest values ever reported in any perovskite lasers.     

多层铁磁二维材料电场效应研究

二维(2D)材料的出现由于其良好的物理特性及对未来纳米电子设备的潜在应用,而引起了研究者的关注。Cr₂Ge₂Te₆(CGT)中的二维铁磁性已得到证明,然而对于二维CGT,一直缺乏电子输运特性与电场效应的研究。文中制备并鉴定了厚度仅为几nm的CGT铁磁薄片,这为由各种2D材料组成的范德华结构提供了前提条件,并进一步的展示了通过电场效应对2D CGT设备通道电阻进行的大幅度调制。实验结果证明了2D CGT栅极电压的可调性,同时也证明了铁磁2D材料CGT作为新型功能量子材料的潜力。     

Features of Electron Transport in Two-Dimensional Quantum Superlattices with the Non-Associative Dispersion Law

Semiconductors - The anisotropy of the conductivity and the shape of the I–V characteristics for a two-dimensional quantum superlattice with the nonharmonic electron dispersion law are...     

Dissipative Dynamics of Polymer Phononic Materials

Phononic materials are artificial composites with unprecedented abilities to control acoustic waves in solids. Their performance is mainly governed by their architecture, determining frequency ranges in which wave propagation is inhibited. However, the dynamics of phononic materials also depends on the mechanical and material properties of their constituents. In the case of viscoelastic constituents, such as most polymers, it is challenging to correctly predict the actual dynamic behavior of real phononic structures. Existing studies on this topic either lack experimental evidence or are limited to specific materials and architectures in restricted frequency ranges. A general framework is developed and employed to characterize the dynamics of polymer phononic materials with different architectures made of both thermoset and thermoplastic polymers, presenting qualitatively different viscoelastic behaviors. Through a comparison of experimental results with numerical predictions, the reliability of commonly used elastic and viscoelastic material models is evaluated in broad frequency ranges. Correlations between viscous effects and the two main band-gap formation mechanisms in phononic materials are revealed, and experimentally verified guidelines on how to correctly predict their dissipative response are proposed in a computationally efficient way. Overall, this work provides comprehensive guidelines for the extension of phononics modeling to applications involving dissipative viscoelastic materials.     

Inorganic Electron Transport Materials in Perovskite Solar Cells

In the past decade, the perovskite solar cell (PSC) has attracted tremendous attention thanks to the substantial efforts in improving the power conversion efficiency from 3.8% to 25.5% for single-junction devices and even perovskite-silicon tandems have reached 29.15%. This is a result of improvement in composition, solvent, interface, and dimensionality engineering. Furthermore, the long-term stability of PSCs has also been significantly improved. Such rapid developments have made PSCs a competitive candidate for next-generation photovoltaics. The electron transport layer (ETL) is one of the most important functional layers in PSCs, due to its crucial role in contributing to the overall performance of devices. This review provides an up-to-date summary of the developments in inorganic electron transport materials (ETMs) for PSCs. The three most prevalent inorganic ETMs (TiO₂, SnO_2, and ZnO) are examined with a focus on the effects of synthesis and preparation methods, as well as an introduction to their application in tandem devices. The emerging trends in inorganic ETMs used for PSC research are also reviewed. Finally, strategies to optimize the performance of ETL in PSCs, effects the ETL has on J–V hysteresis phenomenon and long-term stability with an outlook on current challenges and further development are discussed.     

MOCVD法生长二维范德华材料的研究进展

二维范德华材料凭借其优异的光学和电学特性,自被发现以来一直作为延续集成电路摩尔定律的重要基础电子材料而备受关注.通过机械剥离的方法得到高质量的二维材料进行实验室层面的研究工作已经不能满足现阶段的需要.采用金属有机化学气相沉积(MOCVD)技术可以得到高质量的大面积二维范德华材料,并具有生长层数和成核密度可控的优势.以过渡金属硫化物(TMDC)为例,分别从生长条件、金属有机源材料、衬底、催化剂等方面综述了采用MOCVD技术生长二维范德华材料的研究进展,同时讨论了二维材料的范德华异质结构的特性及应用.利用MOCVD技术优势可以推动二维范德华材料的大规模应用.最后总结了 MOCVD法生长二维范德华材料现阶段的优势与不足,并对其未来的发展进行了展望.     

Exciton Dynamics and Effects of Structural Order in Morphology‐Controlled J‐Aggregate Assemblies

Narrow‐band photoluminescence (PL) together with high quantum efficiency from organic molecules is essential for high‐color‐purity emitters. Supramolecular assemblies like J‐aggregates are promising materials due to their narrow PL signal with full‐width at half maximum <20 nm. However, their microcrystalline nature and coherent exciton migration results in strong nonradiative exciton recombination at the grain boundaries that diminish the photoluminescence quantum yield (PLQY), and possibilities for improving the crystallinity by tuning the growth mechanism are limited. Here, two distinct routes to grow different J‐aggregate morphologies like platelets and lamellar crystals with improved crystallinity by surface‐guided molecular assembly are demonstrated, thereby suppressing nonradiative decay and improving PLQY. Both platelets and lamellar crystals show similar absorbance at room temperature. However, temperature‐dependent PL studies show sevenfold (twofold) higher PLQY for lamellar films compared to platelets at 6 K (300 K). Using time‐resolved PL spectroscopy, different nonradiative decay pathways are identified. The dependence of exciton diffusion on energetic disorder and nonradiative decay is discussed. The results suggest that the difference in domain size and order gives rise to significantly enhanced radiative decay from lamellar films as compared to platelets or films formed by spin‐coating.     

Thermal Transport in Conductive Polymer–Based Materials

The demand for flexible conductive materials has motivated many recent studies on conductive polymer–based materials. However, the thermal conductivity of conductive polymers is relatively low, which may lead to serious heat dissipation problems for device applications. This review provides a summary of the fundamental principles for thermal transport in conductive polymers and their composites, and recent advancements in regulating their thermal conductivity. The thermal transport mechanisms in conductive polymer–based materials and up‐to‐date experimental approaches for measuring thermal conductivity are first summarized. Effective approaches for the regulation of thermal conductivity are then discussed. Finally, thermal‐related applications and future perspectives are given for conductive polymers and their composites.     

GaN基量子阱激子结合能和激子光跃迁强度

采用变分法,计算了GaN基量子阱中激子结合能和激子光跃选强度。计算结果表明,GaN基量子阱中激子结合能为10－55meV,大于体材料中激子结合能,并随着阱宽减小而增加,在临界阱宽处达到最大。结间带阶同样对激子结合能有着较大的影响,更大带阶对应更大的结合能。同时量子限制效应增加了电子空穴波函数空间重叠,因此加强了激子光跃迁振子强度,导致GaN/AlN量子阱中激子光吸收明显强于体材料中激子光吸收。