Superradiant Emission from Coherent Excitons in van Der Waals Heterostructures

Recent advancements in isolation and stacking of layered van der Waals materials have created an unprecedented paradigm for demonstrating varieties of 2D quantum materials. Rationally designed van der Waals heterostructures composed of monolayer transition-metal dichalcogenides (TMDs) and few-layer hBN show several unique optoelectronic features driven by correlations. However, entangled superradiant excitonic species in such systems have not been observed before. In this report, it is demonstrated that strong suppression of phonon population at low temperature results in a formation of a coherent excitonic-dipoles ensemble in the heterostructure, and the collective oscillation of those dipoles stimulates a robust phase synchronized ultra-narrow band superradiant emission even at extremely low pumping intensity. Such emitters are in high demand for a multitude of applications, including fundamental research on many-body correlations and other state-of-the-art technologies. This timely demonstration paves the way for further exploration of ultralow-threshold quantum-emitting devices with unmatched design freedom and spectral tunability.     

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.     

Exploring a Stable and Dense 3D Lead Chloride Hybrid with Emission of Self-Trapped Excitons toward X-Ray Scintillation

The exceptional photophysical properties of 3D organic–inorganic lead halide hybrids (OILHs) endow their significant potential for usage in optoelectronics, which has sparked intense research on novel 3D OILHs and associated applications. However, constructing new 3D OILHs based on large organic cations suffers from tough challenges due to the limitation of the Goldschmidt tolerance factor rule, let alone further explorations of their practical applications. Herein, a brand-new 3D lead chloride hybrid, (1MPZ)Pb₄Cl₁₀·H₂O ( 1 , 1MPZ = 1-methylpiperazine) is reported, featuring a dense 3D lead chloride framework made of the corner-, edge-, and face-shared lead chloride polyhedra. 1 presents a broadband white light emission with a large Stokes shift and a nanosecond photoluminescence lifetime, which originates from radiative recombination of self-trapped excitons (STEs) induced by the highly distorted structure. Such a reabsorption-free and fast-decayed STEs emission coupling with the dense 3D architecture further enables 1 with effective X-ray scintillation with good sensitivity. Impressively, 1 also shows superior environmental and radiation stability. This study provides a new 3D OILH with appealing luminescence, not only expanding the 3D OILH family but also inspiring the exploitation of their optoelectronic applications.     

Indirect Exciton–Phonon Dynamics in MoS2 Revealed by Ultrafast Electron Diffraction

Transition metal dichalcogenides layered nano-crystals are emerging as promising candidates for next-generation optoelectronic and quantum devices. In such systems, the interaction between excitonic states and atomic vibrations is crucial for many fundamental properties, such as carrier mobilities, quantum coherence loss, and heat dissipation. In particular, to fully exploit their valley-selective excitations, one has to understand the many-body exciton physics of zone-edge states. So far, theoretical and experimental studies have mainly focused on the exciton–phonon dynamics in high-energy direct excitons involving zone-center phonons. Here, ultrafast electron diffraction and ab initio calculations are used to investigate the many-body structural dynamics following nearly- resonant excitation of low-energy indirect excitons in MoS₂. By exploiting the large momentum carried by scattered electrons, the excitation of in-plane K- and Q- phonon modes are identified with 𝑬^′ symmetry as key for the stabilization of indirect excitons generated via near-infrared light at 1.55 eV, and light is shed on the role of phonon anharmonicity and the ensuing structural evolution of the MoS₂ crystal lattice. The results highlight the strong selectivity of phononic excitations directly associated with the specific indirect- exciton nature of the wavelength-dependent electronic transitions triggered in the system.     

Triplet-induced degradation: An important consideration in the design of solution-processed hole injection materials for organic light-emitting devices

Solution-processed organic light-emitting devices (OLEDs) still require improvements in their operational lifetime in order for them to become commercially viable. One factor that limits the lifetime of these devices is the instability of the hole injection layer (HIL). Therefore, understanding its degradation mechanism is crucial for the development of more stable solution-processed OLEDs. In this work, we use an archetypal fluorescent OLED in conjunction with an experimental solution-processed HIL in order to elucidate the degradation mechanism in these HILs. Our studies show that degradation is caused by triplet excitons. This new triplet-induced hole injection degradation is expected to be a common phenomenon in OLEDs, and therefore should have important implications for the design of stable HILs.     

Electron correlation effects on polarons recombination in coupled polymer chains

The recombination dynamics of singlet and triplet oppositely charged polarons under the influence of electron–electron (e–e) interactions in coupled polymer chains are investigated using a multi-configurational time-dependent Hartree–Fock (MCTDHF) method. During recombination processes, singlet and triplet intrachain excitons are important products. By calculating the yields of the singlet and triplet intrachain excitons as a function of the on-site and long-range e–e interactions, it is found that the yields of the singlet and triplet intrachain excitons both decrease with increasing on-site e–e interactions. On the other hand, as the long-range e–e interactions increase, the yields of singlet intrachain excitons initially increase and then maintain a constant value, while the yields of the triplet intrachain excitons decrease. Our results show that the long-range e–e interaction is of fundamental importance and improves the luminescence efficiency in coupled polymer chains. Finally, the influence of the polymer chain length on the yields of singlet and triplet intrachain excitons is discussed.     

周期性多发光层结构单色有机电致发光器件的研究

以具有高离化能的n型小分子材料PBD、BCP作为激子限制层,用交替沉积的方式制备了分别以Alq3/PBD、NPB/BCP为周期结构多发光层的绿光、蓝光器件.周期性多发光层结构的引入大大提高了器件性能,其中,具有双周期3发光层的绿光器件最大亮度和效率分别是常规器件的10.5倍和4.4倍,具有双周期双发光层的蓝光器件最大亮度和效率分别是常规器件的2.75和1.45倍.器件性能提高的主要原因是周期性结构的引入和多发光区域的划分增加了激子产生几率.同时,周期数对器件性能有重要影响.绿光、蓝光器件电致发光(EL)谱谱峰值基本稳定,半高谱宽出现了窄化.     

Charge‐recombination processes in oligomer‐ and polymer‐based light‐emitting diodes: A molecular picture

Abstract— An overview of our recent work on the mechanisms of singlet and triplet exciton formation in electroluminescent π‐conjugated materials will be presented. According to simple spin statistics, only one‐fourth of the excitons are formed as singlets. However, deviations from that statistics can occur if the initially formed triplet charge‐transfer (CT) excited states are amenable to intersystem crossing or dissociation. Although the electronic couplings between the CT states and the neutral exciton states are expected to be largest for the lowest singlet and triplet excitons (S¹ and T¹, respectively), the possibility for direct recombination into T¹ is always very small due to the large exchange energy. In small molecules, spin statistics is expected to be observed because both singlet and triplet exciton formations proceed via higher‐lying S_n/T_n states with similar electronic couplings and fast formation rates. In extended conjugated chains, however, that the ¹CT → S¹ pathway is faster while the ³CT → ^Tn channels become much slower, opening the route to intersystem crossing or dissociation among the ³CT states.     

Hanle Effect of Charged and Neutral Excitons in Quantum Wells

We measured magnetic field depolarization of charged and neutral exciton cw photoluminescence of a system consisting of two coupled quantum wells with a residual concentration of holes. Using the Hanle expression, we obtained exciton lifetime and electron spin relaxation time, which are in agreement with results of time-resolved experiments. We suppose that the tunneling takes place via an emission of an LO phonon and we find this process spin conserving.     

Correlation between ultrafast transient photomodulation spectroscopy and organic photovoltaic solar cell efficiency based on RR-P3HT/PCBM blends

Ultrafast transient spectroscopy was applied to various films of regio-regular polythiophene (RR-P3HT, donor-D) and C₆₀ derivative (PCBM, acceptor-A) blends, in conjunction with organic photovoltaic (OPV) solar cell fabrication and evaluation based on the same blends, for investigating the existence of a correlation between the device efficiency and the transient photophysics characteristics. For our transient spectroscopy measurements we used the ps pump–probe transient photomodulation (PM) technique having a unique probe spectral range in the mid-IR (0.25–1.05 eV). We found that the transient PM spectra contain photoinduced absorption bands of excitons in the donor polymer, charge transfer excitons (CTE) at the D–A interfaces, and free polarons. We compared the relative density of photogenerated CTE in D–A blends having various D–A weight ratio with the photocurrent density of fabricated solar cells based on the same blends. We found that the dissociation of CTE into free charges correlates well with the optoelectronic measurements of the corresponding solar cell. The more efficient CTE dissociation occurs in films having the optimum D–A weight ratio (which is 1.2:1 for the P3HT/PCBM system) that shows the highest OPV power conversion efficiency; this is due to the lowest CTE binding energy for this blend that results from the most suitable D- and A- grain sizes. We also show that the exciton lifetime is the shortest for the optimum blend, and this helps boosting the device efficiency by reducing energy loss.