Photoluminescence Anisotropy Research Articles

Graphene-Templated Achiral Hybrid Perovskite for Circularly Polarized Light Sensing.

This study points out the importance of the templating effect in hybrid organic-inorganic perovskite semiconductors grown on graphene. By combining two achiral materials, we report the formation of a chiral composite heterostructure with electronic band splitting. The effect is observed through circularly polarized light emission and detection in a graphene/α-CH(NH2)2PbI3 perovskite composite, at ambient temperature and without a magnetic field. We exploit the spin-charge conversion by introducing an unbalanced spin population through polarized light that gives rise to a spin photoconductive effect rationalized by Rashba-type coupling. The prepared composite heterostructure exhibits a circularly polarized photoluminescence anisotropy gCPL of ∼0.35 at ∼2.54 × 103 W cm-2 confocal power density of 532 nm excitation. A carefully engineered interface between the graphene and the perovskite thin film enhances the Rashba field and generates the built-in electric field responsible for photocurrent, yielding a photoresponsivity of ∼105 A W-1 under ∼0.08 μW cm-2 fluence of visible light photons. The maximum photocurrent anisotropy factor gph is ∼0.51 under ∼0.16 μW cm-2 irradiance. The work sheds light on the photophysical properties of graphene/perovskite composite heterostructures, finding them to be a promising candidate for developing miniaturized spin-photonic devices.

Recent Excellent Optoelectronic Applications Based on Two-Dimensional WS2 Nanomaterials: A Review.

Tungsten disulfide (WS2) is a promising material with excellent electrical, magnetic, optical, and mechanical properties. It is regarded as a key candidate for the development of optoelectronic devices due to its high carrier mobility, high absorption coefficient, large exciton binding energy, polarized light emission, high surface-to-volume ratio, and tunable band gap. These properties contribute to its excellent photoluminescence and high anisotropy. These characteristics render WS2 an advantageous material for applications in light-emitting devices, memristors, and numerous other devices. This article primarily reviews the most recent advancements in the field of optoelectronic devices based on two-dimensional (2D) nano-WS2. A variety of advanced devices have been considered, including light-emitting diodes (LEDs), sensors, field-effect transistors (FETs), photodetectors, field emission devices, and non-volatile memory. This review provides a guide for improving the application of 2D WS2 through improved methods, such as introducing defects and doping processes. Moreover, it is of great significance for the development of transition-metal oxides in optoelectronic applications.

Scanning the time and space evolution of anisotropy in single molecular crystals based on 3-(furan-2-yl)-2-(4-{[(2-hydroxy-5-methylphenyl)methylidene]amino}phenyl)prop-2-enenitrile

The 3-(furan-2-yl)-2-(4-{[(2-hydroxy-5-methylphenyl)methylidene]amino}phenyl)prop-2-enenitrile (LAXYUI)), acting as a model, is a type of outstanding organic fluorophore. Using a transient absorption approach, the excitation relaxation behavior of LAXYUI in the monomolecular system and ordered crystals was identified. The polarization optical properties of LAXYUI crystals, including anisotropy of absorption and photoluminescence, polarization PL decay at different temperatures, and the evolution of optical anisotropy as a function of propagation length, are thoroughly investigated using a series of home-built polarization optical techniques. Our results can help people better understand the time- and space-dependent optical anisotropy that occurs in organic crystals, which will be important in the future to improve or broaden the performance of polarization optical systems based on organic crystals.

Observation of Strong Anisotropic Interlayer Excitons.

Anisotropic interlayer excitons had been theoretically predicted to exist in two-dimensional (2D) anisotropy/isotropy van der Waals heterojunctions. However, experimental results consolidating the theoretical prediction and exploring the related anisotropic optoelectronic response have not been reported so far. Herein, strong photoluminescence (PL) of anisotropic interlayer excitons is observed in a symmetric anisotropy/isotropy/anisotropy heterojunction exemplified by 3L-ReS2/1L-MoS2/3L-ReS2 using monolayer (1L) MoS2 and trilayer (3L) ReS2 as components. Sharp interlayer exciton PL peaks centered at ∼1.64, ∼1.61, and ∼1.57 eV are only observed at low temperatures of ≤120 K and become more pronounced as the temperature decreases. These interlayer excitons exhibit strong anisotropic PL intensity variations with periodicities of 180° as functions of the incident laser polarization angles. The polarization ratios of these interlayer excitons are calculated to be 1.33-1.45. Our study gives new insight into the manipulation of excitons in 2D materials and paves a new way for a rational design of novel anisotropic optoelectronic devices.

Tuning the Photoluminescence Anisotropy of Semiconductor Nanocrystals.

Semiconductor nanocrystals are promising optoelectronic materials. Understanding their anisotropic photoluminescence is fundamental for developing quantum-dot-based devices such as light-emitting diodes, solar cells, and polarized single-photon sources. In this study, we experimentally and theoretically investigate the photoluminescence anisotropy of CdSe semiconductor nanocrystals with various shapes, including plates, rods, and spheres, with either wurtzite or zincblende structures. We use defocused wide-field microscopy to visualize the emission dipole orientation and find that spheres, rods, and plates exhibit the optical properties of 2D, 1D, and 2D emission dipoles, respectively. We rationalize the seemingly counterintuitive observation that despite having similar aspect ratios (width/length), rods and long nanoplatelets exhibit different defocused emission patterns by considering valence band structures calculated using multiband effective mass theory and the dielectric effect. The principles are extended to provide general relationships that can be used to tune the emission dipole orientation for different materials, crystalline structures, and shapes.

Non-covalent Supramolecular 1D Alternating Copolymer in Crystal toward 2D Anisotropic Photon Transport.

To realize organic integrated optoelectronic circuits, there is a need for anisotropic optical waveguides at the micro/nanoscale. Anisotropic alignment of one-dimensional (1D)-ordered supramolecular structures composed of light-emissive π-conjugated molecules in a crystal may meet the requirements of such waveguides. Here, we designed a bipyridyl-appended acrylonitrile-based π-conjugated molecule 1, which produced a 1D supramolecular polymer constructed through non-covalent bonding between a lone pair in 1 and a σ-hole in 1,4-diiodo-2,3,5,6-tetrafluorobenzene 2. The 1D copolymer of 1 and 2 is aligned horizontally with the two-dimensional (2D) crystal surface because of the angle-controlled supramolecular synthons. As a result of control over the non-covalent bonding direction, anisotropic photoluminescence and photon transport (optical waveguiding) characteristics are realized by orienting the transition dipole moment horizontally with respect to the 2D surface. Compared with the loss coefficient αL =52dBcm-1 for the long-axis direction of the 2D platelet cocrystal, a very large difference of αS =2111dBcm-1 is present in the crystal short-axis direction. The anisotropic waveguiding ability, αL/αS, is estimated to be 41, which is more than an order of magnitude greater than previously reported 2D platelet crystal waveguides. This supramolecular synthon provides an approach to designing anisotropic photon transporters and highly regulated optical logic circuits.

Photoluminescence Anisotropy in Eutectic Crystals of Polynuclear Lanthanide Complexes and Silver Clusters

AbstractAnisotropy is an intrinsic property of crystalline materials. However, the photoluminescence anisotropy in eutectic crystals of organometallic complexes has remained unexplored. Herein, the eutectic of polynuclear lanthanide complexes and Ag clusters was prepared, and the crystal shows significant photoluminescence anisotropy. The polarization anisotropy of emission δ and degree of excitation polarization P are 2.62 and 0.53, respectively. The rare excitation polarization properties have been proved to be related to the regular arrangement of electric transition dipole moments of luminescent molecules in the crystal. Our design provides a reference for developing new photoluminescence anisotropy materials and expanding their applications.

Photoluminescence Anisotropy in Eutectic Crystals of Polynuclear Lanthanide Complexes and Silver Clusters.

Anisotropy is an intrinsic property of crystalline materials. However, the photoluminescence anisotropy in eutectic crystals of organometallic complexes has remained unexplored. Herein, the eutectic of polynuclear lanthanide complexes and Ag clusters was prepared, and the crystal shows significant photoluminescence anisotropy. The polarization anisotropy of emission δ and degree of excitation polarization P are 2.62 and 0.53, respectively. The rare excitation polarization properties have been proved to be related to the regular arrangement of electric transition dipole moments of luminescent molecules in the crystal. Our design provides a reference for developing new photoluminescence anisotropy materials and expanding their applications.

Optical polarization properties of TPP2MnBr4 perovskite crystal adjusted by the self-trapping state.

Low-dimensional networked organic-inorganic hybrid metal halide crystal has become an emerging hotspot material due to its opportunities and advantages in the development of white-light-emitting diodes. Therefore, its photoluminescence (PL) mechanism is important. Herein, we study the PL behavior of columniform TPP2MnBr4 crystals using multi-spectroscopy. The temperature-dependent PL data show that the PL of the TPP2MnBr4 crystal originates from the recombination of a self-trapping exciton. A polarization-dependent PL test suggests that the self-trapping exciton is anisotropic, which indicates that the distribution of self-trapping states is sensitive to the orientation of the crystal axis. Space-resolved PL spectroscopy shows that the anisotropy of PL gradually weakens along the orientation of the columniform crystal, which has a longer relaxation distance than traditional light-wave-guiding behavior. Thus, anisotropy of PL can exist before it disappears in the crystal. Our results elucidate the PL mechanism of low-dimensional networked organic-inorganic hybrid metal halide crystals and provide a foundation for advanced optical polarization devices based on them.

Highly polarized light emission from hybrid of quantum dots and plasmons in the intermediate coupling regime.

Colloidal semiconductor quantum dots (QDs), with a size tunable bandgap and remarkably high quantum efficiency, have been recognized as ideal light sources in quantum information and light emitting devices. For light sources, besides the emission intensity and spectral profile, the degree of polarization (DoP) is an essential parameter. Here, by embedding a monolayer of QDs inside the nanogap between a bottom Au mirror and a top Ag nanowire, we have demonstrated highly polarized light emission from the QDs with an average DoP of 0.89. In addition to the anisotropic photoluminescence (PL) intensity, the PL spectra are distinct at different polarizations, with an asymmetric spectral shape or even two-peak features. Such an anisotropic emission behavior arises from the coupling between the QDs and the largely confined and polarization-dependent gap-plasmons in the Au/QD/Ag nanocavities in the intermediate coupling regime. Our results demonstrate the possibility of achieving highly polarized light sources by coupling spherical QDs to single anisotropic plasmonic nanocavities, to provide new opportunities in the future design of polarized QD-based display devices.

Extending Anisotropy Dynamics of Light‐Emitting Dipoles as Necessary Condition Toward Developing Highly‐Efficient OLEDs

AbstractDesigning in‐plane‐oriented light‐emitting dipoles is known as a critical method to develop high‐efficiency organic light‐emitting diodes (OLEDs) by enhancing light extraction. However, in‐plane‐oriented light‐emitting dipoles must demonstrate sufficient polarization memory extended into light emission lifetime window, generating extended anisotropy dynamics shown as the necessary condition to increase light extraction toward developing high‐efficiency OLEDs. This paper reports experimental studies on anisotropy dynamics of light‐emitting dipoles in both time and energy domains by using time‐resolved and steady‐state photoluminescence anisotropy measurements based on the in‐plane oriented exciplex‐heterostructured [BCzPh:CN‐T2T] host dispersed with phosphorescent molecules. It is found that, when host–guest Coulomb scattering is suppressed by parallel placing of the in‐plane‐configured phosphorescent Ir(ppy)2(acac) molecules into the in‐plane‐oriented exciplex‐heterostructured [BCzPh:CN‐T2T] host, the anisotropy dynamics of light‐emitting dipoles can be extended into microseconds time window comparable with its phosphorescence lifetime, satisfying the necessary condition in time domain to increase light out‐coupling efficiency toward developing high external quantum efficiencies (EQEs) in Ir(ppy)2(acac):exciplex system. More importantly, by suppressing host–guest Coulomb scattering, the high‐energy transition dipoles can still maintain extended anisotropy dynamics in the energy domain in Ir(ppy)2(acac):exciplex system while hot electrons are relaxing toward lowest unoccupied molecular orbital (LUMO). Consequently, the extended anisotropy dynamics of light‐emitting dipoles demonstrate a high EQE of 34.01% in the Ir(ppy)2(acac):exciplex OLED.

Probing the chirality and optical activity of organic molecules through the anisotropic photoluminescence of porous silicon

A new method of using porous silicon as a substrate to identify chiral molecules.

Cubic Halide Double Perovskite Nanocrystals with Anisotropic Free Excitons and Self-Trapped Exciton Photoluminescence

In this work, we first developed Cs2KBiCl6 cubic double perovskite nanocrystals and a series of morphologically isotropic double perovskite nanocrystals. Different contributions of different elements to self-trapped states were revealed by density functional theory. Meanwhile, these double perovskite nanocrystals exhibit the coexistence of free and self-trapped exciton dual-color photoluminescence. Femtosecond transient absorption spectroscopy can confirm that the double perovskite nanocrystals produce a relatively obvious structural deformation in the excited state. We infer that this can lead to a large deviation of the excitation and emission transition dipoles, thus causing large photoluminescence anisotropy. Most importantly, we observe for the first time that both free exciton emission and self-trapped exciton emission are highly anisotropic, which are comparable to or even better than that of lead halide perovskites. This research paves the way for exploring more possibilities and practical applications.

Morphology enhancement of self-assembled CH3NH3PbI3 nanoparticles through customized solvent evaporation temperatures

The CH3NH3PbI3 perovskite nanoparticles are synthesized by the sonication method. It is observed that the perovskite nanoparticles are self-assembled upon solvent evaporation. Differing the drying temperatures induces different morphologies. Confirmed with the repeated experiments, a reproducible approach for acquiring enhanced morphologies and larger grain sizes is established. Perovskite nanoparticles dried at 80 °C had edge-less tetragonal-like shapes and samples dried at 120 °C possessed cubic structures with a crystalline order extending 500 nm. Whereas, solvent evaporation from iodide perovskite dried at room temperature did not yield any ordered morphology. Self-assembled nanostructures showed anisotropic photoluminescence emission that confirms ordered assembly of the structures. Perovskites dried at 80 °C had the highest degree of photoluminescence emission polarization, which is due to their anisotropic micro-crystalline structure. According to FTIR results, the interaction of methylammonium cation with PbI cage in lead iodide perovskites is influenced by temperature treatments, leading to altered crystalline structure and hence diverse morphologies. Furthermore, all of the self-assembled perovskites were highly photo luminescent with slight red-shifts in samples dried at higher temperatures. We also observed up-conversion emission with a 1064 nm excitation, which confirms the existence of nonlinear response in these perovskite structures.

Simulating the Structure of Carbon Dots via Crystalline π‐Aggregated Organic Nanodots Prepared by Kinetically Trapped Self‐Assembly

AbstractThis work reports the successful preparation of a new type of crystalline luminescent organic nanodot (<3.5 nm) by kinetically trapped self‐assembly, which is then used as a simplified π‐packing model to simulate the structure of CDs. The precise structure and J‐aggregation‐induced photoluminescence (PL) of the nanodots are revealed by investigating the structural relationship between the nanodots and the corresponding single crystals and their properties. Compared with the single crystals, crystalline organic nanodots show longer PL lifetime, higher PL quantum yield, and narrower PL peak, indicating that they are potential organic quantum nanodots. In addition, the efficient π‐stacking environment in the corresponding single crystals can promote π‐aggregation‐induced PL anisotropy. This work indicates crystalline organic nanodots with precise structures to be potentially useful for understanding the structures of CDs and to be attractive potential luminescent materials.

Simulating the Structure of Carbon Dots via Crystalline π-Aggregated Organic Nanodots Prepared by Kinetically Trapped Self-Assembly.

This work reports the successful preparation of a new type of crystalline luminescent organic nanodot (<3.5 nm) by kinetically trapped self-assembly, which is then used as a simplified π-packing model to simulate the structure of CDs. The precise structure and J-aggregation-induced photoluminescence (PL) of the nanodots are revealed by investigating the structural relationship between the nanodots and the corresponding single crystals and their properties. Compared with the single crystals, crystalline organic nanodots show longer PL lifetime, higher PL quantum yield, and narrower PL peak, indicating that they are potential organic quantum nanodots. In addition, the efficient π-stacking environment in the corresponding single crystals can promote π-aggregation-induced PL anisotropy. This work indicates crystalline organic nanodots with precise structures to be potentially useful for understanding the structures of CDs and to be attractive potential luminescent materials.

Selective, Anisotropic, or Consistent Polarized‐Photon Out‐Coupling of 2D Organic Microcrystals

AbstractNano‐ and micromaterials with anisotropic photoluminescence and photon transport have widespread application prospects in quantum optics, optoelectronics, and displays. But the nature of the polarization information of the out‐coupled light, with respect to that of the source luminescence, has never been explored in active optical‐waveguiding organic crystals. Herein, three different modes (selective, anisotropic, and consistent) of polarized‐photon out‐coupling are proposed and successfully implemented in a set of 2D organic microcrystals with highly linearly‐polarized luminescence. It is found that the polarization direction and degree of the luminescence out‐coupled through different waveguiding channels can either be essentially retained or distinctly changed with respect to those of the original luminescence, depending on the molecular arrangement and the orientation of transition dipole moments of the crystal. This work demonstrates the promising potential of 2D emissive microcrystals in multi‐channel polarized photon transport.

Selective, Anisotropic, or Consistent Polarized-Photon Out-Coupling of 2D Organic Microcrystals.

Nano- and micromaterials with anisotropic photoluminescence and photon transport have widespread application prospects in quantum optics, optoelectronics, and displays. But the nature of the polarization information of the out-coupled light, with respect to that of the source luminescence, has never been explored in active optical-waveguiding organic crystals. Herein, three different modes (selective, anisotropic, and consistent) of polarized-photon out-coupling are proposed and successfully implemented in a set of 2D organic microcrystals with highly linearly-polarized luminescence. It is found that the polarization direction and degree of the luminescence out-coupled through different waveguiding channels can either be essentially retained or distinctly changed with respect to those of the original luminescence, depending on the molecular arrangement and the orientation of transition dipole moments of the crystal. This work demonstrates the promising potential of 2D emissive microcrystals in multi-channel polarized photon transport.

Metal-free ferroelectric halide perovskite exhibits visible photoluminescence correlated with local ferroelectricity.

Perovskite materials with tunable electronic and structural characteristics can realize various physical properties including electrical/ionic conduction, ferroelectricity, and luminescence. Integrating and coupling these properties in a single perovskite material offer new possibilities for fundamental research and applications. In particular, coupling ferroelectricity and luminescence would enable novel applications. Here, we report that the metal-free ferroelectric perovskite MDABCO (N-methyl-N′-diazabicyclo[2.2.2]octonium)–ammonium triiodide exhibits coupled superior ferroelectricity and visible photoluminescence (PL). Besides strong second-harmonic generation (SHG) associated with its ferroelectricity, MDABCO–ammonium triiodide shows long-lifetime PL at room temperature. Remarkably, the PL intensity depends strongly on the polarization of the excitation light. We found that this anisotropy is coupled to the local crystal orientation that was determined by polarization-resolved SHG. Our results suggest that the anisotropic PL property can be tuned in response to its ferroelectric state via an external field and, thereby, presents a previosuly unobserved functionality in perovskites.

Multicomponent Molecular Assembly of Fluorescent Organic Semiconductors Beyond Three Compounds

AbstractIn contrast to unary assemblies comprising π‐conjugated organic species, elaborate modulation of dimensions, polymorphisms, and compositions of multicomponent assembled architectures with two or more constituent materials has not yet been systematically studied. Herein, a combinatorial library of organic microcrystals made of four components via a solution‐phase assembly route is reported. With the involvement of growth kinetics, four organic species with slight structural modifications can assemble into five unary assemblies, which may endow binary combinations with highly and partially structural miscibility. Consequently, a variety of binary alloyed assemblies and microscale heterostructures with tailorable dimensions, polymorphisms, and emission colors are realized by rational compositional and growth control. The effects of structural relations of binary combinations on their miscibility are systematically uncovered, that gives rise to these intricate microscale architectures as well as diverse energy transfer (ET) efficiencies. Highly efficient ET process in binary alloyed assemblies can be beneficial to steady‐state photoluminescence anisotropy amplification. Benefiting from the information of binary combinations, white‐light‐emitting ternary microsheets can be modulated in a predictable manner. The present work uncovers the rational control of multicomponent microcrystals, which further stretches the boundaries of molecular self‐assembly and may be used to achieve integrated optoelectronic properties, such as multicolor lasers and p–n junctions.