Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics.

Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This paper uncovers the sub- and above-bandgap emission and absorption characteristics of PEA2PbI4 prepared with gap states introduced during single crystal growth. Here, gap states led to coexistent intrinsic and heterostructured electronic frameworks that are selectively accessible with ultraviolet (UV) and infrared (IR) light, respectively, resulting in the phenomenon of photoluminescence (PL) switching from narrowband green to broadband red. Electron-energy dependent cathodoluminescence shows a relative increase in the broadband red PL intensity as the electron penetration depth increases from 30 nm to 2 µm, confirming the heterostructured framework is formed in the bulk of the crystal. Excitation-emission power slope of 2.5 and up-conversion pump transient absorption (TA) spectra suggest that the IR up-conversion excitation with red photoluminescence, peaked at 655 nm, is a multiphoton process occurring in the heterostructured framework through a nonlinear optical response. The energetic pathways toward the dual emission bands are revealed by pump-probe transient absorption spectroscopy, showing energetically broad gap states with high sensitivity to an IR pump are upconverted and subsequently quickly relax from high to low energy levels within 4 ps. Furthermore, the up-conversion red PL demonstrates a linear polarization with magnetic field effects, thus affirming that the band-like heterostructured framework is crystallographically aligned with characteristics of spatially extended charge-transfer states.

Superior External Quantum Efficiency of LEDs via Quasi-2D Perovskite Crystals Implanted with Phenethylammonium Acetate.

The multiple quantum well structure of a quasi-two-dimensional (quasi-2D) perovskite leads to nonradiative Auger recombination (AR). This is due to high local carrier density in recombination centers, although the radiative recombination is improved by efficient energy transfer. In this study, we suppress the AR by introducing phenethylammonium acetate (PEAAc) into the quasi-2D PEA2Csn-1PbnBr3n+1 perovskite. The recombination centers of n ≥ 4 phases can be promoted because the COO- preferentially coordinates with Pb2+, inhibiting the fast formation of n = 1, 2, 3 phases with phenethylammonium anion (PEA+). Thus, the AR is suppressed due to the lower density of local charge carriers. To balance the AR suppression and decreasing binding energy in promoting the n ≥ 4 phases, the PEAAc:PEABr molar ratios are adjusted. At the optimal molar ratio, perovskite light-emitting diodes (PeLEDs) with a maximum luminescence of ∼29942 cd m-2 and a maximum external quantum efficiency of ∼20.2% are achieved. These results confirm the most efficient PeLEDs based on PEA2Csn-1PbnBr3n+1 without passivation. Moreover, the efficiency roll off is significantly mitigated with a high threshold of over 3.51 mA/cm2. This study develops high-efficiency PeLEDs with a low efficiency rolloff.

Packing-Shape Effects of Optical Properties in Amplified Spontaneous Emission through Dynamics of Orbit-Orbit Polarization Interaction in Hybrid Perovskite Quantum Dots Based on Self-Assembly.

This paper reports packing-shape effects of amplified spontaneous emission (ASE) through orbital polarization dynamics between light-emitting excitons by stacking perovskite (MAPbBr3) quantum dots (QDs sized between 10 nm and 14 nm) into rod-like and diamond-like aggregates. The rod-like packing shows a prolonged photoluminescence (PL) lifetime (184 ns) with 3 nm red-shifted peak (525 nm) as compared to the diamond-like packing (PL peak, 522 nm; lifetime, 19 ns). This indicates that the rod-like packing forms a stronger interaction between QDs with reduced surface-charged defects, leading to surface-to-inside property-tuning capability with an ASE. Interestingly, the ASE enabled by rod-like packing shows an orbit-orbit polarization interaction between light-emitting excitons, identified by linearly/circularly polarized pumping conditions. More importantly, the polarization dynamics is extended to the order of nanoseconds in the rod-like assembly, determined by the observation that within the ASE lifetime (2.54 ns) the rotating pumping beam polarization direction largely affects the coherent interaction between light-emitting excitons.

Optically Induced Static Magnetization in Metal Halide Perovskite for Spin-Related Optoelectronics.

Understanding the feasibility to couple semiconducting and magnetic properties in metal halide perovskites through interface design opens new opportunities for creating the next generation spin-related optoelectronics. In this work, a fundamentally new phenomenon of optically induced magnetization achieved by coupling photoexcited orbital magnetic dipoles with magnetic spins at perovskite/ferromagnetic interface is discovered. The depth-sensitive polarized neutron reflectometry combined with in situ photoexcitation setup, constitutes key evidence of this novel effect. It is demonstrated that a circularly polarized photoexcitation induces a stable magnetization signal within the depth up to 7.5 nm into the surface of high-quality perovskite (MAPbBr3) film underneath a ferromagnetic cobalt layer at room temperature. In contrast, a linearly polarized light does not induce any detectable magnetization in the MAPbBr3. The observation reveals that photoexcited orbital magnetic dipoles at the surface of perovskite are coupled with the spins of the ferromagnetic atoms at the interface, leading to an optically induced magnetization within the perovskite's surface. The finding demonstrates that perovskite semiconductor can be bridged with magnetism through optically controllable method at room temperature in this heterojunction design. This provides the new concept of utilizing spin and orbital degrees of freedom in new-generation spin-related optoelectronic devices.

Spin-orbital coupling and slow phonon effects enabled persistent photoluminescence in organic crystal under isomer doping.

When periodically packing the intramolecular donor-acceptor structures to form ferroelectric-like lattice identified by second harmonic generation, our CD49 molecular crystal shows long-wavelength persistent photoluminescence peaked at 542 nm with the lifetime of 0.43 s, in addition to the short-wavelength prompt photoluminescence peaked at 363 nm with the lifetime of 0.45 ns. Interestingly, the long-wavelength persistent photoluminescence demonstrates magnetic field effects, showing as crystalline intermolecular charge-transfer excitons with singlet spin characteristics formed within ferroelectric-like lattice based on internal minority/majority carrier-balancing mechanism activated by isomer doping effects towards increasing electron-hole pairing probability. Our photoinduced Raman spectroscopy reveals the unusual slow relaxation of photoexcited lattice vibrations, indicating slow phonon effects occurring in ferroelectric-like lattice. Here, we show that crystalline intermolecular charge-transfer excitons are interacted with ferroelectric-like lattice, leading to exciton-lattice coupling within periodically packed intramolecular donor-acceptor structures to evolve ultralong-lived crystalline light-emitting states through slow phonon effects in ferroelectric light-emitting organic crystal.

External Field-Tunable Internal Orbit-Orbit Interaction in Flexible Perovskites.

In hybrid metal halide perovskites, electrons carry both orbital and spin momenta through s-p wave function hybridization. This leads to a hypothesis that the orbit-orbit interaction between excitons can occur through orbital magnetic dipoles forming short-range interaction or through orbital polarizations forming long-range interaction to influence optoelectronic properties. This Letter reports an interesting phenomenon: the orbit-orbit interaction can be electrically switched between orbital magnetic dipoles and orbital polarizations in a flexible perovskite (MAPbI3-xClx) solar cell by scanning an external voltage between forward and reverse biases (0.2 and -0.2 V). Essentially, this phenomenon presents an external mechanism for electrically controlling the internal orbit-orbit interaction in hybrid perovskites. It was further observed that this bias-switchable orbit-orbit interaction is sensitive to temperature, becoming negligible when the temperature is decreased from 300 to 250 K. This observation indicates that the mobile ions driven by an external electrical field provide an intrinsic mechanism for electrically switching the orbit-orbit interaction through polarization and spin parameters while applying an external voltage between forward and reverse biases. These results provide a comprehensive understanding of tuning the orbit-orbit interaction in flexible perovskites toward developing orbitronic actions.

Establishing charge-transfer excitons in 2D perovskite heterostructures.

Charge-transfer excitons (CTEs) immensely enrich property-tuning capabilities of semiconducting materials. However, such concept has been remaining as unexplored topic within halide perovskite structures. Here, we report that CTEs can be effectively formed in heterostructured 2D perovskites prepared by mixing PEA2PbI4:PEA2SnI4, functioning as host and guest components. Remarkably, a broad emission can be demonstrated with quick formation of 3 ps but prolonged lifetime of ~0.5 µs. This broad PL presents the hypothesis of CTEs, verified by the exclusion of lattice distortion and doping effects through demonstrating double-layered PEA2PbI4/PEA2SnI4 heterostructure when shearing-away PEA2SnI4 film onto the surface of PEA2PbI4 film by using hand-finger pressing method. The below-bandgap photocurrent indicates that CTEs are vital states formed at PEA2PbI4:PEA2SnI4 interfaces in 2D perovskite heterostructures. Electroluminescence shows that CTEs can be directly formed with electrically injected carriers in perovskite LEDs. Clearly, the CTEs presents a new mechanism to advance the multifunctionalities in 2D perovskites.

Extremely Long Spin Lifetime of Light-Emitting States in Quasi-2D Perovskites through Orbit-Orbit Interaction.

This paper reports an extremely long spin relaxation time of optically polarized light-emitting states at room temperature in quasi-2D perovskites [(PEA)2(MA)4Pb5Br16 with n = 5], when the long-range orbit-orbit interaction between excited states is developed through orbital polarization. Our studies found that the quasi-2D perovskite [(PEA)2(MA)4Pb5Br16 with n = 5] demonstrates a long-range orbit-orbit interaction between excited states to conserve the spins of optically polarized light-emitting states, identified by the positive change on photoluminescence intensity (+ΔPL) in steady state upon switching the photoexcitation from linear to circular polarization. Meanwhile, the PL circular polarization (σ+σ+ - σ+σ-) can maintain in nanosecond under fixed photoexcitation (σ+). In contrast, the 2D/3D mixed perovskite (n > 5) shows a short-range orbit-orbit interaction between excited states through orbital magnetic dipoles, identified by the -ΔPL by switching from linear to circular photoexcitation. At the same time, the spin lifetime of light-emitting states becomes undetectable.

Exploring Orbit-Orbit Interaction in Relationship to Photoluminescence Quantum Efficiency in Perovskite Quantum Dots through Rashba Effect.

This study demonstrates the influence of the orbit-orbit interaction on the photoluminescence quantum efficiency (PLQE) of metal halide perovskite quantum dots (QDs) through the Rashba effect. The orbit-orbit interaction between excitons was characterized by using the minimal excitation intensity required to generate a photoluminescence difference (ΔPL) between linearly and circularly polarized photoexcitations. It was observed that changing the surface functionalization from PFOA-OA to PFSH-OAm and OA can largely increase the minimal excitation intensity for generating ΔPL. This indicates that the orbit-orbit interaction is essentially decreased in CsPbBr1I2 QDs with surface functionalization. Simultaneously, the PLQE is increased from 39% to 59 and 72% in CsPbBr1I2 QDs upon surface functionalization. Furthermore, the PL lifetime is decreased with increasing the PLQE in CsPbBr1I2 QDs upon surface functionalization. This phenomenon implies that decreasing the orbit-orbit interaction can essentially weaken the Rashba effect and consequently reduce the disallowed transitions, leading to an enhancement in the PLQE in perovskite QDs.

Two-Photon Up-Conversion Photoluminescence Realized through Spatially Extended Gap States in Quasi-2D Perovskite Films.

A new approach to generate a two-photon up-conversion photoluminescence (PL) by directly exciting the gap states with continuous-wave (CW) infrared photoexcitation in solution-processing quasi-2D perovskite films [(PEA)2 (MA)4 Pb5 Br16 with n = 5] is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two-photon up-conversion PL occurring in quasi-2D perovskite films. Decreasing the gap states by reducing the n value leads to a dramatic decrease in the two-photon up-conversion PL signal. This confirms that the gap states are indeed responsible for generating the two-photon up-conversion PL in quasi-2D perovskites. Furthermore, mechanical scratching indicates that the different-n-value nanoplates are essentially uniformly formed in the quasi-2D perovskite films toward generating multi-photon up-conversion light emission. More importantly, the two-photon up-conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi-photon excitation. Polarization-dependent up-conversion PL studies reveal that the gap states experience the orbit-orbit interaction through Coulomb polarization to form spatially extended states toward developing multi-photon up-conversion light emission in quasi-2D perovskites.

Revealing the Cooperative Relationship between Spin, Energy, and Polarization Parameters toward Developing High-Efficiency Exciplex Light-Emitting Diodes.

Experimental studies to reveal the cooperative relationship between spin, energy, and polarization through intermolecular charge-transfer dipoles to harvest nonradiative triplets into radiative singlets in exciplex light-emitting diodes are reported. Magneto-photoluminescence studies reveal that the triplet-to-singlet conversion in exciplexes involves an artificially generated spin-orbital coupling (SOC). The photoinduced electron parametric resonance measurements indicate that the intermolecular charge-transfer occurs with forming electric dipoles (D+• →A-• ), providing the ionic polarization to generate SOC in exciplexes. By having different singlet-triplet energy differences (ΔEST ) in 9,9'-diphenyl-9H,9'H-3,3'-bicarbazole (BCzPh):3',3'″,3'″″-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-3-carbonitrile)) (CN-T2T) (ΔEST = 30 meV) and BCzPh:bis-4,6-(3,5-di-3-pyridylphenyl)-2-methyl-pyrimidine (B3PYMPM) (ΔEST = 130 meV) exciplexes, the SOC generated by the intermolecular charge-transfer states shows large and small values (reflected by different internal magnetic parameters: 274 vs 17 mT) with high and low external quantum efficiency maximum, EQEmax (21.05% vs 4.89%), respectively. To further explore the cooperative relationship of spin, energy, and polarization parameters, different photoluminescence wavelengths are selected to concurrently change SOC, ΔEST , and polarization while monitoring delayed fluorescence. When the electron clouds become more deformed at a longer emitting wavelength due to reduced dipole (D+• →A-• ) size, enhanced SOC, increased orbital polarization, and decreased ΔEST can simultaneously occur to cooperatively operate the triplet-to-singlet conversion.

Using Mechanical Stress to Investigate the Rashba Effect in Organic-Inorganic Hybrid Perovskites.

Organic-inorganic hybrid perovskites simultaneously possess strong spin-orbit coupling (SOC) and structure inversion asymmetry, establishing a Rashba effect to influence light emission and photovoltaics. Here, we use mechanical bending as a convenient approach to investigate the Rashba effect through SOC in perovskite (MAPbI3-xClx) films by elastically deforming grains. It is observed that applying a concave bending can broaden the line shape of the magnetophotocurrent, increasing the internal magnetic parameter B0 from 121 to 205 mT, which indicates an enhancement on SOC. Interestingly, the PL lifetime is found to be enlarged from 9.9 to 14.8 ns under this bending, which suggests that introducing compressive strain can essentially increase the Rashba effect through SOC, leading to an increase upon indirect band transition. Furthermore, the PL peak associated with the Rashba effect is shifted from 776 to 780 nm under this mechanical bending. Therefore, mechanical bending provides a convenient experimental method to approach the Rashba effect in hybrid perovskites.

Enabling Self-passivation by Attaching Small Grains on Surfaces of Large Grains toward High-Performance Perovskite LEDs.

This paper reports a new method to generate stable and high-brightness electroluminescence (EL) by subsequently growing large/small grains at micro/nano scales with the configuration of attaching small grains on the surfaces of large grains in perovskite (MAPbBr3) films by mixing two precursor solutions (PbBr2 + MABr and Pb(Ac)2·3H2O + MABr). Consequently, the small and large grains serve, respectively, as passivation agents and light-emitting centers, enabling self-passivation on the defects located on the surfaces of light-emitting large grains. Furthermore, the light-emitting states become linearly polarized with maximal polarization of 30.8%, demonstrating a very stable light emission (49,119 cd/m2 with EQE = 11.31%) and a lower turn-on bias (1.9 V) than the bandgap (2.25V) in the perovskite LEDs (ITO/PEDOT:PSS/MAPbBr3/TPBi[50 nm]/LiF[0.7 nm]/Ag). Therefore, mixing large/small grains with the configuration of attaching small grains on the surfaces of large grains by mixing two precursor solutions presents a new strategy to develop high-performance perovskite LEDs.

Investigating underlying mechanism in spectral narrowing phenomenon induced by microcavity in organic light emitting diodes.

This paper reports our experimental studies on the underlying mechanism responsible for electroluminescence spectral narrowing phenomenon in the cavity-based organic light-emitting diodes. It is found that the microcavity generates an emerging phenomenon: a magneto-photoluminescence signal in Poly(9,9-dioctylfluorene-alt-benzothiadiazole) polymer under photoexcitation, which is completely absent when microcavity is not used. This provides an evidence that microcavity leads to the formation of spatially extended states, functioning as the intermediate states prior to the formation of Frenkel excitons in organic materials. This is confirmed by the magneto-electroluminescence solely observed from the cavity-based light-emitting diodes under electrical injection. Furthermore, the narrowed electroluminescence output shows a linear polarization, concurrently occurred with magneto-electroluminescence. This indicates that the spatially extended sates become aligned towards forming coherent light-emitting excitons within the microcavity through optical resonance. Clearly, the spatially extended states present the necessary condition to realize electroluminescence spectral narrowing phenomenon towards lasing actions in cavity-based organic light-emitting diodes.

Preparation of Sandwich-like NiCo2O4/rGO/NiO Heterostructure on Nickel Foam for High-Performance Supercapacitor Electrodes.

ABSTRACT: A kind of sandwich-like NiCo2O4/rGO/NiO heterostructure composite has been successfully anchored on nickel foam substrate via a three-step hydrothermal method with successive annealing treatment. The smart combination of NiCo2O4, reduced graphene oxide (rGO), and NiO nanostructure in the sandwich-like nano architecture shows a promising synergistic effect for supercapacitors with greatly enhanced electrochemical performance. For serving as supercapacitor electrode, the NiCo2O4/rGO/NiO heterostructure materials exhibit remarkable specific capacitance of 2644 mF cm-2 at current density of 1 mA cm-2, and excellent capacitance retentions of 97.5% after 3000 cycles. It is expected that the present heterostructure will be a promising electrode material for high-performance supercapacitors.