Magneto-Photoluminescence Based on Two-Photon Excitation in Lanthanide-Doped Up-Conversion Crystal Particles.

Experimental studies on magneto-photoluminescence based on two-photon excitation in up-conversion Y2 O2 S:Er, Yb crystal particles are reported. It is found that the up-conversion photoluminescence generated by two-photon excitation exhibits magnetic field effects at room temperature, leading to a two-photon excitation-induced magneto-photoluminescence, when the two-photon excitation exceeds the critical intensity. By considering the spin selection rule in electronic transitions, it is proposed that spin-antiparallel and spin-parallel transition dipoles with spin mixing are accountable for the observed magneto-photoluminescence. Specifically, the two-photon excitation generates spin-antiparallel electric dipoles between 4 S3/2 -4 I15/2 in Er3+ ions. The antiparallel spins are conserved by exchange interaction within dipoles. When the photoexcitation exceeds the critical intensity, the Coulomb screening can decrease the exchange interaction. Consequently, the spin-orbital coupling can partially convert the antiparallel dipoles into parallel dipoles, generating a spin mixing. Eventually, the populations between antiparallel and parallel dipoles reach an equilibrium established by the competition between exchange interaction and spin-orbital coupling. Applying a magnetic field can break the equilibrium by disturbing spin mixing through introducing spin precessions, changing the spin populations on antiparallel and parallel dipoles and leading to the magneto-photoluminescence. Therefore, spin-dependent transition dipoles present a convenient mechanism to realize magneto-photoluminescence in multiphoton up-conversion crystal particles.

Exploiting the full advantages of colloidal perovskite nanocrystals for large-area efficient light-emitting diodes.

Cost-effective, high-throughput industrial applications of metal halide perovskites in large-area displays are hampered by the fundamental difficulty of controlling the process of polycrystalline film formation from precursors, which results in the random growth of crystals, leading to non-uniform large grains and thus low electroluminescence efficiency in large-area perovskite light-emitting diodes (PeLEDs). Here we report that highly efficient large-area PeLEDs with high uniformity can be realized through the use of colloidal perovskite nanocrystals (PNCs), decoupling the crystallization of perovskites from film formation. PNCs were precrystallized and surrounded by organic ligands, and thus they were not affected by the film formation process, in which a simple modified bar-coating method facilitated the evaporation of residual solvent to provide uniform large-area films. PeLEDs incorporating the uniform bar-coated PNC films achieved an external quantum efficiency (EQE) of 23.26% for a pixel size of 4 mm2 and an EQE of 22.5% for a large pixel area of 102 mm2 with high reproducibility. This method provides a promising approach towards the development of large-scale industrial displays and solid-state lighting using perovskite emitters.

Fabrication and photoluminescence of Er(3+)-doped Al2O3 thin films with sol-gel method.

Erbium doped Al2O3 thin films were fabricated on quartz substrates in dip-coating process by sol-gel method, using the aluminum isopropoxide [Al(OC3H7)3]-derived AlOOH sols with the addition of erbium nitrate [Er(NO3)3 x 5H2O]. The as-deposited films, which erbium concentration was between 20 and 43 mol%, were annealed in air from 600 to 1200 degrees C. The phase structure was detected by X-ray diffraction (XRD) and the PL spectra in the wavelength range of 1400-1700 nm were investigated by spectrophotometer, which was exited by a 760 nm semiconductor LD. The PL spectrum shows a broadband extending from 1.430 to 1.670 microm and centered at 1.55 microm, corresponding to the intra-4f transition between the first excited (4I(13/2)) and the ground state (4I(15/2)) of Er3+. The full width at half maximum (FWHM) of PL peaks increase from 60 to 100 nm with temperature increased from 600 to 1200 degrees C.

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.

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.

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.

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.

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.

Experimental studies on magnetization in the excited state by using the magnetic field effect of light scattering based on multi-layer graphene particles suspended in organic solvents.

This article reports on experimental studies on magnetic polarization in the excited state by using magnetic field effects of light scattering (MFELS) together with a photoexcitation beam based on fluorinated multi-layer graphene (FG) particles suspended in an organic solvent. We observe that a magnetic field can change the light scattering of a 532 nm laser beam from the suspended FG particles, generating a MFELS signal with an amplitude of 60% at 900 mT. This phenomenon indicates that the suspended FG particles experience a magnetization force, leading to an orientation of the suspended FG particles in a magnetic field. We find that the magnetization force is a function of a solvent dielectric constant, an analogue phenomenon similar to magneto-electric coupling. More importantly, in the excited state the suspended FG particles exhibit more pronounced MFELS, as compared with the ground state, when the magnetic field effects of light scattering are combined with a photoexcitation beam of 325 nm. Clearly, the FG particles in the excited state possess a stronger magnetization relative to the ground state. This excitation-enhanced magnetization suggests an interaction between the magnetization from the localized spins and the polarization from delocalized π electrons in the FG particles. Therefore, the magnetic field effects of light scattering provide a convenient experimental method to investigate the magnetization of nanoparticles in the excited state.

Magnetodielectric Response from Spin-Orbital Interaction Occurring at Interface of Ferromagnetic Co and Organometal Halide Perovskite Layers via Rashba Effect.

The spin on a ferromagnetic Co surface can interact with the asymmetric orbital on an organometal halide perovskite surface, leading to an anisotropic magnetodielectric effect. This study presents an opportunity to integrate ferromagnetic and semiconducting properties through the Rasbha effect for achieving spin-dependent electronic functionalities based on thin-film design.

Interaction Between Optically-Generated Charge-Transfer States and Magnetized Charge-Transfer States toward Magneto-Electric Coupling.

This article reports the magneto-dielectric studies on the coupling between optically generated CT states and magnetized CT states based on thin-film devices with the architecture of ITO/TPD:BBOT/TPD/Co/Al. The magnetized CT states are generated at the Co/TPD interface, generating a magneto-dielectric response with a broad, non-Lorentzian line-shape. The optically generated CT states are formed at the TPD:BBOT interfaces in the heterojunction under photoexcitation, leading to a magneto-dielectric signal with a narrow, Lorentzian line-shape. We find that combining the optically generated CT states and magnetized CT states yields a new magneto-dielectric signal with distinctive line-shape and amplitude in the ITO/TPD:BBOT/TPD/Co/Al device. The magneto-dielectric analysis indicates that there exists a coupling between optically generated CT states and magnetized CT states through the interactions between the magnetic Co/TPD interface and the optically excited TPD:BBOT heterojunction. Furthermore, we show that the coupling between optically generated CT states and magnetized CT states experiences Coulomb interactions and spin-orbital interaction by changing (i) the density of optically generated CT states and (ii) the separation distance between optically generated CT states and magnetized CT states. Clearly, this coupling provides a new approach to mutually tune magnetic and electronic properties through thin-film engineering by combining magnetic and organic materials.