Toward Broadband Photodetection: Band Alignment and Interlayer Charge Transfer in 2D Transition Metal Dichalcogenides/3D-Ga2O3 Hybrid-Dimensional Heterostructures.

Recently, various transition metal dichalcogenides (TMDs)/Ga2O3 heterostructures have emerged as excellent candidates for the development of broadband photodetection, exhibiting various merits such as broadband optical absorption, efficient interlayer carrier transfer, a relatively simple fabrication process, and potential for flexibility. In this work, vertically stacked MoSe2/Ga2O3, WS2/Ga2O3, and WSe2/Ga2O3 heterostructures were experimentally synthesized, all exhibiting broadband light absorption, spanning at least from 200 to 800 nm. The absorption coefficients of these TMDs/Ga2O3 heterostructures are significantly improved compared to those of individual Ga2O3 films. The superior performance can be attributed to the type-I band alignment and efficient interlayer carrier transfer, which result from various band offsets along with the different doping conditions of the TMD layers, leading to distinct photoluminescence (PL) emission properties. Through a detailed analysis of the excitation-power-dependent PL spectra, we offer an in-depth discussion of the interlayer carrier transfer mechanism in the TMDs/Ga2O3 heterostructures. Regarding interlayer coupling effects, the shift of the EF of TMD layers plays a crucial role in modulating their trion emission properties. These findings suggest that these three TMDs/Ga2O3 heterostructures have great potential in broadband photodetection, and our in-depth physical mechanism analysis lays a solid foundation for a new device design.

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead-free Hybrid Metal Halides.

Generating circularly polarized luminescence (CPL) with simultaneous high photoluminescence quantum yield (PLQY) and dissymmetry factor (glum) is difficult due to usually unmatched electric transition dipole moment (µ) and magnetic transition dipole moment (m) of materials. Herein we tackle this issue by playing a "cascade cationic insertion" trick to achieve strong CPL (with PLQY of ~100 %) in lead-free metal halides with high glum values reaching -2.3×10-2 without using any chiral inducers. Achiral solvents of hydrochloric acid (HCl) and N, N-dimethylformamide (DMF) infiltrate the crystal lattice via asymmetric hydrogen bonding, distorting the perovskite structure to induce the "intrinsic" chirality. Surprisingly, additional insertion of Cs+ cation to substitute partial (CH3)2NH2 + transforms the chiral space group to achiral but the crystal maintains chiroptical activity. Further doping of Sb3+ stimulates strong photoluminescence as a result of self-trapped excitons (STEs) formation without disturbing the crystal framework. The chiral perovskites of indium-antimony chlorides embedded on LEDs chips demonstrate promising potential as CPL emitters. Our work presents rare cases of chiroptical activity of highly luminescent perovskites from only achiral building blocks via spontaneous resolution as a result of symmetry breaking.

In Situ Super-Hindrance-Triggered Multilayer Cracks for Random Lasing in π-Functional Nanopolymer Films.

In situ self-assembly of semiconducting emitters into multilayer cracks is a significant solution-processing method to fabricate organic high-Q lasers. However, it is still difficult to realize from conventional conjugated polymers. Herein, we create the molecular super-hindrance-etching technology, based on the π-functional nanopolymer PG-Cz, to modulate multilayer cracks applied in organic single-component random lasers. Massive interface cracks are formed by promoting interchain disentanglement with the super-steric hindrance effect of π-interrupted main chains, and multilayer morphologies with photonic-crystal-like ordering are also generated simultaneously during the drop-casting method. Meanwhile, the enhancement of quantum yields on micrometer-thick films (Φ = 40% to 50%) ensures high-efficient and ultrastable deep-blue emission. Furthermore, a deep-blue random lasing is achieved with narrow linewidths ~0.08 nm and high-quality factors Q ≈ 5,500 to 6,200. These findings will offer promising pathways of organic π-nanopolymers for the simplification of solution processes applied in lasing devices and wearable photonics.

Hierarchical Nanoarchitectonics of Ultrathin 2D Organic Nanosheets for Aqueous Processed Electroluminescent Devices.

Ultrathin 2D organic nanosheets (2DONs) with high mobility have received tremendous attention due to thickness of few molecular layers. However, ultrathin 2DONs with high luminescence efficiency and flexibility simultaneously are rarely reported. Here, the ultrathin 2DONs (thickness: 19 nm) through the modulation of tighter molecular packing (distance: ≈3.31 Å) achievable from the incorporation of methoxyl and dipenylamine (DPA) groups into 3D spirofluorenexanthene (SFX) building blocks is successfully prepared. Even with closer molecular stacking, ultrathin 2DONs still enable the suppression of aggregation quenching to exhibit higher quantum yields of blue emission (ΦF  = 48%) than that on amorphous film (ΦF  = 20%), and show amplified spontaneous emission (ASE) with a mediate threshold (332 mW cm-2 ). Further, through drop-casting method, the ultrathin 2DONs are self-organized into large-scale flexible 2DONs films (1.5 × 1.5 cm) with the low hardness (H: 0.008 Gpa) and low Young's modulus (Er : 0.63 Gpa). Impressively, the large-scale 2DONs film can realize electroluminescence performances with a maximum luminance (445 cd m-2 ) and low turn on voltage (3.7 V). These ultrathin 2DONs provide a new avenue for the realization of flexible electrically pumping lasers and intelligent quantum tunneling systems.

Nonthermal Ultrafast Optical Control of Magnetization Dynamics by Linearly Polarized Light in Metallic Ferromagnet.

Coherent optical control of the magnetization in ferromagnetic (FM) mediums using ultrafast nonthermal effect paves a promising avenue to improve the speed and repetition rate of the magnetization manipulation. Whereas previously, only heat-induced or helicity-dependent magnetization dynamics are demonstrated in metallic ferromagnets. Here, the linearly-polarized light control of magnetization is demonstrated in FM Co coupled with ferroelectric (FE) BiFeO3 by tuning the light polarization direction. It is revealed that in the Co/BiFeO3 heterostructure excited by femtosecond laser pulses, the magnetization precession amplitude follows a sinusoidal dependence on the laser polarization direction. This nonthermal control of coherent magnetization rotation is attributed to the optical rectification effect in the BiFeO3 layer, which yields a FE polarization depending on the light polarization, and the subsequent modulation of magnetic energy in Co by the electrostriction-induced strain. This work demonstrates an effective route to nonthermally manipulate the ultrafast magnetization dynamics in metallic ferromagnets.

Revealing the Modulation Effects on the Electronic Band Structures and Exciton Properties by Stacking Graphene/h-BN/MoS2 Schottky Heterostructures.

Stacking two dimensional tunneling heterostructures has always been an important strategy to improve the optoelectronic device performance. However, there are still many disputes about the blocking ability of monolayer (1L-) h-BN on the interlayer coupling. Graphene/h-BN/MoS2 optoelectronic devices have been reported for superior device results. In this study, starting with graphene/h-BN/MoS2 heterostructures, we report experimental evidence of 1L-h-BN barrier layer modulation effects about the electronic band structures and exciton properties. We find that 1L-h-BN insertion only partially blocks the interlayer carrier transfer. In the meantime, the 1L-h-BN barrier layer weakens the interlayer coupling effect, by decreasing the efficient dielectric screening and releasing the quantum confinement. Consequently, the optical conductivity and plasmon excitation slightly improve, and the electronic band structures remain unchanged in graphene/h-BN/MoS2, explaining their fascinating optoelectronic responses. Moreover, the excitonic binding energies of graphene/h-BN/MoS2 redshift with respect to the graphene/MoS2 counterparts. Our results, as well as the broadband optical constants, will help better understand the h-BN barrier layers, facilitating the developing progress of h-BN-based tunneling optoelectronic devices.

Gridization-Driven Mesoscale Self-Assembly of Conjugated Nanopolymers into Luminescence-Anisotropic Photonic Crystals.

Organic semiconducting emitters integrated with butterfly-mimetic photonic crystals (PhCs) are fascinating for dramatic advantages over light outcoupling efficiency and multifunctional strain sensors, as well as the key step toward electrically pumped lasers. Herein, an unprecedentedly direct mesoscale self-assembly into 1D PhCs is reported through a covalently gridization-driven approach of wide-bandgap conjugated polymers. A simple solvent-casting procedure allows for in situ self-assembly of the state-of-the-art conjugated nanopolymer, poly{[4-(octyloxy)-9,9-diphenylfluoren-2,7-diyl]grid}-co-{[5-(octyloxy)-9,9-diphenylfluoren-2,7-diyl]grid} (PODPFG), into well-defined multilayer architectures with an excellent toughness (30-40 J m-3 ). This ordered meso-architecture shows a typical Bragg-Snell diffraction behavior to testify the PhC nature, along with a high effective refractive index (1.80-1.88) and optical transmittance (85-87%). The PhC films also exhibit an angle-dependent blue/green photoluminescence switching, an electroluminescence efficiency enhancement by 150-250%, and an amplified spontaneous emission enhancement with ultralow waveguide loss coefficient (2.60 cm-1 ). Gridization of organic semiconductors offers promising opportunities for cross-scale morphology-directed molecular design in multifunctional organic mechatronics and intelligences.

Robust and Swiftly Reversible Thermochromic Behavior of a 2D Perovskite of (C6H4(CH2NH3)2)(CH3NH3)[Pb2I7] for Smart Window and Photovoltaic Smart Window Applications.

Highly robust, swiftly reversible thermochromic nature of a two-dimensional (2D) perovskite of (PDMA)(CH3NH3)n-1PbnI3n+1, nominally prepared as n = 2 is found, where PDMA = C6H4(CH2NH3)2. A wide band gap variation from 700 to 430 nm is observed between room temperature and >60 °C under ambient conditions, resulting from moisture absorption and desorption. X-ray diffraction and Fourier-transform infrared spectroscopy are performed to analyze the hydrated and dehydrated states. Furthermore, the (PDMA)(CH3NH3)n-1PbnI3n+1 film is demonstrated as an active material for smart windows and thermochromic solar cells, which could lower the inside air temperature in an enclosed space and supply a power conversion efficiency of more than 0.5% at a high ambient temperature, respectively. Overall, we may pave a pathway for exploring the novel phenomena and applications of Dion-Jacobson 2D perovskites.

Effect of Thermal Annealing on Conformation of MEH-PPV Chains in Polymer Matrix: Coexistence of H- and J-Aggregates.

In diluted solid solution using poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and polymethyl methacrylate (PMMA) or polystyrene (PS), both aggregated and extended conformations could be formed according to the weight ratio. Aggregated conformation in as-cast MEH-PPV/PMMA film presented a J-aggregate-like photoluminescence (PL) emission. After annealing at 160 °C, its PL showed characteristics of both J- and H-aggregates at the same time; however, extended conformation showed an oligomer-like emission, which was not sensitive to either measurement temperature or annealing temperature. Thus, the conformation transition between aggregated and extended is unlikely to happen in MEH-PPV/PMMA blends during thermal annealing. On the contrary, in MEH-PPV/PS blends, extended conformation dominated in as-cast film with oligomer-like emissions; after annealing at 160 °C, both J- and H- aggregate-like PL emissions were observed, indicating the conformation transitioned from extended to aggregated. Therefore, our work may suggest a new method to manipulate photophysical properties of conjugated polymers by combining appropriate host matrix and thermal annealing processes.

Optical Properties of Two-Dimensional Perovskite Films of (C6H5C2H4NH3)2[PbI4] and (C6H5C2H4NH3)2 (CH3NH3)2[Pb3I10].

The temperature dependence of absorption and photoluminescence (PL) spectroscopies were used to study the optical properties of 2D perovskite films, including n = 1 and 3 of (PEA)2(CH3NH3) n-1[Pb nI3 n+1] (PEA = C6H5(CH2)2NH3). In (PEA)2[Pb1I4] (PEPI), excitons coupling to optical phonons with an average energy of ∼30 meV dominate the photophysics of absorption and PL. (PEA)2(CH3NH3)2[Pb3I10] (shortened as PMPI3), nominally prepared as n = 3, actually was a mixture of multiple layered perovskites with various n. In absorption, a PMPI3 film presents respective n materials' excitonic features, coupling to phonons with an average energy of ∼30 meV; in analyzing PL peaked singly at ∼1.6 eV and its width as a function of temperature, we found that PMPI3 behaves like PEPI at around 80 K but like 3D perovskite near room temperature, with three times larger electron-phonon interaction strength compared to that in PEPI.

Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies.

Two-dimensional (2D) layered hybrid organic-inorganic halide perovskite semiconductors form natural "multiple quantum wells" that have strong spin-orbit coupling due to the heavy elements in their building blocks. This may lead to "Rashba splitting" close to the extrema in the electron bands. We have used a plethora of ultrafast transient, nonlinear optical spectroscopies and theoretical calculations to study the primary (excitons) and long-lived (free carriers) photoexcitations in thin films of 2D perovskite, namely, (C6H5C2H4NH3)2PbI4. The density functional theory calculation shows the occurrence of Rashba splitting in the plane perpendicular to the 2D barrier. From the electroabsorption spectrum and photoinduced absorption spectra from excitons and free carriers, we obtain a giant Rashba splitting in this compound, with energy splitting of (40 ± 5) meV and Rashba parameter of (1.6 ± 0.1) eV·Å, which are among the highest Rashba splitting size parameters reported so far. This finding shows that 2D hybrid perovskites have great promise for potential applications in spintronics.

Temperature-Dependent Electric Field Poling Effects in CH3NH3PbI3 Optoelectronic Devices.

Organo-lead halide perovskites show excellent optoelectronic properties; however, the unexpected inconsistency in forward-backward I-V characteristics remains a problem for fabricating solar panels. Here we have investigated the reasons behind this "hysteresis" by following the changes in photocurrent and photoluminescence under electric field poling in transverse CH3NH3PbI3-based devices from 300 to 10 K. We found that the hysteresis disappears at cryogenic temperatures, indicating the "freeze-out" of the ionic diffusion contribution. When the same device is cooled under continuous poling, the built-in electric field from ion accumulation brings significant photovoltaic effect even at 10 K. From the change of photoluminescence upon polling, we found a second dipole-related mechanism which enhances radiative recombination upon the alignment of the organic cations. The ionic origin of hysteresis was also verified by applying a magnetic field to affect the ion diffusion. These findings reveal the coexistence of ionic and dipole-related mechanisms for the hysteresis in hybrid perovskites.

Long Lived Photoexcitation Dynamics in π-Conjugated Polymer/PbS Quantum Dot Blended Films for Photovoltaic Application.

We used continuous wave photoinduced absorption (PIA) spectroscopy to investigate long-lived polarons in a blend of PbS quantum dot and regio-regular poly (3-hexylthiophene) (RR-P3HT). The charge transfer from RR-P3HT to PbS as well as from PbS to RR-P3HT were observed after changing the capping ligand of PbS from a long chain molecular to a short one. Therefore, PbS could be used to extend the working spectral range in hybrid solar cells with a proper capping ligand. However, we found that the recombination mechanism in the millisecond time region is dominated by the trap/defects in blended films, while it improves to a bimolecular recombination partially after ligand exchange. Our results suggest that passivating traps of nanocrystals by improving surface ligands will be crucial for relevant solar cell applications.

Bright single-mode random laser from a concentrated solution of π-conjugated polymers.

Using thin stripe excitation of a 10 ns pulsed laser, we observed robust and bright random laser (RL) emission in high concentrated solutions of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT). In particular, within the proper excitation intensity range, single line RL emission is observed in both solutions, with full width at half-maximum of 0.17 nm and 0.4 nm for MEH-PPV and PCPDTBT, respectively. The reason for the random laser is that the refractive index fluctuation due to the aggregation in concentrated solution results in spatially extended random lasing modes, which are amplified through traveling light along the interface between solution and cuvette. Our work provides a simple but effective method to achieve bright single-mode RLs, with conversion efficiency on the order of 10%.

Singlet fission of hot excitons in π-conjugated polymers.

We used steady-state photoinduced absorption (PA), excitation dependence (EXPA(ω)) spectrum of the triplet exciton PA band, and its magneto-PA (MPA(B)) response to investigate singlet fission (SF) of hot excitons into two separated triplet excitons, in two luminescent and non-luminescent π-conjugated polymers. From the high energy step in the triplet EXPA(ω) spectrum of the luminescent polymer poly(dioctyloxy)phenylenevinylene (DOO-PPV) films, we identified a hot-exciton SF (HE-SF) process having threshold energy at E≈2E(T) (=2.8 eV, where ET is the energy of the lowest lying triplet exciton), which is about 0.8 eV above the lowest singlet exciton energy. The HE-SF process was confirmed by the triplet MPA(B) response for excitation at E>2E(T), which shows typical SF response. This process is missing in DOO-PPV solution, showing that it is predominantly interchain in nature. By contrast, the triplet EXPA(ω) spectrum in the non-luminescent polymer polydiacetylene (PDA) is flat with an onset at E=E(g) (≈2.25 eV). From this, we infer that intrachain SF that involves a triplet-triplet pair state, also known as the 'dark' 2A(g) exciton, dominates the triplet photogeneration in PDA polymer as E(g)>2E(T). The intrachain SF process was also identified from the MPA(B) response of the triplet PA band in PDA. Our work shows that the SF process in π-conjugated polymers is a much more general process than thought previously.

Exciton versus free carrier photogeneration in organometal trihalide perovskites probed by broadband ultrafast polarization memory dynamics.

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH(3)NH(3)PbI(3) and CH(3)NH(3)PbI(1.1)Br(1.9) using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH(3)NH(3)PbI(3) with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH(3)NH(3)PbI(1.1)Br(1.9). Surprisingly, we also discovered in CH(3)NH(3)PbI(3), but not in CH(3)NH(3)PbI(1.1)Br(1.9), transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH(3)NH(3)PbI(3), D≈0.01 cm(2) s(-1).

Hidden image recovery using a biased photorefractive crystal in the Fourier plane of an optical imaging system.

Self-diffraction can be induced using a biased photorefractive crystal in the Fourier plane of an imaging system where the light beam intensity is naturally high due to the concentration effect of an optical lens. The spatial frequency spectrum of the output image is proportional to the optical power density distribution in the Fourier plane. A photorefractive crystal with small size can be used and hence an reduced amount of biased voltage is needed to obtain significant diffraction effect in the image plane. When the input image is an overlay of a signal and a noise pattern, theoretic model reveals that the induced diffraction in the Fourier plane may be preferably applied on the noise pattern. In order to illustrate the effect experimentally, a signal from a weakly illuminated object is coupled with an overwhelming noise pattern and then the hidden signal is successfully recovered using a SBN61 crystal with an applied voltage of 800 V in the Fourier plane. Such technology can be employed in encrypted spatial communication systems for security purposes.

Nonlinear optical transmission of lead phthalocyanine-doped nematic liquid crystal composites for multiscale nonlinear switching from nanosecond to continuous wave.

We have formulated composites of lead (II) tetrakis (4-cumylphenoxy) phthalocyanine (PbTCPc) doped into nematic liquid crystal (LC), 4(')-pentyl-4-biphenylcarbonitrile (5-CB), that has received a 90 degree twisted alignment and investigated the nonlinear transmission properties using both pulsed (Nd:YLF 524 nm, 5 ns) and cw (532 nm) lasers. In the nanosecond regime, this compound is a reverse saturable absorber performing similarly to low-concentration solutions of PbTCPc. Under cw conditions, we observe optically self-activated polarization switching with low threshold input energy. Our results suggest the potential for an all-optical switch working from the nanosecond time scale to cw.

Time-resolved studies of photoinduced birefringence in azobenzene dye-doped polymer films.

We measured transient photoinduced birefringence (delta n) in various azobenzene dye films by pumping with a nanosecond pulse at 532 nm and probing at 633 nm. The switch-on times for the photoinduced birefringence range from nanoseconds to milliseconds and are systematically related with the lowest optical transition energies for those films. Moreover, our results suggest that the transient photoinduced birefringence measurement is a convenient way to determine the relative energies of pi-pi(*) and n-pi(*) states in azo-based materials.

Observation of nonlinear transmission enhancement in cavities filled with nonlinear organic materials.

We show experimental and theoretical results for enhancement of nonlinear transmission (NT) in moderate finesse cavities filled with nonlinear organic materials (NLOM). Our design for enhancement of nonlinear transmission using micro NLOM cavities compared with reference samples of the same material show that single cavities can enhance the nonlinear response by a factor of 10 or greater under high-absorption conditions. Further enhancement can be achieved in multiple-cavity structures. Other advantages of the cavity structures for nonlinear transmission, such as a higher damage threshold and a broader NT band, are also discussed. Our initial experimental results show a threefold reduction in the nonlinear threshold fluence in a single cavity device compared directly to an identical sample without mirrors, in qualitative agreement with our calculations.