Exciton dynamics in two-dimensional metal halide perovskite: The impact of film processing.

We investigate the hot carrier and exciton dynamics in two-dimensional (2D) metal halide perovskites using time-resolved spectroscopy. 2D perovskite films were prepared with and without dimethyl sulfoxide treatment to elucidate the effect of film processing techniques on optoelectronic properties. Femtosecond transient absorption measurements reveal that the charge carrier dynamics are different in the two samples, and excitons survive for a longer time in the treated sample than the untreated one. While the early-time carrier dynamics in the untreated sample are dominated by charges trapped by defect states, the hot free carriers govern the dynamics in the treated sample due to fewer defects in it. Morphological and other spectroscopic studies, including time-resolved photoluminescence, further suggest the formation of more defects in the untreated sample. These results can guide the future development of efficient 2D perovskite-based optoelectronic devices.

Ultrafast carrier dynamics in vanadium-doped MoS2 alloys.

Substitutional doping is a most promising approach to manipulate the electronic and optical properties of two-dimensional (2D) transition metal dichalcogenides (TMDCs). In addition to inducing magnetism, vanadium (V) doping can lead to semiconductor-metal transition in TMDCs. However, the dynamics of charge carriers that governs the optoelectronic properties of doped TMDCs has been rarely revealed. In this work, we have investigated the dynamics of photocarriers in pristine and V-doped monolayer (ML) MoS2. Comparison of the transient absorption (TA) spectra of ML MoS2 with lightly (≤1%) and heavily (3.62%) V-doped MoS2 infers the induction of additional energy states in the doped materials giving rise to new low energy bleach features in the TA spectra. The quasiparticle band structure of MoS2 is found to disappear at sufficiently high V doping due to the presence of impurity bands. An attempt has also been made to study the manipulation of the carrier lifetime with V doping in MoS2. Our TA kinetic measurements suggest that the decay kinetics of the carriers becomes slower with increasing doping percentage and at a higher doping level the carriers survive for a much longer time compared to pristine MoS2. Furthermore, we have identified a new electronic transition (NET) in heavily V-doped MoS2 at high pump fluences.

Defect-mediated saturable absorption and carrier dynamics in tin (II) monosulfide quantum dots.

Tin (II) monosulfide (SnS) has attracted considerable attention in emerging photonics and optoelectronics because of high carrier mobility, large absorption coefficient, anisotropic linear and nonlinear optical properties, and long-time stability. In this Letter, we report third-order nonlinear absorption and refraction of SnS quantum dots (QDs). Under excitation with 800-nm femtosecond pulses, QDs exhibit saturable absorption (saturation intensity ∼ 47.69 GW/cm2) and positive refractive nonlinearity (nonlinear refraction coefficient ∼ 1.24 × 10-15 cm2/W). Nonetheless, we investigate charge carrier dynamics using femtosecond transient absorption spectroscopy and propose the presence of midgap defect states which not only dictate carrier dynamics but also give rise to nonlinear optical properties in SnS QDs.

Surface Passivation by Sulfur-Based 2D (TEA)2PbI4 for Stable and Efficient Perovskite Solar Cells.

Perovskite solar cells (PSCs) with superior performance have been recognized as a potential candidate in photovoltaic technologies. However, defects in the active perovskite layer induce nonradiative recombination which restricts the performance and stability of PSCs. The construction of a thiophene-based 2D structure is one of the significant approaches for surface passivation of hybrid PSCs that may combine the benefits of the stability of 2D perovskite with the high performance of three-dimensional (3D) perovskite. Here, a sulfur-rich spacer cation 2-thiopheneethylamine iodide (TEAI) is synthesized as a passivation agent for the construction of a three-dimensional/two-dimensional (3D/2D) perovskite bilayer structure. TEAI-treated PSCs possess a much higher efficiency (20.06%) compared to the 3D perovskite (MA0.9FA0.1PbI3) devices (17.42%). Time-resolved photoluminescence and femtosecond transient absorption spectroscopy are employed to investigate the effect of surface passivation on the charge carrier dynamics of the 3D perovskite. Additionally, the stability test of TEAI-treated perovskite devices reveals significant improvement in humid (RH ∼ 46%) and thermal stability as the sulfur-based 2D (TEA)2PbI4 material self-assembles on the 3D surface, making the perovskite surface hydrophobic. Our findings provide a reliable approach to improve device stability and performance successively, paving the way for industrialization of PSCs.

Efficient Multiple Exciton Generation in Monolayer MoS2.

Utilization of the excess energy of photoexcitation that is otherwise lost as thermal effects can improve the efficiency of next-generation light-harvesting devices. Multiple exciton generation (MEG) in semiconducting materials yields two or more excitons by absorbing a single high-energy photon, which can break the Shockley-Queisser limit for the conversion efficiency of photovoltaic devices. Recently, monolayer transition metal dichalcogenides (TMDs) have emerged as promising light-harvesting materials because of their high absorption coefficient. Here, we report efficient MEGs with low threshold energy and high (86%) efficiency in a van der Waals (vdW) layered material, MoS2. Through different experimental approaches, we demonstrate the signature of exciton multiplication and discuss the possible origin of decisive MEG in monolayer MoS2. Our results reveal that vdW-layered materials could be a potential candidate for developing mechanically flexible and highly efficient next-generation solar cells and photodetectors.

Through structural isomerism: positional effect of alkyne functionality on molecular optical properties.

Literature studies on the effects of alkyne functionality in manipulating the optical properties of donor-π-acceptor-type molecular scaffolds have been scarce compared to those on the alkene functional group. Here, two structurally isomeric donor-acceptor (D-A) dyes were synthesized to study the positional effect of alkyne functionality (triple bond) on their optical, electrochemical and charge generation properties in order to design efficient dyes for possible application in dye sensitized solar cells (DSSCs). These dyes, named CAPC and PACC, contain carbazole and cyanoacrylic acid as the donor and acceptor units, respectively, and the π-conjugation length within the molecules was controlled by the introduction of an alkyne group. The D-π-A design was followed in designing CAPC with the alkyne serving as the π-spacer, while in PACC, alkyne was placed on the donor, which was directly in conjugation with the acceptor. This rendered equal conjugation lengths within the designed dyes. With the help of photophysical characterizations, it was concluded that CAPC featured better characteristics for a DSSC dye than PACC. Our conclusions were further supported by the results of transient absorption spectroscopy, electrochemical analysis, fluorescence lifetime studies and density functional theory.

High-performance perovskite photodetectors based on CH3NH3PbBr3 quantum dot/TiO2 heterojunction.

Organo-lead halide perovskite materials have opened up a great opportunity to develop high performance photodetectors because of their superior optoelectronic properties. The main issue with perovskite-only photodetector is severe carrier recombination. Integration of perovskite with high-conductive materials such as graphene or transition metal sulfides certainly improved the photoresponsivity. However, achieving high overall performance remains a challenge. Here, an improved photodetector is constructed by perovskite quantum dots (QDs) and atomic layer deposited ultrathin TiO2 films. The designed CH3NH3PbBr3 QD/TiO2 bilayer device displays inclusive performance with on/off ratio of 6.3 × 102, responsivity of 85 A W-1, and rise/decay time of 0.09/0.11 s. Furthermore, we demonstrate that interface plays a crucial role in determining the device current and enhance the overall performance of heterostructure photodetector through interface engineering. We believe that this work can provide a strategy to accelerate development of high-performance solution-processed perovskite photodetectors.

High-Performance Perovskite Photodetectors Based on CH3NH3PbBr3Quantum Dot/TiO2Heterojunction.

Organo-lead halide perovskite materials have opened up a great opportunity to develop high performance photodetectors because of their superior optoelectronic properties. The main issue with perovskite-only photodetector is severe carrier recombination. Integration of perovskite with high-conductive materials such as graphene or transition metal sulfides certainly improved the photoresponsivity. However, achieving high overall performance remains a challenge. Here, an improved photodetector is constructed by perovskite quantum dots (QDs) and atomic layer deposited (ALD) ultrathin TiO2films. The designed CH3NH3PbBr3QD/TiO2bilayer device displays inclusive performance with on/off ratio of 6.3×102, responsivity of 85 AW-1, and rise/decay time of 0.09/0.11 s. Furthermore, we demonstrate that interface plays a crucial role in determining the device current and enhance the overall performance of heterostructure photodetector through interface engineering. We believe that this work can provide a strategy to accelerate development of high-performance solution-processed perovskite photodetectors.

New Nonlinear Optical Crystal of Rhodamine 590 Acid Phthalate.

The synthesis and crystal structure of rhodamine 590 acid phthalate (RhAP) have been reported. This novel solid-state rhodamine derivative not only has a longer fluorescence lifetime compared to rhodamine solid-state matrixes where emission is quenched but also possesses strong nonlinear optical characteristics. The static and dynamic first- and second-order hyperpolarizabilities were calculated using the time-dependent density functional theory at the B3LYP/6-31+G* level. The computed static values of ß and γ of RhAP by the X-ray diffraction (XRD) structure were 31.9 × 10-30 and 199.0 × 10-36 esu, respectively. These values were about 62 times larger than the corresponding values in urea, an already well-known nonlinear optical material. The second-order hyperpolarizability of the compound was determined experimentally by measuring the two-photon absorption cross section using intensity-modulated light fields. The reported compound, excitable at near-infrared, exhibited frequency upconversion with the two-photon absorption coefficient enhanced by two orders of magnitude compared to that of the dye solution. Hosting the dye in the solid, at high concentrations, exploits the nonlinearity of the dye itself as well as results in significant excitonic effects including formation of broad exciton band and superradiance.

Light-Induced Defect Healing and Strong Many-Body Interactions in Formamidinium Lead Bromide Perovskite Nanocrystals.

Organic lead halide perovskite (OLHP) nanocrystals (NCs) have paved the way to advanced optoelectronic devices through their extraordinary electrical and optical properties. However, understanding of the light-induced complex dynamic phenomena in OLHP NCs remains a subject of debate. Here we used wide field microscopy and time-resolved spectroscopy to correlate the local changes in photophysics and the dynamical behavior of photocarriers. We demonstrate that light-induced brightening of the photoluminescence from the formamidinium lead bromide NC films is related to the film preparation condition and reduction of trap density. The density of trap states is reduced via halide ion migration from interstitial position. Our femtosecond transient absorption study identifies transient Stark effect due to the generation of hot carriers. Because of slow carrier trapping, Auger recombination through many-body carrier-carrier interactions dominates over trion recombination. This work presents unprecedented insights into the light-driven processes enabling better device design in the future.

Postsynthesis Spontaneous Coalescence of Mixed-Halide Perovskite Nanocubes into Phase-Stable Single-Crystalline Uniform Luminescent Nanowires.

All inorganic mixed-halide perovskite, CsPb(Br xI1- x)3 (0 ≤ x ≤ 1), nanocrystals possess tunable photoluminescence with high quantum yield in the visible window. However, the photoluminescence degrades rapidly with postsynthetic aging due to the spontaneous ion separation and phase instability. Here we show that the postsynthetic aging of CsPb(Br xI1- x)3 nanocubes spontaneously forms highly uniform single-crystalline nanowires with a diameter of 9 ± 0.5 nm and length of up to several micrometers. The nanowires show bright photoluminescence with an absolute photoluminescence quantum yield of 41%. Rietveld refinement identifies the stable orthorhombic phase of the nanowires, implying a phase transition from the cubic crystallographic phase of the nanocubes during the morphology evolution. Transient absorption spectroscopy reveals a faster excited-state decay dynamic with a large exciton delocalization length in 1D nanowires. Our findings elucidate the insights into the postsynthesis morphology evolution of mixed-halide perovskite nanocrystals leading to luminescent nanowires with excellent crystal phase stability for potential optoelectronic applications.

Phonon Coupling with Excitons and Free Carriers in Formamidinium Lead Bromide Perovskite Nanocrystals.

Organometal halide perovskites in the form of nanocrystals (NCs) have attracted enormous attention due to their unique optoelectronic and photoluminescence (PL) properties. Here, we examine the phase composition and the temperature dependence of emission line width broadening in formamidinium lead bromide (FAPbBr3) perovskite nanocrystals (NCs) for light-emitting applications and identify different charge-carrier scattering mechanisms. Our results show most of the emission is from the orthorhombic phase. The PL line width broadening at high temperature is dominated by the Fröhlich interaction between the free charge carriers and the optical phonons. At low temperatures, the peak of the PL spectrum exhibits a continuous red shift indicating an increase of excitons contribution at lower temperatures, and concurrently the line width also narrows down due to the inhibition of the optical phonons. From the temperature-dependent measurements, the coupling strength of both the charge phonon interaction and the exciton phonon interaction have been determined. The obtained results indicate that the charge phonon coupling strengths are higher compared to the exciton phonon coupling.

Electron-Phonon Interaction in Organic/2D-Transition Metal Dichalcogenide Heterojunctions: A Temperature-Dependent Raman Spectroscopic Study.

The heterojunctions of organic/two-dimensional transition metal dichalcogenides (TMDs) have the potential to be used in the next-generation optoelectronic and photonic devices. Herein, we have systemically investigated the temperature-dependent Raman spectroscopy to elucidate the phonon shift and thermal properties of the semiconducting TMD nanosheets grafted by a conjugated polymer (PG-MoS2 and PG-MoSe2) forming heterojunctions. Our results reveal that softening of Raman modes of PG-TMDs as temperature increases from 77 to 300 K is due to the negative temperature coefficient (TC) and anharmonicity. The TCs of E1 2g and A1g modes of PG-MoS2 nanosheets and A1g mode of PG-MoSe2 were found to be -0.015, -0.010, and -0.010 cm-1 K-1, respectively. The origin of negative TCs is explained on the basis of a double resonance process, which is more active in single- and few-layer MoS2 and MoSe2. Interestingly, the temperature-dependent behavior of the phonon modes of PG-MoS2 and PG-MoSe2 is similar to that of pristine nanosheets. Grafting by conjugated polymer does not affect the electron-phonon (e-p) interaction in the semiconducting (2H-phase) TMDs, hinting the application potential of such materials in field-effect electronic devices.

Ultrafast multiexponential electron injection dynamics at a dye and ZnO QD interface: a combined spectroscopic and first principles study.

The photophysical properties of a push-pull dye and the dynamics of electron transfer across a dye and ZnO quantum dot (QD) interface have been studied using a combination of steady-state, time-resolved fluorescence and femtosecond transient absorption (TA) spectroscopies. Spectroscopic measurements, along with quantum chemical calculations, provide evidence for the photoinduced intramolecular charge transfer (ICT) in a donor-π-acceptor dye. Wavelength dependent fluorescence decay of the dye infers the solvent relaxation of the ICT state. TA spectral measurements suggest electron transfer from dye to ZnO QD through the ICT state by monitoring the dye radical cation. Multiexponential electron injection with time constants of 775 fs and 25 ps at the dye@QD interface is demonstrated using the TA kinetics results. The thermodynamics of fast and slow electron injections is discussed. Furthermore, density functional theory (DFT) and time-dependent (TD)-DFT simulations were performed to identify the dye cation radical and to get a deep insight into the experimental observations.

Femtosecond insights into direct electron injection in dye anchored ZnO QDs following charge transfer excitation.

The role of the charge transfer (CT) state in interfacial electron transfer in dye-sensitized semiconductor nanocrystals is still poorly understood. To address this problem, femtosecond transient absorption (TA) spectroscopy is used as a probe to investigate the electron injection across a newly synthesized coumarin dye (8-hydroxy-2-oxo-4-phenyl-2 benzo[h]chromene-3-carbonitrile, coded BC5) and ZnO quantum dots (QDs). Steady state and time-resolved spectroscopic measurements reveal that BC5 dye interacts strongly with ZnO QDs in the ground state forming a CT complex. The BC5-ZnO QD complex absorbs more towards red compared to only the dye and QDs, and emits fluorescence due to radiative recombination of photogenerated charges. The formation of charges following the excitation of the CT complex has been demonstrated by observing the signature of dye radical cations and electrons in the conduction band (CB) of the QDs in the TA spectra. The TA signals of these charges grow sharply as a result of ultrafast direct electron injection into the QD. We have monitored the complete dynamics of photogenerated charges by measuring the TA signals of the charges up to a couple of nanoseconds. The injected electrons that are free or shallowly trapped recombine with a time constant of 625 fs, whereas deeply trapped electrons disappear slowly (526 ps) via radiative recombination. Furthermore, theoretical studies based on ab initio calculations have been carried out to complement the experimental findings.

Ab Initio Assessment of the Structural and Optoelectronic Properties of Organic-ZnO Nanoclusters.

Structural, electronic, and optical properties of a new coumarin dye, zinc oxide (ZnO) nanoclusters of varying sizes, and their complexes have been investigated using density functional theory (DFT). The band gap of oxide nanoclusters varies with size validating quantum confinement effect in small particles. Energy level diagrams of dye, ZnO nanoclusters, and redox electrolyte are in favor of efficient electron injection from dye to nanocluster and regeneration of the ionized dye. The adsorption of the organic dye to nanocluster is tested for anchoring through three different functional groups (cyano, carbonyl, and hydroxyl) of the dye. We have compared simulated absorption spectra of the dye, nanoclusters, and dye functionalized nanoclusters and discussed the matching with the solar irradiance spectrum. A strong new band appeared in the low energy side of the absorption spectra for dye adsorbed nanoclusters. Frontier molecular orbital calculations reveal that the first absorption band of dye-ZnO complexes is charge transfer (CT) in character. Excitation of this band leads to direct electron transfer to the conduction band (CB) of the nanocluster, making dye-ZnO complexes suitable for type II DSSCs as well.

Excited state electron transfer from aminopyrene to graphene: a combined experimental and theoretical study.

The quenching of the fluorescence of 1-aminopyrene (1-Ap) by reduced graphene oxide (rGO) has been investigated using spectroscopic techniques. In spite of the upward curvature in the Stern-Volmer plot, the unchanged spectral signature of the absorption of 1-Ap in the presence of rGO and the decrease in fluorescence lifetime with increasing rGO concentration point toward the dynamic nature of the quenching. Detailed analysis of steady state and time-resolved spectroscopic data has shown that the quenching arises due to the photoinduced electron transfer from 1-Ap to rGO. This is again supported by estimating the Gibb's free energy change for the ground as well as excited state electron transfer. Ab initio calculations under the density functional theory (DFT) formalism reveal that the possibility of π-π stacking is very slim in the 1-Ap-rGO system and the electron density resides completely on 1-Ap in the highest occupied molecular orbital (HOMO) and on graphene in the lowest unoccupied molecular orbital (LUMO), supporting the experimental findings of the intermolecular electron transfer between 1-Ap and rGO in the excited state.

Geminate charge recombination in polymer/fullerene bulk heterojunction films and implications for solar cell function.

We have studied the influence of three different fullerene derivatives on the charge generation and recombination dynamics of polymer/fullerene bulk heterojunction (BHJ) solar cell blends. Charge generation in APFO3/[70]PCBM and APFO3/[60]PCBM is very similar and somewhat slower than charge generation in APFO3/[70]BTPF. This difference qualitatively matches the trend in free energy change of electron transfer estimated from the LUMO energies of the polymer and fullerene derivatives. The first order (geminate) charge recombination rate is significantly different for the three fullerene derivatives studied and increases in the order APFO3/[70]PCBM < APFO3/[60]PCBM < APFO3/[70]BTPF. The variation in electron transfer rate cannot be explained from the LUMO energies of the fullerene derivatives and single-step electron transfer in the Marcus inverted region and simple considerations of expected trends for the reorganization energy and free energy change. Instead we suggest that geminate charge recombination occurs from a state where electrons and holes have separated to different distances in the various materials because of an initially high charge mobility, different for different materials. In a BHJ thin film this charge separation distance is not sufficient to overcome the electrostatic attraction between electrons and holes and geminate recombination occurs on the nanosecond to hundreds of nanoseconds time scale. In a BHJ solar cell, we suggest that the internal electric field in combination with polarization effects and the dynamic nature of polarons are key features to overcome electron-hole interactions to form free extractable charges.

Calculations of interfacial interactions in pyrene-Ipa rod sensitized nanostructured TiO2.

Pyrene chromophores carrying different rigid rod spacer groups (ethynylene, ethynylene-phenylene-ethynylene, and ethynylene-bicyclo[2.2.2]octylene-ethynylene) and bound to TiO2 nanostructured materials via an isophthalic acid (Ipa) anchor group have been investigated using quantum chemical calculations in order to elucidate structural and electronic properties of dye-sensitized semiconductor structures capable of long-range photoinduced interfacial electron transfer. The calculations are used to study firstly the effect of the anchor and spacer groups on the electronic properties of the pyrene-dyes, secondly the binding of isophthalic acid to nanostructured TiO2, and thirdly the interfacial electronic interactions for dye-sensitized nanostructured TiO2 relevant to dye-sensitized solar cell applications. Together, these calculations provide theoretical insights into the effect of incorporating rigid rod anchor-cum-spacer group motifs in sensitizers for e.g. solar cell applications. In particular, the calculations help to rationalize the strong influence of the rods on the photophysical properties of the sensitizers in terms of electronic interactions between the individual chromophore, spacer, and anchor segments, as well as to provide information about interfacial electronic interactions of interest for the capabilities of the rods to act as efficient mediators of photoinduced interfacial charge separation.