15 Search Results

A plasmonic Au–MoS ₂ nanosheet composite provides significant enhancement in photocatalytic hydrogen production.

For an excitonic photovoltaic (PV) device to perform efficiently, photogenerated excitons in the charge donor need to be dissociated through charge transfer (CT) to the acceptor rapidly after their photogeneration and remain separated for a longer time to allow the collection of charges. To improve the efficiency of these steps, several combinations of materials have been examined. Due to their excellent optical properties, two-dimensional transition-metal dichalcogenides (2D-TMDs) have recently been explored. Another promising class of materials to platform efficient PVs is organic–inorganic perovskites. Here, we report on the ultrafast exciton dissociation through electron transfer from a 2D tungsten disulfide (WS₂)more » monolayer to a thin layer of methylammonium lead iodide (CH₃NH₃PbI₃) perovskites. Photoluminescence measurements showed that when the 2D-WS₂ monolayer was covered with perovskites, its emission completely quenched, suggesting that the CT process is highly efficient. Despite that pump–probe spectroscopy measurements were carried out with a ~45 fs temporal resolution, the CT dynamics were not captured. A comparison of the ultrafast dynamics of the two band-edge excitons of the charge donor (2D-WS₂) suggested that electron transfer is the dominant pathway of CT. Furthermore, these pump–probe measurements indicated that a small fraction of transferred electrons remained in the perovskites up to almost 2 ns. These findings may open a new horizon for understanding the dissociation of photogenerated excitons in 2D-TMDs through hybridization with another class of nanomaterials.« less

In this study we investigated the spectral dynamics of cesium lead mixed-halide, CsPb(Br_xCl_1–x)₃ perovskite nanocrystals probed with complementary spectral techniques: time-resolved photoluminescence and transient absorption spectroscopy. Mixed-halide perovskite nanocrystals were synthesized via a hot-injection method followed by anion exchange reactions. Our results show that increased Cl content in perovskite nanocrystals (a) diminished the photoluminescence quantum yield and gave rise to rapid radiative recombination of carriers; (b) resulted in rapid thermalization of hot carriers and low carrier temperatures, which suggests weaker hot-phonon bottleneck and Burstein–Moss effects; (c) decreased the bandgap renormalization energy, which suggests high exciton binding energy and poor chargemore » extraction in Cl substituted perovskite nanocrystals; and (d) increased the number of carriers undergoing Auger losses, where Auger processes dominate over trap-assisted recombination. Furthermore, these findings provide a generalized framework to guide researchers as to when mixed-halide perovskite nanocrystals would be useful for optoelectronic technologies and when they would be detrimental to device performance.« less

In this paper, we have examined the ultrafast dynamics of shape- and composition-controlled bimetallic Au/Ag core/shell nanostructures with transient absorption spectroscopy (TAS) as a function of Ag layer thickness (0–15 nm) and pump excitation fluence (50–500 nJ/pulse). Our synthesis approach generated both bimetallic nanocubes and nanopyramids with distinct dipolar plasmon resonances and plasmon dephasing behavior at the resonance. Lifetimes obtained from TAS at low powers (50 nJ/pulse) demonstrated minimal dependence on the Ag layer thickness, whereas at high power (500 nJ/pulse) a rise in electron–phonon coupling lifetime (τ₁) was observed with increasing Ag shell thickness for both nanocubes and nanopyramids.more » This is attributable to the stronger absorption of the 400 nm pump pulse with higher Ag content, which induced higher electron temperatures. The phonon–phonon scattering lifetime (τ₂) also rises with increasing Ag layer, contributed both by the increasing size of the Au/Ag nanostructures as well as by surface chemistry effects. Further, we observed that even the thinnest, 2 nm, Ag shell strongly impacts both τ₁ and τ₂ at high power despite minimal change in overall size, indicating that the nanostructure composition also strongly impacts the thermalization temperature following absorption of 400 nm light. We also observed a shape-dependent trend at high power, where τ₂ increased for the nanopyramids with increasing Ag shell thickness and nanostructure size, but bimetallic nanocubes demonstrated an unexpected decrease in τ₂ for the thickest, 15 nm, Ag shell. This was attributed to the larger number of corners and edges in the nanocubes relative to the nanopyramids.« less

Here in this study, ultrafast transient absorption spectroscopy (TAS) is utilized to examine the excited-state dynamics in methylammonium lead iodide/bromide (MAPb(I_1-xBrx)3) perovskites as a function of bromide content. TAS spectral behavior reveals characteristic lifetimes for thermalization, recombination, and charge carrier injection of MAPb(I_1-xBr_x)₃ from x = 0 to 0.3 infiltrated in mesoporous titania films. Carrier recombination and charge injection lifetimes demonstrated a discernable increase with Br content likely because high carrier populations are supported by the higher density of vacant electronic states in mixed-halide perovskites due to the increased capacity of the conduction band. However, we observe for the firstmore » time that carrier thermalization lifetimes significantly decrease with increasing Br. This suggests that the shift in crystal structure from tetragonal towards pseudocubic accelerates carrier cooling, resulting in the relief of the hot phonon bottleneck. Furthermore, the stabilized MAPb(I_1-xBrx)₃ samples exhibit a lower Burstein–Moss shift of 0.07–0.08 eV compared to pure MAPbI₃ (0.12 eV). Our results provide evidence that Br inclusion contributes to a broadening of the parabolic conduction band and to improvement in electron–phonon coupling and phonon propagation in the lattice.« less

In this paper, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr₃) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3 perovskites.more » TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO₂ prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.« less

With the advanced progress achieved in the field of nanotechnology, localized surface plasmons resonances (LSPRs) are actively considered to improve the efficiency of metal-based photocatalysis, photodetection, and photovoltaics. Here, we report on the exchange of energy and electric charges in a hybrid composed of a two-dimensional tungsten disulfide (2D-WS₂) monolayer and an array of aluminum (Al) nanodisks. Femtosecond pump-probe spectroscopy results indicate that within ~830 fs after photoexcitation of the 2D-WS₂ semiconductor, energy transfer from the 2D-WS₂ excitons excites the plasmons of the Al array. Then, upon the radiative and/or nonradiative damping of these excited plasmons, energy and/or electron transfermore » back to the 2D-WS₂ semiconductor takes place as indicated by an increase in the reflected probe at the 2D exciton transition energies at later time-delays. This simultaneous exchange of energy and charges between the metal and the 2D-WS₂ semiconductor resulted in an extension of the average lifetime of the 2D-excitons from ~15 to ~58 ps in absence and presence of the Al array, respectively. Furthermore, the indirectly excited plasmons were found to live as long as the 2D-WS₂ excitons exist. Furthermore, the demonstrated ability to generate exciton-plasmons coupling in a hybrid nanostructure may open new opportunities for optoelectronic applications such as plasmonic-based photodetection and photocatalysis.« less

We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure formore » optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS₂) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.« less

Strong nonlinear light matter interaction is highly sought-after for a variety of applications including lasing and all-optical light modulation. Recently, resonant plasmonic structures have been considered promising candidates for enhancing nonlinear optical processes due to their ability to greatly enhance the optical near-field; however, their small mode volumes prevent the inherently large nonlinear susceptibility of the metal from being efficiently exploited. We present an alternative approach that utilizes a Fano-resonant silicon metasurface. The metasurface results in strong near-field enhancement within the volume of the silicon resonator while minimizing two photon absorption. Here, we measure a third harmonic generation enhancement factormore » of 1.5 105 with respect to an unpatterned silicon film and an absolute conversion efficiency of 1.2 10 6 with a peak pump intensity of 3.2 GW cm 2. The enhanced nonlinearity, combined with a sharp linear transmittance spectrum, results in transmission modulation with a modulation depth of 36%. Finally, the modulation mechanism is studied by pump probe experiments« less

Twisting adjacent layers in van der Waals solids can significantly alter their interlayer interactions for tunable optical and electronic properties. Here, we report theoretical calculations, fabrication, and detailed characterizations of WSe₂/WS₂ bilayer heterojunctions with various twist angles that were synthesized by artificially stacking monolayers of CVD-grown WS₂ and WSe₂. Density functional calculations predicted the formation of type-II heterojunctions for the stamped bilayers, with band structures that strongly depend on the interlayer twist angle. Raman spectroscopy reveals strong interlayer coupling with the appearance of a layer-number sensitive mode of WS₂ at 311 cm^-1 in WSe₂/WS₂ bilayers. This strong interlayer coupling resultedmore » in a 1~2 order of magnitude quenching of the photoluminescence. The broadening and shifts were observed in micro-absorption spectroscopy of WSe₂/WS₂ bilayers, which resulted in a net ~10% enhancement in integrated absorption strength across the visible spectrum with respect to the sum of the individual monolayer spectra. The observed 24 4 meV broadening of the WSe₂ A-exciton absorption band in the bilayers provided an estimate on the rate of charge transfer between the layers that ranged from 23 to 33 fs, and was supported by direct femtosecond pump-probe measurements. These results indicate that interlayer exciton formation and non-radiative decay channels dominate optical properties in these bilayers, which may be important for tunable future photovoltaics and detector applications.« less