Fluorescence in colloidal solutions: Scattering vs physicochemical effects on line shape.

Line shapes of anionic fluorescein fluorescence in suspensions of polystyrene nanoparticles (PSNP), anionic and cationic micelles, lipid vesicles, and of laurdan in lipid vesicles were investigated. Computed second harmonic of measured spectra indicated three lines for fluorescein and two for laurdan. Accordingly, fluorescein spectra were fit to three Gaussians and laurdan spectra to two lognormal distributions. Resolved line parameters were examined against particle concentration. Scattering, although wavelength dependent, affected intensity but not line shape. Inner filter effects of scattering on line shape are insignificant because multiple scattering, redirection of scattered photons into the detector, and inclusion of scattered photons in collection and detection minimize wavelength dependent effects. Dominant effects on line width and peak positions are due to physicochemical effects of dye-particle-solvent interactions rather than scattering. Fluorescein does not interact with anionic micelles and lipid vesicles, but remains in the aqueous phase, and responds to pH increase induced by these additives. Blue shift in peak position, decrease in line width, and increase in emission intensity in these systems are like those in NaOH solutions. Fluorescein does interact with cationic micelles and hydrophobic PSNP, and its emission is red shifted. Laurdan in lipid vesicles senses interface polarity. Blue shift and decrease in line width of its emission line indicate decreasing polarity with lipid concentration. Scattering, as well as interactions affect emission intensity. Physicochemical effects distort line shape and modify intrinsic spectra. Line shape changes are better markers than intensity to investigate interactions and reactions.

Ultrafast electron transfer at the interface of gold nanoparticles and methylene blue molecular adsorbates.

Due to their unique property of possessing localized surface plasmon resonance (LSPR), metal nanoparticles (MNPs) have drastically impacted many applications. For instance, local field enhancement through LSPRs and plasmonic hot electron transfer are known to enhance the efficiency of MNP-based photoreactions. Here, we report on the ultrafast electron transfer from gold nanoparticles (Au-NPs) to methylene blue (MB) molecular adsorbate using femtosecond pump-probe and steady-state absorption and emission spectroscopy techniques. Although the energy band alignment of the interface allows both dipole-dipole Förster resonance energy transfer (FRET) and charge transfer, because the MB emission intensity at the Au-NPs/MB nanocomposite decreased by a factor of ∼3.6, the FRET process was ruled out. Selective excitation of LSPRs at the Au-NPs/MB nanocomposite sample in pump-probe experiments led to the formation of the MB ground-state depletion and a positive induced absorption at wavelengths shorter than ∼500 nm, which was attributed to the shoulder of the MB- anion absorption. Furthermore, despite the fact that the concentration of Au-NPs in the nanocomposite sample is the same as that in the Au-NPs solution, the initial intensity of the LSPR depletion signal was about six times weaker than that in the Au-NPs sample. These observations suggest that electron transfer from excited Au-NPs to MB adsorbates took place on a time-scale that is shorter than the ∼50 fs experimental temporal resolution.

Filling Exciton Trap-States in Two-Dimensional Tungsten Disulfide (WS2) and Diselenide (WSe2) Monolayers.

Two-dimensional transition metal dichalcogenides (2D-TMDs) hold a great potential to platform future flexible optoelectronics. The beating hearts of these materials are their excitons known as XA and XB, which arise from transitions between spin-orbit split (SOS) levels in the conduction and valence bands at the K-point. The functionality of 2D-TMD-based devices is determined by the dynamics of these excitons. One of the most consequential channels of exciton decay on the device functionality is the defect-assisted recombination (DAR). Here, we employ steady-state absorption and emission spectroscopies, and pump density-dependent femtosecond transient absorption spectroscopy to report on the effect of DAR on the lifetime of excitons in monolayers of tungsten disulfide (2D-WS2) and diselenide (2D-WSe2). These pump-probe measurements suggested that while exciton decay dynamics in both monolayers are driven by DAR, in 2D-WS2, defect states near the XB exciton fill up before those near the XA exciton. However, in the 2D-WSe2 monolayer, the defect states fill up similarly. Understanding the contribution of DAR on the lifetime of excitons and the partition of this decay channel between XA and XB excitons may open new horizons for the incorporation of 2D-TMD materials in future optoelectronics.

Ultrafast dynamics of exciton formation and decay in two-dimensional tungsten disulfide (2D-WS2) monolayers.

Excitons in two-dimensional transition metal dichalcogenide monolayers (2D-TMDs) are of essential importance due to their key involvement in 2D-TMD-based applications. For instance, exciton dissociation and exciton radiative recombination are indispensible processes in photovoltaic and light-emitting devices, respectively. These two processes depend drastically on the photogeneration efficiency and lifetime of excitons. Here, we incorporate femtosecond pump-probe spectroscopy to investigate the ultrafast dynamics of exciton formation and decay in a single crystal of monolayer 2D tungsten disulfide (WS2). Investigation of the formation dynamics of the lowest exciton (XA) indicated that the formation time linearly increases from ∼150 fs upon resonant excitation, to ∼500 fs following excitation that is ∼1.1 eV above the band-gap. This dependence is attributed to the time it takes highly excited electrons in the conduction band (CB) to relax to the CB minimum (CBM) and contribute to the formation of XA. This is confirmed by infrared measurements of electron intraband relaxation dynamics. Furthermore, pump-probe experiments suggested that the XA ground state depletion recovery dynamics depend on the excitation energy as well. The average recovery time increased from ∼10 ps in the case of resonant excitation to ∼50 ps following excitation well above the band-gap. Having the ability to control whether generating short-lived or long-lived electron-hole pairs in 2D-TMD monolayers opens a new horizon for the application of these materials. For instance, long-lived electron-hole pairs are appropriate for photovoltaic devices, but short-lived excitons are more beneficial for lasers with ultrashort pulses.

Bromine substitution improves excited-state dynamics in mesoporous mixed halide perovskite films.

In this study, ultrafast transient absorption spectroscopy (TAS) is utilized to examine the excited-state dynamics in methylammonium lead iodide/bromide (MAPb(I1-xBrx)3) perovskites as a function of bromide content. TAS spectral behavior reveals characteristic lifetimes for thermalization, recombination, and charge carrier injection of MAPb(I1-xBrx)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 first 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(I1-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.

Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites.

In this work, 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. 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.

Capturing the Ultrafast Vibrational Decoherence of Hydrogen Bonding in Interfacial Water.

Vibrational sum-frequency generation (vSFG) measurements in the frequency and time domains reveal that the interfacial hydrogen bonded OH stretch at the water/calcium fluoride interface is composed of two populations oriented oppositely. The time-resolved vSFG free-induction decay suggested that, whereas the strongly hydrogen bonded OH vibrational stretches, centered near 3140 ± 11 cm-1, are oriented toward bulk water and lose their collective coherence within ∼70 ± 7 fs, the weakly hydrogen bonded OH species, centered near 3410 ± 12 cm-1, are pointed toward the interface and dephase within ∼50 ± 6 fs.

Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures.

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, i.e., monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions has 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 for 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/zinc sulfide core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that, following electron transfer from the 2D to the 0D, hybrid excitons, wherein the electron resides in the 0D and the 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.

Tailoring Vacancies Far Beyond Intrinsic Levels Changes the Carrier Type and Optical Response in Monolayer MoSe2-x Crystals.

Defect engineering has been a critical step in controlling the transport characteristics of electronic devices, and the ability to create, tune, and annihilate defects is essential to enable the range of next-generation devices. Whereas defect formation has been well-demonstrated in three-dimensional semiconductors, similar exploration of the heterogeneity in atomically thin two-dimensional semiconductors and the link between their atomic structures, defects, and properties has not yet been extensively studied. Here, we demonstrate the growth of MoSe2-x single crystals with selenium (Se) vacancies far beyond intrinsic levels, up to ∼20%, that exhibit a remarkable transition in electrical transport properties from n- to p-type character with increasing Se vacancy concentration. A new defect-activated phonon band at ∼250 cm(-1) appears, and the A1g Raman characteristic mode at 240 cm(-1) softens toward ∼230 cm(-1) which serves as a fingerprint of vacancy concentration in the crystals. We show that post-selenization using pulsed laser evaporated Se atoms can repair Se-vacant sites to nearly recover the properties of the pristine crystals. First-principles calculations reveal the underlying mechanisms for the corresponding vacancy-induced electrical and optical transitions.

Interlayer Coupling in Twisted WSe2/WS2 Bilayer Heterostructures Revealed by Optical Spectroscopy.

van der Waals (vdW) heterostructures are promising building blocks for future ultrathin electronics. Fabricating vdW heterostructures by stamping monolayers at arbitrary angles provides an additional range of flexibility to tailor the resulting properties than could be expected by direct growth. Here, we report fabrication and comprehensive characterizations of WSe2/WS2 bilayer heterojunctions with various twist angles that were synthesized by artificially stacking monolayers of WS2 and WSe2 grown by chemical vapor deposition. After annealing the WSe2/WS2 bilayers, Raman spectroscopy reveals interlayer coupling with the appearance of a mode at 309.4 cm(-1) that is sensitive to the number of WSe2 layers. This interlayer coupling is associated with substantial quenching of the intralayer photoluminescence. In addition, microabsorption spectroscopy of WSe2/WS2 bilayers revealed spectral broadening and shifts as well as a net ∼10% enhancement in integrated absorption strength across the visible spectrum with respect to the sum of the individual monolayer spectra. The observed broadening of the WSe2 A exciton absorption band in the bilayers suggests fast charge separation between the layers, which was supported by direct femtosecond pump-probe spectroscopy. Density functional calculations of the band structures of the bilayers at different twist angles and interlayer distances found robust type II heterojunctions at all twist angles, and predicted variations in band gap for particular atomistic arrangements. Although interlayer excitons were indicated using femtosecond pump-probe spectroscopy, photoluminescence and absorption spectroscopies did not show any evidence of them, suggesting that the interlayer exciton transition is very weak. However, the interlayer coupling for the WSe2/WS2 bilayer heterojunctions indicated by substantial PL quenching, enhanced absorption, and rapid charge transfer was found to be insensitive to the relative twist angle, indicating that stamping provides a robust approach to realize reliable optoelectronics.

Nonlinear Fano-Resonant Dielectric Metasurfaces.

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. Here, 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. We measure a third harmonic generation enhancement factor of 1.5 × 10(5) 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%. The modulation mechanism is studied by pump-probe experiments.

Patterned arrays of lateral heterojunctions within monolayer two-dimensional semiconductors.

The formation of semiconductor heterojunctions and their high-density integration are foundations of modern electronics and optoelectronics. To enable two-dimensional crystalline semiconductors as building blocks in next-generation electronics, developing methods to deterministically form lateral heterojunctions is crucial. Here we demonstrate an approach for the formation of lithographically patterned arrays of lateral semiconducting heterojunctions within a single two-dimensional crystal. Electron beam lithography is used to pattern MoSe2 monolayer crystals with SiO2, and the exposed locations are selectively and totally converted to MoS2 using pulsed laser vaporization of sulfur to form MoSe2/MoS2 heterojunctions in predefined patterns. The junctions and conversion process are studied by Raman and photoluminescence spectroscopy, atomically resolved scanning transmission electron microscopy and device characterization. This demonstration of lateral heterojunction arrays within a monolayer crystal is an essential step for the integration of two-dimensional semiconductor building blocks with different electronic and optoelectronic properties for high-density, ultrathin devices.

Digital transfer growth of patterned 2D metal chalcogenides by confined nanoparticle evaporation.

Developing methods for the facile synthesis of two-dimensional (2D) metal chalcogenides and other layered materials is crucial for emerging applications in functional devices. Controlling the stoichiometry, number of the layers, crystallite size, growth location, and areal uniformity is challenging in conventional vapor-phase synthesis. Here, we demonstrate a method to control these parameters in the growth of metal chalcogenide (GaSe) and dichalcogenide (MoSe2) 2D crystals by precisely defining the mass and location of the source materials in a confined transfer growth system. A uniform and precise amount of stoichiometric nanoparticles are first synthesized and deposited onto a substrate by pulsed laser deposition (PLD) at room temperature. This source substrate is then covered with a receiver substrate to form a confined vapor transport growth (VTG) system. By simply heating the source substrate in an inert background gas, a natural temperature gradient is formed that evaporates the confined nanoparticles to grow large, crystalline 2D nanosheets on the cooler receiver substrate, the temperature of which is controlled by the background gas pressure. Large monolayer crystalline domains (∼100 µm lateral sizes) of GaSe and MoSe2 are demonstrated, as well as continuous monolayer films through the deposition of additional precursor materials. This PLD-VTG synthesis and processing method offers a unique approach for the controlled growth of large-area metal chalcogenides with a controlled number of layers in patterned growth locations for optoelectronics and energy related applications.

Seeing is believing: hot electron based gold nanoplasmonic optical hydrogen sensor.

We report on the rapid optical detection of gaseous hydrogen using hot electrons generated from resonantly excited substrate-based gold nanohemispheres (Au NHs). We consider hot electron induced H2 dissociation and the subsequent formation of a metastable gold hydride (AuHx) to account for changes in optical transmission. The excitation wavelength was varied to demonstrate a maximum response at the localized surface plasmon resonance (LSPR) wavelength of the AuNHs. Numerical simulations, using the discrete dipole approximation, were employed to corroborate the optical changes associated with the formation of metastable AuHx. Finite time difference domain (FDTD) calculations were also performed to account for the enhanced photocatalytic activity arising due to the confinement of electric fields by the Au NHs. FDTD simulations show that the excitation of the Au NHs plasmon modes generates stronger electric fields at the interface in comparison to a spherical geometry of similar dimensions.

Vibrational Dynamics of Interfacial Water by Free Induction Decay Sum Frequency Generation (FID-SFG) at the Al2O3(1120)/H2O Interface.

The dephasing dynamics of a vibrational coherence may reveal the interactions of chemical functional groups with their environment. To investigate this process at a surface, we employ free induction decay sum frequency generation (FID-SFG) to measure the time that it takes for free OH stretch oscillators at the charged (pH ≈ 13, KOH) interface of alumina/water (Al2O3/H2O) to lose their collective coherence. By employing noncollinear optical parametric amplification (NOPA) technology and nonlinear vibrational spectroscopy, we showed that the single free OH peak actually corresponds to two distinct oscillators oriented opposite to each other and measured the total dephasing time, T2, of the free OH stretch modes at the Al2O3/H2O interface with a sub-40 fs temporal resolution. Our results suggested that the free OH oscillators associated with interfacial water dephase on the time scale of 89.4 ± 6.9 fs, whereas the homogeneous dephasing of interfacial alumina hydroxyls is an order of magnitude slower.

Generation of sub-30-fs microjoule mid-infrared pulses for ultrafast vibrational dynamics at solid/liquid interfaces.

We describe temporal compression of ultrabroadband, few microjoule mid-infrared (mid-IR) pulses from a noncollinear optical parametric amplifier (NOPA) employed in a sum-frequency generation (SFG) vibrational spectroscopic system, operating in total-internal-reflection geometry. The propagation of the mid-IR beam through optical materials results in a significant temporal chirp at the probed interface, which is analyzed and corrected by properly managing the total dispersion of materials introduced into the mid-IR beam path. By employing the simultaneous spatial and temporal focusing of the broadband infrared pulses at the probed interface, we achieve a sub-50-fs full width at half-maximum (FWHM) for the instrument response function, measured via SFG cross correlation of the ultrashort mid-IR pulses with an ultrashort (~30 fs) near-IR pulse from a synchronized, independently tunable NOPA. From the SFG cross-correlation FWHM, we extract a sub-30-fs mid-IR pulse duration, making it a suitable SFG spectroscopic system to investigate vibrational dynamics in hydrogen-bonded systems at interfaces.