Thickness-dependent electronic relaxation dynamics in solution-phase redox-exfoliated MoS2 heterostructures.

Electronic relaxation dynamics of solution-phase redox-exfoliated molybdenum disulfide (MoS2) monolayer and multilayer ensembles are described. MoS2 was exfoliated using polyoxometalate (POM) reductants. This process yields a colloidal heterostructure consisting of MoS2 2D sheet multilayers with surface-bound POM complexes. Using two-dimensional electronic spectroscopy, transient bleaching and photoinduced absorption signals were detected at excitation/detection energies of 1.82/1.87 and 1.82/1.80 eV, respectively. Approximate 100-fs bandgap renormalization (BGR) and subsequent defect- and phonon-mediated relaxation on the picosecond timescale were resolved for several MoS2 thicknesses spanning from 1 to 2 L to ∼20 L. BGR rates were independent of sample thickness and slightly slower than observations for chemical vapor deposition-grown MoS2 monolayers. However, defect-mediated relaxation accelerated ∼10-fold with increased sample thicknesses. The relaxation rates increased from 0.33 ± 0.05 to 1.2 ± 0.1 and 3.1 ± 0.4 ps-1 for 1-2 L, 3-4 L, and 20 L fractions. The thicknesses-dependent relaxation rates for POM-MoS2 heterostructures were modeled using a saturating exponential function that showed saturation at thirteen MoS2 layers. The results suggest that the increased POM surface coverage leads to larger defect density in the POM-MoS2 heterostructure. These are the first descriptions of the influence of sample thickness on electronic relaxation rates in solution-phase redox-exfoliated POM-MoS2 heterostructures. Outcomes of this work are expected to impact the development of solution-phase exfoliation of 2D metal-chalcogenide heterostructures.

Influence of Halogen-Solvent Hydrogen Bonding on Gold Nanocluster Photoluminescence.

The influence of gold nanocluster-solvent interactions on nanostructure optical properties was determined. Using [Au11(BINAP)4X2]+, where X = Cl or Br, as a model system, the dramatic influence of halogen-solvent hydrogen bonding on nanocluster optical properties was resolved. The creation of a nanocluster-solvent hydrogen-bond network yielded intense photoluminescence (PL) and an accompanying 2-fold reduction in vibration-mediated nonradiative decay rates. PL was quenched for systems that did not support hydrogen bonding. As reflected by absorption line widths, Raman scattering, and transient absorption spectroscopy measurements, the hydrogen-bond network increased nanocluster structural rigidity and reduced nonradiative carrier decay rates. The results highlight the significant role of the nanocluster-solvent interface in determining the properties of structurally precise materials.

Coherent Vibrational Dynamics of Au144(SC8H9)60 Nanoclusters.

The coherent vibrational dynamics of Au144(SC8H9)60, obtained from femtosecond time-resolved transient absorption spectroscopy, are described. Two acoustic modes were identified and assigned, including 2.0 THz breathing and 0.7 THz quadrupolar vibrations. These assignments are consistent with predictions using classical mechanics models, indicating that bulk models accurately describe the vibrational properties of Au144(SC8H9)60. Coherent phonon signals were persistent for up to 3 ps, indicating energy dissipation by the nanocluster was the primary dephasing channel. The initial excitation phases of the breathing and quadrupolar modes were π-phase-shifted, reflecting differences in the displacive nuclear motion of the vibrations. The combined agreement of the vibrational frequencies, relative phases, and decoherence times supported predictions based on classical models. The vibrational frequencies were insensitive to silver substitution for gold but did show increased inhomogeneous damping of the coherent phonons. The ability to predict the vibrational properties of metal nanoclusters can have an impact on nanoresonator and mass sensing technologies.

The Evolution from Superatom- to Plasmon-Mediated Magnetic Circular Dichroism in Colloidal Metal Nanoparticles Spanning the Nonmetallic to Metallic Limits.

The magneto-optical absorption properties of colloidal metal nanoclusters spanning nonmetallic to metallic regimes were examined using variable-temperature variable-field magnetic circular dichroism (VTVH-MCD) spectroscopy. Charge neutral Au25(SC8H9)18 exhibited MCD spectra dominated by Faraday C-terms, consistent with expectations for a nonmetallic paramagnetic nanocluster. This response is reconciled by the open-shell superatom configuration of Au25(SC8H9)18. Metallic and plasmon-supporting Au459(pMBA)170 exhibited temperature-independent VTVH-MCD spectra dominated by Faraday A-terms. Au144(SC8H9)60, which is intermediate to the metallic and nonmetallic limits, showed the most complex VTVH-MCD response of the three nanoclusters, consisting of 19 distinguishable peaks spanning the visible and near-infrared (3.0-1.4 eV). Variable-temperature analysis suggested that none of these transitions originated from plasmon excitation. However, evidence for both paramagnetic and mixed (i.e., nondiscrete) transitions of Au144(SC8H9)60 was observed. These results highlight the complexity of gold nanocluster electronic transitions that emerge as sizes approach metallic length scales. Nanoclusters in this regime may provide opportunities for tailoring the magneto-optical properties of colloidal nanostructures.

Distinguishing Single-Metal Nanoparticles with Subdiffraction Spatial Resolution Using Variable-Polarization Fourier Transform Nonlinear Optical Microscopy.

The development and use of interferometric variable-polarization Fourier transform nonlinear optical (vpFT-NLO) imaging to distinguish colloidal nanoparticles colocated within the optical diffraction limit is described. Using a collinear train of phase-stabilized pulse pairs with orthogonal electric field vectors, the polarization of nonlinear excitation fields are controllably modulated between linear, circular, and various elliptical states. Polarization modulation is achieved by precise control over the time delay separating the orthogonal pulse pairs to within hundreds of attoseconds. The resultant emission from gold nanorods is imaged to a 2D array detector and correlated to the excitation field polarization and plasmon resonance frequency by Fourier transformation. Gold nanorods with length-to-diameter aspect ratios of 2 support a longitudinal surface plasmon resonance at approximately 800 nm, which is resonant with the excitation fundamental carrier wavelength. Differences in the intrinsic linear and circular dichroism resulting from variation in their relative alignment with respect to the laboratory frame enable optical differentiation of nanorods separated within 50 nm, which is an approximate 5-fold improvement over the diffraction limit of the microscope. The experimental results are supported by analytical simulations. In addition to subdiffraction spatial resolution, the vpFT-NLO method intrinsically provides the polarization- and frequency-dependent resonance response of the nanoparticles-providing spectroscopic information content along with super-resolution imaging capabilities.

Recent Advances in 2D Material Theory, Synthesis, Properties, and Applications.

Two-dimensional (2D) material research is rapidly evolving to broaden the spectrum of emergent 2D systems. Here, we review recent advances in the theory, synthesis, characterization, device, and quantum physics of 2D materials and their heterostructures. First, we shed insight into modeling of defects and intercalants, focusing on their formation pathways and strategic functionalities. We also review machine learning for synthesis and sensing applications of 2D materials. In addition, we highlight important development in the synthesis, processing, and characterization of various 2D materials (e.g., MXnenes, magnetic compounds, epitaxial layers, low-symmetry crystals, etc.) and discuss oxidation and strain gradient engineering in 2D materials. Next, we discuss the optical and phonon properties of 2D materials controlled by material inhomogeneity and give examples of multidimensional imaging and biosensing equipped with machine learning analysis based on 2D platforms. We then provide updates on mix-dimensional heterostructures using 2D building blocks for next-generation logic/memory devices and the quantum anomalous Hall devices of high-quality magnetic topological insulators, followed by advances in small twist-angle homojunctions and their exciting quantum transport. Finally, we provide the perspectives and future work on several topics mentioned in this review.

Improving Spectral, Spatial, and Mechanistic Resolution Using Fourier Transform Nonlinear Optics: A Tutorial Review.

Fourier transform nonlinear optics (FT-NLO) is a powerful experimental physical chemistry tool that provides insightful spectroscopic and imaging data. FT-NLO has revealed key steps in both intramolecular and intermolecular energy flow. Using phase-stabilized pulse sequences, FT-NLO is employed to resolve coherence dynamics in molecules and nanoparticle colloids. Recent advances in time-domain NLO interferometry using collinear beam geometries makes determination of molecular and material linear and nonlinear excitation spectra, homogeneous line width, and nonlinear excitation pathways straightforward. When combined with optical microscopy, rapid acquisition of hyperspectral images with the information content of FT-NLO spectroscopy is possible. With FT-NLO microscopy, molecules and nanoparticles colocated within the optical diffraction limit can be distinguished based on their excitation spectra. The suitability of certain nonlinear signals for statistical localization present exciting prospects for using FT-NLO to visualize energy flow on chemically relevant length scales. In this tutorial review, descriptions of FT-NLO experimental implementations are provided along with theoretical formalisms for obtaining spectral information from time-domain data. Select case studies that illustrate the use of FT-NLO are presented. Finally, strategies for extending super-resolution imaging capabilities based on polarization-selective spectroscopy are offered.

Magneto-Optical Properties of Noble Metal Nanostructures.

The magneto-optical signatures of colloidal noble metal nanostructures, spanning both discrete nanoclusters (<2 nm) and plasmonic nanoparticles (>2 nm), exhibit rich structure-property correlations, impacting applications including photonic integrated circuits, light modulation, applied spectroscopy, and more. For nanoclusters, electron doping and single-atom substitution modify both the intensity of the magneto-optical response and the degree of transient spin polarization. Nanoparticle size and morphology also modulate the magnitude and polarity of plasmon-mediated magneto-optical signals. This intimate interplay between nanostructure and magneto-optical properties becomes especially apparent in magnetic circular dichroism (MCD) and magnetic circular photoluminescence (MCPL) spectroscopic data. Whereas MCD spectroscopy informs on a metal nanostructure's steady-state extinction properties, its MCPL counterpart is sensitive to electronic spin and orbital angular momenta of transiently excited states. This review describes the size- and structure-dependent magneto-optical properties of nanoscale metals, emphasizing the increasingly important role of MCPL in understanding transient spin properties and dynamics.

Active pixel sensor matrix based on monolayer MoS2 phototransistor array.

In-sensor processing, which can reduce the energy and hardware burden for many machine vision applications, is currently lacking in state-of-the-art active pixel sensor (APS) technology. Photosensitive and semiconducting two-dimensional (2D) materials can bridge this technology gap by integrating image capture (sense) and image processing (compute) capabilities in a single device. Here, we introduce a 2D APS technology based on a monolayer MoS2 phototransistor array, where each pixel uses a single programmable phototransistor, leading to a substantial reduction in footprint (900 pixels in ∼0.09 cm2) and energy consumption (100s of fJ per pixel). By exploiting gate-tunable persistent photoconductivity, we achieve a responsivity of ∼3.6 × 107 A W-1, specific detectivity of ∼5.6 × 1013 Jones, spectral uniformity, a high dynamic range of ∼80 dB and in-sensor de-noising capabilities. Further, we demonstrate near-ideal yield and uniformity in photoresponse across the 2D APS array.

Achieving sub-diffraction spatial resolution using combined Fourier transform spectroscopy and nonlinear optical microscopy.

Fourier transform nonlinear optical microscopy is used to perform nonlinear spectroscopy of single gold nanorods in an imaging platform, which enables sub-diffraction spatial resolution. The nonlinear optical signal is detected as a function of the time delay between two phase-locked pulses, forming an interferogram that can be used to retrieve the resonant response of the nanoparticles. Detection of the nonlinear signal through a microscopy platform enables wide-field hyperspectral imaging of the longitudinal plasmon resonances in individual gold nanorods. Super-resolution capabilities are demonstrated by distinguishing multiple nanorods that are co-located within the optical diffraction limit and are spatially separated by only tens of nanometers. The positions and resonance energies obtained through Fourier transform nonlinear optical microscopy agree with the relative positions and aspect ratios deduced from electron microscopy.

Plasmon-Mediated Chiroptical Second Harmonic Generation from Seemingly Achiral Gold Nanorods.

Throughout nature, simple rules explain complex phenomena, such as the selective interaction of chiral objects with circularly polarized light. Here, we demonstrate chiroptical signals from gold nanorods, which are seemingly achiral structures. Shape anisotropy due to atomic-level faceting and rounding at the tips of nanorods, which are free of chiral surface ligands, induces linear-to-circular polarization modulation during second harmonic generation. The intrinsic nanorod chiroptical response is increased by plasmon-resonant excitation, which preferentially amplifies circularly polarized harmonic signals. This structure-plasmon interplay is uniquely resolved by polarization-resolved second harmonic generation measurements. The material's second-order polarizability is the product of the structure-dependent lattice-normal susceptibility and local surface plasmon field vectors. Synthetically scalable plasmon-supporting nanorods that amplify small circular dichroism signals provide a simple, assembly-free platform for chiroptical transduction.

Ultrafast relaxation dynamics of Au38(SC6H13)24 monolayer-protected clusters resolved by two-dimensional electronic spectroscopy.

Electronic relaxation dynamics of neutral Au38(SC6H13)24 monolayer-protected clusters (MPCs), following excitation of the mixed 15 875 cm-1 charge transfer resonance, were studied using femtosecond transient absorption (fsTA) and two-dimensional electronic spectroscopy (2DES). The excited carriers relax by three different mechanisms, including an ∼100 fs HOMO-12/-13 to HOMO-4/-6 hole transfer, picosecond HOMO-4/-6 to HOMO hole transfer, and subsequent electron-hole recombination that persisted beyond the hundreds of picoseconds measurement range. The fsTA data revealed two transient bleach components at 15 820 and 15 625 cm-1, where the lower frequency component exhibited a delayed first-order buildup of 80 ± 25 fs that matched the decay of the high-energy bleach component (110 ± 45 fs). These results suggested that the excited charge carriers internally relax within the exited-state manifold in ≈100 fs. 2DES resolved multiple electronic fine-structure transient peaks that spanned excitation frequencies ranging from 15 500 to 16 100 cm-1. State-to-state dynamics were understood by the analysis of time-dependent 2DES transient signal amplitudes at numerous excitation-detection frequency combinations. An off-diagonal cross peak at 15 825-15 620 cm-1 excitation-detection signified the HOMO-12/-13 to HOMO-4/-6 hole transfer process. The lowest-frequency (15 620 cm-1) 2DES diagonal fine-structure peak exhibited instantaneous amplitude but intensified following a 75 ± 10 fs buildup when compared to diagonal peaks at higher frequencies. This observation indicated that the charge transfer resonance in Au38(SC6H13)24 MPCs is comprised of several electronic transitions of unique spectral weights, which may result from different orbital contributions associated with specific cluster domains. The use of 2DES in combination with structurally precise MPCs can provide a platform for understanding structure-dependent electronic dynamics in metal nanoclusters and technologically important metal-chalcogenide interfaces.

Atomic-Level Structure Determines Electron-Phonon Scattering Rates in 2-D Polar Metal Heterostructures.

The electron dynamics of atomically thin 2-D polar metal heterostructures, which consisted of a few crystalline metal atomic layers intercalated between hexagonal silicon carbide and graphene grown from the silicon carbide, were studied using nearly degenerate transient absorption spectroscopy. Optical pumping created charge carriers in both the 2-D metals and graphene components. Wavelength-dependent probing suggests that graphene-to-metal carrier transfer occurred on a sub-picosecond time scale. Following rapid (<300 fs) carrier-carrier scattering, charge carriers monitored through the metal interband transition relaxed through several consecutive cooling mechanisms that included sub-picosecond carrier-phonon scattering and dissipation to the silicon carbide substrate over tens of picoseconds. By studying 2-D In, 2-D Ga, and a Ga/In alloy, we resolved accelerated electron-phonon scattering rates upon alloy formation as well as structural influences on the excitation of in-plane phonon shear modes. More rapid cooling in alloys is attributed to increased lattice disorder, which was observed through correlative polarization-resolved second harmonic generation and electron microscopy. This connection between the electronic relaxation rates, far-field optical responses, and metal lattice disorder is made possible by the intimate relation between nonlinear optical properties and atomic-level structure in these materials. These studies provided insights into electronic carrier dynamics in 2-D crystalline elemental metals, including resolving contributions from specific components of a 2-D metal-containing heterojunction. The correlative ultrafast spectroscopy and nonlinear microscopy results suggest that the energy dissipation rates can be tuned through atomic-level structures.

Size-Scalable Near-Infrared Photoluminescence in Gold Monolayer Protected Clusters.

Near-infrared photoluminescence of a series of three gold monolayer protected clusters (MPCs) with volumes spanning 50-200 Å3 was studied by using variable-temperature photoluminescence (VT-PL) spectroscopy. The three MPCs, which included Au20(SC8H9)15-diglyme, Au25(SC8H9)18, and Au38(SC12H25)24, all exhibited temperature-dependent intensities that reflected a few-millielectronvolt energy gap that separated bright emissive and dark nonradiative electronic states. All clusters showed increased PL intensities upon raising the sample temperature from 4.5 K to a cluster-specific value, upon which increased sample temperature resulted in emission quenching. The increased PL in the low-temperature range is attributed to thermally activated carrier transfer from dark to bright states. The quenching at elevated temperatures is attributed to nonradiative vibrational relaxation through Au-Au stretching of the MPCs metal core. Importantly, the results show evidence of a common and size scalable metal-centered intraband PL mechanism that is general for ultrasmall metal nanoclusters, which are expected to show nonscalable optical properties.

Spin-Polarized Photoluminescence in Au25 (SC8 H9 )18 Monolayer-Protected Clusters.

Here, the observation of spin-polarized emission for the Au25 (SC8 H9 )18 monolayer-protected cluster (MPC) is reported. Variable-temperature variable-field magnetic circular photoluminescence (VTV H ⇀ -MCPL) measurements are combined with VT-PL spectroscopy to provide state-resolved characterization of the transient electronic structure and spin-polarized electron-hole recombination dynamics of Au25 (SC8 H9 )18 . Through analysis of VTV H ⇀ -MCPL measurements, a low energy (1.64 eV) emission peak is assigned to intraband relaxation between core-metal-localized superatom-D to -P orbitals. Two higher energy interband components (1.78 eV, 1.94 eV) are assigned to relaxation from superatom-D orbitals to states localized to the inorganic semirings. For both intraband superatom-based or interband relaxation mechanisms, the extent of spin-polarization, quantified as the degree of circular polarization (DOCP), is determined by state-specific electron-vibration coupling strengths and energy separations of bright and dark electronic fine-structure levels. At low temperatures (<60 K), metal-metal superatom-based intraband transitions dominate the global PL emission. At higher temperatures (>60 K), interband ligand-based emission is dominant. In the low-temperature PL regime, increased sample temperature results in larger global PL intensity. In the high-temperature regime, increased temperature quenches interband radiative recombination. The relative intensity for each PL mechanism is discussed in terms of state-specific electronic-vibrational coupling strengths and related to the total angular momentum, quantified by Landé g-factors.

Synthetic Control of Hot-Electron Thermalization Efficiency in Size-Tunable Au-Pt Hybrid Nanoparticles.

Gold nanoparticles are well-known to exhibit size-dependent properties that are responsible for their unique catalytic, optical, and electronic applications. However, electron-phonon coupling, which is important for photocatalysis and light harvesting, is one of the rare properties of gold that is size-independent above a threshold value, e.g., for nanospheres larger than approximately 5 nm in diameter. Here, we show that when interfaced to a comparably sized Pt nanoparticle, the electron-phonon coupling constant of the hybrid material depends on the diameter of the Au domain. This is important because the electron-phonon coupling constant describes the efficiency by which hot electrons are converted to local heat by the primary electron-phonon scattering thermalization channel. We begin by synthesizing a library of Au-Pt hybrid nanoparticle heterodimers by growing size-tunable Au nanoparticles on Pt nanoparticle seeds. By systematically varying reagent concentration and reaction time, the Au domain diameter of the Au-Pt hybrid nanoparticle heterodimers can be tuned between 4.4 and 16 nm while the size of the Pt domain remains constant. Calibration curves allow us to dial in precise Au domain sizes, and microscopic analysis of the Au-Pt heterodimers provides insights into how they grow and how their morphologies evolve. Femtosecond time-resolved transient absorption spectroscopy reveals that for Au-Pt heterodimers having Au domain diameters of 8.7 to 14 nm, the electron-phonon coupling constant decreases by more than 80%, which is not observed for comparably sized Au nanoparticles. Interfacing smaller Au domains with Pt nanoparticle surfaces causes an increase in the density of states near the Fermi level of Au, which results in accelerated thermalization times through an increased number of electron-phonon interactions. The combination of precision hybrid nanoparticle synthesis and size-dependent electron-phonon coupling may be important for designing composite metals for photocatalytic and light-harvesting applications and for engineering different functions into established materials.

Linear and nonlinear chiroptical response from individual 3D printed plasmonic and dielectric micro-helices.

Sub-wavelength chiral resonators formed from artificial structures exhibit exceedingly large chiroptical responses compared to those observed in natural media. Owing to resonant excitation, chiral near fields can be significantly enhanced for these resonators, holding great promise for developing enantioselective photonic components such as biochemical sensors based on circular dichroism (CD) and spin-dependent nonlinear imaging. In the present work, strong linear and nonlinear chiroptical responses (scattering CD > 0.15 and nonlinear differential CDs > 0.4) at visible and near infrared frequencies are reported for the first time for individual micrometer-scale plasmonic and dielectric helical structures. By leveraging dark-field spectroscopy and nonlinear optical microscopy, the circular-polarization-selective scattering behavior and nonlinear optical responses (e.g., second harmonic generation and two-photon photoluminescence) of 3D printed micro-helices with feature sizes comparable to the wavelength (total length is ∼5λ) are demonstrated. These micro-helices provide potential for readily accessible photonic platforms, facilitating an enantiomeric analysis of chiral materials. One such example is the opportunity to explore ultracompact photonic devices based on single, complex meta-atoms enabled by state-of-the-art 3D fabrication techniques.

Unexpected Near-Infrared to Visible Nonlinear Optical Properties from 2-D Polar Metals.

Near-infrared-to-visible second harmonic generation from air-stable two-dimensional polar gallium and indium metals is described. The photonic properties of 2D metals, including the largest second-order susceptibilities reported for metals (approaching 10 nm/V), are determined by the atomic-level structure and bonding of two-to-three-atom-thick crystalline films. The bond character evolved from covalent to metallic over a few atomic layers, changing the out-of-plane metal-metal bond distances by approximately ten percent (0.2 Å), resulting in symmetry breaking and an axial electrostatic dipole that mediated the large nonlinear response. Two different orientations of the crystalline metal atoms, corresponding to lateral displacements <2 Å, persisted in separate micrometer-scale terraces to generate distinct harmonic polarizations. This strong atomic-level structure-property interplay suggests metal photonic properties can be controlled with atomic precision.

Resolving Electron-Electron Scattering in Plasmonic Nanorod Ensembles Using Two-Dimensional Electronic Spectroscopy.

The use of two-dimensional electronic spectroscopy (2DES) to study electron-electron scattering dynamics in plasmonic gold nanorods is described. The 2DES resolved the time-dependent plasmon homogeneous line width Γh(t), which was sensitive to changes in Fermi-level carrier densities. This approach was effective because electronic excitation accelerated plasmon dephasing, which broadened Γh. Analysis of Γh(t) indicated plasmon coherence times were decreased by 20-50%, depending on excitation conditions. Electron-electron scattering rates of approximately 0.01 fs-1 were obtained by fitting the time-dependent Γh broadening; rates increased quadratically with both excitation pulse energy and frequency. This rate dependence agreed with Fermi-liquid theory-based predictions. Hot electron thermalization through electron-phonon scattering resulted in Γh narrowing. To our knowledge, this is the first use of the plasmon Γh(t) to isolate electron-electron scattering dynamics in colloidal metal nanoparticles. These results illustrate the effectiveness of 2DES for studying hot electron dynamics of solution-phase plasmonic ensembles.

Photoluminescence of single gold nanorods following nonlinear excitation.

The photoluminescence (PL) mechanisms of gold nanorods following nonlinear excitation are described. Using single-particle nonlinear optical measurements, we compare PL signals resulting from both the plasmon-resonant and non-resonant excitations. In both cases, spectrally broad interband PL emission was observed. However, we also show that resonant excitation of the longitudinal plasmon mode leads to an increased photonic density of states at energies corresponding to the transverse plasmon resonance. This increased density of states is achieved by a multi-step mechanism, which is initiated by three-photon excitation and followed by an Auger relaxation process. Importantly, the results show that nonlinear excitation can lead to energy and polarization modulation of nanoparticle optical signals that are not observed using linear excitation. This work also demonstrates the effectiveness of single-nanoparticle PL studies for understanding how plasmon-resonant excitations can be used to modify hot carrier distributions.