Strong Sum Frequency Generation Research Articles

Sum-Frequency Generation in High-Q GaP Metasurfaces Driven by Leaky-Wave Guided Modes.

Resonant metasurfaces provide a unique platform for enhancing multiwave nonlinear interactions. However, the difficulties over mode matching and material transparency place significant challenges in the enhancement of these multiwave processes. Here we demonstrate efficient nonlinear sum-frequency generation (SFG) in multiresonant GaP metasurfaces based on guided-wave bound-state in the continuum resonances. The excitation of the metasurface by two near-infrared input beams generates strong SFG in the visible spectrum with a conversion efficiency of 2.5 × 10-4 W-1, 2 orders of magnitude higher than the one reported in Mie-type resonant metasurfaces. In addition, we demonstrate the nontrivial polarization dependence on the SFG process. In contrast to harmonic generation, the SFG process is enhanced when using nonparallel polarized input-beams. Importantly, by varying the input pump beam polarization it is possible to direct the SFG emission to different diffraction orders, thereby opening up new opportunities for nonlinear light sources and infrared to visible light conversion.

Spin engineering of triangulenes and application for nano nonlinear optical materials design.

The recently synthesized triangulenes with non-bonding edge states could have broad potential applications in magnetics, spintronics and electro-optics if they have appropriate electronic structure modulation. In the present work, strategies based on molecular orbital theory through heteroatom doping are proposed to redistribute, reduce or eliminate the spin of triangulenes for novel functional materials design, and the role of B, N, NBN, and BNB in such intended electronic structure manipulation is scrutinized. π-Extended triangulenes with tunable electronic properties could be potential nonlinear optical (NLO) materials with appropriate inhibition of their polyradical nature. The elimination of spin is achieved by B, N, NBN, and BNB doping with the intended geometric arrangement for enhanced polarity. Intended doping of BNB results in an optimal structure with large static first hyperpolarizability (〈β0〉) as well as strong Hyper-Rayleigh scattering (HRS) βHRS(-2ω; ω, ω) (ω = 1064.0 nm), TG7-BNB-ba with a large 〈β0〉 (18.85 × 10-30 esu per heavy atom) and βHRS (1.15 × 10-28 esu per heavy atom) much larger than that of a synthesized triangular molecule (1.12 × 10-30 esu of 〈β0〉 per heavy atom and 5.04 × 10-30 esu of βHRS per heavy atom). The strong second order NLO responses in the near-infrared and visible regions, particularly the strong sum frequency generation, make these B or (and) N doped triangulenes promising candidates for the fabrication of novel carbon-based optoelectronic devices and micro-NLO devices.

Effect of Surfactant Concentration and Hydrophobicity on the Ordering of Water at a Silica Surface.

The performance of nonionic surfactants is mediated by the interfacial interactions at the solid-liquid interface. Here we applied sum frequency generation (SFG) vibrational spectroscopy to probe the molecular structure of the silica-nonionic surfactant solution interface in situ, supplemented by quartz crystal microbalance with dissipation monitoring (QCM-D) and molecular dynamics (MD) simulations. The combined studies elucidated the effects of nonionic surfactant solution concentration, surfactant composition, and rinsing on the silica-surfactant solution interfacial structure. The nonionic surfactants studied include ethylene-oxide (EO) and butylene oxide (BO) components with different ratios. It was found that the CH groups of the surfactants at the silica-surfactant solution interfaces are disordered, but the interfacial water molecules are ordered, generating strong SFG OH signals. Solutions with higher concentrations of surfactant lead to a slightly higher amount of adsorbed surfactant at the silica interface, resulting in more water molecules being ordered at the interface, or a higher ordering of water molecules at the interface, or both. MD simulation results indicated that the nonionic surface molecules preferentially adsorb onto silanol sites on silica. A surfactant with a higher EO/BO ratio leads to more water molecules being ordered and a higher degree of ordering of water molecules at the silica-surfactant solution interface, exhibiting stronger SFG OH signal, although less material is adsorbed according to the QCM-D data. A thin layer of surfactants remained on the silica surface after multiple water rinses. To the best of our knowledge, this is the first time the combined approaches of SFG, QCM-D and MD simulation techniques have been applied to study nonionic surfactants at the silica-solution interface, which enhances our understanding on the interfacial interactions between nonionic surfactants, water and silica. The knowledge obtained from this study can be helpful to design the optimal surfactant concentration and composition for future applications.

Insight on Structure of Water and Ice Next to Graphene Using Surface-Sensitive Spectroscopy.

The water/graphene interface has received considerable attention in the past decade due to its relevance in various potential applications including energy storage, sensing, desalination, and catalysis. Most of our knowledge about the interfacial water structure next to graphene stems from simulations, which use experimentally measured water contact angles (WCAs) on graphene (or graphite) to estimate the water-graphene interaction strength. However, the existence of a wide spectrum of reported WCAs on supported graphene and graphitic surfaces makes it difficult to interpret the water-graphene interactions. Here, we have used surface-sensitive infrared-visible sum frequency generation (SFG) spectroscopy to probe the interfacial water structure next to graphene supported on a sapphire substrate. In addition, the ice nucleation properties of graphene have been explored by performing in situ freezing experiments as graphitic surfaces are considered good ice nucleators. For graphene supported on sapphire, we observed a strong SFG peak associated with highly coordinated, ordered water next to graphene. Similar ordering was not detected next to bare sapphire, implying that the observed ordering of water molecules in the former case is a consequence of the presence of graphene. Our analysis indicates that graphene behaves like a hydrophobic (or negatively charged) surface, leading to enhanced ordering of water molecules. Although liquid water orders next to graphene, the ice formed is proton disordered. This research sheds light on water-graphene interactions relevant in optimizing the performance of graphene in various applications.

Surface-Induced Heterogeneity Analysis of an Alkanethiol Monolayer on Microcrystalline Copper Surface Using Sum Frequency Generation Imaging Microscopy

An octadecanethiol (ODT) self-assembled monolayer on microcrystalline copper is investigated by sum frequency generation (SFG) imaging microscopy and electron backscattering diffraction (EBSD). The strong SFG signal contrast across the domain boundary indicates the existence of grain structures on copper surface, which is further verified by EBSD measurements. The nonresonant contribution of SFG response shows anisotropy with respect to the in-plane rotation of the sample relative to the surface normal and varies in each crystal domain area. The resonant contribution of the monolayer, such as the amplitude ratio of CH3-sym/CH3-asym, is azimuthally nearly isotropic. Since the zzz tensor component of nonlinear susceptibility dominates, the resonant part of SFG spectra on the metal surface does not show any anisotropy. Further, a strong correlation between the local metal structures with the top monolayer packing behaviors is identified based on the statistical distribution analysis. Using the methyl group a...

Absence of Sum Frequency Generation in Support of Orthorhombic Symmetry of α-Chitin

The native polymorphic structures of chitin, namely α- and β-chitin, were studied with X-ray diffraction (XRD), infrared and Raman spectroscopies, and sum-frequency generation (SFG) vibrational spectroscopy. The currently proposed model of α-chitin crystal based on X-ray and electron diffraction study has an antiparallel chain arrangement imposed by the orthorhombic symmetry in contrast to parallel chain arrangements in β-chitin and native cellulose; however, the natural occurrence of antiparallel chain arrangement for α-chitin is controversial to widely accepted biosynthetic mechanisms for structural polysaccharides such as chitin and cellulose, where chains are successively polymerized and crystallized in a unidirectional way. We compared the SFG signals among samples with similar crystallinity, morphology, and textures but differing in allomorphs. The SFG signal from α-chitin was ∼40-fold weaker compared to β-chitin having a similar lateral dimension. The strong SFG signals arising from β-chitin can be...

Characterization of starch polymorphic structures using vibrational sum frequency generation spectroscopy.

The polymorphic structures of starch were characterized with vibrational sum frequency generation (SFG) spectroscopy. The noncentrosymmetry requirement of SFG spectroscopy allows for the detection of the ordered domains without spectral interferences from the amorphous phase and also the distinction of the symmetric elements among crystalline polymorphs. The V-type amylose was SFG-inactive due to the antiparallel packing of single helices in crystal unit cells, whereas the A- and B-type starches showed strong SFG peaks at 2904 cm(-1) and 2952-2968 cm(-1), which were assigned to CH stretching of the axial methine group in the ring and CH2 stretching of the exocyclic CH2OH side group, respectively. The CH2/CH intensity ratios of the A- and B-type starches are significantly different, indicating that the conformation of hydroxymethyl groups in these two polymorphs may be different. Cyclodextrin inclusion complexes were also analyzed as a comparison to the V-type amylose and showed that the head-to-tail and head-to-head stacking patterns of cyclodextrin molecules govern their SFG signals and peak positions. Although the molecular packing is different between V-type amylose and cyclodextrin inclusion complexes, both crystals show the annihilation of SFG signals when the functional group dipoles are arranged pointing in opposite directions.

Raman microspectroscopy and vibrational sum frequency generation spectroscopy as probes of the bulk and surface compositions of size-resolved sea spray aerosol particles

Sea spray aerosol (SSA) represents one of the largest aerosol components in our atmosphere. SSA plays a major role in influencing climate; however the overall impacts remain poorly understood due to the overall chemical complexity. SSA is comprised of a mixture of inorganic and organic components in varying proportions that change as a function of particle size and seawater composition. In this study, nascent SSA particles were produced using breaking waves, resulting in compositions and sizes representative of the open ocean. The composition of individual SSA particles ranging in size from ca. 0.15 to 10 μm is measured using Raman microspectroscopy, while the interfacial composition of collections of size-resolved particles is probed by sum frequency generation (SFG). Raman spectra of single particles have bands in the 980 to 1030 cm(-1) region associated with the symmetric stretch of the sulfate anion, the 2800 to 3000 cm(-1) region associated with carbon-hydrogen stretches, and from 3200-3700 cm(-1) associated with the oxygen-hydrogen stretches of water. The relative intensities of these features showed a strong dependence on particle size. In particular, submicrometer particles exhibited a larger amount of organic matter compared to supermicrometer particles. However, for external surfaces of homogeneous SSA particles (i.e. particles without a solid inclusion), and also the interfaces of mixed-phase particles, there was a strong SFG response in the aliphatic C-H stretching region for both sub- and supermicrometer particles. This finding suggests that organic material present in supermicrometer particles primarily resides at the interface. The presence of methylene contributions in the SFG spectra indicated disordered alkyl chains, in contrast to what one might expect for a surfactant layer on a sea salt particle. Changes in peak frequencies and relative intensities in the C-H stretching region are seen for some particles after the addition of bacteria, phytoplankton, and growth medium to the seawater. This study provides new insights into the bulk and surface composition of SSA particles and represents a step forward in our understanding of this globally abundant aerosol. It also provides insights into the development of model systems for SSA that may more accurately represent the organic layer at the surface.

Strong Sum Frequency Generation in a GaAs/AlAs Coupled Multilayer Cavity Grown on a (113)B-Oriented GaAs Substrate

A strong sum frequency generation (SFG) has been demonstrated using two cavity modes realized in a GaAs/AlAs coupled multilayer cavity structure in which two GaAs half-wavelength cavity layers are coupled by an intermediate distributed Bragg reflector multilayer. The coupled multilayer cavity structure was grown on a (113)B GaAs substrate by molecular beam epitaxy. Two cavity modes with an optical frequency difference of 3.3 THz were clearly observed at 1514 and 1540 nm in the optical reflection spectrum. The room-temperature SFG and second-harmonic generation (SHG) signals were measured by the simultaneous excitation of two cavity modes using 100 fs laser pulses. The peak intensity of the SFG signal was more than 400 times larger than that of the SHG signal from a (113)B GaAs substrate alone, indicating that the effective second-order nonlinearity of GaAs was strongly enhanced by the cavity effect.