Sum Frequency Generation Research Articles

Interfacial molecular structure and orientation evolution of the polystyrene under confinement during annealing revealed by sum frequency generation vibrational spectroscopy

The geometrical confinement directly affects many crucial properties of polymer thin films by interfacial interactions. A key to understanding the role of these interfacial interactions is to specifically probe the confined interface at the molecular level and in situ. However, the direct and nondestructive detection of interfacial polymer structures under confinement is very difficult. In this study, specific interface-sensitive sum frequency generation (SFG) spectroscopy was applied to study the deuterated PS (d8-PS) film confined between hydrogenated poly (methyl methacrylate) (PMMA) films at the molecular level and in situ. The results showed that the ordering/orientation of the PS chain (backbone and phenyl group) evolved at the buried d8-PS/PMMA interface during annealing. The tilt angle of the PS phenyl group increased while the twist angle decreased with elevated annealing temperature. Both overall SFG ssp and ppp intensities decreased after annealing at 433 K for 24 h, indicating that PS chains entangled with or penetrated the PMMA chains at the confined interface. This study qualitatively and quantitatively revealed the interfacial structure and structural evolution of the PS chain confined between PMMA films in situ during annealing, which is beneficial to the molecular-level understanding of the interfacial chain conformational relaxation of polymers under confinement.

Physicochemical control of solvation and molecular assembly of charged amphiphilic oligomers at air-aqueous interfaces

Hypothesis: Understanding the rules that control the assembly of nanostructured soft materials at interfaces is central to many applications. We hypothesize that electrolytes can be used to alter the hydration shell of amphiphilic oligomers at the air-aqueous interface of Langmuir films, thereby providing a means to control the formation of emergent nanostructures.Experiments: Three representative salts – (NaF, NaCl, NaSCN) were studied for mediating the self-assembly of oligodimethylsiloxane methylimidazolium (ODMS-MIM+) amphiphiles in Langmuir films. The effects of the different salts on the nanostructure assembly of these films were probed using vibrational sum frequency generation (SFG) spectroscopy and Langmuir trough techniques. Experimental data were supported by atomistic molecular dynamic simulations.Findings: Langmuir trough surface pressure – area isotherms suggested a surprising effect on oligomer assembly, whereby the presence of anions affects the stability of the interfacial layer irrespective of their surface propensities. In contrast, SFG results implied a strong anion effect that parallels the surface activity of anions. These seemingly contradictory trends are explained by anion driven tail dehydration resulting in increasingly heterogeneous systems with entangled ODMS tails and appreciable anion penetration into the complex interfacial layer comprised of headgroups, tails, and interfacial water molecules. These findings provide physical and chemical insight for tuning a wide range of interfacial assemblies.

GMP affected assembly behaviors of phosphatidylethanolamine monolayers elucidated by multi-resolved SFG-VS and BAM

The interaction between nucleotide molecules and lipid molecules plays important roles in cell activities, but the molecular mechanism is very elusive. In the present study, a small but noticeable interaction between the negatively charged phosphatidylethanolamine (PE) and Guanosine monophosphate (GMP) molecules was observed from the PE monolayer at the air/water interface. As shown by the sum frequency generation (SFG) spectra and Pi-A isotherm of the PE monolayer, the interaction between the PE and GMP molecules imposes very small changes to the PE molecules. However, the Brewster angle microscopy (BAM) technique revealed that the assembly conformations of PE molecules are significantly changed by the adsorption of GMP molecules. By comparing the SFG spectra of PE monolayers after the adsorption of GMP, guanosine and guanine, it is also shown that the hydrogen bonding effect plays an important role in the nucleotide-PE interactions. These results provide fundamental insight into the structure changes during the nucleotide-lipid interaction, which may shed light on the molecular mechanism of viral infection, DNA drug delivery, and cell membrane curvature control in the brain or neurons.

Sum rule comparison of narrowband and broadband sum frequency generation spectra and comparison with theory

Earlier sum frequency generation (SFG) experiments involve one infrared and one visible laser, and a measurement of the intensity of the response, yielding data on the surface sensitive properties of the sample. Recently, both the real and imaginary components of the susceptibility were measured in two different sets of experiments. In one set, a broadband infrared laser was used, permitting observations at very short times, while in another set the infrared laser was narrowband, permitting higher spectral resolution. The differences in the spectrum obtained by the two will be most evident in studying narrow absorption bands, e.g., the band due to dangling OH bonds at a water interface. The direct comparisons in the integrated amplitude (sum rule) of the imaginary part of the dangling OH bond region differ by a factor of 3. Due to variations in experimental setup and data processing, corrections were made for the quartz reference, Fresnel factors, and the incident visible laser wavelength. After the corrections, the agreement differs now by the factors of 1.1 within broadband and narrowband groups and the two groups now differ by a factor of 1.5. The 1.5 factor may arise from the extra heating of the more powerful broadband laser system on the water surface. The convolution from the narrowband SFG spectrum to the broadband SFG spectrum is also investigated and it does not affect the sum rule. Theory and narrowband experiments are compared using the sum rule and agree to a factor of 1.3 with no adjustable parameters.

Optimal vector phase-matching conditions in biaxial crystalline materials determined by the extreme surfaces method: the case of orthorhombic crystals

The optimal geometries of vector phase matching are determined for the cases of second harmonic generation, sum frequency generation, and difference frequency generation in a number of orthorhombic nonlinear optical crystals: KTP, KTA, KB5, KNbO3, LBO, CBO, and LRB4. The extreme surface method was used to define the wave vector directions of highest possible generation efficiency. As shown, in a significant number of cases vector phase matching ensures higher efficiencies than the scalar one.

Cholesterol Changes Interfacial Water Alignment in Model Cell Membranes.

The nanoscopic layer of water that directly hydrates biological membranes plays a critical role in maintaining the cell structure, regulating biochemical processes, and managing intermolecular interactions at the membrane interface. Therefore, comprehending the membrane structure, including its hydration, is essential for understanding the chemistry of life. While cholesterol is a fundamental lipid molecule in mammalian cells, influencing both the structure and dynamics of cell membranes, its impact on the structure of interfacial water has remained unknown. We used surface-specific vibrational sum-frequency generation spectroscopy to study the effect of cholesterol on the structure and hydration of monolayers of the lipids 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), and egg sphingomyelin (SM). We found that for the unsaturated lipid DOPC, cholesterol intercalates in the membrane without significantly changing the orientation of the lipid tails and the orientation of the water molecules hydrating the headgroups of DOPC. In contrast, for the saturated lipids DPPC and SM, the addition of cholesterol leads to clearly enhanced packing and ordering of the hydrophobic tails. It is also observed that the orientation of the water hydrating the lipid headgroups is enhanced upon the addition of cholesterol. These results are important because the orientation of interfacial water molecules influences the cell membranes' dipole potential and the strength and specificity of interactions between cell membranes and peripheral proteins and other biomolecules. The lipid nature-dependent role of cholesterol in altering the arrangement of interfacial water molecules offers a fresh perspective on domain-selective cellular processes, such as protein binding.

Characterization of Buried Interfaces of Silicone Materials in Situ to Understand Their Fouling-Release, Antifouling, and Adhesion Properties.

Poly(dimethylsiloxane) (PDMS) has numerous excellent properties and is extensively used as the main component of many silicone products in a variety of research fields and practical applications such as biomedical materials, aviation, construction, electronic devices, and automobiles. Interfacial structures of PDMS and other components in silicone systems are important for such research and applications. It is difficult to probe interfacial molecular structures of buried solid-liquid and solid-solid interfaces of silicone materials due to the lack of appropriate analytical tools. In this feature article, we presented our research on elucidating the molecular structures of PDMS as well as other additives in silicone samples at buried interfaces in situ at the molecular level using a nonlinear optical spectroscopic technique, sum frequency generation (SFG) vibrational spectroscopy. SFG was applied to study various PDMS surfaces in liquid environments to understand their fouling-release and antifouling activities. SFG has also been used to study buried solid-solid interfaces between silicone adhesives and polymers, elucidating the molecular adhesion mechanisms. Our SFG studies provide important knowledge on interfacial structure-function relationships of silicone materials, helping the design and development of silicone materials with improved properties through optimization of silicone interfacial structures.

The Role of Sum-Frequency Generation Spectroscopy in Understanding On-Surface Reactions and Dynamics in Atmospheric Model-Systems.

Surfaces, both water/air and solid/water, play an important role in mediating a multitude of processes central to atmospheric chemistry, particularly in the aerosol phase. However, the study of both static and dynamic properties of surfaces is highly challenging from an experimental standpoint, leading to a lack of molecular level information about the processes that take place at these systems and how they differ from bulk. One of the few techniques that has been able to capture ultrafast surface phenomena is time-resolved sum-frequency generation (SFG) spectroscopy. Since it is both surface-specific and chemically sensitive, the extension of this spectroscopic technique to the time domain makes it possible to study dynamic processes on the femtosecond time scale. In this Perspective, we will explore recent advances made in the field both in terms of studying energy dissipation as well as chemical reactions and the role the surface geometry plays in these processes.

Analytical solution to second-harmonic generation of ultrashort laser pulse

We present an analytical method to evaluate the second-harmonic generation (SHG) process of ultrashort laser pulses in a nonlinear medium within the small-signal regime. Building upon the broadband nonlinear coupled wave theory, we derive an analytical solution that allows one to investigate the fundamental physics and detailed dynamics of the nonlinear interaction between ultrashort laser pulses. We find that SHG for ultrashort laser pulses in a nonlinear crystal arises from a series of self-SHG and self sum-frequency generation processes involving different frequency components. We have applied the analytical method to investigate specific pulse profiles with Gaussian and sech functions and found good agreement between analytical theory and numerical simulations, validating the accuracy of the analytical approach. The analytical method enables one to explore the evolution of the second-harmonic wave under various pulse profiles, pulse widths, and crystal thicknesses, and offers a more efficient and insightful approach to study the nonlinear optical dynamics of ultrashort laser pulses.

Protein-Mediated Changes in Membrane Fluidity and Ordering: Insights into the Molecular Mechanism and Implications for Cellular Function.

Probing protein-membrane interactions is vital for understanding biological functionality for various applications such as drug development, targeted drug delivery, and creation of functional biomaterials for medical and industrial purposes. In this study, we have investigated interaction of Human Serum Albumin (HSA) with two different lipids, dipalmitoylphosphatidylglycerol (dDPPG) and dipalmitoylphosphatidylcholine (dDPPC), using Vibrational Sum Frequency Generation spectroscopy at different membrane fluidity values. In the liquid-expanded (LE) state of the lipid, HSA (at pH 3.5) deeply intercalated lipid chains through a combination of electrostatic and hydrophobic interactions, which resulted in more ordering of the lipid chains. However, in the liquid-condensed (LC) state, protein intercalation is decreased due to tighter lipid packing. Moreover, our findings revealed distinct differences in HSA's interaction with dDPPG and dDPPC lipids. The interaction with dDPPC remained relatively weak compared to dDPPG. These results shed light on the significance of protein mediated changes in lipid characteristics, which hold considerable implications for understanding membrane protein behavior, lipid-mediated cellular processes, and lipid-based biomaterial design.

Probing Interfacial Aging of Model Adhesion Joints under a Hygrothermal Environment at a Molecular Level.

Generally, for adhesive joints, the polar water molecules in humid environments can have a critical effect on the interfacial structures and structural evolution adjacent to the solid substrates. Regarding this, it is still a big challenge to detect and understand the interfacial hygrothermal aging process at the molecular level in real time and in situ. In this study, to trace the interfacial hygrothermal aging process of a classical epoxy formula containing diglycidyl ether of biphenyl A (DGEBA) and 2,2'-(ethylenedioxy) diethylamine (EDDA) with sapphire and fused silica in a typical hygrothermal environment (85 °C and 85% RH), sum frequency generation (SFG) vibrational spectroscopy was used to probe the molecular-level interfacial structural change over the time. The structural evolution dynamics at the buried epoxy/sapphire and epoxy/silica interfaces upon hygrothermal aging were revealed directly in situ. The interfacial delamination during hygrothermal aging was also elucidated from the molecular level. Upon hygrothermal aging, the interfacial CH signals, such as the ones from methyl, methylene, and phenyl groups, decreased significantly and the water OH signals increased substantially, indicating the water molecules had diffused into the interfaces and destroyed the original interactions between the epoxy formula and the substrates. Further analysis indicates that when the integrated signals in the CH range declined to their minimum and leveled off, the interfacial delamination happened. The tensile experiment proved the validity of these spectroscopic experimental results. Our study provides first-hand and molecular-level evidence on a direct correlation between the diffusion of the surrounding water molecules into the interface and the evolution/destruction of the interfacial structures during hygrothermal aging. More importantly, it is proved, SFG can be developed into a powerful tool to noninvasively reveal the local interfacial delamination in real time and in situ under extreme hygrothermal conditions, complemented by the mechanic test.

Spiral packing and chiral selectivity in model membranes probed by phase-resolved sum-frequency generation microscopy

Since the lipid raft model was developed at the end of the last century, it became clear that the specific molecular arrangements of phospholipid assemblies within a membrane have profound implications in a vast range of physiological functions. Studies of such condensed lipid islands in model systems using fluorescence and Brewster angle microscopies have shown a wide range of sizes and morphologies, with suggestions of substantial in-plane molecular anisotropy and mesoscopic structural chirality. Whilst these variations can significantly alter many membrane properties including its fluidity, permeability and molecular recognition, the details of the in-plane molecular orientations underlying these traits remain largely unknown. Here, we use phase-resolved sum-frequency generation microscopy on model membranes of mixed chirality phospholipid monolayers to fully determine the three-dimensional molecular structure of the constituent micron-scale condensed domains. We find that the domains possess curved molecular directionality with spiralling mesoscopic packing, where both the molecular and spiral turning directions depend on the lipid chirality, but form structures clearly deviating from mirror symmetry for different enantiomeric mixtures. This demonstrates strong enantioselectivity in the domain growth process and indicates fundamental thermodynamic differences between homo- and heterochiral membranes, which may be relevant in the evolution of homochirality in all living organisms.

Heterodyne-Detected Sum-Frequency Generation Vibrational Spectroscopy Reveals Aqueous Molecular Structure at the Suspended Graphene/Water Interface.

Graphene, a transparent two-dimensional conductive material, has brought extensive new perspectives and prospects to various aqueous technological systems, such as desalination membranes, chemical sensors, energy storage, and energy conversion devices. Yet, the molecular-level details of graphene in contact with aqueous electrolytes, such as water orientation and hydrogen bond structure, remain elusive or controversial. Here, we employ surface-specific heterodyne-detected sum-frequency generation (HD-SFG) vibrational spectroscopy to re-examine the water molecular structure at a freely suspended graphene/water interface. We compare the response from the air/graphene/water system to that from the air/water interface. Our results indicate that the spectrum recorded from the air/graphene/water system arises from the topmost 1-2 water layers in contact with the graphene, with the graphene itself not generating a significant SFG response. Compared to the air/water interface response, the presence of monolayer graphene weakly affects the interfacial water. Graphene weakly affects the dangling O-H group, lowering its frequency through its interaction with the graphene sheet, and has a very small effect on the hydrogen-bonded O-H group. Molecular dynamics simulations confirm our experimental observation. Our work provides molecular insight into the interfacial structure at a suspended graphene/water interface, relevant to various technological applications of graphene.

Boosted Second Harmonic Generation and Cascaded Sum Frequency Generation from a Surface Crystallized Glass Ceramic Microcavity.

The development of novel materials and structures for efficient second-order nonlinear micro/nano devices remains a significant challenge. In this study, the remarkable enhancement of second-harmonic generation (SHG) and cascaded sum frequency generation in whispering gallery mode microspheres made of surface-crystallized glass with a 6-µm Ba2TiSi2O8 crystal layer are demonstrated. Attributed to the core-shell design, the Ba2TiSi2O8 located on the surface can be efficiently coupled with whispering gallery modes, resulting in a highly efficient micron-scale cavity-enhanced second-order optical nonlinearity. Greatly enhanced SHG of the microcavity is observed, which is up to 80 times stronger than that of a non-resonant sample. Furthermore, owing to the wavelength non-selectivity of random quasi-phase matching, ultra-wideband SHG with a strong response ranging from 860 to 1600nm and high-contrast polarization characteristics is demonstrated. The glass-ceramic-based microsphere cavity also boosts the cascading optical nonlinearity, manifested by a two-magnitude enhancement of cascaded sum frequency generation. This work delineates an efficient strategy for boosting nonlinear optical response in glass ceramics, which will open up new opportunities for applications in photonics and optical communications.

Charge Transfer Dynamics in Organic-Inorganic Hybrid Heterostructures-Insights by Vibrational-Sum Frequency Generation Spectroscopy.

Organic-inorganic heterostructures play a pivotal role in modern electronic and optoelectronic applications including photodetectors and field effect transistors, as well as in solar energy conversion such as photoelectrodes of dye-sensitized solar cells, photoelectrochemical cells, and in organic photovoltaics. To a large extent, performance of such devices is controlled by charge transfer dynamics at and across (inner) interfaces, e.g., between a wide band gap semiconductor and molecular sensitizers and/or catalysts. Hence, a detailed understanding of the structure-dynamics-function relationship of such functional interfaces is necessary to rationalize possible performance limitations of these materials and devices on a molecular level. Vibrational sum-frequency generation (VSFG) spectroscopy, as an interface-sensitive spectroscopic technique, allows to obtain chemically specific information from interfaces and combines such chemical insights with ultrafast time resolution, when integrated as a spectroscopic probe into a pump-probe scheme. Thus, this minireview discusses the advantages and potential of VSFG spectroscopy for investigating interfacial charge transfer dynamics and structural changes at inner interfaces. A critical perspective of the unique spectroscopic view of otherwise inaccessible interfaces is presented, which we hope opens new opportunities for an improved understanding of function-determining processes in complex materials, and brings together communities who are devoted to designing materials and devices with spectroscopists.

Sum and difference frequency generation in a valley-photonic-crystal-like topological system

Nonlinear sum frequency generation (SFG) and difference frequency generation (DFG) are fundamental methods to obtain new light sources for various applications. However, most of the on-chip SFG and DFG are based on conventional resonators, lacking robustness against fabrication defects. Here, we demonstrate topologically protected SFG and DFG in a second-order topological photonic system. The mechanism is based on the nonlinear interaction between three high-Q corner modes inside dual topological band gaps. The frequency matching condition for SFG and DFG is precisely satisfied by designing a valley-photonic-crystal-like topological system, which provides more freedoms to tune the corner modes. The topological SFG and DFG are achieved with high conversion efficiency, and the underlying topological physics is revealed. This work opens up avenues toward topologically protected nonlinear frequency conversion, and can find applications in the fields of on-chip single-photon detections and optical quantum memories with robustness against defects.

Highly efficient continuous-wave solid-state Raman crystal lasers at 555 and 559 nm

High-power efficient continuous-wave Nd:YVO4/KGW Raman lasers at 555 and 559 nm are achieved by using a double-sided dichroic coating output coupler to improve the resonance quality factor. The Np-cut potassium gadolinium tungstate (KGW) is used to generate the Stokes waves at 1159 and 1177 nm by placing the polarization of the1064 nm fundamental wave parallel to the Ng and Nm axes, respectively. The lithium triborate (LBO) crystal with the cut angle in the XY plane for the type-I phase matching is used to perform the intracavity sum frequency generation for yielding the green light at 555 nm and the lime light at 559 nm at the optimal phase matching temperature. Experimental results were systematically accomplished to comprehend the optimal cavity length for the conversion efficiency. Under the optimal cavity length, the output powers can reach 6.6 and 6.3 W at a pump power of 22 W for the wavelengths of 555 and 559 nm, respectively. The conversion efficiencies can be up to 30% and 28.6% for 555 and 559 nm, respectively.

Compact efficient high-power continuous-wave Nd:YVO4/KGW/LBO Raman lasers for selectable wavelengths within 559-603 nm

Compact efficient high-power continuous-wave Nd:YVO4 Raman lasers for selectable wavelengths within 559-603 nm are achieved by using KGW crystal for intracavity stimulated Raman scattering (SRS) and lithium triborate (LBO) crystal for intracavity sum frequency generation (SFG) and second harmonic generation (SHG). The LBO crystal with the cut angle in the XY plane for the type-I phase matching is used to perform intracavity SHG or SFG. Experimental results reveal that the participated Stokes lines include the internal vibration mode at 901 cm-1, the external vibrational mode at 209 cm-1, and the combination mode of the 901 cm-1 and 209 cm-1 Raman shifts. By tuning LBO temperature for attaining the maximum output power, the output spectrum reveals the triple peaks of 588.7, 595.7, and 603.1 nm with the intensity ratio of 10:4:1. Under this circumstance, the output power can reach the highest value of 10.8 W at a pump power of 40 W. Furthermore, the output spectrum can be simply concentrated on the single peaks among 588.7 (orange), 565.7 (yellow), and 559.1 nm (lime) by tuning LBO temperature to fulfill the selection of the critical phase matching. The output powers at a pump power of 40 W can be up to 8.0, 6.1, and 9.8 W for the single-peak emission at 588.7, 565.7, and 559.1 nm, respectively. Finally, a dual-peak emission of 565.7 and 572.3 nm with total output power of 5.2 W can be generated by tuning LBO temperature to match the SFG for 572.3 nm.

Van der Waals Decoration of Ultra-High-Q Silica Microcavities for χ(2)-χ(3) Hybrid Nonlinear Photonics.

Optical nonlinear processes are indispensable in a wide range of applications, including ultrafast lasers, microscopy, and quantum information technologies. Among the diverse nonlinear processes, second-order effects usually overwhelm the higher-order ones, except in centrosymmetric systems, where the second-order susceptibility vanishes to allow the use of the third-order nonlinearity. Here we demonstrate a hybrid photonic platform whereby the balance between second- and third-order susceptibilities can be tuned flexibly. By decorating ultra-high-Q silica microcavities with atomically thin tungsten diselenide, we observe cavity-enhanced second-harmonic generation and sum-frequency generation with continuous-wave excitation at a power level of only a few hundred microwatts. We show that the coexistence of second- and third-order nonlinearities in a single device can be achieved by carefully choosing the size and location of the two-dimensional material. Our approach can be generalized to other types of cavities, unlocking the potential of hybrid systems with controlled nonlinear susceptibilities for novel applications.

Working on a dream: bringing up the level of interface spectroscopy to the bulk level

Abstract Liquid interfaces are unique environments in which a variety of fundamental phenomena occur. Therefore, it is important to obtain a molecular-level understanding of liquid interfaces for both basic science and industrial applications. However, it is not an easy task to investigate molecules in the interface region that only has nanometer thicknesses. Second-order nonlinear spectroscopy, or even-order nonlinear spectroscopy more generally, is intrinsically interface-selective because the relevant nonlinear signal is generated only in the region in which the inversion symmetry is broken under the dipole approximation. In the past 2 decades, we have been developing and applying new interface nonlinear spectroscopic methods, aiming to bring up the level of knowledge on interfacial molecules to that on molecules in solution. During this attempt, we developed electronic sum-frequency generation spectroscopy, heterodyne-detected electronic sum-frequency generation spectroscopy, and heterodyne-detected vibrational sum-frequency generation spectroscopy, as well as fourth-order Raman spectroscopy. We also extended the methods to femtosecond time-resolved measurements. Using these methods, we are now able to study the structure and dynamics at liquid interfaces, in particular exposed interfaces such as air/liquid interfaces, at a similar level to the study for solution. I overview our interface research while describing thoughts we had at each turning point.