Broadband Sum-frequency Generation Research Articles

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.

Broadband Sum-Frequency Generation of a CO Laser in Antireflection-Coated and Uncoated ZnGeP2 Crystals

Broadband Sum-Frequency Generation of a CO Laser in Antireflection-Coated and Uncoated ZnGeP2 Crystals

Comparison of modified molecules 3-aminopropyltriethoxysilane and 11-aminoundecyltriethoxysilane in orientation angle and interaction with protein by sum frequency vibration spectrum and imaging ellipsometry biosensor

3-Aminopropyltriethoxysilane (APTES) has been widely used in biosensing as a surface-modifying molecule that acts as a bridge. The orientation and structure of APTES at the interface are major factors that affect biosensing efficiency. IgG (immunoglobulin G) is the most used and one of the most abundant immune proteins in the serum. We not only used broadband sum frequency generation vibrational spectroscopy to compare the spectrum of APTES and 11-aminoundecyltriethoxysilane (AUTES) molecules modified on a Si (111) surface but also compared the number and sensitivity of IgG adhered on APTES and AUTES surfaces by the imaging ellipsometry biosensor. We first found that the terminal amino groups of the APTES molecule were disorderly arranged by Sum frequency vibration spectrum (SFVS). Then we compared the performance of IgG immobilization in APTES or AUTES surfaces by imaging ellipsometry biosensor (IEB). In IEB, the anti-IgG detection LOD (limit of detection) on the APTES-modified surface(51 ng/mL) was higher than that on the AUTES-modified surface(380 ng/mL). We explored the relationship between the stability of aminosilane and the stability of biomolecules, and provided a reference for the selection of surface modification methods using aminosilane as a self-assembled membrane.

Broadband yellow-orange light generation based on a step-chirped PPMgLN ridge waveguide.

Yellow-orange lights, valuable in photodynamic therapies, spectroscopy, and optogenetics, are limited by the narrow bandwidth and bulky setup via the conventional Raman or optical parametric oscillation processes. Moreover, flatness in the broad-band spectrum is also important for the aforementioned applications with extended functions. In this paper, by carefully designing grating-periods of a step-chirped PPMgLN ridge waveguide for sum frequency generation (SFG), we report a compact broad-band yellow-orange light with bandwidth of 5.6 nm and an un-reported flatness (<1.5 dB). Correspondingly, the optical conversion efficiency is 232.08%/W, which is the best SFG efficiency for PPMgLN at the yellow-orange region, to the best of our knowledge. The results could also be adopted for other broad-band SFG process toward the vis-infrared region in an integrated structure.

Mechanism by Which Cholesterol Induces Sphingomyelin Conformational Changes at an Air/Water Interface.

This work investigates the interactions in cholesterol and sphingomyelin monolayers at the molecular level by high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The SFG spectra of natural egg sphingomyelin (ESM) as a function of cholesterol concentration are obtained at an air/water interface under different polarization combinations. The analysis of the spectra shows that cholesterol can induce sphingomyelin conformational changes at an air/water interface. The mechanism is proposed. When cholesterol is inserted into the ESM monolayer, the inherent intramolecular hydrogen bonds between the phosphate moiety and 3OH in the sphingosine backbones are destroyed. During this process, the sphingosine backbones become more ordered, while the conformation of the N-linked long acid chain remains unaltered. The OH of the cholesterol head group can bind to the -PO-2 of the ESM molecule, and the orientation of the -PO-2 in the head groups changes to be more parallel to the interface.

Investigating Bénard-Marangoni migration at the air-water interface in the time domain using sum frequency generation (SFG) spectroscopy of palmitic acid monolayers.

Sum-frequency generation (SFG) spectroscopy is frequently used to investigate the structure of monolayer films of long-chain fatty acids at the air-water interface. Although labeled a non-invasive technique, introducing intense SFG lasers onto liquid interfaces has the potential to perturb them. In the present work, narrowband picosecond SFG is used to study the structural changes that occur in palmitic acid and per-deuterated palmitic acid monolayers at the air-water interface in response to the high field strengths inherent to SFG spectroscopy. In order to determine structural changes and identify measurement artifacts, the changes in specific resonance intensities were measured in real-time and over a broad range of surface concentrations from films spread onto a stationary Langmuir trough. Using narrowband instead of broadband SFG minimizes the overlap of the incident infrared beam in the lipid C-H stretching region with resonances from the water sub-phase. Nevertheless, narrowband SFG still generates a thermal gradient at the surface, which produces a significant decrease in local concentration in the area of the laser spot caused by Bérnard-Marangoni convection originating in the sub-phase. The decrease in concentration results in an increase in the conformational disorder and a decrease in the tilt angle of lipid tails. Crucially, it is shown that, even at the highest monolayer concentrations, this gives rise to a measurement effect, which manifests itself as a dependence on the spectral acquisition time. This effect should be taken into account when interpreting the structure of monolayer films on liquid surfaces deduced from their SFG spectra.

Observing Two-Dimensional Spontaneous Reaction between a Silicon Electrode and a LiPF6-Based Electrolyte In Situ and in Real Time.

Two-dimensional spontaneous reactions between an electrode and an electrolyte are very important for the formation of a solid electrolyte interphase (SEI) but difficult to study because studying such reactions requires surface/interface sensitive techniques with sufficiently structural and temporal resolutions. In this study, we have applied femtosecond broadband sum-frequency generation vibrational spectroscopy (SFG-VS) to investigate the interaction between a silicon electrode and a LiPF6-based diethyl carbonate electrolyte solution in situ and in real time. We found that two kinds of diethyl carbonate species are present on the silicon surface and their C═O stretching aligns in opposite directions. Intrinsically spontaneous chemical reactions between silicon electrodes and a LiPF6 electrolyte solution are observed. The reactions generate silicon hydride and cause corrosion of the silicon electrodes. Coating of the silicon surface with a poly(vinyl alcohol) layer can effectively retard and attenuate these reactions. This work demonstrates that SFG-VS can provide a unique and powerful state-of-the-art tool for elucidating the molecular mechanisms of SEI formation.

Protein–water coupling tunes the anharmonicity of amide I modes in the interfacial membrane-bound proteins

The diagonal anharmonicity of an amide I mode of protein backbones plays a critical role in a protein's vibrational dynamics and energy transfer. However, this anharmonicity of long-chain peptides and proteins in H2O environment is still lacking. Here, we investigate the anharmonicity of the amide I band of proteins at the lipid membrane/H2O interface using a surface-sensitive pump-probe setup in which a femtosecond infrared pump is followed by a femtosecond broadband sum frequency generation vibrational spectroscopy probe. It is found that the anharmonicity of the amide I mode in ideal α-helical and β-sheet structures at hydrophobic environments is 3-4cm-1, indicating that the amide I mode in ideal α-helical and β-sheet structures is delocalized over eight peptide bonds. The anharmonicity increases as the bandwidth of the amide I mode increases due to the exposure of peptide bonds to H2O. More H2O exposure amounts lead to a larger anharmonicity. The amide I mode of the peptides with large H2O exposure amounts is localized in one to two peptide bonds. Our finding reveals that the coupling between the amide I mode and the H2O bending mode does not facilitate the delocalization of the amide I mode along the peptide chain, highlighting the impact of H2O on energy transfer and structural dynamics of proteins.

Surface Chemistry during Atomic Layer Deposition of Pt Studied with Vibrational Sum-Frequency Generation.

A detailed understanding of the growth of noble metals by atomic layer deposition (ALD) is key for various applications of these materials in catalysis and nanoelectronics. The Pt ALD process using MeCpPtMe3 and O2 gas as reactants serves as a model system for the ALD processes of noble metals in general. The surface chemistry of this process was studied by in situ vibrational broadband sum-frequency generation (BB-SFG) spectroscopy, and the results are placed in the context of a literature overview of the reaction mechanism. The BB-SFG experiments provided direct evidence for the presence of CH3 groups on the Pt surface after precursor chemisorption at 250 °C. Strong evidence was found for the presence of a C=C containing complex (e.g., the form of Cp species) and for partial dehydrogenation of the surface species during the precursor half-cycle. The reaction kinetics of the precursor half-cycle were followed at 250 °C, showing that the C=C coverage saturated before the saturation of CH3. This complex behavior points to the competition of multiple surface reactions, also reflected in the temperature dependence of the reaction mechanism. The CH3 saturation coverage decreased significantly with temperature, while the C=C coverage remained constant after precursor chemisorption on the Pt surface for temperatures from 80 to 300 °C. These SFG results have resulted in a better understanding of the Pt ALD process and also highlight the surface chemistry during thin-film growth as a promising field of study for the BB-SFG community.

Thickness-dependent IR distortion from bulk absorption and refraction and its effects on broadband sum frequency generation spectroscopy

In the characterization of buried interfaces with sum frequency generation spectroscopy (SFG), the bulk thickness-dependent IR distortion effects on delay-dependent SFG spectra were identified: Around time zero, the SFG signal intensity reduced with the film thickness increasing while the overall spectral shape sustained; at positive time delays, bulk refraction ruled, and the distorted SFG spectral shape showed similar features as resonant SFG bands of surface molecular species. Both linear and nonlinear refraction effects were observed based on the delay-dependent and film thickness-dependent results. These results provide useful implications for spectral interpretation for in situ SFG spectroscopy of buried interfaces.

Potential and time dependent broad band sum frequency generation spectroscopic study on electrochemical oxidation of adsorbed CO on Pt(1 1 1) electrode surface in pre-peak region in alkaline solution

• SFG spectra of adsorbed CO on Pt(111) showed on-top peak in HClO 4 and NaOH solutions. • The on-top SFG peak totally disappeared in pre-peak region in NaOH solution. • The on-top SFG peak totally disappeared in the main peak region in HClO 4 solution. • Adsorbed CO was oxidized by reacting with OH − in solution via Eley-Rideal mechanism. • SFG inactive adsorbed CO was oxidized in the main peak region in NaOH solution. In situ broad band sum frequency generation (SFG) spectroscopy was applied to clarify the oxidation mechanism of adsorbed CO on Pt(1 1 1) electrode in alkaline solution in comparison with that in acidic solution. A single SFG peak due to CO adsorbed on-top site of Pt(1 1 1) was observed in the region of 1950 – 2150 cm −1 . While oxidation of adsorbed CO proceeded in a nucleation-growth mode via Langmuir–Hinshelwood (L-H) mechanism by reacting with adsorbed OH in the main peak region in 0.1 M HClO 4 solution, adsorbed CO was oxidized in a random oxidation model via Eley-Rideal (E-R) mechanism by reacting with OH − in the solution in the pre-peak region in 0.1 M NaOH solution. The main anodic peak was still observed even after the SFG peak due to on-top CO was totally disappeared by anodic oxidation in the pre-peak region, showing there existed SFG inactive adsorbed CO, although its structure was not clear.

Broadband sum frequency generation spectroscopy of dark exciton states in hBN-encapsulated monolayer WSe2

We demonstrate that broadband sum frequency generation (SFG) spectroscopy based on a partially incoherent supercontinuum light source can elucidate dark p-series excitons in monolayer WSe2 encapsulated between hexagonal boron nitride (hBN) slabs. The observed 2p exciton peak energy is a few meV higher than that predicted by the Rytova-Keldysh potential model, which is originated from the Berry phase effect. Interestingly, although the radiative relaxation of the 2p exciton is weaker, the 2p exciton peak is broader than the 1s and 2s peaks, which indicates its faster dephasing than the 1s and 2s excitons. Measuring the excitation intensity and temperature dependence, we clarified that this broader linewidth is not caused by excitation- or phonon-induced dephasing, but rather by exciton-electron scattering.

Broadband sum-frequency generation of spectrally incoherent pulses.

We study and demonstrate the nonlinear frequency conversion of broadband optical pulses from 1053 nm to 351 nm using sum-frequency generation with a narrowband pulse at 526.5 nm. The combination of angular dispersion and noncollinearity cancels out the wave-vector mismatch and its frequency derivative, yielding an order-of-magnitude increase in spectral acceptance compared to conventional tripling. This scheme can support the nonlinear frequency conversion of broadband spectrally incoherent nanosecond pulses generated by high-energy lasers and optical parametric amplifiers to mitigate laser-plasma instabilities occurring during interaction with a target. The experimental results obtained with KDP crystals are in excellent agreement with modeling, demonstrating the generation of spectrally incoherent pulses with a bandwidth larger than 10 THz at 351 nm.

Conformational disorder of organic cations tunes the charge carrier mobility in two-dimensional organic-inorganic perovskites

The chemical nature of the organic cations governs the optoelectronic properties of two-dimensional organic-inorganic perovskites. But its mechanism is not fully understood. Here, we apply femtosecond broadband sum frequency generation vibrational spectroscopy to investigate the molecular conformation of spacer organic cations in two-dimensional organic-inorganic perovskite films and establish a correlation among the conformation of the organic cations, the charge carrier mobility, and broadband emission. Our study indicates that both the mobility and broadband emission show strong dependence on the molecular conformational order of organic cations. The gauche defect and local chain distortion of organic cations are the structural origin of the in-plane mobility reduction and broad emission in two-dimensional organic-inorganic perovskites. Both of the interlayer distance and the conformational order of the organic cations affect the out-of-plane mobility. This work provides molecular-level understanding of the conformation of organic cations in optimizing the optoelectronic properties of two-dimensional organic-inorganic perovskites.

Direct visualization of phase-matched efficient second harmonic and broadband sum frequency generation in hybrid plasmonic nanostructures

Second harmonic generation and sum frequency generation (SHG and SFG) provide effective means to realize coherent light at desired frequencies when lasing is not easily achievable. They have found applications from sensing to quantum optics and are of particular interest for integrated photonics at communication wavelengths. Decreasing the footprints of nonlinear components while maintaining their high up-conversion efficiency remains a challenge in the miniaturization of integrated photonics. Here we explore lithographically defined AlGaInP nano(micro)structures/Al2O3/Ag as a versatile platform to achieve efficient SHG/SFG in both waveguide and resonant cavity configurations in both narrow- and broadband infrared (IR) wavelength regimes (1300–1600 nm). The effective excitation of highly confined hybrid plasmonic modes at fundamental wavelengths allows efficient SHG/SFG to be achieved in a waveguide of a cross-section of 113 nm × 250 nm, with a mode area on the deep subwavelength scale (λ2/135) at fundamental wavelengths. Remarkably, we demonstrate direct visualization of SHG/SFG phase-matching evolution in the waveguides. This together with mode analysis highlights the origin of the improved SHG/SFG efficiency. We also demonstrate strongly enhanced SFG with a broadband IR source by exploiting multiple coherent SFG processes on 1 µm diameter AlGaInP disks/Al2O3/Ag with a conversion efficiency of 14.8% MW−1 which is five times the SHG value using the narrowband IR source. In both configurations, the hybrid plasmonic structures exhibit >1000 enhancement in the nonlinear conversion efficiency compared to their photonic counterparts. Our results manifest the potential of developing such nanoscale hybrid plasmonic devices for state-of-the-art on-chip nonlinear optics applications.

Green-Yellow-Orange-Red Spectral Range with Sum-Frequency Generation Using BIBO Crystal Pumped with an Optical Parametric Amplifier

In this letter, we show the broadband sum-frequency generation (SFG) in the Green-Yellow-Orange-Red spectral range using bismuth triborate, BiB3O6 crystal (BIBO) as a nonlinear material. We perform a noncollinear phase-matching configuration within the BIBO crystal using the remaining light behind the second harmonic generation stage and the infrared idler of an optical parametric amplifier (OPA). The obtained mixing radiation of ultrafast light sources to generate femtosecond pulses across the 520.5 to 742.5 nm region is observed. The SFG spectrum from a single-pass cross-correlation intensity over such visible range is shown. The SFG wavelengths as a function of the tunable wavelength idler OPA agree with the expectations of the parametric conversion condition and open the door to practical multi-beam or multi-color sum-frequency generators.

Broadband second-harmonic and sum-frequency generation with a long-wave infrared laser in AgGaGe5Se12.

Using an 8 µm long-wave infrared laser as the fundamental wave, we achieved second-harmonic generation (SHG) and sum-frequency generation simultaneously in AgGaGe5Se12 and obtained a 4 µm laser output. Among them, SHG was achieved in the 173 nm spectral range of the fundamental wave, which was consistent with theoretical calculations. The average power of the obtained 4 µm laser was 41 mW, corresponding to an optical-to-optical conversion efficiency of 3.2%. The measured temperature acceptance bandwidth (LδT) (FWHM) was 50 K·cm; the angular acceptance bandwidth (Lδθ) (FWHM) was 13.3 mrad·cm; and the average absorption coefficient in the wavelength range of 0.86-11.30 µm was 0.07cm-1. In addition, the spectral acceptance bandwidth (Lδλ) of fundamental wave in AgGaGe5Se12 SHG and the spectral gain bandwidth of frequency downconversion in AgGaGe5Se12 were calculated. In view of the small absorption coefficient, the large temperature acceptance bandwidth, and the large spectral gain bandwidth, we conclude that AgGaGe5Se12 is a suitable nonlinear crystal for high-power short/mid/long-wave infrared lasers and frequency conversions of nanosecond-femtosecond infrared lasers. These results are conducive to the further development of AgGaGe5Se12 lasers.

Acidic Environment Significantly Alters Aggregation Pathway of Human Islet Amyloid Polypeptide at Negative Lipid Membrane.

The misfolding and aggregation of human islet amyloid polypeptide (hIAPP) at cell membrane has a close relationship with the development of type 2 diabetes (T2DM). This aggregation process is susceptible to various physiologically related factors, and systematic studies on condition-mediated hIAPP aggregation are therefore essential for a thorough understanding of the pathology of T2DM. In this study, we combined surface-sensitive amide I and amide II spectral signals from the protein backbone, generated simultaneously in a highly sensitive femtosecond broad-band sum frequency generation vibrational spectroscopy system, to examine the effect of environmental pH on the dynamical structural changes of hIAPP at membrane surface in situ and in real time. Such a combination can directly discriminate the formation of β-hairpin-like monomer and oligomer/fibril at the membrane surface. It is evident that, in an acidic milieu, hIAPP slows down its conformational evolution and alters its aggregation pathway, leading to the formation of off-pathway oligomers. When matured hIAPP aggregates are exposed to basic subphase, partial conversion from β-sheet oligomers into ordered β-sheet fibrillar structures is observed. When exposed to acidic environment, however, hIAPP fibrils partially converse into more loosely patterned β-sheet oligomeric structures.

Surface configuration of CO adsorbed on nanostructured Pt electrodes probed using broadband sum frequency generation spectroscopy.

Using broadband sum frequency generation (BB-SFG) spectroscopy, the effect of surface structure on the adsorption states of linearly bonded CO (COL) on a Pt electrode was thoroughly analyzed. Two overlapped SFG peaks with different linewidths and electrochemical Stark slopes were identified, which correspond to COL in different surface configurations.

Abnormal spectral bands in broadband sum frequency generation induced by bulk absorption and refraction.

In this paper, the time-resolved broadband sum frequency generation (BB-SFG) spectra from a bare Au surface with a distorted infrared (introduced with a 10 µm polyethylene film in the IR light path) and principal component generalized projection (PCGP) algorithm were used to investigate the bulk distortion on the measured BB-SFG spectra. Besides the SFG intensity reduction from the bulk absorption, the frequency dependent refraction of the bulk layer led to misleading SFG features at the positive delay times beyond the Au dephasing time. These results suggest that SFG spectroscopy is not entirely 'bulk-free' for the buried interfaces because of the bulk absorption and refraction of the incident pulses.