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The effect of para-substituents on the NC bond of aryl isocyanide molecules adsorbed on Au, Ag, Pt, and Pd surfaces was examined by vibrational sum frequency generation (VSFG) spectroscopy. The frequency of NC stretching vibration, υNC, depended on the electronic property of the substituents. When the substituents were more electron-withdrawing and more electron-donating, υNC shifted to lower and higher frequencies, respectively. However, υNC shifted to lower frequency again when the substituents were too electron-donating. The strong dependence of υNC on metal substrates was also observed, reflecting the difference in metal d-band energies, which leads to the difference in the contributions of σ-donation and π back-donation of the NC–metal coupling. [ABSTRACT FROM AUTHOR]

Yttria-stabilized zirconia (YSZ) is found in a wide range of applications, from solid-oxide fuel cells to medical devices and implants. A molecular-level understanding of the hydration of YSZ surfaces is essential for optimizing its performance and durability in these applications. Nevertheless, only a limited amount of literature is available about the surface hydration of YSZ single crystals. In this study, we employ surface-sensitive non-linear vibrational sum frequency generation spectroscopy to investigate the hydration of YSZ(100), (110), and (111) single crystal substrates under ambient laboratory conditions. Three types of hydroxyl groups were identified at all three YSZ–D2O interfaces: (i) hydroxyls on the metal sites of Zr or Y resulting from the dissociative chemisorption of water, (ii) hydroxyls from proton adsorption to O sites formed from water dissociation, and (iii) hydroxyl groups as part of the physisorbed water at the interface. [ABSTRACT FROM AUTHOR]

Polyethylene glycol (PEG) is a water soluble, non-ionic polymer with applications in drug delivery, protein precipitation, anti-biofouling, water-splitting, Li-ion batteries, and fuel cells. The interaction of PEG with water and electrolytes plays pivotal roles in such applications. Using interface-selective spectroscopy, heterodyne-detected vibrational sum frequency generation, and Raman difference spectroscopy with simultaneous curve fitting analysis, we show that water adopts different structures and orientations at the air/water–PEG interface, which depends on the molar mass of the PEG. At the air/water–PEG4000 (MW 4000u) interface, water is H-up oriented (i.e., water Hs are pointed away from the aqueous bulk) around 3200 cm−1 and H-down oriented (i.e., water Hs are pointed toward the aqueous bulk) around 3470 cm−1. Variation of the bulk concentration of PEG4000 does not change the dual orientation of interfacial water. The presence of an electrolyte (1.0M NaCl) selectively reduces the H-up oriented water without affecting the H-down oriented water at the air/water–PEG4000 interface. The selective reorganization of the interfacial water is assigned to the disruption of the asymmetric hydration around ether-oxygen of the surface-adsorbed PEG4000 by the Na+ ion of the electrolyte. Interestingly, in the case of low molar mass PEG (air/water–PEG200), the interfacial water neither shows the dual orientation nor is affected by 1.0M NaCl. [ABSTRACT FROM AUTHOR]

Aqueous interfaces containing organic/inorganic molecules are important in various biological, industrial, and atmospheric processes. So far, the study on the dynamics of interfacial molecules has been carried out with time-resolved vibrational sum-frequency generation (TR-VSFG) and time-resolved electronic sum-frequency generation (TR-ESFG) techniques. Although the ESFG probe is powerful for investigating interfacial photochemical dynamics of solute molecules by monitoring the electronic transition of transients or photoproducts at the interface, heterodyne detection is highly desirable for obtaining straightforward information, particularly in time-resolved measurements. So far, heterodyne detection has been realized only for TR-VSFG measurements but not for TR-ESFG measurements. In this paper, we report on femtosecond time-resolved heterodyne-detected ESFG (TR-HD-ESFG) spectroscopy for the first time. With TR-HD-ESFG developed, we measured the time-resolved electronic ΔImχ(2) spectra (pump-induced changes in the imaginary part of the second-order susceptibility) of a prototype dye, malachite green (MG), at the air/water interface. The obtained ΔImχ(2) spectra clearly show not only the ground-state bleach but also the excited-state band of MG at the air/water interface, demonstrating the high potential of TR-HD-ESFG as a new powerful tool to investigate ultrafast reaction dynamics at the interface. [ABSTRACT FROM AUTHOR]

The movements of molecules at interfaces and surfaces are restricted by their asymmetric environments, leading to anisotropic orientational motions. In this work, in-plane orientational motions of the –C=O and –CF3 groups of coumarin 153 (C153) at the air/water interface were measured using time-resolved (TR) vibrational sum frequency generation (SFG). The in-plane orientational time constants of the –C=O and –CF3 groups of C153 are found to be 41.5 ± 8.2 and 36.0 ± 4.5 ps. These values are over five-times faster than that of 198 ± 15 ps for the permanent dipole of the whole C153 molecule at the interface, which may indicate that the two groups experience different interfacial friction in the plane. These differences could also be the result of the permanent dipole of C153 being almost five times those of the –C=O and –CF3 groups. The difference in orientational motions reveals the microscopic heterogeneous environment that molecules experience at the interface. While the interfacial dynamics of the two functional groups are similar, our TR-SFG experiments allowed the quantification of the in-plane dynamics of individual functional groups for the first time. Our experimental findings about the interfacial molecular motion have implications for molecular rotations, energy transfer, and charge transfer at material interfaces, photocatalysis interfaces, and biological cell/membrane aqueous interfaces. [ABSTRACT FROM AUTHOR]

The responses of the N-alkyl diamine groups to variations in pH affect their conformations and surface activities, making them relevant to applications relying on interfacial interactions, such as controlled emulsification and mineral flotation. An in-depth understanding of interfacial self-assembly is crucial. Herein, a molecular-level study was performed to investigate the adsorption and self-assembly of N-dodecylpropane-1,3-diamine (DPDA) at the air–water (A/W) interface using sum frequency generation (SFG) spectroscopy and molecular dynamics (MD) simulations. The SFG spectra of DPDA, acquired under three pH conditions, suggest that the protonation of the DPDA diamine group influences the alkyl chain arrangement at a varying degree at the A/W interface. Analysis of the di-cationic DPDA SFG spectrum at a low pH showed fewer gauche defects at low concentration, as indicated by the relatively higher intensity ratio (ICH3SS/ICH2SS) of 18.1 ± 0.6. The density profiles from MD simulations at different surface areas per molecule and pH conditions, showing varying degrees of packing, support the observation of gauche defects in SFG. With MD simulation, the radial distribution factor for di-cationic species has the highest probability of forming hydrogen bonds compared to mono-cationic and non-ionic species. These g(r) probability results conform with observations obtained from SFG spectroscopy, where we observed a strong hydrogen bond interaction at low pH conditions with di-cationic species, forming tetrahedrally arranged water molecules at the A/W interface. Overall, comprehensive insights will facilitate the visualization of alkyl diamines and their potential derivatives at the A/W interface, enabling a better understanding of their behavior across various applications. [ABSTRACT FROM AUTHOR]

The direct air capture (DAC) of CO2 using aqueous solvents is plagued by slow kinetics and interfacial barriers that limit effectiveness in combating climate change. Functionalizing air/aqueous surfaces with charged amphiphiles shows promise in accelerating DAC; however, insight into these interfaces and how they evolve in time remains poorly understood. Specifically, competitive ion interactions between DAC reagents and reaction products feedback onto the interfacial structure, thereby modulating interfacial chemical composition and overall function. In this work, we probe the role of glycine amino acid anions (Gly−), an effective CO2 capture reagent, that promotes the organization of cationic oligomers at air/aqueous interfaces. These surfaces are probed with vibrational sum frequency generation spectroscopy and molecular dynamics simulations. Our findings demonstrate that the competition for surface sites between Gly− and captured carbonaceous anions (HCO3−, CO32−, carbamates) drives changes in surface hydration, which in turn tunes oligomer ordering. This phenomenon is related to a hierarchical ordering of anions at the surface that are electrostatically attracted to the surface and their ability to compete for interfacial water. These results point to new ways to tune interfaces for DAC via stratification of ions based on relative surface propensities and specific ion effects. [ABSTRACT FROM AUTHOR]

Phospholipase A2 (PLA2) catalyzes the hydrolysis of the sn-2 acyl ester linkage in phospholipid, producing lysophospholipid and fatty acid in the presence of Ca2+. The hydrolysis mediated by PLA2 has attracted much interest in various fields, such as pharmacy and biotechnology. It is recognized that PLA2 cannot hydrolyze phospholipid monolayers at high surface coverage. However, the origin of different PLA2 activities is not fully understood yet. The present study investigated the interaction between DPPC (16:0 PC) monolayer and PLA2 using heterodyne-detected sum frequency generation spectroscopy, which is interface-specific spectroscopy and highly sensitive to molecular symmetry based on a second-order nonlinear optical process. It was revealed that PLA2 adsorbs to the DPPC monolayer on the aqueous solution surface only when the surface coverage is low. The adsorption at the low surface coverage significantly changes the interfacial structures of PLA2 and the hydration, which are stabilized by the presence of Ca2+. Therefore, the restriction of the hydrolysis of phospholipid monolayers at high surface coverage can be rationalized by the inhabitation of the PLA2 adsorption. The present study deepens our molecular-level understanding of the hydrolysis of phospholipids by PLA2. [ABSTRACT FROM AUTHOR]

Phase separation is ubiquitous at the interface between two distinct phases. Physical transformation during phase separation often plays a crucial role in many important mechanisms, such as lipid phase separation, which is fundamental for transport through biological membranes. Phase separation can be complex, involving changes in the physical state and the reorganization of molecular structures, influencing the behavior and function of materials and biological systems. Surface-sensitive vibrational sum frequency generation (VSFG) spectroscopy provides a powerful tool for investigating these interfacial processes. As a non-linear optical technique, VSFG spectroscopy is sensitive to changes in molecular orientation and interactions at interfaces, making it an ideal method for studying phase separation processes. Here, we review the molecular interaction mechanisms underlying phase separation. We also explore the application of VSFG spectroscopy in studying phase separation processes at different interfaces. In particular, we focus on oil–water interfaces, which are relevant in environmental and industrial contexts; polymer and lipid surfaces, important for materials science and biological membranes; and intrinsically disordered protein systems, which play key roles in cellular function and disease. [ABSTRACT FROM AUTHOR]

Existing methods to compute theoretical spectra are restricted to the use of time-correlation functions evaluated from accurate atomistic molecular dynamics simulations, often at the ab initio level. The molecular interpretation of the computed spectra requires additional steps to deconvolve the spectroscopic contributions from local water and surface structural populations at the interface. The lack of a standard procedure to do this often hampers rationalization. To overcome these challenges, we rewrite the equations for spectra calculation into a sum of partial contributions from interfacial populations, weighted by their abundance at the interface. We show that SFG signatures from each population can be parameterized into a minimum dataset of reference partial spectra. Accurate spectra can then be predicted by just evaluating the statistics of interfacial populations, which can be done even with force field simulations as well as with analytic models. This approach broadens the range of simulation techniques from which theoretical spectra can be calculated, opening toward non-atomistic and Monte Carlo simulation approaches. Most notably, it allows constructing accurate theoretical spectra for interfacial conditions that cannot even be simulated, as we demonstrate for the pH-dependent SFG spectra of silica/water interfaces. [ABSTRACT FROM AUTHOR]

Controlling composition and plasmonic response of bimetallic nanoparticles (NPs) is of great relevance to tune their catalytic activity. Herein, we demonstrate reversible composition and plasmonic response transitions from a core/shell to a bimetallic alloyed palladium/gold NP triggered by CO adsorption and sample temperature. The use of self-organized growth on alumina template film allows scrutinizing the impact of core size and shell thickness onto NP geometry and plasmonic response. Topography, molecular adsorption, and plasmonic response are addressed by scanning tunneling microscopy, vibrational sum frequency generation (SFG) spectroscopy, and surface differential reflectance spectroscopy, respectively. Modeling CO dipolar interaction and optical reflectivity corroborate the experimental findings. We demonstrate that probing CO adsorption sites by SFG is a remarkably sensitive and relevant method to investigate shell composition and follow in real-time Pd atom migration between the core and the shell. Pd–Au alloying is limited to the first two monolayers of the shell and no plasmonic response is found, while for a thicker shell, a plasmonic response is observed, concomitant with a lower Pd concentration in the shell. Above 10−4 mbar, at room temperature, CO adsorption triggers the shell restructuration, forming a Pd–Au alloy that weakens the plasmonic response via Pd migration from the core to the shell. NP annealing at 550 K, after pumping CO, leads to the desorption of remaining CO and gives enough mobility for Pd to migrate back inside the core and recover a pure gold shell with its original plasmonic response. This work demonstrates that surface stoichiometry and plasmonic response can be tuned by using CO adsorption and NP annealing. [ABSTRACT FROM AUTHOR]

Sum frequency generation vibrational spectroscopy (SFG) was applied to characterize the interfacial adhesion chemistry at several buried polymer interfaces in both model systems and blown multilayer films. Anhydride/acid modified polyolefins are used as tie layers to bond dissimilar polymers in multilayer barrier structures. In these films, the interfacial reactions between the barrier polymers, such as ethylene vinyl alcohol (EVOH) or nylon, and the grafted anhydrides/acids provide covalent linkages that enhance adhesion. However, the bonding strengths vary for different polymer–tie layer combinations. Here, using SFG, we aim to provide a systematic study on four common polymer–tie interfaces, including EVOH/polypropylene–tie, EVOH/polyethylene–tie, nylon/polypropylene–tie, and nylon/polyethylene–tie, to understand how the adhesion chemistry varies and its impact on the measured adhesion. Our SFG studies suggest that adhesion enhancement is driven by a combination of reaction kinetics and the interfacial enrichment of the anhydride/acid, resulting in stronger adhesion in the case of nylon. This observation matches well with the higher adhesion observed in the nylon/tie systems in both lap shear and peel test measurements. In addition, in the polypropylene–tie systems, grafted oligomers due to chain scission may migrate to the interface, affecting the adhesion. These by-products can react or interfere with the barrier–tie chemistry, resulting in reduced adhesion strength in the polypropylene–tie system. [ABSTRACT FROM AUTHOR]

Two-dimensional electronic spectroscopy (2D-ES) has become an important technique for studying energy transfer, electronic coupling, and electronic–vibrational coherence in the past ten years. However, since 2D-ES is not interface specific, the electronic information at surfaces and interfaces could not be demonstrated clearly. Two-dimensional electronic sum-frequency generation (2D-ESFG) is an emerging spectroscopic technique that explores the correlations between different interfacial electronic transitions and is the extension of 2D-ES to surface and interfacial specificity. In this work, we present the detailed development and implementation of phase-cycling 2D-ESFG spectroscopy using an acousto-optic pulse shaper in a pump–probe geometry. With the pulse pair generated by a pulse shaper rather than optical devices based on birefringence or interference, this 2D-ESFG setup enables rapid scanning, phase cycling, and the separation of rephasing and nonrephasing signals. In addition, by collecting data in a rotating frame, we greatly improve experimental efficiency. We demonstrate the method for azo-derivative molecules at the air/water interface. This method could be readily extended to different interfaces and surfaces. The unique phase-cycling 2D-ESFG technique enables one to quantify the energy transfer, charge transfer, electronic coupling, and many other electronic properties and dynamics at surfaces and interfaces with precision and relative ease of use. Our goal in this article is to present the fine details of the fourth-order nonlinear optical technique in a manner that is comprehensive, succinct, and approachable such that other researchers can implement, improve, and adapt it to probe unique and innovative problems to advance the field. [ABSTRACT FROM AUTHOR]

Experimental methods capable of selectively probing water at the DNA minor groove, major groove, and phosphate backbone are crucial for understanding how hydration influences DNA structure and function. Chiral-selective sum frequency generation spectroscopy (chiral SFG) is unique among vibrational spectroscopies because it can selectively probe water molecules that form chiral hydration structures around biomolecules. However, interpreting chiral SFG spectra is challenging since both water and the biomolecule can produce chiral SFG signals. Here, we combine experiment and computation to establish a theoretical framework for the rigorous interpretation of chiral SFG spectra of DNA. We demonstrate that chiral SFG detects the N–H stretch of DNA base pairs and the O–H stretch of water, exclusively probing water molecules in the DNA first hydration shell. Our analysis reveals that DNA transfers chirality to water molecules only within the first hydration shell, so they can be probed by chiral SFG spectroscopy. Beyond the first hydration shell, the electric field-induced water structure is symmetric and, therefore, precludes chiral SFG response. Furthermore, we find that chiral SFG can differentiate chiral subpopulations of first hydration shell water molecules at the minor groove, major groove, and phosphate backbone. Our findings challenge the scientific perspective dominant for more than 40 years that the minor groove "spine of hydration" is the only chiral water structure surrounding the DNA double helix. By identifying the molecular origins of the DNA chiral SFG spectrum, we lay a robust experimental and theoretical foundation for applying chiral SFG to explore the chemical and biological physics of DNA hydration. [ABSTRACT FROM AUTHOR]

Polyyne bridges have attracted extensive interest as molecular wires due to their shallow distance dependence during charge transfer. Here, we investigate whether triplet energy transfer from cadmium selenide (CdSe) quantum dots (QDs) to anthracene acceptors benefits from the high conductance associated with polyyne bridges, especially from the potential cumulene character in their excited states. Introducing π-electron rich oligoyne bridges between the surface-bound anthracene-based transmitter ligands, we explore the triplet energy transfer rate between the CdSe QDs and anthracene core. Our femtosecond transient absorption results reveal that a rate constant damping coefficient of β is 0.118 ± 0.011 Å−1, attributed to a through-bond coupling mechanism facilitated by conjugation among the anthracene core, the oligoyne bridges, and the COO⊖ anchoring group. In addition, oligoyne bridges lower the T1 energy level of the anthracene-based transmitters, enabling efficient triplet energy transfer from trapped excitons in CdSe QDs. Density-functional theory calculations suggest a slight cumulene character in these oligoyne bridges during triplet energy transfer, with diminished bond length alternation. This work demonstrates the potential of oligoyne bridges in mediating long-distance energy transfer. [ABSTRACT FROM AUTHOR]

Vibrational sum frequency generation can provide valuable structural information at surfaces and buried interfaces. Relating the measured spectra to the complex-valued second-order susceptibility χ(2) is at the heart of the technique and a requisite step in nearly all subsequent analyses. The magnitude and phase of χ(2) as a function of frequency reveal important information about molecules and materials in regions where centrosymmetry is broken. In this tutorial-style perspective, the origins of the χ(2) phase are first described, followed by the utility of phase determination. Finally, some practical methods of phase extraction are discussed. [ABSTRACT FROM AUTHOR]

Within cell plasma membranes, unsaturated lipids are asymmetrically distributed over the inner and outer leaflets, offering an attractive local structural feature. However, the mechanism to keep lipid transmembrane asymmetry and the closely related transmembrane movement (flip-flop) for unsaturated lipids remain poorly understood. Here, we applied sum frequency generation vibrational spectroscopy to investigate this lipid transmembrane asymmetry upon mimicking the cell membrane homeostatic processes. On the one hand, unsaturated lipids were found to hinder the flip-flop process and preserve lipid transmembrane asymmetry in model cell membranes, owing to the steric hindrance caused by their bent tails. On the other hand, local unsaturated lipids in the mixed unsaturated/saturated lipid bilayer were conducive to the formation of the local asymmetry. Therefore, lipid unsaturation can be recognized as an intrinsic key factor to form and maintain lipid transmembrane asymmetry in cell membranes. [ABSTRACT FROM AUTHOR]

Surface-specific sum frequency generation vibrational spectroscopy is applied to study the molecular configuration of short-chain n-alkanethiol self-assembled monolayers (SAMs with n = 2–6) on the Au surface. For monolayers with n ≥ 3, the alkanethiols are upright-oriented, with the CH3 tilt angle varying between ∼33° and ∼46° in clear even–odd dependency. The ethanethiol monolayer (n = 2) is, however, found to exhibit a distinct lying-down configuration with a larger methyl tilt angle (67°–79°) and a smaller CH2 tilt angle (56°–68°). Such a unique configurational transition from n = 2 to n ≥ 3 discloses the steric effect owing to chain–chain interaction among neighboring molecules. Through density functional theory calculations, the transition is further confirmed to be energetically favorable for thiols on a defective reconstructed Au(111) surface but not on the pristine one. Our study highlights the roles of the chain–chain interaction and the substrate surface atomic structure when organizing SAMs, offering a strategic pathway for exploiting their applications. [ABSTRACT FROM AUTHOR]

Lanthanide-doped upconversion (UC) luminescent materials display multicolor emissions, making them ideal for a variety of applications, such as multi-channel biological imaging, fluorescence encryption, anti-counterfeiting, and 3D display. Manipulating the UC emissions of the luminescent materials with a fixed composition is crucial for their applications. Herein, we propose a facile strategy to achieve pulse-width-dependent multicolor UC emissions in NaYF4:Yb/Er/Tm nanocrystals. Upon excitation with a 980 nm continuous-wave laser diode, Er3+ ions in NaYF4:20%Yb,15%Er,1%Tm nanocrystals exhibited UC emissions with a red-to-green (R/G) ratio of 11.3. Nevertheless, by employing a 980 nm pulse laser with pulse widths from 0.1 to 10 ms, the UC R/G ratio can be easily adjusted from 0.9 to 11.3, resulting in continuous and remarkable color transformation from green, yellow, orange, to red. By virtue of the dynamic luminescence color variation of these NaYF4:20%Yb,15%Er,1%Tm nanocrystals, we demonstrated their potential applications in the areas of anti-counterfeiting and information encryption. These findings provide deep insights into the excited-state dynamics and energy transfer of Er3+ in NaYF4:Yb/Er/Tm nanocrystals upon 980 nm pulse excitation, which may pave the way for designing multicolor UC materials toward versatile applications. [ABSTRACT FROM AUTHOR]

The intriguing network of antibody–antigen (Ab–Ag) interactions is highly governed by environmental perturbations and the nature of biomolecular interaction. Protein–protein interactions (PPIs) have potential applications in developing protein-adsorption-based sensors and nano-scale materials. Therefore, characterizing PPIs in the presence of a nanomaterial at the molecular level becomes imperative. The present work involves the investigation of antiferritin–ferritin (Ab–Ag) protein interactions under the influence of tungsten disulfide quantum dots (WS2 QDs). Isothermal calorimetry and contact angle measurements validated the strong influence of WS2 QDs on Ab–Ag interactions. The interfacial signatures of nano–bio-interactions were evaluated using sum frequency generation vibration spectroscopy (SFG-VS) at the air–water interface. Our SFG results reveal a variation in the tilt angle of methyl groups by ∼12° ± 2° for the Ab–Ag system in the presence of WS2 QDs. The results illustrated an enhanced ordering of water molecules in the presence of QDs, which underpins the active role of interfacial water molecules during nano–bio-interactions. We have also witnessed a differential impact of QDs on Ab–Ag by raising the concentration of the Ab–Ag combination, which showcased an increased inter-molecular interaction among the Ab and Ag molecules and a minimal influence on the methyl tilt angle. These findings suggest the formation of stronger and ordered Ab–Ag complexes upon introducing WS2 QDs in the aqueous medium and signify the potentiality of WS2 QDs relevant to protein-based sensing assays. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) is a two-dimensional, mechanically strong, and chemically tunable material for separations. Elucidating GO–ion–water interactions at the molecular scale is highly important for predictive understanding of separation systems. However, direct observations of the nanometer region by GO surfaces under operando conditions are not trivial. Therefore, thin films of GO at the air/water interface can be used as model systems. With this approach, we study the effects of alkali metal ions on water organization near graphene oxide films at the air/water interface using vibrational sum frequency generation (SFG) spectroscopy. We also use an arachidic acid Langmuir monolayer as a benchmark for a pure carboxylic acid surface. Theoretical modeling of the concentration-dependent sum frequency signal from graphene oxide and arachidic acid surfaces reveals that the adsorption of monovalent ions is mainly controlled by the carboxylic acid groups on graphene oxide. An in-depth analysis of sum frequency spectra reveals at least three distinct water populations with different hydrogen bonding strengths. The origin of each population can be identified from concentration dependent variations of their SFG signal. Interestingly, an interfacial water structure seemed mostly insensitive to the character of the alkali cation, in contrast to similar studies conducted at the silica/water interface. However, we observed an ion-specific effect with lithium, whose strong hydration prevented direct interactions with the graphene oxide film. [ABSTRACT FROM AUTHOR]

Chirality-selective vibrational sum frequency generation (chiral SFG) spectroscopy has emerged as a powerful technique for the study of biomolecular hydration water due to its sensitivity to the induced chirality of the first hydration shell. Thus far, water O–H vibrational bands in phase-resolved heterodyne chiral SFG spectra have been fit using one Lorentzian function per vibrational band, and the resulting fit has been used to infer the underlying frequency distribution. Here, we show that this approach may not correctly reveal the structure and dynamics of hydration water. Our analysis illustrates that the chiral SFG responses of symmetric and asymmetric O–H stretch modes of water have opposite phase and equal magnitude and are separated in energy by intramolecular vibrational coupling and a heterogeneous environment. The sum of the symmetric and asymmetric responses implies that an O–H stretch in a heterodyne chiral SFG spectrum should appear as two peaks with opposite phase and equal amplitude. Using pairs of Lorentzian functions to fit water O–H stretch vibrational bands, we improve spectral fitting of previously acquired experimental spectra of model β-sheet proteins and reduce the number of free parameters. The fitting allows us to estimate the vibrational frequency distribution and thus reveals the molecular interactions of water in hydration shells of biomolecules directly from chiral SFG spectra. [ABSTRACT FROM AUTHOR]

Doubly resonant sum frequency generation (DR-SFG) serves as a potent characteristic technique for probing the electronic spectra and vibronic coupling of molecules on surfaces. In this study, we successfully developed a novel infrared (IR)–white light (WL) DR-SFG spectroscopy based on narrowband IR and tunable broadband WL. This novel method was employed to explore the excitation spectrum and vibronic couplings of sub-monolayer Rhodamine 6G molecules. Our findings elucidate that the xanthene skeleton vibrational modes exhibit strong coupling with the S0–S1 electronic transition. Notably, we observed not only the 0–0 transition of the S0–S1 electronic continuum but also the 0–1 transition, a first time observation in the realm of DR-SFG spectroscopy. This advanced DR-SFG spectroscopy methodology facilitates a more sensitive examination of electronic spectra and the coupling between electronic transitions and vibrational modes, heralding a significant advancement in the understanding of molecular interactions on surfaces. [ABSTRACT FROM AUTHOR]

Polymer chains at a buried interface with an inorganic solid play a critical role in the performance of polymer nanocomposites and adhesives. Sum frequency generation (SFG) vibrational spectroscopy with a sub-nanometer depth resolution provides valuable information regarding the orientation angle of functional groups at interfaces. However, in the case of conventional SFG, since the signal intensity is proportional to the square of the second-order nonlinear optical susceptibility and thereby loses phase information, it cannot be unambiguously determined whether the functional groups face upward or downward. This problem can be solved by phase-sensitive SFG (ps-SFG). We here applied ps-SFG to poly(methyl methacrylate) (PMMA) chains in direct contact with a quartz surface, shedding light on the local conformation of chains adsorbed onto the solid surface. The measurements made it possible to determine the absolute orientation of the ester methyl groups of PMMA, which were oriented toward the quartz interface. Combining ps-SFG with all-atomistic molecular dynamics simulation, the distribution of the local conformation and the driving force are also discussed. [ABSTRACT FROM AUTHOR]

Sum frequency generation (SFG) spectroscopy is an interface-selective spectroscopic technique that enables us to selectively observe the vibrational or electronic resonances of molecules within a very thin interface layer. The interfacial properties probed by SFG are contained in a complex quantity called the second-order nonlinear susceptibility ( χ 2 ). It is usually believed that the imaginary part of χ 2 (Im χ 2 ) exhibits the resonant responses of the system, whereas the nonresonant responses appear solely in the real part of χ 2 (Re χ 2 ). However, it was recently theoretically pointed out that a portion of the nonresonant responses actually contributes to the observed Im χ 2 spectra when the finite thickness of the interface layer is taken into account. In this study, by considering a simple air/liquid interface without any solutes as a model system, we theoretically evaluate the nonresonant contribution to experimentally accessible Im χ 2 as well as to Re χ 2 , from which the complex phase of the nonresonant background is estimated. It is shown that the deviation of the complex phase from 0° or 180° is less than 1° even if the thickness of the interface layer is taken into account. This means that the nonresonant contribution to Im χ 2 is practically negligible, and it is a very good approximation to think that the nonresonant background appears solely in Re χ 2 in the case of air/liquid interfaces. This result implies that Im χ 2 practically contains only the resonant responses of the system, and molecular resonances at the interface can be conveniently studied using Im χ 2 spectra at such interfaces. [ABSTRACT FROM AUTHOR]

Nonlinear optical methods, such as vibrational sum frequency generation (vSFG) and second harmonic generation (SHG), are powerful techniques to study elusive structures at charged buried interfaces. However, for the separation and determination of the Stern and diffuse layer spectra at these charged interfaces, complex vSFG spectra and, hence, the absolute phase need to be retrieved. The maximum entropy method is a useful tool for the retrieval of complex spectra from the intensity spectra; however, one caveat is that an understanding of the error phase is required. Here, for the first time, we provide a physically motivated understanding of the error phase. Determining the error phase from simulated spectra of oscillators with a spectral overlap, we show that for broadband vSFG spectra, such as for the silica/water interface, the diffuse and Stern layers' spectral overlap within the O–H stretching window results in a correlation between the error phase and the phase shift between the responses of these layers. This correlation makes the error phase sensitive to changes in Debye length from varying the ionic strength among other variations at the interface. Furthermore, the change in the magnitude of the error phase can be related to the absolute SHG phase, permitting the use of an error phase model that can utilize the SHG phase to predict the error phase and, hence, the complex vSFG spectra. Finally, we highlight limitations of this model for vSFG spectra with a poor overlap between the diffuse and Stern layer spectra (silica/HOD in D2O system). [ABSTRACT FROM AUTHOR]

In view of the current situation in which non-polarizable rigid water models have been scarcely examined against surface-specific properties, we appraise TIP4P-type models at the liquid water surface on the basis of heterodyne-detected sum frequency generation (HD-SFG) spectroscopy. We find in the HD-SFG spectrum of the water surface that the peak frequency of the hydrogen-bonded OH band, the half width at half maximum of the hydrogen-bonded OH band, and the full width at half maximum of the free OH band are best reproduced by TIP4P, TIP4P/Ew, and TIP4P/Ice, respectively, whereas it is already well known that TIP4P/2005 best reproduces the surface tension. These TIP4P-type models perform better at the water surface in terms of the present appraisal items than some polarizable models in the literature. [ABSTRACT FROM AUTHOR]

This study offers and explores an ultra-high efficiency up-converter to convert three mid-infrared frequency bands to three visible frequency bands. Our purpose is to explore frequency analysis in the up-conversion process. In our suggested band-to-band up-conversion device, the time-varying mid-infrared light signals are converted into time-varying electrical currents; these time-varying electrical currents are amplified by the transistor. Finally, these amplified currents produce time-varying visible light currents and power through the usage of organic light-emitting diodes (LEDs). This up-conversion device includes: (1) Doped nanocrystalline layers of PbSe, CdSe, and CdTe as photodetectors to detect three different central frequencies of 100, 70, and 56 THz, (2) the NPN BJT as a current amplifier and output quantum efficiency (QE) improvement, (3) blue, green, red organic LEDs for producing visible light currents and powers; these OLEDs operate at central frequencies of 667, 545, and 484 THz, respectively. In this investigation, narrow-band mid-infrared light is converted into broadband visible light considering conventional LEDs. The mid-infrared input optical signal with a bandwidth of 0.004, 0.0006, and 0.004 THz is converted to visible optical bandwidth of 0.425, 0.52, and 0.37 THz, respectively. The output QE of the proposed structure for the frequency of 100, 70, and 56 THz is 2 4 × 1 0 3 %, 5 6 × 1 0 3 %, and 1 6 × 1 0 3 %, respectively. The results indicate more excellent QE than other research. Also, it is the first study about the frequency response of the up-conversion device to convert narrowband mid-infrared lights into broadband visible lights. [ABSTRACT FROM AUTHOR]

Luminescent materials usually suffer from thermal quenching at high temperature due to the aggravation of nonradiation relaxations. Herein, a giant enhancement of up conversion (UC) luminescence is observed in negative thermal expansion (NTE) Y 2 W 3 O 12 :Nd phosphor upon increasing the temperature from 310 to 790 K. In addition, the temperature-dependent UC emission is reversible. To penetrate into the mechanisms, the temperature-dependent luminescence intensity and lifetime are investigated for Nd doped negative and positive thermal expansion (PTE) phosphors. Based these investigation, we infer that the underlying mechanism of the giant enhancement for Y 2 W 3 O 12 :Nd phosphor are due to combined effects of phonon assisted absorptions and contraction of NTE crystals. Moreover, the observation of temperature-dependent near-infrared spectra (NIR) can support the mechanism from the other side. The present findings pave the way to overcome thermal quenching of Nd3+ ions and explore new thermal enhancement materials sensitized by Nd3+ ions. [ABSTRACT FROM AUTHOR]

A series of solid-state triplet–triplet annihilation upconversion systems have been developed utilizing a penta-nuclear Yb complex as the sensitizer, converting near-infrared light into blue, green and red photons. The endothermic sensitization of organic annihilators by the Yb complex enables an anti-Stokes shift exceeding 1.3 eV. [ABSTRACT FROM AUTHOR]

In this work, SrLaAlO 4 :Er3+ (2 mol%),Yb3+ (4 mol%) upconversion phosphor was synthesized by using a combustion method. Later, CsPbBr 3-x I x (x = 0, 1.5 and 0.75) perovskite quantum dots (QDs) were synthesized by using hot injection method. According the analysis by X-ray diffraction, the SrLaAlO 4 :Er,Yb (SL:Er,Yb) phosphors and QDs had tetragonal and cubic phases, respectively. Moreover, the analysis by microscopy revealed that the SL:Er,Yb phosphors are composed of micro-grains with irregular morphology, while the CsPbBr 3-x I x QDs had a morphology of cubes. The surface of the SL:Er,Yb phosphors was decorated with CsPbBr 3-x I x QDs and obtained three composite powders: CsPbBr 3 +SL:Er,Yb, CsPbBr 1.5 I 1.5 +SL:Er,Yb and CsPbBr 2.25 I 0.75 +SL:Er,Yb. Those composites were firstly excited with UV light (380 nm) and produced emissions in the green and orange-red regions by downconversion. Interestingly, the emission intensity of the composite powders was 45–75 % higher than that for the individual CsPbBr 3-x I x QDs or SL:Er,Yb phosphors. Later, the same composite powders were excited with NIR light (980 nm), in consequence, intense green and yellow emissions were produced by upconversion. In particular, the CsPbBr 1.5 I 1.5 + SL:Er,Yb composite produced strong red emission by upconversion because the presence of the QDs on the SL:Er,Yb surface promoted the following cross relaxation process: 4I 11/2 (Er3+)+ 4F 7/2 (Er3+)→4F 9/2 (Er3+)+ 4F 9/2 (Er3+). In general, the quantum dots deposited on the SL:Er,Yb surface not only enhanced the red upconversion emission, but also provoked a color tuning when they are excited with NIR or UV light. Those last effects have not been reported in the literature previously. Thus, the results of this investigation demonstrate that combining perovskite quantum dots and the SL:Er,Yb forms a luminescent material able to tune its emission by upconversion or downconversion. This last property can be utilized for the design of new LED based lamps, which are employed for general illumination in houses and buildings. [ABSTRACT FROM AUTHOR]

Porphyrins and their derivatives have drawn extensive attention as promising nonlinear optical (NLO) materials especially for biological applications owing to its large aromatic conjugation and special biological activity and compatibility. However, it is still critical to strategically design porphyrin derivatives materials with high performance in second order NLO applications and disclose the structure property correlation. In the present work, a series of dual-metallic-porphyrin derivatives are designed by incorporating a heptagon between two porphyrins with further addition of heteroatoms and metals. The doping of B and N along the dipole direction induces large static first hyperpolarizability, and strong charge transfer occurs with further introduction of Mg, thus ultimately achieving excellent second order NLO properties including strong sum frequency generation and difference frequency generations under external fields. The doping of heteroatoms and metals synergistically tunes the electronic structure of porphyrin-based derivatives and brings about high performance in biological nonlinear optics. [ABSTRACT FROM AUTHOR]

Pump-probe excitation technique using mid-infrared free electron laser and Nd:YVO4 ps-laser from Kyoto University free electron laser facility was implied to selectively excite a Raman inactive phonon mode of a semiconductor single crystal sample. The LO3 phonon mode of strontium titanate was chosen and the MIR-FEL photon energy was adjusted to match the target phonon mode energy, which corresponded to a wavelength of 12.5 µm. Temporal and spatial overlapping of MIR-FEL pulses and probe laser pulses were performed and confirmed through sum frequency generation from ZnS cleartran®. Confirmation of the Raman forbidden mode excitation was achieved through the anti-Stokes hyper-Raman scattering (ASHRS) spectroscopy method. Successful excitation was observed at 5 K, where thermal excitation of all other phonon modes was suppressed. The recorded spectrum showed a signal that was red-shifted from 800 to around 761 cm−1. The broadened line width (FWHM) and the red-shifting phenomenon in the recorded result have been observed due to the restraint of the spectrometer slit width function and the intense irradiation of the picosecond laser for hyper-Raman scattering spectroscopy, which have also led to surface damage on the crystal sample. [ABSTRACT FROM AUTHOR]

The performance control and multidimensional applications of upconversion phosphor have become the hotspot and difficulty in current research and application due to the complex luminescence mechanism. Based on the efficient Gd2O2S: Er3+ upconversion luminescence of 1550 nm excitation and design strategy for co‐doped materials, the multicolor (light green to red) and multifunctional upconversion phosphor Gd2O2S: Er3+, Ho3+ is successfully prepared. Benefiting from the clear mechanism of three‐photon upconversion and energy transfer after co‐doping, the novel applications of Gd2O2S: Er3+, Ho3+ can greatly be expanded. This phosphor can be well used as a fluorescence thermometer due to the higher sensitivity (2.46% K−1@170 K), wider temperature sensing range (170–267 K, Sr > 1% K−1), and greater color variation (Δx = 0.2416, Δy = 0.2483) relative to Gd2O2S: Er3+ and other same type of material. In addition, multiple patterns and encoded outputs are also effectively achieved by the combination of phosphors under multiple light stimuli response. This shows the greater application potential of phosphor in the fields of anti‐counterfeiting and information encryption. This study can also provide a new view to study the more high‐performance and multifunctional upconversion phosphor. [ABSTRACT FROM AUTHOR]

Metal nanoclusters have emerged as new triplet sensitizers of photo‐upconversion, while the strategy of engineering their electronic properties for efficient utilization of triplet energy remains elusive. Au16Cu6(tBuPhC≡C)18 (Au16Cu6) metal nanocluster shows near‐unity near‐infrared (NIR) phosphorescent quantum yield at room temperature and near‐unity intersystem crossing quantum yield, which is an ideal platform for understanding the mechanism of triplet energy transfer (TET). Here, a model system is designed to probe the TET from Au16Cu6 to different organic acceptors and obtained kTET from Stern–Volmer plots. Transient absorption spectroscopy clearly shows the formation of T1 signals in organic molecules accompanied by the decay of T1 signals in Au16Cu6, which indicates a direct TET mechanism. Among four organic molecules, the TET between Au16Cu6 and perylene possesses the highest TET quantum yield. Moreover, a relatively small threshold intensity of 0.4 W cm−2 is obtained with 532 nm excitation and a large anti‐Stokes shift of 0.68 eV with 635 nm excitation in triplet‐triplet annihilation (TTA) upconversion (UC). The efficient TET and UC in Au16Cu6 nanoclusters and the underlying mechanism will pave the way for optimizing their performance and expanding their utilization in optoelectronic devices. [ABSTRACT FROM AUTHOR]

Phosphonate compounds have been proposed as atypical chromophores, but their luminescence properties, especially in combination with flexible aliphatic chains, remain underexplored. In this study, we have synthesized a series of novel siloxane‐containing phosphonate esters as organofluorophores through a catalyst‐free, one‐pot Kabachnik–Fields (K–F) reaction. This reaction involved acetone, cyclohexanone, or cyclopentanone, with siloxanes containing aliphatic amines and phosphonate diesters as reactants. The resulting compounds exhibit blue fluorescence. Fluorescence tests confirmed that all synthesized materials display aggregation‐induced emission (AIE) phenomena, with some also exhibiting upconversion. Notably, the luminescence intensity can be modulated by altering the steric hindrance near the phosphonate ester group. Mechanistic studies indicate that the strong blue photoluminescence observed in the aggregated state results from restricted intramolecular motion (RIM) and spatial electronic delocalization. These findings demonstrate that even simple phosphonates, when combined with flexible aliphatic chains, can exhibit significant AIE luminescence properties. [ABSTRACT FROM AUTHOR]

Hexagonal Er3+/Yb3+ co‐doped LaZrTa3O11 (LZTO) phosphor was prepared by molten salt synthesis with B2O3 flux. Holding temperature, holding time, solute and solvent ratio were regulated. The green upconversion luminescence (UCL) integral intensity of the optimal sample can reach 29.2% of β‐NaYF4:Er3+/Yb3+ under 980 nm laser excitation. This outstanding pure green UCL is due to the low phonon energy, Er3+/Yb3+ monolayer (2D) distribution, asymmetry of Er3+/Yb3+ doped lattice sites, and low oxygen vacancy. The maximum relative temperature sensitivity attains 0.01221 K−1 at 303 K by employing luminescence intensity ratio (LIR) technique. LZTO:Er3+/Yb3+ phosphor can be used in temperature sensing. [ABSTRACT FROM AUTHOR]

In this work, a novel Y-NaBi(MoO 4) 2 @NaYF 4 :Yb, Tm composite was successfully synthesized for the first time by hydrothermal method. The lamellar Y-NaBi(MoO 4) 2 was dispersed on the surface of the hexagonal prism NaYF 4 :Yb, Tm without aggregation. The composite achieved a broad spectral response. The NaYF 4 :Yb, Tm absorbed near-infrared light and emitted ultraviolet and visible light by the energy transfer upconversion process. The emitted light was reabsorbed by Y-NaBi(MoO 4) 2 through the fluorescence resonance energy transfer process. Moreover, the doping of Y3+ ions enhanced the light response capability of the composite. The experimental results revealed that the photocatalytic degradation efficiency of ciprofloxacin (CIP) reached 96.2 % after 180 min of illumination under simulated sunlight. Meanwhile, the degradation pathways and attack sites of CIP were intensively investigated by liquid chromatography-mass spectrometry analysis and density functional theory theoretical calculations. The upconversion process, the separation of photogenerated carriers and rare earth metal ion doping all contributed to the high effective photodegradation. This work provided a new strategy for effective utilization of solar energy for the degradation of emerging pollutants to mitigate environmental pollution. [ABSTRACT FROM AUTHOR]

This work presents a novel and highly secure anticounterfeiting strategy based on high entropy upconversion perovskite halides with thermally responsive multicolor emissions excited by a single laser. The perovskite halides are doped with rare earth cations and oxygen anions simultaneously and form the high entropy crystal structure by using a solid‐state reaction method. The color‐shifting emissions stem from luminescent kinetics transformation from energy transfer upconversion at low temperature to excited state absorption at high temperature. The multicolor emissions can also be trigged by the 975 nm laser heating effect. The results indicate the great potential of the high entropy upconversion perovskites for anticounterfeiting applications with a convenient recognition method. [ABSTRACT FROM AUTHOR]

Fluorescence nanomaterial sensors have exhibited excellent application potential in biothiols analyses. The fluorescence sensor arrays constructed from upconversion luminescence metal-organic frameworks nanocomposites (LMOFs) can provide impressive discrimination and exquisite fingerprinting capabilities for extremely similar analytes. Herein, an upconversion fluorescence sensor array based on LMOFs featuring UiO-type metal-organic frameworks-functionalized lanthanide-doped upconversion nanoparticles was proposed, wherein Cu2+ can make the fluorescence quenching of LMOFs and preferentially bind biothiols to recover fluorescence in different degrees forming unique fingerprinting. The fluorescence sensor array displayed an excellent pattern recognition for five biothiols (glutathione, homocysteine, N-acetylcysteine, and L/D-cysteine) even at 50 µM by linear discriminant analysis, and the discernment for the enantiomers of L/D-cysteine, as well as the accurate identification (90.0% accuracy) of biothiols in food samples (tea beverage and white wine). Such fluorescence sensor array might provide a simple and efficient detection method for biothiols. [ABSTRACT FROM AUTHOR]

Embedding donor–acceptor type thermally activated delayed fluorescence (TADF) molecules in a rigid surrounding lead to structural inhomogeneity, and deteriorating emission decay rates. Designing TADF structures with hampered rotational flexibility between donor and acceptor structural units is shown to lower the conformational disorder. However, in this work, it is shown that it is not always enough. In fact, the negative impact of conformational inhomogeneity may be reduced by lowering the singlet‐triplet energy gap (ΔEST) and boosting the reverse intersystem crossing (rISC) rate while preserving the same donor‐acceptor orientation. In such cases the lower ΔEST enables the early triplet upconversion even from the conformers with unfavorably low D‐A twist angles, which is not observed in compounds with larger ΔEST. In this way, the temporal shifts of prompt and delayed fluorescence are evidently reduced. When the reverse intersystem crossing is inactive at low temperatures, nearly the same fluorescence peak shifts are observed, as expected for compounds with similar molecular geometry. In this way, low ΔEST and rapid rISC are shown to be of fundamental importance not only for TADF efficiency but also for the temporal dynamics in the solid‐state. [ABSTRACT FROM AUTHOR]

The design and experimental demonstration of double‐step, 1D amorphous germanium grating structures supporting quasi bound‐states‐in‐continuum (quasi‐BIC) resonance at 3.2 µm wavelength and its application to third‐order sum‐frequency generation‐based up‐conversion are reported. Linear transmission measurements on the fabricated metasurface with loosely focussed excitation spanning 0–3° angles show very good agreement with ideal plane‐wave excitation of the periodic photonic structure. TSFG measurements performed on the same structures with tightly focusing mid‐infrared signal and pump beams using a reflective‐type objective with 15–40° angular excitation show ≈375 times enhancement with significant blue‐shift in the resonance feature by ≈300 nm. To understand this excitation angle dependence of the resonance characteristics, a generalized plane‐wave expansion (PWE) model is developed by considering varying excitation angle plane‐waves incident on the metasurface with a discretized angular spectrum representation used to coherently combine the resultant electric and magnetic fields to obtain the linear transmission characteristics and nonlinear TSFG spectra. The PWE method is found to be particularly effective in modeling linear and nonlinear responses under realistic illumination conditions while ensuring optimal utilization of computational resources. Good agreement is obtained between the PWE simulations, linear transmission, and nonlinear TSFG measurements by considering appropriate angular excitation. [ABSTRACT FROM AUTHOR]

A series of Tb3+–Yb3+co-doped transparent glass ceramics (GCs) containing NaBi(MoO4)2 were synthesized. Comparison of their X-ray diffraction (XRD) patterns with standard cards showed that the crystal phase in the glass ceramics was NaBi(MoO4)2. Optimal heat-treatment conditions for the GCs were obtained through differential scanning calorimetry-thermogravimetry (DSC-TG), light transmittance and scanning electron microscopy (SEM) analyses. At 980 nm, the upconversion luminescence intensity of the GCs doped with 0.8%Tb3+–0.6%Yb3+ was the strongest. Based on an increase in emission intensity with an increase in pump power, the mechanism of upconversion luminescence was studied. The color purity was calculated using upconversion emission spectra. The final results showed that the GCs have latent development and utilization value in the solar-energy-spectrum conversion of solar cells and optoelectronic communication devices. [ABSTRACT FROM AUTHOR]

In recent years, people have higher requirements for temperature measurement with the development of optical temperature measurement. Meanwhile, the emission intensity of most fluorescent materials is quenched by thermal effects as the temperature rises, making it challenging to meet the specifications of fluorescent materials employed in the field of pyrometry. In this work, the pure phase of Yb3+/Er3+ ions co-doped Sc 2 W 3 O 12 phosphor was successfully prepared. Sc 2 W 3 O 12 : Yb3+, Er3+ samples showed strong green emission and weak red emission. The optimal doping concentrations of Yb3+ and Er3+ ions are 0.3 and 0.02, respectively. The potential upconversion luminescence (UCL) mechanism was investigated by analyzing the UCL spectra, downshift emission spectra and power dependence spectra of Yb3+/Er3+ ions co-doped Sc 2 W 3 O 12. The upconversion emission excitation path is mainly through Er3+ ions from 4I 11/2 absorption photon excitation to 4F 7/2 energy level, then the photons of 4F 7/2 relaxes to green and red emission energy levels and returns to ground state for emitting green and red light. In addition, according to the UCL green light intensity increasing with temperature, it serves as an optical temperature sensor. The temperature sensitivity of the sample was explored in the temperature range of 298 K–673 K. This study provides new materials and ideas for non-contact temperature sensing. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel ZnO/Bi 3 Ti 2 O 8 F:Yb3+, Er3+ Z-scheme heterojunction was synthesized. • The IEF of ZnO/BTOFYE heterojunction improves the carrier separation efficiency. • The IEF of ZnO/BTOFYE heterojunction improves the UC luminescence intensity. • ZnO/BTOFYE showed better photocatalytic degradation efficiency than BTOFYE. Exploring strategies to improve the near-infrared response of photocatalysts is an urgent challenge that can be overcome by utilizing upconversion (UC) luminescence to enhance photocatalysis. This paper reports the fabrication of a ZnO/Bi 3 Ti 2 O 8 F:Yb3+, Er3+ (ZnO/BTOFYE) Z-scheme heterojunction based on a Bi 3 Ti 2 O 8 F:Yb3+, Er3+ (BTOFYE) UC photocatalyst via electrostatic self-assembly. Fermi energy difference at the interface of BTOFYE and ZnO generates a strong internal electric field (IEF) in the Z-scheme heterojunction, offering a novel charge transfer mode that promotes carrier transfer and separation while retaining the strong redox capability. These results are confirmed through in situ X-ray photoelectron spectroscopy, in situ Kelvin probe force microscopy, electron spin resonance, and density functional theory calculations. In addition, the effect of the IEF on the UC luminescence process of Er3+ enhances the luminescence intensity, considerably improving the UC utilization efficiency. The optimal ZnO/BTOFYE degrades 64 % of ciprofloxacin in 120 min, which is 2.3 times more than that degraded by BTOFYE. Overall, the results of this study offer a reference for the rational development of high efficiency UC photocatalysts by generating IEF in Z-scheme heterojunctions. [ABSTRACT FROM AUTHOR]

Solid state photon upconversion by triplet‐triplet annihilation (TTA), particularly near‐infrared (NIR)‐to‐blue upconversion, holds instant promise for enhancing optoelectronic and photochemical applications. Despite extensive studies, NIR‐to‐blue upconversion has remained particularly challenging and elusive due to inherent multiple energy‐downhill processes in TTA upconversion. In this study, using atomically thin two dimensional (2D) monolayer semiconductor as a triplet sensitizer, we demonstrate an efficient and robust solid‐state NIR‐to‐blue photon upconversion system. The ultrathin and flexible organic/2D bilayer heterostructure exhibits a NIR‐to‐blue upconversion with high quantum yield (ΦUC=1.2 %, out of 50 %), low threshold power density (Ith=110 mW/cm2) and a record‐high apparent anti‐Stokes shift of 1.12 eV. Further spin‐ and time‐resolved spectroscopy reveals an ultrafast (<500 fs) electron spin flip to triplet‐like excitons in semiconductor sensitizer and subsequent picosecond (~6×1010 s−1) interfacial Dexter energy transfer to annihilator molecules. The triplet energy transfer rate and efficiency depend strongly on driving force, exhibiting Marcus normal region behavior. This work demonstrates 2D monolayer semiconductor as a superior ultrathin light harvesting and triplet sensitization layer and reveals the key knob to overcome the compromise between upconversion efficiency and energy loss, offering a viable pathway to efficient solid state NIR‐to‐blue photon upconversion and implementation. [ABSTRACT FROM AUTHOR]

As a van der Waals (vdW) layered semiconductor material, lead iodide (PbI2) possessing a direct bandgap with strong photoluminescence emission in visible range has gained wide attention in applications of photonic and optoelectronic devices. Here, upconversion photoluminescence (UPL) in exfoliated PbI2 flakes is demonstrated at room temperature and elevated temperatures. The linear power dependence of UPL emission with 532 nm excitation suggests the one-photon involved multiphonon-assisted UPL emission process, which is revealed by the temperature-dependent UPL emission measurement. Meanwhile, the nonlinear power dependence of UPL emission with 561 nm excitation indicates the transition of UPL emission mechanism from linear to nonlinear regime, and the temperature-dependent UPL emission study further shows that the upconversion is contributed by both the multiphonon-assisted UPL process and the two-photon absorption induced PL process. This study will provide an insight to the understanding of photon upconversion in vdW layered semiconductors and advancing applications in temperature-controlled photon upconversion, tunable photonics, photodetection and imaging. [ABSTRACT FROM AUTHOR]

Two-step photon upconversion solar cells (TPU-SCs) based on III–V semiconductors can achieve enhanced sub-bandgap photon absorption because of intraband transitions at the heterointerface. From a technological aspect, the question arose whether similar intraband transitions can be realized by using perovskite/III–V semiconductor heterointerfaces. In this article, we demonstrate a TPU-SC based on a CsPbBr3/GaAs heterointerface. Such a solar cell can ideally achieve an energy conversion efficiency of 48.5% under 1-sun illumination. This is 2.1% higher than the theoretical efficiency of an Al0.3Ga0.7As/GaAs-based TPU-SC. Experimental results of the CsPbBr3/GaAs-based TPU-SC show that both the short-circuit current JSC and the open-circuit voltage VOC increase with additional illumination of sub-bandgap photons. We analyze the excitation power dependence of JSC for different excitation conditions to discuss the mechanisms behind the enhancement. In addition, the observed voltage-boost clarifies that the JSC enhancement is caused by an adiabatic optical process at the CsPbBr3/GaAs heterointerface, where sub-bandgap photons efficiently pump the electrons accumulated at the heterointerface to the conduction band of CsPbBr3. Besides the exceptional optoelectronic properties of CsPbBr3 and GaAs, the availability of a CsPbBr3/GaAs heterointerface for two-step photon upconversion paves the way for the development of high-efficiency perovskite/III–V semiconductor-based single-junction solar cells. [ABSTRACT FROM AUTHOR]

Organic upconverters made by integrating an infrared‐sensitive photodetector with a light‐emitting diode offer a low‐cost route to visualize images taken in the infrared. However, making such devices sufficiently efficient is challenging. Here, upconversion devices are demonstrated with an efficiency of 13.9% for converting infrared photons (980 nm, 5 mW cm−2) to visible photons (575 nm). Infrared photons are detected with a photomultiplication photodetector that includes a copper thiocyanate electron‐blocking/injection layer and an infrared‐sensitive squaraine dye dispersed (3 wt−%) in a fullerene matrix. At turn‐on, the detector achieves an external quantum efficiency of 1200% (at 1020 nm, −10 V, 44 µW cm−2). Photomultiplication occurs via hole trap‐induced injection of electrons. In the upconverter, these electrons are driven into the emitter and recombine with holes under visible light emission. During operation the photodetector current increases because, presumably, rearranging mobile ions in copper thiocyanate narrows the injection barrier. Thereby, the upconverter photoconversion efficiency gradually increases to 18.7%. The performance of the present upconverter is limited by the not‐yet‐ideal charge‐blocking/injection layer, which is too thick and blocks electrons in the dark insufficiently. With thin and compact charge‐blocking layers at hand, the device concept paves the way for widespread use in sensitive infrared imaging. [ABSTRACT FROM AUTHOR]

The relative fluorescence intensity from different multi-photon processes is affected by the excitation light source fluctuation, which reduces the anti-interference and sensitivity of thermometers based on fluorescence intensity ratio (FIR) in upconversion (UC) luminescence. Ca 1-x Mg x WO 4 : Yb3+, Er3+ phosphors with scheelite structure were synthesized to investigate their anti-interference and higher temperature sensitivity. With x increasing from 0 to 1, the Bragg angle shifted toward higher angle, indicating that the larger disorders were introduced into the phosphors. The emissions assigned to Er3+ were enhanced with Mg2+ concentration increasing, attributed to oxygen vacancies according to the results of electron paramagnetic resonance. The photon numbers of upconversion luminescence assigned to 2H 11/2 → 4I 15/2 , 4S 3/2 → 4I 15/2 and 4F 9/2 → 4I 15/2 transitions of Er3+ were three- and two-photon processes, respectively. The ratio between the cube of 4S 3/2 and the square of 2H 11/2 emissions revealed higher temperature sensing performance and anti-interference on the excitation source power than the that between 4S 3/2 and 2H 11/2. The maximum relative sensitivity was 0.66 % K−1 at 300 K based on the common optical ratiometric thermometry. The maximum relative sensitivity based on the emissions assigned to different multi-photon processes was 7.2 % K−1 at 573 K. The dopants of Mg2+ composited of oxygen vacancies in CaWO 4 crystals improved the luminous intensity and temperature sensing performance. This suggested the potential application of optical ratiometric thermometers based on different multi-photons of UC luminescence in temperature sensing field. [ABSTRACT FROM AUTHOR]