Anti-Stokes/Stokes temperature calibration and its application in laser-heating diamond anvil cells

Anti-Stokes/Stokes Raman peak intensity ratio was used to infer sample temperatures,but the influence factors of system correction factors were not clear.Non-contact in-situ anti-Stokes/Stokes temperature calibration was carried out for up to 1500 K based on six different samples under two excitation light sources(±50 K within 1000 K,±100 K above1000 K),and the system correction factorγwas systematically investigated.The results show that the correction factorγof anti-Stokes/Stokes thermometry is affected by the wavelength of the excitation light source,Raman mode peak position,temperature measurement region and other factors.The anti-Stokes/Stokes thermometry was applied to the laser-heating diamond anvil cell(LHDAC)experiment to investigate the anharmonic effect of h BN under high temperature and high pressure.It is concluded that the strong anharmonic effect caused by phonon scattering at low pressure gradually changes into the predominance of localized molecular lattice thermal expansion at high pressure.

氢中后向anti-Stokes辐射产生机制的分析

分析了在受激Raman散射中后向anti-Stokes辐射产生的几种可能性,与氢的实验结果作了比较,进一步支持了氢中后向anti-Stokes辐射来源于受激Brillouin散射感生的轴向相位失配的四波混频过程的观点。

Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

In broadband coherent anti-Stokes Raman scattering （CARS） spectroscopy with supercontinuum （SC）, the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.

Selective excitation of molecular mode in a mixture by femtosecond resonance-enhanced coherent anti-Stokes Raman scattering spectroscopy

Femtosecond time-resolved coherent anti-Stokes Raman scattering （CARS） spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this broad spectroscopy. However, it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible. Using an electronically resonance-enhanced effect, iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm （corresponding to a saturation iodine vapour as low as about 35 Pa）. The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies （vacuum, heated and pure iodine） in the femtoseeond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.

Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering （CARS） suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump （or Stokes） spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump （or Stokes） spectrum with the π spectral phase step.

Coherent coupling between vibrational modes of C-H bonds at different positions studied by femtosecond time-resolved coherent anti-Stokes Raman scattering

We performed femtosecond time-resolved coherent anti-Stokes Raman scattering （fs-CARS） measurements on liquid toluene and PVK film. For both samples, we selectively excited the CH stretching vibrational modes and observed the expected quantum beat signals. The frequency of the well-defined beats is in good agreement with the energy difference between the two simultaneously excited modes, which demonstrates that a coherent coupling between the vibrational modes of the C H chemical bonds exists at the different positions of the molecules. The dephasing times of the excited modes are obtained simultaneously.

High-resolution imaging of graphene by tip-enhanced coherent anti-Stokes Raman scattering

Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.

Laser Cooling Using Anti-Stokes Fluorescence in Yb^(3+)-Doped Fluorozirconate Glasses

The fluorozirconate glasses ZBLANP( ZrF\-4-BaF\-2-LaF\-3-AlF\-3-NaF-PbF\-2) doped with different Yb\+ 3+ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb\+ 3+-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb\+ 3+-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about -4.09 ℃/W and the cooling efficiency reaches 1.76%.

COHERENT ANTI-STOKES RAMAN SCATTERING MICROSCOPY TO MONITOR DRUG DISSOLUTION IN DIFFERENT ORAL PHARMACEUTICAL TABLETS

Coherent anti-Stokes Raman scattering(CARS)microscopy is used to visualize the release of a model drug(theophylline)from a lipid(tripalmitin)based tablet during dissolution.The effects of transformation and dissolution of the drug are imaged in real time.This study reveals that the manufacturing process causes significant differences in the release process:tablets prepared from powder show formation of theophylline monohydrate on the surface which prevents a controlled drug release,whereas solid lipid extrudates did not show formation of monohydrate.This visualization technique can aid future tablet design.

Wide-Field Vibrational Phase Contrast Imaging Based on Coherent Anti-Stokes Raman Scattering Holography

We propose and implement a wide-field vibrational phase contrast detection to obtain imaging of imaginary components of third-order nonlinear susceptibility in a coherent anti-Stokes Raman scattering （CARS） microscope with full suppression of the non-resonant background. This technique is based on the unique ability of recovering the phase of the generated CARS signal based on holographic recording. By capturing the phase distributions of the generated CARS field from the sample and from the environment under resonant illumination, we demonstrate the retrieval of imaginary components in the CARS microscope and achieve background free coherent Raman imaging.

Analysis of detection limit to time-resolved coherent anti-Stokes Raman scattering nanoscopy

In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume can be detected. Here reported is a theoretical analysis of detection limit （DL） to time-resolved CARS （T-CARS） nanoscopy based on our proposed additional probe-beam-induced phonon depletion （APIPD） method for the low concentration samples. In order to acquire a detailed shot-noise limited signal-to-noise （SNR） and the involved parameters to evaluate DL, the T-CARS process is described with full quantum theory to estimate the extreme power density levels of the pump and Stokes beams determined by saturation behavior of coherent phonons, which are both actually on the order of ~ 109 W/cm2. When the pump and Stokes intensities reach such values and the total intensity of the excitation beams arrives at a maximum tolerable by most biological samples in a certain suppressed focal volume （40-nm suppressed focal scale in APIPD method）, the DL correspondingly varies with exposure time, for example, DL values are 103 and 102 when exposure times are 20 ms and 200 ms respectively.

Theoretical and experimental investigations of coherent phonon dynamics in sapphire crystal using femto-second time-resolved coherent anti-Stokes Raman scattering

We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering （fs-CARS） technique. The temporal chirped white-light continuum （WLC） is used for the Stokes pulse, therefore we can perform the selective excitation of the phonon modes without using a complicated laser system. The expected quantum beat phenomenon is clearly observed. The theoretical formulas consist very well with the experimental results. The dephasing times of the excited phonon modes, the wavenumber difference, and the phase shift between the simultaneously excited modes are obtained and discussed. This work opens up a way to study directly high-frequency coherent phonon dynamics in bulk crystals on a femtosecond time scale and is especially helpful for understanding the nature of coherent phonons.

Supercontinuum fiber laser-based coherent anti-Stokes Raman scattering microscopy for label-free chemical imaging

Coherent anti-Stokes Raman scattering(CA RS)microscopy can resolve the chemical compo-nents and distribution of living biological systems in a label-firee manner and is favored in several disciplines.Current CA RS microscopes typically use bulky,high-performance solid-state lasers,which are expensive and sensitive to environmental changes.With their relatively low cost and environmental sensitivity,supercontinum fiber(SF)lasers with a small footprint have found increasing use in biomedical applications.Upon these features,in this paper,we homebuilt a low-cost CARS microscope based on a SF laser module(scCA RS microscope).This SF laser module is specially customized by adding a time synchronized seed source channel to the SF laser to form a dual-channel output laser.The performance of the scCARS microscope is evaluated with dimethyl sulfoxide,whose results confirm a spatial resolution of better than 500nm and a detection sensitivity of millimolar concentrations.The dual-color imaging capability is further demonstrated by imaging different species of mixed microspheres.We finally explore the potential of our scCARS microscope by mapping lipid droplets in different cancer cells and corneal stromal lenses.

Improved anti-Stokes energy transfer between rare earth ions in Er(0.5)Yb(9.5):FOV oxyfluoride vitroceramics explains the strong color reversal

The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er（0.5）Yb（9.5）：FOV is reported in the present article. The range of the intensity reversal Z was measured to be 877. Dynamic processes for 16 levels were simulated. A coefficient, the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory, is introduced to successfully describe the anti-Stokes energy transfer. A new method to calculate the distance between the rare earth ions, which is critical for the energy transfer calculation, is proposed. The validity of these important improvements is also proved by experiment.

Improvement in the calculation of anti-Stokes energy transfer and experimental justification based on Er_(0.01)Yb_xY_(1 0.01 x)VO_4 crystal

The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering theory as compared with the classical Raman theory is introduced to successfully describe the anti-Stokes energy transfer. The theoretical formula for the improvement on the calculation of anti-Stokes energy transfer rate is derived for the first time in this study. The correctness of introducing coefficient exp{△E/kT} from well-known Raman scatter theory is demonstrated also. Moreover, the experimental lifetime measurement in Er0.01YbxY1-0.01-xVO4 crystal is performed to justify the validity of our important improvement in the original phonon-assisted energy transfer theory for the first time.

Selective Excitation of Two-pulse Femtosecond Coherent Anti-Stokes Raman Scattering in a Mixture

In this paper, we experimentally study the selective excitation of two-pulse femtosecond coherent anti-Stokes Raman scattering (CARS) in a mixture of dibromomethane (CH2Br2) and chloroform (CHCl3) by adaptive pulse shaping based on genetic algorithm. Second harmonic generation frequency-resolved optical gating (SHG-FROG) traces indicate that the spectral amplitude and phase of the optimal pulse are both modulated. Finally, we discuss the physical mechanism for the selective excitation of femtosecond CARS based on the retrieved information from SHG-FROG traces.

用液芯光纤研究stokes/anti-stokes拉曼强度比测温

液芯光纤可以使拉曼光谱强度提高103倍。研究了在stokes/anti stokes拉曼光谱强度比测温中如何获得理想测温结果的方法。用长为5.20m、内径为50μm的含C6H6和CCl4混合液体的液芯光纤,获得了高强度CCl4的±218cm-1,±314cm-1和±459cm-1的拉曼光谱。利用各光谱带的stokes与anti stokes的强度比(Is/Ia),确定了液芯光纤所在处的温度。实验结果表明,±459cm-1的强度比的实验值与理论值符合得很好,±218cm-1为较好,±314cm-1稍差一些。从理论和实验两方面总结了拉曼频移、光纤损耗、溶剂效应、仪器响应等对测温结果的影响。

Low threshold anti-Stokes Raman laser on-chip

Raman lasers based on integrated silica whispering gallery mode resonant cavities have enabled numerous applications from telecommunications to biodetection. To overcome the intrinsically low Raman gain value of silica, these devices leverage their ultrahigh quality factors(Q), allowing submilliwatt stimulated Raman scattering(SRS) lasing thresholds to be achieved. A closely related nonlinear behavior to SRS is stimulated anti-Stokes Raman scattering(SARS). This nonlinear optical process combines the pump photon with the SRS photon to generate an upconverted photon. Therefore, in order to achieve SARS, the efficiency of the SRS process must be high. As a result, achieving SARS in on-chip resonant cavities has been challenging due to the low lasing efficiencies of these devices. In the present work, metal-doped ultrahigh Q(Q > 10~7) silica microcavity arrays are fabricated on-chip. The metal-dopant plays multiple roles in improving the device performance. It increases the Raman gain of the cavity material, and it decreases the optical mode area, thus increasing the circulating intensity. As a result, these devices have SRS lasing efficiencies that are over 10× larger than conventional silica microcavities while maintaining low lasing thresholds. This combination enables SARS to be generated with submilliwatt input powers and significantly improved anti-Stokes Raman lasing efficiency.

Se-sensitized NIR hot band absorption photosensitizer for anti-Stokes excitation deep photodynamic therapy

Conventional anti-Stokes materials-involved deep photodynamic therapy(dPDT)requires much high-intensity irradiance due to low photosensitization efficiency.Herein,we proposed a"booster effector"approach to construct highly efficient hot band absorption phototherapeutics for low/biosafety power anti-Stokes light-triggered d PDT.Se,as"booster effector",was introduced into hot band absorption luminophores(HBAs),which not only significantly facilitated intersystem crossing,but also simultaneously enhanced hot band excitation efficiency atν808,as a result successfully enabling excellent photogenerated singlet oxygen capability of HBAs under ultra-low power anti-Stokes excitation(10 mW cm^(-2)in vitro).As far as we know,such low laser power-initiated photosensitization activity has never been reported in the existing anti-Stokes material systems.Importantly,FUC-Se ME can self-assemble into uniform nanospheres in water,greatly boosting cellular uptake(>25-fold larger than FUC-Se),and achieve superior cancer-killing effect(808 nm,10 mW cm^(-2),5 min,the half-maximal inhibitory concentration IC50=1.36μM).After further PEGylation with folate-attached polymer,the resultant FUC-Se ME@FA can effectively enrich at the tumor(signal-to-background ratio,10).Under safety irradiation(330 mW cm^(-2)),FUC-Se ME@FA effectively inhibits deep-seated tumor progression(the tumor growth inhibition rate,84%).This work provides a successful paradigm,possibly being more clinically beneficial than conventional anti-Stokes materials.

High enhancement factor of Au nano triangular prism structure for surface enhanced coherent anti-Stokes Raman scattering

Coherent anti-Stokes Raman scattering spectroscopy（CARS） is a well-known detecting tool in biosensing and nonlinear spectroscopy. It can provide a non-invasive alternative without the need for exogenous labels,while the enhancement factor for surface plasmon resonances（SPR） are extensively used to increase the local field close to the oscillators and which can obtain high enhancement. In this work, we investigate the enhancement factor of our structure for surface-enhanced coherent anti-Stokes Raman scattering. The absorption spectrum of the structure has been studied, a wide range of absorption has been realized. The enhancement can be as high as 10^（16） over standard CARS. Our design is very useful for improving the enhancement factor of surface-enhanced coherent anti-Stokes Raman scattering.