Resonant Raman scattering in GaN single crystals and GaN-based heterostructures: feasibility for laser cooling

The recent progress on Raman scattering in GaN single crystals and GaN/A1N heterostructures is re- viewed. Anti-Stokes Raman scattering is used to determine electron-phonon scattering time and decay time constant for longitudinal-opticat phonons. In a typical high electron mobility transistor based on GaN/A1N heterostructures, strong resonances are reached for the first-order and second-order Raman scattering processes. Therefore, both Stokes and anti-Stokes Raman intensities are dramatically enhanced. The feasibility for laser cooling of a nitride structure is studied. A further optimization will enable us to reach the threshold for laser cooling. Raman scattering have potential applications in up-conversion lasers and laser cooling of nitride ultrafast electronic and optoelectronic devices.

Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering （SERRS） of Rhodamine 6G （R6G） adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ＂breathing＂ of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.

The stimulated Raman scattering competition between solute and solvent in Rhodamine B solution

The competition between the stimulated resonance Raman scattering （SRRS） of Rhodamine B （RhB） and the stimulated Raman scattering （SRS） of ethanol （C2H50H） is observed at the RhB in C2H5OH solution. For different concentrations of the solution, the peak wavelengths of the SRRS, the amplified spontaneous emission （ASE）, the fluorescence and the absorption of RhB are different. The SRRS of RhB and the SRS of C2H50H are simultaneously generated when the concentration of the solution is 10-5 mol/L and the energy of the excitation laser is 20.4 mJ. Otherwise, only either the SRRS of RhB or the SRS of C2H5OH is generated. The SRRS can be amplified by the ASE gain when the SRRS is near the peak of the ASE, and the peak wavelength of the SRRS coincides with the wavelength of the maximal intensity ASE.

Robust and high-sensitivity thermal probing at the nanoscale based on resonance Raman ratio (R3)

Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber,linewidth and intensity,and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade.The temperature coefficients of these Raman properties are highly material-dependent,and are subjected to local optical scattering influence.As a result,Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity.Here,a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial(nm WS_(2) film in this work)from 170 to 470 K.A 532 nm laser(2.33 eV photon energy)is used to conduct the Raman experiment.Its photon energy is very close to the excitonic transition energy of WS_(2) at temperatures close to room temperature.A parameter,termed resonance Raman ratio(R3)Ω=I_(A1g)/IE_(2g) is introduced to combine the temperature effects on resonance Raman scattering for the A_(1g) and E_(2g) modes.Ω has a change of more than two orders of magnitude from 177 to 477 K,and such change is independent of film thickness and local optical scattering.It is shown that when Ω is varied by 1%,the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures,respectively.Based on Ω,the in-plane thermal conductivity(k)of a∼25 nm-thick suspended WS_(2) film is measured using our energy transport state-resolved Raman(ET-Raman).k is found decreasing from 50.0 to 20.0 Wm^(−1) K^(−1) when temperature increases from 170 to 470 K.This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman.The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization,non-destructive evaluation,and manufacturing monitoring.

Influence of tip geometry on the spatial resolution of tip enhanced Raman mapping

In 2013,a breakthrough experiment pushed the Raman mapping of molecules via the tip-enhanced Raman scattering（TERS） technique to a sub-nanometer spatial resolution,going into the single-molecule level.This surprising result was well explained by accounting for the critical role of elastic molecule Rayleigh scattering within a plasmonic nanogap in enhancing both the localization and the intensity level of the Raman scattering signal.In this paper,we theoretically explore the influence of various geometric factors of the TERS system on the spatial resolution of Raman mapping,such as the tip curvature radius,tip conical angle,tip–substrate distance,and tip–molecule vertical distance.This investigation can help to find out the most critical geometric factor influencing the spatial resolution of TERS and march along in the right direction for further improving the performance of the TERS system.

Surface-enhanced Raman scattering on dielectric microspheres with whispering gallery mode resonance

Conventionally, metallic nanostructures are used for surface-enhanced Raman spectroscopy(SERS), but recently there has been increasing interest in the enhancement of Raman scattering from dielectric substrates due to their improved stability and biocompatibility compared with metallic substrates. Here, we report the observation of enhanced Raman scattering from rhodamine 6 G molecules coated on silica microspheres. We excite the whispering gallery modes(WGMs) supported in the microspheres with a tapered fiber coupler for efficient WGM excitation, and the Raman enhancement can be attributed to the WGM mechanism. Strong resonance enhancement in pump laser intensity and modified Raman emission from the Purcell effect in the microsphere resonator are observed from the experiment and compared with theoretical results. A total Raman enhancement factor of 1.4 × 10~4 is observed, with contribution mostly from the enhancement in pump laser intensity. Our results show that, with an efficient pumping scheme, dielectric microspheres are a viable alternative to metallic SERS substrates.

Study of second-order nonlinear hyperpolarisability of all-trans-β-carotene in solutions by linear spectroscopic technique

This paper demonstrates the second-order nonlinear hyperpolarisability γ of all-trans-β-carotene in different solvents by linear spectroscopic technique that is based on resonance Raman scattering and UV-VIS （Ultraviolet-visible） absorption spectroscopy. Owing to the two-level model well describing the link that exists between the resonance Raman scattering and stimulated Raman scattering, the stimulated Raman polarisability αR can be calculated through the two-photon resonance system. The value of γ of all-trans-β-carotene in carbon bisulfide solution is 6.435×10^-33 esu （1 esu of resistance = 8.98755×10^11Ω） that is close to the true value, because the solution of all-trans-β-carotene in carbon bisulfide satisfies the rigid resonance Raman scattering condition. This method is expected to be worthy of applications to measure the second-order nonlinear hyperpolaxisability of a conjugate organic molecule.

Enhancing sensitivity of SERRS nanoprobes by modifying heptamethine cyanine-based reporter molecules

Surface enhanced resonance Raman scattering(SERRS)is a physical phenomenon that occurs when the energy of incident light is dose to that of electronic excitation of reporter molecules(RMs)attached on substrates.SERRS has showed great promise in healthcare applications such as tumor diagnosis,image guided tumor surgery and real-time evaluation of therapeutic response due to its ultra-sensitivity,manipulating convenience and easy acessibility.As the most widely used organic near-infrared(NIR)fuorophore,heptamethine cyanines possess the electronic ex-citation energy that is close to the plasmon absorption energy of the gold nano scafolds,which results in the extraordinary enhancement of the SERRS signal.However,the effect of hepta-methine cyanine structure and the gold nanoparticle morphology to the SERRS intensity are barely investigated.This work developed a series of SERRS nanoprobes in which two hepta-methine cyanine derivatives(IR783 and IR780)were used as the RM and three gold nanoparticles(nanorod,nanosphere and nanostar)were used as the substrates.Interestingly,even though IR780 and IR783 possess very similar chemical structure,SERRS signal produced by IR780 was determined as 14 times higher than that of IR783 when the RM concentration was6.5 × 10^(-6) M.In contrast,less than 4.0 fold SERRS signal intensity increase was measured by changing the substrate morphologies.Above experimental results indicate that finely tuning the chemical structure of the heptamethine cyanine could be a feasible way to develop robust SERRS probes to visualize tumor or guide tumor resection with high sensitivity and target to background ratio.

A dual-functional membrane for bisphenol A enrichment and resonance amplification by surface-enhanced Raman scattering

Bisphenol A （BPA） was one of the environmental hormones that would cause endocrine and metabolic disorders in human or wildlife. This paper proposed a method to detect the trace amounts of BPA in water samples by fully utilizing the enrichment and resonance amplification functions of a new dual-functional membrane. In this work, gold nanoparticles （AuNPs） modified by 3-amino-5-mercapto-1,2,4-triazole （AMT） were embedded in nylon66 membrane to produce a dual-functional membrane which could carry out sample enrichment by capturing BPA molecules from water and achieve resonance amplification by connecting BPA to the surfaces of AuNPs. By designing an automatic sampler for large-volume enrichment, the SERS enhancement factor （EF） of the method was further improved to 1.2 × 105. The present method had been successfully applied to detect BPA in drinking water and environmental water by SERS with the detection limit of 0.012 μg/L. It had the potential for on-site detecting of BPA in various water samples.

Breakdown of Raman selection rules by Frohlich interaction in few-layer WS_(2)

The polarization selection rule of Raman scattering is crucial in symmetry analysis of elementary excitations in semiconductors and correlated electron systems.Here we reported the observation of breakdown of Raman selection rules in few-layer WS_(2) by using resonant Raman spectroscopy.When the excitation energy is close to the dark A exciton state,we observed some infrared active modes and backscattering forbidden modes.Importantly,we found that all observed phonon modes follow the same paralleled-polarization behavior.According to the electron-phonon coupling near the band edge in WS_(2),we proposed a theoretical model based on the intraband Frohlich interaction.In this case,the polarization response of the scattering signal is no longer determined by the original Raman tensor of scattered phonons.Instead,it is determined by a new isotropic Raman tensor that generated from this intraband Frohlich interaction between dark A exciton and phonons.We found that this theoretical model is in excellent agreement with the observed results.The breakdown of Raman selection rules can violate the conventional limitations of the optical response and provide an effective method to control the polarization of Raman scattering signals in two-dimensional materials.