Cavity Enhanced Raman Scattering Research Articles

Cavity-Enhanced Raman Scattering from 2D Hybrid Perovskites

Cavity-Enhanced Raman Scattering from 2D Hybrid Perovskites

Temperature-Controlled Dual-Beam Optical Trap for Single Particle Studies of Organic Aerosol.

An optical trapping cell that is capable of suspending particles using two counter-propagating beams in a temperature-controlled environment is reported here. With this dual-beam optical trap, we are able to hold single micron-sized droplets at temperatures down to 253 K (-20 °C) for hours at a time and in metastable (supercooled) states. As particles are trapped at the shared focal points of two intense beams, strong cavity-enhanced Raman scattering (CERS) is observed and allows for high precision measurements of physical properties. Here, the evaporation of highly oxygenated organic systems was monitored using CERS and was used to determine temperature-dependent vapor pressures and enthalpies of vaporization. The wavelength- and temperature-dependent optical properties were also simultaneously retrieved using CERS.

Cavity-Enhanced Raman Scattering for In Situ Alignment and Characterization of Solid-State Microcavities

We report cavity-enhanced Raman scattering from a single-crystal diamond membrane embedded in a highly miniaturized fully-tunable Fabry-P\'{e}rot cavity. The Raman intensity is enhanced 58.8-fold compared to the corresponding confocal measurement. The strong signal amplification results from the Purcell effect. We show that the cavity-enhanced Raman scattering can be harnessed as a narrowband, high-intensity, internal light-source. The Raman process can be triggered in a simple way by using an optical excitation frequency outside the cavity stopband and is independent of the lateral positioning of the cavity mode with respect to the diamond membrane. The strong Raman signal emerging from the cavity output facilitates in situ mode-matching of the cavity mode to single-mode collection optics; it also represents a simple way of measuring the dispersion and spatial intensity-profile of the cavity modes. The optimization of the cavity performance via the strong Raman process is extremely helpful in achieving efficient cavity-outcoupling of the relatively weak emission of single color-centers such as nitrogen-vacancy centers in diamond or rare-earth ions in crystalline hosts with low emitter density.

Determining the size and refractive index of homogeneous spherical aerosol particles using Mie resonance spectroscopy.

Methods for determining the size and refractive index of single, homogeneous, micrometer-sized aerosol particles using Mie resonance spectroscopy are studied using measurements from optically trapped particles and light-scattering calculations based on Mie theory. We consider both single-particle broadband light scattering and cavity-enhanced Raman scattering (CERS) and demonstrate that, when resonances observed in either type of spectroscopy are fitted using Mie theory, the accuracy of the best fits are similar. However, broadband measurements can yield more resonances than CERS, thus reducing the uncertainty in the retrieved parameters of best fit and increasing the range of particles that can be characterized. Resonance fitting methods are also compared to methods that fit the entire Mie scattering spectrum. Through calculations, it is shown that measured scattering spectra are sensitive to small changes in how light is collected, while Mie resonance positions are much less sensitive. This means that additional parameters are required to accurately fit entire light-scattering spectra using Mie theory, but these parameters are not needed to accurately determine Mie resonance positions.

A Comparative Study of the Mass and Heat Transfer Dynamics of Evaporating Ethanol/Water, Methanol/Water, and 1-Propanol/Water Aerosol Droplets

The mass and heat transfer dynamics of evaporating multicomponent alcohol/water droplets have been probed experimentally by examining changes in the near surface droplet composition and average droplet temperature using cavity-enhanced Raman scattering (CERS) and laser-induced fluorescence (LIF). The CERS technique provides a sensitive measure of the concentration of the volatile alcohol component in the outer shell of the droplet, due to the exponential relationship between CERS intensity and species concentration. Such volatile droplets, which are probed on a millisecond time scale, evaporate nonisothermally, resulting in both temperature and concentration gradients, as confirmed by comparisons between experimental measurements and quasi-steady state model calculations. An excellent agreement between the experimental evaporation trends and quasi-steady state model predictions is observed. An unexpectedly slow evaporation rate is observed for the evaporation of 1-propanol from a multicomponent droplet when compared to the model; possible explanations for this observation are discussed. In addition, the propagation depth of the CERS signal, and, therefore, the region of the droplet from which compositional measurements are made, can be estimated. Such measurements, when considered in conjunction with quasi-steady state theory, can allow droplet temperature gradients to be measured and vapor pressures and activity coefficients of components within the droplet to be determined.

A quantitative demonstration of the enhancement of cavity enhanced Raman scattering by broad band external laser seeding

We demonstrate in this letter an ability to manipulate threshold concentrations for the observation of cavity enhanced Raman scattering (CERS) in microdroplets, and to enhance the intensity of scatter from a selected component in binary component (nitrate/water) droplets. Measurements from droplets of varying composition have shown that the concentration of the minor component can be quantitatively determined from the optically seeded signal. Various strategies are described by which this method may be more generally applied to enhance stimulated Raman scattering intensities of minor components in multicomponent droplets.

Determining the composition of aqueous microdroplets with broad-band cavity enhanced Raman scattering

We demonstrate that broad-band cavity enhanced Raman scattering (CERS) can be used to determine the composition of binary alcohol-water aerosol droplets over a wide compositional range from 10% v/v to 90% v/v. In contrast to conventional CERS using narrow-band laser excitation, the excitation is provided by a broad-band Nd:YAG pumped dye laser. A change in the spontaneous spectrum resulting from the change of the linewidth of the excitation laser permits tuning of the sensitivity range over which the droplet composition can be determined by CERS. We demonstrate that this change in sensitivity can be estimated using a simulation of the change in the sensitivity to the species in spontaneous bulk phase measurements. We further show that the compositional calibration is independent of droplet radius in the range 33-56 microm. The compositional range over which CERS is sensitive can be controlled and optimised for any particular application by exploiting the dependence of the stimulated Raman scattering on the laser linewidth and wavelength. Thus, quantitative measurements of droplet composition can be made in situ with high accuracy, providing a valuable new tool for analysing aerosol composition.

Evaporation of Ethanol/Water Droplets: Examining the Temporal Evolution of Droplet Size, Composition and Temperature

The evolving size, composition, and temperature of evaporating ethanol/water aerosol droplets 25-57 microm in radius are probed by cavity enhanced Raman scattering (CERS) and laser induced fluorescence. This represents the first study in which the evolving composition of volatile droplets has been probed with spatial selectivity on the millisecond time scale, providing a new strategy for exploring mass and heat transfer in aerosols. The Raman scattering intensity is shown to depend exponentially on species concentration due to the stimulated nature of the CERS technique, providing a sensitive measure of the concentration of the volatile ethanol component. The accuracy with which we can determine droplet size, composition, and temperature is discussed. We demonstrate that the CERS measurements of evolving size and composition of droplets falling in a train can be used to characterize, and thus avoid, droplet coagulation. By varying the surrounding gas pressure (7-77 kPa), we investigate the dependence of the rate of evaporation on the rate of gas diffusion, and behavior consistent with gas diffusion-limited evaporation is observed. We suggest that such measurements can allow the determination of the vapor pressures of components within the droplet and can allow the determination of activity coefficients of volatile species.

An investigation of the factors influencing the detection sensitivity of cavity enhanced Raman scattering for probing aqueous binary aerosol droplets

Stimulated Raman scattering (SRS) from single aerosol droplets can be observed at extremely low laser threshold intensities at wavelengths commensurate with whispering gallery modes. Although droplet size can routinely be determined from the ensuing cavity enhanced Raman scattering (CERS) fingerprint, determining droplet composition is a considerably more challenging measurement. We present here an examination of the factors that influence and limit the detection sensitivity of CERS in quantifying the concentrations of sulfate and nitrate in water droplets, 20-50 microm in radius. In particular, we consider the variation in nitrate and sulfate SRS signal with variation in species concentration, probe laser intensity and droplet size. We illustrate that the band contour of the OH stretching band can be used as a relative measure of the internal light intensity circulating within the droplet and experimentally investigate how the threshold condition for SRS is achieved.

Control and characterisation of a single aerosol droplet in a single-beam gradient-force optical trap

Optical tweezers are used to control aerosol droplets, 4–14 μm in diameter, over time frames of hours at trapping powers of less than 10 mW. When coupled with cavity enhanced Raman scattering (CERS), the evolution of the size of a single droplet can be examined with nanometre accuracy. Trapping efficiencies for water and decane droplets are reported and the possible impact of droplet heating is discussed. We demonstrate that the unique combination of optical tweezing and CERS can enable the fundamental factors governing the coagulation of two liquid droplets to be studied.

Determination and validation of water droplet size distributions probed by cavity enhanced Raman scattering

Cavity enhanced Raman scattering (CERS) fingerprints are obtained on a single particle basis, providing a spectroscopic signature of the water droplet sizes generated by a vibrating orifice aerosol generator (VOAG). By sampling the aerosol train generated by the VOAG over a period of seconds, the size distribution of water droplets can be accumulated. The objective of this paper is to validate the size distribution measurements made and to quantify the accuracy of the sizes measured, along with providing an examination of the dependence of the CERS fingerprint on illumination geometry and laser pulse energy. The size distribution measurements are verified by elastic light scattering data, confirming both the sizes measured by CERS and the evolving droplet sizes produced by the VOAG during an operating time of 5 min. The experimental limitations imposed on the accuracy of the sizes measured by CERS are discussed and estimated. The estimated uncertainty in the droplet radius increases from 4 nm for a 10 μm radius droplet to 22 nm for a 50 μm radius droplet.

An optical method for determining size distributions of water droplets

A method for determining aerosol size distributions by single laser-shot single droplet cavity enhanced Raman scattering (CERS) is presented. Droplets are illuminated with the tripled output from a Nd:YAG laser at 355 nm and the CERS fingerprint acquired with a spectrograph and CCD. Droplets with radii in the range 10–50 μm are probed. The extension of this to the determination of a distribution of droplet sizes is illustrated. We suggest that the CERS signature from water could be used to determine droplet size while the observation of Raman scattering from other constituents could be used to identify trace chemical constituents within water droplets.