Improved scanning range for coherent anti-stokes Raman spectroscopy using a tunable optical parametric oscillator

Coherent anti-Stokes Raman spectroscopy (CARS) is a well-known form of nonlinear spectroscopy that has been used for a wide range of specialized quantitative applications. From an analytical chemist's point of view, however, conventional CARS is impractical as a tool for qualitative and quantitative analyses because the scan range is too short to produce complete vibrational spectra. This paper introduces a new technique, synchronously scanned optical parametric oscillator (OPO) CARS, that improves the potential for using nonlinear spectroscopy as an analytical technique in both gas- and condensed-phase samples. First, it uses a broadly tunable OPO to increase the scan range. Second, phase matching problems that limit scans in condensed-phase CARS are reduced by using both the signal and the idler beams in a synchronous scanning manner. Finally, this synchronous scanning method generates an output signal that remains fixed at a single wavelength (single-wavelength detection). Advantages of single-wavelength detection include reduction of stray light, simplicity, and elimination of the need for wavelength calibration of the detection optics. Results are presented on neat and mixed samples in gas and condensed phases.     

Limits to remote molecular detection via coherent anti-Stokes raman spectroscopy using a maximal coherence control technique

ABSTRACT

The demand for remote molecular detection has been rising in recent years. The technique of coherent anti-Stokes Raman spectroscopy (CARS) has become one of the most optimal methods due to its high efficiency, fast response time and ease of use. In this article, we estimate the number of detectable photons from a CARS signal by using a semiclassical nonlinear optics approach. Several key parameters and their effect on the signal are studied in the following discussion. We also provide a method to prepare the maximum coherence between vibrational states in an effective two level system.     

Experimental comparison of single-shot broadband vibrational and dual-broadband pure rotational coherent anti-Stokes Raman scattering in hot air

Broadband vibrational and dual-broadband pure rotational coherent anti-Stokes Raman scattering (CARS) have been compared in a high-temperature oven, in which the accuracy and single-shot precision of gas temperature and relative O(2)- and N(2)-concentration measurements in hot air were probed over a temperature range that is typical for many combustion processes. To ensure a realistic comparison, we used nearly the same experimental setup for both CARS techniques. Besides temperature information, dual-broadband pure rotational CARS offers the possibility of achieving simultaneous single-shot concentration measurements. The comparison shows that this technique also has significant advantages in temperature evaluation over a large temperature range in comparison with vibrational CARS.     

Diagnostic study of four-wave-mixing-based electric-field measurements in high-pressure nitrogen plasmas

We present the results of a diagnostic study of the use of coherent four wave mixing for in situ measurement of an electric field in air or in nitrogen-containing plasmas. Static electric fields in air at a nominal pressure of 625 Torr and temperature of 300 K are detected using vibrational CARS of nitrogen. It is shown that the ratio of the infrared signal to the vibrational N(2) CARS signal is equal to approximately 10(-8) at 8.33 kV/cm, a factor of approximately 50 less than that predicted assuming equal third-order nonlinear susceptibilities. It is also shown that the spatial resolution of a typical collinear geometry measurement is approximately 1 cm. Finally, it is shown that achieving sensitivities of the order of 1 kV/cm requires that the coherent Raman pumping be performed in the highly saturated and Stark broadened regime.     

Refractive effects in coherent anti-Stokes Raman scattering microscopy

Coherent anti-Stokes Raman scattering (CARS) microscopy with high sensitivity and high three- dimensional resolution has been developed for the vibrational imaging of chemical species. Due to the coherent nature of the CARS emission, it has been reported that the detection of epi-CARS and forward-CARS (F-CARS) signals depends on the size and shape of the sample. We investigate theoretically and experimentally the effects on the CARS signal of refractive index mismatches between the sample and its surroundings. Backward-CARS and F-CARS signals are measured for different polystyrene bead diameters embedded in different refractive index solvents. We show that index mismatches result in a backward-reflected F-CARS signal that generally dominates the experimentally backward-detected signal. Simulations based on geometrical and wave optics comparing forward- and backward-detected signals for polystyrene beads embedded in different index solvents confirm our findings. Furthermore, we demonstrate that the maxima of forward- and backward-detected signals are generated at different positions along the optical axis in the sample if refractive index mismatches are present between the sample and its surroundings.     

Coherent anti-Stokes Raman scattering measurements of N(2)(X, v) at low pressures corrected for stimulated Raman scattering

Number density measurements of the populations of the vibrational states of the electronic ground state of molecules that use scanning coherent anti-Stokes Raman scattering (CARS) spectroscopy at pressures in which Doppler broadening dominates can be strongly influenced by population changes caused by the stimulated Raman process. Such measurements have been carried out in heterogeneous deactivation studies of vibrationally excited N(2) on various solid surfaces at 17 Torr. This process perturbs the populations of the states connected by the incident fields. It typically reduces the population difference and therefore reduces the observed CARS signal. Thus, as the incident laser irradiance increases, the observed signal exhibits saturation. A linear relationship for this effect in terms of the average laser powers is derived, providing a scheme for calibrating the initial onset of this saturation process. This calibration method permits simple corrections of the CARS data for saturation.     

Simultaneous vibrational and pure rotational coherent anti-stokes Raman spectroscopy for temperature and multispecies concentration measurements demonstrated in sooting flames

The potential of measuring temperature and multiple species concentrations (N2, O2, CO) by use of combined vibrational coherent anti-Stokes Raman spectroscopy (CARS) and pure rotational CARS has been investigated. This was achieved with only one Nd:YAG laser and one dye laser together with a single spectrograph and CCD camera. From measurements in premixed sooting C2H4-air flames it was possible to evaluate temperatures from both vibrational CARS and rotational CARS spectra, O2 concentration from the rotational CARS spectra, and CO concentration from the vibrational CARS spectra. Quantitative results from premixed sooting C2H4-air flames are presented, and the uncertainties in the results as well as the possibility of extending the combined CARS technique for probing of additional species are discussed.     

Improving signal-to-interference ratio in rich hydrocarbon-air flames using picosecond coherent anti-Stokes Raman scattering

There is growing interest in the use of short-pulse lasers for coherent anti-Stokes Raman scattering (CARS) to minimize non-resonant background (NRB) contributions in a variety of applications. Using time-coincident picosecond (ps) pump and Stokes beams and a time-delayed ps probe beam, we show that a three orders of magnitude reduction in NRB interference can be achieved in rich hydrocarbon-air flames while preserving 60% to 80% of the CARS signal. This represents a significant improvement in signal-to-interference ratio compared with previous measurements in room temperature air and is attributable to reduced rates of collisional dephasing and relaxation at flame temperatures. Measurements within the flame zone of a laminar flat-flame burner are used to investigate the characteristics of time-coincident and probe-delayed broadband ps N(2)-CARS spectra for C(2)H(4)-air equivalence ratios of 0.5 to 1.2. Up to three ro-vibrational bands of N(2) are excited with each laser shot using 135 ps pump and 106 ps Stokes beams, and the CARS signal is generated using a 135 ps probe beam delayed by 165 ps. The enhanced signal-to-interference ratio achieved in the current work is one to two orders of magnitude higher than that previously achieved using polarization-selection techniques without sensitivity to the effects of birefringence caused by density gradients or test cell windows. Moreover, the use of a 135 ps laser source in this study enables frequency domain "broadband" CARS with sufficient resolution to extract ro-vibrational spectral features under various flame conditions. The effect of probe delay and NRB suppression on characteristics of these broadband CARS spectra are investigated, and evidence of preferential collisional dephasing and relaxation of different ro-vibrational transitions is not detected. This is a promising but preliminary result to be investigated further in future work.     

Crossed two-beam coherent anti-stokes Raman spectroscopy in dispersive media

Coherent anti-Stokes Raman spectroscopy (CARS) is a nonlinear optical wave mixing process that is used in gas-phase systems to determine the energy distribution of the probed species (usually N2) and, through a fitting procedure, the temperature giving rise to it. CARS signal strengths are maximized when the phase matching condition is met. Because gases are generally non-dispersive, this phase matching condition can be found geometrically as a function of the crossing angles between the CARS beams and their wavelengths. In addition, perfect phase matching in non-dispersive media occurs automatically for collinear beams. To improve spatial resolution, however, intersecting the laser beams is desirable. Being a third-order process, phase matching for CARS in gases typically requires three input laser beams. This paper discusses and demonstrates the issues of phase matching for CARS when the medium is dispersive, and the ability for CARS phase matching to occur with only two crossed laser beams (one pump and one probe). This two-beam X-CARS in dispersive media can be used as an alignment tool for gas-phase CARS and may be relevant as a simpler diagnostic in high-pressure environments. The paper also discusses the effects of non-ideal phase matching in dispersive and non-dispersive media.     

Comparison of Gas Temperatures Measured by Coherent Anti-Stokes Raman Spectroscopy (CARS) of O(2) and N(2)

We investigate the accuracy of temperature measurements by coherent anti-Stokes Raman spectroscopy (CARS) of O(2) and use measurements taken with N(2) CARS and a thermocouple for comparison. Scanning vibrational CARS spectra of O(2) and N(2) were recorded over a broad range of temperatures: between 294 K and 1900 K in air that was heated in a tube furnace and at approximately 2450 K in a fuel-lean CH(4)-O(2)-N(2) flame. Temperatures were derived from least-squares fits of simulated and experimental spectra. Both the fundamental vibrational band and the first hot vibrational band were included in fitting. In the case of the tube furnace, the N(2) and the O(2) CARS temperature measurements agreed to within 3%, and results were similar with the thermocouple; in the flame the agreement was to within 1%. We conclude that, for cases in which O(2) is present in sufficient concentrations ( approximately 10% or greater), the accuracy of O(2) thermometry is comparable with that of N(2).     

Focus-engineered coherent anti-Stokes Raman scattering microscopy: a numerical investigation

The coherent anti-Stokes Raman scattering (CARS) signal is calculated as a function of focal-field distributions with engineered phase jumps. We show that the focal fields in CARS microscopy can be shaped such that the signal from the bulk is suppressed in the forward detection mode. We present the field distributions that display enhanced sensitivity to vibrationally resonant object interfaces in the lateral dimension. The use of focus-engineered CARS provides a simple means to detect chemical edges against the strong background signals from the bulk.     

Dynamic Range Enhancement for Pure Rotational Coherent Anti-Stokes Raman Scattering Thermometry by use of an Optical Arrangement with Two Dye Lasers

A disadvantage of pure rotational coherent anti-Stokes Raman scattering (CARS) compared with vibrational CARS is the limited dynamic range for temperature measurements. Here an optical configuration is described that overcomes this limitation by the use of two different center-frequency dye lasers in a dual-broadband CARS approach. Its performance is demonstrated for simultaneous pure rotational CARS temperature and relative N(2)-O(2)concentration measurements up to 1950 K at ambient pressure.     

Stray Light Rejection in Rotational Coherent Anti-Stokes Raman Spectroscopy by use of a Sodium-Seeded Flame

A common experimental problem with rotational coherent anti-Stokes Raman spectroscopy (CARS) is undesired spectral interference that is due to stray light from the primary laser beams. Also, for the most developed approach, dual-broadband rotational CARS, practical measurements often suffer from stray light interference from the narrow-band laser, inasmuch as the CARS signal is produced inherently in the spectral vicinity of the narrow-band laser beam. An optical filter does not provide a sufficiently sharp transmission profile, thus leading to signal loss and spectral distortion of the rotational CARS signal. An atomic filter consisting of a sodium-seeded flame is presented here as a solution to the problem, and its usefulness was demonstrated in dual-broadband rotational CARS experiments.     

Gas-phase thermometry using delayed-probe-pulse picosecond coherent anti-Stokes Raman scattering spectra of H2

We report the development and application of a simple theoretical model for extracting temperatures from picosecond-laser-based coherent anti-Stokes Raman scattering (CARS) spectra of H2 obtained using time-delayed probe pulses. This approach addresses the challenges associated with the effects of rotational-level-dependent decay lifetimes on time-delayed probing for CARS thermometry. A simple procedure is presented for accurate temperature determination based on a Boltzmann distribution using delayed-probe-pulse vibrational CARS spectra of H2; this procedure requires measurement at only a select handful of probe-pulse delays and requires no assumptions about sample environment.     

Noise in single-shot broadband coherent anti-Stokes Raman spectroscopy that employs a modeless dye laser

The noise in single-shot coherent anti-Stokes Raman (CARS) spectroscopy that employs a broadband modeless dye laser (MDL) is examined and the results are compared with those of a conventional dye laser. The noise of the dye-laser, the nonresonant CARS, and the resonant N(2) CARS signals are determined. The use of a MDL is shown to result in substantially reduced CARS noise when the CARS signal is generated with a single-mode pump laser, but only a marginal reduction of noise is observed with a multimode pump source The noise measurements are compared with theoretical predictions that are based on models that assume modes of random amplitudes and phases in the multimode laser sources. The combination of a MDL and a single-mode pump laser is shown to increase the precision of single-shot N(2) CARS temperature measurements.     

Quantitative one-dimensional imaging using picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy

We employ picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) in a one-dimensional (1D) imaging configuration. Temperature and O(2):N(2) concentration ratios are measured along a 1D line of up to 12 mm in length. The images consist of up to 330 individual rotational CARS (RCARS) spectra, corresponding to 330 spatially resolved volume elements in the probe volume. Signal levels are sufficient for the collection of single-laser-pulse images at temperatures of up to approximately 1200 K and shot-averaged images at flame temperatures, demonstrated at 2100 K. The precision of picosecond pure-rotational 1D imaging CARS is assessed by acquiring a series of 100 single-laser-pulse images in a heated flow of N(2) from 410 K-1200 K and evaluating a single volume element for temperature in each image. Accuracy is demonstrated by comparing temperatures from the evaluated averaged spectra to thermocouple readings in the heated flow. Deviations from the thermocouple of <30 K in the evaluated temperature were found at up to 1205 K. Accuracy and single-shot precision are compared to those reported for single-point nanosecond dual-broadband pure-RCARS and nanosecond 1D vibrational CARS.     

Broadband coherent anti-Stokes Raman spectroscopy characterization of polymer thin films

Broadband coherent anti-Stokes Raman spectroscopy (CARS) is demonstrated as an effective probe of polymer thin film materials. A simple modification to a 1 kHz broad bandwidth sum frequency generation (SFG) spectrometer permits acquisition of CARS spectra for polymer thin films less than 100 nm thick, a dimension relevant to organic electronic device applications. CARS spectra are compared to the conventional Raman spectra of polystyrene and the resonance-enhanced Raman spectra of poly(3-hexylthiophene). The CARS spectra obtained under these conditions consistently demonstrate enhanced signal-to-noise ratio compared to the spontaneous Raman scattering. The sensitivity of the CARS measurement is limited by the damage threshold of the samples. The dielectic properties of the substrate have a dramatic effect on the detected signal intensity. For ultrathin films, the strongest signals are obtained from fused silica surfaces. Similar to surface-enhanced Raman scattering (SERS), Au also gives a large signal, but contrary to SERS, no surface roughening is necessary.     

Detection of chemical interfaces in coherent anti-Stokes Raman scattering microscopy: D-CARS. II. Arbitrary interfaces

We address the general problem of detecting chemical interfaces arbitrarily oriented in space in coherent anti-Stokes Raman scattering (CARS) microscopy. Such a task is accomplished by using a beam reversal scheme, as recently demonstrated experimentally [J. Biomed. Opt. 16, 086006 (2011)]. We develop a full vectorial theoretical analysis of the situation and show that transverse chemical interfaces are readily highlighted without special care in the CARS signal detection. In addition, a finer analysis reveals that adequate angular analysis of the CARS far-field radiation pattern enables the detection of axial interfaces. Background-free CARS microscopy and spectroscopy are thus achievable through the combined application of excitation beam reversal and angular analysis of the CARS far-field radiation pattern. This differential CARS (D-CARS) technique is relevant for fast detection of interfaces between molecularly different media.     

Development of multipoint vibrational coherent anti-Stokes Raman spectroscopy for flame applications

A novel technique for coherent anti-Stokes Raman spectroscopy (CARS) measurements in multiple points is presented. In a multipass cavity the pump and Stokes laser beams are multiply reflected and refocused into a measurement volume with an adjustable number of separated points along a line. This optical arrangement was used in a vibrational CARS setup with planar BOXCARS phase-matching configuration. The CARS spectra from spatially separated points were recorded at different heights on a CCD camera. Measurements of temperature profiles were carried out in the burned gas zone of a premixed one-dimensional flame to demonstrate the applicability of this method for temperature measurements in high-temperature regions. The ability to measure in flames with strong density gradients was demonstrated by simultaneous measurements of Q-branch spectra of N2 and CO in a Wolfhard-Parker burner flame. Interference phenomena found in multipoint spectra are discussed, and possible solutions are proposed. Merits and limitations of the technique are discussed.     

Supercontinuum dynamically visualizes a dividing single cell

During cell division, various organelles behave dynamically. Visualization of these dynamic behaviors of organelles is a promising one step forward for understanding life at the molecular level. One- or two-photon excited fluorescence microscopy has so far been used for visualizing these cell dynamics. The fluorescent probe introduced into a living cell can visualize the spatial distribution of a target molecule in real time, enabling the tracing of cell dynamics at the molecular level. Introducing a fluorescent probe into a cell, however, may alter the physical and chemical conditions of the cell. Here we show a new method for direct (no need for staining cells) visualization of living cell processes with coherent anti-Stokes Raman scattering (CARS) spectroscopy. A new light source, supercontinuum generated from a photonic crystal fiber, has facilitated ultrabroadband (>3500 cm(-1)) multiplex CARS spectroscopy and imaging with high molecular specificity. Using this multiplex CARS technique, we have been successful in tracing the whole cell division process, the splitting of a mother cell into two daughter cells, appearance and disappearance of septum, and dynamic distribution changes of organelles consisting of lipid membrane. The supercontinuum has also facilitated simultaneous measurement of the CARS and two-photon excited fluorescence (TPEF) spectra, enabling what we call multiple nonlinear spectral imaging. Three-dimensional image reconstruction of a living cell with high speed is now possible to elucidate more detailed molecular-level dynamics inside a dividing living cell.