Ultrafast laser spectroscopy

Ultrafast laser spectroscopy is a category of spectroscopic techniques using ultrashort pulse lasers for the study of dynamics on extremely short time scales. Different methods are used to examine the dynamics of charge carriers, atoms, and molecules. Many different procedures have been developed spanning different time scales and photon energy ranges; some common methods are listed below.

Attosecond-to-picosecond spectroscopy

Dynamics on the femtosecond time scale are in general too fast to be measured electronically. Most measurements are done by employing a sequence of ultrashort light pulses to initiate a process and record its dynamics. The temporal width of the light pulses has to be on the same scale as the dynamics that are to be measured or even shorter.

Light sources

Titanium-sapphire laser

s are tunable lasers that emit red and near-infrared light.Ti-sapphire laser oscillators use Ti doped-sapphire crystals as a gain medium and Kerr-lens mode-locking to achieve sub-picosecond light pulses. Typical Ti:sapphire oscillator pulses have nJ energy and repetition rates 70-100 MHz. Chirped pulse amplification through regenerative amplification can be used to attain higher pulse energies. For amplification, laser pulses from the Ti:sapphire oscillator must first be stretched in time to prevent damage to optics, and then are injected into the cavity of another laser where pulses are amplified at a lower repetition rate. Regeneratively amplified pulses can be further amplified in a multi-pass amplifier. Following amplification, the pulses are recompressed to pulse widths similar to the original pulse widths.

Dye laser

A dye laser is a four-level laser that uses an organic dye as the gain medium. Pumped by a laser with a fixed wavelength, due to various dye types you use, different dye lasers can emit beams with different wavelengths. A ring laser design is most often used in a dye laser system. Also, tuning elements, such as a diffraction grating or prism, are usually incorporated in the cavity. This allows only light in a very narrow frequency range to resonate in the cavity and be emitted as laser emission. The wide tunability range, high output power, and pulsed or CW operation make the dye laser particularly useful in many physical & chemical studies.

Fiber laser

A fiber laser is usually generated first from a laser diode. The laser diode then couples the light into a fiber where it will be confined. Different wavelengths can be achieved with the use of doped fiber. The pump light from the laser diode will excite a state in the doped fiber which can then drop in energy causing a specific wavelength to be emitted. This wavelength may be different from that of the pump light and more useful for a particular experiment.

X-ray generation

Ultrafast optical pulses can be used to generate x-ray pulses in multiple ways. An optical pulse can excite an electron pulse via the photoelectric effect, and acceleration across a high potential gives the electrons kinetic energy. When the electrons hit a target they generate both characteristic x-rays and bremsstrahlung. A second method is via laser-induced plasma. When very high-intensity laser light is incident on a target, it strips electrons off the target creating a negatively charged plasma cloud. The strong Coulomb force due to the ionized material in the center of the cloud quickly accelerates the electrons back to the nuclei left behind. Upon collision with the nuclei, Bremsstrahlung and characteristic emission x-rays are given off. This method of x-ray generation scatters photons in all directions, but also generates picosecond x-ray pulses.

Conversion and characterization

Pulse characterization

For accurate spectroscopic measurements to be made, several characteristics of the laser pulse need to be known; pulse duration, pulse energy, spectral phase, and spectral shape are among some of these. Information about pulse duration can be determined through autocorrelation measurements, or from cross-correlation with another well-characterized pulse. Methods allowing for complete characterization of pulses include frequency-resolved optical gating and spectral phase interferometry for direct electric-field reconstruction.

Pulse shaping

is to modify the pulses from the source in a well-defined manner, including manipulation on pulse's amplitude, phase, and duration.
To amplify pulse's intensity, chirped pulse amplification is generally employed, which includes a pulse stretcher, amplifier, and compressor. It will not change the duration or phase of the pulse during the amplification. Pulse compression is achieved by first chirping the pulse in a nonlinear material and broadening the spectrum, with the following compressor for chirp compensation. A fiber compressor is generally used in this case.
Pulse shapers usually refer to optical modulators which apply Fourier transforms to a laser beam. Depending on which property of light is controlled, modulators are called intensity modulators, phase modulators, polarization modulators, spatial light modulators. Depending on the modulation mechanism, optical modulators are divided into Acoustic-optic modulators, Electro-optic modulators, Liquid crystal modulators, etc. Each is dedicated to different applications.

High harmonic generation

is a nonlinear process where intense laser radiation is converted from one fixed frequency to high harmonics of that frequency by ionization and recollision of an electron. It was first observed in 1987 by McPherson et al. who successfully generated harmonic emission up to the 17th order at 248 nm in neon gas.
HHG is seen by focusing an ultra-fast, high-intensity, near-IR pulse into a noble gas at intensities of 10¹³–10¹⁴ W/cm² and it generates coherent pulses in the XUV to Soft X-ray region of the spectrum. It is realizable on a laboratory scale as opposed to large free electron-laser facilities.
High harmonic generation in atoms is well understood in terms of the three-step model.
Ionization: The intense laser field modifies the Coulomb potential of the atom, electron tunnels through the barrier and ionize.
Propagation: The free-electron accelerates in the laser field and gains momentum.
Recombination: When the field reverses, the electron is accelerated back toward the ionic parent and releases a photon with very high energy.

Frequency conversion techniques

Different spectroscopy experiments require different excitation or probe wavelengths. For this reason, frequency conversion techniques are commonly used to extend the operational spectrum of existing laser light sources.
The most widespread conversion techniques rely on using crystals with second-order non-linearity to perform either parametric amplification or frequency mixing.
Frequency mixing works by superimposing two beams of equal or different wavelengths to generate a signal which is a higher harmonic or the sum frequency of the first two.
Parametric amplification overlaps a weak probe beam with a higher energy pump beam in a non-linear crystal such that the weak beam gets amplified and the remaining energy goes out as a new beam called the idler. This approach has the capability of generating output pulses that are shorter than the input ones. Different schemes of this approach have been implemented. Examples are optical parametric oscillator, optical parametric amplifier, non-collinear parametric amplifier.

Techniques

Ultrafast transient absorption

This method is typical of 'pump-probe' experiments, where a pulsed laser is used to excite the electrons in a material from their ground states to higher-energy excited states. A probing light source, typically a xenon arc lamp or broadband laser pulse created by supercontinuum generation, is used to obtain an absorption spectrum of the compound at various times following its excitation. As the excited molecules absorb the probe light, they are further excited to even higher states or induced to return to the ground state radiatively through stimulated emission. After passing through the sample, the unabsorbed probe light continues to a photodetector such as an avalanche photodiode array or CMOS camera, and the data is processed to generate an absorption spectrum of the excited state. Since all the molecules or excitation sites in the sample will not undergo the same dynamics simultaneously, this experiment must be carried out many times, and the data must be averaged to generate spectra with accurate intensities and peaks. Because photobleaching and other photochemical or photothermal reactions can happen to the samples, this method requires evaluating these effects by measuring the same sample at the same location many times at different pump and probe intensities. Most time the liquid samples are stirred during measurement making relatively long-time kinetics difficult to measure due to flow and diffusion. Unlike time-correlated single photon counting, this technique can be carried out on non-fluorescent samples. It can also be performed on non-transmissive samples in a reflection geometry.
Ultrafast transient absorption can use almost any probe light, so long as the probe is of a pertinent wavelength or set of wavelengths. A monochromator and photomultiplier tube in place of the avalanche photodiode array allows observation of a single probe wavelength, and thus allows probing of the decay kinetics of the excited species. The purpose of this setup is to take kinetic measurements of species that are otherwise nonradiative, and specifically it is useful for observing species that have short-lived and non-phosphorescent populations within the triplet manifold as part of their decay path. The pulsed laser in this setup is used both as a primary excitation source, and a clock signal for the ultrafast measurements. Although laborious and time-consuming, the monochromator position may also be shifted to allow absorbance decay profiles to be constructed, ultimately to the same effect as the above method.
The data of UTA measurements usually are reconstructed absorption spectra sequenced over the delay time between the pump and probe. Each spectrum resembles a normal steady-state absorption profile of the sample after the delay time of the excitation with the time resolution convoluted from the pump and probe time resolutions. The excitation wavelength is blinded by the pump laser and cut out. The rest of the spectra usually have a few bands such as ground-state absorption, excited-state absorption, and stimulated emission. Under normal conditions, the angles of the emission are randomly orientated and not detected in the absorption geometry. But in UTA measurement, the stimulated emission resembles the lasing effect, is highly oriented, and is detected. Many times this emission overlaps with the absorption bands and needs to be deconvoluted for quantitative analysis. The relationship and correlation among these bands can be visualized using the classical spectroscopic two-dimensional correlation analysis.