Multiple-pass or long path absorption cells are commonly used in spectroscopy to measure low-concentration components or to observe weak spectra in gases or liquids. Several important advances were made in this area beginning in the 1930s, and research into a wide range of applications continues to the present day.
Generally the goal of this type of sample cell is to improve detection sensitivity by increasing the total optical path length that travels through a small, constant sample volume. In principle, a longer path length results in greater detection sensitivity. Focusing mirrors must be used to redirect the beam at each reflection point, resulting in the beam being restricted to a predefined space along a controlled path until it exits the optical cavity. The output of the cell is the input of an optical detector (a specialized type of transducer), which senses specific changes in the properties of the beam that occur during interaction with the test sample. For instance, the sample may absorb energy from the beam, resulting in an attenuation of the output that is detectable by the transducer. Two conventional multipass cells are called the White cell and Herriott cell. [1]
In the late 1930s August Pfund used a triple-pass cell like the one shown above for atmospheric study. The cell, which became known as the Pfund cell, is constructed using two identical spherical mirrors, each having a hole carefully machined into its center. The separation distance between the mirrors is equal to the mirror focal length. A source enters from a hole in either mirror, is redirected twice at two reflection points, and then exits the cell through the other mirror on the third pass. The Pfund cell was one of the earliest examples of this type of spectroscopic technique and is noted for having used multiple passes. [2]
The White cell was first described in 1942 by John U. White in his paper Long Optical Paths of Large Aperture, [3] and was a significant improvement over previous long path spectroscopic measurement techniques. A White cell is constructed using three spherical, concave mirrors having the same radius of curvature. The mirrors are separated by a distance equal to their radii of curvature. The animation on the right shows a White Cell in which a beam makes eight reflective passes or traversals. The number of traversals can be changed quite easily by making slight rotational adjustments to either M2 or M3; however, the total number of traversals must always occur in multiples of four. The entering and exiting beams do not change position as traversals are added or removed, while the total number of traversals can be increased many times without changing the volume of the cell, and therefore the total optical path length can be made large compared to the volume of the sample under test. The spots from various passes can overlap on mirrors M2 and M3 but must be distinct on mirror M1. If the input beam is focused in the plane of M1, then each round trip will also be focused in this plane. The tighter the focus, the more nonoverlapping spots there can be on M1 and thus the higher the maximum pathlength.
At present the White cell is still the most commonly used multipass cell and provides many advantages. [4] For example,
White cells are available with path lengths ranging from less than a meter to many hundreds of meters. [5]
The Herriott cell first appeared in 1965 when Donald R. Herriott and Harry J. Schulte published Folded Optical Delay Lines while at Bell Laboratories. [6] The Herriott cell is made up of two opposing spherical mirrors. A hole is machined into one of the mirrors to allow the input and output beams to enter and exit the cavity. Alternatively, the beam may exit through a hole in the opposite mirror. In this fashion the Herriott cell can support multiple light sources by providing multiple entrance and exit holes in either of the mirrors. Unlike the White cell, the number of traversals is controlled by adjusting the separation distance D between the two mirrors. This cell is also commonly used and has some advantages [4] over the White cell:
However, the Herriot cell does not accept high numerical aperture beams. In addition, larger sized mirrors must be used when longer path lengths are needed.
Another category of multipass cells is generally referred to as circular multipass reflection cells. They were first introduced by Thoma and co-workers in 1994. [7] Such cells rely on a circular arrangement of mirrors. The beam enters the cell under an angle and propagates on a star-shaped pattern (see picture on the right). The path length in circular multipass cells can be varied by adjusting the incidence angle of the beam. An advantage lies in their robustness towards mechanical stress such as vibrations or temperature changes. Furthermore, circular multipass cells stand out because of the small detection volumes they provide. [8] A stable beam propagation is achieved by shaping individual reflection points to form a non-concentric mirror-arrangement. [9] [10]
In a special case, a circular mirror is used, allowing continuous adjustment of the angle of incidence. A drawback of this circular cell configuration is the inherent concentric mirror arrangement which leads to imperfect imaging after a large number of reflections.
Microscopy is the technical field of using microscopes to view objects and areas of objects that cannot be seen with the naked eye. There are three well-known branches of microscopy: optical, electron, and scanning probe microscopy, along with the emerging field of X-ray microscopy.
Interferometry is a technique which uses the interference of superimposed waves to extract information. Interferometry typically uses electromagnetic waves and is an important investigative technique in the fields of astronomy, fiber optics, engineering metrology, optical metrology, oceanography, seismology, spectroscopy, quantum mechanics, nuclear and particle physics, plasma physics, remote sensing, biomolecular interactions, surface profiling, microfluidics, mechanical stress/strain measurement, velocimetry, optometry, and making holograms.
Optical tweezers are scientific instruments that use a highly focused laser beam to hold and move the microscopic and sub-microscopic objects like atoms, nanoparticles and droplets, in a manner similar to tweezers. If the object is held in air or vacuum without additional support, it can be called optical levitation.
Optics is the branch of physics which involves the behavior and properties of light, including its interactions with matter and the construction of instruments that use or detect it. Optics usually describes the behavior of visible, ultraviolet, and infrared light. Because light is an electromagnetic wave, other forms of electromagnetic radiation such as X-rays, microwaves, and radio waves exhibit similar properties.
A dye laser is a laser that uses an organic dye as the lasing medium, usually as a liquid solution. Compared to gases and most solid state lasing media, a dye can usually be used for a much wider range of wavelengths, often spanning 50 to 100 nanometers or more. The wide bandwidth makes them particularly suitable for tunable lasers and pulsed lasers. The dye rhodamine 6G, for example, can be tuned from 635 nm (orangish-red) to 560 nm (greenish-yellow), and produce pulses as short as 16 femtoseconds. Moreover, the dye can be replaced by another type in order to generate an even broader range of wavelengths with the same laser, from the near-infrared to the near-ultraviolet, although this usually requires replacing other optical components in the laser as well, such as dielectric mirrors or pump lasers.
Tunable diode laser absorption spectroscopy is a technique for measuring the concentration of certain species such as methane, water vapor and many more, in a gaseous mixture using tunable diode lasers and laser absorption spectrometry. The advantage of TDLAS over other techniques for concentration measurement is its ability to achieve very low detection limits. Apart from concentration, it is also possible to determine the temperature, pressure, velocity and mass flux of the gas under observation. TDLAS is by far the most common laser based absorption technique for quantitative assessments of species in gas phase.
In physics, the Mach–Zehnder interferometer is a device used to determine the relative phase shift variations between two collimated beams derived by splitting light from a single source. The interferometer has been used, among other things, to measure phase shifts between the two beams caused by a sample or a change in length of one of the paths. The apparatus is named after the physicists Ludwig Mach and Ludwig Zehnder; Zehnder's proposal in an 1891 article was refined by Mach in an 1892 article. Demonstrations of Mach–Zehnder interferometry with particles other than photons had been demonstrated as well in multiple experiments.
An optical cavity, resonating cavity or optical resonator is an arrangement of mirrors that forms a standing wave cavity resonator for light waves. Optical cavities are a major component of lasers, surrounding the gain medium and providing feedback of the laser light. They are also used in optical parametric oscillators and some interferometers. Light confined in the cavity reflects multiple times, producing standing waves for certain resonance frequencies. The standing wave patterns produced are called modes; longitudinal modes differ only in frequency while transverse modes differ for different frequencies and have different intensity patterns across the cross-section of the beam.
Cavity ring-down spectroscopy (CRDS) is a highly sensitive optical spectroscopic technique that enables measurement of absolute optical extinction by samples that scatter and absorb light. It has been widely used to study gaseous samples which absorb light at specific wavelengths, and in turn to determine mole fractions down to the parts per trillion level. The technique is also known as cavity ring-down laser absorption spectroscopy (CRLAS).
X-ray optics is the branch of optics that manipulates X-rays instead of visible light. It deals with focusing and other ways of manipulating the X-ray beams for research techniques such as X-ray crystallography, X-ray fluorescence, small-angle X-ray scattering, X-ray microscopy, X-ray phase-contrast imaging, X-ray astronomy etc.
A fiber laser is a laser in which the active gain medium is an optical fiber doped with rare-earth elements such as erbium, ytterbium, neodymium, dysprosium, praseodymium, thulium and holmium. They are related to doped fiber amplifiers, which provide light amplification without lasing. Fiber nonlinearities, such as stimulated Raman scattering or four-wave mixing can also provide gain and thus serve as gain media for a fiber laser.
An integrating sphere is an optical component consisting of a hollow spherical cavity with its interior covered with a diffuse white reflective coating, with small holes for entrance and exit ports. Its relevant property is a uniform scattering or diffusing effect. Light rays incident on any point on the inner surface are, by multiple scattering reflections, distributed equally to all other points. The effects of the original direction of light are minimized. An integrating sphere may be thought of as a diffuser which preserves power but destroys spatial information. It is typically used with some light source and a detector for optical power measurement. A similar device is the focusing or Coblentz sphere, which differs in that it has a mirror-like (specular) inner surface rather than a diffuse inner surface.
Photothermal spectroscopy is a group of high sensitivity spectroscopy techniques used to measure optical absorption and thermal characteristics of a sample. The basis of photothermal spectroscopy is the change in thermal state of the sample resulting from the absorption of radiation. Light absorbed and not lost by emission results in heating. The heat raises temperature thereby influencing the thermodynamic properties of the sample or of a suitable material adjacent to it. Measurement of the temperature, pressure, or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic measurements.
Laser absorption spectrometry (LAS) refers to techniques that use lasers to assess the concentration or amount of a species in gas phase by absorption spectrometry (AS).
Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectral range. This confers a significant advantage over a dispersive spectrometer, which measures intensity over a narrow range of wavelengths at a time.
In nonlinear optics z-scan technique is used to measure the non-linear index n2 and the non-linear absorption coefficient Δα via the "closed" and "open" methods, respectively. As nonlinear absorption can affect the measurement of the non-linear index, the open method is typically used in conjunction with the closed method to correct the calculated value. For measuring the real part of the nonlinear refractive index, the z-scan setup is used in its closed-aperture form. In this form, since the nonlinear material reacts like a weak z-dependent lens, the far-field aperture makes it possible to detect the small beam distortions in the original beam. Since the focusing power of this weak nonlinear lens depends on the nonlinear refractive index, it would be possible to extract its value by analyzing the z-dependent data acquired by the detector and by cautiously interpreting them using an appropriate theory. To measure the imaginary part of the nonlinear refractive index, or the nonlinear absorption coefficient, the z-scan setup is used in its open-aperture form. In open-aperture measurements, the far-field aperture is removed and the whole signal is measured by the detector. By measuring the whole signal, the beam small distortions become insignificant and the z-dependent signal variation is due to the nonlinear absorption entirely. Despite its simplicity, in many cases, the original z-scan theory is not completely accurate, e.g. when the investigated sample has inhomogeneous optical nonlinear properties, or when the nonlinear medium response to laser radiation is nonlocal in space. Whenever the laser induced nonlinear response at a certain point of the medium is not solely determined by the laser intensity at that point, but also depends on the laser intensity in the surrounding regions, it will be called a nonlocal nonlinear optical response. Generally, a variety of mechanisms may contribute to the nonlinearity, some of which may be nonlocal. For instance, when the nonlinear medium is dispersed inside a dielectric solution, reorientation of the dipoles as a result of the optical field action is nonlocal in space and changes the electric field experienced by the nonlinear medium. The nonlocal z-scan theory, can be used for systematically analyzing the role of various mechanisms in producing the nonlocal nonlinear response of different materials.
Gas in scattering media absorption spectroscopy (GASMAS) is an optical technique for sensing and analysis of gas located within porous and highly scattering solids, e.g. powders, ceramics, wood, fruit, translucent packages, pharmaceutical tablets, foams, human paranasal sinuses etc. It was introduced in 2001 by Prof. Sune Svanberg and co-workers at Lund University (Sweden). The technique is related to conventional high-resolution laser spectroscopy for sensing and spectroscopy of gas, but the fact that the gas here is "hidden" inside solid materials give rise to important differences.
The technique of vibrational analysis with scanning probe microscopy allows probing vibrational properties of materials at the submicrometer scale, and even of individual molecules. This is accomplished by integrating scanning probe microscopy (SPM) and vibrational spectroscopy. This combination allows for much higher spatial resolution than can be achieved with conventional Raman/FTIR instrumentation. The technique is also nondestructive, requires non-extensive sample preparation, and provides more contrast such as intensity contrast, polarization contrast and wavelength contrast, as well as providing specific chemical information and topography images simultaneously.
A common-path interferometer is a class of interferometers in which the reference beam and sample beams travel along the same path. Examples include the Sagnac interferometer, Zernike phase-contrast interferometer, and the point diffraction interferometer. A common-path interferometer is generally more robust to environmental vibrations than a "double-path interferometer" such as the Michelson interferometer or the Mach–Zehnder interferometer. Although travelling along the same path, the reference and sample beams may travel along opposite directions, or they may travel along the same direction but with the same or different polarization.
Vernier spectroscopy is a type of cavity enhanced laser absorption spectroscopy that is especially sensitive to trace gases. The method uses a frequency comb laser combined with a high finesse optical cavity to produce an absorption spectrum in a highly parallel manner. The method is also capable of detecting trace gases in very low concentration due to the enhancement effect of the optical resonator on the effective optical path length.