Photothermal microspectroscopy

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Photothermal microspectroscopy (PTMS), alternatively known as photothermal temperature fluctuation (PTTF), [1] [2] is derived from two parent instrumental techniques: infrared spectroscopy and atomic force microscopy (AFM). In one particular type of AFM, known as scanning thermal microscopy (SThM), the imaging probe is a sub-miniature temperature sensor, which may be a thermocouple or a resistance thermometer. [3] This same type of detector is employed in a PTMS instrument, enabling it to provide AFM/SThM images: However, the chief additional use of PTMS is to yield infrared spectra from sample regions below a micrometer, as outlined below.

Contents

Technique

The AFM is interfaced with an infrared spectrometer. For work using Fourier transform infrared spectroscopy (FTIR), the spectrometer is equipped with a conventional black body infrared source. A particular region of the sample may first be chosen on the basis of the image obtained using the AFM imaging mode of operation. Then, when material at this location absorbs the electromagnetic radiation, heat is generated, which diffuses, giving rise to a decaying temperature profile. The thermal probe then detects the photothermal response of this region of the sample. The resultant measured temperature fluctuations provide an interferogram that replaces the interferogram obtained by a conventional FTIR setup, e.g., by direct detection of the radiation transmitted by a sample. The temperature profile can be made sharp by modulating the excitation beam. This results in the generation of thermal waves whose diffusion length is inversely proportional to the root of the modulation frequency. An important advantage of the thermal approach is that it permits to obtain depth-sensitive subsurface information from surface measurement, thanks to the dependence of thermal diffusion length on modulation frequency.

Applications

The two particular features of PTMS that have determined its applications so far are 1) spectroscopic mapping may be performed at a spatial resolution well below the diffraction limit of IR radiation, ultimately at a scale of 20-30 nm. In principle, this opens the way to sub-wavelength IR microscopy (see scanning probe microscopy) where the image contrast is to be determined by the thermal response of individual sample regions to particular spectral wavelengths and 2) in general, no special preparation technique is required when solid samples are to be studied. For most standard FTIR methods, this is not the case.

This spectroscopic technique complements another recently developed method of chemical characterisation or fingerprinting, namely micro-thermal analysis (micro-TA). [4] [5] This also uses an “active” SThM probe, which acts as a heater as well as a thermometer, so as to inject evanescent temperature waves into a sample and to allow sub-surface imaging of polymers and other materials. The sub-surface detail detected corresponds to variations in heat capacity or thermal conductivity. Ramping the temperature of the probe, and thus the temperature of the small sample region in contact with it, allows localized thermal analysis and/or thermomechanometry to be performed.

Related Research Articles

<span class="mw-page-title-main">Infrared spectroscopy</span> Interaction of infrared radiation with matter

Infrared spectroscopy is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functional groups in solid, liquid, or gaseous forms. It can be used to characterize new materials or identify and verify known and unknown samples. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer which produces an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance on the vertical axis vs. frequency, wavenumber or wavelength on the horizontal axis. Typical units of wavenumber used in IR spectra are reciprocal centimeters, with the symbol cm−1. Units of IR wavelength are commonly given in micrometers, symbol μm, which are related to the wavenumber in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.

<span class="mw-page-title-main">Microscopy</span> Viewing of objects which are too small to be seen with the naked eye

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.

<span class="mw-page-title-main">Raman spectroscopy</span> Spectroscopic technique

Raman spectroscopy is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman spectroscopy is commonly used in chemistry to provide a structural fingerprint by which molecules can be identified.

Force spectroscopy is a set of techniques for the study of the interactions and the binding forces between individual molecules. These methods can be used to measure the mechanical properties of single polymer molecules or proteins, or individual chemical bonds. The name "force spectroscopy", although widely used in the scientific community, is somewhat misleading, because there is no true matter-radiation interaction.

<span class="mw-page-title-main">Atomic force microscopy</span> Type of microscopy

Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-resolution type of scanning probe microscopy (SPM), with demonstrated resolution on the order of fractions of a nanometer, more than 1000 times better than the optical diffraction limit.

Scanning probe microscopy (SPM) is a branch of microscopy that forms images of surfaces using a physical probe that scans the specimen. SPM was founded in 1981, with the invention of the scanning tunneling microscope, an instrument for imaging surfaces at the atomic level. The first successful scanning tunneling microscope experiment was done by Gerd Binnig and Heinrich Rohrer. The key to their success was using a feedback loop to regulate gap distance between the sample and the probe.

Fluorescence correlation spectroscopy (FCS) is a statistical analysis, via time correlation, of stationary fluctuations of the fluorescence intensity. Its theoretical underpinning originated from L. Onsager's regression hypothesis. The analysis provides kinetic parameters of the physical processes underlying the fluctuations. One of the interesting applications of this is an analysis of the concentration fluctuations of fluorescent particles (molecules) in solution. In this application, the fluorescence emitted from a very tiny space in solution containing a small number of fluorescent particles (molecules) is observed. The fluorescence intensity is fluctuating due to Brownian motion of the particles. In other words, the number of the particles in the sub-space defined by the optical system is randomly changing around the average number. The analysis gives the average number of fluorescent particles and average diffusion time, when the particle is passing through the space. Eventually, both the concentration and size of the particle (molecule) are determined. Both parameters are important in biochemical research, biophysics, and chemistry.

<span class="mw-page-title-main">Near-field scanning optical microscope</span>

Near-field scanning optical microscopy (NSOM) or scanning near-field optical microscopy (SNOM) is a microscopy technique for nanostructure investigation that breaks the far field resolution limit by exploiting the properties of evanescent waves. In SNOM, the excitation laser light is focused through an aperture with a diameter smaller than the excitation wavelength, resulting in an evanescent field on the far side of the aperture. When the sample is scanned at a small distance below the aperture, the optical resolution of transmitted or reflected light is limited only by the diameter of the aperture. In particular, lateral resolution of 6 nm and vertical resolution of 2–5 nm have been demonstrated.

Chemical imaging is the analytical capability to create a visual image of components distribution from simultaneous measurement of spectra and spatial, time information. Hyperspectral imaging measures contiguous spectral bands, as opposed to multispectral imaging which measures spaced spectral bands.

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.

<span class="mw-page-title-main">Fourier-transform infrared spectroscopy</span> Technique to analyze the infrared spectrum of matter

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.

<span class="mw-page-title-main">Scanning thermal microscopy</span>

Scanning thermal microscopy (SThM) is a type of scanning probe microscopy that maps the local temperature and thermal conductivity of an interface. The probe in a scanning thermal microscope is sensitive to local temperatures – providing a nano-scale thermometer. Thermal measurements at the nanometer scale are of both scientific and industrial interest. The technique was invented by Clayton C. Williams and H. Kumar Wickramasinghe in 1986.

Photothermal optical microscopy / "photothermal single particle microscopy" is a technique that is based on detection of non-fluorescent labels. It relies on absorption properties of labels, and can be realized on a conventional microscope using a resonant modulated heating beam, non-resonant probe beam and lock-in detection of photothermal signals from a single nanoparticle. It is the extension of the macroscopic photothermal spectroscopy to the nanoscopic domain. The high sensitivity and selectivity of photothermal microscopy allows even the detection of single molecules by their absorption. Similar to Fluorescence Correlation Spectroscopy (FCS), the photothermal signal may be recorded with respect to time to study the diffusion and advection characteristics of absorbing nanoparticles in a solution. This technique is called photothermal correlation spectroscopy (PhoCS).

<span class="mw-page-title-main">Raman microscope</span>

The Raman microscope is a laser-based microscopic device used to perform Raman spectroscopy. The term MOLE is used to refer to the Raman-based microprobe. The technique used is named after C. V. Raman, who discovered the scattering properties in liquids.

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.

The photoacoustic effect or optoacoustic effect is the formation of sound waves following light absorption in a material sample. In order to obtain this effect the light intensity must vary, either periodically or as a single flash. The photoacoustic effect is quantified by measuring the formed sound with appropriate detectors, such as microphones or piezoelectric sensors. The time variation of the electric output from these detectors is the photoacoustic signal. These measurements are useful to determine certain properties of the studied sample. For example, in photoacoustic spectroscopy, the photoacoustic signal is used to obtain the actual absorption of light in either opaque or transparent objects. It is useful for substances in extremely low concentrations, because very strong pulses of light from a laser can be used to increase sensitivity and very narrow wavelengths can be used for specificity. Furthermore, photoacoustic measurements serve as a valuable research tool in the study of the heat evolved in photochemical reactions, particularly in the study of photosynthesis.

<span class="mw-page-title-main">Infrared Nanospectroscopy (AFM-IR)</span> Infrared microscopy technique

AFM-IR or infrared nanospectroscopy is one of a family of techniques that are derived from a combination of two parent instrumental techniques. AFM-IR combines the chemical analysis power of infrared spectroscopy and the high-spatial resolution of scanning probe microscopy (SPM). The term was first used to denote a method that combined a tuneable free electron laser with an atomic force microscope equipped with a sharp probe that measured the local absorption of infrared light by a sample with nanoscale spatial resolution.

<span class="mw-page-title-main">Geology applications of Fourier transform infrared spectroscopy</span>

Fourier transform infrared spectroscopy (FTIR) is a spectroscopic technique that has been used for analyzing the fundamental molecular structure of geological samples in recent decades. As in other infrared spectroscopy, the molecules in the sample are excited to a higher energy state due to the absorption of infrared (IR) radiation emitted from the IR source in the instrument, which results in vibrations of molecular bonds. The intrinsic physicochemical property of each particular molecule determines its corresponding IR absorbance peak, and therefore can provide characteristic fingerprints of functional groups.

<span class="mw-page-title-main">Nano-FTIR</span> Infrared microscopy technique

Nano-FTIR is a scanning probe technique that utilizes as a combination of two techniques: Fourier transform infrared spectroscopy (FTIR) and scattering-type scanning near-field optical microscopy (s-SNOM). As s-SNOM, nano-FTIR is based on atomic-force microscopy (AFM), where a sharp tip is illuminated by an external light source and the tip-scattered light is detected as a function of tip position. A typical nano-FTIR setup thus consists of an atomic force microscope, a broadband infrared light source used for tip illumination, and a Michelson interferometer acting as Fourier transform spectrometer. In nano-FTIR, the sample stage is placed in one of the interferometer arms, which allows for recording both amplitude and phase of the detected light. Scanning the tip allows for performing hyperspectral imaging with nanoscale spatial resolution determined by the tip apex size. The use of broadband infrared sources enables the acquisition of continuous spectra, which is a distinctive feature of nano-FTIR compared to s-SNOM. Nano-FTIR is capable of performing infrared (IR) spectroscopy of materials in ultrasmall quantities and with nanoscale spatial resolution. The detection of a single molecular complex and the sensitivity to a single monolayer has been shown. Recording infrared spectra as a function of position can be used for nanoscale mapping of the sample chemical composition, performing a local ultrafast IR spectroscopy and analyzing the nanoscale intermolecular coupling, among others. A spatial resolution of 10 nm to 20 nm is routinely achieved.

References

  1. Hammiche, A.; Pollock, H. M.; Reading, M.; Claybourn, M.; et al. (1999). "Photothermal FT-IR Spectroscopy: A Step Towards FT-IR Microscopy at a Resolution Better Than the Diffraction Limit". Applied Spectroscopy. 53 (7): 810. Bibcode:1999ApSpe..53..810H. doi:10.1366/0003702991947379. S2CID   93359289.
  2. H M Pollock & D A Smith (2002). "The use of near-field probes for vibrational spectroscopy and photothermal imaging". In J.M. Chalmers & P.R. Griffiths (eds.). Handbook of vibrational spectroscopy. Vol. 2. John Wiley & Sons. pp. 1472–1492.
  3. Majumdar, A. (1999). "Scanning thermal microscopy". Annual Review of Materials Science . 29: 505–585. Bibcode:1999AnRMS..29..505M. doi:10.1146/annurev.matsci.29.1.505. S2CID   98802503.
  4. H. M. Pollock & A. Hammiche (2001). "Micro-thermal analysis: techniques and applications". J Phys D. 34 (9): R23–R53. Bibcode:2001JPhD...34R..23P. doi:10.1088/0022-3727/34/9/201. S2CID   250838172.
  5. J. Ye; et al. (2007). "Scanning thermal probe microscopy: nano thermal analysis with Raman microscopy". Microscopy and Analysis: S5–S8. Archived from the original on 2011-07-14.

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