Far infrared micro-spectroscopy: an innovative method to detect individual metal-organic framework particles.

The purpose of this study is to extend the spectral range of a differential method of infrared micro-spectroscopy in order to allow the accurate detection of nanoparticles of interest for biomedical applications. Among these, metal-organic framework (MOF) nanoparticles have attracted increasing interest due to their capacity to incorporate high drug payloads, biodegradability, and possibility of tailoring their surfaces by grafting specific ligands. However, MOF particle detection in biological media without grafting or incorporating fluorescent molecules is challenging. We took advantage here of the presence of the specific absorption bands of nanoscale MOFs in far infrared in order to individually discriminate them. Here we show that single MOF nanoparticles can be imaged with a spatial resolution of a few tens of nanometers.

Local terahertz microspectroscopy with λ/100 spatial resolution.

We have extended the spectral range of a differential method of infrared microspectroscopy in order to operate in the terahertz spectral region. We show on samples of graphite embedded in a matrix of polymers that the spatial resolution is practically independent of the wavelength and is at least λ/100. This method aims at performing "chemical mapping" of various objects since it is sensitive only to the imaginary part of the index of refraction.

Sub-100 nm IR spectromicroscopy of living cells.

We have performed IR spectromicroscopy of cells immersed in liquid water, with a lateral resolution better than 100 nm. Here, we use the motion of an atomic force microscope tip, probing the local transient deformation induced by an IR pulsed laser tuned at a sample absorbing wavelength. By Fourier analysis of the vibration of the cantilever tip, we can discriminate frequencies that are characteristic of the object, thus eliminating the influence of the water absorption. This opens the door of chemical imaging of living species in vivo, with spatial resolution of the order of the size of cell components.

Chemical mapping of the distribution of viruses into infected bacteria with a photothermal method.

We show that an infrared spectromicroscopy method based on a photo-thermal effect, is able to localize single viruses as well when they are isolated and when they are located inside the bacteria they have infected. In this latter case, although the topography performed by an AFM cannot image the viruses, the AFMIR is able to do so. In addition, we are able to determine different stages of the bacteria infection.

Analysis of nano-chemical mapping performed by an AFM-based ("AFMIR") acousto-optic technique.

In this paper, we analyze in detail a new method of infrared micro-spectroscopy, which aims at performing "chemical mapping" of various objects with sub-wavelength lateral resolution by using the infrared vibrational signature characterizing different molecular species. Its principle consists in an atomic force microscope tip, probing the local transient deformation induced by an infrared pulsed laser tuned at a sample absorbing wavelength. The cantilever oscillates at resonant frequencies, which amplitudes can be correlated with local absorption. We show that the system acts as an amplifier of extremely small motions induced by optical absorption and that different frequencies provide different informations, leading to a full description of the sample deformation. We estimate also the influence of the light confinement in the sample and exemplify the accuracy of the method by mapping Escherichia coli bacteria at different cantilever frequencies.

Local infrared microspectroscopy with subwavelength spatial resolution with an atomic force microscope tip used as a photothermal sensor.

We describe a new method of infrared microspectroscopy. It is intended for performing chemical mapping of various objects with subwavelength lateral resolution by using the infrared vibrational signature characterizing different molecular species. We use the photothermal expansion effect, detected by an atomic force microscope tip, probing the local transient deformation induced by an infrared pulsed laser tuned at a sample absorbing wavelength. We show that this new tool opens the way for measuring and identifying spectroscopic contrasts not accessible by far-field or near-field optical methods and with a subwavelength lateral resolution.

Long polaron lifetime in InAs/GaAs self-assembled quantum dots.

We have investigated the polaron dynamics in n-doped InAs/GaAs self-assembled quantum dots by pump-probe midinfrared spectroscopy. A long T1 polaron decay time is measured at both low temperature and room temperature, with values around 70 and 37 ps, respectively. The decay time decreases for energies closer to the optical phonon energy. The relaxation is explained by the strong coupling for the electron-phonon interaction and by the finite lifetime of the optical phonons. We show that, even for a large detuning of 19 meV from the LO photon energy in GaAs, the carrier relaxation remains phonon assisted.

Gas phase infrared spectroscopy of selectively prepared ions.

The first example of direct structural characterization of polyaromatic ions by coupling a Fourier transform ion cyclotron resonance mass spectrometer with an infrared free-electron laser is presented. Measurement of the IR spectra of selectively prepared ionic reactive intermediates is allowed by the association of the high peak power and wide tunability of the laser with the flexibility of the spectrometer, where several mass selection and ion reaction steps can be combined, as demonstrated in the case of iron cation complexes of hydrocarbons. The present experimental setup opens the way to understanding chemical reaction paths.

Spectroscopic Techniques using Synchrotron Radiation and Free-Electron and Conventional Lasers.

Considerable progress in the investigation of the electronic and vibrational properties of atoms, molecules, materials, surfaces and interfaces has been achieved by combining different photon sources of complementary characteristics. In this paper some experimental results obtained recently at LURE by using two synchronized sources, such as the IR free-electron laser (FEL) CLIO, the VUV storage ring FEL, synchrotron radiation and table lasers, are presented. Using CLIO synchronized with a YAG laser allows the investigation of the vibrational properties of adsorbed species by the non-linear optical technique of visible-IR sum (difference) frequency generation, as shown for the adsorption of hydrogen on platinum in the electrochemical environment. The second result reported here relates to the study of the intersubband stimulated emission in GaAs/GaAlAs quantum wells by pump-probe experiments using the two-colour configuration of CLIO. The combination of a mode-locked Ar(+) laser and synchrotron radiation has been used for investigations in a pump-probe arrangement of the ionization of Xe atoms via the resonant state Xe* 5p(5)5d [3/2](1). The final example is a time-resolved core-level spectroscopy study of photoexcited Si(111) 2 x 1 surfaces by using a combination of the naturally synchronized UV storage ring laser and synchrotron radiation.