The photothermal transparent transducer method applied to the spectroscopy of liquids

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The open-ended photothermal cell with LiTaO3 and its use in determining the photochemical loss

Comparative determinations of the noise equivalent power (NEP) of open-ended photothermal cells are performed using LiTaO3 and LiNbO3 crystals with and without indium tin oxide (ITO) transparent electrodes. Open-ended cells can be used for in vivo measurements, which are important when considering the achievability for continuous monitoring of a plant, verifying, for example, the effect of water stress or UV-B radiation on a leaf. We also show the results obtained with one of these cells in the determination of photochemical loss of plant leaves. (c) 2007 Elsevier B.V. All rights reserved.

Photopyroelectric spectroscopy of polyaniline films

Photopyroelectric spectroscopy (PPES), in the 400 < lambda < 900 nm wavelength range, was used to study thermal properties of differently doped polyaniline (PAN) films. The photopyroelectric intensity signal V-n(lambda) and its phase F-n(lambda) were independently measured, as well as the intensity V-n(f) and the phase F-n(f) (f being the chopping frequency) for a given A of the saturation part of the PPES spectrum. Equations of both the intensity and the phase of the PPES signal, taking into account the thermal and the optical characteristics of the PAN films and the pyroelectric detector, were used to fit the experimental results. From the fittings we obtained, with great accuracy, the values of thermal conductivity k and thermal diffusivity coefficient a of PAN films of different doping degrees. It was observed that, in contrast with the strong doping-dependence of the electrical conductivity, the thermal parameters of PAN films remained practically unchanged under doping. This apparent discrepancy is explained by the granular metal model of doped PAN. (C) 2000 John Wiley & Sons, Inc.

Determination of thermal and optical parameters of melanins by photopyroelectric spectroscopy

Photopyroelectric spectroscopy (PPE) was used to study the thermal and optical properties of melanins. The photopyroelectric intensity signal and its phase were independently measured as a function of wavelength and chopping frequency for a given wavelength in the saturation part of the PPE spectrum. Equations for both the intensity and the phase of the PPE signal were used to fit the experimental results. From these fits we obtained for the first time, with great accuracy, the thermal diffusivity coefficient, the thermal conductivity, and the specific heat of the samples, as well as a value for the condensed phase optical gap, which we found to be 1.70 eV. (c) 2005 American Institute of Physics.

Study of optical properties of electropolymerized melanin films by photopyroelectric spectroscopy

Photopyroelectric (PPE) spectroscopy, in the 350-1,075 nm wavelength range, was used to study the optical properties of electropolymerized melanin films on indium tin oxide (ITO) coated glass. The PPE intensity signal as a function of the wavelength lambda, V (n)(lambda) and its phase F (n)(lambda) were independently measured. Using the PPE signal intensity and the thermal and optical properties of the pyroelectric detector, we were able to calculate the optical absorption coefficient beta of melanin in the solid-state. We believe this to be the first such measurement of its kind on this material. Additionally, we found an optical gap in these melanin films at 1.70 eV.

The adsorption of dopamine on gold and its interactions with iron(III) ions studied by microcantilevers

The adsorption of dopamine (DA) molecules on gold and their interactions with Fe3+ were studied by a microcantilever in a flow cell. The microcantilever bent toward the Au side with the adsorption of DA due to the change Of Surface stress induced by the intermolecular hydrogen bonds of DA or the charge transfer effect between adsorbates and the Substrate. The interaction process between DA adsorbates and Fe3+ was revealed by the deflection curves of microcantilever. As indicated by the appearance of a variation during the decline of curves, two steps were observed in the curve at relative high concentrations of Fe3+. In this case, Fe3+ reacted with DA molecules only in the outer layers and the complexes removed with solution. Then Fe3+ reacted further with DA molecules forming the surface complex in the first layer next to the gold. At this stage, the stability Of Surface complexes was time dependent, i.e., unstable initially and stable finally. This may be due to the surface complexes change from mono-dentate to bi-dentate complexes. In another case, i.e., at relative low concentration of Fe3+, only the first step was observed as indicated by the absence of a variation.

Thermal transport properties of selected ferroelectrics, mixed valance perovskites and dielectric ceramics using photopyroelectric technique

Photothermal spectroscopy is a group of high sensitivity methods used to measure optical absorption and thermal characteristics of a sample.The basis of photothermal spectroscopy is a photo-induced change in the thermal state of the sample.Light energy absorbed and not lost by subsequent emission results in sample heating.This heating results in a temperature change as well as changes in thermodynamic parameters of the sample which are related to temperature.Measurements of the temperature,pressure,or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic methods.This is a more direct measure of optical absorption than optical transmission based spectroscopies.Sample heating is a direct consequence of optical absorption and so photothermal spectroscopy signals are directly dependent on light absorption.Scattering and reflection losses do not produce photothermal signals.Subsequently,photothermal spectroscopy more accurately measures optical absorption in scattering solutions,in solids,and at interfaces.This aspect makes it particularly attractive for application to surface and solid absorption studies,and studies in scattering media.

Non-Destructive Evaluation of Ion-Implanted Semiconductor Thin Films Using Photothermal Deflections Spectroscopy

Materials and equipment which fail to achieve the design requirements or projected life due to undetected defects may require expensive repair or early replacement. Such defects may also be the cause of unsafe conditions or catastrophic unexpected failure, and will lead to loss of revenue due to plant shutdown. Non-Destructive Evaluation (NDE) / Non Destructive Testing (NDT) is used for the examination of materials and components without changing or destroying their usefulness. NDT can be applied to each stage of a system’s construction, to monitor the integrity of the system or structure throughout its life.

Identification and characterization of shallow impurity states in gallium arsenide and indium phosphide using photothermal ionization spectroscopy

A model of far infrared (FIR) dielectric response of shallow impurity states in a semiconductor has been developed and is presented for the specific case of the shallow donor transitions in high purity epitaxial GaAs. The model is quite general, however, and should be applicable with slight modification, not only to shallow donors in other materials such as InP, but also to shallow acceptors and excitons. The effects of the enormous dielectric response of shallow donors on the FIR optical properties of reflectance, transmittance, and absorptance, and photoconductive response of high purity epitaxial GaAs films are predicted and compared with experimental photothermal ionization spectra. The model accounts for many of the peculiar features that are frequently observed in these spectra, one of which was the cause of erroneous donor identifications in the early doping experiments. The model also corrects some commonly held misconceptions concerning photo-thermal ionization peak widths and amplitudes and their relationships to donor and acceptor concentrations. These corrections are of particular relevance to the proper interpretation of photothermal ionization spectra in the study of impurity incorporation in high purity epitaxial material. The model also suggests that the technique of FIR reflectance, although it has not been widely employed, should be useful in the study of shallow impurities in semiconductors.

Novel ultrahigh resolution silverless photothermal imaging in obliquely deposited amorphous Se-Ge films

A new photothermal imaging process which utilizes no silver has been demonstrated in obliquely deposited Se-Ge films. Band-gap irradiation of Se-Ge films has been found to give rise to phases of the type SeOx, GeO, and Se as borne by x-ray initiated Auger electron spectroscopy and x-ray photoelectron spectroscopy. Annealing of SeOx leads to the formation of SeO2. The large (several orders of magnitude) difference in vapor pressures of SeO2 and Se-Ge films results in differential evaporation of the films when annealed around 200 °C, thereby leading to imaging. Such a large contrast in evaporation rates between the exposed and unexposed regions has great potential applications in high resolution image storage and phase holography. Applied Physics Letters is copyrighted by The American Institute of Physics.

Photothermal Investigations on Certain Plasma Polymerized Thin Films and Near IR Overtone Studies of Some Organic Molecules

Photothermal effect refers to heating of a sample due to the absorption of electromagnetic radiation. Photothermal (PT) heat generation which is an example of energy conversion has in general three kinds of applications. 1. PT material probing 2. PT material processing and 3. PT material destruction. The temperatures involved increases from 1-. 3. Of the above three, PT material probing is the most important in making significant contribution to the field of science and technology. Photothermal material characterization relies on high sensitivity detection techniques to monitor the effects caused by PT material heating of a sample. Photothermal method is a powerful high sensitivity non-contact tool used for non-destructive thermal characterization of materials. The high sensitivity of the photothermal methods has led to its application for analysis of low absorbance samples. Laser calorimetry, photothermal radiometry, pyroelectric technique, photoacoustic technique, photothermal beam deflection technique, etc. come under the broad class ofphotothermal techniques. However the choice of a suitable technique depends upon the nature of the sample, purpose of measurement, nature of light source used, etc. The present investigations are done on polymer thin films employing photothermal beam deflection technique, for the successful determination of their thermal diffusivity. Here the sample is excited by a He-Ne laser (A = 6328...\ ) which acts as the pump beam. Due to the refractive index gradient established in the sample surface and in the adjacent coupling medium, another optical beam called probe beam (diode laser, A= 6500A ) when passed through this region experiences a deflection and is detected using a position sensitive detector and its output is fed to a lock-in amplifier from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the signal is suitably analysed for determining the thermal diffusivity.The production of polymer thin film samples has gained considerable attention for the past few years. Plasma polymerization is an inexpensive tool for fabricating organic thin films. It refers to formation of polymeric materials under the influence of plasma, which is generated by some kind of electric discharge. Here plasma of the monomer vapour is generated by employing radio frequency (MHz) techniques. Plasma polymerization technique results in homogeneous, highly adhesive, thermally stable, pinhole free, dielectric, highly branched and cross-linked polymer films. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer.Near IR overtone investigations on some organic molecules using local mode model are also done. Higher vibrational overtones often provide spectral simplification and greater resolution of peaks corresponding to nonequivalent X-H bonds where X is typically C, N or O. Vibrational overtone spectroscopy of molecules containing X-H oscillators is now a well established tool for molecular investigations. Conformational and steric differences between bonds and structural inequivalence ofCH bonds (methyl, aryl, acetylenic, etc.) are resolvable in the higher overtone spectra. The local mode model in which the X-H oscillators are considered to be loosely coupled anharmonic oscillators has been widely used for the interpretation of overtone spectra. If we are exciting a single local oscillator from the vibrational ground state to the vibrational state v, then the transition energy of the local mode overtone is given by .:lE a......v = A v + B v2 • A plot of .:lE / v versus v will yield A, the local mode frequency as the intercept and B, the local mode diagonal anharmonicity as the slope. Here A - B gives the mechanical frequency XI of the oscillator and B = X2 is the anharmonicity of the bond. The local mode parameters XI and X2 vary for non-equivalent X-H bonds and are sensitive to the inter and intra molecular environment of the X-H oscillator.

Raman spectroscopy of the molybdate minerals chillagite (tungsteinian wulfenite-I4), stolzite, scheelite, wolframite and wulfenite

Raman spectra of chillagite, wulfenite, stolzite, scheelite and wolframite were obtained at 298 and 77 K using a Raman microprobe in combination with a thermal stage. Chillagite is a solid solution of wulfenite and stolzite. The spectra of these molybdate minerals are orientation dependent. The band at 695 cm-1 is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The bands at 790 and 881 cm-1 are associated with the antisymmetric and symmetric Ag modes of terminal WO2 whereas the origin of the 806 cm-1 band remains unclear. The 4(Eg) band was absent for scheelite. The bands at 353 and 401 cm-1 are assigned as either deformation modes or as r(Bg) and (Ag) modes of terminal WO2. The band at 462 cm-1 has an equivalent band in the infrared at 455 cm-1 assigned as as(Au) of the (W2O4)n chain. The band at 508 cm-1 is assigned as sym(Bg) of the (W2O4)n chain.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].