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.

Photothermal and photoacoustic investigations on certain polymers and semi conducting materials

Material synthesizing and characterization has been one of the major areas of scientific research for the past few decades. Various techniques have been suggested for the preparation and characterization of thin films and bulk samples according to the industrial and scientific applications. Material characterization implies the determination of the electrical, magnetic, optical or thermal properties of the material under study. Though it is possible to study all these properties of a material, we concentrate on the thermal and optical properties of certain polymers. The thermal properties are detennined using photothermal beam deflection technique and the optical properties are obtained from various spectroscopic analyses. In addition, thermal properties of a class of semiconducting compounds, copper delafossites, arc determined by photoacoustic technique.Photothermal technique is one of the most powerful tools for non-destructive characterization of materials. This forms a broad class of technique, which includes laser calorimetry, pyroelectric technique, photoacollstics, photothermal radiometric technique, photothermal beam deflection technique etc. However, the choice of a suitable technique depends upon the nature of sample and its environment, purpose of measurement, nature of light source used etc. The polynler samples under the present investigation are thermally thin and optically transparent at the excitation (pump beam) wavelength. Photothermal beam deflection technique is advantageous in that it can be used for the detennination of thermal diffusivity of samples irrespective of them being thermally thick or thennally thin and optically opaque or optically transparent. Hence of all the abovementioned techniques, photothemlal beam deflection technique is employed for the successful determination of thermal diffusivity of these polymer samples. However, the semi conducting samples studied are themlally thick and optically opaque and therefore, a much simpler photoacoustic technique is used for the thermal characterization.The production of polymer thin film samples has gained considerable attention for the past few years. Different techniques like plasma polymerization, electron bombardment, ultra violet irradiation and thermal evaporation can be used for the preparation of polymer thin films from their respective monomers. Among these, plasma polymerization or glow discharge polymerization has been widely lIsed for polymer thin fi Im preparation. At the earlier stages of the discovery, the plasma polymerization technique was not treated as a standard method for preparation of polymers. This method gained importance only when they were used to make special coatings on metals and began to be recognized as a technique for synthesizing polymers. Thc well-recognized concept of conventional polymerization is based on molecular processcs by which thc size of the molecule increases and rearrangemcnt of atoms within a molecule seldom occurs. However, polymer formation in plasma is recognized as an atomic process in contrast to the above molecular process. These films are pinhole free, highly branched and cross linked, heat resistant, exceptionally dielectric etc. The optical properties like the direct and indirect bandgaps, refractive indices etc of certain plasma polymerized thin films prepared are determined from the UV -VIS-NIR absorption and transmission spectra. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer. The thermal diffusivity has been measured using the photothermal beam deflection technique as stated earlier. This technique measures the refractive index gradient established in the sample surface and in the adjacent coupling medium, by passing another optical beam (probe beam) through this region and hence the name probe beam deflection. The deflection 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 deflection signal is suitably analyzed for determining the thermal diffusivity.Another class of compounds under the present investigation is copper delafossites. These samples in the form of pellets are thermally thick and optically opaque. Thermal diffusivity of such semiconductors is investigated using the photoacoustic technique, which measures the pressure change using an elcctret microphone. The output of the microphone is fed to a lock-in-amplificr to obtain the amplitude and phase from which the thermal properties are obtained. The variation in thermal diffusivity with composition is studied.

Studies on Heat Diffusion in Selected Conducting Polymers using Probe Beam Deflection and Photoacoustic Techniques

In the present study, radio frequency plasma polymerization technique is used to prepare thin films of polyaniline, polypyrrole, poly N-methyl pyrrole and polythiophene. The thermal characterization of these films is carried out using transverse probe beam deflection method. Electrical conductivity and band gaps are also determined. The effect of iodine doping on electrical conductivity and the rate of heat diffusion is explored.Bulk samples of poyaniline and polypyrrole in powder form are synthesized by chemical route. Open photoacoustic cell configuration is employed for the thermal characterization of these samples. The effect of acid doping on heat diffusion in these bulk samples of polyaniline is also investigated. The variation of electrical conductivity of doped polyaniline and polypyrrole with temperature is also studied for drawing conclusion on the nature of conduction in these samples. In order to improve the processability of polyaniline and polypyrrole, these polymers are incorporated into a host matrix of poly vinyl chloride. Measurements of thermal diffusivity and electrical conductivity of these samples are carried out to investigate the variation of these quantities as a function of the content of polyvinyl chloride.

Mechanism of electrical conduction in plasma polymerized furfural thin films

Polyfurfural thin films lying in the thickness range of 1300–2000 A˚ were prepared by ac plasma polymerization technique. The current–voltage characteristics in symmetric and asymmetric electrode configuration were studied with a view to determining the dominant conduction mechanism.It was found that the Schottky conduction mechanism is dominant in plasma polymerized furfural thin films.The predominance of Schottky mechanism was further confirmed based on the thermally stimulated current measurements.

Formation And Electrical Properties Of Polyacrylonitrile Thin Films Prepared By Plasma - Polymerisation

Due to the great versatility of the properties of polymer thin films, special interest has been taken in recent years on their preparation and electrical properties. The present thesis is entirely devoted to the study of the formation, structure and electrical properties of plasma» polymerised polyacrylonitrile (PAN) thin films. Eventhough the studies are confined to a single polymer film, the results in general are applicable to similar polar polymer films.

On the optical and electrical properties of rf and a.c. plasma polymerized aniline thin films

Polyaniline is a widely studied conducting polymer and is a useful material in its bulk and thin film form for many applications, because of its excellent optical and electrical properties. Pristine and iodine doped polyaniline thin films were prepared by a.c. and rf plasma polymerization techniques separately for the comparison of their optical and electrical properties. Doping of iodine was effected in situ. The structural properties of these films were evaluated by FTIR spectroscopy and the optical band gap was estimated from UV-vis-NIR measurements. Comparative studies on the structural, optical and electrical properties of a.c. and rf polymerization are presented here. It has been found that the optical band gap of the polyaniline thin films prepared by rf and a.c. plasma polymerization techniques differ considerably and the band gap is further reduced by in situ doping of iodine. The electrical conductivity measurements on these films show a higher value of electrical conductivity in the case of rf plasma polymerized thin films when compared to the a.c. plasma polymerized films. Also, it is found that the iodine doping enhanced conductivity of the polymer thin films considerably. The results are compared and correlated and have been explained with respect to the different structures adopted under these two preparation techniques

Low k thin films based on rf plasma-polymerized aniline

Thermally stable materials with low dielectric constant (k < 3.9) are being hotly pursued. They are essential as interlayer dielectrics/intermetal dielectrics in integrated circuit technology, which reduces parasitic capacitance and decreases the RC time constant. Most of the currently employed materials are based on silicon. Low k films based on organic polymers are supposed to be a viable alternative as they are easily processable and can be synthesized with simpler techniques. It is known that the employment of ac/rf plasma polymerization yields good quality organic thin films, which are homogenous, pinhole free and thermally stable. These polymer thin films are potential candidates for fabricating Schottky devices, storage batteries, LEDs, sensors, super capacitors and for EMI shielding. Recently, great efforts have been made in finding alternative methods to prepare low dielectric constant thin films in place of silicon-based materials. Polyaniline thin films were prepared by employing an rf plasma polymerization technique. Capacitance, dielectric loss, dielectric constant and ac conductivity were evaluated in the frequency range 100 Hz– 1 MHz. Capacitance and dielectric loss decrease with increase of frequency and increase with increase of temperature. This type of behaviour was found to be in good agreement with an existing model. The ac conductivity was calculated from the observed dielectric constant and is explained based on the Austin–Mott model for hopping conduction. These films exhibit low dielectric constant values, which are stable over a wide range of frequencies and are probable candidates for low k applications.

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.

Investigations on the stability of plasma modified silicone surfaces

In this work it was investigated the effect of the exposure to different plasmas on the wettability of silicone samples. We have observed that oxygen. argon, and hydrogen glow discharges are quite effective in reducing the water contact angle of such polymer. However, indifferently to efficiency of the treatment, practically all the modified surfaces recovered great part of their original hydrophobicity. We have investigated this hydrophobic recovery using surface energy measurements and theoretical simulations based on the exponential decay of the population of polar groups on the surface. According to our results such recovery can be attributed to the decrease of polar species at the interface water-polymer surface.

XPS investigation of plasma-deposited polysiloxane films irradiated with helium ions

This work describes an XPS investigation of plasma-deposited polysiloxane films irradiated with 170 keV He+ ions at fluences, Phi, ranging from 1 x 10(14) to 1 x 10(16) cm(-2). Modifications in the atomic concentrations of the surface atoms with (D were revealed by changes in the [O]/[Si], [O]/[C] and [C]/[Si] atomic ratios. Surface chemical structure modifications were evidenced by the increasing C1s peak width and asymmetry as Phi was increased, due to the formation of ether and carboxyl functionalities. Moreover, structural transformations were indicated by the positive binding energy shift of the Si2p peaks, due to the increasing Si oxidation. Correlations of the XPS data with other results from previous work on polysiloxanes illustrate the role of ion beam-induced bond breaking on the structural modifications.

RELATIONSHIPS BETWEEN THE PLASMA ENVIRONMENT AND THE COMPOSITION AND OPTICAL-PROPERTIES OF PLASMA-POLYMERIZED THIN-FILMS PRODUCED IN RF DISCHARGES OF C2H2-SF6 MIXTURES

Polymer films were grown in rf discharges containing different proportions of C2H2 and SF6. Quantitative optical emission spectrometry (actinometry) was used to follow the trends in the plasma concentrations of the species H and F, and more tentatively, of CH, CF, and CF2, as a function of the feed composition. Infrared spectroscopy revealed the density of CH and CF bonds in the deposited material. As the partial pressure of SF6 in the feed was increased, the degree of fluorination of the polymer also rose. The form of the dependency of the deposition rate on the proportion of SF6 in the feed was in good qualitative agreement with the activated growth model. From transmission ultraviolet visible spectroscopy data the refractive index and the absorption coefficient of the polymers were calculated as a function of the deposition parameters. Since the optical gap depended to some extent upon the degree of fluorination, it could, within limits, be determined by a suitable choice of the proportion of SF6 in the feed. A qualitative explanation of this relationship is given.

Hydrophilization of PVC surfaces by argon plasma immersion ion implantation

Commercial polyvinylchloride (PVC) sheets were treated by plasma immersion ion implantation, PIII. Samples were immersed in argon glow discharges and biased with 25 kV negative pulses. Exposure time to the bombardment plasma changed from 900 to 10,800 s. Through contact angle measurements, the effect of the exposure time on the PVC wettability was investigated. Independent of t, all samples presented contact angles, theta, equal to zero after the treatment. However, in some cases, surface hydrophilization was not stable, as revealed by the temporal evolution of theta. Samples bombarded for shorter periods recovered partially or totally the hydrophobic character while the one exposed for the longest time stayed highly hydrophilic. These modifications are ascribed to the Cl loss and O incorporation as shown by XPS measurements. Furthermore, the mobility of surface polar groups and the variation in the cross-linking degree can also affect the PVC wettability.

AN ACTINOMETRIC STUDY OF C2H2 PLASMA POLYMERIZATION AND FILM PROPERTIES

Thin polymer films were grown in radio frequency discharges containing C2H2. Actinometry revealed the trend in the plasma concentration of the CH species as a function of the operating pressure. The C-H bond density in the films, revealed by infrared analysis, was found to increase with the pressure of C2H2 in a similar way to that of the concentration of the CH species in the discharge. From transmission ultraviolet-visible spectroscopy data, optical parameters of the polymers, namely, the refractive index and the optical gap, were calculated. For the range of pressure studied, the refractive index decreased from 1.73 to 1.63 and the optical gap increased from 2.4 to 3.3 eV. Finally, measurements of the residual stress of the polymer films were carried out by the bending beam method, using a He-Ne laser, yielding values from 0.05 to 0.3 GPa. (C) 1995 American Vacuum Society.

Plasma-deposition of Ag-containing polyethyleneoxide-like coatings

Ag-containing polyethyleneoxide (FEO)-like thin films have been deposited in Radio Frequency Glow Discharges fed with vapors of diethyleneglycol-dimethyl-ether and argon. Proper experimental conditions have been utilized in order to fragment the monomer in the glow and, at the same time, sputter Ag from the silver RF cathode of the reactor, in a way that polyethyleneoxide(PEO)-like coatings with embedded Ag clusters have been deposited at the ground electrode. The composition of the coatings has been investigated by means of different techniques; the plasma process has been investigated by means of Actinometric Optical Emission Spectroscopy. A correlation has been found between the amount of silver embedded in the coatings and that sputtered in the discharge, monitored by actinometry, that could eventually be utilized to control in situ the deposition process.

The improvement of thin polymer film properties through plasma immersion ion implantation and deposition technique

Thin polymer films were deposited from acetylene and argon mixtures by plasma immersion ion implantation and deposition. The effect of the pulse frequency, v, on molecular structure, optical gap, contact angle and hardness of the films was investigated. It was observed progressive dehydrogenation of the samples and increment in the concentration of unsaturated carbon bonds as the pulse frequency was increased. Film hardness and contact angle increased and optical gap decreased with v. These results are interpreted in terms of the chain unsaturation and crosslinking.