Polymer film transfer

One can polymerize monolayer film on water subphase (Day and Ringsdorf (1978)) and so formed polymer monolayer can be transferred on a substrate. Polymer chains of obtained in this way thin film are parallel to the substrate (cf. Kajzar et al (I988)). The thickness of thin film can be increased by increasing the number of monomolecular polymer film transfers. 

Fig. 1. The hthographic process. A substrate is coated with a photosensitive polymer film called a resist. A mask with transparent and opaque areas directs radiation to preselected regions of the resist film. Depending on resist characteristics, exposed or unexposed portions of the film are removed using a developer solvent. The resulting pattern is then transferred to the substrate surface and the resist is stripped.

If a paint film is to prevent this reaction, it must be impervious to electrons, otherwise the cathodic reaction is merely transferred from the surface of the metal to the surface of the film. Organic polymer films do not contain free electrons, except in the special case of pigmentation with metallic pigments consequently it will be assumed that the conductivity of paint films is entirely ionic. In addition, the films must be impervious to either water or oxygen, so that they prevent either from reaching the surface of the metal. 

The proposed scenario is mainly based on the molecular approach, which considers conjugated polymer films as an ensemble of short (molecular) segments. The main point in the model is that the nature of the electronic state is molecular, i.e. described by localized wavefunctions and discrete energy levels. In spite of the success of this model, in which disorder plays a fundamental role, the description of the basic intrachain properties remains unsatisfactory. The nature of the lowest excited state in m-LPPP is still elusive. Extrinsic dissociation mechanisms (such as charge transfer at accepting impurities) are not clearly distinguished from intrinsic ones, and the question of intrachain versus interchain charge separation is not yet answered. 

The electrochemistry of a polymer-modified electrode is determined by a combination of thermodynamics and the kinetics of charge-transfer and transport processes. Thermodynamic aspects are highlighted by cyclic voltammetry, while kinetic aspects are best studied by other methods. These methods will be introduced here, with the emphasis on how they are used to measure the rates of electron and ion transport in conducting polymer films. Charge transport in electroactive films in general has recently been reviewed elsewhere.9,11... 

Impedance spectroscopy is best suited for the measurement of electronic conductivities in the range 10 -7to 10 2S cm 1.145 In principle, it is perhaps the best method for this range, but it is often difficult to interpret impedance data for conducting polymer films. The charge-transfer resistance can make measurements of bulk film resistances inaccurate,145 and it is often difficult to distinguish between the film s ionic and electronic resistances.144 This is even more of a problem with chronoamperometry146 and chronopotentiometry,147 so that these methods are best avoided. 

The kinetics of charge transfer between metallic electrodes and conducting polymer films have proved to be difficult to investigate, and little reliable data exist. Charge-transfer limitations have been claimed in cyclic voltammetry, and Butler-Volmer kinetics have been used in a number of... 

Polymer films that are sensitive to light, x-rays, or electrons— known as photoresists—are nsed extensively to transfer the pattern of an electronic circuit onto a semiconductor surface. Such films must adhere to the semiconductor surface, cross-link or decompose on exposure to radiation, and nndergo development in a solvent to achieve pattern definition. Virtually all aspects of photoresist processing involve surface and interfacial phenomena, and there are many outstanding problems where these phenomena mnst be controlled. For example, the fabrication of multilayer circuits requires that photoresist films of about 1-pm thickness be laid down over a semiconductor surface that has already been patterned in preceding steps. 

In Ref. 30, the transfer of tetraethylammonium (TEA ) across nonpolarizable DCE-water interface was used as a model experimental system. No attempt to measure kinetics of the rapid TEA+ transfer was made because of the lack of suitable quantitative theory for IT feedback mode. Such theory must take into account both finite quasirever-sible IT kinetics at the ITIES and a small RG value for the pipette tip. The mass transfer rate for IT experiments by SECM is similar to that for heterogeneous ET measurements, and the standard rate constants of the order of 1 cm/s should be accessible. This technique should be most useful for probing IT rates in biological systems and polymer films. 

Therefore, recent interest has been focused prevailingly on electrodes modified by a multilayer coverage, which can easily be achieved by using polymer films on electrodes. In this case, the mediated electron transfer to solution species can proceed inside the whole film (which actually behaves as a system with a homogeneous catalyst), and the necessary turnover rate is relatively lower than in a monolayer. 

A discussion of the charge transfer reaction on the polymer-modified electrode should consider not only the interaction of the mediator with the electrode and a solution species (as with chemically modified electrodes), but also the transport processes across the film. Let us assume that a solution species S reacts with the mediator Red/Ox couple as depicted in Fig. 5.32. Besides the simple charge transfer reaction with the mediator at the interface film/solution, we have also to include diffusion of species S in the polymer film (the diffusion coefficient DSp, which is usually much lower than in solution), and also charge propagation via immobilized redox centres in the film. This can formally be described by a diffusion coefficient Dp which is dependent on the concentration of the redox sites and their mutual distance (cf. Eq. (2.6.33). 

Fig. 5.32 Scheme of the reduction of a solution species Sox within the polymer film. Electron transfer is mediated by the immobilized redox active sites Red/Ox... 

Regarding the question of the rate of electron transport through polymer films, it is not yet clear what ultimate rate can be achieved. In solar energy applications the important issue is whether the rate can be high enough so that the net electron transfer rate is light intensity limited. 

A.J. Bard, University of Texas The fact that one can generate chemiluminescence in polymer films containing Ru-(bpy)3 2 implies that the excited state may not be quenched completely by electron transfer reactions. Are the photoreactions you describe thermodynamically uphill (i.e., with chemical storage or radiant energy) or are they photocatalytic ... 

The surface pressure-area (tc-A) isotherm measurements and LB film transfer were performed with the use of a KSV 5000 minitrough (KSV Instrument Co., Finland) operated at a continuous speed for two barriers of 10 cm2/min at 20°C. The buffer used in the present work was composed of 10 mM MES, 2 mM ascorbic acid sodium salt, and a given concentration of salt or polymers (pH =7.0). The accuracy of the surface pressure measurement was 0.01 mN/m. Monolayers of the PS I were transferred at 10 mN/m on hydrophobic substrate surface by horizontal lifting method. 

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