Absorption polymer films

One interesting new field in the area of optical spectroscopy is near-field scaiming optical microscopy, a teclmique that allows for the imaging of surfaces down to sub-micron resolution and for the detection and characterization of single molecules [, M]- Wlien applied to the study of surfaces, this approach is capable of identifying individual adsorbates, as in the case of oxazine molecules dispersed on a polymer film, illustrated in figure Bl.22,11 [82], Absorption and emission spectra of individual molecules can be obtamed with this teclmique as well, and time-dependent measurements can be used to follow the dynamics of surface processes. 

In each of these approaches, imaging is confined to the top of a single polymeric film by adjusting optical absorption. The penetration depth of the silylation agent and the attendant swelling of the polymer film must also be controlled to avoid distortion of the silylated image. Resists of this type are capable of very high resolution (Fig. 37). 

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

When the AAM monomer was grafted onto polymer films, the grafted films showed much higher water absorption than the original ungrafted films. This is due to... 

Temperature An examination has been made of the effect of temperature on the structural changes in polymer films produced from the three vehicles described earlier s. Three methods were used dilatometry, water absorption and ionic resistance. 

Platinum was added to Nation before Incorporating CdS In order to avoid the reduction of CdS during the platlnlzatlon process. Nation (DuPont 117, 0.018 cm thick) films were soaked In Pt(NH2)2l2 (0.1 mM) solution for 4 hr. The amount of the Pt complex Incorporated was determined by measuring the optical absorption change In the liquid phase. The films were subsequently reduced with NaBH (0.1 M) solution for one day to produce Pt metal dispersed throughout the polymer film. The amount of Pt was found to be about 0.02 mg cm 2. 

In order to follow progress of elimination, reactions were also performed on thin films in a special sealed glass cell which permitted in situ monitoring of the electronic or infrared spectra at room temperature (23°C). Typically, the infrared or electronic spectrum of the pristine precursor polymer film was obtained and then bromide vapor was introduced into the reaction vessel. In situ FTIR spectra in the 250-4000 cm-- - region were recorded every 90 sec with a Digilab Model FTS-14 spectrometer and optical absorption spectra in the 185-3200 nm (0.39-6.70 eV) range were recorded every 15 min with a Perkin-Elmer Model Lambda 9 UV-vis-NIR spectrophotometer. The reactions were continued until no visible changes were detected in the spectra. 

The reduced absorption and desorption curves do not depend on the thickness of the polymer film. 

Fluorescence Lifetimes. Fluorescence lifetimes were determined by the phase shift method, utilizing a previously-described phase fluorimeter. The emission from an argon laser was frequency doubled to provide a 257 nm band for excitation. Fluorescence lifetimes of anisole and polymer 1 in dichloro-methane solution were 2.2 and 1.4 nsec, respectively. Fluorescence lifetimes of polymer films decreased monotonically with increasing DHB concentration from 1.8 (0) to 0.7 nsec (9.2 x 10 3 MDHB). Since fluorescence lifetimes (in contrast to fluorescence intensities) are unaffected by absorption effects of the stabilizer, these results provide direct evidence in support of the intensity measurements for RET from polymer to stabilizer. 

The parameters K1/ K2/ and K3 are defined by the refractive indices of the crystal and sample and by the incidence angle [32]. If the sample has uniaxial symmetry, only two polarized spectra are necessary to characterize the orientation. If the optical axis is along the plane of the sample, such as for stretched polymer films, only the two s-polarized spectra are needed to determine kz and kx. These are then used to calculate a dichroic ratio or a P2) value with Equation (25) (replacing absorbance with absorption index). In contrast, a uniaxial sample with its optical axis perpendicular to the crystal surface requires the acquisition of spectra with both p- and s-polarizations, but the Z- and X-axes are now equivalent. This approach was used, through dichroic ratio measurements, to monitor the orientation of polymer chains at various depths during the drying of latex [33]. This type of symmetry is often encountered in non-polymeric samples, for instance, in ultrathin films of lipids or self-assembled monolayers. 

Methyl- and 3-ethylsydnone have been used as aprotic solvents for electrolytes <2000MI20, 2002MI334>, whereas 3-phenylsydnone has been employed as a filter for recording the absorption spectra and refractive indexes of polymer films containing other mesoionic compounds <2002MI2290>. 

The film that was obtained was very thin and it was not possible to grow thicker films. This result was most probably caused by absorption of the incident radiation by the film formed on the interior of the quartz reactor, thereby blocking the incoming UV light and preventing the activation of the monomer and continous polymerization. The UV absorption of the monomer and of polymer film reside in the same region. Figure 18.5 and 18.6 show the UV absorption spectra of the precursor and the polymer film as deposited on the quartz surface, respectively. 

Each solvent used was observed to contain no impurities which fluoresce in the spectral region of interest. All solution concentrations used were in the range 10-5 to 10 4 M. Polymer films were cast onto quartz plates from either chloroform or dichloromethane solutions containing 4% (wt/wt) of polymer. The films were air dried at room temperature and had an average thickness of 65 10 )lm. The absorption spectra of the polymer films were measured using an appropriate PMMA or PS film as the reference. 

The ground states of the TIN and TINS stabilizers respond to the influence of the molecular environment in polymer films in almost the same manner as they do in solution. The absorption spectra of TIN in PMMA film (Figure 9) and TIN in PS film are similar to those observed for TIN in low polarity, non hydrogen-bonding solvents. A linear combination of the TIN planar) and TIN(non-planar) component spectra from the PCOMP analysis was used to fit the absorption spectrum of TIN in PMMA. 

The absorption spectra of the hydroxyphenylbenzo-triazole derivatives in various solvents and polymer films indicate that two ground-state forms of the molecules exist. These species are proposed to be a planar and non-planar form of the stabilizers. The position of the equilibrium between these two forms is affected by both the polarity and the hydrogen-bonding strength of the medium. The blue fluorescence (A.max = 400 nm) observed for these stabilizers originates from an excited-state species in which intramolecular proton transfer is disrupted. 

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