Chad R. Snyder

Film morphology evolution during solvent vapor annealing of highly efficient small molecule donor/acceptor blends

Solution-processable small molecule photovoltaics based on the novel molecular donor, benzodithiophene terthiophene rhodanine (BTR), recently have shown maximum power conversion efficiencies above 8 % for active layer thicknesses up to 400 nm, using post process solvent vapor annealing (SVA) with tetrahydrofuran (THF). Here we report an in-situ study on the morphology evolution during SVA using the moderate solvent THF and the good solvent chloroform (CF). The combination of real-time grazing incidence X-ray diffraction (GIXD) and grazing incidence small angle X-ray scattering (GISAXS) allows us to draw a complete picture of the evolution of crystallinity and phase purity during post process annealing. We find that the relative crystallinity compared to the as-cast films is only modestly affected by SVA and solvent choice. However, both the phase purity and the characteristic domain sizes within the film vary significantly and are controlled by the solvent quality as well as exposure time. Using THF, films with high phase purity and desirable characteristic length scales of about 30 nm can be achieved, while the use of CF rapidly leads to excessive film coarsening and less preferable domain sizes on the order of 60 nm, too large for optimized charge separation.

A precision capacitance cell for measurement of thin film out-of-plane expansion. II. Hygrothermal expansion

The data reduction techniques necessary for utilizing the capacitance cell described previously by us for thickness measurements [C. R. Snyder and F. I. Mopsik, Rev. Sci. Instrum. 69, 3889 (1998)] in a humid environment are presented. It is demonstrated that our data reduction techniques provide thicknesses that are equivalent to those measured under dry conditions within the expected experimental uncertainty. The utility of this technique is demonstrated by the measurement of the hygrothermal expansion (swelling) of a bisphenol-A based epoxy with novolac hardener and fused silica filler. Our technique is shown to have a higher sensitivity than most current thermomechanical analysis techniques and is readily amenable to humid conditions.

Limitations on Distinguishing Between Representations of Relaxation Data Over Narrow Frequency Ranges

In this article, we examine the ability to distinguish between relaxation functions with data over a limited range of frequency. It is demonstrated that over these limited frequency ranges under a variety of conditions, the Cole–Cole equation can be used to fit data generated by the Havriliak–Negami equation. These results show that discerning between several very different broad relaxation functions fit to data obtained over narrow time or frequency ranges is nearly impossible within experimental accuracy. Therefore, the uniqueness of the fit parameters, and hence the ability to verify model predictions, is brought into question. Furthermore, as this conclusion is drawn from comparison of exact functions that experience no dispersion overlaps or instrumental systematic errors that can mask exact fits, the true situation with experimental data is even worse. The same conclusion can be applied to time domain data.

Determining conformational order and crystallinity in polycaprolactone via Raman spectroscopy

Raman spectroscopy is a popular method for non-invasive analysis of biomaterials containing polycaprolactone in applications such as tissue engineering and drug delivery. However there remain fundamental challenges in interpretation of such spectra in the context of existing dielectric spectroscopy and differential scanning calorimetry results in both the melt and semi-crystalline states. In this work, we develop a thermodynamically informed analysis method which utilizes basis spectra - ideal spectra of the polymer chain conformers comprising the measured Raman spectrum. In polycaprolactone we identify three basis spectra in the carbonyl region; measurement of their temperature dependence shows that one is linearly proportional to crystallinity, a second correlates with dipole-dipole interactions that are observed in dielectric spectroscopy and a third which correlates with amorphous chain behavior. For other spectral regions, e.g. C-COO stretch, a comparison of the basis spectra to those from density functional theory calculations in the all-trans configuration allows us to indicate whether sharp spectral peaks can be attributed to single chain modes in the all-trans state or to crystalline order. Our analysis method is general and should provide important insights to other polymeric materials.

Dynamically induced loss and its implications on temperature scans of relaxation processes

It is demonstrated that a constant frequency measurement of a purely real property that varies due to a change in some state variable (e.g., pressure, volume, or temperature) with time will show a dynamically induced loss that is not present when the variable is held constant. This conclusion is demonstrated through both generalized arguments and by examining some specific functional forms of time evolution equations, including one that resembles a glass transition. Our results show that techniques such as dielectric thermal analysis, dynamic mechanical thermal analysis, and modulated differential scanning calorimeter, which perform measurements of complex quantities while scanning in temperature, may have some serious problems. Therefore, results obtained from these techniques should be examined carefully before using them to prove or disprove theoretical model predictions, especially in the neighborhood of a phase transition.

Reduced bimolecular recombination in blade-coated, high-efficiency, small-molecule solar cells

To realize the full promise of solution deposited photovoltaic devices requires processes compatible with high-speed manufacturing. We report the performance and morphology of blade-coated bulk heterojunction devices based on the small molecule donor p-DTS(FBTTh2)2 when treated with a post-deposition solvent vapor annealing (SVA) process. SVA with tetrahydrofuran improves the device performance of blade-coated films more than solvent additive processing (SA) with 1,8-diiodooctane. In spin-coating, SA and SVA achieve similar device performance. Our optimized, blade coated, SVA devices achieve power conversion efficiencies over 8 % and maintain high efficiencies in films up to ≈ 250 nm thickness, providing valuable resilience to small process variations in high-speed manufacturing. Using impedance spectroscopy, we show that this advantageous behavior originates from highly suppressed bimolecular recombination in the SVA-treated films. Electron microscopy and grazing-incidence X-ray scattering experiments show that SA and SVA both produce highly crystalline donor domains, but SVA films have a radically smaller domain size compared to SA films. We attribute the different behavior to variations in initial nucleation density and relative ability of SVA and SA to control subsequent crystal growth.

Exact solution of the thermodynamics and size parameters of a polymer confined to a lattice of finite size: large chain limit.

We extend the exact solutions of the Di Marzio-Rubin matrix method for the thermodynamic properties, including chain density, of a linear polymer molecule confined to walk on a lattice of finite size. Our extensions enable (a) the use of higher dimensions (explicit 2D and 3D lattices), (b) lattice boundaries of arbitrary shape, and (c) the flexibility to allow each monomer to have its own energy of attraction for each lattice site. In the case of the large chain limit, we demonstrate how periodic boundary conditions can also be employed to reduce computation time. Advantages to this method include easy definition of chemical and physical structure (or surface roughness) of the lattice and site-specific monomer-specific energetics, and straightforward relatively fast computations. We show the usefulness and ease of implementation of this extension by examining the effect of energy variation along the lattice walls of an infinite rectangular cylinder with the idea of studying the changes in properties caused by chemical inhomogeneities on the surface of the box. Herein, we look particularly at the polymer density profile as a function of temperature in the confined region for very long polymers. One particularly striking result is the shift in the critical condition for adsorption due to surface energy inhomogeneities and the length scale of the inhomogeneities; an observation that could have important implications for polymer chromatography. Our method should have applications to both copolymers and biopolymers of arbitrary molar mass.

A precision capacitance cell for measurement of thin film out-of-plane expansion. III. Conducting and semiconducting materials

For pt. II see Rev. Sci. Instrum., vol. 70, pp. 2424-2431 (1999).This paper describes the construction, calibration, and use of a precision capacitance-based metrology for the measurement of the thermal and hygrothermal (swelling) expansion of thin films. It is demonstrated that with this version of our capacitance cell, materials ranging in electrical properties from insulators to conductors can be measured. The results of our measurements on p-type -oriented single crystal silicon are compared to the recommended standard reference values from the literature and are shown to be in excellent agreement.

Phase behavior of poly(3‐hexylthiophene‐2,5‐diyl)

The phase behavior of many conjugated polymers is rich with both crystalline and liquid crystalline phases. Recent computational efforts have identified the isotropic-to-nematic transition temperature for polymers such as poly(3-hexylthiophene-2,5-diyl) (P3HT). Herein, model predictions are combined with experimentally determined values of the equilibrium melting temperature as a function of chain length to provide the complete phase behavior for P3HT. Additionally, because a full description of the phase behavior requires proper accounting for the regioregularity of the chain, a thermodynamic relationship is derived to predict this behavior as a function of both chain length and regioregularity and the impact of regioregularity on the expected phase diagram is discussed.

Characterization of clay composite ballistic witness materials

Mechanical and thermal properties of Roma Plastilina Clay #1 (RP1) were studied through small-amplitude oscillatory shear (SAOS), large-amplitude oscillatory shear (LAOS), and differential scanning calorimetry (DSC), supplemented with thermogravimetric analysis, X-ray diffraction, and X-ray florescence. Rheological characterizations of RP1 through SAOS indicate that the clay composite softens as it is worked and slowly stiffens as it rests. Upon heating, the clay composite softens, prior work history is erased, and the composite undergoes a melting transition, although melted clay is significantly stiffer when returned to the usage temperature. Continuing mechanical characterizations into the LAOS or nonlinear region, RP1 transitions from a transient network to a viscous shear-thinning material as the temperature is increased. Using the MITlaos framework, RP1 exhibits intra-cycle strain stiffening and intra-cycle shear thinning at all temperatures.