Dynamics of domain boundaries at metal-organic interfaces.

Domain boundaries are a determining factor in the performance of organic electronic devices since they can trap mobile charge carriers. We point out the possibility of time-dependent motion of these boundaries and suggest that their thermal fluctuations can be a source of dynamic disorder in organic films. In particular, we study the C8-BTBT monolayer films with several different domain boundaries. After characterizing the crystallography and diversity of structures in the first layer of C8-BTBT on Au(111), we focus on quantifying the domain boundary fluctuations in the saturated monolayer. We find that the mean squared displacement of the boundary position grows linearly with time at early times but tends to saturate after about 7 s. This behavior is ascribed to confined diffusion of the interface position based on fits and numerical integration of a Langevin equation for the interface motion.

Suppression of dynamic disorder in fullerenes at metal-organic interfaces.

Organic semiconductors are prone to strong disorder effects that often exhibit significant dynamic characteristics. In this study, static disorder and dynamic disorder of fullerene molecules at the interface of Au(111) are directly distinguished using Scanning Tunneling Microscopy (STM) and Scanning Tunneling Spectroscopy. We consider an STM image consisting of hundreds of different molecules, as an ensemble which exhibits conductance fluctuations due to both dynamic disorder and static disorder. On the other hand, local conductance measurement of single molecules over time reflects only dynamic disorder. We demonstrate that dynamic disorder is always smaller than static disorder at the C60/Au(111) interface due to structural constraints of molecules at the interface. Dynamic disorder in our experiment is due to small librations of individual molecules that are restricted by the metal surface, while static disorder is related to different bonding orientations of the C60 cage that are frozen-in at room temperature. Our experimental results can be modeled with direct simulations of differential tunneling conductance.

Role of Polymer Segregation on the Mechanical Behavior of All-Polymer Solar Cell Active Layers.

An all-polymer bulk heterojunction (BHJ) active layer that removes the use of commonly used small molecule electron acceptors is a promising approach to improve the thermomechanical behavior of organic solar cells. However, there has been limited research on their mechanical properties. Here, we report on the mechanical behavior of high-performance blade-coated all-polymer BHJ films cast using eco-friendly solvents. The mechanical properties considered include the elastic modulus, crack onset strain, and cohesive fracture energy. We show that the mechanical behavior of the blend is largely unaffected by significant changes in the segregation characteristics of the polymers, which was varied systematically through solvent formulation. In comparison to a polymer:fullerene BHJ counterpart, the all-polymer films were found to have lower stiffness and increased ductility. Yet, the fracture energy of the all-polymer films is not significantly improved compared to that of the polymer:fullerene films. This study highlights that improved mechanical behavior of all-polymer systems cannot be assumed, and that details of the molecular structure, molecular weight, and film morphology play an important role in both the optoelectronic and mechanical properties. Furthermore, we show that simple composite modeling provides a predictive tool for the mechanical properties of the polymer blend films, providing a framework to guide future optimization of the mechanical behavior.

Coverage dependent molecular assembly of anthraquinone on Au(111).

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Monitoring Charge Separation Processes in Quasi-One-Dimensional Organic Crystalline Structures.

We perform the transient absorption spectroscopy experiments to investigate the dynamics of the low-energy collective electron-hole excitations in α-copper phthalocyanine thin films. The results are interpreted in terms of the third-order nonlinear polarization response function. It is found that, initially excited in the molecular plane, the intramolecular Frenkel exciton polarization reorients with time to align along the molecular chain direction to form coupled Frenkel-charge-transfer exciton states, the eigenstates of the one-dimensional periodic molecular lattice. The process pinpoints the direction of the charge separation in α-copper phthalocyanine and similar organic molecular structures. Being able to observe and monitor such processes is important both for understanding the physical principles of organic thin film solar energy conversion device operation and for the development of organic optoelectronics in general.

Intrinsic Charge Trapping Observed as Surface Potential Variations in diF-TES-ADT Films.

Spatial variations in surface potential are measured with Kelvin probe force microscopy for thin films of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophenes (diF-TES-ADT) grown on SiO2 and silane-treated SiO2 substrates by organic molecular beam deposition. The variations are observed both between and within grains of the polycrystalline organic film and are quantitatively different than electrostatic variations on the substrate surfaces. The skewness of surface potential distributions is larger on SiO2 than on HMDS-treated substrates. This observation is attributed to the impact of substrate functionalization on minimizing intrinsic crystallographic defects in the organic film that can trap charge.

Significantly Increasing the Ductility of High Performance Polymer Semiconductors through Polymer Blending.

Polymer semiconductors based on donor-acceptor monomers have recently resulted in significant gains in field effect mobility in organic thin film transistors (OTFTs). These polymers incorporate fused aromatic rings and have been designed to have stiff planar backbones, resulting in strong intermolecular interactions, which subsequently result in stiff and brittle films. The complex synthesis typically required for these materials may also result in increased production costs. Thus, the development of methods to improve mechanical plasticity while lowering material consumption during fabrication will significantly improve opportunities for adoption in flexible and stretchable electronics. To achieve these goals, we consider blending a brittle donor-acceptor polymer, poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]thiadiazolo[3,4-c]pyridine] (PCDTPT), with ductile poly(3-hexylthiophene). We found that the ductility of the blend films is significantly improved compared to that of neat PCDTPT films, and when the blend film is employed in an OTFT, the performance is largely maintained. The ability to maintain charge transport character is due to vertical segregation within the blend, while the improved ductility is due to intermixing of the polymers throughout the film thickness. Importantly, the application of large strains to the ductile films is shown to orient both polymers, which further increases charge carrier mobility. These results highlight a processing approach to achieve high performance polymer OTFTs that are electrically and mechanically optimized.

Molecular electronic level alignment at weakly coupled organic film/metal interfaces.

Electronic level alignment at interfaces of molecular materials with inorganic semiconductors and metals controls many interfacial phenomena. How the intrinsic properties of the interacting systems define the electronic structure of their interface remains one of the most important problems in molecular electronics and nanotechnology that can be solved through a combination of surface science experimental techniques and theoretical modeling. In this article, we address this fundamental problem through experimental and computational studies of molecular electronic level alignment of thin films of C(6)F(6) on noble metal surfaces. The unoccupied electronic structure of C(6)F(6) is characterized with single molecule resolution using low-temperature scanning tunneling microscopy-based constant-current distance-voltage spectroscopy. The experiments are performed on several noble metal surfaces with different work functions and distinct surface-normal projected band structures. In parallel, the electronic structures of the quantum wells (QWs) formed by the lowest unoccupied molecular orbital state of the C(6)F(6) monolayer and multilayer films and their alignment with respect to the vacuum level of the metallic substrates are calculated by solving the Schrödinger equation for a semiempirical one-dimensional (1D) potential of the combined system using input from density functional theory. Our analysis shows that the level alignment for C(6)F(6) molecules bound through weak van der Waals interactions to noble metal surfaces is primarily defined by the image potential of metal, the electron affinity of the molecule, and the molecule surface distance. We expect the same factors to determine the interfacial electronic structure for a broad range of molecule/metal interfaces.

Iron(II) spin crossover films on Au(111): scanning probe microscopy and photoelectron spectroscopy.

The growth of films of [H2B(pz)2]Fe(ii)(bpy) on Au(111) is characterized from the bilayer film to multilayer film regime. Scanning tunneling microscopy shows a transition from a well-ordered, uniform bilayer film to a poorly-ordered film at larger thicknesses. Previous local tunneling spectroscopy and conductance mapping in bilayer films permit the identification of coexisting molecular spin-states at all temperatures. New ultraviolet photoelectron spectroscopy is consistent with this picture and in agreement with the density of states calculated by density functional theory. In thicker films with a polycrystalline morphology, evidence for a more bulk-like change in spin composition as a function of temperature is obtained by observing the reduction in intensity of Fe 2p core level satellites in X-ray photoelectron spectra.

Modification of molecular spin crossover in ultrathin films.

Scanning tunneling microscopy and local conductance mapping show spin-state coexistence in bilayer films of Fe[(H2Bpz2)2bpy] on Au(111) that is independent of temperature between 131 and 300 K. This modification of bulk behavior is attributed in part to the unique packing constraints of the bilayer film that promote deviations from bulk behavior. The local density of states measured for different spin states shows that high-spin molecules have a smaller transport gap than low-spin molecules and are in agreement with density functional theory calculations.

Increasing the perceptual salience of relationships in parallel coordinate plots.

We present three extensions to parallel coordinates that increase the perceptual salience of relationships between axes in multivariate data sets: (1) luminance modulation maintains the ability to preattentively detect patterns in the presence of overplotting, (2) adding a one-vs.-all variable display highlights relationships between one variable and all others, and (3) adding a scatter plot within the parallel-coordinates display preattentively highlights clusters and spatial layouts without strongly interfering with the parallel-coordinates display. These techniques can be combined with one another and with existing extensions to parallel coordinates, and two of them generalize beyond cases with known-important axes. We applied these techniques to two real-world data sets (relativistic heavy-ion collision hydrodynamics and weather observations with statistical principal component analysis) as well as the popular car data set. We present relationships discovered in the data sets using these methods.

Complex materials for molecular spintronics applications: cobalt bis(dioxolene) valence tautomers, from molecules to polymers.

Using first principles calculations, we predict a complex multifunctional behavior in cobalt bis(dioxolene) valence tautomeric compounds. Molecular spin-state switching is shown to dramatically alter electronic properties and corresponding transport properties. This spin state dependence has been demonstrated for technologically relevant coordination polymers of valence tautomers as well as for novel conjugated polymers with valence tautomeric functionalization. As a result, these materials are proposed as promising candidates for spintronic devices that can couple magnetic bistability with novel electrical and spin conduction properties. Our findings pave the way to the fundamental understanding and future design of active multifunctional organic materials for spintronics applications.

Band formation in a molecular quantum well via 2D superatom orbital interactions.

By scanning tunneling microscopy and spectroscopy, we study nearly free electron band formation of the σ* lowest unoccupied molecular orbital of C6F6 on a Cu(111) surface. In fractal islands, the lowest unoccupied molecular orbital energy systematically stabilizes with the number of interacting near-neighbor C6F6 molecules. Density functional theory calculations reveal the origin of effective intermolecular orbital overlap in the previously unrecognized superatom character of the σ* orbital of C6F6 molecules. The discovery of superatom orbitals in planar molecules offers a new universal principle for effective band formation, which can be exploited in designing organic semiconductors with nearly free electron properties.

C60-pentacene network formation by 2-D co-crystallization.

We report experiments highlighting the mechanistic role of mobile pentacene precursors in the formation of a network C(60)-pentacene co-crystalline structure on Ag(111). This co-crystalline arrangement was first observed by low temperature scanning tunneling microscopy (STM) by Zhang et al. (Zhang, H. L.; Chen, W.; Huang, H.; Chen, L.; Wee, A. T. S. J. Am. Chem. Soc. 2008, 130, 2720-2721). We now show that this structure forms readily at room temperature from a two-dimensional (2-D) mixture. Pentacene, evaporated onto Ag(111) to coverages of 0.4-1.0 ML, produces a two-dimensional (2-D) gas. Subsequently deposited C(60) molecules combine with the pentacene 2-D gas to generate a network structure, consisting of chains of close-packed C(60) molecules, spaced by individual C(60) linkers and 1 nm x 2.5 nm pores containing individual pentacene molecules. Spontaneous formation of this stoichiometric (C(60))(4)-pentacene network from a range of excess pentacene surface coverage (0.4 to 1.0 ML) indicates a self-limiting assembly process. We refine the structure model for this phase and discuss the generality of this co-crystallization mechanism.

Nonlocal dissociative chemistry of adsorbed molecules induced by localized electron injection into metal surfaces.

We present a novel approach to surface chemistry studies using scanning tunneling microscopy (STM), where dissociation of molecules adsorbed on metal surfaces is induced nonlocally in a 10-100 nm radius around the STM tip by hot electrons that originate from the STM tip and transport on the surface. Nonlocal molecular excitation eliminates the influence of the STM tip on the outcome of the electron-induced chemical reaction. The spatial attenuation of the nonlocal reaction is used as a direct measure of hot-electron transport on the surface.

Assembly of linear clusters of iodobenzene dimers on Cu(110).

Low-temperature STM observations of the low-coverage chemisorption behavior of iodobenzene on Cu(110) are presented at two annealing temperatures. When a random distribution of isolated iodobenzene molecules deposited at T < 100 K is annealed to approximately 170 K, the undissociated molecules assemble into chainlike clusters composed of identical subunits. An STM tip-induced dissociation reaction is used to determine that the individual units in the chains are composed of pairs of iodobenzene molecules. A model is proposed in which iodine atoms on each member of the pair are directed toward one another. The driving force for the formation of such clusters is suggested to be the dispersion interactions between the polarizable iodobenzene molecules.

Edge-on bonding of benzene molecules in the second adsorbed layer on Cu(110).

The bilayer of benzene on Cu(110) was studied with temperature-programmed desorption (TPD), time-of-flight electron stimulated desorption ion angular distribution (TOF-ESDIAD), and scanning tunneling microscopy (STM). TPD spectra show that three well-defined adsorption states exist. The alpha layer corresponds to the first layer containing flat-lying benzene molecules. As coverage increases, the beta layer forms on top of the alpha layer, and eventually, a multilayer, gamma, forms. TPD measurements show that the number of benzene molecules in the beta layer is equal to the number of benzene molecules in the alpha layer. ESDIAD measurements establish that the orientation of the benzene molecules in the beta layer is edge-on, with two C-H bonds directed toward the surface. STM images of the beta layer reveal closely spaced edge-on benzene molecules arranged in repeating hexagons, as well as loosely spaced benzene molecules with greater apparent height, which are also edge-on species. Correlation between the different measurements suggests a structural model for the benzene bilayer.

Semi-mechanistic partial buffer approach to modeling pH, the buffer properties, and the distribution of ionic species in complex solutions.

In many biological science and food processing applications, it is very important to control or modify pH. However, the complex, unknown composition of biological media and foods often limits the utility of purely theoretical approaches to modeling pH and calculating the distributions of ionizable species. This paper provides general formulas and efficient algorithms for predicting the pH, titration, ionic species concentrations, buffer capacity, and ionic strength of buffer solutions containing both defined and undefined components. A flexible, semi-mechanistic, partial buffering (SMPB) approach is presented that uses local polynomial regression to model the buffering influence of complex or undefined components in a solution, while identified components of known concentration are modeled using expressions based on extensions of the standard acid-base theory. The SMPB method is implemented in a freeware package, (pH)Tools, for use with Matlab. We validated the predictive accuracy of these methods by using strong acid titrations of cucumber slurries to predict the amount of a weak acid required to adjust pH to selected target values.

Chemisorbed benzoate-to-benzene conversion via phenyl radicals on Cu(110): kinetic observation of conformational effects.

The adsorption and decomposition of benzoic acid on the Cu(110) surface has been investigated using temperature-programmed reaction (TPR) spectroscopy and scanning tunneling microscopy (STM). The benzoate species is found to exist in two conformations: a phase containing upright species at monolayer saturation and a phase containing many tilted species at lower coverages. Thermal decomposition begins to occur near 500 K, yielding benzene and CO2. It is found that phenyl radicals, generated preferentially from the tilted benzoate species, efficiently abstract H atoms from undecomposed benzoate species to produce benzene in a rate-controlling process with an activation energy of about 29 kcal/mol. Using deuterium atom substitution at the 4-C position on the benzoate ring, it is found that the hydrogen abstraction reaction is selective for 2-,3- and 5-,6-C-H bonds. This observation indicates that the mobile phenyl radical is surface bound and preferentially attacks C-H bonds which are nearest the Cu surface binding the benzoate species, either as an upright species or as a tilted species.

Phenyl species formation and preferential hydrogen abstraction in the decomposition of chemisorbed benzoate on Cu(110).

The adsorption and decomposition of benzoic acid on the Cu(110) surface has been investigated using temperature-programmed reaction (TPR) spectroscopy and scanning tunneling microscopy (STM). The benzoate species is found to exist in two conformations--a phase containing upright species at monolayer saturation and a phase containing many lying-down species at lower coverages. Thermal decomposition begins to occur near 500 K, yielding benzene and CO(2). It is found that phenyl species, generated preferentially from the lying-down benzoate species, efficiently abstract H atoms from undecomposed benzoate species to produce benzene in a rate-controlling process with an activation energy of about 29 kcal/mol. Using deuterium-atom substitution at the 4-C position on the benzoate ring it is found that the hydrogen-abstraction reaction is selective for 2,3 and 5,6 C-H bonds. This observation indicates that the mobile phenyl species is surface bound and preferentially attacks C-H bonds which are nearest the Cu surface and bind the benzoate species as either an upright species or a tilted species.