Stephanie S. Lee

Role of Majority and Minority Carrier Barriers Silicon/ Organic Hybrid Heterojunction Solar Cells

A hybrid approach to solar cells is demonstrated in which a silicon p-n junction, used in conventional silicon-based photovoltaics, is replaced by a room-temperature fabricated silicon/organic heterojunction. The unique advantage of silicon/organic heterojunction is that it exploits the cost advantage of organic semiconductors and the performance advantages of silicon to enable potentially low-cost, efficient solar cells.

Transient photovoltaic behavior of air-stable, inverted organic solar cells with solution-processed electron transport layer

The short-circuit current density of inverted organic solar cells comprising a solution-processed titania electron transport layer increases with continuous illumination in air and saturates after 10 min. On extended exposure (>2 days), the open-circuit voltage of the devices increases also. The improvement in device characteristics over short time scales is attributed to the filling of shallow electron traps in titania. With an increase in photoconductivity of titania, the short-circuit current increases accordingly. The increase in open-circuit voltage on extended exposure to air is attributed to an increase in the electrostatic field across the diodes when polythiophene is doped by oxygen.

Solvent-dependent electrical characteristics and stability of organic thin-film transistors with drop cast bis(triisopropylsilylethynyl) pentacene

The solvent from which the active layer is drop cast dramatically influences the electrical characteristics and electrical stability of thin-film transistors comprising bis(triisopropylsilylethynyl) pentacene. Casting from high boiling solvents allows slower crystallization; devices cast from toluene and chlorobenzene thus exhibit mobilities >0.1 cm2/V s and on/off ratios of ∼106. More importantly, the solvent choice influences the device stability. Devices from toluene exhibit stable characteristics, whereas devices from chlorobenzene show hystereses on cycling, with dramatic threshold voltage shifts toward positive voltages. The instability in chlorobenzene devices is attributed to the migration of water and solvent impurities to the charge transport interface on repetitive testing.

Structural Complexities in the Active Layers of Organic Electronics

The field of organic electronics has progressed rapidly in recent years. However, understanding the direct structure-function relationships between the morphology in electrically active layers and the performance of devices composed of these materials has proven difficult. The morphology of active layers in organic electronics is inherently complex, with heterogeneities existing across multiple length scales, from subnanometer to micron and millimeter range. A major challenge still facing the organic electronics community is understanding how the morphology across all of the length scales in active layers collectively determines the device performance of organic electronics. In this review we highlight experiments that have contributed to the elucidation of structure-function relationships in organic electronics and also point to areas in which knowledge of such relationships is still lacking. Such knowledge will lead to the ability to select active materials on the basis of their inherent properties for the fabrication of devices with prespecified characteristics.

Guiding Crystallization around Bends and Sharp Corners

Control over the molecular orientation in organic thin films is demonstrated with precise in-plane spatial resolution over large areas. By exploiting the differential crystallization rates on substrates with different surface energies, the radial symmetry of spherulitic growth can be disrupted by preferentially selecting the molecular orientations that promote growth along the paths of the underlying patterns.

Orientation-independent charge transport in single spherulites from solution-processed organic semiconductors.

Due to the rapidity of morphological development during deposition, solution-processed organic semiconductor thin films exist in semicrystalline or polycrystalline states, incorporating a high degree of local variations in molecular orientation compared to their single-crystal counterparts. Spherulites, a common crystalline superstructure found in these systems, for example, incorporate a large distribution of molecular orientations about the radial axis to maintain their space-filling growth habit. Here, we aim to determine how this distribution of molecular orientations influences charge transport by fabricating arrays of devices on single spherulites. Given that the orientation distribution that is present about the radial axis mandates the presence of low-angle grain boundaries within single spherulites, we find intraspherulitic charge transport to be independent of the general direction of π-stacking; organic field-effect transistors exhibit comparable mobilities regardless of how their channels are oriented with respect to the general π-stacking direction.

Quantifying resistances across nanoscale low- and high-angle interspherulite boundaries in solution-processed organic semiconductor thin films.

The nanoscale boundaries formed when neighboring spherulites impinge in polycrystalline, solution-processed organic semiconductor thin films act as bottlenecks to charge transport, significantly reducing organic thin-film transistor mobility in devices comprising spherulitic thin films as the active layers. These interspherulite boundaries (ISBs) are structurally complex, with varying angles of molecular orientation mismatch along their lengths. We have successfully engineered exclusively low- and exclusively high-angle ISBs to elucidate how the angle of molecular orientation mismatch at ISBs affects their resistivities in triethylsilylethynyl anthradithiophene thin films. Conductive AFM and four-probe measurements reveal that current flow is unaffected by the presence of low-angle ISBs, whereas current flow is significantly disrupted across high-angle ISBs. In the latter case, we estimate the resistivity to be 22 MΩμm(2)/width of the ISB, only less than a quarter of the resistivity measured across low-angle grain boundaries in thermally evaporated sexithiophene thin films. This discrepancy in resistivities across ISBs in solution-processed organic semiconductor thin films and grain boundaries in thermally evaporated organic semiconductor thin films likely arises from inherent differences in the nature of film formation in the respective systems.

Post-deposition processing methods to induce preferential orientation in contorted hexabenzocoronene thin films.

The structuring in organic electrically active thin films critically influences the performance of devices comprising them. Controlling film structure, however, remains challenging and generally requires stringent deposition conditions or modification of the substrate. To this end, we have developed post-deposition processing methods that are decoupled from the initial deposition conditions to induce different out-of-plane molecular orientations in contorted hexabenzocoronene (HBC) thin films. As-deposited HBC thin films lack any long-range order; subjecting them to post-deposition processing, such as hexanes-vapor annealing, thermal annealing, and physical contact with elastomeric poly(dimethyl siloxane), induces crystallization with increasing extents of preferential edge-on orientation, corresponding to greater degrees of in-plane π-stacking. Accordingly, transistors comprising HBC thin films that have been processed under these conditions exhibit field-effect mobilities that increase by as much as 2 orders of magnitude with increasing extents of molecular orientation. The ability to decouple HBC deposition from its subsequent structuring through post-deposition processing affords us the unique opportunity to tune competing molecule-molecule and molecule-solvent interactions, which ultimately leads to control over the structure and electrical function of HBC films.

Manipulating crystallization with molecular additives

Given the importance of organic crystals in a wide range of industrial applications, the chemistry, biology, materials science, and chemical engineering communities have focused considerable attention on developing methods to control crystal structure, size, shape, and orientation. Tailored additives have been used to control crystallization to great effect, presumably by selectively binding to particular crystallographic surfaces and sites. However, substantial knowledge gaps still exist in the fundamental mechanisms that govern the formation and growth of organic crystals in both the absence and presence of additives. In this review, we highlight research discoveries that reveal the role of additives, either introduced by design or present adventitiously, on various stages of formation and growth of organic crystals, including nucleation, dislocation spiral growth mechanisms, growth inhibition, and nonclassical crystal morphologies. The insights from these investigations and others of their kind are likely to guide the development of innovative methods to manipulate crystallization for a wide range of materials and applications.

Electric-Field-Induced Reversible Phase Transitions in Two-Dimensional Colloidal Crystals

Two-dimensional colloidal crystals confined within electric field traps on the surface of a dielectrophoretic cell undergo reversible phase transitions that depend on the strength of the applied AC electric field. At low field strengths, the particles adopt a two-dimensional hexagonal close-packed lattice with p6m plane group symmetry and the maximum achievable packing fraction of φ = 0.91. Higher electric field strengths induce dipoles in the particles that provoke a phase transition to structures that depend on the number of particles confined in the trap. Whereas traps containing N = 24 particles transform to a square-packed lattice with p4m symmetry and φ = 0.79 is observed, traps of the same size containing N = 23 particles can also pack in a lattice with p2 symmetry and φ = 0.66. Traps with N = 21, 22, and 25 particles exhibit a mixture of packing structures, revealing the influence of lateral compressive forces, in addition to induced dipole interactions, in stabilizing loosely packed arrangements. These observations permit construction of a phase diagram based on adjustable parameters of electric field strength (0-750 V/cm) and particle number (N = 21-25).