Anisotropic Vapor-Deposited Glasses: Hybrid Organic Solids

The term "organic solids" encompasses both crystals and glasses. Organic crystals are commonly grown for purification and structure determination and are being extensively explored for applications in organic electronics including field effect transistors. The ability to control the packing of one molecule relative to its neighbors is of critical importance for most uses of organic crystals. Often, anisotropic packing is also highly desirable as it enhances charge transport and optimizes light absorption/emission. When compared to crystals, the local packing in organic glasses is highly disordered and often isotropic. Glasses, however, offer two key advantages with respect to crystals. First, glasses typically lack grain boundaries and thus exhibit better macroscopic homogeneity. Second, glass composition can often be varied over a wide range while maintaining homogeneity. Besides electronic materials, many modern plastics used in a wide range of technologies are organic glasses, and the glassy state is being increasingly utilized to deliver pharmaceuticals because of higher bioavailability. In this article, we introduce vapor-deposited organic glasses as hybrid materials that combine some of the useful features of crystals and traditional liquid-cooled glasses. Physical vapor deposition produces glasses by directly condensing molecules from the gas phase onto a temperature-controlled substrate and allows film thickness to be controlled with nanometer precision. Just as liquid-cooled glasses, vapor-deposited glasses have smooth surfaces and lack grain boundaries. These attributes are critical for applications such as organic light emitting diodes (OLEDs), in which vapor-deposited glasses of organic semiconductors form the active layers. In common with crystals, vapor-deposited glasses can exhibit anisotropic packing, and the extent of anisotropy can be comparable to that of the typical organic crystal. For vapor-deposited glasses, in contrast to crystals, anisotropic packing can generally be controlled as a continuous variable. Deposition conditions can be chosen to produce glasses with significant molecular orientation (molecules "standing up" or "lying down" relative to the substrate), and π-stacking can be directed along different directions relative to the substrate. Over the last five years, we have gained a fundamental understanding of the mechanism that controls the anisotropy of vapor-deposited glasses and learned how to control many aspects of anisotropic packing. Two key elements that enable such control are the high mobility present at the surface of an organic glass and the tendency of the surface to promote anisotropic packing of molecules. In contrast to traditional epitaxial growth, for vapor-deposited glasses, the free surface (not the substrate) acts as a template that controls the structure of a growing film. The structure of any given layer is decoupled from those beneath it, thereby providing considerable freedom in producing layered glassy structures.