Electronic Structure of Organic Solids

Through injection or extraction of an electron at the interface between a metal electrode and the molecule, as is typically the case in the operation of a device such as light-emitting diodes (LED). 

Through reduction or oxidation of the molecule by a dopant molecule. Atoms or molecules with high electron affinity, such as iodine, antimony pentafluoride (SbCls), or 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), may oxidize a typical organic semiconductor such as poly(p-phenylene) derivatives, leaving them positively charged. Reduction, i.e., addition of an electron, may be obtained by doping with alkali metals. 

Through exothermic dissociation of a neutral excited state in molecule by electron transfer to an adjacent molecule. This process leads to the generation of geminately bound electron-hole pairs as precursors of free positive and negative charges in an organic solar cell. 

A charged molecule may absorb light in the same fashion as does a neutral molecule, thereby promoting an electron from a lower to a higher molecular orbital. Possible optical transitions are indicated in Fig. 2a by arrows. These optical transitions can easily be observed in doped molecular films as well as in solution (see below). We note that, analogous to transitions in neutral molecules, absorption 

So far we have outlined the conceptual framework in which we discuss charge transfer in organic semiconductors. It is based on a molecular picture where the molecular unit is considered central, with interactions between molecular units added afterwards. For amorphous molecular solids and for molecular crystals this approach is undisputed. In the case of semiconducting polymers, a conceptually different view has been proposed that starts from a one-dimensional (ID) semiconductor band picture, and that is generally known as the Su-Schrieffer-Heeger (SSH) model [21-24]. 

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General Vieu/of Electronic Structure of Organic Solids 69... 

This contribution deals with the use of ultraviolet photoelectron spectroscopy (UPS) for the study of the surface and bulk electronic structure of organic molecular and polymeric solids. In so far as is necessary, some features of the UPS of isolated model monomer molecules in the gas phase are described in order to provide a basis for an understanding of certain phenomena that occur in the corresponding condensed molecular and polymeric solids. Some features of photoelectron spectroscopy in general are outlined with an emphasis on the phenomenological interpretation of spectra for the several case studies to be reviewed. The complimentary nature of X-ray photoelectron spectroscopy (XPS or sometimes ESCA) and UPS is pointed out. The discussions presented are focused upon the experimental aspects of the UPS of insulating organic molecular and polymeric solids, but specific hardware considerations are not included. A variety of references, some of a review nature, are included, but the content is not intended to be historically complete. Examples for examination are drawn primarily from the author s own experience. 

This chapter describes fundamental aspects of the electronic structure of organic semiconductors (small molecules and polymers), and their interfaces, and the method to bridge the electronic structure and electrical property more directly using ultraviolet photoemission spectroscopy (UPS). Penning ionization electron spectroscopy (PIES), which is the most surface-sensitive method, is also introduced for study of electronic states at outermost surfaces of solids, which are responsible for charge exchange through the interfaces between different materials when they get contact to form a hybrid system. 

In a very successful metaphoric style, all items of the computer world that have to do with programs are called software, while all the rest (electronic parts, wires, input-output devices) are called hardware. Partly countering the intrinsic semantics of these two words, in the last years software has become much more expensive than hardware. Computer elaboration is a matter of switching between electronic zero and electronic one, and therefore on the hardware side computer speed depends on the speed at which the electronic status of a solid device can be modified. This response of electrons to an electric stimulus in turn is a matter of the electronic structure of the solid (see Section 6.2). This is a technical matter. On the software side, higher speed depends on a better organization of the code. Computer speed is anyway an essential variable in the development of computational theoretical chemistry [3]. 

Joseph Riga Is currently a senior staff member at Namur working mainly on molecular solids and polymers using XPS. He obtained his Ph.D. degree from the Facultes Universitaires Notre Dame de la Palx, Namur, Belgium with a thesis on the electronic structure of organic disulfides. 

Stannylenes are in the first place Lewis acids (electron acceptors) as can be easily derived from the structures of the solids (Chapter 3). When no Lewis bases (electron donors) are present, they may also act as Lewis bases via their non-bonding electron pair (see polymerization of organic stannylenes). 

The scale of components in complex condensed matter often results in structures having a high surface-area-to-volume ratio. In these systems, interfacial effects can be very important. The interfaces between vapor and condensed phases and between two condensed phases have been well studied over the past four decades. These studies have contributed to technologies from electronic materials and devices, to corrosion passivation, to heterogeneous catalysis. In recent years, the focus has broadened to include the interfaces between vapors, liquids, or solids and self-assembled structures of organic, biological, and polymeric nature. 

Notably, SVO can display a variety of phases, both stoichiometric and nonstoichiometric. Thus, variations in reaction conditions, starting materials, and reagent stoichiometries for the preparation of SVO can result in a wealth of products that display different structures and different properties. In addition, the variety of oxidation states available to the silver and especially the vanadium components of SVO, plus the open structure of some of the SVO materials, suggest that these materials are well suited for electron transfer applications. It is thus logical and not surprising that reports of SVO battery applications and SVO redox catalyst applications appear within similar time frames. Some reports involving the structure of SVO solids and the catalysis of organic substrate oxidation by SVO-based catalysts will be described in Section 13.2, due to their possible relevance to the SVO battery chemistry described in Section 13.3. 

The structural disorder formalism has been mostly utilized to discuss electronic transport in organic solids [29,38] (cf. Sec. 4.6), and only a few works show its applicability to interpret optical spectra [62,67], and, recently, quantum efficiency of organic LEDs [68]. The absorption spectrum of an organic material with impurities disorder, local electric fields, or strong exciton-phonon coupling exhibits an exponential tail, commonly referred to as the Urbach tail [69,70]. Such a spectrum can often be decomposed into broad bands featuring... 

The one-electron band structure of organic conductors is typical of molecular solids with a narrow bandwidth. In particular, the bandwidth W is significantly smaller than the on-site Coulomb repulsion U, in general (see also Chapter 2), so that the electrical properties of these conductors are strongly influenced by electron-electron interactions. 

Electronic Structure of Solids Fluorides Solid-state Chemistry Halides Solid-state Chemistry Macrocyclic Ligands Metallic Materials Deposition Metal-organic Precursors Oxides Solid-state Chemistry Periodic Table Trends in the Properties of the Elements Sol-Gel Synthesis of Solids Sohds Characterization by Powder Diffraction Structure Property Maps for Inorganic Solids Superconductivity Thin Film Synthesis of Solids. 

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