Singlet fission (SF), the photophysical process converting an excited singlet exciton into two triplet excitons, is a promising approach to boost solar cell efficiencies. It is controlled by various parameters such as intermolecular interactions, energetics, entropy and vibronic coupling and a controlled modification of these parameters is key to a fundamental understanding. Blends of organic semiconductors present an interesting alternative to established methods of chemical functionalization and their potential for the study of SF pathways will be discussed using acene blends as example. Mixed thin films of SF chromophores and weakly interacting, high-bandgap spacer molecules allow one to study the impact of a replacement of nearest neighbors on the SF rates. While the SF rate in pentacene, for which SF is a coherent process, is unaffected by the introduction of spacer molecules into the film, we observe a significant decrease in the SF rate in tetracene, indicating incoherent SF. Mixing the two SF chromophores pentacene and tetracene with low pentacene concentrations leads to heterofission of a singlet on pentacene into two triplets on pentacene and tetracene, respectively, when selectively exciting pentacene. This heterofission process is outcompeted by pentacene homofission if the pentacene concentration exceeds 5%. Photoexcitation above the tetracene band gap additionally allows for energy transfer from tetracene to pentacene and results in complex dynamics.
Due to their ease of processing, organic semiconductors are promising candidates for applications in high performance flexible displays and fast organic electronic circuitry. Recently, a lot of advances have been made on organic semiconductors exhibiting surprisingly high performance and carrier mobilities exceeding those of amorphous silicon. However, there remain significant concerns about their operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode (OLED) displays.
Here, we report a novel technique for dramatically improving the operational stress stability, performance and uniformity of high mobility polymer field-effect transistors by the addition of specific small molecule additives to the polymer semiconductor film. We demonstrate for the first time polymer FETs that exhibit stable threshold voltages with threshold voltage shifts of less than 1V when subjected to a constant current operational stress for 1 day under conditions that are representative for applications in OLED active matrix displays. The approach constitutes in our view a technological breakthrough; it also makes the device characteristics independent of the atmosphere in which it is operated, causes a significant reduction in contact resistance and significantly improves device uniformity. We will discuss in detail the microscopic mechanism by which the molecular additives lead to this significant improvement in device performance and stability.
Transport in organic semiconductors has traditionally been investigated using measurements of the temperature and gate voltage dependent mobility of charge carriers within the channel of organic field-effect transistors (OFETs). In such measurements, the behavior of charge carrier mobility with temperature and gate voltage, studied together with carrier activation energies, provide a metric to quantify the extent of disorder within these van der Waals bonded materials. In addition to the mobility and activation energy, another potent but often-overlooked transport coefficient useful in understanding disorder is the Seebeck coefficient (also known as thermoelectric power). Fundamentally, the Seebeck coefficient represents the entropy per charge carrier in the solid state, and thus proves powerful in distinguishing materials in which charge carriers move freely from those where a high degree of disorder causes the induced carriers to remain trapped. This paper briefly covers the recent highlights in the field of organic thermoelectrics, showing how significant strides have been made both from an applied standpoint as well as from a viewpoint of fundamental thermoelectric transport physics. It shall be illustrated how thermoelectric transport parameters in organic semiconductors can be tuned over a significant range, and how this tunability facilitates an enhanced performance for heat-to-electricity conversion as well as quantifies energetic disorder and the nature of the density of states (DOS). The work of the authors shall be spotlighted in this context, illustrating how Seebeck coefficient measurements in the polymer indacenodithiophene-co-benzothiadiazole (IDTBT) known for its ultra-low degree of torsion within the polymer backbone, has a trend consistent with low disorder. 1 Finally, using examples of the small molecules C8-BTBT and C10-DNTT, it shall be discussed how the Seebeck coefficient can aid the estimation of the density and distribution of trap states within these materials. 2, 3
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