We describe at the quantum-chemical level the main parameters that control charge transport at the molecular scale in discotic liquid crystals. The focus is on stacks made of triphenylene, hexaazatriphenylene, hexaazatrinaphthylene, and hexabenzocoronene molecules and derivatives thereof. It is found that a subtle interplay between the chemical structure of the molecules and their relative positions within the stacks determines the charge transport properties; the molecular features required to promote high charge mobilities in discotic materials are established on the basis of the calculated structure-property relationships. We predict a significant increase in the charge mobility when going from triphenylene to hexaazatrinaphthylene; this finding has been confirmed by measurements carried out with the pulse-radiolysis time-resolved microwave conductivity technique.

The photogeneration quantum yield and dynamics of charge carriers and excitons in thin films of neat regioregular poly(3-hexylthiophene) (P3HT) and blends with [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM) were studied with ultrafast optical pump-probe spectroscopy. In neat P3HT the quantum yield for direct photogeneration of charge carriers amounts to 0.15 per absorbed photon. The remaining fraction of absorbed photons leads to formation of excitons. Recombination of charges reduces the quantum yield to about 25% of its initial value on a time scale of 100 ps followed by decay to a no longer observable yield after 1 ns. Addition of 50% PCBM by weight leads to ultrafast (<200 fs) formation of charge pairs with a total quantum yield of 0.5. The presence of 50% PCBM causes exciton decay to be about an order of magnitude faster than in neat P3HT, which is expected to be at least in part due to interfacial exciton dissociation into charge carriers. The yield of charges in the blend has decayed to about half its initial value after 100 ps, while no further decay is observed within 1 ns. The small fraction (∼1%) of excitons in neat P3HT that is probed by photoluminescence measurements has a lifetime of 660 ps, which significantly exceeds the 200 ps lifetime of nonfluorescent excitons that are probed by transient absorption measurements. The nonfluorescent excitons have a diffusion coefficient of about 2 × 10-4 cm 2 /s, which is an order of magnitude smaller than reported values for fluorescent excitons. The interaction radius for second-order decay of photoexcitations is as large as 8-17 nm, in agreement with an earlier result in the literature.

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Efficient carrier multiplication has been reported for several semiconductor nanocrystals: PbSe, PbS, PbTe, CdSe, InAs, and Si. Some of these reports have been challenged by studies claiming that carrier multiplication does not occur in CdSe, CdTe, and InAs nanocrystals, thus raising legitimate doubts concerning the occurrence of carrier multiplication in the remaining materials. Here, conclusive evidence is given for its occurrence in PbSe nanocrystals using femtosecond transient photobleaching. In addition, it is shown that a correct determination of carrier-multiplication efficiency requires spectral integration over the photobleach feature. The carrier multiplication efficiency we obtain is significantly lower than what has been reported previously, and it remains an open question whether it is higher in nanocrystals than it is in bulk semiconductors.

The effect of temperature on the quantum yield for charge carrier photogeneration in P3HT−PCBM blend films was studied using ultrafast transient absorption and microwave photoconductance techniques. The quantum yield was found to be virtually independent of temperature for time scales up to tens of nanoseconds after photoexcitation of P3HT. Implications of this observation for the mechanism of free charge carrier generation are discussed. The decay of charges due to recombination and/or trapping on longer times becomes faster at higher temperature, as a result of thermally activated electron and hole mobilities. The magnitude of the quantum yield depends on the morphology of the blend film, which is determined by the spin-coating solvent and annealing conditions.

The optical absorption and charge transport properties of a series of discotic molecules consisting of peripherally alkyl-substituted polycyclic aromatic cores have been investigated for core sizes, n, of 24, 42, 60, 78, 96, and 132 carbon atoms. In dilute solution, the wavelength maximum of the first absorption band increases linearly with n according to lambda(max) = 280 + 2n and the spectral features become increasingly broadened. The two smallest core compounds display a slight red-shift and increased spectral broadening in spin-coated films. For derivatives with n = 24, 42, 60, and 96, the one-dimensional, intracolumnar charge mobility, Sigma mu(1D), was determined using the pulse-radiolysis time-resolved microwave conductivity technique. For the compounds which were crystalline solids at room temperature, Sigma mu(1D) lay within the range 0.4-1.0 cm(2)/Vs. In the discotic mesophases at ca. 100 degrees C, Sigma mu(1D) was somewhat lower and varied from 0.08 to 0.38 cm(2)/Vs. The mobility values in both phases are considerably larger than the maximum values found previously for discotic triphenylene derivatives. However, the recently proposed trend toward increasing mobility with increasing core size is not substantiated by the results on the present series of increasingly large aromatic core compounds.

Hydrogen bonding can be used to significantly enforce the intra‐columnar stacking order in discotic mesogens. The ordered hexagonal columnar mesophase of a HAT‐CONHR derivative is characterized by the smallest inter‐disk distance ever found in columnar liquid crystals (3.18–3.20 Å). This additional attractive interaction between the disks in the column results in a regular disc stacking and thus in a high charge‐carrier mobility over the whole investigated temperature range (from room temperature up to 200 °C).

The second peak in the optical absorption spectrum of PbSe nanocrystals is arguably the most discussed optical transition in semiconductor nanocrystals. Ten years of scientific debate have produced many theoretical and experimental claims for the assignment of this feature as the 1P e1P h as well as the 1S h,e1P e,h transitions. We studied the nature of this absorption feature by pump-probe spectroscopy, exactly controlling the occupation of the states involved, and present conclusive evidence that the optical transition involves neither 1S e nor 1S h states. This suggests that it is the 1P h1P e transition that gives rise to the second peak in the absorption spectrum of PbSe nanocrystals.