Sequence effects in donor-acceptor oligomeric semiconductors comprising benzothiadiazole and phenylenevinylene monomers

To understand the influence of monomer sequence on the properties and performance of conjugated oligomers, a series of dimers, trimers, and tetramers were prepared from phenylene (P) and benzothiadiazole (B) monomers linked by vinylene groups. Optical and electrochemical studies established the influence of sequence on both the λmax and redox potentials of this series of structurally related oligomers. For tetramers with bromo end groups (PBBP, BPPB, PBPB, PPBB), the λmax ranged from 493 to 512 nm (Δ = 19 nm), the electrochemical oxidation potential from 0.65 to 0.82 (Δ = 0.17 V) and the reduction potential from-1.45 to-1.31 (Δ = 0.14 V), all of which are sequence-dependent. The effect of end groups (cyano, bromo, and alkyl) was also demonstrated to be important for the properties of these oligomers. DFT calculations of the tetramers were performed and the energy levels were correlated well with the experimentally determined spectroscopic data. Bulk heterojunction (BHJ) solar cells fabricated with selected tetramers as the donor and PC61BM as the acceptor exhibited power conversion efficiencies that varied by a factor of 3 as a function of sequence (0.47-1.85%). These results suggest that sequence control is important for tuning optoelectronic properties and photovoltaic performance of these structurally related conjugated oligomers

Ratio Estimation in SIMS Analysis

The determination of an isotope ratio by secondary ion mass spectrometry (SIMS) traditionally involves averaging a number of ratios collected over the course of a measurement. We show that this method leads to an additive positive bias in the expectation value of the estimated ratio that is approximately equal to the true ratio divided by the counts of the denominator isotope of an individual ratio. This bias does not decrease as the number of ratios used in the average increases. By summing all counts in the numerator isotope, then dividing by the sum of counts in the denominator isotope, the estimated ratio is less biased: the bias is approximately equal to the ratio divided by the summed counts of the denominator isotope over the entire measurement. We propose a third ratio estimator (Beale's estimator) that can be used when the bias from the summed counts is unacceptably large for the hypothesis being tested. We derive expressions for the variance of these ratio estimators as well as the conditions under which they are normally distributed. Finally, we investigate a SIMS dataset showing the effects of ratio bias, and discuss proper ratio estimation for SIMS analysis

Anode interfacial engineering approaches to enhancing anode/hole transport layer interfacial stability and charge injection efficiency in organic light-emitting diodes

The integrity of anode/organic interfacial contact is shown to be crucial to the performance and stability of archetypical small molecule organic light-emitting diodes (OLEDs). In this contribution, vapor-deposited lipophilic, hole-transporting 1,4-bis(phenyl-m-tolylamino)biphenyl (TPD) and 1,4-bis(1-naphthylphenylamino)biphenyl (NPB) thin films are shown to undergo decohesion on ITO anode surfaces under mild heating. An effective approach to ameliorate such interfacial decohesion is introduction, via self-assembly or spin-coating, of covalently bound N(p-C6H4CH2CH2CH2 SiCl3)3 (TAA)- and 4,4′-bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl (TPD-Si2)-derived adhesion/injection layers at the anode/hole transport layer interface. The resulting angstrom-scale hole transport layers prevent decohesion of vapor-deposited hole transport layers and significantly enhance OLED hole injection fluence. OLEDs fabricated with these modified interfaces exhibit appreciably reduced turn-on voltages, considerably higher luminous intensities, and enhanced thermal robustness versus bare ITO-based control devices. Spin-coated, cross-linked TPD-Si2 films, in particular, prove to be superior to conventional ITO functionalization interlayers, including copper phthalocyanine, in this regard. The present ITO-functionalized devices achieve maximum external forward quantum efficiencies as high as 1.2% and a luminous level of 15 000 cd/m2 in simple ITO/interlayer/HTL/Alq/Al heterostructures. We also show that Cu(Pc) interlayers actually suppress, rather than enhance, hole injection and template crystallization of vapor-deposited TPD and NPB at modest temperatures, resulting in poor OLED thermal stability