Plasmonic enhancement of aqueous processed organic photovoltaics.

Sodium tungsten bronze (Na x WO3) is a promising alternative plasmonic material to nanoparticulate gold due to its strong plasmonic resonances in both the visible and near-infrared (NIR) regions. Additional benefits include its simple production either as a bulk or a nanoparticle material at a relatively low cost. In this work, plasmonic Na x WO3 nanoparticles were introduced and mixed into the nanoparticulate zinc oxide electron transport layer of a water processed poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PC61BM) nanoparticle (NP) based organic photovoltaic device (NP-OPV). The power conversion efficiency of NP-OPV devices with Na x WO3 NPs added was found to improve by around 35% compared to the control devices, attributed to improved light absorption, resulting in an enhanced short circuit current and fill factor.

Standardizing resolution definition in scanning helium microscopy.

Resolution is a key parameter for microscopy, but methods for standardizing its definition are often poorly defined. For a developing technique such as scanning helium microscopy, it is critical that a consensus-based protocol for determining instrument resolution is prepared as a written standard to allow both comparable quantitative measurements of surface topography and direct comparisons between different instruments. In this paper we assess a range of quantitative methods for determining instrument resolution and determine their relative merits when applied to the specific case of the scanning helium microscope (SHeM). Consequently, we present a preliminary protocol for measuring the resolution in scanning helium microscopy based upon utilizing appropriate test samples with sets of slits of well-defined dimensions to establish the quantitative resolution of any similar instrument.

Evolution of the nanomorphology of photovoltaic polyfluorene blends: sub-100 nm resolution with x-ray spectromicroscopy.

We investigate the influence of annealing on the morphology of intimately mixed blends of the conjugated polymers poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) with scanning transmission x-ray microscopy (STXM). Through the use of a zone plate with theoretical Rayleigh resolution of 30 nm, we are able to resolve sub-100 nm bulk structure in these films. Surprisingly, for unannealed films spin-coated from chloroform we observe features with an average diameter of 85 nm. The high degree of photoluminescence quenching in these as-spun films (>95%) implies that there is significant intermixing within the 85 nm structures, indicating that a hierarchy of phase separation exists even on the length scale of less than 100 nm. With annealing up to 160 °C, close to the T(g) of the components, there is little change in the feature sizes observed by STXM, although an increase in variation of the composition is observed. With annealing above 160 °C the imaged features begin to evolve in size, increasing to 225 nm in extent, alongside large changes in composition with annealing to 200 °C. Comparing the evolution of morphology imaged by STXM with the change in photoluminescence quenching with annealing, we propose that phase separation first evolves via the evolution of relatively pure phases on the length scale of a few to tens of nanometres within the larger 85 nm structures. Once the length scale of compositional fluctuations exceeds 85 nm (for anneal temperatures above 160 °C) the hierarchy of phase separation is lost and the subsequent morphological evolution is readily imaged by STXM. Applying the results of an exciton diffusion and quenching model, we find good agreement between the size of the domains measured by STXM (above 180 °C) and the results of the model for an exciton diffusion length of 15 nm. The growth in domain size and towards purer structures has also been observed with resonant soft x-ray scattering.

Investigation of the photochemistry of the poly{p-phenylenevinylene} precursor system: implications for nanolithography.

The photochemistry of poly{p-phenylene[1-(tetrahydrothiophen-1-io)ethylene chloride]} (PPTEC), a water soluble precursor of the semiconducting polymer, poly{p-phenylenevinylene} (PPV), has been studied both under atmospheric conditions and in environments devoid of oxygen. UV-visible spectroscopy and photoluminescence data has been used to provide a picture of the mechanistic pathways involved in UV irradiation of the PPTEC material. A new quantitative model for the effect of UV irradiation upon film morphology is presented, which leads to insights for the improved control of the characteristics of PPV nanostructures produced via near-field scanning optical lithography.

Oxonium ions from aqua regia: isolation by hydrogen bonding to crown ethers.

The preparation and structures of a variety of oxonium ion tetrachloroaurate(III) salts isolated from aqua regia are reported. The new compounds are [(H(5)O(2))(2)(12-crown-4)(2)][AuCl(4)](2) (1), [(H(7)O(3))(15-crown-5)][AuCl(4)] (2), [(H(5)O(2))(benzo-15-crown-5)(2)][AuCl(4)] (3), [(H(3)O)(18-crown-6)][AuCl(4)] (4), [(H(5)O(2))(dibenzo-24-crown-8)][AuCl(4)] (5), [(H(5)O(2))(4-nitrobenzo-15-crown-5)(2)][AuCl(4)] (6), [(H(3)O)(4-nitrobenzo-18-crown-6)][AuCl(4)] (7), [(H(11)O(5))(tetrachlorodibenzo-18-crown-6)(2)][AuCl(4)] (8), and [(H(7)O(3))(dinitrodibenzo-30-crown-10)][AuCl(4)] (9). A significant correlation between the degree of proton hydration and crown ether size is observed. Aryl crown ethers are nitrated in concentrated aqua regia, but nonnitrated products may be obtained in a dilute solution of aqua regia by reaction with aqueous HAuCl(4).