Tuning the work function of nickel oxide using triethoxysilane functionalized monolayers.

The work function of nickel oxide (NiOx) electrodes was tuned by the covalent attachment of commercially available as well as specially synthesized triethoxysilane functionalized molecules with a range of dipole moments. The presence of the silane molecular layers on the NiOx surface was verified using Fourier Transform Infrared (FTIR) spectroscopy and contact angle measurements. While these tests indicated the surface coverage was incomplete, Kelvin probe measurements showed that the coverage was sufficient to change the work function of the NiOx across a range of ∼900 meV.

Molecular Design for Tuning Work Functions of Transparent Conducting Electrodes.

In this Perspective, we provide a brief background on the use of aromatic phosphonic acid modifiers for tuning work functions of transparent conducting oxides, for example, zinc oxide (ZnO) and indium tin oxide (ITO). We then introduce our preliminary results in this area using conjugated phosphonic acid molecules, having a substantially larger range of dipole moments than their unconjugated analogues, leading to the tuning of ZnO and ITO electrodes over a 2 eV range as derived from Kelvin probe measurements. We have found that these work function changes are directly correlated to the magnitude and the direction of the computationally derived molecular dipole of the conjugated phosphonic acids, leading to the predictive power of computation to drive the synthesis of new and improved phosphonic acid ligands.

Phosphonic Acid Modification of GaInP2 Photocathodes Toward Unbiased Photoelectrochemical Water Splitting.

The p-type semiconductor GaInP2 has a nearly ideal bandgap (∼1.83 eV) for hydrogen fuel generation by photoelectrochemical water splitting but is unable to drive this reaction because of misalignment of the semiconductor band edges with the water redox half reactions. Here, we show that attachment of an appropriate conjugated phosphonic acid to the GaInP2 electrode surface improves the band edge alignment, closer to the desired overlap with the water redox potentials.

Conjugated phosphonic acid modified zinc oxide electron transport layers for improved performance in organic solar cells.

Phosphonic acid modification of zinc oxide (ZnO) electron transport layers in inverted P3HT:ICBA solar cells was studied to determine the effect of conjugated linkages between the aromatic and phosphonic acid attachment groups. For example, zinc oxide treated with 2,6-difluorophenylvinylphosphonic acid, having a conjugated vinyl group connecting the aromatic moiety to the phosphonic acid group, showed a 0.78 eV decrease in the effective work function versus unmodified ZnO, whereas nonconjugated 2,6-difluorophenylethylphosphonic acid resulted in a 0.

Semi-random vs Well-Defined Alternating Donor-Acceptor Copolymers.

The influence of backbone composition on the physical properties of donor-acceptor (D-A) copolymers composed of varying amounts of benzodithiophene (BDT) donor with the thienoisoindoledione (TID) acceptor is investigated. First, the synthesis of bis- and tris-BDT monomers is reported; these monomers are subsequently used in Stille copolymerizations to create well-defined alternating polymer structures with repeating (D-A), (D-D-A), and (D-D-D-A) units. For comparison, five semi-random D-A copolymers with a D:A ratio of 1.

Efficient modification of metal oxide surfaces with phosphonic acids by spray coating.

We report a rapid method of depositing phosphonic acid molecular groups onto conductive metal oxide surfaces. Solutions of pentafluorobenzyl phosphonic acid (PFBPA) were deposited on indium tin oxide, indium zinc oxide, nickel oxide, and zinc oxide by spray coating substrates heated to temperatures between 25 and 150 °C using a 60 s exposure time. Comparisons of coverage and changes in work function were made to the more conventional dip-coating method utilizing a 1 h exposure time.

Improvement of interfacial contacts for new small-molecule bulk-heterojunction organic photovoltaics.

The influence of protonation reactions between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and a thiadiazolo[3,4-c]pyridine small-molecule donor are reported; these result in poor solar-cell performance due to a barrier for charge extraction. The use of a NiO(x) contact eliminates such deleterious chemical interactions and results in substantial improvements in open-circuit voltage, fill factor, and an increased power conversion efficiency from 2.3% to 5.

Photoinduced carrier generation and decay dynamics in intercalated and non-intercalated polymer:fullerene bulk heterojunctions.

The dependence of photoinduced carrier generation and decay on donor-acceptor nanomorphology is reported as a function of composition for blends of the polymer poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT-C(14)) with two electron-accepting fullerenes: phenyl-C(71)-butyric acid methyl ester (PC(71)BM) or the bisadduct of phenyl-C(61)-butyric acid methyl ester (bis-PC(61)BM). The formation of partially or fully intercalated bimolecular crystals at weight ratios up to 1:1 for pBTTT-C(14):PC(71)BM blends leads to efficient exciton quenching due to a combination of static and dynamic mechanisms. At higher fullerene loadings, pure PC(71)BM domains are formed that result in an enhanced free carrier lifetime, as a consequence of spatial separation of the electron and hole into different phases, and the dominant contribution to the photoconductance comes from the high-frequency electron mobility in the fullerene clusters.

Photovoltaic devices with a low band gap polymer and CdSe nanostructures exceeding 3% efficiency.

We report the fabrication and measurement of solar cells approaching a power conversion efficiency of 3.2% using a low band gap conjugated polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] and CdSe nanoparticles. These devices exhibit an external quantum efficiency (EQE) of >30% in a broad range of 350-800 nm with a maximum EQE of 55% in a range of 630-720 nm.

Direct synthesis of CdSe nanoparticles in poly(3-hexylthiophene).

A new approach was developed for the synthesis of nearly monodisperse CdSe nanoparticles directly in a polymer-containing solution in the absence of any other surface capping molecules. The comparatively high synthesis temperature reaction produces good quality crystalline CdSe nanoparticles. Time-resolved microwave conductivity measurements show that photoinduced charge separation occurs at the interface between the CdSe quantum dots and the polymer.