Role of Crystallization in the Morphology of Polymer:Non-fullerene Acceptor Bulk Heterojunctions.

Many high efficiency organic photovoltaics use fullerene-based acceptors despite their high production cost, weak optical absorption in the visible range, and limited synthetic variability of electronic and optical properties. To circumvent this deficiency, non-fullerene small-molecule acceptors have been developed that have good synthetic flexibility, allowing for precise tuning of optoelectronic properties, leading to enhanced absorption of the solar spectrum and increased open-circuit voltages (VOC). We examined the detailed morphology of bulk heterojunctions of poly(3-hexylthiophene) and the small-molecule acceptor HPI-BT to reveal structural changes that lead to improvements in the fill factor of solar cells upon thermal annealing. The kinetics of the phase transformation process of HPI-BT during thermal annealing were investigated through in situ grazing incidence wide-angle X-ray scattering studies, atomic force microscopy, and transmission electron microscopy. The HPI-BT acceptor crystallizes during film formation to form micron-sized domains embedded within the film center and a donor rich capping layer at the cathode interface reducing efficient charge extraction. Thermal annealing changes the surface composition and improves charge extraction. This study reveals the need for complementary methods to investigate the morphology of BHJs.

Boron-rich benzene and pyrene derivatives for the detection of thermal neutrons.

A synthetic methodology is developed to generate boron rich aromatic small molecules based on benzene and pyrene moieties for the detection of thermal neutrons. The prepared aromatic compounds have a relatively high boron content up to 7.4 wt%, which is important for application in neutron detection as (10)B (20% of natural abundance boron) has a large neutron induced reaction cross-section. This is demonstrated by preparing blends of the synthesized molecules with fluorescent dopants in poly(vinyltoluene) matrices resulting in comparable scintillation light output and neutron capture as state-of-the art commercial scintillators, but with the advantage of much lower cost. The boron-rich benzene and pyrene derivatives are prepared by Suzuki conditions using both microwave and traditional heating, affording yields of 40-93%. This new procedure is simple and straightforward, and has the potential to be scaled up.

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. We demonstrate that this surface modification approach is able to adjust the energetic position of the band edges by as much as 0.8 eV, showing that it may be possible to engineer the energetics at the semiconductor/electrolyte interface to allow for unbiased water splitting with a single photoelectrode having a bandgap of less than 2 eV.

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 0.57 eV decrease, as measured by Kelvin probe. This resulted in an average power conversion efficiency of 5.89% for conjugated 2,6-difluorophenyvinylphosphonic acid modified solar cells, an improvement over unmodified (5.24%) and nonconjugated phosphonic acid modified devices (5.64%), indicating the importance of the conjugated linkage.

Tuning interlayer coupling in large-area heterostructures with CVD-grown MoS2 and WS2 monolayers.

Band offsets between different monolayer transition metal dichalcogenides are expected to efficiently separate charge carriers or rectify charge flow, offering a mechanism for designing atomically thin devices and probing exotic two-dimensional physics. However, developing such large-area heterostructures has been hampered by challenges in synthesis of monolayers and effectively coupling neighboring layers. Here, we demonstrate large-area (>tens of micrometers) heterostructures of CVD-grown WS2 and MoS2 monolayers, where the interlayer interaction is externally tuned from noncoupling to strong coupling. Following this trend, the luminescence spectrum of the heterostructures evolves from an additive line profile where each layer contributes independently to a new profile that is dictated by charge transfer and band normalization between the WS2 and MoS2 layers. These results and findings open up venues to creating new material systems with rich functionalities and novel physical effects.

25th anniversary article: high-mobility hole and electron transport conjugated polymers: how structure defines function.

The structural organization of three different families of semicrystalline π-conjugated polymers is reported (poly(3-hexylthiophene) (P3HT), poly[2,6-(4,4-bis-alkyl-4H-cyclopenta-[2,1-b;3,4-b0]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)](cyclopentadithiophene-benzothiadiazole) (CDT-BTZ) and poly(N,N"-bis-2-octyldodecylnaphtalene-1,4,5,8-bis-dicarboximide-2,6-diyl-alt-5,5-2,2-bithiophene (P(NDI2OD-T2))). These have triggered significant interest for their remarkable charge-transport properties. By performing molecular mechanics/dynamics simulations with carefully re-parameterized force fields, it is illustrated in particular how the supramolecular organization of these conjugated polymers is driven by an interplay between the length and nature of the conjugated monomer unit and the packing of their alkyl side chains, and to what extent it impacts the charge-carrier mobility, as monitored by quantum-chemical calculations of the intermolecular hopping transfer integrals. This Progress Report is concluded by providing generic guidelines for the design of materials with enhanced degrees of supramolecular organization.

Aesthetically pleasing conjugated polymer:fullerene blends for blue-green solar cells via roll-to-roll processing.

The practical application of organic photovoltaic (OPV) cells requires high throughput printing techniques in order to attain cells with an area large enough to provide useful amounts of power. However, in the laboratory screening of new materials for OPVs, spin-coating is used almost exclusively as a thin-film deposition technique due its convenience. We report on the significant differences between the spin-coating of laboratory solar cells and slot-die coating of a blue-green colored, low bandgap polymer (PGREEN). This is one of the first demonstrations of slot-die-coated polymer solar cells OPVs not utilizing poly(3-hexylthiophene):(6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM) blends as a light absorbing layer. Through synthetic optimization, we show that strict protocols are necessary to yield polymers which achieve consistent photovoltaic behavior. We fabricated spin-coated laboratory scale OPV devices with PGREEN: PCBM blends as active light absorbing layers, and compare performance to slot die-coated individual solar cells, and slot-die-coated solar modules consisting of many cells connected in series. We find that the optimum ratio of polymer to PCBM varies significantly when changing from spin-coating of thinner active layer films to slot-die coating, which requires somewhat thicker films. We also demonstrate the detrimental impacts on power conversion efficiency of high series resistance imparted by large electrodes, illustrating the need for higher conductivity contacts, transparent electrodes, and high mobility active layer materials for large-area solar cell modules.

White emitting polyfluorene functionalized with azide hybridized on near-UV light emitting diode for high color rendering index.

We develop and demonstrate high-quality white light generation that relies on the use of a single-type simple conjugated polymer of polyfluorene functionalized with azide groups (PFA) integrated on a near-UV LED platform. The high-quality white emission from the polyfluorene is achieved by using the azide functionalization to facilitate cross-linking intentionally when cast into solid-state form. Hybridized on n-UV InGaN/GaN LED at 378 nm, the PFA emitters collectively generate a very broad down-converting photoluminescence at longer wavelengths across the entirety of the visible spectrum, yielding high color rendering indices up to 91.