Dirhodium C-H Functionalization of Hole-Transport Materials.

Hole-transport materials (HTMs) based on triarylamine derivatives play important roles in organic electronics applications including organic light-emitting diodes and perovskite solar cells. For some applications, triarylamine derivatives bearing appropriate binding groups have been used to functionalize surfaces, while others have been incorporated as side chains into polymers to manipulate the processibility of HTMs for device applications. However, only a few approaches have been used to incorporate a single surface-binding group or polymerizable group into triarylamine materials. Here, we report that Rh-carbenoid chemistry can be used to insert carboxylic esters and norbornene functional groups into sp2 C-H bonds of a simple triarylamine and a 4,4'-bis(diarylamino)biphenyl, respectively. The norbenene-functionalized monomer was polymerized by ring-opening metathesis; the electrochemical, optical, and charge-transport properties of these materials were similar to those of related materials synthesized by conventional means. This method potentially offers straightforward access to a diverse range of HTMs with different functional groups.

Delayed Luminescence in 2-Methyl-5-(penta(9-carbazolyl)phenyl)-1,3,4-oxadiazole Derivatives.

2,5-Diphenyl-1,3,4-oxadiazole has been widely used as an acceptor portion of donor-acceptor fluorophores that exhibit thermally activated delayed fluorescence (TADF), but analogous 2-alkyl-5-phenyl-1,3,4-oxadiazoles have been much less widely investigated. Here the properties of carbazole-substituted 2-methyl-5-phenyl-1,3,4-oxadiazoles are compared to those of their 2,5-diphenyl analogues. The fluorescence of each of the former compounds is blue-shifted by ca. 50-100 meV relative to that in the latter, while similar estimated values of the singlet-triplet energy separation (ΔEST) are maintained. In particular, 2-methyl-5-(penta(9-carbazolyl)phenyl)-1,3,4-oxadiazole and 2-methyl-5-(penta(3,6-di-tert-butyl-9-carbazolyl)phenyl)-1,3,4-oxadiazole exhibit solution fluorescence maxima of 466 and 485 nm and estimated ΔEST values of 0.12 and 0.03 eV, respectively. In both cases the reverse intersystem crossing (RISC) rates inferred from their solution fluorescence behavior are over twice those of the corresponding 2-phenyl derivatives. Organic light-emitting diodes (OLEDs) in which the 2-methyl derivatives are used as emitters yield external quantum efficiency (EQE) values of up to 23%. OLEDs with 2-methyl-5-(penta(9-carbazolyl)phenyl)-1,3,4-oxadiazole and 2-methyl-5-(penta(3,6-di-tert-butyl-9-carbazolyl)phenyl)-1,3,4-oxadiazole emitters show reduced efficiency rolloff at high current densities relative to their 2-phenyl counterparts, the latter exhibiting an EQE of 16% at 1000 cd m-2.

Solution-based electrical doping of semiconducting polymer films over a limited depth.

Solution-based electrical doping protocols may allow more versatility in the design of organic electronic devices; yet, controlling the diffusion of dopants in organic semiconductors and their stability has proven challenging. Here we present a solution-based approach for electrical p-doping of films of donor conjugated organic semiconductors and their blends with acceptors over a limited depth with a decay constant of 10-20 nm by post-process immersion into a polyoxometalate solution (phosphomolybdic acid, PMA) in nitromethane. PMA-doped films show increased electrical conductivity and work function, reduced solubility in the processing solvent, and improved photo-oxidative stability in air. This approach is applicable to a variety of organic semiconductors used in photovoltaics and field-effect transistors. PMA doping over a limited depth of bulk heterojunction polymeric films, in which amine-containing polymers were mixed in the solution used for film formation, enables single-layer organic photovoltaic devices, processed at room temperature, with power conversion efficiencies up to 5.9 ± 0.2% and stable performance on shelf-lifetime studies at 60 °C for at least 280 h.

Efficient Colorful Perovskite Solar Cells Using a Top Polymer Electrode Simultaneously as Spectrally Selective Antireflection Coating.

Organometal halide perovskites have shown excellent optoelectronic properties and have been used to demonstrate a variety of semiconductor devices. Colorful solar cells are desirable for photovoltaic integration in buildings and other aesthetically appealing applications. However, the realization of colorful perovskite solar cells is challenging because of their broad and large absorption coefficient that commonly leads to cells with dark-brown colors. Herein, for the first time, we report a simple and efficient strategy to achieve colorful perovskite solar cells by using the transparent conducting polymer (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS) as a top electrode and simultaneously as an spectrally selective antireflection coating. Vivid colors across the visible spectrum are attained by engineering optical interference effects among the transparent PEDOT:PSS polymer electrode, the hole-transporting layer and the perovskite layer. The colored perovskite solar cells display power conversion efficiency values from 12.8 to 15.1% (from red to blue) when illuminated from the FTO glass side and from 11.6 to 13.8% (from red to blue) when illuminated from the PEDOT:PSS side. The new approach provides an advanced solution for fabricating colorful perovskite solar cells with easy processing and high efficiency.

Self-(Un)rolling Biopolymer Microstructures: Rings, Tubules, and Helical Tubules from the Same Material.

We have demonstrated the facile formation of reversible and fast self-rolling biopolymer microstructures from sandwiched active-passive, silk-on-silk materials. Both experimental and modeling results confirmed that the shape of individual sheets effectively controls biaxial stresses within these sheets, which can self-roll into distinct 3D structures including microscopic rings, tubules, and helical tubules. This is a unique example of tailoring self-rolled 3D geometries through shape design without changing the inner morphology of active bimorph biomaterials. In contrast to traditional organic-soluble synthetic materials, we utilized a biocompatible and biodegradable biopolymer that underwent a facile aqueous layer-by-layer (LbL) assembly process for the fabrication of 2D films. The resulting films can undergo reversible pH-triggered rolling/unrolling, with a variety of 3D structures forming from biopolymer structures that have identical morphology and composition.

Tetracyano isoindigo small molecules and their use in n-channel organic field-effect transistors.

N,N'-Dihexyl-6,6'-dicyanoisoindigo, N,N'-didecyl-5,5',6,6'-tetracyanoisoindigo, N,N'-dihexyl-5,5',6,6'-tetracyanoisoindigo, and N,N'-dihexyl-5,5',6,6'-tetracyanothienoisoindigo have been synthesised in moderate yields by the reaction of corresponding di and tetrabromo species with CuCN, with microwave heating leading to higher yields and fewer side products for the tetrasubstituted species. Di- and tetracyano substitution anodically shifts the molecular reduction potential relative to the unsubstituted cores by ca. 0.4 and 0.8 V, respectively, with the resultant values for the tetracyano derivatives (-0.58 to -0.67 V vs. FeCp2(+/0)) suggesting the possibility of air-stable electron transport. All the synthesised cyano derivatives operate in n-channel OFETs, while the tetrabromothienoisoindigo derivative functions in a p-channel transistor. The tetracyanothienoisoindigo derivative exhibits the highest field-effect electron mobility values - up to 0.04 and 0.09 cm(2) V(-1) s(-1) in spin-coated and inkjet-printed devices respectively - and OFETs incorporating this compound have been shown to operate in air without significant degradation of their mobility values in the saturation regime.

The modification of indium tin oxide with phosphonic acids: mechanism of binding, tuning of surface properties, and potential for use in organic electronic applications.

Transparent metal oxides, in particular, indium tin oxide (ITO), are critical transparent contact materials for applications in next-generation organic electronics, including organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs). Understanding and controlling the surface properties of ITO allows for the molecular engineering of the ITO-organic interface, resulting in fine control of the interfacial chemistries and electronics. In particular, both surface energy matching and work function compatibility at material interfaces can result in marked improvement in OLED and OPV performance. Although there are numerous ways to change the surface properties of ITO, one of the more successful surface modifications is the use of monolayers based on organic molecules with widely variable end functional groups. Phosphonic acids (PAs) are known to bind strongly to metal oxides and form robust monolayers on many different metal oxide materials. They also demonstrate several advantages over other functionalizing moieties such as silanes or carboxylic acids. Most notably, PAs can be stored in ambient conditions without degradation, and the surface modification procedures are typically robust and easy to employ. This Account focuses on our research studying PA binding to ITO, the tunable properties of the resulting surfaces, and subsequent effects on the performance of organic electronic devices. We have used surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and infrared reflection adsorption spectroscopy (IRRAS) to determine that PAs bind to ITO in a predominantly bidentate fashion (where two of three oxygen atoms from the PA are involved in surface binding). Modification of the functional R-groups on PAs allows us to control and tune the surface energy and work function of the ITO surface. In one study using fluorinated benzyl PAs, we can keep the surface energy of ITO relatively low and constant but tune the surface work function. PA modification of ITO has resulted in materials that are more stable and more compatible with subsequently deposited organic materials, an effective work function that can be tuned by over 1 eV, and energy barriers to hole injection (OLED) or hole-harvesting (OPV) that can be well matched to the frontier orbital energies of the organic active layers, leading to better overall device properties.

Ultrafast nonlinear mirrors with broad spectral and angular bandwidths in the visible spectral range.

A novel nonlinear mirror structure is presented. A 23 nm-thick Au thin film separated from a 100 nm-thick Ag film by a dielectric spacer is used to drive the nonlinear optical response of the mirror. The linear and nonlinear optical properties of the mirror can be tuned by optimizing its layer thickness distribution. A figure-of-merit for the change in reflectance is derived for the nonlinear mirror and the nonlinear refractive index change of the Au layer is shown to be significantly enhanced in the mirror structure. The ultrafast reflectance change of the nonlinear mirror, studied using femtosecond white-light continuum pump-probe experiments, shows an extremely large magnitude and is both spectrally and angularly broad in the visible range.

Linear and nonlinear optical properties of Ag/Au bilayer thin films.

The linear and nonlinear optical properties of Ag/Au bilayer metallic thin films with a total thickness of around 20 nm and with different Ag/Au mass-thickness ratios were studied. This study shows that the spectral dispersion of the effective refractive index of bilayer films can be tuned by controlling the mass-thickness ratio between Au and Ag. Improvement of the figure-of-merit for potential plasmonic applications and linear optical filters in the visible spectral range are reported and discussed. The nonlinear optical properties of bilayer metal films studied using femtosecond white-light continuum pump-probe experiments are also shown to be tunable with this ratio. The nonlinear change of optical path length is extracted from the pump-probe data and agrees with simulated values derived from a combination of the two-temperature model, describing the ultrafast electron heating dynamics, and a physical model that describes the dielectric permittivity of Au as a function of electron and lattice temperature.

Easily reducible materials from the reactions of diselenopheno[3,2-b:2',3'-d]pyrrole and dithieno[3,2-b:2',3'-d]pyrrole with tetracyanoethylene.

A new core, 4H-diselenopheno[3,2-b:2',3'-d]pyrrole (DSP), was reacted with tetracyanoethylene, and three products, mono-tricyanovinyl, bis-tricyanovinyl, and quinoidal, were isolated and compared with the respective 4H-dithieno[3,2-b:2',3'-d]pyrrole (DTP) derivatives using cyclic voltammetry, UV-vis absorption, and differential scanning calorimetry analyses. Organic field-effect transistors were fabricated using solution-processed films, and only one derivative, bis-tricyanovinyl-DSP, exhibited transistor behavior with µ(e) reaching 8.7 × 10(-4) cm(2)/V·s. This enhancement of the electron-transporting properties in comparison with DTP derivative is attributed to stronger LUMO-LUMO interaction due to a larger size of selenium atom, which in the case of the bis-tricyanovinyl derivative, has wave function density on the chalcogen.

Direct correlation between work function of indium-tin-oxide electrodes and solar cell performance influenced by ultraviolet irradiation and air exposure.

We report on reversible changes of the work function (WF) values of indium-tin-oxide (ITO) under prolonged ultraviolet (UV) and air exposure. The WF of ITO is reduced from 4.7 eV to 4.2 eV by photon absorption in ITO under UV illumination or an air mass 1.5 solar simulator (100 mW cm(-2)). Air or oxygen exposure is found to increase the WF of ITO (UV-exposed) to a value of 4.6 eV. These changes of ITO's WF lead to reversible variations of the performance of organic photovoltaic devices where ITO acts primarily as the electron collecting or hole collecting electrode. These variations can be reflected in the disappearance (or appearance) of an S-shaped kink in the J-V characteristics upon continuous UV or solar simulator illumination (or air exposure). This reversible phenomenon is ascribed to the adsorption and desorption of oxygen on the surface and grain boundaries of ITO. The use of surface modifiers to either decrease or increase the WF of ITO in organic photovoltaic devices with inverted and conventional geometries is also shown to be an effective route to stabilize the device performance under UV illumination.

Thermal Insolubilization of Electrically n-Doped Films Achieved Using 7-Alkoxy-Benzocyclobutene-Substituted Fullerene and Dopant Molecules.

Insoluble electrically n-doped fullerene-containing films have been obtained by thermal annealing of a fullerene compound and a 1,3-dimethyl-2,3-dihydro-1H-benzo[d]imidazole n-dopant moiety, both of which are functionalized with a 7-butoxybenzocyclobutene group. The covalent tethering and electrical doping reactions are studied by mass spectrometry as well as electron paramagnetic resonance. Optical absorption spectra on BBCB-N-DMBI-H-doped BBCBP indicate films heated at 150 °C for 10 min are unaffected by immersion for 10 min in ortho-dichlorobenzene. Although films containing a 10 mol % loading of the dopant showed electrical conductivity values of 1.1 × 10-5 ± 3.4 × 10-7 S cm-1 prior to heating, the thermal insolubilization process led to values around two orders-of-magnitude lower. However, the thermal insolubilization also leads to immobilization of the dopant molecule and the corresponding cation, reducing their ability to diffuse into an adjacent layer of a stronger electron acceptor.

ITO-free large-area organic light-emitting diodes with an integrated metal grid.

We report on ITO-free large-area organic light-emitting diodes (OLEDs) fabricated on glass substrates comprising α-NPD as a hole transport layer (HTL) and coevaporated CBP:Ir(ppy)(3) as the emission layer. Indium-tin-oxide (ITO) was replaced with a conductive polymer electrode and an electroplated thick metal grid was used to improve the homogeneity of the potential distribution over the transparent polymer electrode. An electrical model of a metal grid integrated OLED shows the benefits of the use of metal grids in terms of improving the uniformity of the light emitted as the area of the OLED increases as well as the conductivity of the transparent electrode decreases. By integrating metal grids with polymer electrodes, the luminance increases more than 24% at 6 V and 45% at 7 V compared to the polymer electrode devices without a metal grid. This implies that a lower voltage can be applied to achieve the same luminance, hence lowering the power consumption. Furthermore, metal grid integrated OLEDs exhibited less variation in light emission compared to devices without a metal grid.

Skin-like low-noise elastomeric organic photodiodes.

Stretchable optoelectronics made of elastomeric semiconductors could enable the integration of intelligent systems with soft materials, such as those of the biological world. Organic semiconductors and photodiodes have been engineered to be elastomeric; however, for photodetector applications, it remains a challenge to identify an elastomeric bulk heterojunction (e-BHJ) photoactive layer that combines a low Young's modulus and a high strain at break that yields organic photodiodes with low electronic noise values and high photodetector performance. Here, a blend of an elastomer, a donor-like polymer, and an acceptor-like molecule yields a skin-like e-BHJ with a Young's modulus of a few megapascals, comparable to values of human tissues, and a high strain at break of 189%. Elastomeric organic photodiodes based on e-BHJ photoactive layers maintain low electronic noise current values in the tens of femtoamperes range and noise equivalent power values in the tens of picowatts range under at least 60% strain.

Increasing Volume in Conjugated Polymers to Facilitate Electrical Doping with Phosphomolybdic Acid.

Molecular p-type electrical dopants have been proven useful to fine-tune the optoelectronic properties of bulk organic semiconductors and their interfaces. Here, the volume in polymer films and its role in solution-based electrical p-type doping using phosphomolybdic acid (PMA) are studied. The polymer film volume was controlled using two approaches. One is based on heating both the PMA solution and the film prior to immersion. The second is based on coating the polymer film with a liquid blend that contains the PMA solution and a swelling solvent. 31P NMR and FTIR experiments indicate that the Keggin structure appears to be preserved throughout the doping process. Results show that increasing the polymer volume facilitates the infiltration of the PMA Keggin structure, which results in an increased electrical p-type doping level.

Critical interfaces in organic solar cells and their influence on the open-circuit voltage.

Organic photovoltaics, which convert sunlight into electricity with thin films of organic semiconductors, have been the subject of active research over the past 20 years. The global energy challenge has greatly increased interest in this technology in recent years. Low-temperature processing of organic small molecules from the vapor phase or of polymers from solution can confer organic semiconductors with a critical advantage over inorganic photovoltaic materials since the high-temperature processing requirements of the latter limit the range of substrates on which they can be deposited. Unfortunately, despite significant advances, the power conversion efficiency of organic solar cells remains low, with maximum values in the range of 6%. A better understanding of the physical processes that determine the efficiency of organic photovoltaic cells is crucial to enhancing their competitiveness with other thin-film technologies. Maximum values for the photocurrent can be estimated from the light-harvesting capability of the individual molecules or polymers in the device. However, a better understanding of the materials-level processes, particularly those in layer-to-layer interfaces, that determine the open-circuit voltage (V(OC)) in organic solar cells is critical and remains the subject of active research. The conventional wisdom is to use organic semiconductors with smaller band gaps to harvest a larger portion of the solar spectrum. This method is not always an effective prescription for increasing efficiency: it ignores the fact that the value of V(OC) is generally decreased in devices employing materials with smaller band gaps, as is the case with inorganic semiconductors. In this Account, we discuss the influence of the different interfaces formed in organic multilayer photovoltaic devices on the value of V(OC); we use pentacene-C(60) solar cells as a model. In particular, we use top and bottom electrodes with different work function values, finding that V(OC) is nearly invariant. In contrast, studies on devices incorporating hole-transport layers with different ionization potentials confirm that the value of V(OC) depends largely on the relative energy levels of the donor and acceptor species that form the essential heterojunction. An analysis of the properties of solar cells using equivalent-circuit methods reveals that V(OC) is proportional to the logarithm of the ratio of the photocurrent density J(ph) divided by the reverse saturation current density J(0). Hence, an understanding of the physical origin of J(0) directly yields information on what limits V(OC). We assign the physical origin of J(0) to the thermal excitation of carriers from the donor to the acceptor materials that form the organic heterojunction. Finally, we show that the solution to achieving higher power conversion efficiency in organic solar cells will be to control simultaneously the energetics and the electronic coupling between the donor and acceptor materials, in both the ground and excited state.

Optics in Energy: the power of optical solutions.

Editorial for the inaugural issue of Energy Express.

ITO-free large-area organic solar cells.

We report on large-area pentacene / C60 organic solar cells in which indium-tin-oxide (ITO) is replaced with a conductive polymer electrode and a 5 µm-thick metal grid is used to reduce resistive power losses. The performance of cells with the polymer electrode was compared with that of pentacene / C60 devices using ITO as the transparent electrode. For large-area devices (7.3 cm²) on glass substrates with an integrated metal grid, the performance of a device with the polymer electrode is comparable to that of a device with an ITO electrode combined with a grid.

Nonlinear optical properties of induced transmission filters.

The nonlinear optical (NLO) properties of induced transmission filters (ITFs) based on Ag are experimentally determined using white light continuum pump-probe measurements. The experimental results are supported using simulations based on the matrix transfer method. The magnitude of the NLO response is shown to be 30 times that of an isolated Ag film of comparable thickness. The impacts of design variations on the linear and NLO response are simulated. It is shown that the design can be modified to enhance the NLO response of an ITF by a factor of 2 or more over a perfectly matched ITF structure.