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For organic photovoltaic (OPV) cells based on the bulk heterojunction (BHJ) structure, it remains challenging to rationally control the degree of phase separation and percolation within blends of donors and acceptors to secure optimal charge separation and transport. Reported is a bottom-up, supramolecular approach to BHJ OPVs wherein tailored hydrogen bonding (H-bonding) interactions between π-conjugated electron donor molecules encourage formation of vertically aligned donor π-stacks while simultaneously suppressing lateral aggregation; the programmed arrangement facilitates fine mixing with fullerene acceptors and efficient charge transport. The approach is illustrated using conventional linear or branched quaterthiophene donor chromophores outfitted with terminal functional groups that are either capable or incapable of self-complementary H-bonding. When applied to OPVs, the H-bond capable donors yield a twofold enhancement in power conversion efficiency relative to the comparator systems, with a maximum external quantum efficiency of 64%. H-bond promoted assembly results in redshifted absorption (in neat films and donor:C 60 blends) and enhanced charge collection efficiency despite disparate donor chromophore structure. Both features positively impact photocurrent and fill factor in OPV devices. Film structural characterization by atomic force microscopy, transmission electron microscopy, and grazing incidence wide angle X-ray scattering reveals a synergistic interplay of lateral H-bonding interactions and verticalmore » π-stacking for directing the favorable morphology of the BHJ.« less

We previously reported that a branched quaterthiophene donor chromophore functionalized with a phthalhydrazide hydrogen bonding (H-bonding) unit (MeBQPH) gives twofold more efficient bulk heterojunction organic solar cells (with C60 acceptors) compared to a nearly identical donor incapable of H-bonding (MeBQPME). Here, scanning tunneling microscopy (STM) studies confirm the formation of MeBQPH trimer rosettes on Au(1 1 1) through phthalhydrazide H-bonding interactions that are sufficiently strong to compete with adsorbate/substrate interactions. The MeBQPME comparator molecule void of hydrogen bonding functionality does not similarly assemble on the metal surface. Complementary density functional theory (DFT) calculations facilitate a structural understanding of the MeBQPH donor assemblies and their strong stabilization through formation of six hydrogen bonds. STM studies also reveal the templated growth of C60 on ordered MeBQPH monolayers with C60 molecules preferentially occupying the threefold interstitial sites of the MeBQPH monolayer. This work supports the idea that H-bonding interactions can be used to control the morphology of organic donor–acceptor blends to potentially create efficient and stable bulk heterojunction photovoltaic devices.

We report full-color quantum-dot-based light-emitting diodes (QLEDs) with high efficiency and long-lifetime by employing high quantum-yield core/shell QDs with thick shells. The increased shell thickness improves the confinement of excitons in the QD cores, and helps to suppress Auger recombination and Forster resonant energy transfer among QDs. Along with optimizing the QD emitting layer thickness and hole transport materials, we achieved significant improvements in device performance as a result of increasing the QD shell thickness to above 5 nm. By using poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB) as a HTL with a 38 nm thick QD layer, these QLEDs show maximum current efficiencies of 18.9 cd A−1, 53.4 cd A−1, and 2.94 cd A−1, and peak external quantum efficiencies (EQEs) of 10.2%, 15.4%, and 15.6% for red, green, and blue QLEDs, respectively, all of which are well maintained over a wide range of luminances from 102 to 104 cd m−2. To the best of our knowledge, this is the first report of blue QLEDs with ηEQE > 15%. Most importantly, these devices also possess long lifetimes with T70 (the time at which the brightness is reduced to 70% of its initial value) of 117 h (red, with an initial luminance of 8000 cd m−2), 84 h (green, 6000 cd m−2) and 47 h (blue, 420 cd m−2). With further optimization of QD processing and device structures, these LEDs based on thick-shell QDs show great promise for use in next-generation full-color displays and lighting devices.

Three stereochemically pure isomers and two isomeric mixtures of a solution-processable diketopyrrolopyrrole-containing oligothiophene (SMDPPEH) have been used to study the effect of 2-ethylhexyl solubilizing group stereochemistry on the film morphology and bulk heterojunction (BHJ) solar cell characteristics of small molecule organic photovoltaics. The different SMDPPEH stereoisomer compositions exhibit nearly identical optoelectronic properties in the molecularly dissolved state, as well as in amorphous films blended with PCBM. However, for films in which SMDPPEH crystallization is induced by thermal annealing, significant differences in molecular packing between the different stereoisomer formulations are observed. These differences are borne out in photovoltaic device characteristics for which unannealed devices show very similar behavior, while after annealing the RR- and SS-SMDPPEH enantiomers show blue-shifted peak EQE relative to the SMDPPEH isomer mixtures. Unannealed devices made from the most crystalline stereoisomer, meso RS-SMDPPEH, are not completely amorphous, and show improved photocurrent generation as a result. Unlike the other compounds, after thermal annealing the RS-SMDPPEH devices show reduced device performance. The results reveal that the chirality of commonly used 2-ethylhexyl solubilizing chains can have a significant effect on the morphology, absorption, and optimum processing conditions of small molecule organic thin films used as photovoltaic device active layers.

Reported is a systematic molecular structure–property relationship study to evaluate the consequences of dedicated H-bonding interactions between molecular electron donors on molecular assembly, absorption, charge collection, and performance in small-molecule bulk heterojunction organic photovoltaic devices. Three families of branched quaterthiophene donor chromophores have been synthesized with members that share nearly identical electronic and optical properties in the molecularly dispersed state but are either capable or incapable of self-association by hydrogen bonding (H-bonding). Phthalhydrazide-functionalized quaterthiophenes are H-bond “active” and show signatures of H-bond promoted assembly in solution (by 1H NMR) and in both neat and blended (with C60) films (by IR). Compared to control compounds with H-bonding “turned off”, the H-bonded derivatives show red-shifted thin film absorption (neat and as blends with C60), different colors as bulk solids, and increased decomposition and melt temperatures. Photovoltaic devices made from blends of H-bonded donor molecules with C60 as the electron acceptor show improved charge collection length and external quantum efficiency resulting in a more than two-fold enhancement in power conversion efficiency relative to non-H-bonding controls, from 0.49% to 1.04%. We anticipate this approach could be generalized to include other donor chromophores with lower optical gap to harvest more longer-wavelength photons and achieve higher power conversion efficiencies.

Thin-film optoelectronic devices based on polycrystalline organolead-halide perovskites have recently become a topic of intense research. Single crystals of these materials have been grown from solution with electrical properties superior to those of polycrystalline films. In order to enable the development of more complex device architectures based on organolead-halide perovskite single crystals, we developed a process to form epitaxial layers of methylammonium lead iodide (MAPbI3) on methylammonium lead bromide (MAPbBr3) single crystals. The formation of the MAPbI3 layer is found to be dominated by the diffusion of halide ions, leading to a shift in the photoluminescence and absorption spectra. X-ray diffraction measurements confirm the single-crystal nature of the MAPbI3 layer, while carrier transport measurements show that the converted layer retains the high carrier mobility typical of single-crystal perovskite materials. Such heterostructures on perovskite single crystals open possibilities for new ...

Interfaces between donor and acceptor in a polymer solar cell play a crucial role in exciton dissociation and charge photogeneration. While the importance of charge transfer (CT) excitons for free carrier generation is intensively studied, the effect of blending on the nature of the polymer excitons in relation to the blend nanomorphology remains largely unexplored. In this work, electroabsorption (EA) spectroscopy is used to study the excited-state polarizability of polymer excitons in several polymer:fullerene blend systems, and it is found that excited-state polarizability of polymer excitons in the blends is a strong function of blend nanomorphology. The increase in excited-state polarizability with decreased domain size indicates that intermixing of states at the interface between the donor polymers and fullerene increases the exciton delocalization, resulting in an increase in exciton dissociation efficiency. This conclusion is further supported by transient absorption spectroscopy and time-resolved photoluminescence measurements, along with the results from time-dependent density functional theory calculations. These findings indicate that polymer excited-state polarizability is a key parameter for efficient free carrier generation and should be considered in the design and development of high-performance polymer solar cells.

Perovskite solar cells have attracted tremendous attention for their outstanding energy conversion efficiency in the past few years. Due to the development of active materials, device architectures and processing methods, power conversion efficiency (PCE) of perovskite solar cells is now growing up to 20%. Beyond the efficiency, to get rid of Lead, the widely-used toxic element in the perovskite layers, as well as to improve the device/module operation lifetime are the other two major challenges that need to be solved before their commercialization. Here, we apply a layer of ZnO nanoparticles onto to a planar perovskite solar cell, which can not only improve the electron transport/extraction in the devices but highly improve the device operation lifetime. The devices were fabricated by spin-coating a poly(3,4-ethylenedioxythuiphene):polystyrene sulfonate (PEDOT:PSS) layer onto a glass/ITO substrate, followed by the deposition of a perovskite layer from a lead chloride (PbCl2) and methyl ammonium iodine (MAI) blend precursor solution. After that, a layer of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and a layer of ZnO nanoparticles were successively deposited as the electron transport layers, and the device was finished by thermally evaporation Al as the cathode. Such planar perovskite solar cell with ZnO NPs exhibits a maximum PCE of up to 14.1%, which is about 35% higher than that without the ZnO layer. Moreover, the device remains 80% of its initial PCE after 2500 hours under 1 sum illumination, majorly due to the protection of ZnO layer that prevent the diffusion of oxygen and moisture molecules into the perovskite layers as revealed by x-ray photoelectron spectroscopy studies.

We report high-efficiency blue-violet quantum-dot-based light-emitting diodes (QD-LEDs) by using high quantum yield ZnCdS/ZnS graded core-shell QDs with proper surface ligands. Replacing the oleic acid ligands on the as-synthesized QDs with shorter 1-octanethiol ligands is found to cause a 2-fold increase in the electron mobility within the QD film. Such a ligand exchange also results in an even greater increase in hole injection into the QD layer, thus improving the overall charge balance in the LEDs and yielding a 70% increase in quantum efficiency. Using 1-octanethiol capped QDs, we have obtained a maximum luminance (L) of 7600 cd/m(2) and a maximum external quantum efficiency (ηEQE) of (10.3 ± 0.9)% (with the highest at 12.2%) for QD-LEDs devices with an electroluminescence peak at 443 nm. Similar quantum efficiencies are also obtained for other blue/violet QD-LEDs with peak emission at 455 and 433 nm. To the best of our knowledge, this is the first report of blue QD-LEDs with ηEQE10%. Combined with the low turn-on voltage of ∼2.6 V, these blue-violet ZnCdS/ZnS QD-LEDs show great promise for use in next-generation full-color displays.

We demonstrate a clear dependence of the growth and photovoltaic performance of zinc phthalocyanine (ZnPc) films on the presence of dual organic interlayers of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and tetracene on the transparent indium-tin oxide anode. The PEDOT:PSS layer enables the two-dimensional growth of tetracene, which in turn leads to enhanced molecular packing and exciton diffusion in the ZnPc film. Coupled with exciton blocking provided by tetracene, this results in a more than 100% increase in the external quantum efficiency for ZnPc absorption in bilayer ZnPc/C60 devices. The power conversion efficiency is increased from 2.0% to 3.5% for bilayer devices, and from 3.8% to 5.0% for the more efficient planar-mixed devices.

The effect of 1 sun illumination for 24 h on encapsulated inverted organic photovoltaic devices is studied through a series of electrical and optical characterizations for donor/acceptor polymer solar cells based on poly(dithienogermole-alt-thienopyrrolodione)/[6,6]-phenyl C71 butyric acid methyl ester blends. Power conversion efficiency is significantly reduced after light exposure due to a 45% drop in the device fill factor and a 40% drop in both the open circuit voltage and short circuit current. The decrease in open circuit voltage is attributed to a reduction in the built-in field in the device due to photodegradation of the ZnO interlayer. The reduction in fill factor and short circuit current is shown to be due to the formation of an extraction barrier for hole collection as a result of photodegradation of the MoOx interlayer. Using a 400 nm long pass filter to block the UV light, device stability is significantly enhanced, resulting in a decrease in power conversion efficiency of less than 5% under the same operation conditions.

Hexagonal noncontiguously packed (HNCP) arrays of submicrometer-sized particles trapped at an air-water interface are successfully transferred to solid substrates. The long-range order of the hexagonal arrays at the interface can be improved by compression-relaxation cycles. The interparticle distance (i.e., the periodicity of the hexagonal array) can be controlled by varying the degree of compression of the particle film. The critical characteristics of the substrate surface are hydrophobicity (advancing water contact angle of >70 degrees) and a charge complementary to the surface of the particles. Suitable silicon and glass substrates are easily prepared by treatment with commercially available organosilicon compounds. Two transfer processes have been developed. When the parallel transfer process is used, the HNCP arrays are deposited on the solid substrates with minimal pattern distortion. The vertical dipping transfer distorts the pattern and renders a sense of directionality perpendicular to the dipping direction. This surface patterning technique is applied to fabrication of subwavelength grating for antireflection in the visible region. Antireflective HNCP arrays comprising varied particle diameters and pattern periodicities are fabricated on glass substrates to demonstrate the effects of these parameters on the antireflection performance.