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A novel zwitterion composed of an imidazolium tethered to an anionic sulfonyl(trifluoromethane sulfonyl)imide group was prepared as an alternative dielectric material to traditional ionic liquids. The zwitterion not only melted below 100 °C but also proved to be nonhygroscopic. High-capacitance organic dielectric materials were obtained by blending this compound with poly(methyl methacrylate) over a range of concentrations and thicknesses. Above a specific temperature and concentration, films exhibit a capacitance nearly equivalent to that of an electrostatic double layer, approximately 10 µF/cm2, regardless of their thickness. Grazing-incidence wide-angle X-ray scattering experiments suggest that the zwitterions adopt a lamellar ordering at their surface above a critical concentration. The observed ordering is correlated with a 1000-fold increase in capacitance. The behavior suggests that the zwitterions exhibit strong electrostatic correlations throughout the film bulk, pointing the way toward a novel class of organic dielectric materials.
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Sustainable processing solvents, photoactive materials, and scalable manufacturing will play a key role in commercializing printed organic photovoltaics (OPVs). The record-breaking pioneering OPV reports have done an outstanding job in accelerating the discovery of champion photoactive materials and device engineering practices; however, these works predominantly involve health-hazardous halogenated processing solvents/additives and non-scalable thin-film coating methods. Herein, large-area slot-die-manufactured OPV cells from eco-friendly halogen-free solvents and synthetically scalable materials are showcased. All the four layers; electron transport layer (SnO2), cathode interlayer (PDIN-H), bulk-heterojunction (BHJ, PTQ-10:BTP-4F-12), and hole transport layer [poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS] are slot-die-coated in air. A non-halogenated co-solvent mixture of toluene and 2-methyl tetrahydrofuran is presented as an optimal processing solvent to realize the high-quality thin films of PTQ10:BTP-4F-12. The unencapsulated champion solar cells characterized in ambient conditions (RH = 30%, T = 22 °C) exhibit power conversion efficiencies (PCEs) of 12.1 and 17.8% under 1 Sun (100 mW/cm2) and indoor light-emitting diode lighting (580 µW/cm2) conditions, respectively. Additionally, PEDOT:PSS is successfully slot-die-coated atop BHJ by mitigating wettability challenges with the aid of surface treatment. The all four-layer slot-die-coated OPVs exhibit a PCE of 9.55%.
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The widespread realization of wearable electronics requires printable active materials capable of operating at low voltages. Polymerized ionic liquid (PIL) block copolymers exhibit a thickness-independent double-layer capacitance that makes them a promising gating medium for the development of organic thin-film transistors (OTFTs) with low operating voltages and high switching speed. PIL block copolymer structure and self-assembly can influence ion conductivity and the resulting OTFT performance. In an OTFT, self-assembly of the PIL gate on the semiconducting polymer may differ from bulk self-assembly, which would directly influence electrical double-layer formation. To this end, we used poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)) as a model semiconductor for our OTFTs, on which our PILs exhibited self-assembly. In this study, we explore this critical interface by grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM) of P(NDI2OD-T2) and a series of poly(styrene)-b-poly(1-(4-vinylbenzyl)-3-butylimidazolium-random-poly(ethylene glycol) methyl ether methacrylate) (poly(S)-b-poly(VBBI+[X]-r-PEGMA)) block copolymers with varying PEGMA/VBBI+ ratios and three different mobile anions (where X = TFSI-, PF6-, or BF4-). We investigate the thin-film self-assembly of block copolymers as a function of device performance. Overall, a mixed orientation at the interface leads to improved device performance, while predominantly hexagonal packing leads to nonfunctional devices, regardless of the anion present. These PIL gated OTFTs were characterized with a threshold voltage below 1 V, making understanding of their structure-property relationships crucial to enabling the further development of high-performance gating materials.
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Metal and metalloid phthalocyanines are an abundant and established class of materials widely used in the dye and pigment industry as well as in commercial photoreceptors. Silicon phthalocyanines (SiPcs) are among the highest-performing n-type semiconductor materials in this family when used in organic thin-film transistors (OTFTs) as their performance and solid-state arrangement are often increased through axial substitution. Herein, we study eight axially substituted SiPcs and their integration into solution-processed n-type OTFTs. Electrical characterization of the OTFTs, combined with atomic force microscopy (AFM), determined that the length of the alkyl chain affects device performance and thin-film morphology. The effects of high-temperature annealing and spin coating time on film formation, two key processing steps for fabrication of OTFTs, were investigated by grazing-incidence wide-angle X-ray scattering (GIWAXS) and X-ray diffraction (XRD) to elucidate the relationship between thin-film microstructure and device performance. Thermal annealing was shown to change both film crystallinity and SiPc molecular orientation relative to the substrate surface. Spin time affected film crystallinity, morphology, and interplanar d-spacing, thus ultimately modifying device performance. Of the eight materials studied, bis(tri-n-butylsilyl oxide) SiPc exhibited the greatest electron field-effect mobility (0.028 cm2 V-1 s-1, a threshold voltage of 17.6 V) of all reported solution-processed SiPc derivatives.
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Perylene diimide (PDI) has attracted widespread interest as an inexpensive electron acceptor for photovoltaic applications; however, overcrystallization in the bulk heterojunction typically leads to low device performance. Recent work has addressed this issue by forming bay-linked PDI dimers and oligomers, where the steric bulk of adjacent PDI units forces the molecule to adopt a nonplanar structure. This disrupts the molecular packing and limits domain sizes in the bulk heterojunction. Unfortunately, the introduction of electron-donating/-withdrawing groups in the bay region is also the best way to fine-tune the frontier molecular orbitals (FMOs) of PDI, which is highly desirable from a device optimization standpoint. This competition for the bay region has made it difficult for PDI to keep pace with other non-fullerene acceptors. Here, we report the synthesis of regioisomerically pure 1,7-dicyanoperylene diimide and its dimerization through an imide linkage. We show that this is an effective strategy to tune the energies of the FMOs while simultaneously suppressing overcrystallization in the bulk heterojunction. The resulting acceptor has a low LUMO energy of -4.2 eV and is capable of accepting photogenerated electrons from donor polymers with high electron affinities, even when conventional acceptors such as PDI, PC71BM, and ITIC cannot.
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The commercialization of organic solar cell (OSC) technology will require highly reproducible techniques for controlling the morphology of bulk heterojunction blends. Variable-pressure solvent vapor annealing (VP-SVA) is one method for postprocessing organic solar cells with high precision; it can prevent the overannealing of cells that plagues conventional SVA processes. To gain insight into the dynamics of the VP-SVA process, we carried out operando measurements on OSCs with correlated in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. We show that the partial pressure of solvent vapor controls the length scale of film reordering, with optimal restructuring taking place below the saturation vapor pressure of the solvent. The experiments reveal how the film crystallinity, domain sizes, and percolation pathways evolve over the course of the VP-SVA process and how subtle differences in these morphological parameters differentiate good OSCs from champion cells.
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Typical syntheses of conjugated polymers rely heavily on organometallic reagents and metal-catalyzed cross-coupling reactions. Here, we show that an environmentally benign aldol polymerization can be used to synthesize poly(bisisoindigo), an analog of polyisoindigo with a ring-fused structural repeat unit. Owing to its extended conjugation length, poly(bisisoindigo) absorbs across the UV/vis/NIR spectrum, with an absorption tail that reaches 1000 nm. Due to the four electron-deficient lactam units on each repeat unit, poly(bisoindigo) possesses a low-lying LUMO, which lies at -3.94 eV relative to vacuum. Incorporation of the ring-fused monomer unit also lowered the overall torsional strain in the polymer backbone (relative to polyisoindigo), and the polymer was successfully used in prototype unipolar n-channel organic thin-film transistors.
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Over the past decade, isoindigo has become a widely used electron-deficient subunit in donor-acceptor organic semiconductors, and these isoindigo-based materials have been widely used in both organic photovoltaic (OPV) devices and organic field effect transistors (OFETs). Shortly after the development of isoindigo-based semiconductors, researchers began to modify the isoindigo structure in order to change the optoelectronic properties of the resulting materials. This led to the development of many new isoindigo-inspired compounds; since 2012, the Kelly Research Group has synthesized a number of these isoindigo analogues and produced a variety of new donor-acceptor semiconductors. In this Personal Account, recent progress in the field is reviewed. We describe how the field has evolved from relatively simple donor-acceptor small molecules to structurally complex, highly planarized polymer systems. The relevance of these materials in OPV and OFET applications is highlighted, with particular emphasis on structure-property relationships.
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Low-band-gap organic semiconductors are important in a variety of organic electronics applications, such as organic photovoltaic devices, photodetectors, and field effect transistors. Building on our previous work, which introduced 7-azaisoindigo as an electron-deficient building block for the synthesis of donor-acceptor organic semiconductors, we demonstrate how Lewis acids can be used to further tune the energies of the frontier molecular orbitals. Coordination of a Lewis acid to the pyridinic nitrogen of 7-azaisoindigo greatly diminishes the electron density in the azaisoindigo π-system, resulting in a substantial reduction in the lowest unoccupied molecular orbital (LUMO) energy. This results in a smaller highest occupied molecular orbital-LUMO gap and shifts the lowest-energy electronic transition well into the near-infrared region. Both H+ and BF3 are shown to coordinate to azaisoindigo and affect the energy of the S0 â S1 transition. A combination of time-dependent density functional theory and UV/vis and 1H NMR spectroscopic titrations reveal that when two azaisoindigo groups are present and high concentrations of acid are used, both pyridinic nitrogens bind Lewis acids. Importantly, we demonstrate that this acid-base chemistry can be carried out at the solid-vapor interface by exposing thin films of aza-substituted organic semiconductors to vapor-phase BF3·Et2O. This suggests the possibility of using the BF3-bound 7-azaisoindigo-based semiconductors as n-type materials in various organic electronic applications.
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Perovskite solar cells have experienced a remarkably rapid rise in power conversion efficiencies, with state-of-the-art devices now competing with multicrystalline silicon and thin-film cadmium telluride in terms of efficiency. Unfortunately, the lead halide perovskite absorbers suffer from a lack of chemical stability and decompose in response to a variety of environmental stimuli. In this Forum Article, we provide a brief overview of the decomposition mechanisms in lead halide perovskite thin films, as well as the processes contributing to cell failure in finished devices. We finish by briefly surveying recent efforts to extend the device lifetime. Ultimately, if perovskite solar cells can be made stable, they will be an exciting, highly complementary addition to existing photovoltaic technologies.
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Triangular silver nanoparticles are promising materials for light harvesting applications because of their strong plasmon bands; these absorption bands are highly tunable, and can be varied over the entire visible range based on the particle size. A general concern with these materials is that they are unstable at elevated temperatures. When thermally annealed, they suffer from changes to the particle morphology, which in turn affects their optical properties. Because of this stability issue, these materials cannot be used in applications requiring elevated temperatures. In order to address this problem, it is important to first understand the degradation mechanism. Here, we measure the changes in particle morphology, oxidation state, and coordination environment of Ag@SiO2 nanotriangles caused by thermal annealing. UV-vis spectroscopy and TEM reveal that upon annealing the Ag@SiO2 nanotriangles in air, the triangular cores are truncated and smaller nanoparticles are formed. Ag K-edge X-ray absorption spectroscopy (XANES and EXAFS) shows that the small particles consist of Ag(0), and that there is a decrease in the Ag-Ag coordination number with an increase in the annealing temperature. We hypothesize that upon annealing Ag in air, it is first oxidized to AgxO, after which it subsequently decomposes back to well-dispersed Ag(0) nanoparticles. In contrast, when the Ag@SiO2 nanotriangles are annealed in N2, since there is no possibility of oxidation, no small particles are formed. Instead, the triangular core rearranges to form a disc-like shape.
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Due to the hygroscopic nature of organolead halide perovskites, humidity is one of the most important factors affecting the efficiency and longevity of perovskite solar cells. Although humidity has a long term detrimental effect on device performance, it also plays a key role during the initial growth of perovskite crystals. Here we demonstrate that atmospheric relative humidity (RH) plays a key role during the formation of perovskite thin films via the sequential deposition technique. Our results indicate that the RH has a substantial impact on the crystallization process, and hence on device performance. SEM and pXRD analysis show an increase in crystallite size with increasing humidity. At low RH, the formation of small cubic crystallites with large gaps between them is observed. The presence of these voids adversely affects device performance and leads to substantial hysteresis in the device. At higher RH, the perovskite crystals are larger in size, with better connectivity between the crystallites. This produced efficient planar heterojunction solar cells with low hysteresis. By careful control of the RH during the cell fabrication process, efficiencies of up to 12.2% are reached using P3HT as the hole-transport material.
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Perovskite solar cells have rapidly advanced to the forefront of solution-processable photovoltaic devices, but the CH3NH3PbI3 semiconductor decomposes rapidly in moist air, limiting their commercial utility. In this work, we report a quantitative and systematic investigation of perovskite degradation processes. By carefully controlling the relative humidity of an environmental chamber and using in situ absorption spectroscopy and in situ grazing incidence X-ray diffraction to monitor phase changes in perovskite degradation process, we demonstrate the formation of a hydrated intermediate containing isolated PbI6(4-) octahedra as the first step of the degradation mechanism. We also show that the identity of the hole transport layer can have a dramatic impact on the stability of the underlying perovskite film, suggesting a route toward perovskite solar cells with long device lifetimes and a resistance to humidity.
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The recent breakthrough of organometal halide perovskites as the light harvesting layer in photovoltaic devices has led to power conversion efficiencies of over 16%. To date, most perovskite solar cells have adopted a structure in which the perovskite light absorber is placed between carrier-selective electron- and hole-transport layers (ETLs and HTLs). Here we report a new type of compact layer free bilayer perovskite solar cell and conclusively demonstrate that the ETL is not a prerequisite for obtaining excellent device efficiencies. We obtained power conversion efficiencies of up to 11.6% and 13.5% when using poly(3-hexylthiophene) and 2,2',7,7'-tetrakis(N,N-di(4-methoxyphenyl)amino)-9,9'-spirobifluorene, respectively, as the hole-transport material. This performance is very comparable to that obtained with the use of a ZnO ETL. Impedance spectroscopy suggests that while eliminating the ZnO leads to an increase in contact resistance, this is offset by a substantial decrease in surface recombination.
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Fontes de Energia Elétrica , Energia Solar , Elétrons , Propriedades de SuperfícieRESUMO
Plasmonic enhancement is an attractive method for improving the efficiency of dye-sensitized solar cells (DSSCs). Plasmonic materials with sharp features, such as triangular metal nanoparticles, show stronger plasmonic effects than their spherical analogues; however, these nanoparticles are also often thermally unstable. In this work, we investigated the thermal stability of Au@SiO2 triangular nanoprisms by annealing at different temperatures. Morphological changes were observed at temperatures greater than 250 °C, which resulted in a blue shift of the localized surface plasmon resonance (LSPR). Annealing at 450 °C led to a further blue shift; however, this resulted in better overlap of the LSPR with the absorption spectrum of black dye. By introducing 0.05% (w/w) Au@SiO2 nanoprisms into DSSCs, we were able to achieve a panchromatic enhancement of the light-harvesting efficiency. This led to a 15% increase in the power conversion efficiency from 3.9 ± 0.6% to 4.4 ± 0.4%.
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Ouro/química , Dióxido de Silício/química , TemperaturaRESUMO
Anisotropic metal nanoparticles have found use in a variety of plasmonic applications because of the large near-field enhancements associated with them; however, the very features that give rise to these enhancements (e.g., sharply curved edges and tips) often have high surface energies and are easily degraded. This paper describes the stability and degradation mechanisms of triangular silver, gold-coated silver, and gold nanoprisms upon exposure to a wide variety of adverse conditions, including halide ions, thiols, amines and elevated temperatures. The silver nanoprisms were immediately and irreversibly degraded under all of the conditions studied. In contrast, the core-shell Ag@Au nanoprisms were less susceptible to etching by chlorides and bromides, but were rapidly degraded by iodides, amines and thiols by a different degradation pathway. Only the pure gold nanoprisms were stable to all of the conditions tested. These results have important implications for the suitability of triangular nanoprisms in many applications; this is particularly true in biological or environmental fields, where the nanoparticles would inevitably be exposed to a wide variety of chemical stimuli.
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Recently, plasmonic metal nanoparticles have been shown to be very effective in increasing the light harvesting efficiency (LHE) of dye-sensitized solar cells (DSSCs). Most commonly, spherical nanoparticles composed of silver or gold are used for this application; however, the localized surface plasmon resonances of these isotropic particles have maxima in the 400-550 nm range, limiting any plasmonic enhancements to wavelengths below 600 nm. Herein, we demonstrate that the incorporation of anisotropic, triangular silver nanoprisms in the photoanode of DSSCs can dramatically increase the LHE in the red and near-infrared regions. Core-shell Ag@SiO2 nanoprisms were synthesized and incorporated in various quantities into the titania pastes used to prepare the photoanodes. This optimization led to an overall 32 ± 17% increase in the power conversion efficiency (PCE) of cells made using 0.05% (w/w) of the Ag@SiO2 composite. Measurements of the incident photon-to-current efficiency provided further evidence that this increase is a result of improved light harvesting in the red and near-infrared regions. The effect of shell thickness on nanoparticle stability was also investigated, and it was found that thick (30 nm) silica shells provide the best protection against corrosion by the triiodide-containing electrolyte, while still enabling large improvements in PCE to be realized.
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In this paper, we describe a procedure for the phase transfer of silver nanoprisms (AgNPrs) from aqueous solution to chloroform via an amide coupling reaction. AgNPrs are first modified with 16-mercaptohexadecanoic acid (MHA), and then primary or secondary amines are attached to the carboxylic acid end of the MHA ligand through a carbodiimide-mediated amide coupling step. Secondary amines, such as dicyclohexylamine and diphenylamine, are found to solubilize the nanoparticles in chloroform, whereas primary amines (e.g., butylamine and hexadecylamine) do not result in phase transfer. It is found that the AgNPrs functionalized with dicyclohexylamine show the highest stability and the least aggregation after undergoing phase transfer; in contrast, with a less nucleophilic amine, such as diphenylamine, the amide coupling reaction does not go to completion and the resultant AgNPrs are less stable and more prone to aggregation.
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Amidas/química , Nanopartículas Metálicas/química , Ácidos Palmíticos/química , Prata/química , Estrutura Molecular , Transição de Fase , Solventes/química , Água/químicaRESUMO
A stable, label-free optical biosensor based on a porous silicon-carbon (pSi-C) composite is demonstrated. The material is prepared by electrochemical anodization of crystalline Si in an HF-containing electrolyte to generate a porous Si template, followed by infiltration of poly(furfuryl) alcohol (PFA) and subsequent carbonization to generate the pSi-C composite as an optically smooth thin film. The pSi-C sensor is significantly more stable toward aqueous buffer solutions (pH 7.4 or 12) compared to thermally oxidized (in air, 800 °C), hydrosilylated (with undecylenic acid), or hydrocarbonized (with acetylene, 700 °C) porous Si samples prepared and tested under similar conditions. Aqueous stability of the pSi-C sensor is comparable to related optical biosensors based on porous TiO(2) or porous Al(2)O(3). Label-free optical interferometric biosensing with the pSi-C composite is demonstrated by detection of rabbit IgG on a protein-A-modified chip and confirmed with control experiments using chicken IgG (which shows no affinity for protein A). The pSi-C sensor binds significantly more of the protein A capture probe than porous TiO(2) or porous Al(2)O(3), and the sensitivity of the protein-A-modified pSi-C sensor to rabbit IgG is found to be ~2× greater than label-free optical biosensors constructed from these other two materials.
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Técnicas Biossensoriais/métodos , Carbono/química , Fenômenos Ópticos , Silício/química , Animais , Estabilidade de Medicamentos , Eletroquímica , Furanos/química , Imunoensaio , Imunoglobulina G/análise , Imunoglobulina G/imunologia , Porosidade , CoelhosRESUMO
Porous thin films of TiO(2) are prepared and their use as chemical sensors for organic vapor analytes is investigated. Thin-film optical interference (Fabry-Perot) fringes in the reflectance spectrum are monitored using Reflectometric Interference Fourier Transform Spectroscopy (RIFTS). Three analytes are employed to probe the sensitivity of the porous TiO(2)-based sensors as a function of analyte vapor pressure: dodecane, isopropyl alcohol (IPA), and pentane. Measured lower limits of detection (3, 30, and 11, 000 ppmv for dodecane, IPA, and pentane, respectively) track the saturation vapor pressures (P(sat)) of the analytes (0.134, 45, and 513 Torr at 25°C for dodecane, IPA, and pentane, respectively); the analyte with the lowest value of P(sat) shows the lowest LLOD. Recovery of the sensor after a saturation dose of analyte is also dependent on P(sat): the sensor displays good recovery from pentane and IPA, and sluggish and incomplete recovery from dodecane. However, irradiation of the porous TiO(2) sensor with UV light in the presence of air accelerates recovery, and this process is attributed to photo-catalyzed oxidation of the analyte at the TiO(2) surface.