Efficient and Stable Air-Processed Ternary Organic Solar Cells Incorporating Gallium-Porphyrin as an Electron Cascade Material.

Two gallium porphyrins, a tetraphenyl GaCl porphyrin, termed as (TPP)GaCl, and an octaethylporphyrin GaCl porphyrin, termed as (OEP)GaCl, were synthesized to use as an electron cascade in ternary organic bulk heterojunction films. A perfect matching of both gallium porphyrins' energy levels with that of poly(3-hexylthiophene-2,5-diyl) (P3HT) or poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) polymer donor and the 6,6-phenyl C71 butyric acid methyl ester (PCBM) fullerene acceptor, forming an efficient cascade system that could facilitate electron transfer between donor and acceptor, was demonstrated. Therefore, ternary organic solar cells (OSCs) using the two porphyrins in various concentrations were fabricated where a performance enhancement was obtained. In particular, (TPP)GaCl-based ternary OSCs of low concentration (1:0.05 vv%) exhibited a ~17% increase in the power conversion efficiency (PCE) compared with the binary device due to improved exciton dissociation, electron transport and reduced recombination. On the other hand, ternary OSCs with a high concentration of (TPP)GaCl (1:0.1 vv%) and (OEP)GaCl (1:0.05 and 1:0.1 vv%) showed the poorest efficiencies due to very rough nanomorphology and suppressed crystallinity of ternary films when the GaCl porphyrin was introduced to the blend, as revealed from X-ray diffraction (XRD) and atomic force microscopy (AFM). The best performing devices also exhibited improved photostability when exposed to sunlight illumination for a period of 8 h than the binary OSCs, attributed to the suppressed photodegradation of the ternary (TPP)GaCl 1:0.05-based photoactive film.

Photonic nanostructures mimicking floral epidermis for perovskite solar cells.

Here, we report photonic nanostructures replicated from the adaxial epidermis of flower petals onto light-polymerized coatings using low-cost nanoimprint lithography at ambient temperature. These multifunctional nanocoatings are applied to confer enhanced light trapping, water repellence, and UV light and environmental moisture protection features in perovskite solar cells. The former feature helps attain a maximum power conversion efficiency of 24.61% (21.01% for the reference cell) without any additional device optimization. Added to these merits, the nanocoatings also enable stable operation under AM 1.5G and UV light continuous illumination or in real-world conditions. Our engineering approach provides a simple way to produce multifunctional nanocoatings optimized by nature's wisdom.

Carbon Nanodots as Electron Transport Materials in Organic Light Emitting Diodes and Solar Cells.

Charge injection and transport interlayers play a crucial role in many classes of optoelectronics, including organic and perovskite ones. Here, we demonstrate the beneficial role of carbon nanodots, both pristine and nitrogen-functionalized, as electron transport materials in organic light emitting diodes (OLEDs) and organic solar cells (OSCs). Pristine (referred to as C-dots) and nitrogen-functionalized (referred to as NC-dots) carbon dots are systematically studied regarding their properties by using cyclic voltammetry, Fourier-transform infrared (FTIR) and UV-Vis absorption spectroscopy in order to reveal their energetic alignment and possible interaction with the organic semiconductor's emissive layer. Atomic force microscopy unravels the ultra-thin nature of the interlayers. They are next applied as interlayers between an Al metal cathode and a conventional green-yellow copolymer-in particular, (poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,1',3}-thiadiazole)], F8BT)-used as an emissive layer in fluorescent OLEDs. Electrical measurements indicate that both the C-dot- and NC-dot-based OLED devices present significant improvements in their current and luminescent characteristics, mainly due to a decrease in electron injection barrier. Both C-dots and NC-dots are also used as cathode interfacial layers in OSCs with an inverted architecture. An increase of nearly 10% in power conversion efficiency (PCE) for the devices using the C-dots and NC-dots compared to the reference one is achieved. The application of low-cost solution-processed materials in OLEDs and OSCs may contribute to their wide implementation in large-area applications.

Enhanced Organic and Perovskite Solar Cell Performance through Modification of the Electron-Selective Contact with a Bodipy-Porphyrin Dyad.

Photovoltaic devices based on organic semiconductors and organo-metal halide perovskites have not yet reached the theoretically predicted power conversion efficiencies while they still exhibit poor environmental stability. Interfacial engineering using suitable materials has been recognized as an attractive approach to tackle the above issues. We introduce here a zinc porphyrin-triazine-bodipy donor-π bridge-acceptor dye as a universal electron transfer mediator in both organic and perovskite solar cells. Thanks to its "push-pull" character, this dye enhances electron transfer from the absorber layer toward the electron-selective contact, thus improving the device's photocurrent and efficiency. The direct result is more than 10% average power conversion efficiency enhancement in both fullerene-based (from 8.65 to 9.80%) and non-fullerene-based (from 7.71 to 8.73%) organic solar cells as well as in perovskite ones (from 14.56 to 15.67%), proving the universality of our approach. Concurrently, by forming a hydrophobic network on the surface of metal oxide substrates, it improves the nanomorphology of the photoactive overlayer and contributes to efficiency stabilization. The fabricated devices of both kinds preserved more than 85% of their efficiency upon exposure to ambient conditions for more than 600 h without any encapsulation.

Multi-electron reduction of Wells-Dawson polyoxometalate films onto metallic, semiconducting and dielectric substrates.

The investigation of conditions allowing multi-electron reduction and reoxidation of polyoxometalate (POM) films onto solid substrates is considered an issue of critical importance for their successful incorporation in electronic devices, different types of sensors and catalytic systems. In the present paper, the rich multi-electron redox chemistry of films of Wells-Dawson ammonium salts, namely (NH4)6P2Mo18O62 and (NH4)6P2W18O62, on top of metallic (Al), semiconducting (ITO) and dielectric (SiO2) substrates under ambient conditions is investigated. The respective Keggin heteropolyacids, H3PMo12O40 and H3PW12O40, are also investigated for comparison. On Al substrates, the Wells-Dawson ammonium salts are found to be significantly more reduced (4-6e-) compared to the respective Keggin heteropolyacids (∼2e-), in accordance with their deeper lying lowest unoccupied molecular orbital (LUMO) level. Subsequent thermal treatment in air results in reoxidation of the initially highly reduced POM films. Similar behavior is found on ITO substrates, but in initially less reduced (2-4e-) Wells-Dawson POM films. On the other hand, on SiO2 substrates, the thermal reduction of (NH4)6P2Mo18O62 film is observed and attributed to the thermal oxidation of ammonium counterions by [P2Mo18O62]6- anions. Overall, the multi-electron reduction of Wells-Dawson ammonium salts onto metallic and semiconducting substrates (Al, ITO) is determined by the relative position of the LUMO level of POMs in relation to the Fermi level of the substrate (i.e. substrate work function) and affected in a synergistic way by the presence of ammonium counterions. In contrast, on dielectric substrates (SiO2) the reduction of Wells-Dawson POMs ((NH4)6P2Mo18O62) is attributed only to the oxidation of ammonium counterions.

Engineering of Porphyrin Molecules for Use as Effective Cathode Interfacial Modifiers in Organic Solar Cells of Enhanced Efficiency and Stability.

In the present work, we effectively modify the TiO2 electron transport layer of organic solar cells with an inverted architecture using appropriately engineered porphyrin molecules. The results show that the optimized porphyrin modifier bearing two carboxylic acids as the anchoring groups and a triazine electron-withdrawing spacer significantly reduces the work function of TiO2, thereby reducing the electron extraction barrier. Moreover, the lower surface energy of the porphyrin-modified substrate results in better physical compatibility between the latter and the photoactive blend. Upon employing porphyrin-modified TiO2 electron transport layers in PTB7:PC71BM-based organic solar cells we obtained an improved average power conversion efficiency up to 8.73%. Importantly, porphyrin modification significantly increased the lifetime of the devices, which retained 80% of their initial efficiency after 500 h of storage in the dark. Because of its simplicity and efficacy, this approach should give tantalizing glimpses and generate an impact into the potential of porphyrins to facilitate electron transfer in organic solar cells and related devices.

Role of the Metal-Oxide Work Function on Photocurrent Generation in Hybrid Solar Cells.

ZnO is a widely used metal-oxide semiconductor for photovoltaic application. In solar cell heterostructures they not only serve as a charge selective contact, but also act as electron acceptor. Although ZnO offers a suitable interface for exciton dissociation, charge separation efficiencies have stayed rather poor and conceptual differences to organic acceptors are rarely investigated. In this work, we employ Sn doping to ZnO nanowires in order to understand the role of defect and surface states in the charge separation process. Upon doping we are able to modify the metal-oxide work function and we show its direct correlation with the charge separation efficiency. For this purpose, we use the polymer poly(3-hexylthiophene) as donor and the squaraine dye SQ2 as interlayer. Interestingly, neither mobilities nor defects are prime performance limiting factor, but rather the density of available states around the conduction band is of crucial importance for hybrid interfaces. This work highlights crucial aspects to improve the charge generation process of metal-oxide based solar cells and reveals new strategies to improve the power conversion efficiency of hybrid solar cells.

Functionalized Zinc Porphyrins with Various Peripheral Groups for Interfacial Electron Injection Barrier Control in Organic Light Emitting Diodes.

Here, we use a simple and effective method to accomplish energy level alignment and thus electron injection barrier control in organic light emitting diodes (OLEDs) with a conventional architecture based on a green emissive copolymer. In particular, a series of functionalized zinc porphyrin compounds bearing π-delocalized triazine electron withdrawing spacers for efficient intramolecular electron transfer and different terminal groups such as glycine moieties in their peripheral substitutes are employed as thin interlayers at the emissive layer/Al (cathode) interface to realize efficient electron injection/transport. The effects of spatial (i.e., assembly) configuration, molecular dipole moment and type of peripheral group termination on the optical properties and energy level tuning are investigated by steady-state and time-resolved photoluminescence spectroscopy in F8BT/porphyrin films, by photovoltage measurements in OLED devices and by surface work function measurements in Al electrodes modified with the functionalized zinc porphyrins. The performance of OLEDs is significantly improved upon using the functionalized porphyrin interlayers with the recorded luminance of the devices to reach values 1 order of magnitude higher than that of the reference diode without any electron injection/transport interlayer.

Low Work Function Lacunary Polyoxometalates as Electron Transport Interlayers for Inverted Polymer Solar Cells of Improved Efficiency and Stability.

Effective interface engineering has been shown to play a vital role in facilitating efficient charge-carrier transport, thus boosting the performance of organic photovoltaic devices. Herein, we employ water-soluble lacunary polyoxometalates (POMs) as multifunctional interlayers between the titanium dioxide (TiO2) electron extraction/transport layer and the organic photoactive film to simultaneously enhance the efficiency, lifetime, and photostability of polymer solar cells (PSCs). A significant reduction in the work function (WF) of TiO2 upon POM utilization was observed, with the magnitude being controlled by the negative charge of the anion and the selection of the addenda atom (W or Mo). By inserting a POM interlayer with ∼10 nm thickness into the device structure, a significant improvement in the power conversion efficiency was obtained; the optimized POM-modified poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2- 33 ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]:[6,6]-phenyl-C70 butyric acid methyl ester (PTB7:PC70BM)-based PSCs exhibited an efficiency of 8.07%, which represents a 21% efficiency enhancement compared to the reference TiO2 cell. Similar results were obtained in POM-modified devices based on poly(3-hexylthiophene) (P3HT) with electron acceptors of different energy levels, such as PC70BM or indene-C60 bisadduct (IC60BA), which enhanced their efficiency up to 4.34 and 6.21%, respectively, when using POM interlayers; this represents a 25-33% improvement as compared to the reference cells. Moreover, increased lifetime under ambient air and improved photostability under constant illumination were observed in POM-modified devices. Detailed analysis shows that the improvements in efficiency and stability synergistically stem from the reduced work function of TiO2 upon POM coverage, the improved nanomorphology of the photoactive blend, the reduced interfacial recombination losses, the superior electron transfer, and the more effective exciton dissociation at the photoactive layer/POM/TiO2 interfaces.

Surface Modification of ZnO Layers via Hydrogen Plasma Treatment for Efficient Inverted Polymer Solar Cells.

Modifications of the ZnO electron extraction layer with low-pressure H plasma treatment increased the efficiency of inverted polymer solar cells (PSCs) based on four different photoactive blends, namely, poly(3-hexylthiophene):[6,6]-phenyl C71 butyric acid methyl ester (P3HT:PC71BM), P3HT:1',1″,4',4″-tetrahydro-di[1,4]methanonaphthaleno-[5,6]ullerene-C60 (P3HT:IC60BA), poly[(9-(1-octylnonyl)-9H-carbazole-2,7-diyl)-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]:PC71BM (PCDTBT:PC71BM), and (poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-(2-ethylhexy)carbonyl]thieno[3,4-b]thiophenediyl]]):PC71BM (PTB7:PC71BM), irrespective of the donor:acceptor combination in the photoactive blend. The drastic improvement in device efficiency is dominantly attributable to the reduction in the work function of ZnO followed by a decreased energy barrier for electron extraction from fullerene acceptor. In addition, reduced recombination losses and improved nanomorphology of the photoactive blend in the devices with the H plasma treated ZnO layer were observed, whereas exciton dissociation also improved with hydrogen treatment. As a result, the inverted PSC consisting of the P3HT:PC71BM blend exhibited a high power conversion efficiency (PCE) of 4.4%, the one consisting of the P3HT:IC60BA blend exhibited a PCE of 6.6%, and our champion devices with the PCDTBT:PC71BM and PTB7:PC71BM blends reached high PCEs of 7.4 and 8.0%, respectively.

Old metal oxide clusters in new applications: spontaneous reduction of Keggin and Dawson polyoxometalate layers by a metallic electrode for improving efficiency in organic optoelectronics.

The present study is aimed at investigating the solid state reduction of a representative series of Keggin and Dawson polyoxometalate (POM) films in contact with a metallic (aluminum) electrode and at introducing them as highly efficient cathode interlayers in organic optoelectronics. We show that, upon reduction, up to four electrons are transferred from the metallic electrode to the POM clusters of the Keggin series dependent on addenda substitution, whereas a six electron reduction was observed in the case of the Dawson type clusters. The high degree of their reduction by Al was found to be of vital importance in obtaining effective electron transport through the cathode interface. A large improvement in the operational characteristics of organic light emitting devices and organic photovoltaics based on a wide range of different organic semiconducting materials and incorporating reduced POM/Al cathode interfaces was achieved as a result of the large decrease of the electron injection/extraction barrier, the enhanced electron transport and the reduced recombination losses in our reduced POM modified devices.

All-organic sulfonium salts acting as efficient solution processed electron injection layer for PLEDs.

Herein we introduce the all-organic triphenylsulfonium (TPS) salts cathode interfacial layers (CILs), deposited from their methanolic solution, as a new simple strategy for circumventing the use of unstable low work function metals and obtaining charge balance and high electroluminescence efficiency in polymer light-emitting diodes (PLEDs). In particular, we show that the incorporation of TPS-triflate or TPS-nonaflate at the polymer/Al interface improved substantially the luminous efficiency of the device (from 2.4 to 7.9 cd/A) and reduced the turn-on and operating voltage, whereas an up to 4-fold increase in brightness (∼11 250 cd/m(2) for TPS-triflate and ∼14 682 cd/m(2) for TPS-nonaflate compared to ∼3221 cd/m(2) for the reference device) was observed in poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-2,1',3-thiadiazole)] (F8BT)-based PLEDs. This was mainly attributed to the favorable decrease of the electron injection barrier, as derived from the open-circuit voltage (Voc) measurements, which was also assisted by the conduction of electrons through the triphenylsulfonium salt sites. Density functional theory calculations indicated that the total energy of the anionic (reduced) form of the salt, that is, upon placing an electron to its lowest unoccupied molecular orbital, is lower than its neutral state, rendering the TPS-salts stable upon electron transfer in the solid state. Finally, the morphology optimization of the TPS-salt interlayer through controlling the processing parameters was found to be critical for achieving efficient electron injection and transport at the respective interfaces.

The influence of hydrogenation and oxygen vacancies on molybdenum oxides work function and gap states for application in organic optoelectronics.

Molybdenum oxide is used as a low-resistance anode interfacial layer in applications such as organic light emitting diodes and organic photovoltaics. However, little is known about the correlation between its stoichiometry and electronic properties, such as work function and occupied gap states. In addition, despite the fact that the knowledge of the exact oxide stoichiometry is of paramount importance, few studies have appeared in the literature discussing how this stoichiometry can be controlled to permit the desirable modification of the oxide's electronic structure. This work aims to investigate the beneficial role of hydrogenation (the incorporation of hydrogen within the oxide lattice) versus oxygen vacancy formation in tuning the electronic structure of molybdenum oxides while maintaining their high work function. A large improvement in the operational characteristics of both polymer light emitting devices and bulk heterojunction solar cells incorporating hydrogenated Mo oxides as hole injection/extraction layers was achieved as a result of favorable energy level alignment at the metal oxide/organic interface and enhanced charge transport through the formation of a large density of gap states near the Fermi level.

Dynamics of energy transfer of a dioxolane-substituted pentacene dispersed in 4,4-bis[N-1-naphthyl-N-phenylamino]biphenyl.

We examine the steady-state and time-resolved photoluminescence of guest-host films featuring a dioxolane-substituted pentacene derivative (2,2,10,10-tetraethyl-6,14-bis(triisopropylsilylethynyl)-1,3,9,11-tetraoxadicyclopenta[b,m]pentacene, EtTP-5) dispersed in the hole transporting material (4,4-bis[N-1-naphthyl-N-phenylamino]biphenyl, alpha-NPD). The films show bright red emission (lambda(max) = 640 nm) as a result of efficient Förster energy transfer from alpha-NPD host molecules to EtTP-5 guest molecules. High absolute photoluminescence (PL) quantum yield (phi(PL) = 76% +/- 4%) and fluorescence lifetime (tau = 18.6 +/- 0.8 ns) were measured at low concentration (0.28 mol % EtTP-5), with moderate PL quenching observed upon increasing the EtTP-5 concentration. The concentrated films (> or = 1.50 mol % EtTP-5) show less evidence of aggregation than previously seen when EtTP-5 was dispersed in tris(quinolin-8-olato)aluminum(III), making alpha-NPD a superior host for the red-emitting EtTP-5.

Photophysical properties of dioxolane-substituted pentacene derivatives dispersed in tris(quinolin-8-olato)aluminum(III).

Two novel dioxolane-substituted pentacene derivatives, namely, 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (TP-5) and 2,2,10,10-tetraethyl-6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5), have been synthesized and spectroscopically characterized. Here, we examine the steady-state and time-resolved photoluminescence (PL) of solid-state composite films containing these pentacene derivatives dispersed in tris(quinolin-8-olato)aluminum(III) (Alq(3)). The films show narrow red emission and high absolute photoluminescence quantum yields (phi(PL) = 59% and 76% for films containing approximately 0.25 mol % TP-5 and EtTP-5, respectively). The Förster transfer radius for both guest-host systems is estimated to be approximately 33 A. The TP-5/Alq(3) thin films show a marked decrease in phi(PL) with increasing guest molecule concentrations, accompanied by dramatic changes in the PL spectra, suggesting that intermolecular interactions between pentacene molecules result in the formation of weakly radiative aggregates. In contrast, a lesser degree of fluorescence quenching is observed for EtTP-5/Alq(3) films. The measured fluorescence lifetimes of TP-5 and EtTP-5 are similar (approximately 18 ns) at low concentrations but deviate at higher concentrations as aggregation begins to play a role in the TP-5/Alq(3) films. The onset of aggregation in EtTP-5/Alq(3) films occurs at higher guest molecule concentrations (>1.00 mol %). The addition of ethyl groups on the terminal dioxolane rings leads to an increase in the intermolecular spacing in the solid, thereby reducing the tendency for pi-pi molecular stacking and aggregation.

Excitation energy transfer in tris(8-hydroxyquinolinato)aluminum doped with a pentacene derivative.

We investigate the excitation energy transfer in a guest-host molecular system consisting of a pentacene derivative, namely 6,13-bis(2,6-dimethylphenyl)pentacene (DMPP), doped into tris(8-hydroxyquinolinato)aluminum (Alq(3)) using steady-state and time-resolved photoluminescence (PL) spectroscopy. The concentration dependent energy transfer rate and efficiency are calculated and analyzed in terms of the Förster resonance energy transfer model. A relatively long excitation transfer time ( approximately 0.6-3.4 ns depending on the DMPP concentration) and a large transfer radius (31-36 A) are obtained. The Förster radius calculated directly from the Alq(3) PL-DMPP absorption spectral overlap (26 A) is smaller than the transfer radii obtained from the PL studies, which suggests that excitation energy migration within Alq(3) plays an important role in the energy transfer process, effectively elongating the transfer radius and increasing the transfer rate and efficiency.