Progress towards fully spray-coated semitransparent inverted organic solar cells with a silver nanowire electrode

We demonstrated a fully spray-coated semitransparent organic solar cell, from the lowermost organic layer to the uppermost top electrode. The fabricated devices based on a poly (3-hexylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester (P3HT:PCBM) are semitransparent (∼70% transparency at long wavelength beyond 650 nm), fully spray-coated from organic layer to top electrode, highly efficient (∼80% of that of a device with a conventional metal electrode).     

Highly conductive silver nanowire networks by organic matrix assisted low-temperature fusing

In silver nanowire (AgNW) percolation network electrodes, the junction resistance at the wire-to-wire contact is crucial for the electrode performance. We introduce an organic sublayer between the substrate and the AgNW electrode to improve the sheet resistance and avoid the frequently applied high-temperature post-annealing process. Upon introduction of such a sublayer, a strong reduction of the sheet resistance (R_S) in the same order as it would be expected from a post-annealing process (e.g. 90 min@210 °C) is observed. This effect is investigated in-depth by using different sublayer material classes such as polyelectrolytes, tensides or differently charged polymers. Independent of charge and material class, especially those materials with hydrophobic and hydrophilic parts, dramatically reduce the sheet resistance. Consequently, hydrophobic interaction between substrate and nanowires and capillary forces during drying can be attributed as driving force. Using polyvinylpyrrolidone (PVP), also used as stabilizer for the AgNWs, leads to the largest reduction in sheet resistance of the investigated materials resulting in AgNW electrodes exhibiting R_S = 10.8 Ω/□ at 80.4% transparency (including substrate) without additional post-annealing at high temperatures.     

Aerosol jet printed top grids for organic optoelectronic devices

Aerosol jet deposited metallic grids are very promising as transparent electrodes for large area organic solar cells and organic light emitting diodes. However, the homogeneity and the printing speed remain a challenge. We report homogeneous and rapidly printed metallic lines based on a complex-based metal–organic silver ink using a processing temperature of 140 °C. We show that inhomogeneities, which are present in printed structures at increased printing speeds and mainly caused by drying effects, can be improved by adding high boiling point solvents. We demonstrate solution processed highly conductive and transparent hybrid electrodes on inverted organic solar cells comprising digitally printed top silver grids.     

Ultrasmooth,highly conductive and transparent PEDOT:PSS/silver nanowire composite electrode for flexible organic light-emitting devices

The next generation of optoelectronic devices requires transparent conductive electrodes to be flexible, inexpensive and compatible with large scale manufacturing processes. We report an ultrasmooth, highly conductive and transparent composite electrode on a flexible photopolymer substrate by employing a template stripping method. A random silver nanowire (AgNW) network buried in poly(3,4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film constituted the composite electrode. Besides the effectively decreased surface roughness, its sheet resistance and transmittance are comparable to those of conventional PEDOT:PSS electrode. As a result, the efficiency of the OLEDs based on the composite electrode exhibited 25% enhancement compared to the OLEDs with conventional PEDOT:PSS electrode. Moreover, the performance of the flexible OLEDs remains stable after over one hundred bending cycles.     

Efficient flexible organic photovoltaics using silver nanowires and polymer based transparent electrodes

Planarization and filling voids between wires are key issues when using nanowire electrodes in flexible solar cells such as organic photovoltaics (OPV). For this purpose, we use poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) which leads to an electrically well connected silver nanowire (AgNW) network. Furthermore, the use of water based PEDOT: PSS leads to humidity assisted AgNW fusing, resulting in a maximum processing temperature of only 120 °C. OPV cells using this AgNW/PEDOT: PSS transparent electrodes exhibit power conversion efficiencies up to 7.15%. Moreover, OPV devices on PET substrates with an alumina encapsulation and barrier adhesive show excellent mechanical flexibility.     

Inkjet printed silver nanowire percolation networks as electrodes for highly efficient semitransparent organic solar cells

In this work, we demonstrate inkjet printing of silver nanowires (AgNW) with an average length of 10's of μm using industrial printheads with nozzle diameters in the same size range. The printed silver nanowire mesh reveals uniform distribution and a good balance between conductivity and transmittance, which is comparable to layers fabricated by conventional methods like slot-die or spray coating. Employing a novel AgNW ink formulation based on a high boiling alcohol allows printing directly on PEDOT:PSS and prevents nozzle clogging. Using silver nanowire meshes as bottom and top electrodes, a fully inkjet printed semitransparent organic solar cell with a power conversion efficiency of 4.3% for 1 cm² area is demonstrated, which is the highest value reported so far for fully inkjet printed organic photovoltaic cells.     

Sub 30 nm silver nanowire synthesized using KBr as co-nucleant through one-pot polyol method for optoelectronic applications

Ultrathin, high aspect ratio silver nanowires synthesized in solution has attracted significant attention for fabricating optoelectronic devices with good properties and relatively low cost, and has been the most promising material to replace ITO. In this paper, a novel method is proposed to synthesis ultrathin nanowires through facile one-pot polyol method using KBr as a co-nucleant to NaCl. The effect of three common nucleants NaCl, FeCl₃ and KBr on nucleation rate and product size were well studied. KBr is found to be beneficial for decreasing product size but unable to generate nanowires effectively alone. By adjusting the exact concentration of KBr, silver nanowires with an average length of 21 μm and average diameter of 26 nm could be synthesized conveniently. Conductive film prepared using these nanowires had transmittance over 90% and sheet resistance about 10 Ω/□, which is better than the average level of common ITO-glass and highly potential to be applied in optoelectronic applications.     

Fluorene-based cathode interlayer polymers for high performance solution processed organic optoelectronic devices

A hydrophilic polyfluorene-based conjugated polyelectrolyte (CPE) Poly[9,9-bis(4′-(6″-(diethanolamino)hexyloxy) phenyl)fluorene], PPFN-OH (Scheme 1) has been synthesized and utilized as cathode interlayer for both polymer light emitting diodes (PLEDs) and solar cells (PSCs). For comparison, another CPE namely Poly[9,9-bis(6′-(diethanolamino)hexyl)fluorene] (PFN-OH) has also been investigated. They comprise the same polyfluorene backbone structures with, respectively, diethanolaminohexyl (PFN-OH) and diethanolaminohexoxyphenyl (PPFN-OH) substituents attached to the C9 carbon of the fluorene repeat unit. In comparison to reference devices with more reactive Ca/Al cathodes, utilizing these CPEs as interlayers allowed an Al cathode to be used for blue light emission PLEDs, yielding 51% and 92% enhancement of maximum luminous efficiency (LE) for PFN-OH and PPFN-OH, respectively. The PLEDs with PPFN-OH showed both higher maximum LE and maximum luminance (L) (LE = 2.53 cd/A at 6.2 V, L = 9917 cd/m² at 8.3 V) than devices with PFN-OH (2.00 cd/A at 4.1 V, 3237 cd/m² at 7.2 V). The PPFN-OH PLEDs also showed no significant roll-off in efficiency with increasing current density up to 400 mA/cm², indicating excellent electron injection ability and stability for this interlayer. The insertion of alkoxy-phenyl groups at the C9-position in PPFN-OH is clearly advantageous. This simple modification significantly improves the CPE cathode interlayer performance. Parallel investigations of the electron extraction properties of PPFN-OH in inverted architecture PSCs with PCDTBT:PC₇₀BM bulk heterojunction active layers demonstrated a power conversion efficiency enhancement of ∼19% (from 4.99% to 5.95%) for indium tin oxide cathode devices compared with reference devices using Ca/Al cathodes. These results confirm PPFN-OH to be a promising interlayer material for high performance solution processed organic optoelectronic devices.     

Suppression of efficiency roll-off in highly efficient blue phosphorescent organic light-emitting devices using novel iridium phosphors with good electron mobility

High-efficiency blue organic light-emitting diodes were reported by adopting two novel iridium phosphors. Due to phosphoryl moiety in ancillary ligands, both complexes (dfppy)₂Ir(ppp) and (dfppy)₂Ir(dpp) (dyppy = 2-(2,4-difluorophenyl)pyridine, ppp = phenyl(pyridin-2-yl)phosphinate, dpp = dipyridinylphosphinate) own high electron mobility which can balance the injection and transport of carriers. Furthermore, the double light-emitting layers with TcTa (4,4′,4″-tris(carbazol-9-yl)triphenylamine) and 26DCzPPy (2,6-bis(3-(carbazol-9-yl)phenyl)pyridine) hosts broaden the exciton formation zone and suppress efficiency roll-off. The optimized double light-emitting layers devices exhibited decent performances with peak current efficiency near 50 cd/A and external quantum efficiency above 20% as well as negligible efficiency roll-off.     

Low sublimation temperature cesium pivalate complex as an efficient electron injection material for organic light-emitting diode devices

Cesium pivalate ((CH₃)₃CCOOCs) has been synthesized and applied as an electron injection material for organic light-emitting diodes, which showed low sublimation temperature of 180 °C. Typical bilayer structure of ITO/NPB (60 nm)/Alq₃ (50 nm)/EIL/Al was used to evaluate the electron injection efficacy of (CH₃)₃CCOOCs, the results showed (CH₃)₃CCOOCs/Al exhibits better electron injection than LiF/Al cathode and the power efficiency was improved by about 19% at current density of 50 mA/cm². More interestingly, in the typical three layer OLED structure ITO/2-TNATA (60 nm)/NPB (10 nm)/Alq₃:2% C545T (40 nm)/MADN (15 nm)/(CH₃)₃CCOOCs (2 nm)/Al, the maximum current efficiency is up to 20 cd/A with Commission Internationale d’Eclairage (CIE_x,_y) color coordinates of (x = 0.30, y = 0.65) at current density of 140 mA/cm², which indicates that the non-aromatic alkali metal complex can also have good match with the chemically stable compound and exhibit good electron injection properties.     

Large-area,high-quality self-assembly electron transport layer for organic optoelectronic devices

We propose a self-assembly method for forming large-area high-quality solution-processed titanium oxide (TiO₂) films as efficient electron transport layer for organic solar cells. The self-assembled solution-processed TiO₂ layers are highly ordered and significantly improved in surface morphology over commonly-used spin-coating process resulting in better charge collection and significant material saving. When incorporated into polymer solar cells, the TiO₂ device shows enhanced performance. Furthermore, we demonstrate the TiO₂ can form large-area films, and achieve very uniform and improved device performances. Consequently, the self-assembled TiO₂ films can be efficient and low-cost electron transport layer potentially for large-area organic optoelectronics.     

Fluorene bilayer for polymer organic light-emitting diode using efficient ionization method for atomized droplet

We present a solution-processed planar fluorene bilayer by an ultrasonic atomized deposition method in combination with a needle electrode as an ionization part for an atomized droplet. An important advantage of our method is that the atomized droplet is efficiently charged using a needle electrode, which speeds up the deposition rate of the polymer thin film. The deposition rate increases 2 to 3 times compared to a that obtained with a conventional technique without using the ionization method, and real-time monitoring of landed droplets indicates that the number of droplets increased as the voltage applied to the needle electrode was increased, owing to the highly charged atomized droplets. Furthermore, the TFB/F8BT bilayer was achieved by optimizing the substrate temperature, and the polymer organic light-emitting diode exhibits a luminance value exceeding 12,000 cd/m² by insertion of the TFB as an electron blocking layer. The maximum current efficiency of the fluorene bilayer device was 6.64 cd/A, which was a 3.2-fold increase compared to that obtained with the reference device without the TFB electron blocking layer.     

Triphenylamine-cored star-shape compounds as non-fullerene acceptor for high-efficiency organic solar cells: Tuning the optoelectronic properties by S/Se-annulated perylene diimide

Three novel star-shaped S/Se-annulated perylene diimide (PDI) small molecule acceptors with triphenylamine as the core, namely TPA-PDI, TPA-PDI-S and TPA-PDI-Se, were designed and synthesized. Using the wideband-gap polymer PDBT-T1 as the donor and Se-annulated perylene diimide (TPA-PDI-Se) as the acceptor, power conversion efficiencies (PCE) of up to 6.10% was achieved, which is 38% higher than the reference of TPA-PDI without heteroatom annulation. Impressively, the S/Se-annulated perylene diimides as acceptors showed high open-circuit voltage (V_OC) of 1.00 V. The high efficiency for TPA-PDI-Se can be attributed to complementary absorption spectra with the donor material, relatively high-lying LUMO level, balanced carrier transport and favorable morphologies. To the best of our knowledge, this PCE of 6.10% is among the highest values based on star-shaped non-fullerene acceptors so far.     

Surface modification of printed silver electrodes for efficient carrier injection in organic thin-film transistors

The modification of printed silver electrode surfaces for use as the bottom-contact electrodes of organic thin-film transistors (OTFTs) is reported. Printed silver electrodes fabricated using the surface photoreactive nanometal printing (SuPR-NaP) technique are inevitably covered with an inert surface layer of alkylamines that is originally used for encapsulation of the silver nanoparticles (AgNPs). However, it may act as a built-in protective layer against carrier injections. We demonstrate that a simple vapor exposure method is sufficient for converting the protective layer into a layer that assists carrier injection. As modifiers, we used various types of fluorinated benzenethiols that exhibit a stronger coordination with the silver surfaces than the alkylamimes. We detected the chemical conversion from alkylamine encapsulation to thiol coordination by surface enhanced Raman spectroscopy (SERS) and evaluated the improvement in the carrier injection using a transfer length method (TLM) for the OTFTs. Among the modifiers, the pentafluorobenzenethiol (PFBT) treatment significantly improves the device performance and stability of the OTFTs.     

Softening temperature on sputtered ZnO interfacial barrier layer for an efficient charge transfer P3HT/ZnO and better interfacial stability in plastic organic photovoltaic devices

We demonstrate the usefulness of RF magnetron sputtering ZnO thin film at softening temperature, as interfacial barrier layer in air stable flexible inverted organic photovoltaic devices. We investigate the influence of annealing on the ZnO crystallinity, on the ITO substrate morphology and charge transport at the ZnO/active layer interface. The photo-physical and structural characteristics of P3HT beside ZnO interfacial layer and the photovoltaic device performances were also studied using UV–vis spectroscopy, photoluminescence (PL) and J-V characteristic. Finally, we study the interfacial stability of devices with and without ZnO interfacial layer in both normal and inverted structure OPVs. We show that under optimized sputtering conditions, higher order and orientation structure of P3HT, the ZnO thermally annealed beside active layer offers better efficiency of contact between the active layer and interfacial layer. We also show that ZnO annealed at a softening temperature of 180 °C is functional for both photovoltaic devices (rigid and plastic substrates), leading to improved performance and stability of plastic solar cell devices.