Oxide Sandwiched Metal Thin‐Film Electrodes for Long‐Term Stable Organic Solar Cells

Oxide/silver/oxide multilayers as semitransparent top electrode for small molecule organic solar cells (OSCs) are presented. It is shown that two oxide layers sandwiching a central metal layer greatly improve the stability and lifetime of the organic solar cell. Thermally evaporated MoO₃, WO₃, or V₂O₅ layers are employed as an interlayer for subsequent silver deposition and significantly change the morphology of the ultrathin silver layer, improving charge extraction and electrodes series resistance. The transmittance of the electrode is increased by introducing oxide or oxide and organic multilayers as capping layer, which leads to higher photocurrent generation in the absorber layer. Application of 1 nm MoO₃/11 nm Ag/10 nm MoO₃/50 nm Alq₃ multilayer electrodes in OSCs lead to an efficiency of 2.6% for a standard ZnPc:C60 cell, showing superior performance compared to devices with pure silver top contacts. The device lifetime is also strongly increased. MoO₃ layers can saturate and stabilize the inner and outer metal surface, passivating it against most of the degradation mechanisms. With such an oxide/silver/oxide multilayer electrode, the time until the glass encapsulated OSC is degraded to 80% of its starting efficiency is enhanced from 86 h to approximately 4500 h compared to an OSC without an oxide interlayer.     

Research on the impact of spin coating silver nano clusters on the performance of OLED devices

To achieve uniform distribution of silver nano clusters (SNCs) on substrate and reveal its effect on the performance of organic light-emitting diode (OLED), the SNCs incorporated OLED was fabricated and SNCs were coated by multi-step spin coating. Compared with the device without SNCs film, the brightness and current efficiency of the OLED devices with SNCs film were highly raised. The enhancement is attributed to SNCs induced local surface plasmon (LSP) oscillation, which can increase the radiative rate of excitons on Alq₃ molecules.     

Influence of connecting units’ thicknesses on tandem organic devices’ performances

The present work investigates the influence of the Alq₃:Mg and MoO₃ thicknesses in the connecting unit on the performance of tandem organic light-emitting devices (OLEDs). By systematically varying the Alq₃:Mg and MoO₃ thicknesses, we obtained a higher current efficiency of 37.3 cd/A for a device with 30 nm Alq₃:Mg and 3 nm MoO₃ layer as connecting units. The optimal device performance is enhanced by at least 14%, compared with those of devices we fabricated in this paper. It suggests that appropriate Alq₃:Mg and MoO₃ thicknesses can enhance the charge generating ability for connecting units. On the other hand, it was found that the charge transporting layer would decrease strongly because of much thicker or thinner MoO₃ thicknesses. The results demonstrate that it is an effective method to improve the performance of OLEDs by using a optimal thickness for Alq₃:Mg and MoO₃ layers.     

High Definition Digital Fabrication of Active Organic Devices by Molecular Jet Printing

We introduce a high resolution molecular jet (MoJet) printing technique for vacuum deposition of evaporated thin films and apply it to fabrication of 30 μm pixelated (800 ppi) molecular organic light emitting devices (OLEDs) based on aluminum tris(8‐hydroxyquinoline) (Alq₃) and fabrication of narrow channel (15 μm) organic field effect transistors (OFETs) with pentacene channel and silver contacts. Patterned printing of both organic and metal films is demonstrated, with the operating properties of MoJet‐printed OLEDs and OFETs shown to be comparable to the performance of devices fabricated by conventional evaporative deposition through a metal stencil. We show that the MoJet printing technique is reconfigurable for digital fabrication of arbitrary patterns with multiple material sets and high print accuracy (of better than 5 μm), and scalable to fabrication on large area substrates. Analogous to the concept of “drop‐on‐demand” in Inkjet printing technology, MoJet printing is a “flux‐on‐demand” process and we show it capable of fabricating multi‐layer stacked film structures, as needed for engineered organic devices.     

Inverted polymer solar cells integrated with small molecular electron collection layer

An efficient inverted polymer solar cell (PSC) is reported by integrating a small molecular electron collection layer (ECL) between indium tin oxide (ITO) cathode and the photoactive layer of blended poly(3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester (P3HT:PCBM). The ECL is composed of a cesium carbonate-doped tris(8-hydroxyquinolinato) aluminum (Cs₂CO₃:Alq₃) layer. As determined by photoelectron spectroscopy and electrical measurements, the Cs₂CO₃ doping induces suitable energy level alignment at the ITO/Cs₂CO₃:Alq₃/PCBM interface and the increase in bulk conductivity of organic ECL, which are favorable to electron extraction through Cs₂CO₃:Alq₃ to ITO cathode. In addition, optical simulation indicates that the Cs₂CO₃:Alq₃ layer can act as an optical spacer to modulate the region of highest incident light intensity within the photoactive layer, where absorption and charge dissociation are efficient. The inverted PSC with an optimized Cs₂CO₃:Alq₃ ECL exhibits a power conversion efficiency of 4.83%. The method reported here provides a facile approach to achieve high-performance inverted PSCs at low processing temperature.     

A low-cost and low-temperature processable zinc oxide-polyethylenimine (ZnO:PEI) nano-composite as cathode buffer layer for organic and perovskite solar cells

Nanocomposite buffer layer based on metal oxide and polymer is merging as a novel buffer layer for organic solar cells, which combines the high charge carrier mobility of metal oxide and good film formation properties of polymer. In this work, a nanocomposite of zinc oxide and a commercialized available polyethylenimine (PEI) was developed and used as the cathode buffer layer (CBL) for the inverted organic solar cells and p-i-n heterojunction perovskite solar cells. The cooperation of PEI in nano ZnO offers a good film forming ability of the composite material, which is an advantage in device fabrication. In addition, power conversion efficiency (PCE) of the ZnO:PEI CBL based device was also improved when compared to that of ZnO-only and PEI-only devices. The highest PCE of P3HT:PC₆₁BM and PTB7-Th:PC₆₁BM devices reached to 3.57% and 8.16%, respectively. More importantly, there is no obvious device performance loss with the increase of the layer thickness of ZnO:PEI CBL to 60 nm in organic solar cells, which is in contrast to the PEI based devices, whose device performance decreases dramatically when the PEI layer thickness is higher than 6 nm. Such a nano composite material is also applicable in inverted heterojunction perovskite solar cells. A PCE of 11.76% was achieved for the perovskite solar cell with a thick ZnO:PEI CBL (150 nm) CBL, which is around 1.71% higher than that of the reference cell without CBL, or with ZnO CBL. In addition, stability of the organic and perovskite solar cells having ZnO:PEI CBL was also found to be improved in comparison with that of PEI based device.     

Efficiency enhancement in organic solar cells by configuring hybrid interfaces with narrow bandgap PbSSe nanocrystals

We hereby present an incorporation technique for inorganic nanocrystals (NCs) in organic solar cells (OSCs) for the improvement of power conversion efficiency (PCE). Ternary PbSSe NCs constitute stable conformations with regular poly(3-hexylthiophene):phenyl-C₇₀ butyric acid methyl ester (P3HT:PCBM) organic composites under two heterojunction systems, and significant solar performance modification was obtained, depending on the incorporation type. Bilayer heterojunction (Bi-HJ) SCs, in which a pristine NC layer is sandwiched between the organic composite and cathode, showed significantly broadened photon-harvesting resulting from combination of both layers and energetic carrier transport as a result of reduced recombination losses. In contrast, bulk heterojunction (BHJ) SCs comprising combined composites of P3HT:PCBM:NCs in a single layer suffered from inefficient charge transport as a result of ubiquitous charge traps. Use of Bi-HJ cells with an NC layer of optimal thickness greatly enhanced the short-circuit current (J_SC) to 10.54 mA cm^?2 and a PCE of 3.12% was achieved; this is a 31% improvement over the conversion efficiency of purely organic cells without NCs. The separate PbSSe NC layer coupled well with the organic composite to provide a broad-range photon-harvesting ability and vertically efficient interfacial junctions for systematic charge transport; this greatly enhances the photovoltaic performances of the OSCs.     

Origin of improvement in device performance via the modification role of cesium hydroxide doped tris(8-hydroxyquinoline) aluminum interfacial layer on ITO cathode in inverted bottom-emission organic light-emitting diodes

It has been found that cesium hydroxide (CsOH) doped tris(8-hydroxyquinoline) aluminum (Alq₃) as an interfacial modification layer on indium-tin-oxide (ITO) is an effective cathode structure in inverted bottom-emission organic light-emitting diodes (IBOLEDs). The efficiency and high temperature stability of IBOLEDs with CsOH:Alq₃ interfacial layer are greatly improved with respect to the IBOLEDs with the case of Cs₂CO₃:Alq₃. Herein, we have studied the origin of the improvement in efficiency and high temperature stability via the modification role of CsOH:Alq₃ interfacial layer on ITO cathode in IBOLEDs by various characterization methods, including atomic force microscopy (AFM), ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS) and capacitance versus voltage (C–V). The results clearly demonstrate that the CsOH:Alq₃ interfacial modification layer on ITO cathode not only enhances the stability of the cathode interface and electron-transporting layer above it, which are in favor of the improvement in device stability, but also reduces the electron injection barrier and increases the carrier density for current conduction, leading to higher efficiency.     

Cover Picture: High Definition Digital Fabrication of Active Organic Devices by Molecular Jet Printing (Adv. Funct. Mater. 15/2007)

A new method for direct patterning of organic optoelectronic/electronic devices using a reconfigurable and scalable printing method is reported by Vladimir Bulovic and co‐workers on p. 2722. The printing technique is applied to the fabrication of high‐resolution printed organic light emitting devices (OLEDs) and organic field effect transistors (OFETs). Remarkably, the final print‐deposited films are evaporated onto the substrate (rather than solvent printed), giving high‐quality, solvent‐free, molecularly flat structures that match the performance of comparable high‐performance unpatterned films. We introduce a high resolution molecular jet (MoJet) printing technique for vacuum deposition of evaporated thin films and apply it to fabrication of 30 μm pixelated (800 ppi) molecular organic light emitting devices (OLEDs) based on aluminum tris(8‐hydroxyquinoline) (Alq₃) and fabrication of narrow channel (15 μm) organic field effect transistors (OFETs) with pentacene channel and silver contacts. Patterned printing of both organic and metal films is demonstrated, with the operating properties of MoJet‐printed OLEDs and OFETs shown to be comparable to the performance of devices fabricated by conventional evaporative deposition through a metal stencil. We show that the MoJet printing technique is reconfigurable for digital fabrication of arbitrary patterns with multiple material sets and high print accuracy (of better than 5 μm), and scalable to fabrication on large area substrates. Analogous to the concept of “drop‐on‐demand” in Inkjet printing technology, MoJet printing is a “flux‐on‐demand” process and we show it capable of fabricating multi‐layer stacked film structures, as needed for engineered organic devices.     

An easily prepared Ag8GeS6 nanocrystal and its role on the performance enhancement of polymer solar cells

Novel Ag₈GeS₆ nanocrystal materials (AGS NCs) have recently earned affectionate attention due to its bulk band-gap of 1.4 eV, which makes it ideal as a broad-spectrum absorber material for both semiconductor photocatalyst and photovoltaic devices. In this paper, we investigated the role of AGS NCs as molecular dopant on solution-processed polymer solar cells (PSCs). Argyrodite AGS NCs was prepared via a colloidal synthesis process using simple inorganic compounds as precursors. Incorporating AGS NCs into PSCs leads to not only improved light absorption of active layer but also increased phase separation of donor and acceptor. Moreover, the doping effect of AGS NCs was also confirmed by nanoscale morphology and photocurrent generation mechanism analysis, revealing that AGS NCs could serve as both exciton dissociation centers and charge transfer medium. This study shows that employment of AGS NCs is a facile way to improve the electrical and optical properties of organic photovoltaic devices.     

Polymer photovoltaic devices with highly transparent cathodes

In this paper, we demonstrate semi-transparent polymer solar cells employing a transparent cathode configuration, made of cesium carbonate (Cs₂CO₃)/silver (Ag)/indium tin oxide (ITO), which exhibited high transmittance in the visible regime. The device performance of the semi-transparent devices was significantly improved after thermal post-annealing and incorporating an Al counter-electrode (CE) grid. Further, the short-circuit current density increased almost linearly with the incident light intensity, suggesting efficient charge collection ability of the transparent cathode. Overall, the semi-transparent polymer solar cell exhibits a remarkable power conversion efficiency of 2.09%.     

Color switching behaviors of organic bistable light-emitting devices fabricated utilizing an aluminum-nanoparticle-embedded tris(8-hydroxyquinoline)aluminum layer and double emitting layers

Organic bistable light-emitting devices (OBLEDs) with an aluminum (Al)-nanoparticle-embedded tris(8-hydroxyquinoline)aluminum (Alq₃) layer and double emitting layers (EMLs) were fabricated to investigate their color switching behaviors. Scanning electron microscopy images showed that Al nanoparticles were formed on the Alq₃ layer. The Al nanoparticles in the Alq₃ layer improved the storage margin of the organic bistable devices (OBDs), and the double EMLs changed the emission color of the organic light-emitting devices (OLEDs) according to the variations of the ON and the OFF states of the OBDs. The variations of the ON and the OFF states of the OBDs could be clearly distinguished by the color switching of the OLED. The luminances of the OBLEDs with double EMLs in the ON and the OFF states were 641.80 and 22.25 cd/m², respectively, and their CIE coordinates at 20 V were (0.42, 0.46) and (0.51, 0.47), respectively, which corresponded to the ON and the OFF states of the OBLEDs.     

Enhanced power conversion efficiency of organic photovoltaic devices due to the surface plasmonic resonance effect generated utilizing Au-WO3 nanocomposites

Au-WO₃ nanocomposites (NCs) were used as a hole transport layer (HTL) to enhance the power conversion efficiency (PCE) of organic photovoltaic (OPV) cells. The photon absorption of the active layer in the OPV cells was increased due to the plasmonic effect caused by the Au-WO₃ NCs, resulting in an enhanced short-circuit current density for the OPV cells with the Au-WO₃ NC HTL. The value of the root-mean-square roughness of the Au-WO₃ NC film was smaller than that of the WO₃ NP film, resulting in a more efficient transport of holes from the active layer. The PCE of the OPV cell with an Au-WO₃ NCs HTL with an Au NP concentration of 10 wt% was improved by 60.37% in comparison with that with WO₃ nanoparticles. The enhancement of the PCE was attributed to both an increase in the efficiency of the hole transport at an Au-WO₃ NCs HTL with an Au NP concentration of 10 wt%/active layer heterointerface and an enhanced photon absorption due to the localized surface plasmon resonance effect of the Au-WO₃ NCs.     

Cover Picture: An Organic Light‐Emitting Diode with Field‐Effect Electron Transport (Adv. Funct. Mater. 1/2008)

The cover shows an organic light‐emitting diode with remote metallic cathode, reported by Sarah Schols and co‐workers on p. 136. The metallic cathode is displaced from the light‐emission zone by one to several micrometers. The injected electrons accumulate at an organic heterojunction and are transported to the light‐emission zone by field‐effect. The achieved charge‐carrier mobility and in combination with reduced optical absorption losses because of the remoteness of the cathode may lead to applications as waveguide OLEDs and possibly a laser structure. (The result was obtained in the EU‐funded project “OLAS” IST‐ FP6‐015034.) We describe an organic light‐emitting diode (OLED) using field‐effect to transport electrons. The device is a hybrid between a diode and a field‐effect transistor. Compared to conventional OLEDs, the metallic cathode is displaced by one to several micrometers from the light‐emitting zone. This micrometer‐sized distance can be bridged by electrons with enhanced field‐effect mobility. The device is fabricated using poly(triarylamine) (PTAA) as the hole‐transport material, tris(8‐hydroxyquinoline) aluminum (Alq₃) doped with 4‐(dicyanomethylene)‐2‐methyl‐6‐(julolindin‐4‐yl‐vinyl)‐4H‐pyran (DCM₂) as the active light‐emitting layer, and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C₁₃H₂₇), as the electron‐transport material. The obtained external quantum efficiencies are as high as for conventional OLEDs comprising the same materials. The quantum efficiencies of the new devices are remarkably independent of the current, up to current densities of more than 10 A cm^–2. In addition, the absence of a metallic cathode covering the light‐emission zone permits top‐emission and could reduce optical absorption losses in waveguide structures. These properties may be useful in the future for the fabrication of solid‐state high‐brightness organic light sources.     

Organic light-emitting devices with double-block layer

We report on the fabrication of organic light-emitting devices (OLEDs) using double-block layers on the electron transport layer and emitting layer. The current efficiency of the organic light-emitting diode is improved by 43% to 9.16 cd A⁻¹ as compared to the device with a single host of Alq₃ as the electron transport layer. The maximum luminance is over 23 750 cd m⁻² at the bias of 18 V and the current of 338.3 mA cm⁻², which is 33% higher than the single host Alq₃ device without block layer. Using a step-by-step procedure to smooth electron injection and transport, the energy levels introduced by the insertion layers are an effective method of improving the luminance characteristics.     

Optimising the efficiency of carbazole co-polymer solar-cells by control over the metal cathode electrode

We have explored the effect of a range of different cathode materials on the power conversion efficiency of organic (polymer) solar cells based on a blend of the conjugated polymer poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) with the fullerene acceptor PC₇₀BM. We use a transfer matrix reflectivity model to quantify the optical properties of the cathode and the device structure on its operational efficiency and compare this with the results of experimental measurements. We show that both optical and electrical effects play a role in determining overall device efficiency through their impact on short-circuit current, open circuit voltage and fill-factor. We use our model to demonstrate that devices composed of a thin (60–70 nm) active semiconductor layer and a composite cathode composed of a 5 nm thick layer of calcium capped by aluminium combine low optical loss and improved charge extraction and optimised power conversion efficiency.     

Improved property in organic light-emitting diode utilizing two Al/Alq3 layers

We reported on the fabrication of organic light-emitting devices (OLEDs) utilizing the two Al/Alq₃ layers and two electrodes. This novel green device with structure of Al(110 nm)/tris(8-hydroxyquinoline) aluminum (Alq₃)(65 nm)/Al(110 nm)/Alq₃(50 nm)/N,N′-dipheny1-N, N′-bis-(3-methy1phyeny1)-1, 1′-bipheny1-4, 4′-diamine (TPD)(60 nm)/ITO(60 nm)/Glass. TPD were used as holes transporting layer (HTL), and Alq₃ was used as electron transporting layer (ETL), at the same time, Alq₃ was also used as emitting layer (EL), Al and ITO were used as cathode and anode, respectively. The results showed that the device containing the two Al/Alq₃ layers and two electrodes had a higher brightness and electroluminescent efficiency than the device without this layer. At current density of 14 mA/cm², the brightness of the device with the two Al/Alq₃ layers reach 3693 cd/m², which is higher than the 2537 cd/m² of the Al/Alq₃/TPD:Alq₃/ITO/Glass device and the 1504.0 cd/m² of the Al/Alq₃/TPD/ITO/Glass. Turn-on voltage of the device with two Al/Alq₃ layers was 7 V, which is lower than the others.     

Investigation of TDAPBs as hole‐transporting materials for organic light‐emitting devices (OLEDs)

The performance of organic light‐emitting devices (OLEDs) is strongly influenced by the electronic properties of the employed materials. In order to determine the effect of these materials' parameters, several different hole‐transporting 1,3,5‐tris(4‐diphenylaminophenyl)benzenes (TDAPBs) were synthesised. These TDAPBs contained different substituents, different numbers of substituents and different positions of theses substituents. For the evaluation of the electronic properties, cyclic voltammetry was employed in order to determine the HOMO values, and time‐of‐flight (TOF) measurements to obtain the hole mobilities. OLEDs were prepared consisting of the TDAPBs blended in a polymer matrix, and of Alq₃ as electron‐conducting and light‐emitting layer. These devices were investigated regarding their current density/voltage characteristics, efficiencies, onset voltages for electroluminescence, and lifetimes. For hole‐transporting blend systems an exponential relationship between the current density and the HOMO levels of the TDAPBs was found. However, even though the HOMO values cover a range from −5.09 to −5.35 eV, no effects on the performance of the OLEDs were detected for electroluminescent two‐layer systems. In this case the initial voltage seems to be a determining parameter for the behaviour of the devices during operation. Copyright © 1999 John Wiley & Sons, Ltd.     

Enhanced power conversion efficiency of organic solar cells by embedding Ag nanoparticles in exciton blocking layer

We demonstrate the power conversion efficiency of bulk heterojunction organic solar cells can be enhanced by introducing Ag nanoparticles into organic exciton blocking layer. The Ag nanoparticles were incorporated into the exciton blocking layer by thermal evaporation. Compared with the conventional cathode contact materials such as Al, LiF/Al, devices with Ag nanoparticles incorporated in the exciton blocking layer showed lower series resistances and higher fill factors, leading to a 3.2% power conversion efficiency with a 60 nm active layer; whereas, the conventional devices have only 2.0–2.3% power conversion efficiency. Localized surface plasmon resonances by the Ag nanoparticles and their contribution to photocurrent were also discussed by simulating optical absorptions using a FDTD (finite-difference-time-domain) method.     

Improved solar cell performance by adding ultra-thin Alq3 at the cathode interface

We report a new finding that ultra-thin Tris(8-hydroxyquinoline) aluminum (Alq₃) improves an Al cathode interface for photovoltaic (PV) with inorganic amorphous silicon (a-Si) as well as organic bulk heterojunction (BHJ) photoactive layers. Contact resistance characterization is used to investigate the effect of the added Alq₃. The experimental results show that the inserted Alq₃ is observed to reduce the contact resistance at the cathode interface. Supported by our numerical analysis, the enhanced cathode interface by Alq₃ provides better Ohmic contact, thereby increasing V_oc. The overall power efficiency is enhanced accordingly benefited by the Alq₃ added cathode regardless of photoactive layers.