Work‐Function Engineering of Graphene Anode by Bis(trifluoromethanesulfonyl)amide Doping for Efficient Polymer Light‐Emitting Diodes

Graphene has been considered to be a potential alternative transparent and flexible electrode for replacing commercially available indium tin oxide (ITO) anode. However, the relatively high sheet resistance and low work function of graphene compared with ITO limit the application of graphene as an anode for organic or polymer light‐emitting diodes (OLEDs or PLEDs). Here, flexible PLEDs made by using bis(trifluoromethanesulfonyl)amide (TFSA, [CF₃SO₂]₂NH) doped graphene anodes are demonstrated to have low sheet resistance and high work function. The graphene is easily doped with TFSA by means of a simple spin‐coating process. After TFSA doping, the sheet resistance of the TFSA‐doped five‐layer graphene, with optical transmittance of ≈88%, is as low as ≈90 Ω sq^?1. The maximum current efficiency and power efficiency of the PLED fabricated on the TFSA‐doped graphene anode are 9.6 cd A^?1 and 10.5 lm W^?1, respectively; these values are markedly higher than those of the PLED fabricated on pristine graphene anode and comparable to those of an ITO anode.     

A stacked chalcopyrite thin‐film tandem solar cell with 1.2 V open‐circuit voltage

CuGaSe₂ (CGS) thin films were prepared on tin‐doped indium oxide (ITO) coated soda‐lime glass substrates by thermal co‐evaporation to fabricate transparent solar cells. The films consisted of columnar grains with a diameter of approximately 1 μm. Some deterioration of the transparency of the ITO was observed after deposition of the CGS film. The CGS solar cells were electrically connected in series with Cu(In,Ga)Se₂ (CIGS) solar cells and mechanically stacked on the CIGS cells to construct tandem cells. The tandem solar cell with the CGS cell as the top cell showed an efficiency of 7.4% and an open‐circuit voltage of 1.18 V (AM 1.5, total area). Copyright © 2003 John Wiley & Sons, Ltd.     

An Indium‐Free Anode for Large‐Area Flexible OLEDs: Defect‐Free Transparent Conductive Zinc Tin Oxide

Flexible large‐area organic light‐emitting diodes (OLEDs) require highly conductive and transparent anodes for efficient and uniform light emission. Tin‐doped indium oxide (ITO) is the standard anode in industry. However, due to the scarcity of indium, alternative anodes that eliminate its use are highly desired. Here an indium‐free anode is developed by a combinatorial study of zinc oxide (ZnO) and tin oxide (SnO₂), both composed of earth‐abundant elements. The optimized Zn–Sn–O (ZTO) films have electron mobilities of up to 21 cm² V^?1 s^?1, a conductivity of 245 S cm^?1, and <5% absorptance in the visible range of the spectrum. The high electron mobilities and low surface roughness (<0.2 nm) are achieved by producing dense and void‐free amorphous layers as confirmed by transmission electron microscopy. These ZTO layers are evaluated for OLEDs in two anode configurations: i) 10 cm² devices with ZTO/Ag/ZTO and ii) 41 cm² devices with ZTO plus a metal grid. The ZTO layers are compatible with OLED processing steps and large‐area white OLEDs fabricated with the ZTO/grid anode show better performance than those with ITO/grid anodes. These results confirm that ZTO has the potential as an In‐free and Earth‐abundant alternative to ITO for large‐area flexible OLEDs.     

Highly Conductive and Transparent PEDOT:PSS Films with a Fluorosurfactant for Stretchable and Flexible Transparent Electrodes

Highly conductive and transparent poly‐(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) films, incorporating a fluorosurfactant as an additive, have been prepared for stretchable and transparent electrodes. The fluorosurfactant‐treated PEDOT:PSS films show a 35% improvement in sheet resistance (R_s) compared to untreated films. In addition, the fluorosurfactant renders PEDOT:PSS solutions amenable for deposition on hydrophobic surfaces, including pre‐deposited, annealed films of PEDOT:PSS (enabling the deposition of thick, highly conductive, multilayer films) and stretchable poly(dimethylsiloxane) (PDMS) substrates (enabling stretchable electronics). Four‐layer PEDOT:PSS films have an R_s of 46 Ω per square with 82% transmittance (at 550 nm). These films, deposited on a pre‐strained PDMS substrate and buckled, are shown to be reversibly stretchable, with no change to R_s, during the course of over 5000 cycles of 0 to 10% strain. Using the multilayer PEDOT:PSS films as anodes, indium tin oxide (ITO)‐free organic photovoltaics are prepared and shown to have power conversion efficiencies comparable to that of devices with ITO as the anode. These results show that these highly conductive PEDOT:PSS films can not only be used as transparent electrodes in novel devices (where ITO cannot be used), such as stretchable OPVs, but also have the potential to replace ITO in conventional devices.     

Fully Transparent p‐MoTe2 2D Transistors Using Ultrathin MoOx/Pt Contact Media for Indium‐Tin‐Oxide Source/Drain

Since transition metal dichalcogenide (TMD) semiconductors are found as 2D van der Waals materials with a discrete energy bandgap, many 2D‐like thin field effect transistors (FETs) and PN diodes are reported as prototype electrical and optoelectronic devices. As a potential application of display electronics, transparent 2D FET devices are also reported recently. Such transparent 2D FETs are very few in report, yet no p‐type channel 2D‐like FETs are seen. Here, 2D‐like thin transparent p‐channel MoTe₂ FETs with oxygen (O₂) plasma‐induced MoO_x/Pt/indium‐tin‐oxide (ITO) contact are reported for the first time. For source/drain contact, 60 s short O₂ plasma and ultrathin Pt‐deposition processes on MoTe₂ surface are sequentially introduced before ITO thin film deposition and patterning. As a result, almost transparent 2D FETs are obtained with a decent mobility of ≈5 cm² V^?1 s^?1, a high ON/OFF current ratio of ≈10⁵, and 70% transmittance. In particular, for normal MoTe₂ FETs without ITO, O₂ plasma process greatly improves the hole injection efficiency and device mobility (≈60 cm² V^?1 s^?1), introducing ultrathin MoO_x between Pt source/drain and MoTe₂. As a final device application, a photovoltaic current modulator, where the transparent FET stably operates as gated by photovoltaic effects, is integrated.     

Reducible‐Shell‐Derived Pure‐Copper‐Nanowire Network and Its Application to Transparent Conducting Electrodes

The concept of using core Cu nanowires (CuNWs) that are conformally encapsulated by a reducible fugitive material for transparent conducting electrodes (TCEs) with high oxidation stability is presented. By the chemical reaction of an acid with surface oxide and hydroxide, a uniform surface shell layer is readily obtained on each CuNW upon adding lactic acid to the CuNW dispersion. The Cu lactate shell prevents the core CuNW from oxidizing during storage and film formation, enabling the core Cu nanowires to maintain their characteristic optoelectronic properties. Through simple thermal annealing under a nitrogen atmosphere, the Cu lactate shell is easily decomposed to expose the underlying pure Cu, providing an effective way to produce a pure‐CuNW‐network TCE with a sheet resistance of 19.8 Ω sq^?1 and an optical transmittance of 85.5% at 550 nm. The application of the CuNW‐based TCE to the transparent top electrode in organometallic halide perovskite solar cells is further demonstrated for the first time, yielding a power‐conversion efficiency 9.88% as compared to that of 13.39% for conventional perovskite solar cells with an indium–tin‐oxide electrode. This study proposes the high feasibility of these CuNWs as a vacuum‐free and noble‐metal‐free transparent‐window electrode in perovskite solar cells.     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

Does Electronic Type Matter when Single‐Walled Carbon Nanotubes are Used for Electrode Applications?

Single‐walled carbon nanotube (SWNT) electrodes that are chemically and mechanically robust are fabricated using a simple drop cast method with thermal annealing and acid treatment. An electronic‐type selective decrease in sheet resistance of SWNT electrodes with HNO₃ treatment is shown. Semiconducting SWNTs show a significantly higher affinity toward hole doping in comparison to metallic SWNTs; a ≈12‐fold and a ≈fivefold drop in sheet resistance, respectively. The results suggest the insignificance of the electronic type of the SWNTs for the film conductivity after hole doping. The SWNT films have been employed as transparent hole extracting electrodes in bulk heterojunction (BHJ) organic photovoltaics. Performances of the devices enlighten the fact that the electrode film morphology dominates over the electronic type of the doped SWNTs with similar sheet resistance and optical transmission. The power conversion efficiency (PCE) of 4.4% for the best performing device is the best carbon nanotube transparent electrode incorporated large area BHJ solar cell reported to date. This PCE is 90% in terms of PCEs achieved using indium tin oxide (ITO) based reference devices with identical film fabrication parameters indicating the potential of the SWNT electrodes as an ITO replacement toward realization of all carbon solar cells.     

Thermally Stable Transparent Resistive Random Access Memory based on All‐Oxide Heterostructures

An all‐oxide transparent resistive random access memory (T‐RRAM) device based on hafnium oxide (HfO_x) storage layer and indium‐tin oxide (ITO) electrodes is fabricated in this work. The memory device demonstrates not only good optical transmittance but also a forming‐free bipolar resistive switching behavior with room‐temperature R_OFF/R_ON ratio of 45, excellent endurance of ≈5 × 10⁷ cycles and long retention time over 10⁶ s. More importantly, the HfO_x based RRAM carries great ability of anti‐thermal shock over a wide temperature range of 10 K to 490 K, and the high R_OFF/R_ON ratio of ≈40 can be well maintained under extreme working conditions. The field‐induced electrochemical formation and rupture of the robust metal‐rich conductive filaments in the mixed‐structure hafnium oxide film are found to be responsible for the excellent resistance switching of the T‐RRAM devices. The present all‐oxide devices are of great potential for future thermally stable transparent electronic applications.     

Nanostructured Antimony‐Doped Tin Oxide Layers with Tunable Pore Architectures as Versatile Transparent Current Collectors for Biophotovoltaics

Nanostructured transparent conducting oxide (TCO) layers gain increasing importance as high surface area electrodes enabling incorporation of functional redox species with high loading. The fabrication of porous TCO films, namely, antimony‐doped tin oxide (ATO), is reported using the self‐assembly of preformed ATO nanocrystals with poly(ethylene oxide‐b‐hexyl acrylate) (PEO‐b‐PHA) block copolymer. The high molar mass of the polymer and tunable solution processing conditions enable the fabrication of TCO electrodes with pore sizes ranging from mesopores to macropores. Particularly notable is access to uniform macroporous films with a nominal pore size of around 80 nm, which is difficult to obtain by other techniques. The combination of tunable porosity with a large conducting interface makes the obtained layers versatile current collectors with adjustable performance. While all the obtained electrodes incorporate a large amount of small redox molecules such as molybdenum polyoxometalate, only the electrodes with sufficiently large macropores are able to accommodate high amounts of bulky photoactive photosystem I (PSI) protein complexes. The 11‐fold enhancement of the current response of PSI modified macroporous ATO electrodes compared to PSI on planar indium tin oxide (ITO), makes this type of electrodes promising candidates for the development of biohybrid devices.     

TiN Nanofibers: A New Material with High Conductivity and Transmittance for Transparent Conductive Electrodes

Motivated by the rising cost of tin‐doped indium oxide (ITO), the search for new transparent electrode materials to replace ITO is ongoing. TiN exhibits high electric conductivity, however, it is generally non‐transparent. Here, nanostructured TiN fiber patterns are synthesized on quartz glass and the resulting materials have a combination of high electric conductivity and optical transparency. A low sheet resistance of 15.8 Ohm sq^?1 at 84% transparency is achieved on TiN nanofiber arrayed quartz glass. The achievements show a successful integration of electric and optical properties in ceramic nanofibers and provide a method for finding new materials to replace traditional ITO‐based transparent electrodes.     

Aqueous Deposition of Ultraviolet Luminescent Columnar Tin‐Doped Indium Hydroxide Films

Indium tin oxide (ITO) has attracted intense interest as the most important transparent conducting oxide (TCO) that sees wide use in many opto‐electronic and photo‐chemical devices. The goal of this study is to explore the possibility of depositing ITO thin films using a bioinspired aqueous deposition route as an alternative. On the surface of sulfonated‐self assembled monolayers, Sn‐doped indium hydroxide films are obtained via a hydrogen peroxide‐assisted method. As a result, the as‐deposited indium tin hydroxide films possess a single hexagonal phase of In(OH)₃· xH₂O (0 ≤ x ≤ 1) with Sn doping percentage of (1.7 ± 0.2) at % and a column‐like hierachical microstructure. Structural, compositional and property studies, including electron microscopy, X‐ray diffraction, photoelectron spectroscopy, optical transmittance, photoluminescence and four‐probe conductivity measurements, are conducted. The possible mechanism based on oriented attachment is discussed for the film growth. Strong room temperature photoluminescence within the near UV range is observed in the case of Sn‐doped, but not in the one of the pure In(OH)₃· xH₂O films. Annealing of the indium tin hydroxide films above 200 °C gives nanocrystalline Sn:In₂O₃ films with higher UV and visible transparency and electrical conductivity compared with those of pure In₂O₃ films. The influence of annealing atmosphere is investigated.     

Light‐Responsive Ion‐Redistribution‐Induced Resistive Switching in Hybrid Perovskite Schottky Junctions

Hybrid Perovskites have emerged as a class of highly versatile functional materials with applications in solar cells, photodetectors, transistors, and lasers. Recently, there have also been reports on perovskite‐based resistive switching (RS) memories, but there remain open questions regarding device stability and switching mechanism. Here, an RS memory based on a high‐quality capacitor structure made of an MAPbBr₃ (CH₃NH₃PbBr₃) perovskite layer sandwiched between Au and indium tin oxide (ITO) electrodes is reported. Such perovskite devices exhibit reliable RS with an ON/OFF ratio greater than 10³, endurance over 10³ cycles, and a retention time of 10⁴ s. The analysis suggests that the RS operation hinges on the migration of charged ions, most likely MA vacancies, which reversibly modifies the perovskite bulk transport and the Schottky barrier at the MAPbBr₃/ITO interface. Such perovskite memory devices can also be fabricated on flexible polyethylene terephthalate substrates with high bendability and reliability. Furthermore, it is found that reference devices made of another hybrid perovskite MAPbI₃ consistently exhibit filament‐type switching behavior. This work elucidates the important role of processing‐dependent defects in the charge transport of hybrid perovskites and provides insights on the ion‐redistribution‐based RS in perovskite memory devices.     

Reduced Graphene Oxide Micromesh Electrodes for Large Area,Flexible, Organic Photovoltaic Devices

A laser‐based patterning technique—compatible with flexible, temperature‐sensitive substrates—for the production of large area reduced graphene oxide micromesh (rGOMM) electrodes is presented. The mesh patterning can be accurately controlled in order to significantly enhance the electrode transparency, with a subsequent slight increase in the sheet resistance, and therefore improve the tradeoff between transparency and conductivity of reduced graphene oxide (rGO) layers. In particular, rGO films with an initial transparency of ≈20% are patterned, resulting in rGOMMs films with a ≈59% transmittance and a sheet resistance of ≈565 Ω sq^?1, that is significantly lower than the resistance of ≈780 Ω sq^?1, exhibited by the pristine rGO films at the same transparency. As a proof‐of‐concept application, rGOMMs are used as the transparent electrodes in flexible organic photovoltaic (OPV) devices, achieving power conversion efficiency of 3.05%, the highest ever reported for flexible OPV devices incorporating solution‐processed graphene‐based electrodes. The controllable and highly reproducible laser‐induced patterning of rGO hold enormous promise for both rigid and flexible large‐scale organic electronic devices, eliminating the lag between graphene‐based and indium–tin oxide electrodes, while providing conductivity and transparency tunability for next generation flexible electronics.     

Development of Nano‐TiO2 dye sensitised solar cells on high mobility transparent conducting oxide thin films

The optical transmission of dye‐sensitised solar cells (DSCs) can be tuned by altering the dye and/or particle size of the mesoporous TiO₂ layers, to allow their application as the top device in tandem solar cells. To benefit from this semi‐transparency, parasitic optical losses by the transparent electrodes must be minimised. This work investigates the influence of using two different transparent conductors, namely, the high mobility material titanium doped indium oxide (ITiO) and fluorine doped tin oxide (FTO) as electrodes for semi‐transparent DSCs. The overall NIR transparency through the DSCs increased significantly as each FTO electrode was replaced by an ITiO electrode. This increase was from 20–45% in the 1300–700 nm wavelength range for fully FTO‐based cells, to about 60% for fully ITiO‐based cells, across the same spectrum. DSCs prepared on these electrodes exhibited short circuit currents ranging from 14·0–14·9 mA/cm². The conversion efficiency of the cell with ITiO as both the front and rear electrodes was 5·8%, which though significant, was lower than the 8·2% attained by the cell using FTO electrodes, as a result of a lower fill factor. Improvements in the ITiO thermal stability and in the processing of the TiO₂ interfacial layer are expected to improve the cell efficiency of such single DSC devices. The high current density and optical transparency of ITiO‐based DSCs make them an interesting option for tandem solar cells. Copyright © 2008 John Wiley & Sons, Ltd.     

Trilayer Nanomesh Films with Tunable Wettability as Highly Transparent,Flexible, and Recyclable Electrodes

Metallic mesh materials are promising candidates to replace traditional transparent conductive oxides such as indium tin oxide (ITO) that is restricted by the limited indium resource and its brittle nature. The challenge of metal based transparent conductive networks is to achieve high transmittance, low sheet resistance, and small perforation size simultaneously, all of which significantly relate to device performances in optoelectronics. In this work, trilayer dielectric/metal/dielectric (D/M/D) nanomesh electrodes are reported with precisely controlled perforation size, wire width, and uniform hole distribution employing the nanosphere lithography technique. TiO₂/Au/TiO₂ nanomesh films with small hole diameter (≤700 nm) and low thickness (≤50 nm) are shown to yield high transmittance (>90%), low sheet resistance (≤70 Ω sq^?1), as well as outstanding flexural endurance and feasibility for large area patterning. Further, by tuning the surface wettability, these films are applied as easily recyclable flexible electrodes for electrochromic devices. The simple and cost‐effective fabrication of diverse D/M/D nanomesh transparent conductive films with tunable optoelectronic properties paves a way for the design and realization of specialized transparent electrodes in optoelectronics.     

Low‐Temperature,Nontoxic Water‐Induced Metal‐Oxide Thin Films and Their Application in Thin‐Film Transistors

Here, a simple, nontoxic, and inexpensive “water‐inducement” technique for the fabrication of oxide thin films at low annealing temperatures is reported. For water‐induced (WI) precursor solution, the solvent is composed of water without additional organic additives and catalysts. The thermogravimetric analysis indicates that the annealing temperature can be lowered by prolonging the annealing time. A systematic study is carried out to reveal the annealing condition dependence on the performance of the thin‐film transistors (TFTs). The WI indium‐zinc oxide (IZO) TFT integrated on SiO₂ dielectric, annealed at 300 °C for 2 h, exhibits a saturation mobility of 3.35 cm² V^?1 s^?1 and an on‐to‐off current ratio of ≈10⁸. Interestingly, through prolonging the annealing time to 4 h, the electrical parameters of IZO TFTs annealed at 230 °C are comparable with the TFTs annealed at 300 °C. Finally, fully WI IZO TFT based on YO_x dielectric is integrated and investigated. This TFT device can be regarded as “green electronics” in a true sense, because no organic‐related additives are used during the whole device fabrication process. The as‐fabricated IZO/YO_x TFT exhibits excellent electron transport characteristics with low operating voltage (≈1.5 V), small subthreshold swing voltage of 65 mV dec^?1 and the mobility in excess of 25 cm² V^?1 s^?1.     

Strongly Anisotropic Thermal Conductivity of Free‐Standing Reduced Graphene Oxide Films Annealed at High Temperature

Thermal conductivity of free‐standing reduced graphene oxide films subjected to a high‐temperature treatment of up to 1000 °C is investigated. It is found that the high‐temperature annealing dramatically increases the in‐plane thermal conductivity, K, of the films from ≈3 to ≈61 W m^?1 K^?1 at room temperature. The cross‐plane thermal conductivity, K_⊥, reveals an interesting opposite trend of decreasing to a very small value of ≈0.09 W m^?1 K^?1 in the reduced graphene oxide films annealed at 1000 °C. The obtained films demonstrate an exceptionally strong anisotropy of the thermal conductivity, K/K_⊥ ≈ 675, which is substantially larger even than in the high‐quality graphite. The electrical resistivity of the annealed films reduces to 1–19 Ω □^?1. The observed modifications of the in‐plane and cross‐plane thermal conductivity components resulting in an unusual K/K_⊥ anisotropy are explained theoretically. The theoretical analysis suggests that K can reach as high as ≈500 W m^?1 K^?1 with the increase in the sp² domain size and further reduction of the oxygen content. The strongly anisotropic heat conduction properties of these films can be useful for applications in thermal management.     

Highly Conductive Poly(3,4‐ethylenedioxythiophene):Poly (styrenesulfonate) Films Using 1‐Ethyl‐3‐methylimidazolium Tetracyanoborate Ionic Liquid

Highly conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films are obtained using ionic liquids as additives. Upon adding 1‐ethyl‐3‐methylimidazolium tetracyanoborate (EMIM TCB) to the conducting polymer, the conductivity increases to 2084 S cm^?1; this is attributed to the phase separation of PSS leading to a structural change in the film. A comparative study with 1‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMIM BF₄) shows that EMIM TCB gives higher conductivity and transmittance and can be regarded as one of the most promising additives for the preparation of indium tin oxide (ITO)‐free organic devices using PEDOT:PSS/EMIM TCB as electrodes.     

Low‐Temperature‐Processed Printed Metal Oxide Transistors Based on Pure Aqueous Inks

Additive patterning of transparent conducting metal oxides at low temperatures is a critical step in realizing low‐cost transparent electronics for display technology and photovoltaics. In this work, inkjet‐printed metal oxide transistors based on pure aqueous chemistries are presented. These inks readily convert to functional thin films at lower processing temperatures (T ≤ 250 °C) relative to organic solvent‐based oxide inks, facilitating the fabrication of high‐performance transistors with both inkjet‐printed transparent electrodes of aluminum‐doped cadmium oxide (ACO) and semiconductor (InO_x ). The intrinsic fluid properties of these water‐based solutions enable the printing of fine features with coffee‐ring free line profiles and smoother line edges than those formed from organic solvent‐based inks. The influence of low‐temperature annealing on the optical, electrical, and crystallographic properties of the ACO electrodes is investigated, as well as the role of aluminum doping in improving these properties. Finally, the all‐aqueous‐printed thin film transistors (TFTs) with inkjet‐patterned semiconductor (InO_x ) and source/drain (ACO) layers are characterized, which show ideal low contact resistance (R _c < 160 Ω cm) and competitive transistor performance (µ _lin up to 19 cm² V^?1 s^?1, Subthreshold Slope (SS) ≤150 mV dec^?1) with only low‐temperature processing (T ≤ 250 °C).