Jinhong Du

25th Anniversary Article: Carbon Nanotube‐ and Graphene‐Based Transparent Conductive Films for Optoelectronic Devices

Carbon nanotube (CNT)- and graphene (G)-based transparent conductive films (TCFs) are two promising alternatives for commonly-used indium tin oxide-based TCFs for future flexible optoelectronic devices. This review comprehensively summarizes recent progress in the fabrication, properties, modification, patterning, and integration of CNT- and G-TCFs into optoelectronic devices. Their potential applications and challenges in optoelectronic devices, such as organic photovoltaic cells, organic light emitting diodes and touch panels, are discussed in detail. More importantly, their key characteristics and advantages for use in these devices are compared. Despite many challenges, CNT- and G-TCFs have demonstrated great potential in various optoelectronic devices and have already been used for some products like touch panels of smartphones. This illustrates the significant opportunities for the industrial use of CNTs and graphene, and hence pushes nanoscience and nanotechnology one step towards practical applications.

The fabrication of a carbon nanotube transparent conductive film by electrophoretic deposition and hot-pressing transfer

A super-flexible single-walled carbon nanotube (SWCNT) transparent conductive film (TCF) was produced based on a combination of electrophoretic deposition (EPD) and hot-pressing transfer. EPD was performed in a diluted SWCNT suspension with high zeta potential prepared by a pre-dispersion-then-dilution procedure using sodium dodecyl sulfate as the surfactant and negative charge supplier. A SWCNT film was deposited on a stainless steel anode surface by direct current electrophoresis and then transferred to a poly(ethylene terephthalate) substrate by hot-pressing to achieve a flexible SWCNT TCF. The SWCNT TCF obtained by this technique can achieve a sheet resistance of 220 Omega/sq with 81% transparency at 550 nm wavelength and a strong adhesion to the substrate. More importantly, no decrease in the conductivity of the SWCNT TCF was detected after 10 000 cycles of repeated bending. The result indicates that the EPD and hot-pressing transfer technique is an effective approach for fabricating a carbon nanotube TCF with excellent flexibility.

Tuning the Electrical and Optical Properties of Graphene by Ozone Treatment for Patterning Monolithic Transparent Electrodes

Tunable electrical and optical properties of graphene are vital to promote its use as film electrodes in a variety of devices. We developed an etching-free ozone treatment method to continuously tune the electrical resistance and optical transmittance of graphene films by simply varying the time and temperature of graphene exposure to ozone. Initially, ozone exposure dramatically decreases the electrical resistance of graphene films by p-doping, but this is followed by increases in the resistance and optical transmittance as a result of surface oxidation. The rate of resistance increase can be significantly increased by raising the treatment temperature. The ozone-oxidized graphene is not removed but is gradually transformed to graphene oxide (GO). On the basis of such effects of ozone treatment, we demonstrate a well-defined graphene pattern by using ozone photolithography, in which the ozone-treated graphene electrodes are monolithic but separated by insulating GO regions. Such a monolithic graphene pattern shows low optical contrast, a clean and more hydrophilic surface, indicating the promising use of ozone treatment to achieve high-performance graphene-based optoelectronic devices.

Reduced graphene oxide with a highly restored π-conjugated structure for inkjet printing and its use in all-carbon transistors

AbstractAn inkjet-printed graphene film is of great importance for next-generation flexible, low cost and high performance electronic devices. However, due to the limitation of the inkjet printing process, the electrical conductivity of inkjet-printed graphene films is limited to ∼10 S·cm−1, and achieving a high conductivity of the printed graphene films remains a big challenge. Here, we develop a “weak oxidation-vigorous exfoliation” strategy to tailor graphene oxide (GO) for meeting all the requirements of highly conductive inkjet-printed graphene films, including a more intact carbon plane and suitable size. The π-conjugated structure of the resulting graphene has been restored to a high degree, and its printed films show an ultrahigh conductivity of ∼420 S·cm−1, which is tens of times higher than previously reported results, suggesting that, aside from developing a highly efficient reduction method, tuning the GO structure could be an alternative way to produce high quality graphene sheets. Using inkjet-printed graphene patterns as source/drain/gate electrodes, and semiconducting single-walled carbon nanotubes (SWCNTs) as channels, we fabricated an all-carbon field effect transistor which shows excellent performance (an on/off ratio of ∼104 and a mobility of ∼8 cm2·V−1·s−1) compared to previously reported CNT-based transistors, promising the use of nanocarbon materials, graphene and SWCNTs in printed electronics, especially where high performance and flexibility are needed.

Rosin-enabled ultraclean and damage-free transfer of graphene for large-area flexible organic light-emitting diodes

The large polymer particle residue generated during the transfer process of graphene grown by chemical vapour deposition is a critical issue that limits its use in large-area thin-film devices such as organic light-emitting diodes. The available lighting areas of the graphene-based organic light-emitting diodes reported so far are usually <1 cm2. Here we report a transfer method using rosin as a support layer, whose weak interaction with graphene, good solubility and sufficient strength enable ultraclean and damage-free transfer. The transferred graphene has a low surface roughness with an occasional maximum residue height of about 15 nm and a uniform sheet resistance of 560 Ω per square with about 1% deviation over a large area. Such clean, damage-free graphene has produced the four-inch monolithic flexible graphene-based organic light-emitting diode with a high brightness of about 10,000 cd m−2 that can already satisfy the requirements for lighting sources and displays.

Positive temperature coefficient thermistors based on carbon nanotube/polymer composites

In order to explore availability of carbon nanotube (CNT)-based positive temperature coefficient (PTC) thermistors in practical application, we prepared carbon nanotube (CNT) filled high density polyethylene (HDPE) composites by using conventional melt-mixing methods, and investigated their PTC effects in details. The CNT-based thermistors exhibit much larger hold current and higher hold voltage, increasing by 129% in comparison with the commercial carbon black (CB) filled HDPE thermistors. Such high current-bearing and voltage-bearing capacity for the CNT/HDPE thermistors is mainly attributed to high thermal conductivity and heat dissipation of entangled CNT networks. Moreover, the CNT/HDPE thermistors exhibit rapid electrical response to applied voltages, comparable to commercial CB-based thermistors. In light of their high current-bearing capacity and quick response, the CNT-based thermistors have great potential to be used as high-performance thermistors in practical application, especially in some critical circumstances of high temperature, large applied currents, and high applied voltages.

Direct writing of graphene patterns and devices on graphene oxide films by inkjet reduction

Direct writing of graphene patterns and devices may significantly facilitate the application of graphene-based flexible electronics. In terms of scalability and cost efficiency, inkjet printing is very competitive over other existing directwriting methods. However, it has been challenging to obtain highly stable and clog-free graphene-based ink. Here, we report an alternative and highly efficient technique to directly print a reducing reagent on graphene oxide film to form conductive graphene patterns. By this “inkjet reduction” method, without using any other microfabrication technique, conductive graphene patterns and devices for various applications are obtained. The ionic nature of the reductant ink makes it clog-free and stable for continuous and large-area printing. The method shows self-limited reduction feature, which enables electrical conductivity of graphene patterns to be tuned within 5 orders of magnitude, reaching as high as 8,000 S·m–1. Furthermore, this method can be extended to produce noble metal/graphene composite patterns. The devices, including transistors, biosensors, and surfaceenhanced Raman scattering substrates, demonstrate excellent functionalities. This work provides a new strategy to prepare large-area graphene-based devices that is low-cost and highly efficient, promising to advance research on graphenebased flexible electronics.