Reverse-Offset Printing of Polymer Resist Ink for Micrometer-Level Patterning of Metal and Metal-Oxide Layers.

Printed electronics has advanced during the recent decades in applications such as organic photovoltaic cells and biosensors. However, the main limiting factors preventing the more widespread use of printing in flexible electronics manufacturing are (i) the poor attainable linewidths via conventional printing methods (≫10 µm), (ii) the limited availability of printable materials (e.g., low work function metals), and (iii) the inferior performance of many printed materials when compared to vacuum-processed materials (e.g., printed vs sputtered ITO). Here, we report a printing-based, low-temperature, low-cost, and scalable patterning method that can be used to fabricate high-resolution, high-performance patterned layers with linewidths down to ∼1 µm from various materials. The method is based on sequential steps of reverse-offset printing (ROP) of a sacrificial polymer resist, vacuum deposition, and lift-off. The sharp vertical sidewalls of the ROP resist layer allow the patterning of evaporated metals (Al) and dielectrics (SiO) as well as sputtered conductive oxides (ITO), where the list is expandable also to other vacuum-deposited materials. The resulting patterned layers have sharp sidewalls, low line-edge roughness, and uniform thickness and are free from imperfections such as edge ears occurring with other printed lift-off methods. The applicability of the method is demonstrated with highly conductive Al (∼5 × 10-8 Ωm resistivity) utilized as transparent metal mesh conductors with ∼35 Ω□ at 85% transparent area percentage and source/drain electrodes for solution-processed metal-oxide (In2O3) thin-film transistors with ∼1 cm2/(Vs) mobility. Moreover, the method is expected to be compatible with other printing methods and applicable in other flexible electronics applications, such as biosensors, resistive random access memories, touch screens, displays, photonics, and metamaterials, where the selection of current printable materials falls short.

Reverse Offset Printing of Semidried Metal Acetylacetonate Layers and Its Application to a Solution-Processed IGZO TFT Fabrication.

The submicrometer resolution printing of various metal acetylacetonate complex inks including Fe, V, Mn, Co, Ni, Zn, Zr, Mo, and In was enabled by a robust ink formulation scheme which adopted a ternary solvent system where solubility, surface wettability, and drying as well as absorption behavior on a polydimethylsiloxane sheet were optimized. Hydrogen plasma in heated conditions resulted in bombarded, resistive, or conductive state depending on the temperature and the metal species. With a conductivity-bestowed layer of MoO x and a plasma-protecting layer of ZrO x situated on the top of an IGZO layer, a solution-processed TFT exhibiting an average mobility of 0.17 cm2/(V s) is demonstrated.

Far-UV Annealed Inkjet-Printed In2O3 Semiconductor Layers for Thin-Film Transistors on a Flexible Polyethylene Naphthalate Substrate.

The inkjet-printing process of precursor solutions containing In nitrate dissolved in 2-methoxyethanol is optimized using ethylene glycol as a cosolvent that allows the stabilization of the droplet formation, leading to a robust, repeatable printing process. The inkjet-printed precursor films are then converted to In2O3 semiconductors at flexible-substrate-compatible low temperatures (150-200 °C) using combined far-ultraviolet (FUV) exposure at ∼160 nm and thermal treatment. The compositional nature of the precursor-to-metal oxide conversion is studied using grazing incidence X-ray diffraction (GIXRD), X-ray reflectivity (XRR), and Fourier transform infrared (FTIR) spectroscopy that indicate that amorphous, high density (up to 5.87 g/cm3), and low impurity In2O3 films can be obtained using the combined annealing technique. Prolonged annealing (180 min) at 150 °C yields enhancement-mode TFTs with saturation mobility of 4.3 cm2/(Vs) and ∼1 cm2/(Vs) on rigid Si/SiO2 and flexible plastic PEN substrates, respectively. This paves the way for manufacturing relatively high-performance, printed metal-oxide TFT arrays on cheap, flexible substrate for commercial applications.

Flexography-Printed In2 O3 Semiconductor Layers for High-Mobility Thin-Film Transistors on Flexible Plastic Substrate.

Industrially scalable and roll-to-roll-compatible fabrication methods are utilized to fabricate high-mobility (≈8 cm(2) V(-1) s(-1) ) nanocrystalline In2 O3 thin-film transistors (TFTs) on an flexible plastic substrate. Flexographic printing of multiple thin In2 O3 semiconductor layers from precursor-solution is performed on a Al2 O3 gate dielectric obtained via atomic layer deposition. A low-temperature post-contact-annealing step allows control of the TFT device turn-on voltage to ≈0 V for enhancement-mode operation.

Roll-to-roll printed resistive WORM memory on a flexible substrate.

The fabrication process and the operation characteristics of a fully roll-to-roll printed resistive write-once-read-many memory on a flexible substrate are presented. The low-voltage (<10 V) write operation of the memories from a high resistivity '0' state to a low resistivity '1' state is based on the rapid electrical sintering of bits containing silver nanoparticles. The bit ink is formulated by mixing two commercially available silver nanoparticle inks in order to tune the initial square resistance of the bits and to create a self-organized network of percolating paths. The electrical performance of the memories, including read and write characteristics, is described and the long-term stability of the less stable '0' state is studied in different environmental conditions. The memories can find use in low-cost mass printing applications.

Substrate-facilitated nanoparticle sintering and component interconnection procedure.

Room temperature substrate-facilitated sintering of nanoparticles is demonstrated using commercially available silver nanoparticle ink and inkjet printing substrates. The sintering mechanism is based on the chemical removal of the nanoparticle stabilizing ligand and is shown to provide conductivity above one-fourth that of bulk silver. A novel approach to attach discrete components to printed conductors is presented, where the sintered silver provides the metallic interconnects with good electrical and mechanical properties. A process for printing and chip-on-demand assembly is suggested.