Gravure-Printed Sol-Gels on Flexible Glass: A Scalable Route to Additively Patterned Transparent Conductors.

Gravure printing is an attractive technique for patterning high-resolution features (<5 µm) at high speeds (>1 m/s), but its electronic applications have largely been limited to depositing nanoparticle inks and polymer solutions on plastic. Here, we extend the scope of gravure to a new class of materials and on to new substrates by developing viscous sol-gel precursors for printing fine lines and films of leading transparent conducting oxides (TCOs) on flexible glass. We explore two strategies for controlling sol-gel rheology: tuning the precursor concentration and tuning the content of viscous stabilizing agents. The sol-gel chemistries studied yield printable inks with viscosities of 20-160 cP. The morphology of printed lines of antimony-doped tin oxide (ATO) and tin-doped indium oxide (ITO) is studied as a function of ink formulation for lines as narrow as 35 µm, showing that concentrated inks form thicker lines with smoother edge morphologies. The electrical and optical properties of printed TCOs are characterized as a function of ink formulation and printed film thickness. XRD studies were also performed to understand the dependence of electrical performance on ink composition. Printed ITO lines and films achieve sheet resistance (Rs) as low as 200 and 100 Ω/□, respectively (ρ≈2×10(-3) Ω-cm) for single layers. Similarly, ATO lines and films have Rs as low as 700 and 400 Ω/□ with ρ≈7×10(-3) Ω-cm. High visible range transparency is observed for ITO (86-88%) and ATO (86-89%). Finally, the influence of moderate bending stress on ATO films is investigated, showing the potential for this work to scale to roll-to-roll (R2R) systems.

Cell filling in gravure printing for printed electronics.

Highly scaled direct gravure is a promising printing technique for printed electronics due to its large throughput, high resolution, and simplicity. Gravure can print features in the single micron range at printing speeds of ∼1 m/s by using an optimized cell geometry and optimized printing conditions. The filling of the cells on the gravure cylinder is a critical process, since the amount of ink in the cells strongly impacts printed feature size and quality. Therefore, an understanding of cell filling is crucial to make highly scaled gravure printed electronics viable. In this work we report a novel experimental setup to investigate the filling process in real time, coupled with numerical simulations to gain insight into the experimental observations. By varying viscosity and filling speed, we ensure that the dimensionless capillary number is a good indicator of filling regime in real gravure printing. In addition, we also examine the effect of cell size on filling as this is important for increasing printing resolution. In the light of experimental and simulation results, we are able to rationalize the dominant failure in the filling process, i.e., air entrapment, which is caused by contact line pinning and interface deformation over the cell opening.

Systematic design of jettable nanoparticle-based inkjet inks: rheology, acoustics, and jettability.

Drop-on-demand inkjet printing of functional inks has received a great deal of attention for realizing printed electronics, rapidly prototyped structures, and large-area systems. Although this method of printing promises high processing speeds and minimal substrate contamination, the performance of this process is often limited by the rheological parameters of the ink itself. Effective ink design must address a myriad of issues, including suppression of the coffee-ring effect, proper drop pinning on the substrate, long-term ink reliability, and, most importantly, stable droplet formation, or jettability. In this work, by simultaneously considering optimal jetting conditions and ink rheology, we develop and experimentally validate a jettability window within the capillary number-Weber number space. Furthermore, we demonstrate the exploitation of this window to adjust nanoparticle-based ink rheology predictively to realize a jettable ink. Finally, we investigate the influence of mass loading on jettability to establish additional practical limitations on nanoparticle ink design.

Lubrication-related residue as a fundamental process scaling limit to gravure printed electronics.

In gravure printing, excess ink is removed from a patterned plate or roll by wiping with a doctor blade, leaving a thin lubrication film in the nonpatterned area. Reduction of this lubrication film is critical for gravure printing of electronics, since the resulting residue can lower device performance or even catastrophically impact circuit yield. We report on experiments and quantitative analysis of lubrication films in a highly scaled gravure printing process. We investigate the effects of ink viscosity, wiping speed, loading force, blade stiffness and blade angle on the lubrication film, and further, use the resulting data to investigate the relevant lubrication regimes associated with wiping during gravure printing. Based on this analysis, we are able to posit the lubrication regime associated with wiping during gravure printing, provide insight into the ultimate limits of residue reduction, and, furthermore, are able to provide process guidelines and design rules to achieve these limits.

Transparent high-performance thin film transistors from solution-processed SnO2 /ZrO2 gel-like precursors.

This work employs novel SnO(2) gel-like precursors in conjunction with sol-gel deposited ZrO(2) gate dielectrics to realize high-performance transparent transistors. Representative devices show excellent performance and transparency, and deliver mobility of 103 cm(2) V(-1) s(-1) in saturation at operation voltages as low as 2 V, a sub-threshold swing of only 0.3 V/decade, and /(on) //(off) of 10(4) ~10(5) .

Femtoliter-scale patterning by high-speed, highly scaled inverse gravure printing.

Pattern printing techniques have advanced rapidly in the past decade, driven by their potential applications in printed electronics. Several printing techniques have realized printed features of 10 µm or smaller, but unfortunately, they suffer from disadvantages that prevent their deployment in real applications; in particular, process throughput is a significant concern. Direct gravure printing is promising in this regard. Gravure printing delivers high throughput and has a proven history of being manufacturing worthy. Unfortunately, it suffers from scalability challenges because of limitations in roll manufacturing and limited understanding of the relevant printing mechanisms. Gravure printing involves interactions between the ink, the patterned cylinder master, the doctor blade that wipes excess ink, and the substrate to which the pattern is transferred. As gravure-printed features are scaled, the associated complexities are increased, and a detailed study of the various processes involved is lacking. In this work, we report on various gravure-related fluidic mechanisms using a novel highly scaled inverse direct gravure printer. The printer allows the overall pattern formation process to be studied in detail by separating the entire printing process into three sequential steps: filling, wiping, and transferring. We found that pattern formation by highly scaled gravure printing is governed by the wettability of the ink to the printing plate, doctor blade, and substrate. These individual functions are linked by the apparent capillary number (Ca); the printed volume fraction (φ(p)) of a feature can be constructed by incorporating these basis functions. By relating Ca and φ(p), an optimized operating point can be specified, and the associated limiting phenomena can be identified. We used this relationship to find the optimized ink viscosity and printing speed to achieve printed polymer lines and line spacings as small as 2 µm at printing speeds as high as ∼1 m/s.

Superhydrophobic surfaces using selected zinc oxide microrod growth on ink-jetted patterns.

The synthesis and properties of superhydrophobic surfaces based on binary surface topography made of zinc oxide (ZnO) microrod-decorated micropatterns are reported. ZnO is intrinsically hydrophilic but can be utilized to create hydrophobic surfaces by creating artificial roughness via microstructuring. Micron scale patterns consisting of nanocrystalline ZnO seed particles were applied to glass substrates with a modified ink-jet printer. Microrods were then grown on the patterns by a hydrothermal process without any further chemical modification. Water contact angle (WCA)(1) up to 153° was achieved. Different micro array patterned surfaces with varying response of static contact angle or sessile droplet analysis are reported.