We have been developing a new approach to layered hybrid (inorganic/organic) photovoltaic materials for fabrication by Roll-to-Roll (R2R) manufacturing. In this report, we combine the low cost and processability of organic electrically conducting polymers with the efficiency of dye sensitized titanium dioxide, semi-conductor quantum dots (CdSe) self-assembled on layered clay materials (Laponite) onto indium tin oxide coated flexible substrate polyethylene terephthalate (PET) substrates. We have shown electron transfer, guest-guest and host-guest interactions, charge separation, spectral line broadening, and quenching of fluorescence signals which indicate electronic coupling of the dye [Ru(bpy)3]2+ on a CdSe nanocrystal and titanium dioxide nanoparticles. Scanning electron microscopy and atomic force microscopy demonstrate successful nanoparticle formation and thin film self-assembly, as well as surface morphology and polymer thickness.

The development of electric circuit fabrication on heat and chemically sensitive polymer substrates has attracted significant interest as a pathway to low-cost or large-area electronics. We demonstrated the large area, direct patterning of microelectronic structures by selective laser sintering of nanoparticles without using any conventional, very expensive vacuum or photoresist deposition steps. Surface monolayer protected gold nanoparticles suspended in organic solvent was spin coated on a glass or polymer substrate. Then low power continuous wave Ar-ion laser was irradiated as a local heat source to induce selective laser sintering of nanoparticles by a scanning mirror system. Metal nanoparticle possessed low melting temperature (<150°C) due to thermodynamic size effect, and high laser absorption due to surface plasmon mode. These make metal nanoparticles ideal for the low temperature, low laser energy selective laser processing, and further applicable for electronics fabrication on a heat sensitive polymer substrate. We extended our laser selective sintering of nanoparticles research to a large area (> 4” wafer) using scanning mirror to demonstrate current technology for industry level fabrication.

A print technique of an electrode on a plastic substrate is one of the most important techniques for developing a printed large area device. Especially, preparation of a metal electrode with low work function by printing is very important to develop printed active devices such as diode and transistors. Work function values of electrodes strongly affect device properties (1,2), because the work function difference between a semiconductor and an electrode is related to charge injection from the electrode to the semiconductor. Recently, many solution-processable n-type semiconductors have been developed (3), because these are required to fabricate printable EL devices, printable CMOS devices, and so on. Low-work function metals are necessary to inject electrons to n-type semiconductor. In spite of this fact, very few printable low-work function metal inks have been developed, because low-work function metals are easily oxidized during print process owing to high temperature annealing treatment and their conductivities are lost.

In this study, we have examined to develop a new annealing technique on a printed electrode to reduce the process temperature during metal printing. We have newly developed a mechanical sintering technique in which mechanical forces is applied on a printed metal pattern. Control of the direction balance of applied mechanical force was effective to reduce resistivity of the printed metal without any destruction of plastic substrate. Furthermore, distribution control of metal particle in the metal ink was also effective to reduce resistivity. By using this technique, we have succeeded in the preparation of an aluminum, zinc, copper and tin electrode on a plastic substrate. On the other hand, we have tried to prepare a metal alloy ink to control the work function of printed electrode. Metal alloy ink was composed of two kinds of metal particles. Work function of the electrode was controlled by changing composition of these metal contents in an alloy ink. By applying our developed mechanical sintering technique on the printed alloy pattern, printed electrode with various work functions from 3.5eV to 5eV could be prepared on a plastic substrate. These printed alloys were effective to improve the performance of printed diode and transistors.

It is mostly important to develop the fabrication technology of the dielectric thin film with high insulation performance and surface flatness by large-area printing process. We have developed a technique to fabricate a silicon dioxide (SiO2) dielectric thin film by the low temperature solution process. The thin film prepared by about 170°C showed excellent dielectric performance with high resistivity in the order of 10 to the 16 Ωcm and surface flatness with the same degree of thermal oxidized SiO2 thin film on the silicon wafer (RMS=0.15nm). In addition, it is showed that the production of thick film of SiO2 with high dielectric performance and surface flatness is possible by applying over-coating technique. These indicate that this SiO2 production technique is greatly useful for the large-area printed electronics technology.

We have demonstrated a 5-inch flexible color liquid crystal display (LCD) and organic light emitting display (OLED) driven by low-voltage operation organic TFT. In order to achieve high-quality and high-resolution moving images, OTFTs with high performances such as a high mobility, high ON/OFF ratio, low sub-threshold slope (SS) and low operating voltage, are developed. We fabricated pentacene-based low-voltage operation OTFT with a Ta2O5 gate dielectric prepared at a low temperature process. The resulting OTFT array showed a high mobility of 0.3-0.4 cm2/Vs, ON/OFF ratio over 107, VTH=2.7V, and low SS=0.3 V/decade. OTFTs with solution-processable materials such as fluoropolymer gate dielectric and liquid-crystalline semiconducting polymers, PBTTT, were also investigated. Electrical characteristics and stabilities of these devices will be discussed. In the final section, we will demonstrate OTFT-driven flexible displays. Both of the flexible LC device and the OLED device were successfully integrated on the pentacene-based OTFT arrays. Printing and lamination techniques were introduced to assemble the flexible LC device. Phosphorescent polymer materials, which can be patterned by ink-jet printing, were used for emitting layer of OLED. Color moving images were successively shown on the resulting 5-inch displays using an active-matrix driving technique of the OTFT at a low driving voltage of 15V.

Polymers are receiving considerable attention as components in novel optical systems because of the tailored functionality, easy manufacturing, and relatively low cost. The processing of layered polymeric systems by coextrusion is a method to produce films comprising hundreds to thousands of alternating layers with thickness spanning the nanoscale to microscale in a single, one-step roll-to-roll process. Several layered polymer optical systems have been fabricated by coextrusion, including tunable refractive index elastomers, photonic crystals, and mechanically tunable photonic crystals. Layered polymeric optical systems made by coextrusion can also incorporate active components such as laser dyes for all-polymer laser systems.

We developed an ultrafast microfluidic approach to self-assemble microparticles in threedimensions by taking advantage of simple photolithography and capillary action of microparticle-dispersed suspensions. The experimental verifications of the assembly of various sizes of silica microspheres and silica gel microspheres within thin and long open microchannels by using this approach have been demonstrated. We anticipate that the presented technique will be widely used in semiconductor and Bio-MEMS (microelectromechanical Systems) fields because it offers a fast way to control 3D, microscale particle assemblies and also has superb compatibility with photolithography, which can lead to an easy integration of particle assembly with existing CMOS (complementary metal-oxide-semiconductor) and MEMS fabrication processes.

The stiff SiNx gate dielectric in conventional amorphous silicon thin film transistors (TFTs) limits their flexibility by brittle fracture when in tension. We report the effect on the overall flexibility of TFTs of replacing the brittle SiNx gate dielectric with a new, resilient SiO2-silicone hybrid material, which is deposited by plasma enhanced chemical vapor deposition. Individual TFTs on a 50μm-thick polyimide foil were bent to known radii, and measurement of transfer characteristics were made both during strain and after re-flattening. Compared with conventional TFTs made with SiNx, TFTs made with the new hybrid material demonstrated similar flexibility when strained in compression and significantly increased flexibility when strained in tension. Under bending to compressive strain, all TFTs tested delaminated from the substrate for compressive strains greater than 2%. Conventional a-Si:H/SiNx TFTs have been previously found to delaminate at a similar compressive strain. Under bending to tensile strain, the most flexible TFTs made with the new hybrid material that were tested after re-flattening did not exhibit significant changes in transfer characteristics up to strains of ∼2.5%. Conventional a-Si:H/SiNx TFTs have been found to remain functional for strains of up to 0.5%, a value only one-fifth of that for TFTs made with the new hybrid material.

For several years there have been many efforts to employ ink jet technologies in the fabrication of consumer electronics. The potential of displacing large and expensive pieces of electronic fabrication equipment and processes with seemingly appropriately scaled inexpensive alternatives is attractive. However, of course, the devil is in the details. Feature size, accuracy, registration and materials all have sever impacts on design rules, processing, performance and the types of devices appropriate to the technology. Here we present a look at some of the materials and deposition challenges along with solutions developed at PARC. The discussion will include the defining of printed features >5μm with ±1.5μm drop placement and layer to layer alignment accuracy, the materials characteristics of the generally complex functional fluids of interest required for reliable jetting and device performance. Examples of ink jet fabricated integrated circuits, working displays, imagers and RGB color filters for LCD displays will be shared.

Silver sulfide (Ag2S) and cadmium sulfide (CdS) nanoparticles of adjustable sizes are synthesized using a water-in-hexane microemulsion method and stabilized by dodecanethiol. The stabilized metal sulfide nanoparticles can be deposited homogenously on flat substrates forming ordered 2D arrays in supercritical fluid carbon dioxide (Sc-CO2). The use of Sc-CO2 leaves the particles unaffected by de-wetting effects and surface tension caused by traditional solvents and produces uniform arrays. The Sc-CO2 deposition technique can effectively fill the metal sulfide nanoparticles into nanoscale features, which is difficult to achieve by conventional solvent evaporation methods.

Atmospheric Pressure Chemical Vapor Deposition (APCVD) thin film coating process is one of the most cost efficient large area thin film coating solutions presently available on the market and can be up to 2.5 times lower in cost compared with a low pressure sputtering system. Advanced materials such as transparent conductive oxides (TCO) used for solar panel manufacturing and for energy saving (Low-E) windows already have been deposited with APCVD Tools incorporating one or more deposition modules. Thin films such as SiO2, TiO2 and F: SnO2, etc have been successfully deposited onto glass sheets. However further improvement in material efficiencies and operational cost reductions are needed to satisfy the growing demand for such highly customized materials. It is also desirable in the future to be able to deposit other material films which traditionally have not yet been available on this lower cost APCVD manufacturing platform, such as zinc oxide (ZnO).

To investigate in a quantitative manner the improvement potential for the traditional APCVD deposition module design solution we performed a multidimensional computational fluid dynamics (CFD) parametric study using ANSYS FLUENT V12. As a baseline deposition module design we used a commercially available APCVD deposition module originally developed by Watkins-Johnson for SiO2 deposition trench fill of Si wafers from TEOS, O2 and Ozone from which we could locate in previously published papers for both experiment and CFD modeling results. The CFD software enabled us to perform a full parametric APCVD deposition module design study and allowed us to quantify the efficiency and throughput gains/losses of a wide variety of design change options. The main driver for this study was to learn in a quantitative, cost efficient and time efficient manner about what system design modifications have the potential for significant precursor efficiency increase and/or deposition throughput gain for a particular APCVD deposition process. The results of this study will be utilized to accelerate our proprietary, next generation Off-line and On-line CVDgCoat™ APCVD platform development.

Electronic systems that offer elastic mechanical responses to high strain deformations are of growing interest, due to their ability to enable new electrical, optical and biomedical devices and other applications whose requirements are impossible to satisfy with conventional wafer-based technologies or even with those that offer simple bendability. This talk describes materials and mechanical design strategies for classes of electronic circuits that offer extremely high flexibility and stretchability over large area, enabling them to accommodate even demanding deformation modes, such as twisting and linear stretching to ‘rubber-band’ levels of strain over 100%. The use of printed single crystalline silicon nanomaterials for the semiconductor provides performance in flexible and stretchable complementary metal-oxide-semiconductor (CMOS) integrated circuits approaching that of conventional devices with comparable feature sizes formed on silicon wafers. Comprehensive theoretical studies of the mechanics reveal the way in which the structural designs enable these extreme mechanical properties without fracturing the intrinsically brittle active materials or even inducing significant changes in their electrical properties. The results, as demonstrated through electrical measurements of arrays of transistors, CMOS inverters, ring oscillators and differential amplifiers, suggest a valuable route to high performance stretchable electronics that can be integrated with nearly arbitrary substrates. We show examples ranging from plastic and rubber, to vinyl, leather and paper, with capability for large area coverage.