Sungjun Park

Flexible metal-oxide devices made by room-temperature photochemical activation of sol-gel films

Amorphous metal-oxide semiconductors have emerged as potential replacements for organic and silicon materials in thin-film electronics. The high carrier mobility in the amorphous state, and excellent large-area uniformity, have extended their applications to active-matrix electronics, including displays, sensor arrays and X-ray detectors. Moreover, their solution processability and optical transparency have opened new horizons for low-cost printable and transparent electronics on plastic substrates. But metal-oxide formation by the sol–gel route requires an annealing step at relatively high temperature, which has prevented the incorporation of these materials with the polymer substrates used in high-performance flexible electronics. Here we report a general method for forming high-performance and operationally stable metal-oxide semiconductors at room temperature, by deep-ultraviolet photochemical activation of sol–gel films. Deep-ultraviolet irradiation induces efficient condensation and densification of oxide semiconducting films by photochemical activation at low temperature. This photochemical activation is applicable to numerous metal-oxide semiconductors, and the performance (in terms of transistor mobility and operational stability) of thin-film transistors fabricated by this route compares favourably with that of thin-film transistors based on thermally annealed materials. The field-effect mobilities of the photo-activated metal-oxide semiconductors are as high as 14 and 7 cm2 V−1 s−1 (with an Al2O3 gate insulator) on glass and polymer substrates, respectively; and seven-stage ring oscillators fabricated on polymer substrates operate with an oscillation frequency of more than 340 kHz, corresponding to a propagation delay of less than 210 nanoseconds per stage.

Significant vertical phase separation in solvent-vapor-annealed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composite films leading to better conductivity and work function for high-performance indium tin oxide-free optoelectronics.

In the present study, a novel polar-solvent vapor annealing (PSVA) was used to induce a significant structural rearrangement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films in order to improve their electrical conductivity and work function. The effects of polar-solvent vapor annealing on PEDOT:PSS were systematically compared with those of a conventional solvent additive method (SAM) and investigated in detail by analyzing the changes in conductivity, morphology, top and bottom surface composition, conformational PEDOT chains, and work function. The results confirmed that PSVA induces significant phase separation between excess PSS and PEDOT chains and a spontaneous formation of a highly enriched PSS layer on the top surface of the PEDOT:PSS polymer blend, which in turn leads to better 3-dimensional connections between the conducting PEDOT chains and higher work function. The resultant PSVA-treated PEDOT:PSS anode films exhibited a significantly enhanced conductivity of up to 1057 S cm(-1) and a tunable high work function of up to 5.35 eV. The PSVA-treated PEDOT:PSS films were employed as transparent anodes in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs). The cell performances of organic optoelectronic devices with the PSVA-treated PEDOT:PSS anodes were further improved due to the significant vertical phase separation and the self-organized PSS top surface in PSVA-treated PEDOT:PSS films, which can increase the anode conductivity and work function and allow the direct formation of a functional buffer layer between the active layer and the polymeric electrode. The results of the present study will allow better use and understanding of polymeric-blend materials and will further advance the realization of high-performance indium tin oxide (ITO)-free organic electronics.

Large-Scale Precise Printing of Ultrathin Sol-Gel Oxide Dielectrics for Directly Patterned Solution-Processed Metal Oxide Transistor Arrays.

Ultrathin and dense metal oxide gate di-electric layers are reported by a simple printing of AlOx and HfOx sol-gel precursors. Large-area printed indium gallium zinc oxide (IGZO) thin-film transistor arrays, which exhibit mobilities >5 cm(2) V(-1) s(-1) and gate leakage current of 10(-9) A cm(-2) at a very low operation voltage of 2 V, are demonstrated by continuous simple bar-coated processes.

Low-Voltage Flexible Organic Electronics Based on High-Performance Sol–Gel Titanium Dioxide Dielectric

In this letter, we report that high-performance insulating films can be generated by judicious control over the microstructure of sol-gel-processed titanium dioxide (TiO2) films, typically known as wide-bandgap semiconductors. The resultant device made of 23 nm-thick TiO2 dielectric layer exhibits a low leakage current density of ∼1 × 10(-7) A cm(-2) at 2 V and a large areal capacitance of 560 nF cm(-2) with the corresponding dielectric constant of 27. Finally, low-voltage flexible organic thin-film transistors were successfully demonstrated by incorporating this versatile solution-processed oxide dielectric material into pentacene transistors on polyimide substrates.

Direct patterning of sol–gel metal oxide semiconductor and dielectric films via selective surface wetting

We report the simple, photolithography-free, direct patterning of both solution-processed metal oxide semiconductors and dielectrics via selective surface wetting. This technique was directly applied to fabrication of low-voltage all-solution metal oxide thin-film transistors with minimal channel and gate leakage currents.

Sub-0.5 V Highly Stable Aqueous Salt Gated Metal Oxide Electronics

Recently, growing interest in implantable bionics and biochemical sensors spurred the research for developing non-conventional electronics with excellent device characteristics at low operation voltages and prolonged device stability under physiological conditions. Herein, we report high-performance aqueous electrolyte-gated thin-film transistors using a sol-gel amorphous metal oxide semiconductor and aqueous electrolyte dielectrics based on small ionic salts. The proper selection of channel material (i.e., indium-gallium-zinc-oxide) and precautious passivation of non-channel areas enabled the development of simple but highly stable metal oxide transistors manifested by low operation voltages within 0.5 V, high transconductance of ~1.0 mS, large current on-off ratios over 107, and fast inverter responses up to several hundred hertz without device degradation even in physiologically-relevant ionic solutions. In conjunction with excellent transistor characteristics, investigation of the electrochemical nature of the metal oxide-electrolyte interface may contribute to the development of a viable bio-electronic platform directly interfacing with biological entities in vivo.

Controlled Charge Trapping and Retention in Large-Area Monodisperse Protein Metal-Nanoparticle Conjugates

Here, we report on charge-retention transistors based on novel protein-mediated Au nanoparticle (NP) arrays, with precise control over dimension and distribution. Individual NPs are coated with alpha-synuclein, an amyloidogenic protein responsible for Lewy body formation in Parkinsons disease. Subsequently, a monolayer of protein-NP conjugates is successfully created via a simple and scalable solution deposition to function as distributed nanoscale capacitors. Controllability over the film structure translates into the tunability of the electrical performance; pentacene-based organic transistors feature widely varying programmability and relaxation dynamics, providing versatility for various unconventional memory applications.

Optically transparent semiconducting polymer nanonetwork for flexible and transparent electronics

Significance When various electronic appliances used in everyday life become deformable and transparent, they will provide tremendous versatility in the design and use of see-through, smart mobile applications, exceeding the limitations of the best developed conventional silicon technologies, which are available only in rigid, opaque forms. However, even recently discovered innovative semiconducting components have failed to simultaneously achieve such flexibility and transparency. Thus, the existing options still comprise only hard, planar, or opaque materials, and obtaining a “key” material for creating truly flexible and transparent electronics has presented a formidable challenge. We report an effective means of creating a “truly flexible, perfectly transparent” and high-mobility semiconducting material and demonstrate several high-end flexible and transparent applications based on a polymeric semiconductor system. Simultaneously achieving high optical transparency and excellent charge mobility in semiconducting polymers has presented a challenge for the application of these materials in future “flexible” and “transparent” electronics (FTEs). Here, by blending only a small amount (∼15 wt %) of a diketopyrrolopyrrole-based semiconducting polymer (DPP2T) into an inert polystyrene (PS) matrix, we introduce a polymer blend system that demonstrates both high field-effect transistor (FET) mobility and excellent optical transparency that approaches 100%. We discover that in a PS matrix, DPP2T forms a web-like, continuously connected nanonetwork that spreads throughout the thin film and provides highly efficient 2D charge pathways through extended intrachain conjugation. The remarkable physical properties achieved using our approach enable us to develop prototype high-performance FTE devices, including colorless all-polymer FET arrays and fully transparent FET-integrated polymer light-emitting diodes.

Hydrogen production based on a photoactivated nanowire-forest

For several decades, the key challenge associated with thermochemical hydrogen generation has been the achievement of water splitting and catalyst regeneration at low temperatures while maintaining a reasonably high conversion efficiency over many cycles. Herein, we report low-temperature thermochemical hydrogen generation using hierarchically assembled iron oxide nanoarchitectures. Iron oxide nanoparticles conformally deposited onto a SnO2 nanowire forest allowed the splitting of water molecules and the production of hydrogen gas at temperatures of 400–800 °C, with a high specific gas-forming rate as high as ∼25000 μmol per g per cycle (250 min). More remarkably, deep-ultraviolet photoactivation enabled low-temperature (200 °C) catalyst regeneration and thereby multiple cycles of hydrogen production without any significant coalescence of the oxide nanoparticles nor substantial loss of the water-splitting efficiency. Hierarchically arranged iron oxide nanoarchitectures, in combination with photochemical catalyst regeneration, are promising for practical hydrogen generation by harvesting wasted thermal energy, even at temperatures below 500 °C.

Influence of PEDOT:PSS crystallinity and composition on electrochemical transistor performance and long-term stability

Owing to the mixed electron/hole and ion transport in the aqueous environment, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)-based organic electrochemical transistor has been regarded as one of the most promising device platforms for bioelectronics. Nonetheless, there exist very few in-depth studies on how intrinsic channel material properties affect their performance and long-term stability in aqueous environments. Herein, we investigated the correlation among film microstructural crystallinity/composition, device performance, and aqueous stability in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films. The highly organized anisotropic ordering in crystallized conducting polymer films led to remarkable device characteristics such as large transconductance (∼20 mS), extraordinary volumetric capacitance (113 F·cm−3), and unprecedentedly high [μC*] value (∼490 F·cm−1V−1s−1). Simultaneously, minimized poly(styrenesulfonate) residues in the crystallized film substantially afforded marginal film swelling and robust operational stability even after >20-day water immersion, >2000-time repeated on-off switching, or high-temperature/pressure sterilization. We expect that the present study will contribute to the development of long-term stable implantable bioelectronics for neural recording/stimulation.The lack of understanding of mixed transport in ion-permeable conjugated polymer films hinders the advance of organic electrochemical transistors for bioelectronics. Here, the authors elucidate the structure-property-performance relationships for conventional and crystallized PEDOT:PSS films.