Optimization of Al2O3/TiO2 nanolaminate thin films prepared with different oxide ratios, for use in organic light-emitting diode encapsulation, via plasma-enhanced atomic layer deposition.

Encapsulation is essential for protecting the air-sensitive components of organic light-emitting diodes (OLEDs), such as the active layers and cathode electrodes. Thin film encapsulation approaches based on an oxide layer are suitable for flexible electronics, including OLEDs, because they provide mechanical flexibility, the layers are thin, and they are easy to prepare. This study examined the effects of the oxide ratio on the water permeation barrier properties of Al2O3/TiO2 nanolaminate films prepared by plasma-enhanced atomic layer deposition. We found that the Al2O3/TiO2 nanolaminate film exhibited optimal properties for a 1 : 1 atomic ratio of Al2O3/TiO2 with the lowest water vapor transmission rate of 9.16 × 10(-5) g m(-2) day(-1) at 60 °C and 90% RH. OLED devices that incorporated Al2O3/TiO2 nanolaminate films prepared with a 1 : 1 atomic ratio showed the longest shelf-life, in excess of 2000 hours under 60 °C and 90% RH conditions, without forming dark spots or displaying edge shrinkage.

Solution-Processed Transistors Using Colloidal Nanocrystals with Composition-Matched Molecular "Solders": Approaching Single Crystal Mobility.

Crystalline silicon-based complementary metal-oxide-semiconductor transistors have become a dominant platform for today's electronics. For such devices, expensive and complicated vacuum processes are used in the preparation of active layers. This increases cost and restricts the scope of applications. Here, we demonstrate high-performance solution-processed CdSe nanocrystal (NC) field-effect transistors (FETs) that exhibit very high carrier mobilities (over 400 cm(2)/(V s)). This is comparable to the carrier mobilities of crystalline silicon-based transistors. Furthermore, our NC FETs exhibit high operational stability and MHz switching speeds. These NC FETs are prepared by spin coating colloidal solutions of CdSe NCs capped with molecular solders [Cd2Se3](2-) onto various oxide gate dielectrics followed by thermal annealing. We show that the nature of gate dielectrics plays an important role in soldered CdSe NC FETs. The capacitance of dielectrics and the NC electronic structure near gate dielectric affect the distribution of localized traps and trap filling, determining carrier mobility and operational stability of the NC FETs. We expand the application of the NC soldering process to core-shell NCs consisting of a III-V InAs core and a CdSe shell with composition-matched [Cd2Se3](2-) molecular solders. Soldering CdSe shells forms nanoheterostructured material that combines high electron mobility and near-IR photoresponse.

High-resolution patterns of quantum dots formed by electrohydrodynamic jet printing for light-emitting diodes.

Here we demonstrate materials and operating conditions that allow for high-resolution printing of layers of quantum dots (QDs) with precise control over thickness and submicron lateral resolution and capabilities for use as active layers of QD light-emitting diodes (LEDs). The shapes and thicknesses of the QD patterns exhibit systematic dependence on the dimensions of the printing nozzle and the ink composition in ways that allow nearly arbitrary, systematic control when exploited in a fully automated printing tool. Homogeneous arrays of patterns of QDs serve as the basis for corresponding arrays of QD LEDs that exhibit excellent performance. Sequential printing of different types of QDs in a multilayer stack or in an interdigitated geometry provides strategies for continuous tuning of the effective, overall emission wavelengths of the resulting QD LEDs. This strategy is useful to efficient, additive use of QDs for wide ranging types of electronic and optoelectronic devices.

Promotion of Processability in a p-Type Thin-Film Transistor Using a Se-Te Alloying Channel Layer.

p-type thin-film transistors (pTFTs) have proven to be a significant impediment to advancing electronics beyond traditional Si-based technology. A recent study suggests that a thin and highly crystalline Te layer shows promise as a channel for high-performance pTFTs. However, achieving this still requires specific conditions, such as a cryogenic growth temperature and an extremely thin channel thickness on the order of a few nanometers. These conditions critically limit the practical feasibility of the fabrication process. Here, we report a high-performance pTFT incorporating a 60-nm-thick highly crystalline Se-Te alloyed channel layer, produced using pulsed laser ablation at room temperature. The Se0.5Te0.5 alloy system enhances crystalline temperature and widens the band gap compared to a pure Te channel. Consequently, this approach results in a field-effect mobility of 3 cm2/V·s, with an on/off current ratio of 3 × 105, a subthreshold slope of 2.1 V/decade, and a turn-on voltage of 6.5 V, achieved through conventional annealing at 250 °C. To demonstrate its applicability in complementary circuit applications, we integrate a complementary-type inverter using a p-type Se0.5Te0.5 TFT and an n-type Al-doped InZnSnO, demonstrating a high voltage gain of 12 and a low static power consumption of 17 nW. This suggests that the Se-Te alloyed channel approach paves the way to a more straightforward and cost-effective process for Te-based pTFT devices and their applications.

Tuning the Threshold Voltage of an Oxide Thin-Film Transistor by Electron Injection Control Using a p-n Semiconductor Heterojunction Structure.

Herein, a heterojunction structure integrating p-type tellurium (Te) and n-type aluminum-doped indium-zinc-tin oxide (Al:IZTO) is shown to precisely modulate the threshold voltage (VT) of the oxide thin-film transistor (TFT). The proposed architecture integrates Te as an electron-blocking layer and Al:IZTO as a charge-carrier transporting layer, thereby enabling controlled electron injection. The effects of incorporating the Te layer onto Al:IZTO are investigated, with a focus on X-ray photoelectron spectroscopy (XPS) analysis, in order to explain the behavior of oxygen vacancies and to depict the energy band structure configurations. By modulating the thickness and employing both single and double deposition methods for the heterojunction Te layer, a remarkable VT shift of up to +20 V is achieved. Furthermore, this study also shows excellent stability to a positive bias stress of +2 MV/cm for 10,000 s without additional passivation layers, demonstrating the robustness of the designed TFT. By a thorough optimization of the Al:IZTO/Te interface, the results demonstrate not only the substantial impact of the introduced heterojunction structure on VT control but also the endurance, durability, and stability of the optimized TFTs under prolonged long-term operating stress, thus offering promising prospects for tailored semiconductor device applications.

Ferroelectric Hafnia-Based M3D FeTFTs Annealed at Extremely Low Temperatures and TCAM Cells for Computing-in-Memory Applications.

In order to overcome the bottleneck between the central processor unit and memory as well as the issue of energy consumption, computing-in-memory (CIM) is becoming more popular as an alternative to the traditional von Neumann structure. However, as artificial intelligence advances, the networks require CIM devices to store billions of parameters in order to handle huge data traffic demands. Monolithic three-dimensional (M3D) stacked ferroelectric thin-film transistors (FeTFTs) are one of the promising techniques for realizing high-density CIM devices that can store billions of parameters. In particular, oxide channel-based FeTFTs are well suited for these applications due to low-temperature processes, nonvolatility, and 3D integration capability. Nevertheless, the M3D-integrated CIM devices including hafnia ferroelectric films need the high-temperature annealing process to crystallize the ferroelectric layer, making M3D integration difficult. When the FeTFTs are fabricated with an M3D structure, the high-temperature process causes thermal issues in the underlying devices. Here, we present the focused microwave annealed (FMA) oxide FeTFTs with M3D integration at a low temperature of 250 °C. We confirmed that the FeTFTs with metal-ferroelectric-metal-insulator-semiconductor structure exhibited a large memory window of 3.2 V, good endurance over 106 cycles, and a long retention time of 105 s. To understand the different electrical characteristics of FeTFTs in the top and bottom layers, we experimentally analyzed the density of the state of the oxide channel and ferroelectric properties of the ferroelectric gate insulator by using multifrequency capacitance-voltage measurement and nucleation-limited-switching model analysis, respectively. With our approach, we demonstrate for the first time a vertical stacked FeTFTs-based ternary-content-addressable memory (TCAM) cell for CIM application. We believe that the proposed M3D-stacked TCAM cells composed of FeTFTs can be used in high-density memory, energy-efficient memory, and CIM technology.

Solvent-assisted strongly enhanced light-emitting electrochemiluminescent devices for lighting applications.

Rubrene-based electrochemiluminescence (r-ECL) cells with two different solvent systems is prepared, one in a co-solvent system with a mixture of 1,2-dichlorobenzene and propylene carbonate (DCB : PC, v/v 3 : 1) and another in a single solvent system of tetrahydrofuran (THF), as the medium to form a liquid-electrolyte (L-El). By simply changing the solvent systems, from the co-solvent DCB : PC (v/v 3 : 1) to the single solvent THF, with the same amount of electrochemiluminescent rubrene (5 mM) and Li-based salt, a dramatically enhanced brightness of over 30 cd m-2 is observed for the r-ECL cell in L-ElTHF which is approximately 7-times higher than the brightness of 5 cd m-2 observed for the r-ECL in L-ElDCB:PC(v/v 3:1).

Organic/Inorganic Hybrid Thin-Film Encapsulation Using Inkjet Printing and PEALD for Industrial Large-Area Process Suitability and Flexible OLED Application.

We present herein the first report of organic/inorganic hybrid thin-film encapsulation (TFE) developed as an encapsulation process for mass production in the display industry. The proposed method was applied to fabricate a top-emitting organic light-emitting device (TEOLED). The organic/inorganic hybrid TFE has a 1.5 dyad structure and was fabricated using plasma-enhanced atomic layer deposition (PEALD) and inkjet printing (IJP) processes that can be applied to mass production operations in the industry. Currently, industries use inorganic thin films such as SiNx and SiOxNy fabricated through plasma-enhanced chemical vapor deposition (PECVD), which results in film thickness >1 µm; however, in the present work, an Al2O3 inorganic thin film with a thickness of 30 nm was successfully fabricated using ALD. Furthermore, to decouple the crack propagation between the adjacent Al2O3 thin films, an acrylate-based polymer layer was printed between these layers using IJP to finally obtain the 1.5 dyad hybrid TFE. The proposed method can be applied to optoelectronic devices with various form factors such as rollables and stretchable displays. The hybrid TFE developed in this study has a transmittance of 95% or more in the entire visible light region and a very low surface roughness of less than 1 nm. In addition, the measurement of water vapor transmission rate (WVTR) using commercial MOCON equipment yielded a value of 5 × 10-5 gm-2 day-1 (37.8 °C and 100% RH) or less, approaching the limit of the measuring equipment. The TFE was applied to TEOLEDs and the improvement in optical properties of the device was demonstrated. The OLED panel was manufactured and operated stably, showing excellent consistency even in the actual display manufacturing process. The panel operated normally even after 363 days in air. The proposed organic/inorganic hybrid encapsulant manufacturing process is applicable to the display industry and this study provides basic guidelines that can serve as a foothold for the development of various technologies in academia and industry alike.

Direct Patterned Zinc-Tin-Oxide for Solution-Processed Thin-Film Transistors and Complementary Inverter through Electrohydrodynamic Jet Printing.

The solution-processed deposition of metal-oxide semiconducting materials enables the fabrication of large-area and low-cost electronic devices by using printing technologies. Additionally, the simple patterning process of these types of materials become an important issue, as it can simplify the cost and process of fabricating electronics such as thin-film transistors (TFTs). In this study, using the electrohydrodynamic (EHD) jet printing technique, we fabricated directly patterned zinc-tin-oxide (ZTO) semiconductors as the active layers of TFTs. The straight lines of ZTO semiconductors were successfully drawn using a highly soluble and homogeneous solution that comprises zinc acrylate and tin-chloride precursors. Besides, we found the optimum condition for the fabrication of ZTO oxide layers by analyzing the thermal effect in processing. Using the optimized condition, the resulting devices exhibited satisfactory TFT characteristics with conventional electrodes and conducting materials. Furthermore, these metal-oxide TFTs were successfully applied to complementary inverter with conventional p-type organic semiconductor-based TFT, showing high quality of voltage transfer characteristics. Thus, these printed ZTO TFT results demonstrated that solution processable metal-oxide transistors are promising for the realization of a more sustainable and printable next-generation industrial technology.

Enhanced device lifetime of double-heterojunction nanorod light-emitting diodes.

Colloidal quantum dots (QDs) are emerging as solution-processable, high-performance materials for light-emitting diodes (LEDs). Understanding the failure mechanism(s) is of both fundamental and practical importance, yet little is known of how QD-LEDs fail. Here, we have carried out accelerated device lifetime measurements on double heterojunction nanorod- (DHNR) and QD-LEDs. A common dependence of device lifetime on the initial driving voltage is observed over more than two orders of magnitude range in the initial luminance. This behavior is independent of whether the emitting materials are DHNRs or QDs prepared under different conditions. Reducing the hole injection barrier by doping HTL allows lower voltage operation, leading to longer device lifetimes. DHNRs with a band structure that further lowers the hole injection barrier require even lower driving voltages and therefore lead to longer device lifetimes than core/shell QDs. At 1000 cd m-2, the DHNR-LED exhibits no significant degradation even after more than 200 h of continuous operation. QD-LEDs, on the other hand, are completely degraded in less than ∼100 h under the same initial luminance conditions. Hole accumulation/trapping leading to HTL degradation, which in turn deteriorates electroluminescence but not the photoluminescence, is suggested to be the main cause of degradation of both DHNR- and QD-LEDs.

Tuning the Work Function of Printed Polymer Electrodes by Introducing a Fluorinated Polymer To Enhance the Operational Stability in Bottom-Contact Organic Field-Effect Transistors.

Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is a promising electrode material for organic electronic devices due to its high conductivity, good mechanical flexibility, and feasibility of easy patterning with various printing methods. The work function of PEDOT:PSS needs to be increased for efficient hole injection, and the addition of a fluorine-containing material has been reported to increase the work function of PEDOT:PSS. However, it remains a challenge to print PEDOT:PSS electrodes while simultaneously tuning their work functions. Here, we report work function tunable PEDOT:PSS/Nafion source/drain electrodes formed by electrohydrodynamic printing technique with PEDOT:PSS/Nafion mixture solutions for highly stable bottom-contact organic field-effect transistors (OFETs). The surface properties and work function of the printed electrode can be controlled by varying the Nafion ratio, due to the vertical phase separation of the PEDOT:PSS/Nafion. The PEDOT:PSS/Nafion electrodes exhibit a low hole injection barrier, which leads to efficient charge carrier injection from the electrode to the semiconductor. As a result, pentacene-based OFETs with PEDOT:PSS/Nafion electrodes show increased charge carrier mobilities of 0.39 cm2/(V·s) compared to those of devices with neat PEDOT:PSS electrodes (0.021 cm2/(V·s)). Moreover, the gate-bias stress stability of the OFETs is remarkably improved by employing PEDOT:PSS/Nafion electrodes, as demonstrated by a reduction of the threshold voltage shift from -1.84 V to -0.28 V.

Double-heterojunction nanorod light-responsive LEDs for display applications.

Dual-functioning displays, which can simultaneously transmit and receive information and energy through visible light, would enable enhanced user interfaces and device-to-device interactivity. We demonstrate that double heterojunctions designed into colloidal semiconductor nanorods allow both efficient photocurrent generation through a photovoltaic response and electroluminescence within a single device. These dual-functioning, all-solution-processed double-heterojunction nanorod light-responsive light-emitting diodes open feasible routes to a variety of advanced applications, from touchless interactive screens to energy harvesting and scavenging displays and massively parallel display-to-display data communication.

Photo-Patternable ZnO Thin Films Based on Cross-Linked Zinc Acrylate for Organic/Inorganic Hybrid Complementary Inverters.

Complementary inverters consisting of p-type organic and n-type metal oxide semiconductors have received considerable attention as key elements for realizing low-cost and large-area future electronics. Solution-processed ZnO thin-film transistors (TFTs) have great potential for use in hybrid complementary inverters as n-type load transistors because of the low cost of their fabrication process and natural abundance of active materials. The integration of a single ZnO TFT into an inverter requires the development of a simple patterning method as an alternative to conventional time-consuming and complicated photolithography techniques. In this study, we used a photocurable polymer precursor, zinc acrylate (or zinc diacrylate, ZDA), to conveniently fabricate photopatternable ZnO thin films for use as the active layers of n-type ZnO TFTs. UV-irradiated ZDA thin films became insoluble in developing solvent as the acrylate moiety photo-cross-linked; therefore, we were able to successfully photopattern solution-processed ZDA thin films using UV light. We studied the effects of addition of a tiny amount of indium dopant on the transistor characteristics of the photopatterned ZnO thin films and demonstrated low-voltage operation of the ZnO TFTs within ±3 V by utilizing Al2O3/TiO2 laminate thin films or ion-gels as gate dielectrics. By combining the ZnO TFTs with p-type pentacene TFTs, we successfully fabricated organic/inorganic hybrid complementary inverters using solution-processed and photopatterned ZnO TFTs.

Multilayer Transfer Printing for Pixelated, Multicolor Quantum Dot Light-Emitting Diodes.

Here, we report multilayer stacking of films of quantum dots (QDs) for the purpose of tailoring the energy band alignment between charge transport layers and light emitting layers of different color in quantum dot light-emitting diodes (QD LED) for maximum efficiency in full color operation. The performance of QD LEDs formed by transfer printing compares favorably to that of conventional devices fabricated by spin-casting. Results indicate that zinc oxide (ZnO) and titanium dioxide (TiO2) can serve effectively as electron transport layers (ETLs) for red and green/blue QD LEDs, respectively. Optimized selections for each QD layer can be assembled at high yields by transfer printing with sacrificial fluoropolymer thin films to provide low energy surfaces for release, thereby allowing shared common layers for hole injection (HIL) and hole transport (HTL), along with customized ETLs. This strategy allows cointegration of devices with heterogeneous energy band diagrams, in a parallelized scheme that offers potential for high throughput and practical use.

High efficiency and optical anisotropy in double-heterojunction nanorod light-emitting diodes.

Recent advances in colloidal quantum dot light-emitting diodes (QD-LEDs) have led to efficiencies and brightness that rival the best organic LEDs. Nearly ideal internal quantum efficiency being achieved leaves light outcoupling as the only remaining means to improve external quantum efficiency (EQE) but that might require radically different device design and reoptimization. However, the current state-of-the-art QD-LEDs are based on spherical core/shell QDs, and the effects of shape and optical anisotropy remain essentially unexplored. Here, we demonstrate solution-processed, red-emitting double-heterojunction nanorod (DHNR)-LEDs with efficient hole transport exhibiting low threshold voltage and high brightness (76,000 cd m(-2)) and efficiencies (EQE = 12%, current efficiency = 27.5 cd A(-1), and power efficiency = 34.6 lm W(-1)). EQE exceeding the expected upper limit of ∼ 8% (based on ∼ 20% light outcoupling and solution photoluminescence quantum yield of ∼ 40%) suggests shape anisotropy and directional band offsets designed into DHNRs play an important role in enhancing light outcoupling.

Reduced Water Vapor Transmission Rate of Graphene Gas Barrier Films for Flexible Organic Field-Effect Transistors.

Preventing reactive gas species such as oxygen or water is important to ensure the stability and durability of organic electronics. Although inorganic materials have been predominantly employed as the protective layers, their poor mechanical property has hindered the practical application to flexible electronics. The densely packed hexagonal lattice of carbon atoms in graphene does not allow the transmission of small gas molecules. In addition, its outstanding mechanical flexibility and optical transmittance are expected to be useful to overcome the current mechanical limit of the inorganic materials. In this paper, we reported the measurement of the water vapor transmission rate (WVTR) through the 6-layer 10 × 10 cm(2) large-area graphene films synthesized by chemical vapor deposition (CVD). The WVTR was measured to be as low as 10(-4) g/m(2)·day initially, and stabilized at ∼0.48 g/m(2)·day, which corresponds to 7 times reduction in WVTR compared to bare polymer substrates. We also showed that the graphene-passivated organic field-effect transistors (OFETs) exhibited excellent environmental stability as well as a prolonged lifetime even after 500 bending cycles with strain of 2.3%. We expect that our results would be a good reference showing the graphene's potential as gas barriers for organic electronics.

Double-heterojunction nanorods.

As semiconductor heterostructures play critical roles in today's electronics and optoelectronics, the introduction of active heterojunctions can impart new and improved capabilities that will enable the use of solution-processable colloidal quantum dots in future devices. Such heterojunctions incorporated into colloidal nanorods may be especially promising, since the inherent shape anisotropy can provide additional benefits of directionality and accessibility in band structure engineering and assembly. Here we develop double-heterojunction nanorods where two distinct semiconductor materials with type II staggered band offset are both in contact with one smaller band gap material. The double heterojunction can provide independent control over the electron and hole injection/extraction processes while maintaining high photoluminescence yields. Light-emitting diodes utilizing double-heterojunction nanorods as the electroluminescent layer are demonstrated with low threshold voltage, narrow bandwidth and high efficiencies.

High-performance organic complementary inverters using monolayer graphene electrodes.

Chemical vapor deposition-grown graphene has been an attractive electrode material for organic electronic devices, such as organic field-effect transistors (OFETs), because it is highly conductive and provides good oxidation and thermal stability properties. However, it still remains a challenge to demonstrate organic complementary circuits using graphene electrodes because of the relatively poor performance of n-type OFETs. Here, we report the development of high-performance organic complementary inverters using graphene as source/drain electrodes and N, N'-ditridecyl-3,4,9,10-perylenetetracarboxylic diimide (PTCDI-C13) and pentacene as n- and p-type organic semiconductors, respectively. Graphene electrodes were n-doped via the formation of NH2-terminated self-assembled monolayers that lowered the work function and the electron injection barrier between the graphene and PTCDI-C13. Thermal annealing improved the molecular packing among PTCDI-C13 groups on the graphene surface, thereby increasing the crystallinity and grain size. The thermally annealed PTCDI-C13 OFETs prepared using n-doped graphene electrodes exhibited a good field-effect mobility of up to 0.43 cm2/(V s), which was comparable to the values obtained from other p-type pentacene OFETs. By integrating p- and n-type OFETs, we successfully fabricated organic complementary inverters that exhibited highly symmetric operation with an excellent voltage gain of up to 124 and good noise margin.

High-performance triethylsilylethynyl anthradithiophene transistors prepared without solvent vapor annealing: the effects of self-assembly during dip-coating.

Solution-processable small-molecule organic semiconductors have recently attracted significant attention for use as the active channel layers in organic field-effect transistors due to their good intrinsic charge carrier mobility and easy processability. Dip-coating is a good method for optimizing the film morphology and molecular ordering of the small-molecular semiconductors because the drying speed can be quantitatively controlled at the air-solution-substrate contact line. Here, we report the preparation of highly crystalline triethylsilylethynyl-anthradithiophene (TES-ADT) crystal arrays that exhibit an excellent field-effect mobility (up to 1.8 cm(2)/(V s)) via an optimized one-step dip-coating process. High-quality TES-ADT crystals were grown without solvent vapor annealing postprocessing steps, which were previously thought to be essential for improving the morphology, crystallinity, and electrical characteristics of TES-ADT thin films. An interesting correlation between the optimal pull-out rate and the self-assembly tendencies of some soluble acene semiconductors was observed, and the origin of the correlation was investigated. Our work demonstrates an alternative simple approach to achieving highly crystalline TES-ADT thin films, and further proposes a prospective method for optimizing the formation of thin films via the molecular self-assembly of soluble acenes.

Self-organizing properties of triethylsilylethynyl-anthradithiophene on monolayer graphene electrodes in solution-processed transistors.

Graphene has shown great potential as an electrode material for organic electronic devices such as organic field-effect transistors (FETs) because of its high conductivity, thinness, and good compatibility with organic semiconductor materials. To achieve high performance in graphene-based organic FETs, favorable molecular orientation and good crystallinity of organic semiconductors on graphene are desired. This strongly depends on the surface properties of graphene. Here, we investigate the effects of polymer residues that remain on graphene source/drain electrodes after the transfer/patterning processes on the self-organizing properties and field-effect characteristics of the overlying solution-processed triethylsilylethynyl-anthradithiophene (TES-ADT). A solvent-assisted polymer residue removal process was introduced to effectively remove residues or impurities on the graphene surface. Unlike vacuum-deposited small molecules, TES-ADT displayed a standing-up molecular assembly, which facilitates lateral charge transport, on both the residue-removed clean graphene and as-transferred graphene with polymer residues. However, TES-ADT films grown on the cleaned graphene showed a higher crystallinity and larger grain size than those on the as-transferred graphene. The resulting TES-ADT FETs using cleaned graphene source/drain electrodes therefore exhibited a superior device performance compared to devices using as-transferred graphene electrodes, with mobilities as high as 1.38 cm(2) V(-1) s(-1).