Engineering Dielectric Materials for High-Performance Organic Light Emitting Transistors (OLETs)

Organic light emitting transistors (OLETs) represent a relatively new technology platform in the field of optoelectronics. An OLET is a device with a two-fold functionality since it behaves as a thin-film transistor and at the same time can generate light under appropriate bias conditions. This Review focuses mainly on one of the building blocks of such device, namely the gate dielectrics, and how it is possible to engineer it to improve device properties and performances. While many findings on gate dielectrics can be easily applied to organic light emitting transistors, we here concentrate on how this layer can be exploited and engineered as an active tool for light manipulation in this novel class of optoelectronic devices.     

Organic Field-Effect Transistors Based on a Liquid-Crystalline Polymeric Semiconductor using SU-8 Gate Dielectrics on Flexible Substrates

In this work, the insulating properties of poly(4-vinylphenol) (PVP) and SU-8 (MicroChem, Westborough, MA, USA) dielectrics are analyzed and compared with each other. We further investigate the performance behavior of organic field-effect transistors based on a semiconducting liquid-crystal polymer (LCP) using both dielectric materials and evaluate the results regarding the processability. Due to the lower process temperature needed for the SU-8 deposition, the realization of organic transistors on flexible substrates is demonstrated showing comparable charge carrier mobilities to devices using PVP on glass. In addition, a µ-dispensing procedure of the LCP on SU-8 is presented, improving the switching behavior of the organic transistors, and the promising stability data of the SU-8/LCP stack are verified after storing the structures for 60 days in ambient air showing negligible irreversible degradation of the organic semiconductor.     

Effect of Solvents,Their Mixture and Thermal Annealing on the Performance of Solution Processed Polymer Light-Emitting Diodes

In this study, we first investigated changes seen in electrical and optical properties of a polymer light-emitting diode due to using different kinds of solvents and their mixture. Two-layer light emitting diodes with organic small molecules doped in a PVK polymer host were fabricated using (i) non-aromatic solvent chloroform with a high evaporation rate; (ii) aromatic solvent chlorobenzene with a low evaporation rate, and (iii) their mixture with different relative ratios. The effect of nano-scale layer thickness, surface roughness and internal nano-morphology on threshold voltage and the amount of electric current, the luminance and efficiency of a device were assessed. Results indicated the importance of majority charge carriers’ type in the selection of solvent and tuning its properties. Then, the effect of thermal annealing on electrical and optical properties of polymer light emitting diodes was investigated. During the device fabrication, pre-annealing in 80 and/or 120 °C and post-annealing in 120 °C were performed. The nano-scale effect of annealing on polymer-metal interface and electric current injection was described thoroughly. A comparison between threshold voltage, luminance and electric current efficiency of luminescence for different annealing processes was undertaken, so that the best electric current efficiency of luminescence achieved at 120 °C pre-annealing accompanied with 120 °C post-annealing.     

High-κ oxide nanoribbons as gate dielectrics for high mobility top-gated graphene transistors

Deposition of high-κ dielectrics onto graphene is of significant challenge due to the difficulties of nucleating high quality oxide on pristine graphene without introducing defects into the monolayer of carbon lattice. Previous efforts to deposit high-κ dielectrics on graphene often resulted in significant degradation in carrier mobility. Here we report an entirely new strategy to integrate high quality high-κ dielectrics with graphene by first synthesizing freestanding high-κ oxide nanoribbons at high temperature and then transferring them onto graphene at room temperature. We show that single crystalline Al₂O₃ nanoribbons can be synthesized with excellent dielectric properties. Using such nanoribbons as the gate dielectrics, we have demonstrated top-gated graphene transistors with the highest carrier mobility (up to 23,600 cm²/V·s) reported to date, and a more than 10-fold increase in transconductance compared to the back-gated devices. This method opens a new avenue to integrate high-κ dielectrics on graphene with the preservation of the pristine nature of graphene and high carrier mobility, representing an important step forward to high-performance graphene electronics.     

Large Area Emission in p-Type Polymer-Based Light-Emitting Field-Effect Transistors by Incorporating Charge Injection Interlayers

Organic light-emitting field-effect transistors (LEFETs) provide the possibility of simplifying the display pixilation design as they integrate the drive-transistor and the light emission in a single architecture. However, in p-type LEFETs, simultaneously achieving higher external quantum efficiency (EQE) at higher brightness, larger and stable emission area, and high switching speed are the limiting factors for to realise their applications. Herein, we present a p-type polymer heterostructure-based LEFET architecture with electron and hole injection interlayers to improve the charge injection into the light-emitting layer, which leads to better recombination. This device structure provides access to hole mobility of ~2.1 cm² V⁻¹ s⁻¹ and EQE of 1.6% at a luminance of 2600 cd m⁻². Most importantly, we observed a large area emission under the entire drain electrode, which was spatially stable (emission area is not dependent on the gate voltage and current density). These results show an important advancement in polymer-based LEFET technology toward realizing new digital display applications.     

Extrinsic and Intrinsic Frequency Dispersion of High-k Materials in Capacitance-Voltage Measurements

In capacitance-voltage (C-V) measurements, frequency dispersion in high-k dielectrics is often observed. The frequency dependence of the dielectric constant (k-value), that is the intrinsic frequency dispersion, could not be assessed before suppressing the effects of extrinsic frequency dispersion, such as the effects of the lossy interfacial layer (between the high-k thin film and silicon substrate) and the parasitic effects. The effect of the lossy interfacial layer on frequency dispersion was investigated and modeled based on a dual frequency technique. The significance of parasitic effects (including series resistance and the back metal contact of the metal-oxide-semiconductor (MOS) capacitor) on frequency dispersion was also studied. The effect of surface roughness on frequency dispersion is also discussed. After taking extrinsic frequency dispersion into account, the relaxation behavior can be modeled using the Curie-von Schweidler (CS) law, the Kohlrausch-Williams-Watts (KWW) relationship and the Havriliak-Negami (HN) relationship. Dielectric relaxation mechanisms are also discussed.     

Organic transistors manufactured using inkjet technology with subfemtoliter accuracy

A major obstacle to the development of organic transistors for large-area sensor, display, and circuit applications is the fundamental compromise between manufacturing efficiency, transistor performance, and power consumption. In the past, improving the manufacturing efficiency through the use of printing techniques has inevitably resulted in significantly lower performance and increased power consumption, while attempts to improve performance or reduce power have led to higher process temperatures and increased manufacturing cost. Here, we lift this fundamental limitation by demonstrating subfemtoliter inkjet printing to define metal contacts with single-micrometer resolution on the surface of high-mobility organic semiconductors to create high-performance p-channel and n-channel transistors and low-power complementary circuits. The transistors employ an ultrathin low-temperature gate dielectric based on a self-assembled monolayer that allows transistors and circuits on rigid and flexible substrates to operate with very low voltages.     

The Challenge of Producing Fiber-Based Organic Electronic Devices

The implementation of organic electronic devices on fibers is a challenging task, not yet investigated in detail. As was shown earlier, a direct transition from a flat device structure to a fiber substrate is in principle possible. However, a more detailed investigation of the process reveals additional complexities than just the transition in geometry. It will be shown, that the layer formation of evaporated materials behaves differently due to the multi-angled incidence on the fibers surface. In order to achieve homogenous layers the evaporation process has to be adapted. Additionally, the fiber geometry itself facilitates damaging of its surface due to mechanical impact and leads to a high surface roughness, thereby often hindering commercial fibers to be used as substrates. In this article, a treatment of commercial polymer-coated glass fibers will be demonstrated that allows for the fabrication of rather flexible organic light-emitting diodes (OLEDs) with cylindrical emission characteristics. Since OLEDs rely the most on a smooth substrate, fibers undergoing the proposed treatment are applicable for other organic electronic devices such as transistors and solar cells. Finally, the technique also supports the future fabrication of organic electronics not only in smart textiles and woven electronics but also in bent surfaces, which opens a wide range of applications.     

Bottom Contact Metal Oxide Interface Modification Improving the Efficiency of Organic Light Emitting Diodes

The performance of solution-processed organic light emitting diodes (OLEDs) is often limited by non-uniform contacts. In this work, we introduce Ni-containing solution-processed metal oxide (MO) interfacial layers inserted between indium tin oxide (ITO) and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) to improve the bottom electrode contact for OLEDs using the poly(p-phenylene vinylene) (PPV) derivative Super-Yellow (SY) as an emission layer. For ITO/Ni-containing MO/PEDOT:PSS bottom electrode structures we show enhanced wetting properties that result in an improved OLED device efficiency. Best performance is achieved using a Cu-Li co-doped spinel nickel cobaltite [(Cu-Li):NiCo₂O₄], for which the current efficiency and luminous efficacy of SY OLEDs increased, respectively, by 12% and 11% from the values obtained for standard devices without a Ni-containing MO interface modification between ITO and PEDOT:PSS. The enhanced performance was attributed to the improved morphology of PEDOT:PSS, which consequently increased the hole injection capability of the optimized ITO/(Cu-Li):NiCo₂O₄/PEDOT:PSS electrode.     

Hysteresis in Lanthanide Aluminum Oxides Observed by Fast Pulse CV Measurement

Oxide materials with large dielectric constants (so-called high-k dielectrics) have attracted much attention due to their potential use as gate dielectrics in Metal Oxide Semiconductor Field Effect Transistors (MOSFETs). A novel characterization (pulse capacitance-voltage) method was proposed in detail. The pulse capacitance-voltage technique was employed to characterize oxide traps of high-k dielectrics based on the Metal Oxide Semiconductor (MOS) capacitor structure. The variation of flat-band voltages of the MOS structure was observed and discussed accordingly. Some interesting trapping/detrapping results related to the lanthanide aluminum oxide traps were identified for possible application in Flash memory technology. After understanding the trapping/detrapping mechanism of the high-k oxides, a solid foundation was prepared for further exploration into charge-trapping non-volatile memory in the future.     

Water-stable organic transistors and their application in chemical and biological sensors

The development of low-cost, reliable sensors will rely on devices capable of converting an analyte binding event to an easily read electrical signal. Organic thin-film transistors (OTFTs) are ideal for inexpensive, single-use chemical or biological sensors because of their compatibility with flexible, large-area substrates, simple processing, and highly tunable active layer materials. We have fabricated low-operating voltage OTFTs with a cross-linked polymer gate dielectric, which display stable operation under aqueous conditions over >10⁴ electrical cycles using the p-channel semiconductor 5,5′-bis-(7-dodecyl-9H-fluoren-2-yl)-2,2′-bithiophene (DDFTTF). OTFT sensors were demonstrated in aqueous solutions with concentrations as low as parts per billion for trinitrobenzene, methylphosphonic acid, cysteine, and glucose. This work demonstrates of reliable OTFT operation in aqueous media, hence opening new possibilities of chemical and biological sensing with OTFTs.     

Sigma-pi molecular dielectric multilayers for low-voltage organic thin-film transistors

Very thin (2.3-5.5 nm) self-assembled organic dielectric multilayers have been integrated into organic thin-film transistor structures to achieve sub-1-V operating characteristics. These new dielectrics are fabricated by means of layer-by-layer solution phase deposition of molecular silicon precursors, resulting in smooth, nanostructurally well defined, strongly adherent, thermally stable, virtually pinhole-free, organosiloxane thin films having exceptionally large electrical capacitances (up to approximately 2,500 nF.cm(-2)), excellent insulating properties (leakage current densities as low as 10(-9) A.cm(-2)), and single-layer dielectric constant (k)of approximately 16. These 3D self-assembled multilayers enable organic thin-film transistor function at very low source-drain, gate, and threshold voltages (<1 V) and are compatible with a broad variety of vapor- or solution-deposited p- and n-channel organic semiconductors.     

A Method to Realize Efficient Deep-Red Phosphorescent OLEDs with a Broad Spectral Profile and Low Operating Voltages

Organic light-emitting diodes (OLEDs) used as phototherapy light sources require sufficient spectral distribution in the effective wavelength ranges and low operating voltages. Herein, a double emitting layer structure consisting of a red-emitting Ir(piq)₂acac and a deep-red Ir(fliq)₂acac was designed to generate a broad electroluminescence spectrum. An efficient TCTA:CN-T2T exciplex system was used as the host of the emitting layer, facilitating effective energy transfer from the exciplex host to the red and deep-red phosphors. The materials used in the exciplex host were also used as the carrier transport layers to eliminate the energy barriers and thus increase the current density. The hole injection layer structures were varied to examine the hole injection capabilities and the carrier balance. The resulting optimized phosphorescent OLEDs with a broad spectral profile exhibit a 90% coverage ratio in the target ranges from 630 to 690 nm, together with a high peak efficiency of 19.1% (10.2 cd/A and 13.8 lm/W). The proposed device only needs 5.2 V to achieve a power density of 5 mW/cm², implying that the device could be driven via two series-connected button cell batteries. These results illustrate the feasibility of our design concepts and demonstrate the realization of a portable and lightweight OLED phototherapy light source.     

Low-Temperature-Processed High-Performance Pentacene OTFTs with Optimal Nd-Ti Oxynitride Mixture as Gate Dielectric

When processed at a low temperature of 200 °C, organic thin-film transistors (OTFTs) with pentacene channel adopting high-k Neodymium-Titanium oxynitride mixtures (NdTiON) with various Ti contents as gate dielectrics are fabricated. The Ti content in the NdTiON is varied by co-sputtering a Ti target at 0 W, 10 W, 20 W and 30 W, respectively, while fixing the sputtering power of an Nd target at 45 W. High-performance OTFT is obtained for the 20 W-sputtered Ti, including a small threshold voltage of −0.71 V and high carrier mobility of 1.70 cm²/V·s. The mobility improvement for the optimal Ti content can be attributed to smoother dielectric surface and resultant larger overlying pentacene grains as reflected by Atomic Force Microscopy measurements. Moreover, this sample with the optimal Ti content shows much higher mobility than its counterpart processed at a higher temperature of 400 °C (0.8 cm²/V·s) because it has a thinner gate-dielectric/gate-electrode interlayer for stronger screening on the remote phonon scattering by the gate electrode. In addition, a high dielectric constant of around 10 is obtained for the NdTiON gate dielectric that contributes to a threshold voltage smaller than 1 V for the pentacene OTFT, implying the high potential of the Nd-Ti oxynitride in future high-performance organic devices.     

Design of Higher-k and More Stable Rare Earth Oxides as Gate Dielectrics for Advanced CMOS Devices

High permittivity (k) gate dielectric films are widely studied to substitute SiO₂ as gate oxides to suppress the unacceptable gate leakage current when the traditional SiO₂ gate oxide becomes ultrathin. For high-k gate oxides, several material properties are dominantly important. The first one, undoubtedly, is permittivity. It has been well studied by many groups in terms of how to obtain a higher permittivity for popular high-k oxides, like HfO₂ and La₂O₃. The second one is crystallization behavior. Although it’s still under the debate whether an amorphous film is definitely better than ploy-crystallized oxide film as a gate oxide upon considering the crystal boundaries induced leakage current, the crystallization behavior should be well understood for a high-k gate oxide because it could also, to some degree, determine the permittivity of the high-k oxide. Finally, some high-k gate oxides, especially rare earth oxides (like La₂O₃), are not stable in air and very hygroscopic, forming hydroxide. This topic has been well investigated in over the years and significant progresses have been achieved. In this paper, I will intensively review the most recent progresses of the experimental and theoretical studies for preparing higher-k and more stable, in terms of hygroscopic tolerance and crystallization behavior, Hf- and La-based ternary high-k gate oxides.     

Conformally Gated Surface Conducting Behaviors of Single-Walled Carbon Nanotube Thin-Film-Transistors

Semiconducting single-walled carbon nanotubes (s-SWCNTs) have gathered significant interest in various emerging electronics due to their outstanding electrical and mechanical properties. Although large-area and low-cost fabrication of s-SWCNT field effect transistors (FETs) can be easily achieved via solution processing, the electrical performance of the solution-based s-SWCNT FETs is often limited by the charge transport in the s-SWCNT networks and interface between the s-SWCNT and the dielectrics depending on both s-SWCNT solution synthesis and device architecture. Here, we investigate the surface and interfacial electro-chemical behaviors of s-SWCNTs. In addition, we propose a cost-effective and straightforward process capable of minimizing polymers bound to s-SWCNT surfaces acting as an interfering element for the charge carrier transport via a heat-assisted purification (HAP). With the HAP treated s-SWCNTs, we introduced conformal dielectric configuration for s-SWCNT FETs, which are explored by a carefully designed wide array of electrical and chemical characterizations with finite-element analysis (FEA) computer simulation. For more favorable gate-field-induced surface and interfacial behaviors of s-SWCNT, we implemented conformally gated highly capacitive s-SWCNT FETs with ion-gel dielectrics, demonstrating field-effect mobility of ~8.19 cm²/V⋅s and on/off current ratio of ~10⁵ along with negligible hysteresis.     

Nanocluster-Based Ultralow-Temperature Driven Oxide Gate Dielectrics for High-Performance Organic Electronic Devices

The development of novel dielectric materials with reliable dielectric properties and low-temperature processibility is crucial to manufacturing flexible and high-performance organic thin-film transistors (OTFTs) for next-generation roll-to-roll organic electronics. Here, we investigate the solution-based fabrication of high-k aluminum oxide (Al₂O₃) thin films for high-performance OTFTs. Nanocluster-based Al₂O₃ films fabricated by highly energetic photochemical activation, which allows low-temperature processing, are compared to the conventional nitrate-based Al₂O₃ films. A wide array of spectroscopic and surface analyses show that ultralow-temperature photochemical activation (<60 °C) induces the decomposition of chemical impurities and causes the densification of the metal-oxide film, resulting in a highly dense high-k Al₂O₃ dielectric layer from Al-13 nanocluster-based solutions. The fabricated nanocluster-based Al₂O₃ films exhibit a low leakage current density (<10⁻⁷ A/cm²) at 2 MV/cm and high dielectric breakdown strength (>6 MV/cm). Using this dielectric layer, precisely aligned microrod-shaped 2,7-dioctyl[1]benzothieno [3,2-b][1] benzothiophene (C8-BTBT) single-crystal OTFTs were fabricated via solvent vapor annealing and photochemical patterning of the sacrificial layer.     

Towards the Bisbenzothienocarbazole Core: A Route of Sulfurated Carbazole Derivatives with Assorted Optoelectronic Properties and Applications

Ladder-type molecules, which possess an extended aromatic backbone, are particularly sought within the optoelectronic field. In view of the potential of the 14H-bis[1]benzothieno[3,2-b:2’,3’-h]carbazole core as a p-type semiconductor, herein we studied a set of two derivatives featuring a different alkylation patterning. The followed synthetic route, involving various sulfurated carbazole-based molecules, also resulted in a source of fluorophores with different emitting behaviors. Surprisingly, the sulfoxide-containing fluorophores substantially increased their blue fluorescence with respect to the nearly non-emitting sulfur counterparts. On this basis, we could shed light on the relationship between their chemical structure and their emission as an approach for future applications. Considering the performance in organic thin-film transistors, both bisbenzothienocarbazole derivatives displayed p-type characteristics, with hole mobility values up to 1.1 × 10⁻³ cm² V⁻¹ s⁻¹ and considerable air stability. Moreover, the role of the structural design has been correlated with the device performance by means of X-ray analysis and the elucidation of the corresponding single crystal structures.     

Comprehensive Study of Lanthanum Aluminate High-Dielectric-Constant Gate Oxides for AdvancedCMOS Devices

A comprehensive study of the electrical and physical characteristics of Lanthanum Aluminate (LaAlO₃) high-dielectric-constant gate oxides for advanced CMOS devices was performed. The most distinctive feature of LaAlO₃ as compared with Hf-based high-k materials is the thermal stability at the interface with Si, which suppresses the formation of a low-permittivity Si oxide interfacial layer. Careful selection of the film deposition conditions has enabled successful deposition of an LaAlO₃ gate dielectric film with an equivalent oxide thickness (EOT) of 0.31 nm. Direct contact with Si has been revealed to cause significant tensile strain to the Si in the interface region. The high stability of the effective work function with respect to the annealing conditions has been demonstrated through comparison with Hf-based dielectrics. It has also been shown that the effective work function can be tuned over a wide range by controlling the La/(La + Al) atomic ratio. In addition, gate-first n-MOSFETs with ultrathin EOT that use sulfur-implanted Schottky source/drain technology have been fabricated using a low-temperature process.     

Investigations of Structural and Electrical Properties of ALD Films Formed with the Ozone Precursor

The continuous development of ALD thin films demands ongoing improvements and changes toward fabricating materials with tailored properties that are suitable for different practical applications. Ozone has been recently established as a precursor, with distinct advantages over the alternative oxidizing precursors in the ALDs of advanced dielectric films. This study reports alumina (Al₂O₃) and hafnia (HfO₂) formation using an O₃ source and compares the obtained structural and electrical properties. The performed structural examinations of ozone-based materials proved homogenous high-k films with less vacancy levels compared to water-based films. The enhanced structural properties also result in the problematic incorporation of different dopants through the bulk layer. Furthermore, analysis of electrical characteristics of the MIS structures with ALD gate dielectrics demonstrated the improved quality and good insulating properties of ozone-based films. However, further optimization of the ALD technique with ozone is needed as a relatively low relative permittivity characterizes the ultra-thin films.