Highly Stable Thin-Film Transistors Based on Indium Oxynitride Semiconductor.

In this study, the properties of indium oxynitride (InON) semiconductor films grown by reactive radio frequency sputtering were examined both experimentally and theoretically. Also, thin-film transistors (TFTs) incorporating InON as the active layer were evaluated for the first time. It is found that InON films exhibit high stability upon prolonged exposure to air and the corresponding TFTs are more stable when subjected to negative bias illumination stress, compared to devices based on indium oxide (In2O3) or zinc oxynitride (ZnON) semiconductors. X-ray photoelectron spectroscopy analyses of the oxygen 1s peaks suggest that as nitrogen is incorporated into In2O3 to form InON, the relative fraction of oxygen-deficient regions decreases significantly, which is most likely to occur by having the valence band maximum shifted up. Density functional theory calculations indicate that the formation energy of InN is much lower than Zn3N2, thus accounting for the higher stability of InON compared to ZnON in air.

Interstitial Mo-Assisted Photovoltaic Effect in Multilayer MoSe2 Phototransistors.

Thin-film transistors (TFTs) based on multilayer molybdenum diselenide (MoSe2 ) synthesized by modified atmospheric pressure chemical vapor deposition (APCVD) exhibit outstanding photoresponsivity (103.1 A W-1 ), while it is generally believed that optical response of multilayer transition metal dichalcogenides (TMDs) is significantly limited due to their indirect bandgap and inefficient photoexcitation process. Here, the fundamental origin of such a high photoresponsivity in the synthesized multilayer MoSe2 TFTs is sought. A unique structural characteristic of the APCVD-grown MoSe2 is observed, in which interstitial Mo atoms exist between basal planes, unlike usual 2H phase TMDs. Density functional theory calculations and photoinduced transfer characteristics reveal that such interstitial Mo atoms form photoreactive electronic states in the bandgap. Models indicate that huge photoamplification is attributed to trapped holes in subgap states, resulting in a significant photovoltaic effect. In this study, the fundamental origin of high responsivity with synthetic MoSe2 phototransistors is identified, suggesting a novel route to high-performance, multifunctional 2D material devices for future wearable sensor applications.

Performance and Stability Enhancement of In-Sn-Zn-O TFTs Using SiO2 Gate Dielectrics Grown by Low Temperature Atomic Layer Deposition.

Silicon dioxide (SiO2) films were synthesized by plasma-enhanced atomic layer deposition (PEALD) using BTBAS [bis(tertiarybutylamino) silane] as the precursor and O2 plasma as the reactant, at a temperature range from 50 to 200 °C. While dielectric constant values larger than 3.7 are obtained at all deposition temperatures, the leakage current levels are drastically reduced to below 10-12 A at temperatures above 150 °C, which are similar to those obtained in thermally oxidized and PECVD grown SiO2. Thin film transistors (TFTs) based on In-Sn-Zn-O (ITZO) semiconductors were fabricated using thermal SiO2, PECVD SiO2, and PEALD SiO2 grown at 150 °C as the gate dielectrics, and superior device performance and stability are observed in the last case. A linear field effect mobility of 68.5 cm2/(V s) and a net threshold voltage shift (ΔVth) of approximately 1.2 V under positive bias stress (PBS) are obtained using the PEALD SiO2 as the gate insulator. The relatively high concentration of hydrogen in the PEALD SiO2 is suggested to induce a high carrier density in the ITZO layer deposited onto it, which results in enhanced charge transport properties. Also, it is most likely that the hydrogen atoms have passivated the electron traps related to interstitial oxygen defects, thus resulting in improved stability under PBS. Although the PECVD SiO2 contains a hydrogen concentration similar to that of PEALD SiO2, its relatively large surface roughness appears to induce scattering effects and the generation of electron traps, which result in inferior device performance and stability.

Improving the Stability of High-Performance Multilayer MoS2 Field-Effect Transistors.

In this study, we propose a method for improving the stability of multilayer MoS2 field-effect transistors (FETs) by O2 plasma treatment and Al2O3 passivation while sustaining the high performance of bulk MoS2 FET. The MoS2 FETs were exposed to O2 plasma for 30 s before Al2O3 encapsulation to achieve a relatively small hysteresis and high electrical performance. A MoOx layer formed during the plasma treatment was found between MoS2 and the top passivation layer. The MoOx interlayer prevents the generation of excess electron carriers in the channel, owing to Al2O3 passivation, thereby minimizing the shift in the threshold voltage (Vth) and increase of the off-current leakage. However, prolonged exposure of the MoS2 surface to O2 plasma (90 and 120 s) was found to introduce excess oxygen into the MoOx interlayer, leading to more pronounced hysteresis and a high off-current. The stable MoS2 FETs were also subjected to gate-bias stress tests under different conditions. The MoS2 transistors exhibited negligible decline in performance under positive bias stress, positive bias illumination stress, and negative bias stress, but large negative shifts in Vth were observed under negative bias illumination stress, which is attributed to the presence of sulfur vacancies. This simple approach can be applied to other transition metal dichalcogenide materials to understand their FET properties and reliability, and the resulting high-performance hysteresis-free MoS2 transistors are expected to open up new opportunities for the development of sophisticated electronic applications.

Effects of Fluorine Doping on the Electrical Performance of ZnON Thin-Film Transistors.

In this work, the effects of fluorine incorporation in high mobility zinc oxynitride (ZnON) semiconductor are studied by both theoretical calculations and experimental evaluation of thin film transistors (TFTs). From density functional theory (DFT) calculations, fluorine acts as a carrier suppressor in the ZnON matrix when it substitutes a nitrogen vacant site (VN). Thin films of ZnON and ZnON:F were grown by reactively cosputtering Zn metal and ZnF2 targets, and their electrical, physical, and chemical characteristics were studied. X-ray photoelectron spectroscopy (XPS) analyses of the nitrogen 1s peaks in ZnON and ZnON:F suggest that as the fluorine incorporation increases, the relative fraction of Zn-N bonds from stoichiometric Zn3N2 increases. On the other hand, the Zn-N bond characteristics arising from nonstoichiometric ZnxNy and N-N bonds decrease, implying that indeed fluorine anions have an effect of passivating the N-related defects. The corresponding TFTs exhibit optimum transfer characteristics and switching ability when approximately 3.5 atomic percent of fluorine is present in the 40 nm thick ZnON:F active layer.

The resonant interaction between anions or vacancies in ZnON semiconductors and their effects on thin film device properties.

Zinc oxynitride (ZnON) semiconductors are suitable for high performance thin-film transistors (TFTs) with excellent device stability under negative bias illumination stress (NBIS). The present work provides a first approach on the optimization of electrical performance and stability of the TFTs via studying the resonant interaction between anions or vacancies in ZnON. It is found that the incorporation of nitrogen increases the concentration of nitrogen vacancies (VN+s), which generate larger concentrations of free electrons with increased mobility. However, a critical amount of nitrogen exists, above which electrically inactive divacancy (VN-VN)0 forms, thus reducing the number of carriers and their mobility. The presence of nitrogen anions also reduces the relative content of oxygen anions, therefore diminishing the probability of forming O-O dimers (peroxides). The latter is well known to accelerate device degradation under NBIS. Calculations indicate that a balance between device performance and NBIS stability may be achieved by optimizing the nitrogen to oxygen anion ratio. Experimental results confirm that the degradation of the TFTs with respect to NBIS becomes less severe as the nitrogen content in the film increases, while the device performance reaches an intermediate peak, with field effect mobility exceeding 50 cm2/Vs.

High-Performance Zinc Tin Oxide Semiconductor Grown by Atmospheric-Pressure Mist-CVD and the Associated Thin-Film Transistor Properties.

Zinc tin oxide (Zn-Sn-O, or ZTO) semiconductor layers were synthesized based on solution processes, of which one type involves the conventional spin coating method and the other is grown by mist chemical vapor deposition (mist-CVD). Liquid precursor solutions are used in each case, with tin chloride and zinc chloride (1:1) as solutes in solvent mixtures of acetone and deionized water. Mist-CVD ZTO films are mostly polycrystalline, while those synthesized by spin-coating are amorphous. Thin-film transistors based on mist-CVD ZTO active layers exhibit excellent electron transport properties with a saturation mobility of 14.6 cm2/(V s), which is superior to that of their spin-coated counterparts (6.88 cm2/(V s)). X-ray photoelectron spectroscopy (XPS) analyses suggest that the mist-CVD ZTO films contain relatively small amounts of oxygen vacancies and, hence, lower free-carrier concentrations. The enhanced electron mobility of mist-CVD ZTO is therefore anticipated to be associated with the electronic band structure, which is examined by X-ray absorption near-edge structure (XANES) analyses, rather than the density of electron carriers.

Synergistic effect of Indium and Gallium co-doping on growth behavior and physical properties of hydrothermally grown ZnO nanorods.

We synthesized ZnO nanorods (NRs) using simple hydrothermal method, with the simultaneous incorporation of gallium (Ga) and indium (In), in addition, investigated the co-doping effect on the morphology, microstructure, electronic structure, and electrical/optical properties. The growth behavior of the doped NRs was affected by the nuclei density and polarity of the (001) plane. The c-axis parameter of the co-doped NRs was similar to that of undoped NRs due to the compensated lattice distortion caused by the presence of dopants that are both larger (In3+) and smaller (Ga3+) than the host Zn2+ cations. Red shifts in the ultraviolet emission peaks were observed in all doped NRs, owing to the combined effects of NR size, band gap renormalization, and the presence of stacking faults created by the dopant-induced lattice distortions. In addition, the NR/p-GaN diodes using co-doped NRs exhibited superior electrical conductivity compared to the other specimens due to the increase in the charge carrier density of NRs and the relatively large effective contact area of (001) planes. The simultaneous doping of In and Ga is therefore anticipated to provide a broader range of optical, physical, and electrical properties of ZnO NRs for a variety of opto-electronic applications.

Wrinkle-free graphene electrodes in zinc tin oxide thin-film transistors for large area applications.

Wrinkle-free graphene was used to form the source-drain electrodes in thin film transistors based on a zinc tin oxide (ZTO) semiconductor. A 10 nm thick titanium adhesion layer was applied prior to transferring a conductive graphene film on top of it by chemical detachment. The formation of an interlayer oxide between titanium and graphene allows the achievement of uniform surface roughness over the entire substrate area. The resulting devices were thermally treated in ambient air, and a substantial decrease in field effect mobility is observed with increasing annealing temperature. The increase in electrical resistivity of the graphene film at higher annealing temperatures may have some influence, however the growth of the oxide interlayer at the ZTO/Ti boundary is suggested to be most influential, thereby inducing relatively high contact resistance.

A Study on the Electrical Properties of Atomic Layer Deposition Grown InOx on Flexible Substrates with Respect to N2O Plasma Treatment and the Associated Thin-Film Transistor Behavior under Repetitive Mechanical Stress.

Indium oxide (InOx) films were deposited at low processing temperature (150 °C) by atomic layer deposition (ALD) using [1,1,1-trimethyl-N-(trimethylsilyl)silanaminato]indium (InCA-1) as the metal precursor and hydrogen peroxide (H2O2) as the oxidant. As-deposited InOx exhibits a metallic conductor-like behavior owing to a relatively high free-carrier concentration. In order to control the electron density in InOx layers, N2O plasma treatment was carried out on the film surface. The exposure time to N2O plasma was varied (600-2400 s) to evaluate its effect on the electrical properties of InOx. In this regard, thin-film transistors (TFTs) utilizing this material as the active layer were fabricated on polyimide substrates, and transfer curves were measured. As the plasma treatment time increases, the TFTs exhibit a transition from metal-like conductor to a high-performance switching device. This clearly demonstrates that the N2O plasma has an effect of diminishing the carrier concentration in InOx. The combination of low-temperature ALD and N2O plasma process offers the possibility to achieve high-performance devices on polymer substrates. The electrical properties of InOx TFTs were further examined with respect to various radii of curvature and repetitive bending of the substrate. Not only does prolonged cyclic mechanical stress affect the device properties, but the bending direction is also found to be influential. Understanding such behavior of flexible InOx TFTs is anticipated to provide effective ways to design and achieve reliable electronic applications with various form factors.

Influence of Dielectric Layers on Charge Transport through Diketopyrrolopyrrole-Containing Polymer Films: Dielectric Polarizability vs Capacitance.

Field-effect mobility of a polymer semiconductor film is known to be enhanced when the gate dielectric interfacing with the film is weakly polarizable. Accordingly, gate dielectrics with lower dielectric constant (k) are preferred for attaining polymer field-effect transistors (PFETs) with larger mobilities. At the same time, it is also known that inducing more charge carriers into the polymer semiconductor films helps in enhancing their field-effect mobility, because the large number of traps presented in such a disorder system can be compensated substantially. In this sense, it may seem that employing higher k dielectrics is rather beneficial because capacitance is proportional to the dielectric constant. This, however, contradicts with the statement above. In this study, we compare the impact of the two, i.e., the polarizability and the capacitance of the gate dielectric, on the transport properties of poly[(diketopyrrolopyrrole)-alt-(2,2'-(1,4-phenylene)bisthiophene)] (PDPPTPT) semiconductor layers in an FET architecture. For the study, three different dielectric layers were employed: fluorinated organic CYTOP (k = ∼2), poly(methyl methacrylate) (k = ∼4), and relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) (k = ∼60). The beneficial influence of attaining more carriers in the PDPPTPT films on their charge transport properties was consistently observed from all three systems. However, the more dominant factor determining the large carrier mobility was the low polarizability of the gate dielectric rather than its large capacitance; field-effect mobilities of PDPPTPT films were always larger when lower k dielectric was employed than when higher k dielectric was used. The higher mobilities obtained when using lower k dielectrics could be attributed to the suppressed distribution of the density of localized states (DOS) near the transport level and to the resulting enhanced electronic coupling between the macromolecules.

A study on the electron transport properties of ZnON semiconductors with respect to the relative anion content.

High-mobility zinc oxynitride (ZnON) semiconductors were grown by RF sputtering using a Zn metal target in a plasma mixture of Ar, N2, and O2 gas. The RF power and the O2 to N2 gas flow rates were systematically adjusted to prepare a set of ZnON films with different relative anion contents. The carrier density was found to be greatly affected by the anion composition, while the electron mobility is determined by a fairly complex mechanism. First-principles calculations indicate that excess vacant nitrogen sites (VN) in N-rich ZnON disrupt the local electron conduction paths, which may be restored by having oxygen anions inserted therein. The latter are anticipated to enhance the electron mobility, and the exact process parameters that induce such a phenomenon can only be found experimentally. Contour plots of the Hall mobility and carrier density with respect to the RF power and O2 to N2 gas flow rate ratio indicate the existence of an optimum region where maximum electron mobility is obtained. Using ZnON films grown under the optimum conditions, the fabrication of high-performance devices with field-effect mobility values exceeding 120 cm(2)/Vs is demonstrated based on simple reactive RF sputtering methods.

A Study on the Growth Behavior and Stability of Molecular Layer Deposited Alucone Films Using Diethylene Glycol and Trimethyl Aluminum Precursors, and the Enhancement of Diffusion Barrier Properties by Atomic Layer Deposited Al2O3 Capping.

As a route to the production of organic-inorganic hybrid multilayers, the growth behavior of molecular layer deposited (MLD) alucone and atomic layer deposited (ALD) Al2O3 films on top of each other was examined. MLD alucone films were prepared using trimethyl aluminum and diethylene glycol precursors, the latter resulting in faster growth rates than ethylene glycol precursors. The sensitivity of individual alucone films with respect to ambient exposure was found to be related to moisture permeation and hydration reactions, of which the mechanism is studied by density functional theory calculations. Deleterious effects such as thickness reduction over time could be suppressed by applying a protective Al2O3 layer on top of alucone. A preliminary nucleation period was required in the ALD process of Al2O3 films on alucone surfaces, prior to reaching a linear regime where the thickness increases linearly with respect to the number of ALD cycles. The same behavior was observed for alucone growing on Al2O3. The protective Al2O3 films were found to effectively suppress moisture permeation, thus isolating the underlying alucone from the surrounding environment. The water vapor transmission rate was greatly reduced when an Al2O3/alucone/Al2O3 multilayer stack was formed, which suggests that proper combinations of organic/inorganic hybrid structures may provide chemically stable platforms, especially for mechanically flexible applications.

High-Mobility Transistors Based on Large-Area and Highly Crystalline CVD-Grown MoSe2 Films on Insulating Substrates.

Large-area and highly crystalline CVD-grown multilayer MoSe2 films exhibit a well-defined crystal structure (2H phase) and large grains reaching several hundred micrometers. Multilayer MoSe2 transistors exhibit high mobility up to 121 cm(2) V(-1) s(-1) and excellent mechanical stability. These results suggest that high mobility materials will be indispensable for various future applications such as high-resolution displays and human-centric soft electronics.

Highly Crystalline CVD-grown Multilayer MoSe2 Thin Film Transistor for Fast Photodetector.

Hexagonal molybdenum diselenide (MoSe2) multilayers were grown by chemical vapor deposition (CVD). A relatively high pressure (>760 Torr) was used during the CVD growth to achieve multilayers by creating multiple nuclei based on the two-dimensional crystal growth model. Our CVD-grown multilayer MoSe2 thin-film transistors (TFTs) show p-type-dominant ambipolar behaviors, which are attributed to the formation of Se vacancies generated at the decomposition temperature (650 °C) after the CVD growth for 10 min. Our MoSe2 TFT with a reasonably high field-effect mobility (10 cm(2)/V · s) exhibits a high photoresponsivity (93.7 A/W) and a fast photoresponse time (τ(rise) ~ 0.4 s) under the illumination of light, which demonstrates the practical feasibility of multilayer MoSe2 TFTs for photodetector applications.

Study on the photoresponse of amorphous In-Ga-Zn-O and zinc oxynitride semiconductor devices by the extraction of sub-gap-state distribution and device simulation.

Persistent photoconduction (PPC) is a phenomenon that limits the application of oxide semiconductor thin-film transistors (TFTs) in optical sensor-embedded displays. In the present work, a study on zinc oxynitride (ZnON) semiconductor TFTs based on the combination of experimental results and device simulation is presented. Devices incorporating ZnON semiconductors exhibit negligible PPC effects compared with amorphous In-Ga-Zn-O (a-IGZO) TFTs, and the difference between the two types of materials are examined by monochromatic photonic C-V spectroscopy (MPCVS). The latter method allows the estimation of the density of subgap states in the semiconductor, which may account for the different behavior of ZnON and IGZO materials with respect to illumination and the associated PPC. In the case of a-IGZO TFTs, the oxygen flow rate during the sputter deposition of a-IGZO is found to influence the amount of PPC. Small oxygen flow rates result in pronounced PPC, and large densities of valence band tail (VBT) states are observed in the corresponding devices. This implies a dependence of PPC on the amount of oxygen vacancies (VO). On the other hand, ZnON has a smaller bandgap than a-IGZO and contains a smaller density of VBT states over the entire range of its bandgap energy. Here, the concept of activation energy window (AEW) is introduced to explain the occurrence of PPC effects by photoinduced electron doping, which is likely to be associated with the formation of peroxides in the semiconductor. The analytical methodology presented in this report accounts well for the reduction of PPC in ZnON TFTs, and provides a quantitative tool for the systematic development of phototransistors for optical sensor-embedded interactive displays.

Facile Route to the Controlled Synthesis of Tetragonal and Orthorhombic SnO2 Films by Mist Chemical Vapor Deposition.

Two types of tin dioxide (SnO2) films were grown by mist chemical vapor deposition (Mist-CVD), and their electrical properties were studied. A tetragonal phase is obtained when methanol is used as the solvent, while an orthorhombic structure is formed with acetone. The two phases of SnO2 exhibit different electrical properties. Tetragonal SnO2 behaves as a semiconductor, and thin-film transistors (TFTs) incorporating this material as the active layer exhibit n-type characteristics with typical field-effect mobility (µ(FE)) values of approximately 3-4 cm(2)/(V s). On the other hand, orthorhombic SnO2 is found to behave as a metal-like transparent conductive oxide. Density functional theory calculations reveal that orthorhombic SnO2 is more stable under oxygen-rich conditions, which correlates well with the experimentally observed solvent effects. The present study paves the way for the controlled synthesis of functional materials by atmospheric pressure growth techniques.