Solution-processed Oxide Research Articles

Improvement in Switching Characteristics and Bias Stability of Solution-Processed Zinc-Tin Oxide Thin Film Transistors via Simple Low-Pressure Thermal Annealing Treatment.

In this study, we used a low-pressure thermal annealing (LPTA) treatment to improve the switching characteristics and bias stability of zinc-tin oxide (ZTO) thin film transistors (TFTs). For this, we first fabricated the TFT and then applied the LPTA treatment at temperatures of 80 °C and 140 °C. The LPTA treatment reduced the number of defects in the bulk and interface of the ZTO TFTs. In addition, the changes in the water contact angle on the ZTO TFT surface indicated that the LPTA treatment reduced the surface defects. Hydrophobicity suppressed the off-current and instability under negative bias stress because of the limited absorption of moisture on the oxide surface. Moreover, the ratio of metal-oxygen bonds increased, while the ratio of oxygen-hydrogen bonds decreased. The reduced action of hydrogen as a shallow donor induced improvements in the on/off ratio (from 5.5 × 103 to 1.1 × 107) and subthreshold swing (8.63 to V·dec-1 and 0.73 V·dec-1), producing ZTO TFTs with excellent switching characteristics. In addition, device-to-device uniformity was significantly improved because of the reduced defects in the LPTA-treated ZTO TFTs.

The impact of nickel doping on metal-oxide network in solution-processed indium zinc oxide transistors

Solution-processed nickel zinc oxide (IZO) thin-film transistors (TFTs) are of great interest as core elements for future display technology based on the low-cost manufacture. It still remains a challenge to ensure stability in the off-current state of IZO using a dopant that is more resource-friendly than Ga in solution processing. In this study, we suggest a solution-based doping process of the IZO semiconductors with a Ni carrier suppressor and investigated the effects of Ni on their transistor operation. Owing to similar size of Ni2+ to Zn2+, an appropriate concentration of Ni partially substituted Zn sites and the strong bonding force of Ni with O reduces hydroxide groups on the surface bonded to Zn, whereas excess Ni addition rather inhibited the formation of smooth thin film. The resulting Ni-doped IZO TFT devices from an optimized Ni concentration exhibited higher performances with significantly reduced off-state currents while maintaining high on-state currents, compared to IZO TFTs. This approach enriches the current family of solution-processed metal oxide semiconductors by providing another option for resource-friendly carrier suppressor, which can contribute to the inexpensive and simple solution process for fabricating TFTs.

Se-Vacancy Healing with Substitutional Oxygen in WSe2 for High-Mobility p-Type Field-Effect Transistors.

Transition-metal dichalcogenides possess high carrier mobility and can be scaled to sub-nanometer dimensions, making them viable alternative to Si electronics. WSe2 is capable of hole and electron carrier transport, making it a key component in CMOS logic circuits. However, since the p-type electrical performance of the WSe2-field effect transistor (FET) is still limited, various approaches are being investigated to circumvent this issue. Here, we formed a heterostructural multilayer WSe2 channel and solution-processed aluminum-doped zinc oxide (AZO) for compositional modification of WSe2 to obtain a device with excellent electrical properties. Supplying oxygen anions from AZO to the WSe2 channel eliminated subgap states through Se-deficiency healing, resulting in improved transport capacity. Se vacancies are known to cause mobility degradation due to scattering, which is mitigated through ionic compensation. Consequently, the hole mobility can reach high values, with a maximum of approximately 100 cm2/V s. Further, the transport behavior of the oxygen-doped WSe2-FET is systematically analyzed using density functional theory simulations and photoexcited charge collection spectroscopy measurements.

High Performing Inverted Flexible Perovskite Solar Cells via Solution Phase Deposition of Yttrium-Doped SnO2 Directly on Perovskite

Solution processing of flexible perovskite solar cells (f-PSCs) provides an avenue for scalable, high-throughput printing of lightweight, scalable, and cost-effective flexible solar cells. However, the deposition of fully solution-processed metal oxide charge transport layers on perovskites has been limited by solvent incompatibilities and high processing temperatures for metal oxide nanoparticles. In this study, we present high-performance, inverted f-PSCs from the direct deposition of yttrium-doped SnO2 nanoparticles functionalized with acetate on top of perovskite as an ink in anhydrous ethanol via blade coating. Yttrium doping improved device performance by improving the charge extraction with a decreased series resistance leading to improvements in the open-circuit voltage and fill factor. The champion power conversion efficiency for 0.1 cm2 devices increased from 14.3% for undoped SnO2 to 16.5% with 2% Y:SnO2 doping, which is unprecedented for f-PSCs on ITO-PET substrates employing SnO2 as an ETL.

Low-voltage, solution-processed InZnO thin-film transistors with enhanced performance achieved by bilayer gate dielectrics

Fully solution-processed oxide thin-film transistors (TFTs) have shown a great potential in future printable electronics. However, high defect densities at the dielectric/channel interface have limited the simultaneous achievement of low operating voltage and high device performance. In this Letter, we study the effects of bilayer gate dielectrics in potential performance enhancement of solution-processed indium zinc oxide (IZO) TFTs. Several single and bilayer gate dielectrics are studied in terms of their physical and electrical properties. Compared with IZO TFTs using single-layer ZrOx gate dielectrics, optimized TFTs with ZrOx/AlOx gate dielectrics show an increase in carrier mobility and current on/off ratio by a factor of 3.5 and 27, respectively. The inner mechanisms of the performance enhancement are systematically studied, showing that the significantly improved TFT performance originates from the passivation effects of AlOx, which reduce the trap/defect states at the dielectric/channel interface by approximately an order of magnitude. With a low operating voltage of 2 V, a high mobility of over 10 cm2/V s, a subthreshold swing as low as 89 mV/dec, and a high current on/off ratio of >105, the reported devices might have a great potential in future low-cost, low-power printable electronics.

Aqueous electrolyte-gated solution-processed metal oxide transistors for direct cellular interfaces.

Biocompatible field-effect-transistor-based biosensors have drawn attention for the development of next-generation human-friendly electronics. High-performance electronic devices must achieve low-voltage operation, long-term operational stability, and biocompatibility. Herein, we propose an electrolyte-gated thin-film transistor made of large-area solution-processed indium-gallium-zinc oxide (IGZO) semiconductors capable of directly interacting with live cells at physiological conditions. The fabricated transistors exhibit good electrical performance operating under sub-0.5 V conditions with high on-/off-current ratios (>107) and transconductance (>1.0 mS) over an extended operational lifetime. Furthermore, we verified the biocompatibility of the IGZO surface to various types of mammalian cells in terms of cell viability, proliferation, morphology, and drug responsiveness. Finally, the prolonged stable operation of electrolyte-gated transistor devices directly integrated with live cells provides the proof-of-concept for solution-processed metal oxide material-based direct cellular interfaces.

Layer-by-layer solution-processed two-dimensional graphene oxide–polyethylenimine thin-film coatings for enhanced pool boiling heat transfer

Nanostructured surfaces are promising candidates for improving liquid-vapor phase-change heat transfer, and their simple fabrication can offer rapid screening of optimal surface characteristics where the phase change occurs. However, conventional fabrication techniques involve energy-intensive processes, such as high-temperature and vacuum conditions or harsh wet chemical treatments. Herein, we propose the use of Layer-by-Layer (LbL) solution-processed graphene oxide/polyethyleneimine (GO/PEI) coatings as ultrathin two-dimensional (2-D) functional surfaces on stainless-steel heaters to enhance the pool boiling heat transfer. The LbL deposition processes implementing repetitive contact and removal of positive and negatively charged water-based solutions directly fabricated GO/PEI bilayers on the heater surfaces. GO and PEI serve as the core plane-like 2-D nanostructure and the bonding agent, respectively, whereas the number of LbL cycles precisely adjusts the physicochemical properties. In the ultra-thin LbL coating thickness (< 85 nm), the significant enhancement rates of critical heat flux (∼ 125%) were obtained in comparison with the bare heater substrate when the working fluid was deionized water. The optimal LbL GO/PEI bilayers facilitate water molecule transport through the extended GO interlayer nanochannels and high-density pinholes, whereas the outer and inner surface characteristics, such as roughness, wettability, and thickness, manipulate liquid-vapor transition-detachment, as well as bubble dynamics. The simple yet effective LbL solution-processed coatings can pave the way for the development of diverse functional coatings of hybridized 2-D and polymeric materials for thermal energy management involving liquid-vapor phase-change heat transfer.

具有大电导动态范围和多级电导态的铁电Hf0.5Zr0.5O2栅控突触晶体管

Benefiting from the nonvolatile and fast programming operations of ferroelectric materials, ferroelectric synaptic transistors (FSTs) are promising in neuromorphic computing. However, it is challenging to realize conductance with a large dynamic range (Gmax/Gmin) and multilevel states simultaneously under low energy consumption. Here, solution-processed indium oxide (In2O3) synaptic transistors gated by ferroelectric Hf0.5Zr0.5O2 (HZO) are proposed for the first time to address the above problems. Excellent synaptic characteristics were realized through the delicately regulated ferroelectric phase and good inhibition of charge injection in ferroelectric bulk and ferroelectric/semiconductor interface. Long-term potentiation/depression (LTP/D) up to 101 effective conductance states and excellent endurance (>1000 cycles) with large Gmax/Gmin = 32.2 were successfully mimicked under a low energy consumption of 490 fJ per spike event. Besides, the simulation achieved 96.5% recognition accuracy of handwriting digit, which is the highest record for existing FSTs. This work provides a new pathway for developing low-cost, high-performance, and energy-efficient FSTs.

Oxide TFTs with S/D-contacts patterned by high-resolution reverse-offset printed resist layers

Besides the metal oxide thin film transistors (TFTs) in flat-panel displays that are fabricated using vacuum-processes, there is a growing interest in the fabrication of metal oxide TFTs by means of scalable, low-cost solution and printing processes for applications such as flexible displays and biosensors. Although devices with printed semiconductor and gate insulator can exhibit good electrical performance, source/drain-contacts (S/D) printed from silver (Ag) nanoparticles (NPs) typically suffer from deteriorated electrical characteristics and stability problems. On the other hand, metals providing good contacts, such as aluminum (Al), titanium (Ti) and molybdenum (Mo), cannot be formed as air-stable NPs. To overcome these issues, we have developed a patterning method based on high-resolution reverse-offset printing (ROP) of a sacrificial polymer resist layer. ROP delivers patterns with micrometer-level resolution and steep sidewalls, which are ideal for patterning vacuum-deposited metal contacts at high resolution via lift-off process. Solution-processed indium oxide (In2O3) TFTs were successfully fabricated by using ROP lift-off process for patterning of gate and S/D-electrodes using Al. The fabricated In2O3-based TFTs with Al S/D-contacts exhibit good uniformity, constant mobility (μ sat) ∼ 2 cm2 (V s)−1 over a wide range of width/length-ratios (W/L) and almost zero turn-on voltage (V on) ∼ −0.2 V. TFTs down to 5 µm channel lengths were successfully patterned. Further development of the fabrication process could lead to flexible fully-print-patterned high-resolution TFT backplanes for flexible displays, biosensors, photosensors and x-ray detectors.

High-k and high-temperature-resistant polysilsesquioxane: Potential for solution-processed metal oxide semiconductor transistors operating at low voltage

High-k and high-temperature-resistant polysilsesquioxane: Potential for solution-processed metal oxide semiconductor transistors operating at low voltage

Effects of Post-UV/Ozone Treatment on Electrical Characteristics of Solution-Processed Copper Oxide Thin-Film Transistors.

To realize oxide semiconductor-based complementary circuits and better transparent display applications, the electrical properties of p-type oxide semiconductors and the performance improvement of p-type oxide thin-film transistors (TFTs) are required. In this study, we report the effects of post-UV/ozone (O3) treatment on the structural and electrical characteristics of copper oxide (CuO) semiconductor films and the TFT performance. The CuO semiconductor films were fabricated using copper (II) acetate hydrate as a precursor material to solution processing and the UV/O3 treatment was performed as a post-treatment after the CuO film was fabricated. During the post-UV/O3 treatment for up to 13 min, the solution-processed CuO films exhibited no meaningful change in the surface morphology. On the other hand, analysis of the Raman and X-ray photoemission spectra of solution-processed CuO films revealed that the post-UV/O3 treatment induced compressive stress in the film and increased the composition concentration of Cu-O lattice bonding. In the post-UV/O3-treated CuO semiconductor layer, the Hall mobility increased significantly to approximately 280 cm2 V-1 s-1, and the conductivity increased to approximately 4.57 × 10-2 Ω-1 cm-1. Post-UV/O3-treated CuO TFTs also showed improved electrical properties compared to those of untreated CuO TFTs. The field-effect mobility of the post-UV/O3-treated CuO TFT increased to approximately 6.61 × 10-3 cm-2 V-1 s-1, and the on-off current ratio increased to approximately 3.51 × 103. These improvements in the electrical characteristics of CuO films and CuO TFTs can be understood through the suppression of weak bonding and structural defects between Cu and O bonds after post-UV/O3 treatment. The result demonstrates that the post-UV/O3 treatment can be a viable method to improve the performance of p-type oxide TFTs.

Enhanced Photoresponsivity UV-C Photodetectors Using a p-n Junction Based on Ultra-Wide-Band Gap Sn-Doped β-Ga2O3 Microflake/MnO Quantum Dots.

Solar-blind self-powered UV-C photodetectors suffer from low performance, while heterostructure-based devices require complex fabrication and lack p-type wide band gap semiconductors (WBGSs) operating in the UV-C region (<290 nm). In this work, we mitigate the aforementioned issues by demonstrating a facile fabrication process for a high-responsivity solar-blind self-powered UV-C photodetector based on a p-n WBGS heterojunction structure, operating under ambient conditions. Here, heterojunction structures based on p-type and n-type ultra-wide band gap WBGSs (i.e. both are characterized by energy gap ≥4.5 eV) are demonstrated for the first time; mainly p-type solution-processed manganese oxide quantum dots (MnO QDs) and n-type Sn-doped β-Ga2O3 microflakes. Highly crystalline p-type MnO QDs are synthesized using cost-effective and facile pulsed femtosecond laser ablation in ethanol (FLAL), while the n-type Ga2O3 microflakes are prepared by exfoliation. The solution-processed QDs are uniformly dropcasted on the exfoliated Sn-doped β-Ga2O3 microflakes to fabricate a p-n heterojunction photodetector, resulting in excellent solar-blind UV-C photoresponse characteristics (with a cutoff at ∼265 nm) being demonstrated. Further analyses using XPS demonstrate the good band alignment between p-type MnO QDs and n-type β-Ga2O3 microflakes with a type-II heterojunction. Superior photoresponsivity (922 A/W) is obtained under bias, while the self-powered responsivity is ∼86.9 mA/W. The fabrication strategy adopted in this study will provide a cost-effective means for the development of flexible and highly efficient UV-C devices suitable for energy-saving large-scale fixable applications.

Dual Light Temporal Coding Modes Enabled by Nanoparticle-Mediated Phototransistors via Gate Bias Modulation for Brain-Inspired Visual Perception.

The core integration and cooperation of the retina, neurons, and synapses in the visual systems enable humans to effectively sense and process visual information with low power consumption. To mimic the human visual system, an artificial sensory nerve, along with optical sensing─a paired-pulse ratio (PPR) of the light pulse stimulated currents─and neural coding has been developed. For performing the artificial visual perception functions, we consistently reveal the positive and negative correlations between the PPR index and light pulse time interval by applying two consecutive light stimuli with gate voltages of -10 and 5 V, respectively, to a phototransistor. This phototransistor contains a heterostructured channel layer composed of zinc-oxide nanoparticles (ZnO NPs) interconnected with a solution-processed zinc-tin oxide (ZTO) film. The oxygen adsorption and desorption on the ZnO NP surface under light illumination are responsible for the positive-sloped PPR; the electron trapping effect at the ZnO NP/SiO2 interface is attributed to the negative-sloped PPR. The various accountable light power densities and number of surface trap states are considered to be directly realizing these spike-timing interval-dependent characteristics. The actual benefit of these characteristics is the dual temporal coding modes based on multiplicative operation using a ZTO/ZnO NP phototransistor realized via the active gate voltage modulation. The contrary tendency of the PPR index and temporal coding─a major biological neural coding─is well demonstrated by the potential of ZTO/ZnO NP phototransistors to be implemented in sensor networks for an artificial visual perception.

Defect suppression of a perovskite film with In2O3 quantum dots for improved solar cell performance

Solution-processable indium oxide quantum dots (In2O3) were introduced into a MAPbI3 film to solve the problem of low MAPbI3 film quality caused by inherent defects. Compared with the MAPbI3 film, the MAPbI3:In2O3 film exhibited an optimized time-resolved photoluminescence component ratio and improved carrier dissociation and transport efficiency. When the MAPbI3:In2O3 film was used to fabricate solar cells instead of the MAPbI3 film, the fill factor enhanced from 76.32% to 80.63%, the short circuit current density increased from 20.18 mA cm−2 to 21.32 mA cm−2, and the power conversion efficiency improved from 13.96% to 16.18% in the standard AM 1.5 illuminated condition, respectively.

Solution processed low operating voltage SnO2 thin film transistor by using Li2SnO3/TiO2 stacked gate dielectric

A thin layer of sol–gel derived lithium stannate (Li2SnO3) was deposited by a spin coating method that shows high areal capacitance with low DC conductivity which originated due to the mobile lithium ion (Li+) and low carrier concentration. The DC conductivity of this Li2SnO3 thin film has been reduced further by adding a sol–gel derived titanium-oxide (TiO2) layer. Moreover, bilayer thin film effective areal capacitance also increases due to the higher relative permittivity of TiO2 layer. The measured areal capacitance of such Li2SnO3 /TiO2 bilayer thin films is 518 nF/cm2 with a low current density of 3.8 X 10-5 A/cm2 under 5 V external bias, can fulfil the requirement as gate dielectric of a low operating voltage (≤3V) thin film transistor (TFT). For identifying its applicability as gate insulator, a solution-processed tin oxide (SnO2) thin film transistor (TFT) was fabricated with Li2SnO3/TiO2 stacked gate dielectric. In this TFT structure, thin film of TiO2, SnO2 and Li2SnO3 are all polycrystalline in nature. The electrical characterization of TFT has been done under DC mode operation in ambient atmosphere measurement which remain almost unaltered under 11 cyclic measurements. The optimized TFT required only 3.0 V external bias that shows an electron mobility of 3.47 cm2 V−1 s−1 with on/off ratio of 50.

Field-Effect Mobility Extraction of Solution-Processed InGaZnO Thin-Film Transistors Considering Dielectric Dispersion Behavior of AlOx Gate Insulator

We investigated the effect of the dielectric dispersion behavior of solution-processed aluminum oxide (AlOx) on the field-effect mobility estimation of the solution-processed indium–gallium–zinc oxide (IGZO) thin-film transistors (TFTs). In the metal–insulator–metal (MIM) structure, solution-processed AlOx dielectric film annealed at 350 °C showed dielectric dispersion behavior, which was attributed to the electric double layer (EDL) due to the mobile ions, such as a hydrogen ion (H+) or a hydroxyl group (OH–). The annealing process at a higher temperature of 500 °C reduced the number of mobile ions in the AlOx film and removed the dielectric dispersion behavior in the MIM structure. However, solution-processed IGZO TFTs using the AlOx annealed at 500 °C as gate insulator showed dielectric dispersion-related behavior. We found that the chemical reaction to form a solution-processed IGZO layer supplied the mobile ions to the AlOx film, resulting in the EDL and dielectric dispersion phenomenon. Therefore, the dielectric dispersion should be investigated in the metal–insulator–semiconductor–metal structure, although the dispersive behavior does not occur in the MIM structure. Furthermore, the field-effect mobility (μFE) of solution-processed IGZO TFTs was 35.6 and 17.5 cm2/V·s with and without consideration of the dielectric dispersion behavior. The μFE was overestimated by 203% without regard to the dielectric dispersion. Consequently, the dielectric dispersion should be considered to estimate the accurate μFE of solution-processed IGZO TFTs with solution-processed AlOx as the gate insulator layer.

Detection of acetone vapours using solution-processed tin oxide thin-film transistors

Abnormal concentrations of volatile organic compounds (VOCs) in human breathe can be used as disease-specific biomarkers for the non-invasive diagnosis of medical conditions, such as acetone for diabetes. Solution-processed bottom gate top contact metal oxide thin-film transistors (TFTs) are used to detect acetone vapours, as part of a proof-of-concept study. The effect of increasing annealing temperature (T) and channel length (L) on electrical and sensing performance are explored. Drain current (Ids) increases following exposure as acetone undergoes a redox reaction with the adsorbed oxygen species on the semiconductor surface, which results in free electrons being released back into the conduction band. Responsivity (R) is maximized at negative bias (Vgs < 0). For L = 50 μm, the peak R of the TFT annealed at 450 °C is three times greater than that of the TFT annealed at 350 °C, with Vgs = − 37.5 V and − 33 V, respectively.Graphical abstract

Non-Embedded Silver Nanowires/Antimony-Doped Tin Oxide/Polyethylenimine Transparent Electrode for Non-Fullerene Acceptor ITO-Free Inverted Organic Photovoltaics.

Indium tin oxide (ITO)-free solution-processed transparent electrodes are an essential component for the low-cost fabrication of organic optoelectronic devices. High-performance silver nanowires (AgNWs) ITO-free inverted organic photovoltaics (OPVs) usually require a AgNWs-embedded process. A simple cost-effective roll-to-roll production process of inverted ITO-free OPVs with AgNWs as a bottom transparent electrode requires solution-based thick metal oxides as carrier-selective contacts. In this reported study, we show that a solution-processed antimony-doped tin oxide (ATO)/polyethylenimine (PEI) electron-selective contact incorporated on the top of non-embedded AgNWs provides a high-performance ITO-free bottom electrode for non-fullerene acceptor (NFA) inverted OPVs.

High-performance and low-power source-gated transistors enabled by a solution-processed metal oxide homojunction

Cost-effective fabrication of mechanically flexible low-power electronics is important for emerging applications including wearable electronics, artificial intelligence, and the Internet of Things. Here, solution-processed source-gated transistors (SGTs) with an unprecedented intrinsic gain of ~2,000, low saturation voltage of +0.8 ± 0.1 V, and a ~25.6 μW power consumption are realized using an indium oxide In2O3/In2O3:polyethylenimine (PEI) blend homojunction with Au contacts on Si/SiO2. Kelvin probe force microscopy confirms source-controlled operation of the SGT and reveals that PEI doping leads to more effective depletion of the reverse-biased Schottky contact source region. Furthermore, using a fluoride-doped AlOx gate dielectric, rigid (on a Si substrate) and flexible (on a polyimide substrate) SGTs were fabricated. These devices exhibit a low driving voltage of +2 V and power consumption of ~11.5 μW, yielding inverters with an outstanding voltage gain of >5,000. Furthermore, electrooculographic (EOG) signal monitoring can now be demonstrated using an SGT inverter, where a ~1.0 mV EOG signal is amplified to over 300 mV, indicating significant potential for applications in wearable medical sensing and human-computer interfacing.

Correction: Solution-processable Li-doped transition metal oxide hole-injection layer for highly efficient quantum-dot light-emitting diodes

Correction for ‘Solution-processable Li-doped transition metal oxide hole-injection layer for highly efficient quantum-dot light-emitting diodes’ by Jae Seung Shin et al., J. Mater. Chem. C, 2022, 10, 5590–5597, https://doi.org/10.1039/D1TC06117H.