Solution-processed Oxide Thin Film Research Articles

Aqueous solution-processed In2O3 TFTs using focused plasma in gas mixtures

Solution-processed indium oxide (In2O3) thin films have been studied widely as active layers for transparent semiconducting devices because of their high charge carrier concentration, low absorbance, simple fabrication methods, and low cost. Several studies on improving the electrical characteristics of thin-film transistors (TFTs) by optimizing and fine-tuning the fabrication process and using various post-deposition treatments have been conducted to take full advantage of these semiconductor films in high-performance electronics. This study examined the effects of a focused plasma (FP) treatment on In2O3 thin films prepared using a simple solution process at 250 °C. The effects of the FP generated from N2 gas and two gas mixtures (N2-H2 and N2-H2-O2) on the electrical performance of the TFTs were analyzed. The FP treatment enhanced the electrical properties of the device, and the specific performance and stability parameters were improved by the treatment conditions. X-ray photoelectron spectroscopy showed that the FP treatment could effectively control the oxygen vacancies and carrier concentration in the solution-processed In2O3 thin films. Therefore, an FP beam is a viable method for optimizing In2O3 TFTs prepared at low temperatures for application in high-performance transparent electronic devices.

Continuous-Wave Green Laser Activation of Transparent InZnO Electrodes for Fully Solution-Processed Oxide Thin-Film Transistors

Continuous-Wave Green Laser Activation of Transparent InZnO Electrodes for Fully Solution-Processed Oxide Thin-Film Transistors

Effect of the gas flow rate in the focused-oxygen plasma treatment of solution-processed indium oxide thin film transistors

In2O3 is a transparent semiconductor layer due to its transparency, high mobility, and solution processability. In this paper, we study the effect of focused oxygen plasma treatment on solution processed indium oxide films annealed at 250 °C and analyze the effect of the gas flow rate. Thin film transistor devices were prepared based on pristine In2O3 films and films treated with oxygen plasma using flow rates of 3, 6, and 9 sccm. The results show that controlling the plasma flow rate can be used to finetune the device characteristics, and the selecting the optimal flow rate is important to improve the electron mobility, threshold voltage, on/off current ratio, and the electrical stability of the devices. The In2O3 TFTs treated at 6 sccm showed the best performance with mobility of 2.19 cm2V−1s−1, threshold voltage of of 4.25 V, and on/off current ratio of 2.13 × 106. The successful fabrication of high-performance, low-temperature solution deposited indium oxide transistors using the focused oxygen plasma treatment for electrical device applications demonstrates the practical potential of this treatment method for future transparent electronics.

Heterojunction Channel Engineering in Performance Enhancement of Solution-Processed Oxide Thin-Film Transistors

With the continuous development of next-generation display techniques, more and more attention has been put on solution-processed oxide thin-film transistors (TFTs). Here, we report the solution-based growth of InZnO/AlInZnO (IZO/AIZO) heterojunction channel layers and their implementation in high-performance TFTs. It is found that the heterojunction transistors exhibit a band-like electron transport, with both current ON/OFF ratio and mobility values significantly higher than single-layer IZO and AIZO devices by more than one order of magnitude. The marked improvement here is demonstrated to originate from the presence of confined free electrons at the atomically sharp heterointerface induced by the large conduction band offset between IZO and AIZO. Further channel engineering including the modification of In:Zn ratios, IZO, and AIZO thicknesses allows us to obtain high-performance heterojunction oxide TFTs with a high current ON/OFF ratio of <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$&gt;$</tex-math> </inline-formula> 5 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\times$</tex-math> </inline-formula> 10 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{\text{7}}$</tex-math> </inline-formula> , a mobility of 14.4 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\pm$</tex-math> </inline-formula> 1 cm <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{\text{2}}$</tex-math> </inline-formula> /Vs, a turn-on voltage close to zero-volt, and a superb stability against bias stresses and long-term storage. The high performance combined with the solution-processability enables the great potential of our reported TFTs in next-generation printable electronics.

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.

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.

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.

In situphotogenerated hydroxyl radicals in the reaction atmosphere for the accelerated crystallization of solution-processed functional metal oxide thin films

We propose a disruptive method to accelerate the crystallization at low temperatures of functional metal oxide films whereby hydroxyl radicals (•OH) are photogeneratedin situfrom the atmosphere where solution-deposited layers are UV-irradiated.

Effect of channel thickness on radiation hardness of solution-processed oxide thin film transistors

The electrical properties of a-ZITO TFTs with different channel thicknesses were characterized under proton irradiation with electrical stress. The device measurements showed stronger radiation-tolerance of oxide TFTs with smaller channel thickness.

Low-temperature crystallization of indium oxide thin films with a photoactivable additive

In this study, we report a simple route to the low-temperature crystallization of solution-processed indium oxide thin films by introducing ammonium nitrate in the sol–gel metal oxide precursor solution as photoactivable additive and applying deep ultraviolet (DUV) irradiation onto the as-spun oxide films in an inert atmosphere. Thermal and structural analyses revealed that the initial temperatures for condensation and crystallization were reduced down to 130 and 200 °C, respectively, by the in situ generation of reactive chemical species enabled by DUV-assisted nitrate photolysis. Furthermore, transmission electron microscopy confirmed that the degree of indium oxide film crystallinity was gradually enhanced as the amount of nitrate in the precursor solution was increased. Finally, electrical characterizations showed that carrier mobility, threshold voltage, subthreshold swing, and threshold voltage shift under the positive bias stress of sol–gel indium oxide thin-film transistors were improved from 0.21 to 5.03 cm2/V s, from 4.18 to 1.64 V, from 1.33 to 0.72 V/dec, and from 6.44 to 4.04 V, respectively, by combining ammonium nitrate and DUV photoactivation.

Solution-Processed Silicon Doped Tin Oxide Thin Films and Thin-Film Transistors Based on Tetraethyl Orthosilicate

Recently, tin oxide (SnO2) has been the preferred thin film material for semiconductor devices such as thin-film transistors (TFTs) due to its low cost, non-toxicity, and superior electrical performance. However, the high oxygen vacancy (VO) concentration leads to poor performance of SnO2 thin films and devices. In this paper, with tetraethyl orthosilicate (TEOS) as the Si source, which can decompose to release heat and supply energy when annealing, Si doped SnO2 (STO) films and inverted staggered STO TFTs were successfully fabricated by a solution method. An XPS analysis showed that Si doping can effectively inhibit the formation of VO, thus reducing the carrier concentration and improving the quality of SnO2 films. In addition, the heat released from TEOS can modestly lower the preparation temperature of STO films. By optimizing the annealing temperature and Si doping content, 350 °C annealed STO TFTs with 5 at.% Si exhibited the best device performance: Ioff was as low as 10−10 A, Ion/Ioff reached a magnitude of 104, and Von was 1.51 V. Utilizing TEOS as an Si source has a certain reference significance for solution-processed metal oxide thin films in the future.

Local Disordering in the Amorphous Network of a Solution-Processed Indium Tin Oxide Thin Film.

The polyhedra unit structure (MOx) in an amorphous metal oxide network has more freedom and flexibility than the same unit structure in a crystalline phase. Consequently, a mild external stimulus (e.g., instant photonic and acoustic energy) could affect and change this network parameter, thereby enhancing and modulating the electrical properties. However, it is difficult to tune these atomic parameters solely while maintaining the metal oxide's initial global amorphous phase and thereby preventing mechanical instability at the film-substrate interface (i.e., cracking or distortion). Here, we report local disordering in an amorphous network of a solution-processable indium tin oxide (ITO) film, where the disordering is triggered by mild-light irradiation (<0.1 mJ/cm2). Through a combination of systematic characterizations of the global structural and chemical compositional changes in conjunction with extended X-ray absorption fine structure analyses, we revealed the distortion of the atomic structure in the amorphous network of the ITO film led to the formation of additional structural oxygen vacancies. Our findings enabled us to fabricate mechanical-instability-free, perfect amorphous-phase ITO thin films on plastic substrates, where the sheet resistance substantially decreased to ∼ 2 × 103 Ω/□. Furthermore, this sheet resistance did not vary when the film and substrate were bent to a radius of 2 mm and could operate at low temperatures. This work can pave the novel way to fabricate high-quality flexible transparent electrodes suitable for rapid, cost-effective, and patternable processing on plastic substrates, and the domain can be extended to flexible electronics.

Effect of hydrochloric acid addition on dielectric properties of solution-processed aluminum titanium oxide thin film annealed at low temperature

This study investigated the effect of hydrochloric acid (HCl) addition on the dielectric properties of solution-processed aluminum titanium oxide (ATO) applied to thin-film transistors (TFTs) as a gate insulator layer. The formation of the solution-processed ATO film can be accelerated by adding HCl to the precursor solution because of the hydrolysis catalyst effect of HCl. The solution-processed ATO film exhibits higher crystallinity as the amount of HCl added increases. Furthermore, the addition of HCl suppresses the formation of oxygen vacancies, which can act as defect states in the ATO film. Consequently, the optimized ATO film annealed at 450 ℃ exhibited minimum leakage current density level of 5.14×10−9 A/cm2 at 0.33 MV/cm and dielectric constant of 13.9 when HCl of 2 ml was added to the precursor solution. These results are comparable with the dielectric properties of the ATO film annealed at 750 ℃ without HCl addition, because HCl addition catalyses hydrolysis and enhances the formation of metal-oxide bonding. Solution-processed amorphous indium-gallium-zinc oxide (IGZO) TFTs using the optimized ATO/AlOx film as gate insulator displayed excellent electrical properties such as threshold voltage of 0.17 V, field-effect mobility of 2.59 cm2/V∙s, subthreshold swing of 0.22 V/dec, and on/off ratio of 4.54×105. In addition, the IGZO TFT with the ATO gate insulator exhibited superior current driving capability compared to that of silicon dioxide (SiO2). These results indicate that solution-processed ATO films with HCl addition could be promising candidates for gate insulator layers in achieving low power consumption, high performance, and low cost TFTs.

Solution-processed tin oxide thin film for normally-off hydrogen terminated diamond field effect transistor

The solution processed method has been wildly used in the thin film fabrication because of the advantages of low cost, high efficiency, large scale for production, and long-term stability. In this paper, a normally-off hydrogen-terminated diamond field-effect transistor (FET) has been realized by using a solution processed SnO2 (sp-SnO2) film as an insulator layer. X-ray photoelectron spectroscopy results demonstrated the stoichiometry of the sp-SnO2 film, which shows good insulator properties with leakage current density less than 2.1 × 10−5 A·cm−2 at gate voltages from −6.0 to 6.0 V. The drain–source current maximum, threshold voltage, extrinsic transconductance maximum, and effective mobility of the FET with a gate length of 10 μm are −17.6 mA·mm−1, −0.5 V, 5.7 mS·mm−1, and 41.3 cm2/V s, respectively. According to the capacitance voltage characteristic, the enhancement mode could be ascribed to the high positive fixed charge density in the sp-SnO2 film, which will repel the hole in the channel. This paper provides a simple method and a low temperature process to fabricate an insulator layer.

Flexible, solution-processed, indium oxide (In2O3) thin film transistors (TFT) and circuits for internet-of-things (IoT)

Over the last decade, novel approaches to explore low voltage flexible devices and low power flexible circuits are being widely researched by the scientific community. To realize the true potential of energy thrifty Internet-of-Things (IoT) objects, low power circuits and hence their low-voltage operating devices are a paramount prerequisite, especially when their power is constrained by autonomous energy scavenging. At present, through advanced manufacturing processes, silicon-based semiconductor devices are powering the modern electronics industry. However, processing temperatures are inhibiting them from flexible and printed electronics, as well as being too costly for scalability to the trillions of IoT objects anticipated. Therefore, development of solution-processed metal oxide semiconductors creates huge opportunities for IoT and wearables. Here, flexible solution-processed indium oxide (In2O3) thin film transistors (TFT) and inverter circuits with low operating voltage are reported. The operating voltage of the TFTs is ≤ 3 V with threshold voltage (Vth) 0.82 V, on/off ratio 105 and extracted mobility (μ) in saturation regime is 14.5 cm2/V·s. The gain of the inverter at VDD 1, 2 and 3 V was determined to be 10, 22 and 32 respectively. Furthermore, measured transconductance (gm) and subthreshold swing (S) are found to be 140 μS and 0.22 V/dec, respectively.

Solution-Processed Copper Oxide Thin Film as Efficient Hole Transport Layer for Organic Solar Cells

Solution-Processed Copper Oxide Thin Film as Efficient Hole Transport Layer for Organic Solar Cells

Effects of Iodine Doping on Electrical Characteristics of Solution-Processed Copper Oxide Thin-Film Transistors.

In order to implement oxide semiconductor-based complementary circuits, the improvement of the electrical properties of p-type oxide semiconductors and the performance of p-type oxide TFTs is certainly required. In this study, we report the effects of iodine doping 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 to solution processing, and iodine doping was performed using vapor sublimated from solid iodine. Doped iodine penetrated the CuO film through grain boundaries, thereby inducing tensile stress in the film and increasing the film’s thickness. Iodine doping contributed to the improvement of the electrical properties of the solution-processed CuO semiconductor including increases in Hall mobility and hole-carrier concentration and a decrease in electrical resistivity. The CuO TFTs exhibited a conduction channel formation by holes, that is, p-type operation characteristics, and the TFT performance improved after iodine doping. Iodine doping was also found to be effective in reducing the counterclockwise hysteresis in the transfer characteristics of CuO TFTs. These results are explained by physicochemical reactions in which iodine replaces oxygen vacancies and oxygen atoms through the formation of iodide anions in CuO.

Applicability of Atmospheric Pressure Plasma Jet (APPJ) Discharge for the Reduction in Graphene Oxide Films and Synthesis of Carbon Nanomaterials

Atmospheric pressure plasma jets (APPJ) are widely used in industry for surface cleaning and chemical modification. In the recent past, they have gained more scientific attention especially in the processing of carbon nanomaterials. In this work, a novel power generation technique was applied to realize the stable discharge in N2 (10 vol.% H2) forming gas in ambient conditions. This APPJ was used to reduce solution-processed graphene oxide (GO) thin films and the result was compared with an established and optimized reduction process in a low–pressure capacitively coupled (CCP) radiofrequency (RF) hydrogen (H2) plasma. The reduced GO (rGO) films were investigated by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Effective deoxygenation of GO was observed after a quick 2 s treatment by AAPJ. Further deoxygenation at longer exposure times was found to proceed with the expense of GO–structure integrity. By adding acetylene gas into the same APPJ, carbon nanomaterials on various substrates were synthesized. The carbon materials were characterized by Raman spectroscopy, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) analyses. Fullerene-like particles and graphitic carbon with short carbon nanotubes were detected on Si and Ag surfaces, respectively. We demonstrate that the APPJ tool has obvious potential for the versatile processing of carbon nanomaterials.

Zirconium-aluminum co-doping on solution-processed indium oxide thin film and deceives measured by a novel nondestructive method

Solution-processed co-doped indium oxide (In₂O₃) have broad application prospects in the display industry. In this paper, zirconium-aluminium co-doped indium oxide (InxZryAl1-x-yO) thin films and thin film transistors (TFTs) are prepared by the solution method. Doping ratio of Zr-Al is 1:0, 2:1, 1:1, 1:2 and 0:1, respectively, and the total atomic ratio of Zr-Al doping is 10 at.%. A novel nondestructive method, microwave photoconductivity decay (µ-PCD) is used to evaluate the quality of thin films by simply measuring their response under laser irradiation. The result shows that doping Zr-Al can reduce the defects in In₂O₃ thin films effectively. The addition of Zr can effectively reduce oxygen vacancies, and the addition of Al can inhibit the crystallization of In₂O₃ thin films. The optimal InxZryAl1-x-yO thin film with minimum defects is obtained with doping ratio of Zr:Al = 2:1. The roughness of thin films is below 0.37 nm, and possess exceptional transmittance (>95%) in the visible range. The optimized TFT exhibits mobility of 2.3 cm2µV−1µs−1, an on/off current ratio of 2.0 × 104, a threshold voltage of 2.29 V and a subthreshold swing of 1.61 Vµdec−1 with doping ratio of Zr:Al = 2:1.

Multimode Operation of Organic-Inorganic Hybrid Thin-Film Transistors Based on Solution-Processed Indium Oxide Films.

Solution-processed metal oxide (MO) thin films have been extensively studied for use in thin-film transistors (TFTs) due to their high optical transparency, simplicity of fabrication methods, and high electron mobility. Here, we report, for the first time, the improvement of the electronic properties of solution-processed indium oxide (InOx) films by the subsequent addition of an organic p-type semiconductor material, here 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), yielding organic-inorganic hybrid TFTs. The addition of TIPS-pentacene not only improves the electron mobility by enhancing the charge carrier percolation pathways but also improves the electronic and temporal stability of the IDS(VG) characteristics as well as reduces the number of required spin-coating steps of the InOx precursor solution. Very interestingly, the introduction of 10 nm TIPS-pentacene films on top of 15 nm InOx layers allows the fabrication of either enhancement- or depletion-mode devices with only minimal changes to the fabrication process. Specifically, we find that when the TIPS-pentacene layer is added on top of the source/drain electrodes, resulting in devices with embedded source/drain electrodes [embedded electrode TFTs (EETFTs)], the devices exhibit an enhancement-mode behavior with an average mobility (μ) of 6.4 cm2 V-1 s-1, a source-drain current ratio (Ion/Ioff) of around 105, and a near-zero threshold voltage (VTH). When on the other hand the TIPS-pentacene layer is added before the source-drain electrodes, i.e., in top-contact electrode TFTs (TCETFTs), a very clear depletion mode behavior is observed with an average μ of 6.3 cm2 V-1 s-1, an Ion/Ioff ratio of over 105, and a VTH of -80.3 V. Furthermore, a logic inverter is fabricated combining the enhancement (EETFTs)- and depletion (TCETFTs)-mode transistors, which shows a potential for the construction of organic-inorganic hybrid electronics and circuits.