Sol-gel processed high-k aluminum oxide dielectric films for fully solution-processed low-voltage thin-film transistors

High-k oxide dielectric films have attracted intense interest for thin-film transistors (TFTs). However, high-quality oxide dielectrics were traditionally prepared by vacuum routes. Here, amorphous high-k alumina (Al₂O₃) thin films were prepared by the simple sol-gel spin-coating and post-annealing process. The microstructure and dielectric properties of Al₂O₃ dielectric films were systematically investigated. All the Al₂O₃ thin films annealed at 300–600?°C are in amorphous state with ultrasmooth surface (RMS ~ 0.2?nm) and high transparency (above 95%) in the visible range. The leakage current of Al₂O₃ films gradually decreases with the increase of annealing temperature. Al₂O₃ thin films annealed at 600?°C showed the low leakage current density down to 3.9?×?10^?7 A/cm² at 3?MV/cm. With the increase of annealing temperature, the capacitance first decreases then increases to 101.1?nF/cm² (at 600?°C). The obtained k values of Al₂O₃ films are up to 8.2. The achieved dielectric properties of Al₂O₃ thin films are highly comparable with that by vapor and solution methods. Moreover, the fully solution-processed InZnO TFTs with Al₂O₃ dielectric layer exhibit high mobility of 7.23?cm² V^?1 s^?1 at the low operating voltage of 3?V, which is much superior to that on SiO₂ dielectrics with mobility of 1.22?cm²/V^?1 s^?1 at the operating voltage of 40?V. These results demonstrate that solution-processed Al₂O₃ thin films are promising for low-power and high-performance oxide devices.     

Eco-friendly,low-temperature solution production of oxide thin films for high-performance transistors via infrared irradiation of chloride precursors

In this paper, we present the infrared (IR) irradiation of chloride precursors as a promising method for the eco-friendly, low-temperature solution fabrication of oxide film devices, which typically require thermal annealing at temperature over 450?°C. By the IR irradiation of AlCl₃ precursor, high-quality Al₂O₃ dielectric films were prepared at a low temperature of 230?°C. The obtained Al₂O₃ dielectric layers had high dielectric properties, such as a high capacitance of 158?nF/cm² and a small leakage current of 5.4?×?10^?8 A/cm². Various structure characterizations confirmed the high quality of Al₂O₃ films produced by IR irradiation. Moreover, full low-temperature solution-produced thin-film transistors (TFTs) were fabricated through the IR irradiation of chloride precursors. The In₂O₃ TFTs achieved a high mobility of 33.6 cm²V^?1s^?1?at a small operation voltage of 4?V. Compared with the common thermal annealing method, IR irradiation results in better precursor conversion, higher oxygen lattice, and fewer oxygen defects. These results suggest that IR irradiation can serve as a new approach for the eco-friendly, low-temperature solution production of various oxide thin films and devices. The method is also very promising for the low-energy production of functional materials and devices.     

Aqueous Solution‐Processable,Flexible Thin‐Film Transistors Based on Crosslinked Chitosan Dielectric Thin Films

The hydrophilic character of chitosan (CS) limits its use as a gate dielectric material in thin‐film transistors (TFTs) based on aqueous solution‐processable semiconductor materials. In this study, this drawback is overcome through controlled crosslinking of CS and report, for the first time, its application to aqueous solution‐processable TFTs. In comparison to natural CS thin films, crosslinked chitosan (Cr‐CS) thin films are hydrophobic. The dielectric properties of Cr‐CS thin films are explored through fabrication of metal–insulator–metal devices on a flexible substrate. Compared to natural CS, the Cr‐CS dielectric thin films show enhanced environmental and water stabilities, with a high breakdown voltage (10 V) and low leakage current (0.02 nA). The compatibility of Cr‐CS dielectric thin films with aqueous solution‐processable semiconductors is demonstrated by growing ZnO nanorods via a hydrothermal method to fabricate flexible TFT devices. The ZnO nanorod‐based TFTs show a high field‐effect mobility (linear regime) of 10.48 cm² V^?1 s^?1. Low temperature processing conditions (below 100 °C) and water as the solvent are utilized to ensure the process is environmental friendly to address the e‐waste problem.     

Sol‐gel derived TiNb2O7 dielectric thin films for transparent electronic applications

To reduce power consumption of transparent oxide‐semiconductor thin film transistors, a gate dielectric material with high dielectric constant and low leakage current density is favorable. According to previous study, the bulk TiNb₂O₇ with outstanding dielectric properties may have an interest in its thin‐film form. The optical, chemical states and surface morphology of sol‐gel derived TiNb₂O₇ (TNO) thin films are investigated the effect of postannealing temperature lower than 500°C, which is crucial to the glass transition temperature. All films possess a transmittance near 80% in the visible region. The existence of non‐lattice oxygen in the TNO film is proposed. The peak area ratio of non‐lattice oxygen plays an important role in the control of leakage current density of MIM capacitors. Also, the capacitance density and dissipation factor were affected by the indium tin oxide (ITO) sheet resistance at high frequencies. The sample after postannealing at 300°C and electrode‐annealing at 150°C possesses a high dielectric constant (>30 at 1 MHz) and a low leakage current density (<1 × 10^?6 A/cm² at 1 V), which makes it a very promising gate dielectric material for transparent oxide‐semiconductor thin film transistors.     

Effect of Y concentration and film thickness on microstructure and electrical properties of HfO2 based thin films

In this work, we introduced a simple solution processing method to prepare yttrium (Y) doped hafnium oxide (HfO₂) based dielectric films. The films had high densities, low surface roughness, maximum permittivity of about 32, leakage current < 1.0 × 10^?7 A/cm² at 2 MV/cm, and breakdown field >5.0 MV/cm. In addition to dielectric performance, we investigated the influence of YO_1.5 fraction on the electronic structure between Y doped HfO₂ thin films and silicon (Si) substrates. The valence band electronic structure, energy gap and conduction band structure changed linearly with YO_1.5 fraction. Given this cost-effective deposition technique and excellent dielectric performance, solution-processed Y doped HfO₂ based thin films have the potential for insulator applications.     

Carbon nanotube capacitors arrays using high-k dielectrics

The electrical characteristics and fabrication process of nanocapacitor arrays using metal-high-k dielectric-carbon nanotube-metal layers (MICntM) were studied. MWCNTs arrays were fabricated using an electron beam lithography based lift-off process for catalyst definition and the high-k dielectric layer, hafnium oxide (HfO₂), was deposited using rf magnetron sputtering. The MICntM structures show high capacitance and the compatibility with high-k dielectric material and its deposition processes. MICntM capacitors arrays with sputtered HfO₂ show specific capacitance of 0.62 μF/cm². The leakage current density at 1 V is less than 5 μA/cm². The high aspect ratio of MWCNTs increases the effective electrode area and HfO₂ allows higher permittivity, hence, higher capacitance structures are realized.     

Microstructure,optical, electrical properties,and leakage current transport mechanism of sol–gel-processed high-k HfO2 gate dielectrics

Deposition of high-k HfO₂ gate dielectric films on n-type Si and quartz substrates by sol–gel spin-on coating technique has been performed and the structural, optical and electrical characteristics as a function of annealing temperature have been investigated. The structural and optical properties of HfO₂ thin films related to annealing temperature are investigated by X-ray diffraction (XRD), ultraviolet–visible spectroscopy (UV–vis), and spectroscopic ellipsometry (SE). Results indicate that the monoclinic form of HfO₂ appears when temperature rises through and above 500 °C. The reduction in band gap is observed with the increase of annealing temperature. Moreover, the increase of refractive index (n) and density and the decrease of the extinction coefficient with the increase of annealing temperature are obtained by SE measurements. Additionally, the electrical properties based on Al/Si/HfO₂/Al capacitor are analyzed by means of the high frequency capacitance–voltage (C–V) and the leakage current density–voltage (J–V) characteristics. And the leakage current conduction mechanisms as functions of annealing temperatures are also discussed.     

Microstructure,optical and electrical properties of sputtered HfTiO high-k gate dielectric thin films

The microstructure, optical and electrical properties of HfTiO high-k gate dielectric thin films deposited on Si substrate and quartz substrate by RF magnetron sputtering have been investigated. Based on analysis from x-ray diffraction (XRD) measurements, it has been found that the as-deposited HfTiO films remain amorphous regardless of the working gas pressure. Meanwhile, combined with characterization of ultraviolet-visible spectroscopy (UV–vis) and spectroscopy ellipsometry (SE), the deposition rate, band gap and optical properties of sputtered HfTiO gate dielectrics were determined. Besides, by means of the characteristic curves of high frequency capacitance–voltage (C–V) and leakage current density–voltage (J–V), the electrical parameters, such as permittivity, total positive charge density, border trap charge density, and leakage current density, have been obtained. The leakage current mechanisms are also discussed. The energy band gap of 3.70 eV, leakage current density of 1.39×10⁻⁵ A/cm² at bias voltage of 2 V, and total positive charge density and border trap charge density of 9.16×10¹¹ cm⁻² and 1.3×10¹¹ cm⁻², respectively render HfTiO thin films deposited at 0.6 Pa, potential high-k gate dielectrics in future CMOS devices.     

Rapid and facile low-temperature solution production of ZrO2 films as high-k dielectrics for flexible low-voltage thin-film transistors

A rapid lightwave (LW) irradiation method was presented for the low-temperature solution production of ZrO₂ films as high-k dielectrics for flexible high-performance thin-film transistors (TFTs). The LW irradiation process markedly decreased the required processing temperature and processing time. Microstructure characterizations confirmed the successful formation of ZrO₂ films with an ultrasmooth surface, large band gap (>5 eV) and low defect level. The ZrO₂ film produced via LW irradiation at ∼200 °C in only 8 min presented excellent dielectric properties, including a small leakage current of 3.3 × 10⁻⁸ A/cm² and a large capacitance of 296 nF/cm², significantly outperforming the films by the conventional high-temperature annealing process at 400 °C for 60 min. Furthermore, LW irradiation was extended to the channel layer. The rapid low-temperature solution-processed InZrO_x TFTs exhibited superior electrical characteristics, such as a high carrier mobility of 41.3 cm²V⁻¹s⁻¹ and a high on-off current ratio of 10⁵∼10⁶ at a low operation voltage of 3 V due to the employment of high-quality ZrO₂ dielectric films. Moreover, the flexible TFT on a polyimide (PI) plastic substrate achieved a high mobility of nearly 30 cm²V⁻¹s⁻¹, indicating that LW irradiation is highly promising for the rapid and low-temperature solution production of high-quality and flexible oxide electronic devices.     

Thickness dependence of microstructure,dielectric and leakage properties of BaSn0.15Ti0.85O3 thin films

The BaSn_0.15Ti_0.85O₃ (BTS) thin films are prepared on Pt-Si substrates with thickness ranging from ~ 60?nm to ~ 380?nm by radio frequency magnetron sputtering. The effects of thickness on microstructure, surface morphologies and dielectric properties of thin films are investigated. The thickness dependence of dielectric constant is explained based on the series capacitor model that the BTS thin film is consisted by a BTS bulk layer and an interfacial layer (dead layer) between the BTS and bottom electrode. The thin films with thickness of 260?nm give the largest figure of merit of 76.9@100?kHz, while the tunability and leakage current density are 64.6% and 7.46?×?10^?7 A/cm² at 400?kV/cm, respectively.     

Robust SiO2 gate dielectric thin films prepared through plasma-enhanced atomic layer deposition involving di-sopropylamino silane (DIPAS) and oxygen plasma: Application to amorphous oxide thin film transistors

DIPAS (di-isopropylamino silane, H₃Si[N(C₃H₇)₂]) and O₂ plasma were employed, using plasma-enhanced atomic layer deposition (PEALD), to deposit silicon oxide to function as the gate dielectric at low temperature, i.e., below 200 °C. The superior amorphous SiO₂ thin films were deposited through the self-limiting reactions of atomic layer deposition with a deposition rate of 0.135 nm/cycle between 125 and 200 °C. PEALD-based SiO₂ thin layer films were applied to amorphous oxide thin film transistors constructed from amorphous In-Ga-Zn-O (IGZO) oxide layers, which functioned as channel layers in the bottom-gated thin film transistor (TFT) structure, with the aim of fabricating transparent electronics. The SiO₂ gate dielectric exhibited the highest TFT performance through the fabrication of heavily doped n-type Si substrates, with a saturation mobility of 16.42 cm²/V·s, threshold voltage of 2.95 V and large on/off current ratio of 3.69 × 10⁸. Ultimately, the highly doped Si was combined with the ALD-based SiO₂ gate dielectric layers, leading to a saturation mobility of 16.42 cm²/V·s, threshold voltage of 2.95 V, S-slope of 0.1944, and on/off current ratio of 3.69 × 10⁸. Semi-transparent and transparent TFTs were fabricated and provided saturation mobilities of 22.18 and 24.29 cm²/V·s, threshold voltages of 4.18 and 2.17 V, S-slopes of 0.1944 and 0.1945, and on/off current ratios of 9.63 × 10⁸ and 1.03 × 10⁷, respectively.     

High carrier mobility low-voltage ZnO thin film transistors fabricated at a low temperature via solution processing

Wide-bandgap ZnO TFTs have many potential applications in large-area, flexible electronics and transparent devices because of their low cost, high performance and excellent optical transmittance. High-performance ZnO TFTs fabricated via simple solution processing have been widely studied. However, the key issues of solution-processable ZnO TFTs are the relatively high processing temperature (> 300?°C) and the high operating voltage for achieving the desired electrical properties. Here, we successfully fabricated low-voltage ZnO TFTs at an annealing temperature of ≤?250?°C. The resulting ZnO transistors with high-k terpolymer P(VDF-TrFE-CFE) showed a mobility of up to 5.3?cm² V^?1 s^?1 and an on/off ratio of >?10⁵ at 3?V. Furthermore, the influence of the dielectric constant on the carrier mobility was investigated. A lower k-value dielectric resulted in a high carrier mobility under the same carrier density. Therefore, with a low-k CYTOP dielectric applied to modify the interface between the ZnO semiconductor and the P(VDF-TrFE-CFE) layer, ZnO transistors annealed at 250?°C showed an electron mobility of 13.6?cm² V^?1 s^?1 and an on/off ratio of >?10⁵ at 3?V. To the best of our knowledge, this mobility is the highest value reported to date among the low-voltage solution-processable undoped ZnO TFTs annealed at temperatures of ≤?300?°C.     

Regulating crystal structure and ferroelectricity in Sr doped HfO2 thin films fabricated by metallo-organic decomposition

HfO₂ based binary ferroelectric oxides are promising candidate for nonvolatile memory devices due to their compatibility with the current Si-based technology. In this work, Sr doped HfO₂ (Sr:HfO₂) ferroelectric thin films with Sr concentration from 0% to 10?mol% were prepared on the platinum electrodes by metallo-organic decomposition (MOD). It was demonstrated that uniform Sr:HfO₂ thin films with extremely low roughness can be achieved and crystallized by MOD under a 700?°C annealing process. A wake-up stage was believed more essential for the ferroelectricity of the MOD derived Sr:HfO₂ thin film, since the remnant polarization of 13.3 µC/cm² and high dielectric constant of 30 were obtained after 10⁵ cycling tests. The transformation from monoclinic phase to cubic phase was observed with increasing the Sr concentration and the thickness of the films. X-ray photoelectron spectroscopy analysis confirmed the bonding type of O-Hf-O and O-Sr-O bonds in the film. The microscopic crystal structure of ferroelectric orthorhombic phase was observed by high resolution transmission electronic microscope. The intrinsic ferroelectricity of Sr:HfO₂ film was demonstrated by the hysteresis polarization-voltage loops and distinct current peaks in the current-voltage curve. Stable domain structure and its switching dynamics were monitored by piezoresponse force microscopy, indicating the native polarization of Sr:HfO₂. This work will provide a controllable routine to fabricate ferroelectric HfO₂ based thin films using MOD method.     

Solution-processed ytterbium oxide dielectrics for low-voltage thin-film transistors and inverters

High permittivity (high k) metal-oxide thin films fabricated via solution processes have recently received much attention for the construction of low-operating voltage and high-performance thin-film transistors (TFTs). In this report, amorphous ytterbium oxide (Yb₂O₃) thin films were fabricated by spin coating and their applications in TFTs were explored. The physical properties of the solution-processed Yb₂O₃ thin films processed at different annealing temperatures were systematically investigated using various characterization techniques. To explore the feasibility of the Yb₂O₃ thin films as gate dielectrics for oxide TFTs, In₂O₃ TFTs based on Yb₂O₃ dielectrics were integrated. All the devices could be operated at 3 V, which is critical for the applications in portable, battery-driven, and low-power electronic devices. The optimized In₂O₃/Yb₂O₃ TFT exhibits high electrical performances, including field-effect mobility of 4.98 cm²/V s, on/off current ratio of ~ 10⁶, turn-on voltage around 0 V, and subthreshold swing of 70 mV/decade, respectively. To demonstrate the potential of In₂O₃/Yb₂O₃ TFT toward more complex logic application, the unipolar inverter was further constructed.     

Annealing-temperature-modulated optical,electrical properties,and leakage current transport mechanism of sol–gel-processed high-k HfAlOx gate dielectrics

Deposition of HfAlO_x gate dielectric films on n-type Si and quartz substrates by sol-gel technique has been performed and the optical, electrical characteristics of the as-deposited HfAlO_x thin films as a function of annealing temperature have been investigated. The optical properties of HfAlO_x thin films related to annealing temperature are investigated by ultraviolet-visible spectroscopy (UV–vis) and spectroscopy ellipsometry (SE). By measurement of UV–vis, average transmission of all the HfAlO_x samples are about 85% owing to their uniform composition. And the increase in band gap has been observed with the increase of annealing temperature. Moreover, the increase of refractive index (n) and density with the increase of annealing temperature are obtained by SE measurements. Additionally, the electrical properties based on Al/Si/HfAlO_x/Al capacitor are analyzed by means of the high frequency capacitance-voltage (C-V) and the leakage current density-voltage (J-V) characteristics. Results have shown that 400 °C-annealed sample demonstrates good electrical performance, including larger dielectric constant of 12.93 and lower leakage current density of 3.75×10⁻⁷ A/cm² at the gate voltage of 1 V. Additionally, the leakage current conduction mechanisms as functions of annealing temperatures are also discussed systematically.     

Improvement in performance of indium gallium oxide thin film transistor via oxygen mediated crystallization at a low temperature of 200 °C

We report the fabrication of high-performance polycrystalline indium gallium oxide (IGO) thin film transistors (TFTs) at a low temperature of 200 °C. Growth of a highly aligned cubic phase with a bixbyite structure was accelerated at a certain proportion of oxygen plasma density during deposition of the IGO thin film, which leads to outstanding electrical characteristics. The resulting polycrystalline IGO TFT exhibited a high field-effect mobility of 56.0 cm²/V, a threshold voltage (V_TH) of 0.10 V, a low subthreshold gate swing of 0.10 V/decade, and a current modulation ratio of >10⁸. Moreover, the crystalline IGO TFTs have highly stable behaviors with a small V_TH shift of +0.8 and ?1.0 V against a positive bias stress (V_GS,ST ?V_TH = 20 V) and negative bias illumination stress (V_GS,ST ?V_TH = ?20 V) for 3,600 s, which is attributed to the high quality of the bixbyite crystalline structure.     

Preparation of siloxane–silsesquioxane hybrid thin films for large‐scale‐integration interlayer dielectrics with excellent mechanical properties and low dielectric constants

Several kinds of homogeneous organic–inorganic hybrid polymer thin films were designed with improved mechanical properties and low dielectric constants (<3.0). Novel soluble siloxane–silsesquioxane hybrid polymers were synthesized with cyclic and/or cage silane monomers, which had triorganosiloxy (R₃Si_1/2), diorganosiloxane (R₂SiO_2/2), and organosilsesquioxane (RSiO_3/2) moieties with ethylene bridges at the molecular level, by the hydrolysis and condensation of 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane (a cyclic monomer). The electrical properties of these films, including the dielectric constant (～2.51), leakage current (6.4 × 10^?11 A/cm² at 0.5 MV/cm), and breakdown voltage (～5.4 MV/cm) were fairly good. Moreover, the mechanical properties of the hybrid films, including the hardness (～7 GPa), modulus (～1.2 GPa), and crack‐free thickness (<2 μm), were excellent in comparison with those of previous spin‐on‐glass materials with low dielectric constants. The excellent mechanical properties were proposed to be due to the high contents of Si? OH groups (>30%) and the existence of ethylene bridge and siloxane moieties in the hybrid polymer precursors. In addition, the mechanical properties of the hybrid films were affected by the contents of the cagelike structures. The more cagelike structures a hybrid film contained, the worse its mechanical properties were. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 626–634, 2003     

Annealing temperature-dependent structural and electrical properties of (Ta2O5)1-x - (TiO2)x thin films,x ≤ 0.11

(Ta₂O₅)_1-x- (TiO₂)_x (TTO_x) thin films, with x = 0, 0.03, 0.06, 0.08, and 0.11, were deposited using magnetron direct current (DC) sputtering method onto the P/boron-silicon (1 0 0) substrates by varying areas of Tantalum and Titanium metallic targets, in oxygen environment at ambient temperature. The as-deposited thin films were annealed at temperatures ranging from 500 to 800 °C. Generally, the formation of the Ta₂O₅ structure was observed from the X-ray diffraction measurements of the annealed films. The capacitance of prepared metal– oxide– semiconductor (MOS) structures of Ag/TTO_x/p-Si was measured at 1 MHz. The dielectric constant of the deposited films was observed altering with varying composition and annealing temperature, showing the highest value 71, at 1 MHz, for the TTO_x films, x = 0.06, annealed at 700 °C. With increasing annealing temperature, from 700 to 800 °C, the leakage current density was observed, generally decreasing, from 10^?5 to 10^?8 A cm^?2, for the prepared compositions. Among the prepared compositions, films with x = 0.06, annealed at 800 °C, having the observed value of dielectric constant 48, at 1 MHz; and the leakage current density 2.7 × 10^?8 A cm^?2, at the electric field of 3.5 × 10⁵ V cm^?1, show preferred potential as a dielectric for high-density silicon memory devices.     

Performance modulation of contact electrification nanogenerators by controlling the doping concentration of fluorine-doped tin oxide

Contact electrification nanogenerators (CENGs) were fabricated, and their output performance was modulated by controlling the doping concentration of fluorine-doped SnO₂ (FTO) thin films. As the fluorine source content was increased from 0.8 to 1.2?mM during spray pyrolysis deposition, the electron concentration in the FTO thin film increased from 1.84?×?10²⁰ to 5.22?×?10²⁰ cm^?3, which is much larger than the Mott critical carrier concentration of SnO₂. The output voltage and current from the CENGs which were fabricated by the aluminium and FTO surfaces increased from 2.76 to 5.66?V and from 0.003 to 0.005 μA/cm² when controlling the electron concentration in the FTO layer from 5.22 to 1.84?×?10²⁰?cm^?3. The modulation of the output performance of the CENGs originated from the change in work function of the FTO layer by Burstein-Moss shift.     

Electrical properties of nanoporous F doped SiO2 low-k thin films prepared by sol-gel method with catalyst HF

Using hydrofluoric acid as acid catalyst, F doped nanoporous low-k SiO₂ thin films were prepared through sol-gel method. Compared with the hydrochloric acid catalyzed film, the films showed better micro structural and electrical properties. The capacitance-voltage and current-voltage characteristics of F doped SiO₂ thin films were then studied based on the structures of metal-SiO₂-semiconductor and metal-SiO₂-metal, respectively. The density of state (DOS) of samples deposited on metal is found to decrease to a level of 2 × 10¹⁷ eV^?1 cm^?3. The values of mobile ions, fix positive charges, trapped charges and the interface state density between the SiO₂/Si interfaces also decrease obviously, together with the reduction of the leakage current density and the dielectric constant, which imply the improvement of the electrical properties of thin films. After annealing at a temperature of 450^°C, the lower values of the leakage current density and dielectric constant could be obtained, i.e. 1.06 × 10^?9 A/cm² and 1.5, respectively.