High-performance barrier using a dual-layer inorganic/organic hybrid thin-film encapsulation for organic light-emitting diodes

We report an inorganic/organic hybrid barrier that combines the alternating deposition of a layer of ZrO₂ using low temperature atomic layer deposition and a 16-μm-thick layer of UV-curable NOA63 epoxy using spin-coating. The effective water vapor transmission rates of single ZrO₂ film was improved by adding solution epoxy from 3.03 × 10⁻³ g/m² day to 1.27 × 10⁻⁴ g/m² day in the hybrid NOA63/ZrO₂/NOA63/ZrO₂ films at 20 °C and a relative humidity of 60%. In consequence, the organic light-emitting diodes encapsulated with inorganic/organic hybrid barriers were undamaged by environmental oxygen and moisture and their luminance decay time improved by a considerable extent.     

Acrylate-based nanocomposite zirconium-dispersed polymer dielectric for flexible oxide thin-film transistors with a curvature radius of 2 mm

Novel hybrid dielectric film is synthesized at a low temperature of 150 °C using a solution process. Zirconium acrylate (ZrA) and poly(methyl methacrylate) (PMMA) comprise the inorganic and organic components, respectively. The acrylate-based molecular structure of both ingredients allows the facile formation of hybrid ZrA/PMMA dielectric film with neither additional coupling agent nor ultraviolet photon irradiation. The high quality of the hybrid ZrA/PMMA dielectric film is confirmed by its high dielectric constant of 5.5 and low leakage current density of 1.7 × 10⁻⁸ A/cm² at the electric field of 1 MV/cm. The indium gallium tin oxide (IGTO) transistors with the optimal ZrA/PMMA gate insulator layer are fabricated on the polyimide substrate at the maximum high temperature of 150 °C. They exhibit hysteresis-free high performance with high carrier mobility of 24.3 cm²V⁻¹s⁻¹, gate swing of 0.61 V/decade and I_ON/OFF ratio of 4 × 10⁶. Owing to the intrinsic deformability of hybrid dielectric film, these transistors maintained electrical performance after 100 cycles of mechanical bending to the extremely small radius of curvature of 2 mm.     

Photo-patternable high-k ZrOx dielectrics prepared using zirconium acrylate for low-voltage-operating organic complementary inverters

Solution-processed dielectric materials with a high dielectric constant (k) have attracted considerable attention due to their potential applications in low-voltage-operating organic field-effect transistors (OFETs) for realizing large-area and low-power electronic devices. In terms of device commercialization, the patterning of each film component via a facile route is an important issue. In this study, we introduce a photo-patternable precursor, zirconium acrylate (ZrA), to fabricate photo-patterned high-k zirconium oxide (ZrO_x) dielectric layers with UV light. Solution-processed ZrA films were effectively micro-patterned with UV exposure and developing, and transitioned to ZrO_x through a sol-gel reaction during deep-UV annealing. The UV-assisted and ∼10 nm-thick ZrO_x dielectric films exhibited a high capacitance (917.13 nF/cm² at 1 KHz) and low leakage current density (10⁻⁷ A/cm² at 1.94 MV/cm). Those films could be utilized as gate dielectric layers of OFETs after surface modification with ultrathin cyclic olefin copolymer layers. Finally, we successfully fabricated organic complementary inverters exhibiting hysteresis-free operation and high voltage gains of over 42 at low voltages of ≤3 V.     

Al2O3/TiO2 nanolaminate gate dielectric films with enhanced electrical performances for organic field-effect transistors

Nanolamination has entered the spotlight as a novel process for fabricating highly dense nanoscale inorganic alloy films. OFET commercialization requires, above all, excellent dielectric properties of gate dielectric layer. Here, we describe the fabrication and characterization of Al–O–Ti (AT) nanolaminate gate dielectric films using a PEALD process, and their OFET applications. The AT films exhibited a very smooth surface (R_q < 0.3 nm), a high dielectric constant (17.8), and a low leakage current (8.6 × 10⁻⁹ A/cm² at 2 MV/cm) compared to single Al₂O₃ or TiO₂ films. Importantly, a 50 nm thick AT film dramatically enhanced the value of μFET (0.96 cm²/V) on a pentacene device, and the high off-current level in a single TiO₂ film was effectively reduced. The nanolamination process removes the drawbacks inherent in each single layer so that the AT film provides excellent dielectric properties suitable for fabricating high-performance OFETs. Triethylsilylethynyl anthradithiophene (TES-ADT), a solution-processable semiconductor, was combined with the AT film in an OFET, and the electrical properties of the device were characterized. The excellent dielectric properties of the AT film render nanolamination a powerful strategy for practical OFET applications.     

ZrO2 insulator modified by a thin Al2O3 film to enhance the performance of InGaZnO thin-film transistor

A high-performance InGaZnO (IGZO) thin-film transistor (TFT) with ZrO₂–Al₂O₃ bilayer gate insulator is fabricated. Compared to IGZO-TFT with ZrO₂ single gate insulator, its electrical characteristics are significantly improved, specifically, enhancement of I_on/I_off ratios by one order of magnitude, increase of the field-effect mobility (from 9.8 to 14 cm²/Vs), reduction of the subthreshold swing from 0.46 to 0.33 V/dec, the maximum density of surface states at the channel-insulator interface decreased from 4.3 × 10¹² to 2.5 × 10¹² cm⁻². The performance enhancements are attributed to the suppression of leakage current, smoother surface morphology, and suppression of charge trapping by using Al₂O₃ films to modify the high-k ZrO₂ dielectric.     

Structural and frequency-dependent dielectric properties of PVP-SiO2-TMSPM hybrid thin films

In the present study, thin films of PVP-SiO₂-TMSPM (polyvinylpyrrolidone-silicon dioxide- 3-trimethoxysilyl propyl metacrylate) were deposited on p-type Si (111) substrates using spin coating technique. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and energy dispersive X-ray spectrometry (EDS) were applied to investigate the chemical bonds and structural properties of the samples. Morphology of the hybrid thin films was studied using atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. The frequency dependence of dielectric properties such as dielectric constant (ε^′), dielectric loss (ε″), loss tangent (tan δ) as well as the real component of electric modulus (M′), imaginary component of electric modulus (M″), and AC electrical conductivity (σ_AC) was studied in Al/PVP-SiO₂-TMSPM/PSi used as a metal-polymer-semiconductor (MPS) device. Analysis of dielectric relaxation behavior was performed in the frequency range of 0.1 KHz to 1 MHz. In the frequency range of 1 KHz to 1 MHz, the σ_AC data were varied from 6.35 × 10⁻⁶ to 9.02 × 10⁻⁶ for the sample with 0.15 wt ratios of TMSPM and equivalent values of both PVP and SiO₂. The dielectric, modulus, and AC conductivity analyses were considered the useful factors to detect the effects of the capacitance, ionic conductivity, and dielectric relaxation process.     

Electrical properties of low-dielectric-constant films prepared by PECVD in O2/CH4/HMDSO

Low-dielectric constant (low-k) films have been prepared by plasma-enhanced chemical vapor deposition (PECVD) from hexamethyldisiloxane (HMDSO) mixed with oxygen or methane. The films are analyzed by ellipsometry, infrared absorption spectroscopy while their electrical properties are deduced from C–V, I–V and R–f measurements performed on Al/insulator/Si structures. For an oxygen and methane fraction equal to 50% and 22%, respectively, the dielectric constant and losses are decreased compared with those of the film prepared in a pure HMDSO plasma. The effect of adding 22% of CH₄ in HMDSO plasma increases the Si–CH₃ bonds containing in the polymer film and as the constant of methyl groups in the film increased the dielectric constant of the film decreases. For this film, the dielectric constant is 2.8, the dielectric losses at 1 kHz are equal to 2×10⁻³, the leakage current density measured for an electric field of 1 MV/cm is 3×10⁻⁹ A/cm² and the breakdown field is close to 5 MV/cm.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Surface-induced highly oriented perylo[1,12-b,c,d]selenophene thin films for high performance organic field-effect transistors

Epitaxial crystallization of perylo[1,12-b,c,d]selenophene (PESE) on highly oriented polyethylene (PE) substrate through vapor phase deposition has been achieved. Oriented PESE crystals with different crystalline morphologies can be fabricated by changing the temperature of PE substrate during vacuum evaporation. When the PE substrate temperature is lower than 70 °C, sparsely dispersed PESE lathlike crystals are produced with their long axis preferentially aligned perpendicular to the chain direction of PE crystals. While the close films of PESE with lathlike crystals aligned with long axis parallel to the chain direction of PE film were obtained above 90 °C. Transistors based on expitaxially crystallized PESE films have been fabricated and the transistor properties were also studied. It is found that transistors show different electrical characteristics depending on the preparation conditions of expitaxially crystallized PESE films. The transistors based on the PESE/PE-SiO₂/Si with PESE deposited on oriented PE film at low temperature, i.e., <70 °C, display a similar poor properties with the PESE/OTS-SiO₂/Si type transistors. However, when the deposition temperature was elevated to 90 °C, the transistors exhibit a maximum field-effect mobility of 4.4 × 10⁻² cm² V⁻¹ s⁻¹ and maximum on/off ratio of 2.0 × 10⁵, which are about 2 orders of magnitudes higher than the PESE/OTS-SiO₂/Si based transistors.     

Properties of fluorine-doped SnO2 thin films by a green sol–gel method

Fluorine doped tin oxide (FTO) films were fabricated on a glass substrate by a green sol–gel dip-coating process. Non-toxic SnF₂ was used as fluorine source to replace toxic HF or NH₄F. Effect of SnF₂ content, 0–10 mol%, on structure, electrical resistivity, and optical transmittance of the films were investigated using X-ray diffraction, Hall effect measurements, and UV–vis spectra. Structural analysis revealed that the films are polycrystalline with a tetragonal crystal structure. Grain size varies from 43 to 21 nm with increasing fluorine concentration, which in fact critically impacts resultant electrical and optical properties. The 500 °C-annealed FTO film containing 6 mol% SnF₂ shows the lowest electrical resistivity 7.0×10⁻⁴ Ω cm, carrier concentration 1.1×10²¹ cm⁻³, Hall mobility 8.1 cm²V⁻¹ s⁻¹, optical transmittance 90.1% and optical band-gap 3.91 eV. The 6 mol% SnF₂ added film has the highest figure of merit 2.43×10⁻² Ω⁻¹ which is four times higher than that of un-doped FTO films. Because of the promising electrical and optical properties, F-doped thin films prepared by this green process are well-suited for use in all aspects of transparent conducting oxide.     

Effect of barrier layers on BaTiO3 thin film capacitors on Si substrates

The choice of the bottom electrode or barrier layer plays an important role in determining the electrical and structural properties of metal/ferroelectric/metal thin film capacitors. A substantial improvement of the electrical and structural properties of the capacitors was found by using RuO₂ as a bottom electrode. Electrical measurement on a capacitor with a structure of BaTiO₃(246 nm)/RuO₂ (200 nm)/SiO₂/Si, where the BaTiO₃ thin film was deposited at room temperature, showed a dielectric constant of around 15, leakage current density of 1.6 × 10⁻⁷A/cm² at 4 V, a dc conductivity of 9.8 × 10¹⁴S/cm, and a capacitance per unit area of 5.6 × 10⁴pF/cm². A similar structure but with polycrystalline BaTiO³ (273 nm) as the dielectric deposited at 680°C showed a dielectric constant of 290, leakage current density of 1.7 × 10⁻³A/cm² at 4 V, a dc conductivity of 1.2 × 10⁻⁸ S/cm, and a capacitance per unit area of 9.4 × 10⁵ pF/cm². Scanning electron microscopy analysis on the films showed differences in the microstructure due to the use of different bottom electrode materials, such as RuO₂ or Pd.     

Highly-impermeable Al2O3/HfO2 moisture barrier films grown by low-temperature plasma-enhanced atomic layer deposition

Polymer substrates are essential components of flexible electronic applications such as OTFTs, OPVs, and OLEDs. However, high water vapor permeability of polymer films can significantly reduce the lifetime of flexible electronic devices. In this study, we examined the water vapor permeation barrier properties of Al₂O₃/HfO₂ mixed oxide films on polymer substrates. Al₂O₃/HfO₂ films deposited by plasma-enhanced atomic layer deposition were transparent, chemically stable in water and densely amorphous. At 60 °C and 90% relative humidity (RH) accelerated condition, 50-nm-thick Al₂O₃/HfO₂ had water vapor transmission rate (WVTR) = 1.44 × 10⁻⁴ g m⁻² d⁻¹, whereas single layers of Al₂O₃ had WVTR = 3.26 × 10⁻⁴ g m⁻² d⁻¹ and of HfO₂ had WVTR = 6.75 × 10⁻² g m⁻² d⁻¹. At 25 °C and 40% RH, 50-nm-thick Al₂O₃/HfO₂ film had WVTR = 2.63 × 10⁻⁶ g m⁻² d⁻¹, which is comparable to WVTR of conventional glass encapsulation.     

Properties of V–Ce mixed-oxide thin films deposited by RF magnetron sputtering

Thin films of vanadium cerium mixed oxides are good counter-electrodes for electrochromic devices because of their passive optical behavior and very good charge capacity. We deposited thin films of V–Ce mixed oxides on glass substrates by RF magnetron sputtering under argon at room temperature using different power settings. The targets were pressed into pellets of a powder mixture of V₂O₅ and CeO₂ at molar ratios of 2:1, 1:1, and 1:2. For a molar ratio of 2:1, the resulting crystalline film comprised an orthorhombic CeVO₃ phase and the average grain size was 89 nm. For molar ratios of 1:1 and 1:2, the resulting films were completely amorphous in nature. Scanning electron microscopy images and energy-dispersive X-ray spectroscopy data confirmed these results. The optical properties of the films were studied using UV-Vis-NIR spectrophotometry. The transmittance and indirect allowed bandgap for the films increased with the RF power, corresponding to a blue shift of the UV cutoff. The average transmittance increased from 60.9% to 85.3% as the amount of CeO₂ in the target material increased. The optical bandgap also increased from 1.94 to 2.34 eV with increasing CeO₂ content for films prepared at 200 W. Photoacoustic amplitude (PA) spectra were recorded in the range 300–1000 nm. The optical bandgap was calculated from wavelength-dependent normalized PA data and values were in good agreement with those obtained from UV-Vis-NIR data. The thermal diffusivity calculated for the films increased with deposition power. For thin films deposited at 200 W, values of 53.556×10⁻⁸, 1.069×10⁻⁸, and 0.2198×10⁻⁸ m²/s were obtained for 2:1, 1:1, and 1:2 V₂O₅/CeO₂, respectively.     

A novel thermally-stable zirconium amidinate ALD precursor for ZrO2 thin films

ZrO₂ thin films were deposited by the atomic layer deposition process on Si substrates using tetrakis(N,N′-dimethylacetamidinate) zirconium (Zr-AMD) as a Zr precursor and H₂O as an oxidizing agent. Tetrakis (ethylmethylamino) zirconium (TEMA-Zr) was also evaluated for a comparative study. Physical properties of ALD-derived ZrO₂ thin films were studied using ellipsometry, grazing incidence XRD (GI-XRD), high resolution TEM (HRTEM), and atomic force microscopy (AFM). The ZrO₂ deposited using Zr-AMD showed a better thermal stability at high substrate temperature (>300 °C) compared to that using TEMA-Zr. GI-XRD analysis reveals that after 700 °C anneal both ZrO₂ films enter tetragonal phase. The electrical properties of N₂-annealed ZrO₂ film using Zr-AMD exhibit an EOT of 1.2 nm with leakage current density as low as 2 × 10⁻³ A/cm² (@V_fb−1 V). The new Zr amidinate is a promising ALD precursor for high-k dielectric applications.     

UV-curable organic–inorganic hybrid gate dielectrics for organic thin film transistors

UV-curable hybrid thin films were prepared from ZrO₂ hybrid sols containing the acrylic monomer, DPHA, on substrates. The prepared ZrO₂ hybrid sols showed long-term storage stability. Hybrid dielectrics were prepared by sol–gel process and UV cross-linking below 160 °C. Leakage currents of dielectric layers remained below 10⁻⁶ A in 2 MV/cm and dielectric constants were measured to be 3.85–4 at 1 kHz. In addition, organic–inorganic hybrid thin films have smooth and hydrophobic surface. Pentacene OTFTs with thin hybrid dielectrics exhibit of mobility as large as 2.5 cm²/V s, subthreshold swing as low as 0.2 V/decade, an on–off ratio of 10⁵. These results demonstrated that UV-curable sol–gel hybrid systems are suitable for gate dielectrics in OTFTs.     

TiSiOx gate dielectrics produced by reactive sputtering for high performance InGaZnO thin film transistors

High dielectric constant TiSiOx thin films are produced by reactive sputtering under different oxygen partial pressure ratio (P_O2) from 15% to 30%. All the TiSiOx films show an excellent transmittance value of almost 95%. The TiSiOx film has a low leakage current density by optimizing oxygen partial pressure, and the leakage current density of TiSiOx film under P_O2 of 20% is 4.88×10⁻⁷ A/cm² at electrical field strength of 2 MV/cm. Meanwhile, their associated InGaZnO thin-film transistors (IGZO-TFTs) with different P_O2 TiSiOx thin films as gate insulators are fabricated. IGZO-TFTs under P_O2 of 20% shows an optimized electrical performance, and the threshold voltage, sub-threshold swing, field effect mobility and I_on/I_off ratio of this device are 2.22 V, 0.33 V/decade, 29.3 cm²/V s and 5.03×10⁷, respectively. Moreover, the density of states (DOS) is calculated by temperature-dependent field-effect measurement. The enhancements of electrical performance and temperature stability are attributed to better active/insulator interface and smaller DOS.     

Structural phase-dependent resistivity of intrinsic-extrinsic co-doped transparent titanium dioxide films

The authors report a method of enhancing the conductivity of TiO₂ films by controlling their structural phases. Thin films of Nb:TiO₂ (TNO) were prepared on glass and silicon substrates by RF sputtering with varying Nb content at 200 °C. It is shown that fine control over the structural phases of TiO₂ is critical for achieving low resistivity. The resistivity values of the films doped with oxygen vacancies and Nb⁺⁵ decreased from 3.8 × 10⁻¹ to 4.1 × 10⁻³ Ω cm when the weight percent of rutile in anatase-rutile phase mixture decreases from 52.8% to 32%. Furthermore, the lowest resistivity value of 2.37 × 10⁻³ Ω cm was obtained for the doped TiO₂ films having single phase anatase structure. The physical processes responsible for the diverse electrical properties are discussed and are associated with the growth conditions. Our result indicates that highly conductive doped-TiO₂ film can be obtained by controlling the anatase phase formation via the growth temperature. The obtained results can significantly contribute to the development of transparent electrodes by RF sputtering, a suitable technique for coating large area substrates.     

Effects of oxygen content on the structural,optical, and electrical properties of NiO films fabricated by radio-frequency magnetron sputtering

Nickel oxide (NiO) films were deposited on Corning glass substrate with variable (0–100%) oxygen content by radio-frequency sputtering. Effects of different oxygen content on the structural, optical, and electrical properties of NiO films were studied. X-ray diffraction showed that the NiO film deposited on substrate with 0% oxygen content resulted in a random polycrystalline structure and small grain size. The introduction of oxygen gas leaded to a (200) preferential orientation and larger grain size. The transmittance decreases with oxygen content due to the increase of oxygen interstitials in NiO films. The 0%-O₂ deposited NiO film has a tensile strain and a small band gap. Upon introducing 33%-O₂ content, the NiO film exhibits a compressive strain, increasing the bandgap. However, the compressive strain is released and gradually turns into tensile strain, which leads to the narrowing of bandgap with the increase of oxygen content. Hall measurement shows the obtained NiO is p-type and the resistivity decreases from 4.3 × 10⁵ Ω-cm to 5.02 Ω-cm with increasing oxygen content from 0% to 100%. The carrier concentration increases from 6.3 × 10¹⁴ cm⁻³ to 4.6 × 10¹⁸ cm⁻³ and the mobility decreases from 26 cm²/V-s to 0.26 cm²/V-s for the NiO films deposited with oxygen content increasing from 50% to 100%. X-ray photoelectron spectroscopy showed that the Ni⁺³/Ni⁺² ratio is the origin of p-type NiO and the ratio increases from 1.32 to 2.63 by increasing the oxygen content from 0% to 100%, which caused more defects, oxygen interstitials and nickel vacancies.     

Tailoring the structural and optical characteristics of InGaN/GaN multilayer thin films by 12 MeV Si ions irradiations

In this study, the influence of Si ions irradiations (12 MeV energetic) on structural and optical characteristics of InGaN/GaN thin film has been investigated. Irradiation was performed at different Si ions fluences in the range of 1×10¹³ to 1×10¹⁵ ions/cm². X-ray diffraction (XRD) pattern of pristine film indicates only the (0 0 2) oriented crystallites of InGaN while the irradiated films patterns showed other phases (InN and GaN) as well. Ion irradiations at different dose rates have shown no or negligible effect on grain size of InGaN except a shift in the peak position which demonstrates the development of tensile stresses. The existence of other phases in the irradiated films patterns is the indication of InGaN phase separation. Defects produced due to irradiation were also confirmed from peak shifting and appearance of new peak at 669 cm⁻¹ in Raman spectra. A decrease in optical bandgap with the increase of ion irradiation dose rate is being reported in this work.     

Enhancing charge transport in copper phthalocyanine thin film by elevating pressure of deposition chamber

Copper phthalocyanine (CuPc)-based thin film transistors were fabricated using CuPc films grown under different deposition pressure (P_dep) (ranging from 1.8 × 10⁻⁴ Pa to 1.0 × 10⁻¹ Pa). The transistor performance highly depended on P_dep. A field-effect mobility of 2.1 × 10⁻² cm²/(V s) was achieved under 1.0 × 10⁻¹ Pa. Detailed investigations revealed that P_dep modulates the molecular packing and orientation of the organic films grown on a SiO₂/Si substrate and influences the charge transport. Furthermore, from a device physics point of view, contact resistance of the fabricated transistors decreased when P_dep increased, which was beneficial in reducing energy consumption.