Co-sputtered oxide thin film encapsulated organic electronic devices with prolonged lifetime

Effective top-side thin film encapsulation for organic light-emitting devices (OLEDs) was achieved by deposition of a multi-layer water diffusion barrier stack to protect the device against moisture permeation. The barrier stack was formed by alternative depositions of co-oxide and fluorocarbon (CF_x) films. The co-oxide layer was fabricated by magnetron co-sputtering of silicon dioxide (SiO₂) and aluminum oxide (Al₂O₃). While the CF_x layer was formed by plasma enhanced chemical vapor deposition. The water vapor transmission rate of the optimized diffusion barrier stack can be down to 10^− 6 g/m²/day. The OLEDs encapsulated with the multilayer stack have been shown to have operation lifetime of over 18,000 h which is nearly the same as devices with conventional glass-cover encapsulation.     

Investigation of brittle failure in transparent conductive oxide and permeation barrier oxide multilayers on flexible polymers

An oxide multilayer structure—consisting of an indium zinc oxide (IZO) conductive layer, a silicon oxide (SiO_x, x = 1.8) water vapor permeation barrier, and an aluminum oxide (Al₂O₃) interlayer—coated on polyethylene terephthalate (PET) is proposed as a transparent flexible substrate for display and photovoltaic applications. Vital properties of the multilayer, such as the low water vapor impermeability of the SiO_x barrier and the high conductance of the IZO film, degraded considerably because of the crack formation in bend geometries, attributed to the large difference between elastic properties of the oxide films and polymers. In order to suppress the crack formation, a 10-nm-thick Al₂O₃ interlayer was sputtered on Ar ion-beam treated PET surfaces prior to a SiO_x plasma-enhanced chemical vapor deposition (PECVD) process. Changes in the conductance and water vapor impermeability were investigated at different bending radii and bending cycles. It was found that the increases in resistance and water vapor transmission rate (WVTR) were significantly suppressed by the ion-beam PET pretreatment and by the sputtered Al₂O₃ interlayer. The resistance and WVTR of IZO/SiO_x/Al₂O₃/PET systems could be kept low and invariable even in severely bent states by choosing the SiO_x thickness properly. The IZO (135 nm)/SiO_x (90 nm)/Al₂O₃ (10 nm)/PET system maintained a resistance of 3.2 × 10^− 4 Ω cm and a WVTR of < 5 × 10^− 3 g m² d^− 1 after 1000 bending cycles at a bending radius of 35 mm.     

Synthesis and electrophoretic deposition of hydrothermally synthesized multilayer TiO2 nanotubes on conductive filters

TiO₂ nanotubes were synthesized by the decomposition of titanium isopropoxide in water and the calcination at 450 °C for 2 h to form TiO₂ nanoparticles. The synthesized TiO₂ in anatase form nanoparticles were processed hydrothermally in 10 M NaOH solution at 130 °C for 24 h to obtain multilayer TiO₂ nanotubes. TEM analysis revealed that the diameters of the tubes were around 10 nm and they are in the length of 100 nm. Subsequently, colloidal suspensions containing 1% wt. Of TiO2 nanotubes were prepared with TEA and butanol and electrophoretic deposition (EPD) experiments were conducted in order to obtain coatings on Ni and carbon filters using a deposition time of 10 min. and an applied voltage of 65 V. It is also shown that multilayer TiO₂ nanotubes having outer diameter around 10 nm and inner diameters of 4.3 nm can be produced using the described technique. EPD is also shown to be an effective technique to coat three dimensional components, such as Ni and C filters for various applications including water and air purification systems.     

Plasma-enhanced chemical vapor deposition of TiO2 thin films for dielectric applications

Amorphous TiO₂ thin films were formed by plasma-enhanced chemical vapor deposition (PECVD) from mixtures of titanium IV isopropoxide (Ti(O-i-C₃H₇)₄) and oxygen. The deposition rate was found to be weakly activated, with an apparent activation energy of 4.5 kJ/mol. The deposition rate increased with equivalence ratio and decreased with plasma power. This dependence on atomic oxygen density was consistent with behavior observed in other metal oxide PECVD systems. Metal-insulator-silicon devices were fabricated, and characterized using capacitance-voltage measurements. The apparent dielectric constant of the TiO₂ thin films increased from 15 to 82 with film thickness. The observed variations were consistent with the formation of an interfacial SiO₂ layer. Assuming that a TiO₂/SiO₂ bilayer behaves as two capacitors in series, an intrinsic TiO₂ dielectric constant of 82 ± 10 and an interfacial SiO₂ layer thickness of 3 ± 1 nm were extracted from electrical measurements.     

Silicon oxide diffusion barrier coatings on polypropylene

In this study the influence of process conditions for the plasma-enhanced chemical vapor deposition of SiO_x diffusion barrier coatings on polypropylene (PP) is investigated and compared to results obtained on polyethylene terephthalate (PET). It was observed that the thermal load during deposition is much more crucial in the case of PP. If the thermal load is not the limiting factor, the composite parameter (CP) energy input per mass of precursor showed to be valuable to describe plasma conditions at constant oxygen to monomer ratio. Low oxygen transmission rates (OTRs) of 5.1 ± 3.6 and 0.3 ± 0.1 cm³/m²day/atm were achieved on PP and PET foil, respectively, for an optimal CP of 4.1 × 10⁵ J/g. Fourier transform infrared (FTIR) spectroscopy revealed that low carbon and silanol content is necessary for good barrier performance. Low RF power, necessary to reduce thermal load on PP, can be compensated by increasing the oxygen to monomer ratio.For favorable plasma conditions, the dependence of the OTR on the coating thickness follows a similar trend for both substrate materials with a critical thickness of approximately 12 nm. The residual permeation can be correlated to the defect density at each stage of film growth by means of a simple correlation. Further support for permeation through defects is found by the activated rate theory, since the apparent activation energy of oxygen permeation is below typical values of amorphous glasses and remains unchanged due to the deposition of SiO_x on both substrates.     

Aluminum oxide barrier coating on polyethersulfone substrate by atomic layer deposition for barrier property enhancement

Aluminum oxide layers were deposited on flexible polyethersulfone (PES) substrates via plasma enhanced atomic layer deposition (PEALD) process using trimethylaluminum (TMA) and oxygen as precursor and reactant materials. Several process parameters in PEALD process were investigated in terms of refractive index and layer thickness. Number of process cycle increased the thickness and refractive index of the layer to enhance the barrier properties. Non-physisorbed TMA and unreacted oxygen were purged before and after the plasma reaction, respectively. Identical purge time was applied to TMA and oxygen and it was optimized for 10 s. Thinner and denser layer was formed as substrate temperature increased. However, the PES substrate could be deformed above 120 °C. Aluminum oxide layer formed on PES at optimized conditions have 11.8 nm of thickness and reduced water vapor transmission rate and oxygen transmission rate to below 4 × 10^− 3 g/m² day and 4 × 10^− 3 cm³/m² day, respectively. Polycarbonate and polyethylene naphthalate films were also tested at optimized conditions, and they also showed quite appreciable barrier properties to be used as plastic substrates.     

Plastic substrate with gas barrier layer and transparent conductive oxide thin film for flexible displays

A novel plastic substrate for flexible displays was developed. The substrate consisted of a polycarbonate (PC) base film coated with a gas barrier layer and a transparent conductive thin film. PC with ultra-low intrinsic birefringence and high temperature dimensional stability was developed for the base film. The retardation of the PC base film was less than 1 nm at a wavelength of 550 nm (film thickness, 120 µm). Even at 180 °C, the elastic modulus was 2 GPa, and thermal shrinkage was less than 0.01%. The surface roughness of the PC base film was less than 0.5 nm. A silicon oxide (SiO_x) gas barrier layer was deposited on the PC base film by a roll-to-roll DC magnetron reactive sputtering method. The water vapor transmission rate of the SiO_x film was less than 0.05 g/m²/day at 40 °C and 100% relative humidity (RH), and the permeation of oxygen was less than 0.5 cc/m² day atm at 40 °C and 90% RH. As the transparent conductive thin film, amorphous indium zinc oxide was deposited on the SiO_x by sputtering. The transmittance was 87% and the resistivity was 3.5 × 10^− 4 ohm cm.     

Electrical characterization of the polyaniline/p-silicon and polyaniline titanium dioxide tetradecyltrimethylammonium bromide /p-silicon heterojunctions

Au/PANI/p-Si/Al and Au/PANI TiO₂ TTAB/p-Si/Al heterojunctions have been fabricated by spin coating of soluble polyaniline (PANI) and PANI titanium dioxide (TiO₂) tetradecyltrimethylammonium bromide (TTAB) on the chemically cleaned p-Si substrates. The thicknesses of the polymeric films have been determined by a profilometer. The current-voltage (I-V) characteristics of the heterojunctions have been obtained in the temperature range of 98-258 K. These devices have showed the rectifying behavior such as diode. The I-V characteristics of the devices have been analyzed on the basis of the standard thermionic emission theory at low forward bias voltage regime. It has been shown that the values of ideality factor decrease while the values of barrier height increase with increasing temperature. This temperature dependence has been attributed to the presence of barrier inhomogeneities at the organic/inorganic semiconductor interface. Furthermore, analysis of the double logarithmic I-V plots at higher forward bias voltages at all temperatures indicates that transport through the organic thin film is explained by a space-charge-limited current process characterized by exponential distribution of traps within the band gap of the organic film. The total concentration of traps has been found to be 3.52 × 10¹⁴ cm^− 3 and 3.14 × 10¹⁵ cm^− 3 for PANI and PANI TiO₂ TTAB layer, respectively.     

Photocatalytic activities of TiO2 thin films prepared on Galvanized Iron substrate by plasma-enhanced atomic layer deposition

Titanium dioxide (TiO₂) thin films were prepared on Galvanized Iron (GI) substrate by plasma-enhanced atomic layer deposition (PE-ALD) using tetrakis-dimethylamido titanium and O₂ plasma to investigate the photocatalytic activities. The PE-ALD TiO₂ thin films exhibited relatively high growth rate and the crystal structures of TiO₂ thin films depended on the growth temperatures. TiO₂ thin films deposited at 200 °C have amorphous phase, whereas those with anatase phase and bandgap energy about 3.2 eV were deposited at growth temperature of 250 °C and 300 °C. From contact angles measurement of water droplet, TiO₂ thin films with anatase phase and Activ™ glass exhibited superhydrophilic surfaces after UV light exposure. And from photo-induced degradation test of organic solution, anatase TiO₂ thin films and Activ™ glass decomposed organic solution under UV illumination. The anatase TiO₂ thin film on GI substrate showed higher photocatalytic efficiency than Activ™ glass after 5 h UV light exposure. Thus, we suggest that the anatase phase in TiO₂ thin film contributes to both superhydrophilicity and photocatalytic decomposition of 4-chlorophenol solution and anatase TiO₂ thin films are suitable for self-cleaning applications.     

Atomic layer deposition of HfO2 on self-assembled monolayer-passivated Ge surfaces

HfO₂ films are not easily deposited on hydrophobic self-assembled monolayer (SAM)-passivated surfaces. However, in this study, we deposited HfO₂ films on a tetradecyl-modified SAM with a Ge surface using atomic layer deposition at 350 °C. A slightly thinner HfO₂ film thickness was obtained on the tetradecyl-modified SAM passivated samples than that typically obtained on GeO_x-passivated samples. The resulting electrical properties are explained by the physical thickness and stoichiometry of the interfacial layer.     

Super H2O-barrier film using Cat-CVD (HWCVD)-grown SiCN for film-based electronics

“Super H₂O-barrier film” with a water vapor transmission rate (WVTR) less than 1 mg/m²/day has been developed. The barrier layer is a single layer of amorphous SiCN grown by organic Cat-CVD (O-Cat-CVD) with a thickness of 100 nm. SiCN has been grown by using a gas mixture of monomethylsilane (MMS; Si (CH₃)H₃), NH₃ and H₂ on polyethylene-naphthalate (PEN) film substrates. It has been found that the WVTR drastically depends on the W-filament temperature of O-Cat-CVD. The WVTR changed from 5 × 10⁻¹ to 1 × 10⁻³, corresponding to the W-filament temperature increase from 1100 to 1200 C. We have recently succeeded in developing the “super H₂O-barrier film” by the coating of single layers of SiCN for both sides of the PEN film without using the widely used polymer/inorganic multilayer coating. The both-side coating has been found to be crucial to avoid the H₂O penetration into PEN films and also to avoid the breakdown of the SiCN/PEN interface caused by the H₂O accumulation at the interface.     

Optimization of titanium dioxide film prepared by electrophoretic deposition for dye-sensitized solar cell application

Nanocrystalline TiO₂ films were deposited on a conducting glass substrate by the electrophoretic deposition technique. It was found that the thickness of TiO₂ film increased proportionally with an increase in deposition time and deposition voltage. However, as the deposition duration or deposition voltage increased, the film surface was more discontinuous, and microcracks became more evident. The characteristic of the dye-sensitized solar cell using TiO₂ film as a working electrode was analyzed. The results of the energy conversion efficiency and the photocurrent density exhibited a relationship dependent on the TiO₂ thickness. Curve fitting of energy conversion efficiency vs. TiO₂ thickness revealed the optimum solar cell efficiency ~ 2.8% at the film thickness of ~ 14 μm.     

Polythiophene thin films electrochemically deposited on sol-gel based TiO2 for photovoltaic applications

In this work, the influence of titanium dioxide (TiO₂) thin films on the efficiency of organic photovoltaic devices based on electrochemically synthesized polythiophene (PT) was investigated. TiO₂ films were produced by sol-gel methods with controlled thickness. The best TiO₂ annealing condition was determined through the investigation of the temperature influence on the electron charge mobility and resistivity in a range between 723 K and 923 K. The PT films were produced by chronoamperometric method in a 3-electrode cell under a controlled atmosphere. High quality PT films were produced onto 40 nm thick TiO₂ layer previously deposited onto fluorine doped tin oxide (FTO) substrate. The morphology of PT films grown on both substrates and its strong influence on the device performance and PT minimum thickness were also investigated. The maximum external quantum efficiency (IPCE) reached was 9% under monochromatic irradiation (λ = 610 nm; 1 W/m²) that is three orders of magnitude higher than that presented by PT-homolayer devices with similar PT thickness. In addition, the open-circuit voltage (V_oc) was about 700 mV and the short-circuit current density (J_sc) was 0.03 A/m² (λ = 610 nm; 7 W/m²). However, as for the PT-homolayer also the TiO₂/PT based devices are characterized by antibatic response when illuminated through FTO. Finally, the Fill Factor (FF) of these devices is low (25%), indicating that the series resistance (R_s), which is strongly dependent of the PT thickness, is too large. This large R_s value is compensated by TiO₂/PT interface morphology and by FTO/TiO₂ and TiO₂/PT interface phenomena producing preferential paths in which the internal electrical field is higher, improving the device efficiency.     

Characterization of TiO2 thin films prepared by electrolytic deposition for lithium ion battery anodes

The electrolytic deposition of TiO₂ thin films on platinum for lithium batteries is carried out in TiCl₄ alcoholic solution and the films are subsequently annealed. The as-prepared films are amorphous TiO(OH)₂·H₂O, transformed into anatase TiO₂ at 350 °C, and then gradually into rutile TiO₂ at 500 °C. Cyclic voltammograms show oxidation and reduction peaks at 2.20 and 1.61 V, respectively, corresponding to charge and discharge plateaus at 1.98 and 1.75 V vs. Li⁺/Li. The specific capacity decreases with increasing current density for film of 128-nm thickness in the initial discharge. It is observed that the diffusion flux of Li⁺ insertion/extraction into/from TiO₂ controls the reaction rate at higher current densities. Consequently, at low film thickness, high discharge capacity (per weight) is found for the initial cycle at a current density of 10 μA cm^− 2. However, the capacity of prepared films in various thicknesses approach 103 ± 5 mAh g^− 1 after 50 cycles, since the formation of cracks for thicker films offers shorter diffusion paths for Li⁺. In addition, TiO₂ films show electrochromic properties during lithiation and delithiation.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

Sputter deposition of semicrystalline tin dioxide films

Tin dioxide is emerging as an important material for use in copper indium gallium diselenide based solar cells. Amorphous tin dioxide may be used as a glass overlayer for covering the entire device and protecting it against water permeation. Tin dioxide is also a viable semiconductor candidate to replace the wide band gap zinc oxide window layer to improve the long-term device reliability. The film properties required by these two applications are different. Amorphous films have superior water permeation resistance while polycrystalline films generally have better charge carrier transport properties. Thus, it is important to understand how to tune the structure of tin dioxide films between amorphous and polycrystalline. Using X-ray diffraction (XRD) and Hall-effect measurements, we have studied the structure and electrical properties of tin dioxide films deposited by magnetron sputtering as a function of deposition temperature, sputtering power, feed gas composition and film thickness. Films deposited at room temperature are semicrystalline with nanometer size SnO₂ crystals embedded in an amorphous matrix. Film crystallinity increases with deposition temperature. When the films are crystalline, the X-ray diffraction intensity pattern is different than that of the powder diffraction pattern indicating that the films are textured with (101) and (211) directions oriented parallel to the surface normal. This texturing is observed on a variety of substrates including soda-lime glass (SLG), Mo-coated soda-lime glass and (100) silicon. Addition of oxygen to the sputtering gas, argon, increases the crystallinity and changes the orientation of the tin dioxide grains: (110) XRD intensity increases relative to the (101) and (211) diffraction peaks and this effect is observed both on Mo-coated SLG and (100) silicon wafers. Films with resistivities ranging between 8 mΩ cm and 800 mΩ cm could be deposited. The films are n-type with carrier concentrations in the 3 × 10¹⁸ cm^− 3 to 3 × 10²⁰ cm^− 3 range. Carrier concentration decreases when the oxygen concentration in the feed gas is above 5%. Electron mobilities range from 1 to 7 cm²/V s and increase with increasing film thickness, oxygen addition to the feed gas and film crystallinity. Electron mobilities in the 1-3 cm²/V s range can be obtained even in semicrystalline films. Initial deposition rates range from 4 nm/min at low sputtering power to 11 nm/min at higher powers. However, deposition rate decreases with deposition time by as much as 30%.     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.     

Structural evaluation of sol-gel derived lead strontium titanate diffusion barrier for integration in lead zirconate titanate transducer design

Sol-gel derived Pb₄₀Sr₆₀TiO₃ (PST) thin film has been investigated as a diffusion barrier for integrating in PbZr₃₀Ti₇₀O₃ (PZT) device structures on Si substrates. PST film was deposited on SiO₂/Si substrate and annealed at a relatively low temperature range of 550-600 °C producing a crack-free, smooth and textured surface. Following deposition on PST/SiO₂/Si template PZT thin film was crystallised exhibiting random grain orientations and an insertion of the bottom Pt/Ti electrode forming PZT/Pt/Ti/PST/SiO₂/Si stacks promoted the preferred PZT (111) perovskite phase. PZT (111) peak intensity gradually decreased along with slight increase of the PZT (110) peak with increasing annealing temperature of the buffer PST film. The dielectric and ferroelectric properties of the PZT with barrier PST deposited at 550 °C were assessed. The dielectric constant and loss factor were estimated as 390 and 0.034 at 100 kHz respectively and the remnant polarisation was 28 µC/cm² at 19 V. The performance of the PZT/PST device structures was compared to similar PZT transducer stacks having widely used barrier TiO₂ layer.     

Investigation of low resistance transparent MoO3/Ag/MoO3 multilayer and application as anode in organic solar cells

Depending on the resistivity and transmittance, transparent conductive oxides (TCO) are widely used in thin film optoelectronic devices. Thus doped In₂O₃ (ITO), ZnO, SnO₂ are commercially developed. However, the deposition process of these films need sputtering and/or heating cycle, which has negative effect on the performances of the organic devices due to the sputtering and heat damages. Therefore a thermally evaporable, low resistance, transparent electrode, deposited onto substrates room temperature, has to be developed to overcome these difficulties. For these reasons combination of dielectric materials and metal multilayer has been proposed to achieve high transparent conductive oxides. In this work the different structures probed were: MoO₃ (45 nm)/Ag (x nm)/MoO₃ (37.5 nm), with x = 5-15 nm. The measure of the electrical conductivity of the structures shows that there is a threshold value of the silver thickness: below 10 nm the films are semiconductor, from 10 nm and above the films are conductor. However, the transmittance of the structures decreases with the silver thickness, therefore the optimum Ag thickness is 10 nm. A structure MoO₃ (45 nm)/Ag (10 nm)/MoO₃ (37.5 nm) resulted with a resistivity of 8 × 10^− 5 Ω cm and a transmittance, at around 600 nm, of 80%. Such multilayer structure can be used as anode in organic solar cells according to the device anode/CuPc/C₆₀/Alq₃/Al. We have already shown that when the anode of the cells is an ITO film the introduction of a thin (3 nm) MoO₃ layer at the interface anode (ITO)/organic electron donor (CuPc) allows reducing the energy barrier due to the difference between the work function of ITO and the highest occupied molecular orbital of CuPc [1]. This property has been used in the present work to achieve a high hole transfer efficiency between the CuPc and the anode. For comparison MoO₃/Ag/MoO₃/CuPc/C₆₀/Alq₃/Al and ITO/MoO₃/CuPc/C₆₀/Alq3/Al solar cells have been deposited in the same run. These devices exhibit efficiency of the same order of magnitude.