Surface characterisation and functionalisation of indium tin oxide anodes for improvement of charge injection in organic light emitting diodes

Wettability studies have been performed to probe the surface properties of ITO substrates, aimed to be used as hole injecting electrode in OLEDs. The elimination of organic contaminants upon the cleaning treatment (ultrasonic bath in organic solvents) leads to an increase of the free energy of the ITO surface becoming hydrophilic. The surface energy components calculated from the Van Oss model show the appearance of a basic component upon the cleaning treatment. A thermal treatment at 100 °C for 3 h leads to a decrease of the surface free energy due to surface dehydration. These properties are attributed to the hydroxides formed at the ITO surface inducing improved adhesion at the ITO/polymer interface. The ITO surfaces have been functionalised with a chloroethylphosphonic acid mono-layer to increase their stability. The appearance of an acid-base component leads to a dipolar character of the ITO surface. The formation of a compact layer of a spin coated poly(phenylenevinylene) derivative induces the shielding of the ITO basic character. The weakening of the near infrared absorption associated to ITO free carriers confirms the formation of a dipole layer at the interface with the molecular layer in contact with ITO. Improved injection properties, shown by the current/voltage characteristics, result from the interface modifications.     

Stress-corrosion cracking of indium tin oxide coated polyethylene terephthalate for flexible optoelectronic devices

Stress corrosion cracking of transparent conductive layers of indium tin oxide (ITO), sputtered on polyethylene terephthalate (PET) substrates, is an issue of paramount importance in flexible optoelectronic devices. These components, when used in flexible device stacks, can be in contact with acid containing pressure-sensitive adhesives or with conductive polymers doped in acids. Acids can corrode the brittle ITO layer, stress can cause cracking and delamination, and stress-corrosion cracking can cause more rapid failure than corrosion alone.The combined effect of an externally-applied mechanical stress to bend the device and the corrosive environment provided by the acid is investigated in this work. We show that acrylic acid which is contained in many pressure-sensitive adhesives can cause corrosion of ITO coatings on PET. We also investigate and report on the combined effect of external mechanical stress and corrosion on ITO-coated PET composite films. Also, it is shown that the combination of stress and corrosion by acrylic acid can cause ITO cracking to occur at stresses less than a quarter of those needed for failure with no corrosion. In addition, the time to failure, under ~ 1% tensile strain can reduce the total time to failure by as much as a third.     

Monte Carlo simulation of indium tin oxide current spreading layers in light emitting diodes

Transparent conductors such as indium tin oxide (ITO) are used in a range of optoelectronic devices. Such materials provide both the electrical interface with the semiconductor and a transparent window for the injection or extraction of photons. In AlGaInP surface emitting LED device structures, a particular problem is that of providing an efficient current spreading layer in order to ensure that electrons are injected across the whole of the active region. In this way, the light extracted can be maximised as it originates from the region below the transparent conductor rather than the contact metal. This paper describes a Monte Carlo simulation that can assist in the optimisation of current spreading and light transmission of ITO layers in LED devices.     

Influence of oxygen deficiency in indium tin oxide on the performance of polymer light-emitting diodes

We investigated effects of oxygen deficiency in the indium tin oxide (ITO) on the performance of poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV)-based polymer light-emitting diodes, in which the ITO anode was deposited by radio frequency magnetron sputtering at different oxygen flow rates. We found that the degree of oxygen deficiency in the ITO films can affect the device performance significantly and is a source of current leakage. At the optimal oxygen flow rate, the leakage current of devices can be reduced and the balance between hole and electron fluxes can be promoted in the MEH-PPV layer to improve device efficiency.     

Enhancement of light output power in GaN-based light-emitting diodes using indium tin oxide films with nanoporous structures

We fabricated GaN-based light-emitting diodes (LEDs) with a transparent ohmic contact made from nanoporous indium tin oxide (ITO). The nanoporous structures are easily made and controlled using a simple wet etching technique. The transmittance, sheet resistance, and root-mean-square surface roughness of the nanoporous ITO films are correlated strongly with the etch times. On the basis of the experimental values of these parameters, we choose an optimum etch time of 50 s for the fabrication of LEDs. The wall-plug efficiency of the LEDs with nanoporous ITO is increased by 35% compared to conventional LEDs at an injection current of 20 mA. This improvement is attributed to the increase in light scattering at the nanoporous ITO film-to-air interface.     

Pulsed laser deposition of indium tin oxide films on flexible polyethylene naphthalate display substrates at room temperature

Pulsed laser deposition was used to deposit high-quality indium tin oxide (ITO) thin solid films on polyethylene napthalate (PEN) flexible display substrates. The electrical, optical, microstructural, mechanical and adhesive properties of the functional thin layer were investigated as a function of a narrow range of background oxygen gas pressure at room temperature, which is the most desirable thermal condition for growing transparent conducting oxides on flexible display polymer substrates. ITO films (240 ± 35 nm thick) deposited on PEN at room temperature in the range of 0.33 to 2.66 Pa background oxygen pressure are observed to exhibit low electrical resistivity (~ 10^− 4 Ω cm) and high optical transmission (~ 90%). Electromechanical uniaxial tensile testing, of the hybrid thin structures, results in crack onset nominal strains of around 2%. The ITO surface adhesion reaches a maximum at 1.33 Pa deposition pressure.     

Refractive indices of textured indium tin oxide and zinc oxide thin films

The refractive indices of textured indium tin oxide (ITO) and zinc oxide (ZnO) thin films were measured and compared. The ITO thin film grown on glass and ZnO buffered glass substrates by sputtering showed distinct differences; the refractive index of ITO on glass was about 0.05 higher than that of ITO on ZnO buffered glass in the whole visible spectrum. The ZnO thin film grown on glass and ITO buffered glass substrates by filtered vacuum arc also showed distinct differences; the refractive index of ZnO on glass was higher than that of ZnO on ITO buffered glass in the red and green region, but lower in the blue region. The largest refractive index difference of ZnO on glass and ITO buffered glass was about 0.1 in the visible spectrum. The refractive index variation was correlated with the crystal quality, surface morphology and conductivity of the thin films.     

Study on the antimony tin oxide as a hole injection layer for polymer light emitting diodes

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) is commonly used as a hole transfer layer in polymer light emitting diodes (PLEDs). However, Indium tin oxide transparent electrodes are corroded by poly(styrenesulfonate) and the erupted indium diffuses into the active layer, which in turn decreases the brightness, efficiency and lifetime of the device. In this study, therefore, antimony tin oxide (ATO) was introduced as a hole injection layer (HIL) in PLEDs. The work function and pH of ATO were − 5.1 eV and ~ 7.5, respectively. When annealed at 200 °C, high conductivity (~ 0.18 S/cm) was observed, which represents good HIL characteristics. Here, the maximum luminance (26,114 cd/m²) and maximum efficiency (1.55 cd/A) of the PLEDs were increased by 33% and 20% respectively. Their stability improved as well.     

Effects of thermal treatment on the electrical and optical properties of silver-based indium tin oxide/metal/indium tin oxide structures

In this article, we report the results of the study of thermal treatment effects on the electrical and optical properties of silver-based indium tin oxide/metal/indium tin oxide (IMI) multilayer films. Heat treatment conditions such as temperature and gaseous atmosphere was varied to obtain better electrical and optical properties. We obtained improved electrical properties and observed considerable shift in the transmittance curves after heat treatment. Several analytical tools such as X-ray diffraction, spectroscopic ellipsometer and spectrophotometer were used to explore the causes of the changes in electrical and optical properties. The sheet resistance of the structure was severely influenced by deposition conditions of the indium tin oxide (ITO) layer at the top. Moreover, the shift of optical transmittance could be explained on the basis of the change in refractive indices of ITO layers during heat treatment. The properties of Ag-alloy-based IMI films were compared with those of pure Ag-based ones. Some defects originating from Ag layer corrosion were observed on the surface of ITO-pure Ag–ITO structures, however, their number decreased significantly in the cases of Ag-alloys containing Pd, Au and Cu, though the resistivity values of Ag-alloys were slightly higher than those of silver. Atomic force microscopy measurement results revealed that the surface of the IMI multilayer was so smooth that it meets the required qualifications as the bottom electrode of organic light emitting diodes.     

Deposition by magnetron sputtering and characterization of indium tin oxide thin films

In this work the properties of indium tin oxide (ITO) films deposed on glass substrates by magnetron sputtering technique in the temperature range below 200 °C are studied by various methods. The physical properties of ITO thin films have been investigated using optical transmittance, photoluminescence, atomic force microscopy, ellipsometry, Hall-effect and four point probe methods. It is established that properties of ITO layers depend drastically on the temperature and oxygen partial pressure during the deposition process and exhibit some peculiarities of the surface morphology. It is found that the band gap energy of this material varies in the energy range from 4.1 to 4.4 eV and depends on the growth conditions. It is suggested that local deviations from the stoichiometry and defects are the main physical reasons of Burstein-Moss shift of the optical band gap.     

Deposition of indium tin oxide by atmospheric pressure chemical vapour deposition

We report the deposition of indium tin oxide (ITO) by atmospheric pressure chemical vapour deposition (APCVD). This process is potentially scalable for high throughput, large area production. We utilised a previously unreported precursor combination; dimethylindium acetylacetonate, [Me₂In(acac)] and monobutyltintrichloride, MBTC.[Me₂In(acac)] is a volatile solid. It is more stable and easier to handle than traditional indium oxide precursors such as pyrophoric trialkylindium compounds. Monobutyltintrichloride (MBTC) is also easily handled and can be readily vaporised. It is compatible with the process conditions required for using [Me₂In(acac)].Cubic ITO was deposited at a substrate temperature of 550 °C with growth rates exceeding 15 nm/s and growth efficiencies of between 20 and 30%. Resistivity was 3.5 × 10^− 4 Ω cm and transmission for a 200 nm film was > 85% with less than 2% haze.     

Effect of aluminum doping on the high-temperature stability and piezoresistive response of indium tin oxide strain sensors

Ceramic strain sensors based on reactively sputtered indium tin oxide (ITO) thin films doped with aluminum are being considered to improve the high-temperature stability and response. Ceramic strain sensors were developed to monitor the structural integrity of components employed in aerospace propulsion systems operating at temperatures in excess of 1500 °C. Earlier studies using electron spectroscopy for chemical analysis (ESCA) studies indicated that interfacial reactions between ITO and aluminum oxide increase the stability of ITO at elevated temperature. The resulting ESCA depth files showed the presence of two new indium-indium peaks at 448.85 and 456.40 eV, corresponding to the indium 3d5 and 3d3 binding energies. These binding energies are significantly higher than those associated with stoichiometric indium oxide. Based on these studies, a combinatorial chemistry approach was used to screen large numbers of possible concentrations to optimize the stability and performance of Al-doped ceramic strain sensors. Scanning electron microscopy was used to analyze the combinatorial libraries in which varying amounts of aluminum were incorporated into ITO films formed by cosputtering from multiple targets. Electrical stability and piezoresistive response of these films were compared to undoped ITO films over the same temperature range.     

Successive deposition of layered titanium oxide/indium tin oxide films on unheated substrates by twin direct current magnetron sputtering

Layered titanium oxide/indium tin oxide (TiO₂/ITO) films were successively deposited on unheated glass substrates in situ using a twin direct current magnetron sputtering system. The layered TiO₂/ITO films exhibited a strongly polycrystalline structure that comprises anatase and rutile phases, as revealed by X-ray diffraction and Raman spectra. The X-ray photoelectron spectrum of Ti2p also verified the stoichiometric state of titanium oxide near the surface. The photo-induced hydrophilic properties of the films were determined from changes in the water contact angles under ultra-violet (UV) irradiation. The results revealed that the layered TiO₂/ITO films possessed a dissipated rate of 30% when they were stored in the dark for 12 h. This result shows that the layered TiO₂/ITO films acted as “electron pools” with an inherent energy storage capability. This unique property is attributable to the rougher surface and nearly porosity-free columnar structure, which is responsible for increased UV energy absorption and loss-free hole or electron transportation.     

Temperature dependence of resistance and thermopower of thin indium tin oxide films

We have measured the resistance and thermopower of a series of RF sputtered and annealed indium tin oxide (ITO) thin films from 300 K down to liquid-helium temperatures. Thermal annealing was performed to modulate the levels of disorder (i.e., resistivity) of the samples. The measured resistances are well described by the Bloch-Grüneisen law between 150 and 300 K, suggesting that our thin films are metallic. At lower temperatures, a resistance rise with decreasing temperature was observed, which can be quantitatively ascribed to the two-dimensional electron-electron interaction and weak-localization effects. The thermopowers in all samples are negative and reveal fairly linear temperature dependence over the whole measurement temperature range, strongly indicating free-electron like conduction characteristics in ITO thin films. As a result, the carrier concentration in each film can be reliably determined. This work demonstrates that ITO films as thin as 15 nm thick can already possess high metallic conductivity.     

Single step synthesis of indium tin oxide by ultrasonic spray and microwave assisted pyrolysis

Ultrafine indium tin oxide (ITO) powders were successfully synthesised by the combined methods of ultrasonic spray and microwave assisted pyrolysis, which is a single step, facile, rapid and continuous method without post-heating treatment. Crystallinity, morphology and microstructure of the samples were investigated by X-ray diffractometer, scanning electron microscope, transmission electron microscope, energy dispersive X-ray spectroscope, selected area electron diffraction pattern and laser grain size analyser. Results indicate that pure solid solution ITO ultrafine powders with homogeneous and narrow size distribution, highly dense and smooth surface morphology can be obtained under optimum conditions. Each uniform spherical particle consisted of many smaller crystallites with diameter of <10 nm.     

Influence of the sputtering system''s vacuum level on the properties of indium tin oxide films

The influence of the chamber residual pressure level in the radio frequency magnetron sputtering process on the electrical, optical and structural properties of indium thin oxide (ITO) is investigated. Several ITO films were deposited at various residual pressure levels on Corning glass using In₂O₃:SnO₂ target in argon atmosphere and without the addition of oxygen partial pressure. It is found that a very good vacuum is associated to metallic films and results in less transparent ITO films, with some powder formation on the surface. On the contrary highly transparent and conducting films are produced at a higher residual pressure. The best deposition conditions are addressed for ITO films as transparent conducting oxide layers in silicon heterojunction solar cells. Using the optimal vacuum level for ITO fabrication, a maximum short circuit current of 36.6 mA/cm² and a fill-factor of 0.78 are obtained for solar cells on textured substrates with a device conversion efficiency of 16.2%.     

Preparation of transparent conductive indium tin oxide thin films from nanocrystalline indium tin hydroxide by dip-coating method

Indium tin oxide (ITO) thin films with well-controlled layer thickness were produced by dip-coating method. The ITO was synthesized by a sol-gel technique involving the use of aqueous InCl₃, SnCl₄ and NH₃ solutions. To obtain stable sols for thin film preparation, as-prepared Sn-doped indium hydroxide was dialyzed, aged, and dispersed in ethanol. Polyvinylpyrrolidone (PVP) was applied to enhance the stability of the resulting ethanolic sols. The transparent, conductive ITO films on glass substrates were characterized by X-ray diffraction, scanning electron microscopy and UV-Vis spectroscopy. The ITO layer thickness increased linearly during the dipping cycles, which permits excellent controllability of the film thickness in the range ~ 40-1160 nm. After calcination at 550 °C, the initial indium tin hydroxide films were transformed completely to nanocrystalline ITO with cubic and rhombohedral structure. The effects of PVP on the optical, morphological and electrical properties of ITO are discussed.     

A comparative study of the effect of annealing and plasma treatments on the microstructure and properties of colloidal indium tin oxide films and cold-sputtered indium tin oxide films

Indium tin oxide (ITO) films were fabricated by (i) RF sputtering and (ii) spin coating of a colloidal ITO dispersion synthesized in-house. Films were deposited onto glass and quartz substrates and were annealed in air and in argon. The electrical properties of the films were studied as a function of annealing temperature and atmosphere. For the colloidal films, the effect of pre-annealing plasma treatments was also evaluated. Removal of the organic ligands from the colloidal films, in combination with annealing, resulted in over 8 orders of magnitude decrease in the film resistivity. It was found that plasma treatments were particularly effective in reducing film resistivity for low temperature annealed colloidal films. Results for the cold-sputtered films were for the most part as expected, with argon annealing resulting in lower resistivities than films annealed in air.     

Rapid thermal processing of nano-crystalline indium tin oxide transparent conductive oxide coatings on glass by flame impingement technology

Indium tin oxide (ITO) is still the best suited material for transparent conductive oxides, when high transmission in the visible range, high infrared reflection or high electrical conductivity is needed. Current approaches on powder-based printable ITO coatings aim at minimum consumption of active coating and low processing costs. The paper describes how fast firing by flame impingement is used for effective sintering of ITO-coatings applied on glass. The present study correlates process parameters of fast firing by flame impingement with optoelectronic properties and changes in the microstructure of suspension derived nano-particulate films. With optimum process parameters the heat treated coatings had a sheet resistance below 0.5 kΩ/_□ combined with a transparency higher than 80%. To characterize the influence of the burner type on the process parameters and the coating functionality, two types of methane/oxygen burner were compared: a diffusion burner and a premixed burner.     

Characteristics of ITO electrode grown by linear facing target sputtering with ladder type magnetic arrangement for organic light emitting diodes

The preparation and characteristics of indium tin oxide (ITO) electrodes grown using a specially designed linear facing target sputtering (LFTS) system with a ladder type magnet arrangement for organic light emitting diodes (OLED) are described. It was found that the electrical and optical properties of the ITO electrode were critically dependent on the Ar/O₂ flow ratio, while its structural and surface properties remained fairly constant regardless of the Ar/O₂ flow ratio, due to the low substrate temperature during the plasma damage-free sputtering. Under the optimized conditions, we obtained an ITO electrode with the lowest sheet resistance of 39.4 Ω/sq and high transmittance of 90.1% (550 nm wavelength) at room temperature. This suggests that LFTS is a promising low temperature and plasma damage free sputtering technology for preparing high-quality ITO electrodes for OLEDs and flexible OLEDs at room temperature.