Characteristics of ITO films with oxygen plasma treatment for thin film solar cell applications

The influence of oxygen plasma treatment on the electro-optical and structural properties of indium-tin-oxide films deposited by radio frequency magnetron sputtering method were investigated. The films were exposed at different O₂ plasma powers and for various durations by using the plasma enhanced chemical vapor deposition (PECVD) system. The resistivity of the ITO films was almost constant, regardless of the plasma treatment conditions. Although the optical transmittance of ITO films was little changed by the plasma power, the prolonged treatment slightly increased the transmittance. The work function of ITO film was changed from 4.67 eV to 5.66 eV at the plasma treatment conditions of 300 W and 60 min.     

Synthesis and properties of zirconia thin films

Thin films of zirconia have been synthesized using reactive DC magnetron sputtering. It has been found that films with good optical constants, high refractive index (1·9 at 600 nm) and low extinction coefficient can be prepared at ambient temperatures. The optical constants and band gap and hence the composition are dependent on the deposition parameters such as target power, rate of deposition and oxygen background pressure. Thermal annealing of the films revealed that the films showed optical and crystalline inhomogeneity and also large variations in optical constants.     

Electrical and optical properties of ITO:Ca composite thin films for TEOLED cathode

ITO:Ca composite thin films were deposited on glass substrate by the rf magnetron co-sputtering method with various numbers of Ca chips and oxygen partial pressures. The carrier concentration of the ITO:Ca thin film was 7 × 10²⁰ cm^− 3 when the number of Ca chips was 4 at an oxygen partial pressure of 1.4%. The sheet resistance and optical transmittance of the ITO:Ca thin films were 68.2 Ω/sq. and 87%, respectively. The work function of the ITO:Ca thin films with 8 Ca chips was changed from 4.6 eV to 5.0 eV when the oxygen partial pressure was increased from 0.8% to 2.2%. When the oxygen partial pressure was 1.2%, a low work function of 4.6 eV was obtained for the ITO:Ca thin films.     

Optical, electrical and mechanical properties of the tantalum oxynitride thin films deposited by pulsing reactive gas sputtering

Thin films of tantalum oxynitride were prepared by reactive magnetron sputtering using a Ta target and N₂ and O₂ as reactive gases. The nitrogen flow was kept constant while the oxygen flow was pulsed periodically. The film composition evolves progressively from TaO_0.25N_1.51 to TaO_2.42N_0.25 while increasing the oxygen pulse duty cycle without any abrupt change in the elemental content. The optical transmission spectra of the films deposited on glass show a “blue shift” of the absorption edge with increasing oxygen content. X-ray diffraction (XRD) patterns of all films exhibit broad peaks typical for nanocrystalline materials. Cross-section film morphology is rather featureless and surface topography is smooth exhibiting very small grains, in agreement with the results obtained by XRD. The optical properties of the films are very sensitive to their chemical composition. All films exhibit semiconducting behaviour with an optical band gap changing from 1.85 to 4.0 eV with increasing oxygen content. In order to evaluate the potential of the tantalum oxynitride films for microelectronic applications some Ta-O-N films were integrated in a MOS structure. The results of the capacitance-voltage measurements of the system Al//Ta-O-N//p-Si are discussed with respect to the chemical composition of the Ta-O-N films.     

磁控溅射制备增透ITO薄膜及其性能研究

用射频磁控溅射法在低温下制备了光电性能优良的ITO(In2O3:SnO2=1:1)薄膜。质量流量计调节氩气压强PAr为0.2～3.0Pa,氧流量fO2为0～10sccm,并详细探讨了溅射时PAr和fO2变化对ITO薄膜光学性能的影响。结果表明:fO2的改变引起薄膜中氧空位浓度变化而影响ITO薄膜折射率n;fO2对ITO靶材表面的溅射阀值和对Ar 散射而改变溅射速率。衬底表面粗糙度对ITO薄膜的折射率测量准确性有较大影响。PAr为0.8Pa,fO2为2.4sccm,薄膜厚度为241.5nm时,nmin=1.97,最大透过率为89.4%(包括玻璃基体),方阻为75.9?/□,电阻率为8.8×10-4?·cm。AFM分析表明薄膜表面针刺很少,表面平整(RMS=3.04nm)。     

Effect of alumina doping on structural, electrical, and optical properties of sputtered ZnO thin films

A systematic study of the influence of alumina (Al₂O₃) doping on the optical, electrical, and structural characteristics of sputtered ZnO thin films is reported in this study. The ZnO thin films were prepared on 1737F Corning glass substrates by R.F. magnetron sputtering from a ZnO target mixed with Al₂O₃ of 0-4 wt.%. X-ray diffraction (XRD) analysis demonstrates that the ZnO thin films with Al₂O₃ of 0-4 wt.% have a highly (002) preferred orientation with only one intense diffraction peak with a full width at half maximum (FWHM) less than 0.5°. The electrical properties of the Al₂O₃-doped ZnO thin films appear to be strongly dependent on the Al₂O₃ concentration. The resistivity of the films decreases from 74 Ω·cm to 2.2 × 10^− 3 Ω·cm as the Al₂O₃ content increases from 0 to 4 wt.%. The optical transmittance of the Al₂O₃-doped ZnO thin films is studied as a function of wavelength in the range 200-800 nm. It exhibits high transparency in the visible-NIR wavelength region with some interference fringes and sharp ultraviolet absorption edges. The optical bandgap of the Al₂O₃-doped ZnO thin films show a short-wavelength shift with increasing of Al₂O₃ content.     

Properties of Ce-doped ITO films deposited on polymer substrate by DC magnetron sputtering

Ce-doped indium tin oxide (ITO:Ce) films were deposited on flexible polyimide substrates by DC magnetron sputtering using ITO targets containing various CeO₂ contents (CeO₂ : 0, 0.5, 3.0, 4.0, 6.0 wt.%) at room temperature and post-annealed at 200 °C. The crystallinity of the ITO films decreased with increasing Ce content, and it led to a decrease in surface roughness. In addition, a relatively small change in resistance in dynamic stress mode was obtained for ITO:Ce films even after the annealing at high temperature (200 °C). The minimum resistivity of the amorphous ITO:Ce films was 3.96 × 10^− 4 Ωcm, which was deposited using a 3.0 wt.% CeO₂ doped ITO target. The amorphous ITO:Ce films not only have comparable electrical properties to the polycrystalline films but also have a crystallization temperature > 200 °C. In addition, the amorphous ITO:Ce film showed stable mechanical properties in the bended state.     

Structure and optical properties of ZnO:V thin films with different doping concentrations

A series of ZnO thin films doped with various vanadium concentrations were prepared on glass substrates by direct current reactive magnetron sputtering. The results of the X-ray diffraction (XRD) show that the films with doping concentration less than 10 at.% have a wurtzite structure and grow mainly along the c-axis orientation. The residual stress, estimated by fitting the XRD diffraction peaks, increases with the doping concentration and the grain size also has been calculated from the XRD results, decreases with increasing the doping concentration. The surface morphology of the ZnO:V thin films was examined by SEM. The optical constants (refractive index and extinction coefficient) and the film thickness have been obtained by fitting the transmittance. The optical band gap changed from 3.12 eV to 3.60 eV as doping concentration increased from 1.8 at.% to 13 at.% mol. All the results have been discussed in relation with doping concentration.     

室温直流磁控溅射制备ITO膜及光电性能研究

室温条件下,在玻璃衬底上,采用直流磁控溅射法制备了ITO膜.研究了溅射压强,氧流量和溅射功率等工艺参数对薄膜光电性能的影响.结果表明当Ar流量为44.2 sccm和溅射时间20 min等参数不变时,溅射气压0.7 Pa,氧流量0.62 sccm和溅射功率130 W为最佳工艺条件.并得到了电阻率5.02×10-4 Ω·cm,在可见光区平均透过率80%以上ITO薄膜.     

Work function and valence band structure of tin-doped indium oxide thin films for OLEDs

Transparent conducting ITO thin film has been widely used as anode material in OLEDs due to its good optical transparency, low electrical resistivity, ease of patterning, high work function and efficient hole injection properties. The interface between ITO and organic layer in OLED device is thus important and can influence the electrical and luminescent properties. In this report, ITO substrates were treated with 20% H₃PO₄ solution. The corresponding changes in crystalline morphology were studied by X-ray diffraction. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) were performed at ∼10⁻⁹ Torr to study the work function and the valence band structure of ITO substrates. It was found that work function became slightly lower after the treatment, probably caused by the formation of metal complex compounds and metal hydroxides. The binding energy of In 3d_5/2 shifted from 444.6 to 445.3 eV. This shifting was referred to the formation of In-OH bonding. It would be easier to provide electron by In-OH bonding than by In-O-In or Sn-O-Sn when photons reached ITO surface. The interface between ITO and CuPc was improved through polar surface and less aggregation. In addition, the OLED devices exhibited improved performance in both external quantum efficiency and luminescence efficiency.     

Modification of optical and electrical properties of ITO using a thin Al capping layer

In this study, the work function, transmittance, and resistivity of indium tin oxide (ITO) thin films were successfully modified by depositing an Al capping layer on top of ITO with subsequent thermal annealing. The 5 nm thick Al layer was deposited by a conventional dc magnetron sputtering method and the layer was converted into an aluminum oxinitride by subjecting the sample to rapid thermal annealing (RTA) under a nitrogen atmosphere. The films exhibited a high transmittance of 86% on average within the visible wavelength region with an average resistivity value of 7.9 × 10^− 4 Ω cm. Heat-treating the Al/ITO films via RTA resulted in the decrease of the optical band gap from that of bare ITO. In addition, the films showed red-shift phenomena due to their decreased band gaps when the heat-treatment temperature was increased. The resultant electrical and optical characteristics can be explained by the formation of aluminum oxinitride on the surface of the ITO films. The work function of the heat-treated films increased by up to 0.26 eV from that of a bare ITO film. The increase of the work function predicts the reduction of the hole-injection barrier in organic light-emitting diode (OLED) devices and the eventual use of these films could provide much improved efficiency of devices.     

High rate deposition of insulating TiO2 and conducting ITO films for optical and display applications

An innovative reactive pulse magnetron sputtering (PMS-) system allowing to change the pulse mode (unipolar, bipolar or pulse packet) and the pulse parameters (duty cycle, frequency) of the discharge has been used to deposit different materials at high deposition rates. The new pulse packet mode combines the two fundamental pulse modes of unipolar and bipolar by applying ‘packets’ of unidirectional pulses between the two targets and changing the polarity of the discharge after each packet. As a new pulse parameter, the number of pulses of each packet can be varied. The advantages of the PMS-system were demonstrated by the reactive deposition of insulating titanium oxide (TiO₂) and conducting indium tin oxide (ITO) films. The TiO₂ layers sputtered on unheated substrates at deposition rates of up to 50 nm*m/min exhibited amorphous, mixed anatase/rutile or rutile structure in dependence of the pulse mode and the pulse parameters that were applied. Hardness, Young's modulus, roughness and refractive index varied in dependence of the structure of the layers. Although the sputtering from ceramic target is the most common coating technique for ITO, another economical way is the use of metallic InSn-targets. The effect of various pulse modes on the optical and electrical properties of reactively sputtered ITO layers on float glass was investigated. The specific resistivity of ITO was minimized by process parameter optimisation.     

Effect of annealing temperature on structural, electrical and optical properties of B-N codoped ZnO thin films

The B-N codoped p-type ZnO thin films have been prepared by radio frequency magnetron sputtering using a mixture of nitrogen and oxygen as sputtering gas. The effect of annealing temperature on the structural, electrical and optical properties of B-N codoped films was investigated by using X-ray diffraction, Hall-effect, photoluminescence and optical transmission measurements. Results indicated that the electrical properties of the films were extremely sensitive to the annealing temperature and the conduction type could be changed dramatically from n-type to p-type, and finally changed to weak p-type in a range from 600 °C to 800 °C. The B-N codoped p-type ZnO film with good structural, electrical and optical properties can be obtained at an intermediate annealing temperature region (e.g., 650 °C). The codoped p-type ZnO had the lowest resistivity of 2.3 Ω cm, Hall mobility of 11 cm²/Vs and carrier concentration of 1.2 × 10¹⁷ cm^− 3.     

Switching properties of vanadium doped TiO2 thin films prepared by magnetron sputtering

In the present work thin films of Ti-Me (where Me: V, Nb, Ta) were deposited onto glass substrates by magnetron sputtering of mosaic target in reactive oxygen plasma. The properties of the prepared thin films were studied by X-ray diffraction (XRD), electron dispersive spectroscopy, temperature-dependent electrical and optical transmission spectroscopy measurements. The structural investigations indicate that thin films were XRD-amorphous. Reversible thermoresistance effect, recorded at 52 ± 1 °C was found from electrical measurements. The prepared coatings were well transparent in the visible part of the light spectrum from ca. 350 nm.     

Effect of annealing treatment on structural, electrical, and optical properties of Ga-doped ZnO thin films deposited by RF magnetron sputtering

The effect of annealing on structural, electrical, and optical properties of Ga-doped ZnO (GZO) films prepared by RF magnetron sputtering was investigated in air and nitrogen. GZO films are polycrystalline with a preferred 002 orientation. The resistivities of annealed films are larger than the as-deposited. The transmittance in the near IR region increases greatly and the optical band gap decreases after annealing. The photoluminescence spectra is composed of a near band edge emission and several deep level emissions (DLE) which are dominated by a blue emission. After annealing, these DLEs are enhanced evidently.     

Optical and electrical properties of Te-substituted Sn-Sb-Se semiconducting thin films

Thin films of Sn₁₀Sb₂₀Se_70-XTe_X (0 ≤ X ≤ 14) composition were deposited using thermal evaporation technique. As-prepared films were amorphous as studied by X-ray diffraction. Surface morphology studies revealed that films have surface roughness ~ 2 nm and av. grain size ~ 30 nm. Optical band gap E_g showed a sharp decrease for initial substitution of Se with Te upto 2 at.%. A broad hump in the optical band gap is observed for further substitution of Se with Te. The trend of optical band gap variation with tellurium content has been qualitatively explained using band model given by Kastner. The dc-conductivity measurements showed thermally activated conduction with single activation energy for the measured temperature regime and followed Meyer-Neldel rule. The dc-activation energy has nearly half the value as that of optical band gap that revealed the intrinsic nature of semiconductor. The annealing below glass transition T_g led to decrease in optical band gap as well as dc-activation energy that might be related to increase of disorder in material with annealing.     

Preparation and electrical properties of ITO thin films by dip-coating process

Indium tin oxide (ITO) thin films were prepared on quartz glass substrates by a dip-coating process. The starting solution was prepared by mixing indium chloride dissolved in acetylacetone and tin chloride dissolved in ethanol. The ITO thin films containing 0 20 mol% SnO₂ were successfully prepared by heat-treatment at above 400 °C. Chemical stability of sol were investigated by using a FTIR spectrometer. The electrical resistivity of the thin films decreased with increasing heat-treatment temperature, that is carrier concentration increased, and mobility decreased with increasing SnO₂ content. The ITO thin films containing 12 mol% SnO₂ showed the minimum resistivity of =1.2 × 10^–3 ( cm). It also showed high carrier concentration of N=1.2 × 10²⁰(cm^–3) and mobility _H=7.0(cm² V^–1 s^–1).     

Microstructure and optical properties of photoactive TiO2:N thin films

In this work, we have chosen oxidation of TiN thin films as a feasible method for preparation of nitrogen-doped titanium dioxide thin films, TiO₂:N, for photocatalytic applications. DC reactive magnetron sputtering with the plasma emission control was used for deposition of stoichiometric TiN thin films. The microstructure and chemical composition of films before and after oxidation were investigated by means of RBS, X-ray diffraction (XRD) in grazing incidence diffraction (GID) configuration, AFM and XPS techniques. The electrical conductivity was measured by the van der Pauw method as a function of the oxidation temperature. The optical transmittance and reflectance spectra of the films were measured over the visible and UV ranges of the light spectrum. GID diffraction patterns of as-sputtered TiN thin films and those after oxidation indicate that TiO₂ rutile is formed at around 300 °C. Nitrogen is still present as indicated by XPS studies even when XRD detects the rutile only. Optical absorption of thin films oxidized at 450 °C is shifted towards the visible range of the light spectrum.     

Electrical properties of AlNxOy thin films prepared by reactive magnetron sputtering

Direct current magnetron sputtering was used to produce AlN_xO_y thin films, using an aluminum target, argon and a mixture of N₂ + O₂ (17:3) as reactive gases. The partial pressure of the reactive gas mixture was increased, maintaining the discharge current constant. Within the two identified regimes of the target (metallic and compound), four different tendencies for the deposition rate were found and a morphological evolution from columnar towards cauliflower-type, ending up as dense and featureless-type films. The structure was found to be Al-type (face centered cubic) and the structural characterization carried out by X-ray diffraction and transmission electron microscopy suggested the formation of an aluminum-based polycrystalline phase dispersed in an amorphous aluminum oxide/nitride (or oxynitride) matrix. This type of structure, composition, morphology and grain size, were found to be strongly correlated with the electrical response of the films, which showed a gradual transition between metallic-like responses towards semiconducting and even insulating-type behaviors. A group of films with high aluminum content revealed a sharp decrease of the temperature coefficient of resistance (TCR) as the concentration ratio of non-metallic/aluminum atomic ratio increased. Another group of samples, where the non-metallic content became more important, revealed a smooth transition between positive and negative values of TCR. In order to test whether the oxynitride films have a unique behavior or simply a transition between the typical responses of aluminum and of those of the correspondent nitride and oxide, the electrical properties of the ternary oxynitride system were compared with AlN_x and AlO_y systems, prepared in similar conditions.     

Bias effect on microstructure and mechanical properties of magnetron sputtered nanocrystalline titanium carbide thin films

Nanocrystalline titanium carbide (TiC) thin films were prepared by magnetron sputtering deposition at 473 K. The effect of substrate bias on microstructure and mechanical properties was studied in details using X-ray photoelectron spectroscopy, X-ray diffraction, field emission scanning electron microscopy, indentation and scanning microscratch. The TiC films exhibit a (111) preferential orientation. Substrate bias decreases grain size and deposition rate of the TiC films. The TiC films have columnar structure which becomes finer at high substrate bias. Nanoindentation hardness, Young's modulus, and toughness of the films are increased as the substrate bias goes up. However, the adhesion peaks at substrate bias of − 100 V and drops when bias is increased further.