Valence control of cobalt oxide thin films by annealing atmosphere

The cobalt oxide (CoO and Co₃O₄) thin films were successfully prepared using a spin-coating technique by a chemical solution method with CH₃OCH₂CH₂OH and Co(NO₃)₂·6H₂O as starting materials. The grayish cobalt oxide films had uniform crystalline grains with less than 50 nm in diameter. The phase structure is able to tailor by controlling the annealing atmosphere and temperature, in which Co₃O₄ thin film was obtained by annealing in air at 300-600, and N₂ at 300, and transferred to CoO thin film by raising annealing temperature in N₂. The fitted X-ray photoelectron spectroscopy (XPS) spectra of the Co2p electrons are distinguishable from different valence states of cobalt oxide especially for their satellite structure. The valence control of cobalt oxide thin films by annealing atmosphere contributes to the tailored optical absorption property.     

Indium zinc oxide thin films deposited by sputtering at room temperature

The deposition of amorphous indium zinc oxide (IZO) thin films on glass substrates with n-type carrier concentrations between 10¹⁴ and 3 × 10²⁰ cm⁻³ by sputtering from single targets near room temperature was investigated as a function of power and process pressure. The resistivity of the films with In/Zn of ∼0.7 could be controlled between 5 × 10⁻³ and 10⁴ Ω cm by varying the power during deposition. The corresponding electron mobilities were 4-18 cm² V⁻¹ s⁻¹.The surface root-mean-square roughness was <1 nm under all conditions for film thicknesses of 200 nm. Thin film transistors with 1 μm gate length were fabricated on these IZO layers, showing enhancement mode operation with good pitch-off characteristics, threshold voltage 2.5 V and a maximum transconductance of 6 mS/mm. These films look promising for transparent thin film transistor applications.     

Detection of impurity segregation in zone-confined, polycrystalline tin-doped indium oxide thin films by STM and AFM

This paper discusses the possibility of using STM and AFM to image the dopant material in a segregated state. Samples of tin-doped indium oxide were prepared using a zone-confining process. The resultant material has dopant species segregated over certain grain boundaries at desired positions while the others remain dopant free. Samples were then imaged using STM, AFM and STEM. Enhanced contrast from the dopant rich grain boundaries and a larger grain size are observed at the surface making an interface with the substrate as compared to the free surface of the sample, while secondary electron STEM images show these grains to be smaller in size and the boundaries to be almost physically flat. This is interpreted to be a consequence of the zone-confining effect.     

Electrical properties of vacuum-annealed titanium-doped indium oxide films

Titanium-doped indium oxide (ITiO) films were deposited on Corning glass 2000 substrates at room temperature by radio frequency magnetron sputtering followed by vacuum post-annealing. With increasing deposition power, the as-deposited films showed an increasingly crystalline nature. As-deposited amorphous ITiO films obtained at 20 W began to crystallize at the annealing temperature of 155 °C. Although there was no significant change in the crystalline structure of the films, electron mobility improved gradually with further increase in the annealing temperature. After post-annealing at 580 °C, the highest electron mobility of 50 cm² V⁻¹ s⁻¹ was obtained. Compared with the amorphous ITiO films, the ITiO films with a certain degree of crystallinity obtained at high deposition power were less affected by the vacuum annealing. Their electron mobility also improved due to post-annealing, but the increase was insignificant. After post-annealing, the optical transmission of the 325 nm-thick ITiO films showed approximately 80% at wavelengths ranging from 530 to 1100 nm, while the sheet resistance decreased to 10 Ω/sq. This makes them suitable for use as transparent conductive oxide layers of low bandgap solar cells.     

The impact of annealing temperature and time on the electrical performance of Ti/Pt thin films

In this study, we focus on the influence of annealing time t_PDA (i.e. 30 min and 630 min) on the room-temperature resistivity of electron-beam-evaporated titanium/platinum thin films when exposed to thermal loads up to temperatures T_PDA of 700 °C. The titanium has a fixed thickness of 5 nm and serves as an adhesion layer. The thickness d_f,Pt of the platinum top layer is varied between 21 and 97 nm. Up to annealing temperatures of 450 °C, the film resistivity of the bi-layer system is linearly correlated with the reciprocal platinum film thickness independent of t_PDA, as expected from the size effect. At t_PDA = 30 min, the change in intrinsic film stress dominates the electrical behavior in this annealing regime, predominantly at large d_f,Pt values. Compared to t_PDA = 630 min, however, the increase in resistivity especially at low platinum film thickness is substantially larger demonstrating that titanium starts to diffuse at these long annealing times even at moderate temperatures. At T_PDA = 600 °C, the diffusion of titanium into the top layer leads to an enhanced increase in film resistivity ρ_f, especially at low platinum thicknesses and low annealing times, as the mean penetration depth of diffused titanium is under these conditions in order of d_f,Pt. Above T_PDA = 600 °C, ρ_f is slightly increased at t_PDA = 30 min. At t_PDA = 630 min, however, the film resistivity is decreased at d_f,Pt < 58 nm. This is attributed to grain growth and re-crystallization effects. Furthermore, the mean penetration depths of titanium substantially exceed d_f,Pt resulting predominantly in Ti_xO_y formation on the top film surface and hence, having low impact on ρ_f.     

Properties of Eu-doped zinc oxide thin films grown on glass substrates by radio-frequency magnetron sputtering

Eu-doped ZnO (EZO) thin films were prepared on glass substrates at various growth temperatures by radio-frequency magnetron sputtering. The properties of deposited thin films showed a significant dependence on the growth temperature. The preferential growth orientation of all the thin films was occurred along the ZnO (002) plane. The maximum crystallite size and the minimum average transmittance in the wavelength range of 450–1100 nm were observed for the EZO thin film deposited at 25 °C. A red shift of the optical band gap was observed in the growth temperature range of 25–300 °C. The highest figure of merit, an index for evaluating the performance of transparent conducting thin films, was obtained at 200 °C of growth temperature. These results indicated that the high-quality EZO film was obtained at a growth temperature of 200 °C.     

Spray deposition of highly transparent fluorine doped cadmium oxide thin films

The cadmium oxide (CdO) and F:CdO films have been deposited by spray pyrolysis method using cadmium acetate and ammonium fluoride as precursors for Cd and F ions, respectively. The effect of temperature and F doping on the structural, morphological, optical and Hall effect properties of sprayed CdO thin films was investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), optical absorption and electrical measurement techniques. TGA and DTA studies, indicates the formation of CdO by decomposition of cadmium acetate after 250 °C. XRD patterns reveal that samples are polycrystalline with cubic structure and exhibits (2 0 0) preferential orientation. Considerable broading of (2 0 0) peak, simultaneous shifting of corresponding Bragg's angle have been observed with respect to F doping level. SEM and AFM show the heterogeneous distribution of cubical grains all over the substrate, which are randomly distributed. F doping shifts the optical gap along with the increase in the transparency of CdO films. The Hall effect measurement indicates that the resistivity and mobility decrease up to 4% F doping.     

Vanadium oxide thin films produced by magnetron sputtering from a V2O5 target at room temperature

Vanadium oxide thin films were grown by RF magnetron sputtering from a V₂O₅ target at room temperature, an alternative route of production of vanadium oxide thin films for infrared detector applications. The films were deposited on glass substrates, in an argon–oxygen atmosphere with an oxygen partial pressure from nominal 0% to 20% of the total pressure.X-ray diffraction (XRD) and X-ray photon spectroscopy (XPS) analyses showed that the films were a mixture of several vanadium oxides (V₂O₅, VO₂, V₅O₉ and V₂O₃), which resulted in different colors, from yellow to black, depending on composition. The electrical resistivity varied from 1 mΩ cm to more than 500 Ω cm and the thermal coefficient of resistance (TCR), varied from −0.02 to −2.51% K⁻¹.Computational thermodynamics was used to simulate the phase diagram of the vanadium–oxygen system. Even if plasma processes are far from equilibrium, this diagram provides the range of oxygen pressures that lead to the growth of different vanadium oxide phases. These conditions were used in the present work.     

Morphological characterization of ITO thin films surfaces

In this study, indium tin oxide (ITO) thin films were deposited by electron beam evaporation method on glass substrates at room temperature, followed by postannealing at 200 and 300 °C for annealing time up to 1 h. Fractal image processing has been applied to describe the surface morphology of ITO thin films from their atomic force microscopy (AFM) images. These topographical images of the ITO thin films indicate changes in morphological behavior of the film. Also, the results suggest that the fractal dimension D can be used to explain the change of the entire grain morphology along the growth direction.     

Ultrafast laser ablation of indium tin oxide thin films for organic light-emitting diode application

Ultrafast laser ablation of ITO thin film coated on the glass has been investigated as a function of laser fluence as well as the number of laser pulses. The ablation threshold of ITO thin film was found to be 0.07 J/cm² that is much lower than that of glass substrate (about 1.2–1.6 J/cm²), which leads to a selective ablation of ITO film without damage on glass substrate. The changes in the electrical resistance and morphology of ablated trench of ITO electrode were found to be strongly dependent on the processing conditions. We present the performance of organic light-emitting diodes (OLED) fabricated with ITO electrode patterned by ultrafast laser ablation.     

ITO导电膜红外发射率理论研究

根据红外辐射理论和薄膜光学原理计算了高品质ITO(indium tin oxide)导电膜的红外发射 率,其理论曲线与实测曲线基本符合. 并得出方块电阻小于30Ω时,ITO膜在红外波段8—14μ m的平均红外发射率理论值小于0.1.实际制备方块电阻小于10Ω的ITO膜具有优良的红外隐身 性能. 讨论了高品质ITO膜具有低红外发射率的物理机理,并提出了低红外发射率临界方块电 阻值,这有利於理论研究和工艺制备红外隐身ITO膜. 关键词： 红外发射率 ITO薄膜 理论计算 方块电阻     

Laser scribing of indium tin oxide (ITO) thin films deposited on various substrates for touch panels

In this study, a Nd:YAG laser with wavelength of 1064 nm is used to scribe the indium tin oxide (ITO) thin films coated on three types of substrate materials, i.e. soda-lime glass, polycarbonate (PC), and cyclic-olefin-copolymer (COC) materials with thickness of 20 nm, 30 nm, and 20 nm, respectively. The effect of exposure time adjusted from 10 μs to 100 μs on the ablated mark width, depth, and electrical properties of the scribed film was investigated. The maximum laser power of 2.2 W was used to scribe these thin films. In addition, the surface morphology, surface reaction, surface roughness, optical properties, and electrical conductivity properties were measured by a scanning electron microscope, a three-dimensional confocal laser scanning microscope, an atomic force microscope, and a four-point probe. The measured results of surface morphology show that the residual ITO layer was produced on the scribed path with the laser exposure time at 10 μs and 20 μs. The better edge qualities of the scribed lines can be obtained when the exposure time extends from 30 μs to 60 μs. When the laser exposure time is longer than 60 μs, the partially burned areas of the scribed thin films on PC and COC substrates are observed. Moreover, the isolated line width and resistivity values increase when the laser exposure time increases.     

Part 2: Ultra-short pulse laser patterning of very thin indium tin oxide on glass substrates

We investigate selective patterning of ultra-thin 20 nm Indium Tin Oxide (ITO) thin films on glass substrates, using 343, 515, and 1030 nm femtosecond (fs), and 1030 nm picoseconds (ps) laser pulses. An ablative removal mechanism is observed for all wavelengths at both femtosecond and picoseconds time-scales. The absorbed threshold fluence values were determined to be 12.5 mJ cm⁻² at 343 nm, 9.68 mJ cm⁻² at 515 nm, and 7.50 mJ cm⁻² at 1030 nm for femtosecond and 9.14 mJ cm⁻² at 1030 nm for picosecond laser exposure. Surface analysis of ablated craters using atomic force microscopy confirms that the selective removal of the film from the glass substrate is dependent on the applied fluence. Film removal is shown to be primarily through ultrafast lattice deformation generated by an electron blast force. The laser absorption and heating process was simulated using a two temperature model (TTM). The predicted surface temperatures confirm that film removal below 1 J cm⁻² to be predominately by a non-thermal mechanism.     

Growth of Ni-Mn-Ga high-temperature shape memory alloy thin films by magnetron sputtering technique

Ni-Mn-Ga thin films have been fabricated by using magnetron sputtering technique under various substrate negative bias voltages. The effect of substrate negative bias voltage on the compositions and surface morphology of Ni-Mn-Ga thin films was systematically investigated by energy dispersive X-ray spectrum and atomic force microscopy, respectively. The results show that the Ni contents of the thin films increase with the increase of the substrate negative bias voltages, whereas the Mn contents and Ga contents decrease with the increase of substrate negative bias voltages. It was also found that the surface roughness and average particle size of the thin films remarkably decrease with the increase of substrate negative bias voltages. Based on the influence of bias voltages on film compositions, a Ni₅₆Mn₂₇Ga₁₇ thin film was obtained at the substrate negative bias voltage of 30 V. Further investigations indicate that the martensitic transformation start temperature of this film is up to 584 K, much higher than room temperature, and the film has a non-modulated tetragonal martensitic structure at room temperature. Transmission electron microscopy observations reveal that microstructure of the thin film exhibits an internally (1 1 1) type twinned substructure. The fabrication of Ni₅₆Mn₂₇Ga₁₇ high-temperature shape memory alloy thin film will contribute to the successful development of microactuators.     

铟锌氧化物薄膜晶体管局域态分布的提取方法

本文针对铟锌氧化物薄膜晶体管(IZO TFT)的低频噪声特性与变频电容-电压特性展开试验研究,基于上述特性对有源层内局域态密度及其在禁带中的分布进行参数提取.首先,基于IZO TFT的亚阈区I-V特性提取器件表面势随栅源电压的变化关系.基于载流子数随机涨落模型,在考虑有源层内缺陷态俘获/释放载流子效应基础上,通过γ因子提取深能态陷阱的特征温度;基于沟道电流噪声功率谱密度及平带电压噪声功率谱密度的测量,提取IZO TFT有源层内局域态密度及其分布.试验结果表明,带尾态缺陷在禁带内随能量呈e指数变化趋势,其导带底密度N1TA约为3.42×10~(20)cm~(-3)·eV-,特征温度TTA约为135 K.随后,将C-V特性与线性区I-V特性相结合,对栅端寄生电阻、漏端寄生电阻、源端寄生电阻进行提取与分离.在考虑有源层内局域态所俘获电荷与自由载流子的情况下,基于变频C-V特性对IZO TFT有源层内局域态分布进行参数提取.试验结果表明,深能态与带尾态在禁带内随能量均呈e指数变化趋势,深能态在导带底密度NDA约为5.4×10~(15)cm~(-3)·eV~(-1),特征温度TDA约为711 K,而带尾态在导带底密度NTA约为1.99×10~(20)cm~(-3)·eV~(-1),特征温度TTA约为183 K.最后,对以上两种局域态提取方法进行对比与分析.     

An investigation into the effects of oxygen plasma discharge on tin-doped indium oxide thin films

The surfaces of tin-doped indium oxide (ITO) thin films for polymer light-emitting electrochemical cells (LECs) were modified by oxygen plasma discharge. The properties of the ITO surfaces were evaluated by means of the measurements of X-ray photoelectron spectroscopy (XPS), contact angle, surface free energy and polarity. The influence of surface properties of the ITO thin films on the performance of polymer LECs was investigated in terms of the turn-on voltage, injection current and luminance. When oxygen plasma discharge was employed to modify the ITO surfaces, the surface properties of ITO are optimized due to the improvement of surface stoichiometry and the enhancement of wettability. And the improved surface properties benefited from the oxygen plasma discharge is observed to decay with the time after the plasma discharge. The difference in chemical composition, surface free energy and polarity between the non-treated and treated ITO surfaces appears to become smaller with the increase of the time after plasma discharge. In addition, the electrical and optical performance of the devices is found to become worse with the increasing time after plasma discharge on ITO substrates. The results demonstrate that the device performance strongly depends on the ITO surface properties and the ITO/organic interface characteristics.     

In situ growth of Ge-rich poly-SiGe:H thin films on glass by RF magnetron sputtering for photovoltaic applications

Hydrogenated polycrystalline Si_xGe_1−x films, with a varying silicon fraction x ≤ 0.246, were in situ deposited in an argon and hydrogen mixture at 500 °C using radio frequency sputtering with an aim to develop a material for the bottom cell of a low cost monolithic tandem solar cell. Silicon and germanium atomic compositions of the films were determined by X-ray photoelectron spectroscopy (XPS). Structural evolution revealed by Raman and X-ray diffraction (XRD) indicated that the crystallinity of the films was improved with decreasing silicon fraction, accompanied with an increase of surface roughness verified by atomic force microscopy (AFM). Optical band gaps of these films derived from Tauc plots, which were calculated from reflectance/transmittance measurements, decreased with decreasing silicon fraction. Resistivity of the films, determined by four-point-probe technique, significantly decreased as well. High quality with low thermal budget obtained in this work suggests the films could be used in thin film solar cells on glass.     

Structural,luminescent, and morphological properties of Eu3+-doped NaTaO3 thin films grown by magnetron sputtering

Radio-frequency (RF)-sputtered Eu³⁺-doped NaTaO₃ thin films were grown at different deposition temperatures. The X-ray diffraction patterns revealed that all thin films contained two mixed phases of NaTaO₃ and Na₂Ta₈O₂₁. The photoluminescence spectra of the thin films consisted of a strong orange emission (592 nm) and two weak red bands (616 nm and 689 nm), suggesting that more Eu³⁺ ions in the NaTaO₃ host crystal were located at inversion symmetry sites. The maximum intensities of all emission peaks were achieved for the sample grown at 100 °C, in which the gravel-shaped crystallites evolved with a band gap energy of 4.61 eV, chromaticity coordinates of (0.554, 0.434), and average transmittance of 92.4%. These results indicate that the photoluminescence intensity, band gap energy, and color tunability can be achieved for RF-sputtered Eu³⁺-doped NaTaO₃ thin films by varying the growth temperature.     

Effects of annealing on properties of ZnO thin films prepared by electrochemical deposition in chloride medium

The development of cost-effective and low-temperature synthesis techniques for the growth of high-quality zinc oxide thin films is paramount for fabrication of ZnO-based optoelectronic devices, especially ultraviolet (UV)-light-emitting diodes, lasers and detectors. We demonstrate that the properties, especially UV emission, observed at room temperature, of electrodeposited ZnO thin films from chloride medium (at 70 °C) on fluor-doped tin oxide (FTO) substrates is strongly influenced by the post-growth thermal annealing treatments. X-ray diffraction (XRD) measurements show that the films have preferably grown along (0 0 2) direction. Thermal annealing in the temperature range of 150-400 °C in air has been carried out for these ZnO thin films. The as-grown films contain chlorine which is partially removed after annealing at 400 °C. Morphological changes upon annealing are discussed in the light of compositional changes observed in the ZnO crystals that constitute the film. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments due to the reducing of defects levels and of chlorine content. The transmission and absorption spectra become steeper and the optical bandgap red shifted to the single-crystal value. These findings demonstrate that electrodeposition have potential for the growth of high-quality ZnO thin films with reduced defects for device applications.     

Crystal orientation control of polycrystalline TiN thin films using ZnO under layers deposited by magnetron sputtering

The effect of ZnO under layers on crystal growth of TiN thin films was investigated. TiN single layers and double-layered ZnO/TiN thin films were deposited on soda-lime-silicate glass substrates by magnetron sputtering. XRD analysis indicated that TiN single layers exhibited {1 1 1} preferred orientation on glass substrates; on the other hand, the TiN thin films with {1 0 0} preferred orientation were obtained using ZnO under layers and crystallized better than the TiN single layers. This crystal orientation change of TiN thin films should come from heteroepitaxial-like growth because the TiN{1 0 0} and ZnO{0 0 1} crystal lattice planes have similar atomic arrangements. Besides, the possible mismatch between TiN and ZnO atomic arrangements was estimated to be 7.8%. Furthermore, the resistivity and optical absorbance of TiN thin films decreased when they were deposited on ZnO under layers. It can be considered that electrical and optical properties should be improved due to the well-crystallization of TiN thin films using ZnO under layers.