ICMCTF2011 Session CP: Symposium C Poster Session

Thursday, May 5, 2011 5:00 PM in Room Town & Country

Thursday Afternoon

Time Period ThP Sessions | Topic C Sessions | Time Periods | Topics | ICMCTF2011 Schedule

CP-2 AZO Coatings Deposited by Reactive HiPIMS for Modified TCO Properties on Polymeric Web
Paul Barker, Peter Kelly, Glen West (Manchester Metropolitan University, UK); James Bradley (University of Liverpool, UK); Hazel Assender (University of Oxford, UK)
The potential to produce coatings with much enhanced properties has made high power impulse magnetron sputtering (HiPIMS) an area of great interest with the surface engineering community in recent years. Many papers and conference presentations are coming from the academic community but, at present, industry is slow to take up the technology due to known or perceived processing issues (low deposition rates, power supply instabilities, difficulties with reactive process control, etc.). Also, as yet, few applications have emerged to convince industry that this technology merits the significant investment required to move from lab-scale to production-scale processing.

Previous work carried out by this group has shown that the thermal load experienced at the substrate is low when operating in HiPIMS mode, compared to DC and pulsed DC sputtering. It has also been seen that modifications are being made to thin film properties when produced by HiPIMS. AZO coatings have, therefore, been deposited under systematically varied conditions of pulse frequency and pulse width, selected to also vary the degree of ionisation in the plasma and incident at the substrate. The coatings were then characterised in terms of their structural, optical and electrical properties using SEM, EDX, XRD, optical spectroscopy and a Hall probe and the interrelationships between deposition parameters and film properties were explored. Further, different methods of reactive sputter control were tested in an effort to make HiPIMS sputtering onto polymeric web a reliable option for industrial processing.

The work presented here shows that TCO coatings with industrially relevant optical and electrical properties can be readily deposited onto thin, polymeric web. Although this is currently only on laboratory scale systems, transfer to a development-scale roll to roll system is in progress.

CP-4 Study of the Physical Properties of PLD Grown Cobalt Doped Nanocrystalline Zn0.9Cd0.1S Thin Films
Amit Kumar Chawla, Sonal Singhal, Hari Om Gupta, Ramesh Chandra (Indian Institute of Technology Roorkee, India)

Here we report a systematic study of structural, optical, and magnetic measurements on Zn0.9Cd0.1S:yCo films in the concentration range of 0.005 y 0.05 M using pulsed laser deposition technique. Structure, composition analysis, and optical measurements revealed that Cobalt is incorporated into the lattice, as Co2+ substituting Zn2+ ions, forming a solid solution with cubic structure instead of Cobalt precipitates. Low temperature magnetization measurements reveal a paramagnetic behaviour. UV-Vis measurements showed a red shift with respect to undoped sample in the energy band gap with increasing Cobalt concentration. Photoluminescence measurements confirmed the substitution of Cobalt ions in the tetrahedral crystal field by showing the characteristic peaks.

CP-6 Thermal Properties of C-Si-O Composite Thin Films Deposited by PBII Method
Shinya Abe, Nutthanun Moolsradoo, Shuichi Watanabe (Nippon Institute of Technology, Japan)
DLC films are meta-stable amorphous films that exhibit unique combinations of properties such as high hardness, low friction coefficient, and good wear resistance, etc. However, DLC films have several known limitations, such as high internal stress, low thermal stability. In order to solve these problems, enhance the film properties, Si has been incorporated into the amorphous hydrocarbon films. Our study aimed to study the effects of silicon incorporation on the thermal properties of C-Si-O composite thin films deposited by PBII method. The films were deposited by PBII method with gaseous mixtures of C2H2:TMS:O2 on Si (100) wafers. The flow rate ratio range between C2H2 and TMS were from 10:1 to 100:1, while oxygen was kept constant at 1 sccm. The deposition pressure range was from 2-6 Pa. The bias voltage was set 0 kV, at RF power of 300 W. The total deposited thickness of the films was approximately 500 nm. An annealing temperature range of 200-600°C was investigated under high vacuum, air atmosphere and argon atmosphere for 1 hour. The film structure was analyzed using Raman spectroscopy. The thermal properties were analyzed using Differential Thermal Analysis (DTA) and Thermogravimetry (TG). From the results deposited at 2 Pa pressure, the results show that the silicon incorporation is good thermal properties under high vacuum.
CP-7 Influence of Substrate Temperature on Electrical and Optical Properties of Al-Doped ZnO Thin Film
Shiuh-Chuan Her, Tsung-Chi Chi (Yuan Ze University, Taiwan)
The increasing use of transparent conductive oxides (TCO) films in electronics, optoelectronics and information technology devices such as displays, solar cells and sensors has promoted the study of Zinc oxide (ZnO) films. In this regards, aluminum-doped ZnO (AZO) films with high optical transmittance and low electrical resistivity have attracted significant attention in recent years. In this work, aluminum-doped ZnO films were deposited on glass substrate at substrate temperatures from room temperature to 275oC by radio frequency magnetron sputtering. The effect of substrate temperature on the electrical and optical properties together with the surface morphology was investigated. Electrical properties including the resistivity, carrier concentration and mobility of AZO films were evaluated by Hall effect measurements at room temperature. Optical properties including transmittance and reflectance were measured with a Perkin-Elmer Lambda UV/Visible/NIR spectrometer. The crystalline structure and preferred orientation of the AZO films were investigated by X-ray diffraction (XRD). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the surface morphology and roughness of the deposited films. At low substrate temperature (25oC) AZO films have high resistivity (3.01x10-2 Ωcm ) with small carrier concentration (3.3x1019 cm-3 ), while the one prepared at higher temperature (275oC ) has low resistivity (2.14x10-3 Ωcm) with large carrier concentration (1.57x1020 cm-3 ). The increase of substrate temperature enhances the doping efficiency yielding to films with a lower resistivity and a wider band gap energy. It was observed that all the AZO films deposited in the substrate temperature range from room temperature to 275oC were preferentially oriented in the c-axis or (002) plane. The average of the optical transmittance for all the films was close to 81% over the visible wavelength range from 400nm to 800nm. Present work shows that the enhancement of the AZO film performance with high transparency and low resistivity can be achieved by increasing the substrate temperature.
CP-8 Temperature Effect on the Optical and Mechanical Properties of Silver Thin Film Deposited on Glass Substrate
Shiuh-Chuan Her, Yi-Hsiang Wang (Yuan Ze University, Taiwan)
Silver films with high reflectance and low absorption in the visible wavelength region have been widely used in optical applications. Examples are transparent heat mirrors for the reduction of heat load in cars and buildings and for other energy applications such as solar cell. In this investigation, silver optical thin films were prepared on the glass substrate at various temperatures by electron-beam vapor deposition. The reflectance of Ag thin films was measured by a Perkin-Elmer Lambda spectrophotometer in the visible wavelength region of 450-680 nm. The experimental measurements of reflectance were validated with the numerical results using the Essential Macleod software. The surface topology and cross section structure of the films were examined by means of atomic force microscope (AFM) and scanning electron microscope (SEM), respectively. The effects of the substrate temperature on the reflectance were presented through a parametric study. The average reflectance of silver films over the visible wavelength range decreases form 99.26% to 91.15%, while the substrate temperature is increasing from 220C to 3000C. The dispersion curve shows that the reflectance of the silver film increases with the increase of the wavelength in the visible range. The surface morphology of the films revealed that the grain size and surface roughness increased with the increase of the substrate temperature. More energy is supplied to the deposition particles at higher temperatures resulting in the higher migration mobility, which in turn favors the recrystallization. The films prepared at high substrate temperature have a crystalline structure and the films prepared at low temperature have an amorphous structure. Nanoindentation tests were employed to determine the hardness and Young’s modulus of the film. The measured hardness and Young’s modulus of the silver thin film were found to depend on the penetration depth. It can be observed that the Young’s modulus increases with increasing substrate temperature. This increase is attributed largely to the effects of crystalline structure of the film at higher temperature.
CP-9 Charge Trapping Induced Frequency-Dependence Degradation in n-MOSFETs with High-k/Metal Gate Stacks
Chih-Hao Dai (National Sun Yat-sen University, Taiwan)

This letter investigates the reliability issues of HfO2/TixN1-x metal-oxide-semiconductor field effect transistor (MOSFETs) in terms of static and dynamic stress. The results indicate threshold voltage (VT) instability under dynamic stress is more serious than that under static stress, owning to transient charge trapping within high-k dielectric. Using C-V techniques verified that electron trapping under dynamic stress was located in high-k dielectric near the source/drain (S/D) overlap region, rather than the overall dielectric. Furthermore, the VT shift clearly increases with an increase in dynamic stress operation frequency. This phenomenon can be attributed to the fact that electrons injecting to the S/D overlap region have insufficient time to de-trap from high-k dielectric. We further investigated the impact of different TixN1-x composition of metal-gate electrode on charge trapping characteristics, and observed that VT shift decreases significantly with an increase in the ratio of nitride. This is because the nitride atoms fill up oxygen vacancies and reduce the concentration of traps in high-k dielectric.

CP-10 Electrical and Optical Characterization of Fluorine Doped Tin Dioxide Film Grown by Spray Method
Minoru Oshima (Univeristy of Miyazaki, Japan); Kamiya Naomi, Kenji Yoshino (University of Miyazaki, Japan)

Transparent conduction oxides (TCOs) have high electrically conducting and high visible transmittance with widely used as transparent electrode for flat panel displays including liquid crystal display, organic light emitting diodes and plasma displays. The most important TCOs film in practical applications nowadays is Sn-doped In2O3 (ITO)(1). SnO2 is an alternative potential candidate of ITO thin films due to its cheap and abundant raw material(2). Thus, we focused on this material. SnO2 is also a promising material for applications including gas sensors, photovoltaic solar energy conversion, and electrochromic devices. SnO2 behaves like an n-type semiconductor with a wide energy gap (≈ 3.8eV) and has a tetragonal structure similar to the rutile structure.

In our previous paper(3), FTO (0 ~ 5 mol%) films were grown on glass substrates by the spray pyrolysis method at 500˚C. The F-doping caused the resistivity to decrease and the carrier concentration to increase. The undoped and F-doped SnO2 films were all n-types, which indicated that fluorine atoms can act as donor impurities. The lowest resistivity of 1.4 × 10-3 Ωcm was obtained at a fluorine concentration of 4 mol%.

In the present study, transparent conducting F-doped SnO2 films were successfully prepared on glass substrates by spray pyrolysis method in order to find out the effect of high F-doped concentration. The best electrical and optical properties, average transmittance of 82 % and resistivity of 3.9×10-4 Ωcm, carrier concentration of 4.7×1020 cm-3, mobility of 34 cm2/Vs, were achieved with fluorine doing concentration of 17 mol% at substrate temperature of 500°C.

(1) H. Chen, X. Wang, Y. H. Yu, Z. L. Pei, X. D. Bai, C. Sun, R. F. Huang, L. S. Wen, Appl. Surf. Sci 158 (2000) 134.

(2) S. Takaki : Reports on Ashai Glass Co., Ltd. Research Center, 50 (2007) 105.

(3) M. Oshima, Y. Takemoto, K. Yoshino, Phys. Status Solid (C) 6 (2009) 1124.

CP-11 Improving the Visible Transmittance of Low-e Titanium Nitride Based Coatings for Solar Thermal Applications
Miriam Yuste, Ramón Escobar Galindo, Olga Sánchez, Jose María Albella (Instituto de Ciencia de Materiales de Madrid, Spain)

Low-emissivity (low-e) coatings on glass are nowadays extensively used for energy saving applications in architectural windows and on solar thermal collectors. In this work we studied the feasibility of TiN-based layers, deposited by reactive magnetron sputtering, as cost-effective low-emissivity coatings. By changing the deposition parameters, different compositions of the films (measured by Glow Discharge Optical Emission-GDOES and Rutherford Backscattering Spectroscopy- RBS) and different textures and surface morphologies (X-Ray Diffraction-XRD and Scanning Electron Microscope-SEM) can be observed. These changes allow tuning the optical properties of the coatings, in particular, the transmittance (T) in the visible range, measured by Spectroscopic Ellipsometry (SE) and the emissivity (ε), measured both directly by an emissometer and indirectly by Fourier Transform Infrared Spectroscopy (FTIR). In order to improve the visible transmittance of TiN single layers we have proposed three strategies:

- Doping with aluminium, the T of the TiN films improves in a 15% but at the expenses of increasing their ε by a factor 1.3.

- Post-deposition annealing treatments up to 500oC improve in a 10% the T at room temperature while keeping the ε.

- Multilayers structures (TiO2/TiN/TiO2) present the best results improving in a 30% the T of the TiN single layers while keeping the ε.

Hence, based on the control of the optical properties, and taking into account other properties such as thermal stability and long term durability, it is then possible to design selective coatings to be used in industrial solar thermal applications.

CP-13 Processing of TiO2 Films by dc Magnetron Sputtering and Pulsed dc Magnetron Sputtering.
Luis C. Fontana (Universidade do Estado de Santa Catarina, Brazil); Jianliang Lin, John Moore (Colorado School of Mines)
TiO2 thin film has attracted extensive attention in terms of its interesting thermal, electronic and optical properties in recent years. The properties of the magnetron sputtered TiO2 thin films are determined by the phase and microstructure of the films, which can be modified and optimized by usefully controlling the ion bombardment on the growing thin films. TiO2 oxide films are deposited by means of two processes: continuous dc magnetron sputtering and pulsed dc magnetron sputtering. The influence of plasma generated bombardment of ions on TiO2 film growth in pulsed dc Magnetron-Sputtering by controlling the negative substrate bias voltage and the oxygen partial pressure was investigated. An electrostatic quadrupole plasma mass spectrometer was employed to measure the energy of ions in the plasma. The correlation between the energy delivered to film during deposition and the film texture, microstructure, electrical and mechanical properties is investigated.
CP-14 The Band Diagram Constructed by Scanning Surface Potential Microscopy (SSPM) in n-ITO/p-Si Heterojunction Solar Cells
Pi-Chun Juan (Center for Coatings and Laser Applications, Taiwan); Chuan-Hsi Liu (National Taiwan Normal University, Taiwan); Jia-Fu Dai (Ming Chi University of Technology, Taiwan); Cheng-Li Lin (Feng Chia University, Taiwan)
Indium tin oxide (ITO) was deposited on silicon substrate to form an ITO/Si heterojunction for solar cell applications. Before metal top electrode was formed, different oxygen contents in helium ambient were added in the postannealing temperatures of 400oC, 500oC, and 600oC during rapid thermal annealing (RTA). The result shows the optical bandgap of ITO thin films increases with increasing postannealing temperature and/or film thickness, but the bandgap decreases with adding 5% oxygen in the helium gas. The wider bandgap under high temperature annealing and without oxygen added in the helium gas results in better rectifying characteristics for pn heterojunction. The work function of ITO thin films was measured by using the scanning surface potential microscopy (SSPM). The work function of ITO (RTA = 400oC ) is 4.55 eV. The temperature-dependent current-voltage characteristics were also measured and the barrier height between ITO and silicon is extracted to be about 0.16 eV. Therefore, the band diagram before and after two materials contacting with each other can be constructed. From the band diagram proposed, an inversion layer near the silicon surface is easily formed when the ITO contacts with p-type silicon substrate. It is consistent with the reverse rectifying characteristics at the ITO/p-Si interface. Finally, the optoelectronic characteristics such as cell efficiency of ITO/Si heterojunction solar cells are measured and can be well explained by the positions of energy levels of the band diagram.
CP-15 Optical Optimized Transparent Electrode for Thin Film Solar Cell by Atomic Layer Deposition
Chien-Nan Hsiao, Chih-Chieh Yu, Po-Kai Chiu, Chi-Chung Kei, D. Chiang (National Applied Research Laboratories, Taiwan); Hang-Chang Pan (Gintech Energy Corporation, Taiwan)
Optical optimized Al doped ZnO nanolaminates were deposited on glass and Si wafer by atomic layer deposition as a transparent electrode for thin film solar cell . The corresponding properties of the films were investigated by in-situ quartz balance, ellipsometry, spectrometry, Hall-effect measurement, and high-resolution transmission electron microscopy. It was found that the optical, electrical and structural properties were significantly dependent on the growth temperature. For the relatively low temperatures growth condition (< 200˚C), the optical optimized 2% Al doped ZnO nanolaminates transparent electrode with high mobilitity allows film resistivity in the low 10-3 W-cm range and a high transparency > 86% over a wide spectrum, from 400 to 1300 nm. Furthermore, atomic-scale HRTEM (HAADF) revealed that a secondary inter-phase formed between the Al2O3/ZnO interface. In addition, to estimate the reliability of thin film solar cell modules with the ALD AZO transparent electrode, an international standard IEC61646 certified test was performed. The results of efficiency, environmental, and mechanical testing of photovoltaic (PV) modules will be discussed.
CP-16 Helical SiO2 Film for Indiscriminatively Circular Polarization Handedness Inversion
Young-Dueng Kim, Yu Zou, Jin-Joo Kim, Ji-Bum Kim, Chang-Kwon Hwangbo (Inha University, Korea)
Polarization converters have been widely used in optical systems. Semiconductor quantum dots or optical tunnelings have been used as circular-to-linear and linear-to-circular converters. A semiconductor guiding layer, a thin-film grating or a [prism/MgF2 columnar thin film/air] configuration etc. have been used as a linear polarization converter. However, the study on the handedness conversion of circular-polarized light is rare. Since helical films fabricated by oblique angle deposition are known as excellent candidates for circular polarization elements including sources, reflectors, filters, and detectors, they may be used as a circular polarization converter.

In this study, the circular polarization conversion reflectance is studied for [prism/SiO2 helical thin film/air] configuration for the first time according to our knowledge. A circular polarization conversion reflectance from right(left)-circular polarization to left(right)-circular polarization was measured and calculated for a [prism/SiO2 helical thin film/air] configuration under total internal reflection condition. It is found that the handedness of an incident circular-polarized light can be reversed with the highest circular polarization conversion reflectance of 92.2% at an incidence angle of 57.8±0.1°. Principal refractive indices of the helical film were derived by fitting the measured circular polarization conversion reflectance to the calculated one.

CP-17 The Electrical Impedance Spectra Characterization of Electrochromic Glass
Wern-Dare Jheng (National Chin-Yi University of Technology, Taiwan); Chung-Kwei Lin (Feng Chia University, Taiwan); Chien-Chon Chen (National United University, Taiwan)
The electrochromic (EC) glass was fabricated by the sputter deposition process. The EC glass has the configuration glass/ITO/WO3/1M LiClO4-PC/ ITO/glass. When the voltage (-3.5V) was applied to the device, the active layer of the assembled device changed from almost transparent to a translucent blue color (colored). The average transmittance in the visible region of the spectrum for a 100 cm2 EC device was 73% in the bleached state. The device with 140 nm WO3 as the active layer has an average transmittance in the colored and bleached states of 11.9% and 54.8%, respectively. The transmittance spectra results showed a clear color change in the device was observed when the applied voltage was below -3V (colored) and above 2V (bleached). The characteristics of the EC glass were determined using UV–VIS transmittance spectra, cyclic voltammetry, and electrochemical impedance spectrum equipment. Different logotypes were presented onto electrodes by voltage control when the device was applied a positive voltage state (“NCUT”) and applied a negative voltage state (“NUU”), respectively. EC glass structure was simulated using an equivalent circuit where ω1 and ω2 represent the working electrodes, and ω3, ω4 represent the electrolyte and counter electrode. In the circuit, the ohmic impedance includes ITOs resistance and transport wire resistance (R0). The working parts of the ITO/WO3 and WO3/electrolyte interfaces are presented as C1//R1 and C2//R2. The electrolyte presents as C3//(R3+W). The counter part of ITO/electrolyte is presented as C4//R4.
CP-18 Tantalum Oxide Films Prepared by Magnetron Sputtering for All Solid State Electrochromic Devices
Sheng-Chang Wang (Southern Taiwan University, Taiwan); Kuang-Yi Liu, Jow-Lay Huang (National Cheng Kung University, Taiwan)

In this study, inorganic-solid-state electrolyte tantalum oxide thin films were deposited by D.C. reactive magnetron sputtering to improve the leakage and deterioration of the traditional liquid electrolyte of electrochromic device. The parameter of O2 atmospheres (the flow rate range : 1~20sccm) and powers (35~100W) were conducted to prepared the tantalum oxide films with various compositions, microstructures, optical properties and electrochromic properties. The results indicated that tantalum oxide thin films were amorphous, near stoichiometric, porous with loose fibrous structure, and highly transparent in nature. As the oxygen flow rate and power increased, the refractive index increased however the current density and optical transmission change as the film decreased. At the oxygen flow rate of 3sccm and 50W, the transmission change between colored and bleached states at a wavelength of 550nm was 56.7%. The all solid electrochromic device was manufactured as the multilayer of Glass/ITO/WO3/Ta2O5/NiOx/ITO/Glass. The optical transmittance difference of the device increased as the applied voltage increase and the maximum change reached 66.5% in the applied voltage of ±5V.

CP-19 Effect of Annealing Temperature on the Microstructure and Photoluminescence of Low Resistivity Si/Si-N/Ta-N Thin Films Using Magnetron Sputtering
Chen-Kuei Chung, Tai-Sheng Chen, Nei-Wen Chang, Ming-Wei Liao (National Cheng Kung University, Taiwan)
The silicon (Si) is characterized as having a poor efficiency of light emission and only produces light outside the visible range due to its indirect low bandgap material. However, the Si-based nanostructures show the quantum confinement effect, luminescence center and surface chemistry effect to enhance the efficiency and to produce emission of visible light. A lot of studies have been devoted to the fabrication of porous Si, erbium-doped Si and Si embedded in dielectric matrix of Si-O or Si-N together with furnace annealing. But, these Si nanostructured films were high resistivity and non-conducting. In the article, the effect of annealing temperature on the microstructure and photoluminescence of low-resistivity Si/Si-N/Ta-N three-layer thin films deposited by magnetron sputtering and followed by rapid thermal annealing (RTA) has been investigated. Grazing Incidence X-ray Diffraction, Fourier transform infrared transmittance spectra, energy dispersive spectroscopy, scanning electron microscopy and photoluminescence (PL) spectrum were utilized to characterize the evolution of microstructure and PL behavior of multilayer films at different annealing temperature. The main emission peak of PL at about 550 nm was observed and had red shift with increasing annealing temperature. The Si nanocrystals were formed by the post annealing of a Si/Si-N/Ta-N at 90°C. It suggests that the observed PL is originated from electro-hole pair recombination in Si nanocrystals or luminescence center in the film. The relationship between the annealing temperature, microstructure and photoluminescence behavior of Si/Si-N/Ta-N multilayer films is discussed and established.
CP-20 Surfactant Assisted Growth of SnO2 Thin Films for Gas Sensing Applications
Kamalpreet Khun Khun, Aman Mahajan, R.K. Bedi (Guru nanak dev University, Amritsar, India)

Porous nanostructured SnO2 films have been prepared using an ultrasonic spray pyrolysis technique in conjunction with cationic, anionic and non ionic surfactants namely CTAB (Cetyl trimethyl ammonium bromide), SDS (sodium dodecyl sulphate) and PEG (polyethylene glycol) respectively. The effect of surfactants on the structural, electrical, optical and gas sensing properties of SnO2 films were investigated by using different techniques such as X-ray diffraction (XRD), Field emission scanning electroscope microscopy (FESEM), two probe technique and Photoluminiscence (PL) studies. The results reveal that the addition of surfactants in the precursor solutions leads to reduction in crystallite size with significant changes in porosity of SnO2 films. PL studies of the films show emissions in the visible region which exhibit marked changes in the intensities upon variation of surfactants in the precursor solutions. The prepared films were tested for their sensing behaviour towards chlorine and the results reveal that the films prepared in conjunction with cationic surfactant CTAB exhibits a good sensing response towards chlorine at low operating temperatures.

CP-21 Structural Evolution and Photocatalytic Activity of Pulsed Magnetron Sputtered Titania-Based Coatings
Nick Farahani, Peter Kelly, Glen West, Marina Ratova (Manchester Metropolitan University, UK); Claire Hill (Cristal Global, UK); Justyna Kulczyk-Malecka (Manchester Metropolitan University, UK)
It is well known that, depending on deposition conditions, the structure of titania coatings may be amorphous, anatase or rutile, or a mixture of phases, and that the anatase phase is the most promising photocatalyst for the degradation of organic pollutants. The formation of anatase depends on the energy delivered to the growing film, which in turn depends on the operating parameters chosen. In this study, coatings have been deposited onto glass substrates by pulsed magnetron sputtering (100 – 350 kHz) both from metallic targets in reactive mode and directly from oxide powder targets. The as-deposited coatings were analysed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and micro Raman spectroscopy. Selected coatings have been annealed at temperatures in the range of 100 - 800 oC and re-analysed. The photocatalytic activity of the coatings has been investigated through measurements of the degradation of organic dies, such as methyl orange, under the influence of UV light. For both sets of coatings, the influence of deposition parameters, such as pulse frequency, duty and magnetron configuration on the as-deposited and post-annealed structures and properties has been investigated. Further sets of coatings have been produced both from metallic and powder targets in which the titania is doped with a range of transition metal elements. These coatings have also been analysed and the influence of the dopant element on photocatalytic activity has been investigated.
CP-23 Characterization of IZO-Based Thin Film Transistors Fabricated Using a Novel Two-Step Deposition Process
Won Kim, Sang-Hyuk Lee, Jung-Hwan Bang, Hyun-Seok Uhm, Jin-Seok Park (Hanyang University, Korea)

Future active matrix display systems with enhanced performances are likely to be larger than they currently are. With the rapid progress in display technology, there has been increasing interest in developing oxide-based thin film transistors (TFTs) and many studies have been focused on variety oxide semiconductors that can be used as channel layers of the oxide-TFTs. Among those, sputtering-produced amorphous indium-zinc-oxide (a-IZO) thin films exhibit high electron mobility even when it is deposited at room temperature. Also, their conductivity can be controlled by varying the oxygen partial pressure, the sputter power, and the composition of target material. It is possible that a-IZO thin films are used both as a channel layer and as source/drain (S/D) layers of TFTs. To use the a-IZO thin film as a channel layer, it is often deposited in oxygen ambient to reduce the carrier concentration. This manner, however, may significantly increase the electrical resistivity of a-IZO films, leading to the deterioration of a-IZO TFT’s performance.

In this study, we suggest a novel two-step deposition process, by which a-IZO TFTs with excellent on/off current ratios can be achieved without deteriorating their TFT performance. The a-IZO TFTs were fabricated with a bottom gate structure. An n-type Si (100) wafer with a low resistance (below 0.002 Ωcm) was used as a gate, and a gate oxide layer (300 nm) was formed by thermally oxidizing the Si substrate . Then, a-IZO channel layer was deposited on the gate oxide layer via the RF sputtering method by following the two-step deposition procedure. The 1st step deposition was done at a relatively low oxygen partial pressure (i.e., O2/Ar < 5 %) formed to get a higher mobility. The 2nd step deposition was accompanied without stopping the vacuum, only by increasing the oxygen partial pressure (i.e., O2/Ar > 10 %) to maintain low off-current levels. The source/drain contact area was defined by photolithography and the source/drain regions uncovered by photoresists were plasma-treated to reduce the contact resistances. The a-IZO films used for the source/drain contacts were deposited via the same RF sputtering system under a pure Ar environment. For all the deposited IZO films, the electrical, optical, and chemical analyses were carried out and the results were characterized in terms of various O2/Ar ratios and plasma treatment conditions. The device characteristics of the a-IZO TFTs fabricated by the proposed two-step method were compared those fabricated by the conventional single deposition process. The results showed that the on/off current ratio was significantly improved by the proposed two-step process.

CP-24 Effects of Additive Hydrogen Gas on the Instability Due to Air Exposure in ZnO-Based Thin Film Transistors
Jung-Hwan Bang, Sang-Hyeok Lee, Won Kim, Hyun-Seok Uhm, Jin-Seok Park (Hanyang University, Korea)

Thin film transistors (TFTs) made by an amorphous Si (a-Si) have been important elements in the flat-panel display. However, a-Si TFTs have critical problems such as light sensitivity and low mobility (< 1 cm2/V×s). To resolve these problems, use of oxide semiconducting materials as a channel layer for TFT has recently been introduced. The channel materials of most oxide TFTs are comprised of zinc oxide (ZnO) and various compounds based on ZnO. Among those, ZnO is one of the most promising candidates for the transparent TFT applications since it has good crystallinity even when prepared at low temperature and it also has a widely range conductivity from metallic to insulating. When ZnO films are exposed to air, however, they often show unstable electrical properties (e.g., their electrical resistivities significantly increase), resulting in the degradation of the ZnO-based TFT’s device performance. It was also recently observed from our experiment and other group’s works that the electrical properties of hydrogen-incorporated ZnO films showed to be less sensitive to the air exposure. This was believed to be due to the role of hydrogen atoms that limited the adsorption of oxygen at the ZnO surface. However, this issue has scarcely been studied.

Here, we have investigated the effects of additive gases (such as H2 and N2), which are added during ZnO deposition, on the variation in the electrical resistivity of ZnO films and the device characteristic of ZnO-based TFTs due to the long-term air exposure. Thin films of ZnO (including ZnO:H and ZnO:N) used for channel of TFT were deposited at room temperature via RF magnetron sputtering by varying the mixing ratio of the additive gases. The ZnO-based TFTs with a bottom gate structure, which consisted of heavily-doped Si wafer (gate), plasma-enhanced CVD -produced SiOx (gate insulator), and sputtered Al layers (source/drain), were fabricated using a lift off method. All the ZnO films and ZnO-based TFTs prepared were exposed to air for a long time up to 5 days. The variations in the structural, chemical, electrical, and optical properties of ZnO films due to air exposure were monitored by field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), x-ray diffraction (XRD), and secondary ion mass spectroscopy (SIMS). In addition, the I-V characteristics of ZnO-based TFTs and their device parameters (such as threshold voltage, field-effect mobility, and on/off current ratio) were measured and characterized in terms of the air exposure time and the condition of gas addition. Finally, all the experimental results were physically explained by discussing the role of additive gas atoms.
CP-26 CuInSe2 Thin Film Photovoltaic Absorber Formation by Rapid Thermal Annealing of Binary Stacked Precursors
Jaseok Koo, Sung-Cheol Kim, Hyeonwook Park, Woo-Kyoung Kim (Yeungnam University, Korea)

Chalcopyrite Cu(InGa)Se2-based materials have demonstrated the potential of high efficiency thin film solar cells, yielding around 20% cell efficiency. Conventional method to fabricate CIGS absorber follows either elemental coevaporation of individual elements (i.e., Cu, In, Ga and Se) or reactive annealing of metallic precursors (i.e., Cu-Ga-In). The reactive annealing of metallic Cu-Ga-In precursors under Se or H2Se is a likely method of producing effectively large area Cu(InGa)Se2. However, Ga accumulation near the Mo side of substrate/Mo/CIGS structure is often observed during the selenization of Cu-Ga-In precursors yielding phase-separated CuInSe2 and CuGaSe2 which subsequently lead to lower open-circuit voltages.

In this contribution, rapid thermal process (RTP) using stacked binary (metal-Se) precursors, e.g., glass/Mo/InxSey/CuxSe, was explored to reduce the reaction time of CuInSe2 formation drastically, while maintaining compositional depth uniformity. Various binary stacked precursors, including In2Se3/CuSe and InSe/CuSe, were prepared onto Mo-coated glass substrates. The reactive annealing of metal precursors was performed in a rapid thermal process system consisting of a quartz tube reactor with an inner diameter of 62 mm, quartz sample tray and infrared (IR) heater under a Se atmosphere. The quartz sample tray held up to six 1 cm x 1 cm samples. The IR heater ramped temperature rapidly, requiring only 1 min to reach 1,000˚C from room temperature. At a fixed annealing temperature of 550˚C, it was confirmed that reaction time of 2 min was sufficient enough to form CuInSe2 by completely consuming binary reactants. The longer reaction time of 5~10 min caused the formation of MoSe2 at CuInSe2/Mo interface.

Precursor and CuInSe2 structures were characterized by x-ray diffraction (XRD) and scanning electron microscope (SEM). Bulk composition and compositional depth profiles of the films were measured by inductively coupled plasma optical emission spectroscopy (ICP-OES) and secondary ion mass spectrometry (SIMS), respectively.

CP-27 Galvanic Corrosion Behaviour of Al Based Coatings in 0.6 M NaCl Solution
Omoniyi Fasuba, Aleksey Yerokhin, Allan Matthews, Adrian Leyland (University of Sheffield, UK)

In engineering design, care is taken to avoid dissimilar metal contact that cause galvanic corrosion in aqueous environments. Engineers and designers often use coatings to minimize the effect of galvanic attack. Cadmium-based coatings provide excellent barrier and sacrificial corrosion protection on steel, as well as desirable physical and mechanical properties of self-healing and anti-seizure; however, such coatings are effectively banned from many applications due to the toxic nature of both coating and application technique. Ever more stringent environmental regulations lead to an increasing need to develop coatings with equally good corrosion resistant behaviour to that of cadmium, which are also environmentally benign. Aluminium-based coatings can exhibit corrosion potentials similar to cadmium, such that (if the coating is damaged) aluminium will preferentially corrode instead of the exposed substrate. Traditional corrosion evaluation techniques (such as salt spray testing) are useful in screening coating behaviour (ie. acceptable performance or not) but reveal little of the underlying complex electrochemical phenomena that lead to the observed behaviour. Therefore, this study examines the electrochemical behaviour of a selection of commercially available Al based coatings on steel in 0.6 M NaCl solution, to provide in-depth information on the corrosion processes involved, and their evolution with time.

The corrosion performance of the coatings was assessed by various electrochemical techniques. Open-circuit potential (OCP) stability measurements were carried out for a period of 2 hours, against the resting potential of each coating in 0.6 M NaCl solution. Potentiodynamic polarization scanning was performed at a rate of 1.667mV/s starting at – 0.2V vs. OCP and ending at 0V vs. SCE. In the galvanic corrosion tests, uncoated steel was the working electrode while the coated steel substrates were used as the counter electrode, the reference being a saturated calomel electrode (SCE). The data acquisition rate was 0.1 points/second for a duration of 2 hours at 0V vs. OCP. SEM images and EDX analysis were also used to characterise the morphology, elemental composition and the physical degradation of the coatings. Results obtained indicate that thermally sprayed Al coatings give high corrosion current densities with polarisation behaviour similar to that of cadmium. Electroplated and IVD aluminium coatings showed passivation and periodic breakdown and regrowth of the passive film over a range of applied potentials, while coatings containing aluminium particles in a chromate/phosphate inorganic binder give OCP values very close to that of steel.

CP-28 In Situ Thermal Residual Stress Evolution in ZnO Thin Films Deposited by Magnetron Sputtering on Si
Pierre-Olivier Renault, Christopher Krauss, Eric Le Bourhis, Philippe Goudeau (University of Poitiers, France); Etienne Barthel (SVI, Aubervilliers, France); Sergey Grachev, Alessandro Benedetto (SGR, Saint Gobain, France)

Zinc Oxide is a material of technological importance for its practical and potential applications for short wavelength optoelectronic devices and transparent conductive oxide films, such as in UV-lasers, blue to UV light-emitting diodes and solar cells electrodes. This oxide is also used in glass stacking as a UV spectrum filter and can provide other promising technological applications thanks to its adjusting photoluminescence properties. The advantage of the magnetron sputtering technique is the achievement of polycrystalline ZnO films deposition on large flat glass area without intentional substrate heating. However, it results in residual stresses which can be detrimental when occurrence of spontaneous delamination, or under scratch during processing or in service. The control of their mechanical reliability can then be achieved by an in depth comprehension of the residual stresses build up or relaxation mechanisms occurring in the films in relation with the material structure.

Residual stress evolution in sputtered ZnO films has been studied in-situ in a furnace by synchrotron X-ray diffraction. The films sputter deposited on (001) Si substrates were thermally cycled from 25°C up to 700°C and down to 25°C . X-ray diffraction 2D patterns were captured continuously during the heating, plateau and cooling ramps. The corrections carried out for compensating the furnace drift are presented. The obtained stress state is observed to change from compressive to tensile upon cooling. Stress amplitudes increase up to 370°C and, then stress relaxation is detected. The overall behaviour is discussed in terms of structure changes induced during the heat treatment. This work is done in the framework of an ANR project named Merethif.

CP-29 X-ray Photoelectron Spectroscopy Depth Profiling of La2O3/Si Thin Films Deposited by Reactive Magnetron Sputtering
C. Ramana, RamaSesha Vemuri (University of Texas at El Paso); V.V. Kaichev (Boreskov Institute of Catalysis, Russia); V.A. Kochubey (Institute of Semiconductor Physics, Russia); A.A. Saraev (Novosibirsk State University, Russia); V.V. Atuchin (Institute of Semiconductor Physics, Russia)
Lanthanum trioxide (La2O3) is one among the most promising high-k dielectric materials to replace SiO2 and Si3N4 in advanced metal-oxide semiconductor devices in gate stack. La2O3 can be prepared by various techniques; however the film properties are strongly dependent on the fabrication conditions. Reactive magnetron sputtering deposition is widely used for the preparation of high quality transition multivalent metal oxide films with reproducible parameters and controlled thickness. The technique is preferred since it usually offers a high deposition rate for oxide films and a possibility to control the chemical composition of the film by reactive atmosphere in vacuum chamber. The aim of the present study is to understand the surface structure and evaluate the chemical parameters of La2O3 films deposited on Si substrates by reactive magnetron sputtering. La2O3 thin films were deposited onto Si(100) substrates in an argon/oxygen atmosphere using a high purity La target (99.9%). Structural parameters of the films were estimated by reflective high energy electron diffraction (RHEED) method at electron energy of 50 keV. All the films show no diffraction pattern indicating their amorphous nature in the near surface layers. Chemical state examined by the X-ray photoelectron spectroscopy (XPS), SPECS device, monochromatic Al Ka radiation before and after Ar+ ions (2.4 keV, 10 mA/cm2, 2, 15, 30 min) sputtering indicates the stoichiometric film formation. Chemical nature of the species was identified with using binding energy (BE) difference parameter DLa = BE (La 3d5/2) - BE (O 1s). The C 1s signal disappeared after 2 min ion bombardment. So, it may be concluded that multicomponent C 1s spectra found for initial film surface is related to top surface hydrocarbons and carbonate species. For initial surface the atomic ratio [O]/[La] exceeded noticeably the ratio characteristic of La2O3, that is an indicator of presence of COx groups at the surface. The ratio [O]/[La] decreases from 3.66 to 1.41 with increasing duration of ion bombardment revealing removement of COx and partial oxygen loss. Formation of carbonates at the La2O3 surface is confirmed also by complex shape of O 1s spectra. The intensity of high binding energy component is decreasing with increase of ion sputtering time.
CP-30 Microstructure and Dispersive Optical Parameters of Thermally Evaporated Nickel Films
C. Ramana (University of Texas at El Paso); V.V. Atuchin, T.I. Grigorieva, V.N. Kruchinin (Institute of Semiconductor Physics, Russia); D.V. Lychagin (Tomsk State University of Architecture and Building, Russia); L.D. Pokrovsky (Institute of Semiconductor Physics, Russia)

Nickel (Ni) films are widely used in electrochemistry, microelectronics, energy and nanotechnology. In integrated optics, the nanometric Ni films are used as a source for doping LiNbO3 substrate and optical waveguide fabrication by thermal diffusion. Because effective refractive indices of the waveguide modes are strongly dependent on the optical profiles in doped layer, precise control of Ni film thickness (h) is needed in the range h~10-50 nm. Ellipsometry can be successfully applied for nondestructive determination of the thickness of a dielectric and semi-transparent metal film when optical constants of the material are known. Regrettably, noticeable scattering was found for optical constants reported earlier in literature for Ni films and crystals. As it seems, this scattering appeared due to different film quality or crystal surface preparation. The focus of the present work is centered on Ni film fabrication by thermal evaporation, evaluation of their optical parameters with spectroscopic ellipsometry, and compares the results with those determined for Ni single crystal . Nickel single crystals (99,995%) were grown by directional solidification from machined polycrystalline blanks in graphite mold. Laue X-ray back reflection method was used for crystal orientation. Specimens were sliced from the single crystal by means of an acid saw. The specimen with the smoothest polished surface was studied by spectroscopic ellipsometry method. Nickel films were fabricated by thermal evaporation method in vacuum below 10-5 Torr. The substrate temperature was T=100 °C. For precise determination of optical parameters, thick Ni film (h~100 nm by as determined from optical interferometry) was prepared on silica substrate. To increase the metal adhesion, the substrate was subjected to RCA chemical cleaning just before insertion into vacuum chamber. Structural parameters of Ni films were studied with reflection high-energy electron diffraction (RHEED). Thermally evaporated Ni films are polycrystalline. Spectral dependencies of refractive index n(l) and extinction coefficient k(l) were determined with the help of spectroscopic ellipsometry in the spectral range, l~250-1030 nm. The n and k increase continuously with l. Such a behavior is typical for refractive metals. The dependencies k(l) determined for the film and crystal surface are very close. The curves n(l), however, are close in the shape but the refractive index of Ni film is slightly higher than that determined for single crystal. This refractive index gap ~0.1 between the curves may be appeared due to different surface state of Ni film compared to single crystal (100) surface.

CP-31 Effect of Nitrogen Pressure on the Growth, Microstructure and Optical Properties of TiN Thin Films
C. Ramana, N. Esparaja, V. Rangel, S White (University of Texas at El Paso); A.L. Campbell (Wright-Patterson Air Force Base (WPAFB))
Transition metal nitrides (TMNs) are widely used as diffusion barriers in microelectronic applications, heat and corrosion resistance coatings. The unique optical properties of TiN films such as selective spectral range optical transmission and reflection make these materials interesting for application in solar-control windows and optical filters in addition to the traditional electronic and ceramic devices. However, the microstructure of TiN films is very sensitive to the growth conditions, specifically the reactive nitrogen pressure. On the other hand, controlled growth, texture, and composition of the layers can significantly influence their properties, phenomena and performance In present work, TiN films were fabricated using reactive radio frequency magnetron sputter deposition onto silicon (100) and quartz substrates. The nitrogen flow ratio in reactive gas mixture (Ar/N2 ) was varied in a wide range. It was found that the crystal structure, texture and optical quality of the grown TiN layers are dependent on the nitrogen ratio in reactive gas mixture during deposition. TiN coatings shown initially the mixture of (111) and (002) texturing to a completely (111) followed by completely (002) texture with increasing nitrogen content. Correspondingly, the optical quality of the TiN coatings varies depending on the preferred orientation. Chemical composition profiles indicate that the nitrogen incorporation into the layers and the associated chemistry determines the functional physical properties of the coatings. The results will be presented and discussed.
CP-34 Large Area Colloidal Crystals for Photonic Applications
Sabine Portal, Edgar Cabrera, Oriol Arteaga, Mari-Àngels Vallvé (Universitat de Barcelona, Spain); J. Ferre-Borrull (Universitate Rovira i Virgili, Spain); Jordi Ignés-Mullol, Enric Bertran (Universitat de Barcelona, Spain)
Large area colloidal crystals were prepared in one deposition step using a large trough Langmuir-Blodgett system. They were constituted of spherical particles of metal oxide prepared by sol-gel method from hydrolysis of metal ethoxide precursor in ethanol. Particles of different materials were synthesized (titania, silica) with a wide range of size from 50 nm to 1 micron with a narrow dispersion (<10%).

Langmuir-Blodgett self-assembled monolayers of the synthesized particles were deposited on 25-100 cm2–substrates of silicon and glass. Depending on the size distribution, the particle monolayers were characterized by either hexagonal or disordered compact structures.

Morphological properties (particle roughness, shape, surface pattern) were characterized by Atomic Force Microscopy and Scanning Electron Microscopy. Transmittance spectra and ellipsometry measurements provided the optical properties of the colloidal films, which were connected to the degree of their structural order and compactness. The effects of film characteristics on wettability were evaluated by contact angle measurements. Colloidal films can find application in photonics but also as smart surfaces with controllable photo-switched wettability and photocatalytic properties. They are also promising for applications in bioengineering and photovoltaic cells.

CP-35 Diamond Like Carbon/Metal Nanocomposite Films for Solar Harvesting Applications
Harry Zoubos (University of Ioannina, Greece); Soteris Kalogirou, Giorgos Constantinidis, Pantelis Kelires (Cyprus University of Technology, Cyprus); Panos Patsalas (University of Ioannina, Greece)

Diamond-Like Carbon (DLC) has been long studied as a material for surface protection against wear and corrosion; in addition due to the vast range of its optical properties it has been applied in anti-scratch layers in photovoltaics and optical systems. The combination of its exceptional mechanical and optical properties with its reported high thermal conductivity makes it a promising candidate for solar energy harvesting in solar trough collectors. However, its optical transparency is a major drawback for such applications, because the optical absorption spectrum of DLC does not cover the whole solar spectrum.

In this work we incorporated metal nanoparticles into DLC in order to extend its optical absorption into the visible spectral range. We have grown a variety of DLC:Me (Me=Ag, Cu, Ti, Zr, Ni) nanocomposites of varying metal and sp3 volume fractions by pulsed laser deposition. A detailed study of their optical properties has been performed using optical reflectance and transmittance measurements as well as spectroscopic ellipsometry. The optical properties of the DLC films have been correlated with their structural features such as the metal and sp3 volume fractions (measured by in-situ Auger electron spectroscopy) and density (measured by in-situ electron energy loss spectroscopy). In addition, their mechanical performance and adhesion to various materials used for solar trough collectors have been evaluated by nanoindendation and scratch testing. Finally, the various DLC:Me films have been thermally (in a vacuum furnace and in ambient) and optically (using a solar simulator) annealed and the changes in their integrity and optical performance have been evaluated, in an effort to identify their potential for realistic applications in solar harvesting.

CP-36 Temperature Effect on Cu(InGa)Se2 Thin Film Photovoltaic Absorber Formation by Reactive Annealing of Metal Precursors
Hyeonwook Park, Jaseok Koo, Jae-Sung Han, Woo-Kyoung Kim (Yeungnam University, Korea)

The reactive annealing of metallic Cu-Ga-In precursors under Se or H2Se is a likely method of producing effectively large area Cu(InGa)Se2. However, Ga accumulation near the Mo side of substrate/Mo/Cu(InGa)Se2 structure is often observed during the selenization of Cu-Ga-In precursors yielding phase-separated CuInSe2 and CuGaSe2 which subsequently lead to lower open-circuit voltages. Cu(InGa)Se2 films formed by selenization of metal precursors are readily delaminated from Mo layers during CdS chemical bath deposition due to their poor adhesion. It has been suggested that a MoSe2 layer may affect the adhesion at the interface of Cu(InGa)Se2 and Mo. In particular, a MoSe2 layer oriented parallel to the surface of the Mo layer shows poor adhesion because hexagonal MoSe2 compounds are stacked by weak Van der Waals interactions.

In our research group, the reactive annealing of metal precursors was performed in a rapid thermal process (RTP) system consisting of a quartz tube reactor with an inner diameter of 62 mm, quartz sample tray and infrared (IR) heater. The quartz sample tray held up to six 1 cm ´ 1 cm samples. The IR heater ramped temperature rapidly, requiring only 1 min to reach 1,000°C from room temperature. CuGa-In precursors were prepared on Mo-coated thin sodium-free Corning 7059 glass (SFG) of 0.7mm thickness by sequentially or simultaneously sputtering CuGa alloy with 24wt% Ga and elemental In targets. Total thicknesses of precursors were intended to be 600 ~ 700 nm. The atomic compositions of the precursors were confirmed to be Cu/(In+Ga) = 0.9 ~ 1.0 and Ga/(In+Ga) ~ 0.3.

In this paper, the effects of annealing temperature and ramp rate on the properties of Cu(InGa)Se2 fims deposited by rapid thermal annealing were systematically investigated, with particular attention paid to the formation of MoSe2 and compositional depth profiles.

CP-38 Transportation Model Establishment of InGaZnO TFT by Using Vacuum System Measurement
Zong-Ze Li (Minghsin University of Science and Technology, Taiwan); Zhi-Xiang Fu, Yi-Teh Chou, Po-Tsun Liu (National Chiao Tung University, Taiwan); Bing-Mau Chen (Minghsin University of Science and Technology, Taiwan)

The effect of annealing atmosphere on electrical metastability of a-InGaZnO TFT is investigated. The generation of oxygen vacancies by the annealing in a vacuum led to an increased Ioff and large Vth shifts, while N2 and O2 ambience effectively improve the device performance. A physical mechanism is also reasonably proposed. Amorphous transparent conductive oxide (a-TCO) has attracted lots of attention for its superior electrical performance and insensitivity characteristics to visible light. One of the most popular candidates of a-TCO material nowadays is amorphous indium gallium Zinc Oxide (a-IGZO). However, some fundamental transport mechanisms still need to be clarified, otherwise it will limit the technology development for realistic application. In addition, previous studies reported thermal annealing process was able to critically dominate the electrical performance of a-IGZO TFT, but the process factors in the annealing process have not be specified completely. In this study, the effect of annealing atmosphere (pure N2, pure O2, and vacuum) will be studied to explore the optimum annealing conditions for the sputter-deposited a-IGZO TFT. Electrical reliability also will be investigated further by analyzing electrical behavior after gate bias stress in the ambient air and a vacuum. In summary, experimental results indicated the effects of annealing atmosphere on electrical metastability of the a-IGZO TFT under gate bias stresses with different voltage polarities. Annealing temperature would improve the front channel properties while the annealing atmosphere would modify vacancies at the back channel. For the O2-annealed and N2-annealled a-IGZO TFT, the magnitude of the Vth variation was similar in atmosphere and vacuum during positive gate bias stress, because of the lack of oxygen vacancy in backchannel. However, H2O would stay on the surface of a-IGZO and resulted in different Vth variations in atmosphere or vacuum during negative gate bias stress.

CP-41 Electron Microscopy Analysis of the Growth and Interface Structure of Sputter-Deposited ZrO2 Thin Films
C. Ramana, RamaSesha Vemuri, Domingo Ferrer (University of Texas at El Paso)

Zirconium oxide (ZrO2) is an important material with a potential for a wide range of technological applications. The outstanding chemical stability, electrical and mechanical properties, high dielectric constant, and wide band gap of ZrO2 makes it suitable for several industrial applications in the field of optics, electronics, magneto-electronics, and optoelectronics. ZrO2 is frequently used as a high refractive index material in multilayer optical coatings in high power laser systems. ZrO2 is employed in superplastic structural ceramics that demonstrate excellent strength and fracture toughness. ZrO2 has been considered as a promising dielectric to replace SiO2 in advanced metal oxide semiconductor (MOS) devices in gate stack. However, it is well known that the electrical and optical properties of ZrO2 thin films are highly dependent on the film-substrate interface structure, morphology, and chemistry, which are in turn controlled by the film-fabrication technique, growth conditions, and post-deposition processes.

The objective of the present work is to better understand the growth and local structure, interface structure, and chemical reactions at the ZrO2-Si interface using electron microscopy. The ultimate goal is to minimize the interface diffusion using the surface nitridation approach. In the present work, ZrO2 thin films have been prepared by the radio-frequency magnetron sputter-deposition onto Si(100) substrates as a function of growth temperature (Ts) varied in a wide range of 30-500oC. The growth behavior, surface structure and morphological features, interface structure, and chemical analysis of surfaces and interfaces have been examined by the high-resolution transmission electron microscopy (HRTEM) and high-resolution scanning electron microscopy (HR-SEM). HRTEM and HRSEM are considered to be the best capabilities to examine the ultra-microstructure of the ZrO2-Si interface. The results indicate that the effect of Ts on the surface structure, interface layers and morphology of ZrO2 films is significant. ZrO2 films grown at 30oC are amorphous without IL formation. An increase in Ts results in the formation of nanocrystalline ZrO2 films. A significant amount of interface mixing occurs at higher temperatures (Ts=500oC) where the clear distinction between ZrO2 and Si is not possible. The grain sizes determined are in the range 5-40 nm, where the temperature-dependence is clear. Efforts are made to explain the quantitative information, obtained based on the electron microscopy results, making use of the existing models to account for growth behavior and interface structure.

CP-42 High Transparent Soluble Polyimide/Polyimide–Nanocrystalline-Titania Hybrid Optical Materials for Antireflective Applications
Yang-Yen Yu, Wen-Chen Chien, Hui-Huan Yu (Ming Chi University of Technology, Taiwan)
In this study, a new synthetic route was developed to prepare polyimide–nanocrystalline-titania hybrid materials with a relatively high titania content. A soluble polyimide with carboxylic acid end groups (6FDA–6FpDA–COOH) was first synthesized from 4,40-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,40-(hexafluoroisopropylidene) dianiline (6FpDA), and 4-aminobenzoic acid (4ABA). Such end groups could undergo an esterification reaction with titanium butoxide and provide organic–inorganic bonding. A homogeneous hybrid solution was obtained through the mole ratio of titanium butoxide/carboxylic acid, water/acid content, and a mixed solvent system. Then, the polyimide/TiO2 hybrid thin films were prepared by sol-gel process. The effects of TiO2 content (up to 90 wt%) on the hybrid film properties and the optimum operating conditions were also investigated. HRTEM results indicated the formation of nanocrystalline-titania domains of around 5–10 nm in the hybrid films. TGA and DSC analysis showed that the decomposition temperature of polyimide was about 468°C. The Td increased as the titania content in hybrid thin films increased. FTIR spectra indicated that the amidization was complete and the cross-linking Ti-O-Ti network formed. N&k and UV-vis analysis showed that the prepared hybrid films had the good optical properties and high refractive index 1.961. Moreover, the prepared polyimide/titania hybrid thin films were further applied to develop a three layer antireflective (AR) coating on the glass and PMMA substrate. The results showed that the average reflectance of the AR coating on the glass and PMMA substrate was 0.495 and 0.267%, respectively. The transparency at 550nm was greater than 90% for both AR coatings on the glass and PMMA substrates.
CP-43 Preparation and Characterization of P3HT:CuInSe2:TiO2 Thin Film for Application on Hybrid Solar Cell
Yang-Yen Yu, Wen-Chen Chien, Si-Han Chen (Ming Chi University of Technology, Taiwan)

This investigation reports the preparation and characterization of the conductive polymer regular poly(3-hexylthiophene) (rrP3HT) and copper indium diselenide (CuInSe2) and titania (TiO2) nanocrystals and their application in hybrid solar cells. Quantitative area calculation of the 1H NMR spectra showed that the regularity of the prepared rrP3HT was 93.82%. The rrP3HT was further blended with different contents of CuInSe2 and TiO2 nanoparticles and spin cast onto the ITO glass. The prepared nanocomposites were characterized by SEM, AFM, TEM, UV-vis, FTIR, PL, and XRD analysis. TEM and XRD analysis showed that the prepared CuInSe2 and TiO2 nanoparticles had a high degree of crystallinity. UV-vis and PL spectra of the prepared P3HT:CuInSe2:TiO2 nanocomposites indicated that the absorption and emission spectra increased and decreased with increasing amount of titania, respectively. SEM and AFM images showed that no phase separation could be observation for the prepared P3HT:CuInSe2:TiO2 films. Solar cells with a device structure of ITO/NiO/P3HT:CuInSe2:TiO2/Ca/Al were then produced by evaporation of NiO ,Ca and Al as the back contact. Analysis of solar cells showed that the incident photon to converted electron efficiency (IPCE) and energy conversion efficiency (h) increased with the increase in CuInSe2 content. The maximum value of IPCE and h could be obtained as the TiO2 content was 25wt%.

CP-46 Electrical and Morphological Properties of Metal Doped-TiO2 Sol-Gel Thin Films
Rogerio Valaski (Inmetro, Brazil); Marco Cremona (Pontifícia Universidade Católica do Rio de Janeiro, Brazil); Caroline Arantes, Cristiano Legnani, Welber Quirino, Carlos Achete (Inmetro, Brazil)
TiO2 is n-type semiconductor with a large gap which has been successfully used in several applications as photovoltaic, organic photovoltaic and electrochromic devices due to its stability and electronic features. Among the different techniques to produce TiO2 films the sol-gel methods stand out due to be an easier and cheaper process for large area films production without controlled atmosphere or more sophisticated experimental apparatus. However the TiO2 resistivity must be decreased considerably to become its utilization easier and wider. The TiO2 resistivity can be modified and controlled through the precursor solution and post annealing. However, the resistivity decreasing in this case is not large enough for applications as in electrodes development, although feasible results had been obtained in organic photovoltaic devices with TiO2 as intermediate layers. A well established way to decrease the material resistivity is the doping process with metal atoms. This technique was used in the present work. Besides the TiO2 doping process with metals as Al and Zn we also investigated the influence of the material used as source of this metals. As metal source nitrates and chlorates due to their higher solubility in the solvent of TiO2 precursor solution were used. The TiO2 carrier charge mobility, carrier charge density and resistivity were 1.5×101 cm2/V.s, 9.5 × 1012 cm-3 and 5.0 × 104 Ω.cm, respectively, for a 40 nm TiO2 film annealed for one hour at 550oC. Al-TiO2 precursor solution doped films presented carrier charge mobility, carrier charge density and resistivity 1.2×103 cm2/V.s, 3.1 × 1012 cm-3 and 1.9 × 103 Ω.cm, respectively for the same film thickness and annealing conditions. When the precursor solution was doped with Aluminum Nitrate (0.3 mM) the carrier charge density increased to 1.5 × 1014 cm-3. Nevertheless, in this case, the resistivity was the same of pure TiO2 due to the decreasing in the carrier charge mobility. The addition of Aluminum Chlorate in TiO2 precursor solution seems to influence more the morphology that the electronic film features. In order to elucidate these questions, XRD and XPS measurements were carried out as well Al-TiO2 and Zn-TiO2 doped films were developed and characterized with different chlorates and nitrates concentrations. The influence of annealing condition changes was also investigated.
CP-47 Preparation of Impurity-Doped ZnO Transparent Electrodes Suitable for Thin-Film Solar Cell Applications by Various Types of Magnetron Sputtering Depositions
Tadatsugu Minami, Jun-ichi Nomoto, Tomoyasu Hirano, Toshihiro Miyata (Kanazawa Institute of Technology, Japan)

This paper describes the influence of the type of magnetron sputtering deposition (MSDs) on the characteristics of impurity-doped ZnO thin films for applications as transparent electrodes in thin-film solar cells. An r.f. power-superimposed d.c magnetron sputtering deposition (r.f.+d.c.-MSD) that produced a decrease in deposition damage and obtainable resistivity as well as an increase of deposition rate is demonstrated. Transparent conducting Al- and Ga-doped ZnO (AZO and GZO) thin films were deposited using a magnetron sputtering apparatus with an oxide target, and both an d.c. and an r.f. (13.56 MHz) power supply was applied either separately or in combination. The oxide targets used were commercially available high-density-sintered rectangular targets (127 mm×275 mm). A substrate of OA-10 glass (Nippon Electric Glass Co., Ltd.) with an area of 200 mm×200 mm was placed parallel to the target surface at a substrate-target distance of 90 mm. Sputtering depositions were carried out at a deposition temperature of 200oC in a pure Ar gas atmosphere at 0.2 Pa. For transparent conducting AZO and GZO thin films prepared by various types of MSDs, the surface morphology and the crystallinity obtained by supplying r.f. power such as in r.f.-MSD and r.f.+d.c.-MSD outperformed those obtained with d.c.-MSD. A higher deposition rate and lower resistivity exhibited in the AZO and GZO thin films prepared by r.f.+d.c.-MSD were obtained in comparison with those found with r.f.-MSD and d.c.-MSD, respectively. To evaluate the light scattering characteristics suitable for applications in thin-film solar cells, surface texturing of the samples was carried out by wet-chemical etching in a 0.5% HCl solution. Subsequently, surface morphology observation and measurements of the optical transmittance and the diffusive component of the surface-textured AZO and GZO thin films were also performed. The high transmittance and high haze properties obtained by supplying such r.f. power as in r.f.-MSD and r.f.+d.c.-MSD outperformed those obtained with d.c.-MSD. The influence of the type of MSD described above may be attributable to decreases of the amount and activity of oxygen reaching the substrate surface; a lower electric field reflects lower sputter voltage in r.f.-MSD and r.f.+d.c.-MSD. Thus, the demonstrated low-damage and high-rate preparation of impurity-doped ZnO transparent electrodes on low temperature substrates by r.f.+d.c.-MSD are suitable for solar cell applications.

CP-48 PL and EL Characteristics of Rare Earth-Activated BaLa2O4 Phosphor Thin Films with or without Co-doping of Bi
Toshihiro Miyata, Yuki Nishi, Jun-Ichi Ishino, Tadatsugu Minami (Kanazawa Institute of Technology, Japan)

This paper describes the PL and EL characteristics of newly developed rare earth (RE)-activated BaLa2O4 oxide phosphor thin films with or without the co-doping of Bi and prepared by magnetron sputtering depositions. BaLa2O4 phosphor thin films were prepared on thick BaTiO3 ceramic sheets by either a conventional or a combinatorial radio frequency (r.f.) magnetron sputtering (rf-MS) deposition method using a powder target, which was a mixture of oxide powders. In combinatorial rf-MS depositions, BaLa2O4:Bi,RE phosphor thin films with either Bi or RE content that varied across the substrate surface were deposited using a powder target divided into two parts. The sputter depositions were carried out under the following conditions: atmosphere, pure Ar or Ar+H2; pressure, 6 Pa; r.f. power, 100 W; and substrate temperature, 350oC. The thickness of all deposited phosphor thin films was approximately 1.5 μm. After the depositions, postannealing was carried out in a pure Ar or a reducing gas atmosphere at a temperature up to 1100oC. TFEL devices were fabricated by depositing an Al-doped ZnO thin-film transparent electrode and an Al thin-film back electrode on the phosphor thin-film emitting layer and the BaTiO3 ceramic sheet, respectively. As an example, multicolor PL emissions were always observed from BaLa2O4:Bi,Eu phosphor thin films prepared with appropriate Bi and Eu contents and postannealed at 1000-1100oC. However, the spectral shape of the PL emissions observed from the postannealed BaLa2O4:Bi,Eu phosphor thin films were considerably affected by the postannealed atmosphere. In addition, multicolor EL emissions were obtained in TFEL devices fabricated using postannealed BaLa2O4:Bi,Eu thin films prepared by varying either the Bi or Eu content. The observed blue emission band peaking at a wavelength around 420 and 450 nm may reflect the transition in Eu2+ and the 6s2-6s16p1 transition in Bi3+, respectively. The multiple sharp emission peaks involving red emissions peaking around 610 and 620 nm are assigned the transition in Eu3+. It can be concluded that multicolor PL and EL emissions, which were observed from BaLa2O4:Bi,RE phosphor thin films prepared by varying either Bi or RE content, allow the control of emission color over a wide range. In addition, BaLa2O4 is very promising as new host materials for oxide phosphor applications.

CP-49 Exciton Wavefunction Coupled Surface Plasmon Resonance for In-doped ZnO Nanowires with Aluminum Cylindrical Micropillars
Chia-Hui Fang, Yu-Ting Liang, Jen-Cheng Wang, Tzer-En Nee (Chang Gung University, Taiwan)

Zinc oxide (ZnO) has attracted intensive research effort in recent years, due to its unique properties and versatile applications. Besides, ZnO is naturally of n-type conduction due to a large number of native defects. Recently, the researches of ZnO electrical conductivities are focused on the synthesis of p-type ZnO using various techniques and dopants. Recent work on the conservation of surface plasmon and light through period metal arrays has elucidated the propagation of surface plasmon resonance (SPR) behavior. In this paper, we discuss the SPR dispersion relations with various Al cylindrical micropillars by measuring the surface charge displacements. Optical characterization of exciton coupled with SPR for indium-doped ZnO nanowires with Al cylindrical micropillars has been also investigated.

From photoluminescence spectra, it is found that In-doped ZnO nanorods have a blue emission at 425 nm, which resulted form the ZnO band-to-band transition with SPR coupling effect. Prior to the arrays of samples were annealed, a broad green emission centered at 500 nm was observed, which is attributed to ZnO native point defects. The relatively strong green band emission results from the radiative recombination that arises from the ionized oxygen vacancy. Compare the In-doped ZnO on Si substrate, the enhancement of PL intensity for In-doped ZnO with deposited Al cylindrical micropillars can be attributed to strong coupling interaction with SPR and exciton over a broad temperature range. These experimental results indicate that Al cylindrical micropillars can significantly affect carrier confinement and enhance the quantum efficiency of In-doped ZnO/Al heterostructures due to the interaction of SPR coupling between In-doped ZnO nanowire and Al film. The rate equation models are invoked to corroborate the anomalous temperature behaviors. All the calculations are agreement with the experimental observations. The temperature-dependent mechanism of ZnO band-to-band transition with SPR coupling effect will be discussed in detail as well.
CP-50 Preparation and Post Annealing Effect on Physical Properties of Nanostructure ZTO Thin Films
Vipin Kumar Jain (University of Rajasthan, India); Praveen Kumar (National Physical Laboratory, India); Praveen Jain (Indian Institute of Technology, India); Subodh Srivastav, Shweta Agrawal, Y.K. Vijay (University of Rajasthan, India)
Transparent conducting oxide (TCO) films have been widely used in the field of optoelectronics. Recently, Zinc Tin Oxide (ZTO) films have been considered as possible alternative to ITO films due to less expensive, more abundant, and more stable against hydrogen plasma which makes them appropriate for using as anode in flat-panel displays. Zinc tin oxide (ZTO) thin films were deposited on glass substrate with varying concentrations (ZnO:SnO2 - 100:0, 90:10, 70:30 and 50:50 wt.%) at room temperature by flash evaporation technique. These deposited ZTO film were annealed at 450°C in vacuum. These films were characterized to study the effect of annealing on the structural and optical properties. Atomic force microscopy (AFM) and Scanning electron microscopy (SEM) images manifest the surface morphology of these ZTO thin films. The apparent growth of surface features revealed the formation of nanostructured ZTO thin films. The small value of surface roughness (root mean square RRMS) ensures the usefulness in optical coatings. The optical transmittance found to be decreased however blue shift has been observed after annealing. The optical band gap was also found to be decreased for both types of films with increasing concentration of SnO2.
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