ICMCTF2011 Session C3: Optical Characterization of Thin Films, Surfaces, and Devices

Wednesday, May 4, 2011 8:00 AM in Room Sunset

Wednesday Morning

Time Period WeM Sessions | Abstract Timeline | Topic C Sessions | Time Periods | Topics | ICMCTF2011 Schedule

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8:00 AM C3-1 Analysing Solid Surfaces by FT-IR Imaging ANR AFM-Raman-Spectroscopy
Juergen Sawatzki, Matthias Boese, Peng Wang (Bruker Optik GmbH, Germany)
To understand chemical structures on surfaces it is essential to analyze two dimensional samples by FT-IR with high spatial resolution. The conventional approach would be to acquire sequentially single point spectra at predefined locations of the sample. However, for the complete study of bigger areas this “mapping technique” is extremely time consuming. To overcome this hindrance, modern FT-IR imaging instrumentation is based on focal plane array (FPA) detection systems. Using this technology large sample areas can be measured simultaneously while reducing the acquisition time considerably.

Atomic force microscopy is a powerful tool for the characterisation of surfaces down to the molecular and even atomic level. It is based on a microscopically small oscillating tip which fixed to a cantilever. The tip is moved across the sample to obtain topographical information.

Recently, AFM and Raman microscopy were combined to allow morphological/topographical as well as chemical imaging of the same sample area. Raman microscopy ideally complements AFM imaging since it is adding molecular spectroscopic information. In this paper typical examples for analyzing surfaces by FTIR imaging and AFM/Raman microscopy are presented. Data from polymer structures on metallic substrates as well as from polymer structures on different semiconductors are shown. To avoid any modification of these samples during the optical inspection, all experiments were performed contact-free in transmission or reflection mode.

8:40 AM C3-3 X-Ray Fluorescence as a Powerful Tool for the Study of Chemistry of Thin Films
Anastasios Siozios, Dimitrios Anagnostopoulos, Michael Karakassides, Panos Patsalas (University of Ioannina, Greece)

X-ray fluorescence (XRF) is one of the most well-established optical, non-destructive techniques for elemental analysis of bulk materials. Unlike X-Ray Photoelectron Spectroscopy, which is considered the most sensitive technique for chemical analysis of surfaces and thin films, XRF was considered too vague for thin film studies. However, new advances in XRF instrumentation enable today its implementation in studies of thin films and coatings, as well.

In this work we present a case study of XRF analysis of AlN and AlN-based nanostructured thin films. We have selected AlN as an extreme case of a ceramic material, which consists exclusively of light elements where Auger emission and not fluorescent X-Rays is more probable for the recombination of the 1s vacancy and a high-energy level electron.

We have considered AlN and AlNx films grown by reactive magnetron sputtering and pulsed laser deposition and we observed the chemical shifts of the Ka and Kb lines and the emergence of the Kb’ line of Al due to the chemical environment around it (Al or N first neighbors). We compared the chemical shifts observed in AlN thin films to those observed for Al2O3 (useful for studying oxidized Al and AlN) and AlCl3 (the most popular solid precursor for AlN growth by chemical vapor deposition) and we show that there is a rational variation according to the electro-negativity of the ligand. We note that XRF has been able to identify the formation of stoichiometric, yet amorphous, AlN where X-Ray Diffraction was useless due to the absence of crystalline periodicity. Finally, we identified the film thickness limits for which XRF can provide reliable results.

XRF has been also applied in investigating the oxidation of AlN by recording the evolution of oxygen’s Ka line. The strength variation of this line for various AlN thicknesses indicates whether an oxide layer is located at the surface or the interface of the film.

In order to investigate the potential of XRF to study more complex materials, we have employed it for the study of AlN-based films with Ag inclusions in various forms. Thus, we have studied films where Ag was: 1) atomically dispersed into the AlN lattice, 2) nanospheres (~3.5 nm) embedded into an AlN matrix, and 3) Ag nano-sheets into AlN (i.e. AlN/Ag nano-multilayers). Comparing the Ka, Kb and Kb’ chemical shifts in these films to those observed for Al, AlN and AlAg intermetallics, we were able to evaluate the nature of AlN-Ag bonds for the various considered cases.

9:00 AM C3-4 Electrochromic Properties of Nanocrystalline MoO3/V2O5 Composite Thin Films
Chung-Chieh Chang, Chia-Hao Hsu, Kuo-Wei Yeh (Academia Sinica, Taiwan); Chao-Sheng Hsu, Chih-Chieh Chan, Chung-Kwei Lin (Feng Chia University, Taiwan); Mau-Kuen Wu (Academia Sinica, Taiwan)

In the present study, MoO3/V2O5 composite thin films were prepared by sol-gel spin-coating technique. The spin-coated MoO3/V2O5 thin films were amorphous before calcining, nanocrystalline MoO3/V2O5 thin films were afterward. The surface morphology of crystallized MoO3/V2O5 thin films was examined by scanning electron microscope ( SEM ). X-ray diffraction for phase identification was performed by an X-ray diffractometry . Electrochromic properties of these thin films were evaluated by cyclic voltammetry, using a standard three-electrode cell system. All CV measurements were performed from -2 to 2 V at a scan rate 30 mV/sec at room temperature. Transmittance spectra of the films were examined by a spectrophotometer.

The effect of annealing temperature ranged from room temperature to 400 oC on film morphology was investigated. Experimental results showed that after heat-treated MoO3/V2O5 composite thin films exhibited batter electrochromic properties among the films examined in the present study.

9:20 AM C3-5 Nitrogen-Doping Induced Changes in the Microstructure and Optical Properties of Nanocrystalline WO3 Thin Films
RamaSesha Vemuri, SatyaKiran Gullapalli, C. Ramana (University of Texas at El Paso)

Tungsten oxide (WO3) is a wide band gap (Eg) semiconductor (Eg~3.2 eV), which exhibits excellent properties suitable for the development of integrated chemical sensors, electrochromics, and photoelectrochemical cells. Recently, band gap modification with anoion doping has received a significant attention in view the materials’ application as photo-electrode for hydrogen generation by photo catalytic water splitting. The present work was performed to understand the effect of nitrogen-doping induced changes in the microstructure and optical properties of WO3 films grown by reactive magnetron sputter-deposition. The objective of this work is to optimize the conditions to produce materials suitable for photo-electrodes for hydrogen generation by water splitting. The characterizations performed using grazing incidence X-ray diffraction and optical absorption measurements indicate that the effect of reactive nitrogen pressure is significant on the microstructure evolution and optical properties. The films grown at various reactive gas pressures (0–5.6 mTorr) while keeping the deposition temperature fixed at 400oC shown the degradation of crystal quality for the initial nitrogen-doping while higher end nitrogen-pressure leads to the formation of morphological disorders. Optical spectroscopy analysis of the films indicates that Eg becomes narrowed upon nitrogen indicating the electronic structure changes. Eg decreases from 2.98 eV to 2.12 eV with increasing nitrogen pressure. The results will be presented and discussed.

9:40 AM C3-6 Effect of Growth Temperature on the Structure, Electrical and Optical Characteristics of Sputter-Deposited Y2O3 Thin Films
V.H. Mudavakkat, Kamala Bharathi (University of Texas at El Paso); V.N. Kruchinin, L.D. Pokrovsky, V.V. Atuchin (Institute of Semiconductor Physics, Russia); C. Ramana (University of Texas at El Paso)

Significant research efforts have been directed in recent years on the growth of Y2O3 thin films because of their interesting physical, electronic, and optical properties. The diverse range of potential applications of Y2O3 films includes storage capacitors, random access memory (RAM) and metal−insulator−semiconductor (MIS) devices, protective and antireflective coatings for IR detectors, and optical filters. In the present work, Y2O3 films have been produced by the reactive magnetron sputter-deposition. The effect of growth temperature (Ts) on the microstructure, electrical and optical characteristics Y2O3 films has been investigated. The results indicate that the films grown at room temperature (RT) are amorphous while the films grown at the substrate of Ts=300-500ºC are nanocrystalline crystallizing in cubic phase. Scanning electron microscopy analysis of Y2O3 films indicates the fine microstructure and uniform distribution of dense particles. Grain-size increases from ~5 to 50 nm with increasing Ts. Frequency variation of the electrical conductivity measurements in the range 20 Hz - 1 MHz indicate that the conductivity increases with increasing frequency. The conductivity data fits to a modified Debye’s function, which considers multiple ions contributing to the relaxation. Spectroscopic ellipsometry measurements indicate that the refractive index (at 300 nm) of Y2O3 films increase from 2.03 to 2.25 with increasing Ts. This is attributed to the increased packing density and crystallinity of the films with increasing Ts. The results will be discussed and presented to derive a correlation between microstructure, electrical and optical properties in Y2O3 films.

10:00 AM C3-7 Characterization of Nanometer Films by X-Ray and EUV Reflectometry
Stefan Braun, Maik Menzel, Stefan Schädlich, Andreas Leson (IWS Dresden, Fraunhofer Institute for Material and Beam Technology, Germany)

Physical properties of nanometer films are decisive for many optical and electronic devices. Characteristics like thickness, roughness, density and reflectance have a strong impact on the performance of functional coatings. Currently, one of the main driving forces for the development of optical thin films is the extreme ultraviolet (EUV) lithography. EUV lithography will be used for the production of next generation integrated circuits of the 22 nm node. In this technology nanometer multilayers are applied as reflection coatings on every optical element of the beam path (source collector, illumination and projection optics, photomask).

In order to measure the necessary properties of the films X-ray reflectometry is a very powerful tool. Due to the short wavelength the interaction of the radiation with the films results in interference associated with distinctive features in the reflectance spectra.

Initially a short overview about the theoretical background, commonly used experimental equipment and available software algorithms of the reflectometry method will be presented. The influence of specific thin film parameters on the reflectance spectra will be discussed.

Using the example of nanometer single and multilayers for X-ray mirrors the method will be practically applied and current capabilities of X-ray and EUV reflectometry will be shown. It will be demonstrated that thickness differences in the picometer range can clearly be distinguished over macroscopic dimensions of about 500 mm. Furthermore densities of graphite-like and diamond-like carbon layers will be analyzed and roughness results obtained with X-ray reflectometry and atomic force microscopy will be compared.
10:40 AM C3-10 Morphological Evolution and Optical Characterization of ZnO Thin Films on PET and Glass Substrates by RF-Sputtering Technique
José Roberto Bortoleto (State University of São Paulo - UNESP, Brazil); Erica Pereira da Silva, Ellen Amorim, Everson Martins (UNESP - Universidade Estadual Paulista, Brazil); Steven Durrant (State University of São Paulo - UNESP, Brazil); Paulo Noronha Lisboa-Filho (UNESP - Universidade Estadual Paulista, Brazil)

Zinc oxide has been used as transparent and conducting oxide film in solar cells and electrochromic devices. Also, ZnO thin films have great potential for applications in flexible display technology. In this work, surface morphology evolution, and optical and electrical properties of ZnO thin films deposited by RF sputtering technique onto polyethylene terephthalate and glass substrates have been investigated. Surface morphology was measured with atomic force microscopy (XE-100, Park Instruments) operating in air. Both 5 um x 5um and 1um x1um AFM images were acquired and the surface roughness was characterized in terms of root mean square roughness. Optical Transmittance was performed using a Uv-Vis-NIR spectrometer (Lambda 750, Perkin Elmer) ranging from 190 nm to 3300 nm. The crystalline degree of ZnO thin films was measured using a X-ray diffractometer system (D/MAX-2100/PC, Rigaku). X-ray diffraction patterns confirm the proper phase formation of the material. Optical transmittance data show high transparency (more than 85%) of the films in the visible range. Electrical characterizations show the room-temperature conductivity of the films deposited onto polyethylene terephthalate substrates. For films deposited on glass substrates the surface resistivity measures are less than 40 Ω/sq. The authors would like to thank Brazilian agencies CNPq and FAPESP for financial support.

11:00 AM C3-11 Enhanced Photoluminescence from Zn0.55Cd0.45S:Mn/ZnS Core Shell Nanostructures
Sonal Singhal, Amit Kumar Chawla, Hari Om Gupta, Ramesh Chandra (Indian Institute of Technology Roorkee, India)

We hereby report the synthesis of Zn0.55Cd0.45S:Mn/ZnS core shell structured QDs with varying shell thickness by a two step co-precipitation technique at 280K. With increase in shell thickness the intensity of the XRD peaks of core decreases while that of shell increases which is an indication of the formation of core shell nanoparticles. UV-Vis measurements showed a red shift with increase in the shell thickness. The TEM micrograph confirms the formation of core/shell structures. The particle size obtained from TEM and UV-Vis measurements are in well agreement with each other. Photoluminescence spectra reveal that the maximum intensity of the band at ~ 590 nm (which is a characteristic emission of Mn2+ ion) is found for a shell thickness of 0.2 nm and is ~ 35 times higher than the Core QD’s.

11:20 AM C3-12 Environment Sensitivity and Film Stability of InGaZnO TFT with Annealing Temperature Dependence
Zhi-Xiang Fu (National Chiao Tung University, Taiwan); Zong-Ze Li (Minghsin University of Science and Technology, Taiwan); Yi-Teh Chou, Po-Tsun Liu (National Chiao Tung University, Taiwan); Bing-Mau Chen (Minghsin University of Science and Technology, Taiwan)

We investigated the effect of post-annealing temperature with non passivation a-InGaZnO TFT. As increasing the annealing temperature from 25°C to 45°C, the electrical parameter such as threshold voltage、subthreshold swing and mobility improve apparently. The bonding energy of oxygen in a-InGaZnO film became stronger with higher annealing temperature shows in XPS data. In addition to that, the storage of 45°C annealed device was excellent with ±0.5V of Vth variation under the environment after 9 days and the anti-UV ability was also better with 1.5V threshold voltage shift under UV light illumination. After being gate bias stress, the Vth shift decrease with higher post-annealing temperaure and that mean the improvement of film quality were actually better in 45°C. The passivation-free a-InGaZnO TFT annealed in higher temperature performs a better electrical characteristic and the binding energy of oxygen increases in a-InGaZnO film. According to that, the environment storage is stable after 9 days because the film is stable which avoiding the oxygen desorption in the ambient atmosphere. Besides, the anti-UV ability also improves with higher annealing temperature. The Vth shift is also smaller with less interstitial oxygen. The positive gate bias stress (PGBS) also shows a good performance caused by less absorption of oxygen in the ambient atmosphere with high annealing temperature. The thermal annealing could actually improve the a-InGaZnO TFT to be more stable and insensitive to UV light.

11:40 AM C3-13 Structural and Optical Properties of Chlorinated Plasma Polymers
Rafael Turri (State University of São Paulo - UNESP, Brazil); Celso Davanzo (UNICAMP, Brazil); Wido Schreiner (State University of Paraná, Brazil); José Humberto Dias da Silva, Marcelo Borgatto Appolinario, Steven Durrant (State University of São Paulo - UNESP, Brazil)

Amorphous hydrogenated chlorinated carbon (a-C:H:Cl) films were produced by the plasma polymerization of chloroform/acetylene/argon mixtures in an rf PECVD system. The main parameter of interest was the ratio of chloroform to acetylene in the chamber feed. Films were deposited onto aluminum covered glass slides and aluminum plates, respectively, for subsequent characterization by infrared reflection-absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS). IRRAS spectra revealed the presence of C-Cl groups and XPS confirmed the presence of chlorine. Several optical properties were obtained via film thickness data and ultraviolet-visible-near infrared spectra. The latter were obtained using a Perkin Elmer Lambda 750 spectrophotometer. Thus dependencies of the refractive index, n, absorption coefficient, α(E), and optical gap, E04, on the degree of chlorination were obtained.

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