ICMCTF2015 Session C4-2: Thin Films for Energy Related Applications

Monday, April 20, 2015 1:30 PM in Room Sunrise

Monday Afternoon

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1:30 PM C4-2-1 Surface Polarity Effects and New Hydrogen-related Complexes Observed in the High-resolution Luminescence from ZnO
Roger Reeves (University of Canterbury, New Zealand)

Zinc oxide (ZnO) is a wide-band gap semiconductor at the heart of new gallium-indium-zinc-oxide (GIZO) transparent optoelectronic materials that are now deployed as transparent TFT’s in many state-of-the-art displays. However, despite an existing pathway for zinc-oxide based devices there remain some significant stumbling blocks in forming a complete understanding of the basic ZnO optical properties.

The low temperature luminescence from ZnO remains completely dominated by emission from defect-related sources. Our low-temperature photoluminescence (PL) experiments reveal more than 10 different excitonic features involving electron hole-pairs bound to different impurities and second order exciton effects. A challenge when comparing samples of ZnO is that the separation between such excitonic features is comparable to experimental accuracy. Thus careful calibration is required before definitive statements can be made about the defects contained within a particular sample.

Variations in PL emission from different crystallographic faces show intriguing effects that hint at the strong influence of the ionic character of ZnO surfaces. Interestingly surface polarity dependent PL can be modified by both annealing and metal coverage indicating that PL may also play a diagnostic role in device processing. A clue to understanding such ZnO properties is to look at the role of hydrogen. Hydroxl groups on the surfaces appear to act as donors creating unusual 2-D surface electron gases that are possible sources of the polarity differences. Additionally, hydrogen implanted into the bulk material is observed to create new emission lines from hydrogen-other-defect complexes.

This work will present current results from our luminescence studies of ZnO surfaces following treatment processes including annealing and ion implantation.

2:10 PM C4-2-3 Porous Silicon Buffer Layer Effect on ZnO Pyroelectricity
Kenan Cicek (University of Bristol, UK); Tevhit Karacali (Ataturk University, Turkey)

Pyroelectricity is the property of certain materials that generates voltage by temperature variations. The position of the atoms within the crystal structure of these materials slightly changes by simply heating/cooling the material. The displacement of the atoms will alter the polarization state which will result a temporary voltage across the crystal. The zinc oxide semiconductor is one of the materials that possesses great pyroelectric feature. Crystallinity and orientation of zinc oxide thin film play a crucial role in this property. In most studies, ZnO nanostructures are deposited on sapphire substrates in order to obtain a c-axis oriented thin film which is the most thermodynamically favorable and preferred orientation for pyroelectric applications [1,2,3].

Although sapphire has the same hexagonal type lattice structure with ZnO, it is expensive and hard to find in large size compared to silicon. However there is a large lattice missmatch between ZnO and silicon. Porous silicon can be the solution that reduce the degree of missmatch and a suitable substrate for c-axis oriented growth [4]. Porous silicon is not only integrated with silicon, but it also is easy to fabricate and low cost.

In this study the pyroelectrical characteristic of ZnO thin film has been investigated as a sensing element for a pyroelectric sensor application. In order to observe the effect of porous-Si layer, the thin films were deposited on both Si and porous-Si/Si substrates.

The results taken via XRD, AFM and SEM indicated that, the ZnO/porous-Si layers exhibited a dominant peak of (002) plane which means that the film was grown with c-axis orientation. Moreover results showed that ZnO film has larger grains on porous-Si/Si substrate than the thin film on Si substrate and a rough surface.

The pyroelectric analysis shows that the device with porous-Si/Si substrate has considerably high pyroelectric coefficient compared to Si substrated device. In addition the pyroelectric voltage obtained by porous-Si device is also higher than Si device.

The optimization of design and detailed investigation are being carried out to increase pyroelectric voltage and the measurement for thermal isolation effect of Porous-Si is underway.

[1] Wei C.S., Lin Y.Y., Hu Y.C., Wu C.W., Shih C.K., Huang C.T., Chang S.H. Sens. Actuators A. 128,18–24, 2006.

[2] Hsiao C.C., Huang K Y and Hu Y C. Sensors. 8, 185–92, 2008.

[3] Heiland G. and Ibach H. Solid State Communications. 4,353-354, 1966.

[4] Stolyarova S., Baskin E., Nemirovsky Y. Journal of Crystal Growth, 360,131–133, 2012.

2:30 PM C4-2-4 Electronic Band Structure Engineering of Highly Mismatched ZnO1-xTex Alloy Synthesized by Pulsed-Laser Deposition
Min Ting (University of California Berkeley, USA); Roberto dos Reis (Lawrence Berkeley National Laboratory, USA); Mark Hettick, Ali Javey, Samuel Mao (University of California Berkeley, USA); KinMan Yu, Wladek Walukiewicz (Lawrence Berkeley National Laboratory, USA)

It has previously been shown that alloying of Zinc Telluride (ZnTe), with ZnO modifies the band structure of ZnTe by the anticrossing interaction between extended conduction band (CB) states with localized O states at ~0.2 eV below CB edge of ZnTe [1]. On the other hand, incorporating Te into ZnO is expected to modify the valence band (VB) of the ZnO matrix through the valence-band anticrossing interaction between localized Te states at ~1 eV above the VB edge of ZnO and extended VB states of ZnO. The interaction leads to the formation of a new Te-derived VB edge above that of ZnO. The large upward shift of the VB edge could lead to stable p-type doping, and results in a strong reduction of the ZnO band-gap toward the visible range, making this material suitable for solar energy conversion devices[2].

In this study we synthesized ZnO1-xTex alloys with Te composition x < 0.23 by using pulsed laser deposition. We found that alloys with x < 0.06 are crystalline with a columnar growth structure while samples with higher Te content are polycrystalline with random grain orientation. It was found that Te atoms are randomly distributed with no observable clustering. Optical measurements show that incorporation of a small concentration of Te (x~0.01) red shifts the ZnO optical absorption edge by more than 1 eV. The minimum band gap obtained in this work is 1.8 eV for x = 0.23. The optical properties are consistent with the modification of the valence band of ZnO due to anticrossing interactions of the localized Te states with the ZnO valence band extended states. X-ray photoelectron spectroscopy (XPS) results confirm the upward shift of the valence band in ZnO1-xTex alloys. The optical absorption results were explained using the band anticrossing model with the Te level located at 0.95 eV above the VB edge of ZnO and the anticrossing coupling constant of 1.35 eV. Combining these results with our previous work on band anticrossing in Te-rich alloys [1] allows the prediction of the compositional dependence of the band gap as well as the conduction and the valence band offsets in ZnO1-xTex alloys over the full composition range. The large Te- induced upward shift of the VBE in O-rich ZnO1-xTex could alleviate the notorious p-type doping problem in ZnO [3]. Effects of doping with different group V acceptors (N, As, Sb) on electrical properties of ZnO1-xTex will be discussed.

[1] K. M. Yu, et al., Phys. Rev. Lett. 91, 246403 (2003).

[2] A. Janotti, et al., Rep. Prog. Phys.72, 126501 (2009).

[3] E. Fortunato, et al. (2007). MRS Bulletin, 32, pp 242-247.

2:50 PM C4-2-5 Solar Selective Coatings for High Temperature Concentrating Solar Power: Design, Deposition and Ageing Behaviour Characterization
Borja Coto, Javier Barriga (IK4-TEKNIKER, Spain); Hugo Cachafeiro (Aries Ingeniería y Sistemas S.A, Spain); Josu Goikoetxea, Unai Ruiz-de-Gopegui (IK4-TEKNIKER, Spain)

Concentrating Solar Power (CSP) based on parabolic trough receivers is a well established and mature technology to obtain clean energy. Currently, there are around 3 GW of power plants installed world-wide. Nevertheless, there are issues that need to be addressed in order to improve the positioning of this technology in the energy mix. One key issue is to increase the performance of the plant to obtain higher productivity reducing the cost of energy. To this purpose it is necessary to increase the working temperature from current 400ºC to 600ºC. In this sense, it is necessary to have solar selective coatings with good spectral selectivity values which must be able to stand the new higher requirements. On the other hand, the lifetime required for the solar receivers operating in a power plant is 25 years. Currently, there is a lack of standard accelerated tests for solar collectors for high temperature operation. This is a problem to introduce in the market coatings to work at higher temperatures. Thus, it is important to understand how coatings the solar selective coatings behave in terms of degradation of their optical properties when working at high temperatures.

Solar selective coatings are obtained by means of a nanostructured multilayer stack. Each layer plays a different role in order to achieve spectral selectivity values suitable for CSP and optical design is necessary to obtain an optimal multilayer stack with the required properties. Thus the composition and thickness of the layers must be carefully designed and controlled during the deposition process.

In this work, multilayer selective nanocoatings are proposed and analyzed as candidates for 600ºC working temperature applications. Hence, alternatives such as Al and Mo as infrared reflector mirror layer to avoid thermal losses and Si3N4 and Al2O3 matrices for the absorber cermet are designed and deposited in combination with Al2O3 antidiffusion barrier layer and SiO2 antireflective top layer. The proposed coatings are deposited by means of a preindustrial magnetron sputtering equipment able to coat 4 meter long tubes. The coatings obtained have been analyzed with regard to the degradation behavior of the solar selectivity values at high temperatures.

3:10 PM C4-2-6 The Origin of In Solution-processable Bilayer Organometal Halide Hybrid Solar Cells
Yang-Yen Yu, Rih-Sheng Chiang (Ming Chi University of Technology, Taiwan)

The bilayer solar cells based on Active layer and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) by a solution process were fabricated and the effect of Active layer thickness on the cell efficiency was investigated.The results show that the power conversion efficiency (PCE) of 4.7% under simulated AM 1.5G irradiation (100 mW cm2). As the thickness of Active layer increases to 80 nm, a higher PCE of 7.0% could be obtained. This study indicates that the high exciton diffusion efficiency is enabled by the long diffusion length of Active layer relative to its thickness. Furthermore, the low exciton binding energy of Active layer implies that exciton splitting at the Active layer/ PC61BM interface is very efficient.

3:30 PM C4-2-7 LiFePO4-xNy Thin Film Electrodes Coated on Carbon Fiber Modified Current Collectors for Pseudocapacitors
Kuo-Feng Chiu, Shih-Hsuan Su, Hung-Jhih Leu, Wei-Chieh Huang (Feng Chia University, Taiwan)

LiFePO4-xNy thin films have been sputter deposited on micron carbon-fibers (MCFs) under N2/Ar/H2 mixture gas as electrode materials for pseudocapacitors. The MCFs were fabricated using thermal chemical vapor deposition on stainless steel substrates as current collectors. Various amounts of nitrogen were introduced and the gas contents were controlled by the flow ratios of N2 to Ar/H2. The LiFePO4-xNy thin films coated on the surface of MCFs can be observed by field emission scanning electron microscopy. The electrochemical properties of LiFePO4-xNy thin films were characterized using cyclic voltammogram and charge-discharge processes. The LiFePO4-xNy thin film electrode deposited under the optimal N2 content exhibits a high specific capacitance of 722 F/g at 1 A/g. Even at a current as high as 20 A/g, it still delivers a capacitance of 298 F/g. The pseudocapacitors with LiFePO4-xNy thin film electrodes shows no significant capacity fading after 1000 cycles at 1 A/g. The results indicate that nitrogen-doped can improve the electrochemical performance, and LiFePO4-xNy can be a potential candidate as an active material for pseudocapacitors.

3:50 PM C4-2-8 Structural and Photo-electric Properties of Cuprous Oxide (Cu2O) Thin Films Prepared by Ion-beam-assisted Deposition (IBAD)
Che-Kai Chang (Ming Chi University of Technology, Taiwan); Chuan Li (National Yang Ming University, Taiwan); Jang-Hsing Hsieh (Ming Chi University of Technology, Taiwan)
In this study, cuprous oxide (Cu2O) films were prepared by Ion-Beam-Assisted Deposition (IBAD) using with varied Ar/O2 ratios and ion bombardment rate. The effects of ion bombardment rate and Ar/O2 ratios on structural and photo-electric properties were the purpose of this study. These prepared films were characterized by using UV–VIS photometer, four-point probe, and X-ray Diffractometry. The XRD results showed the films were composed of Cu2O and CuO phases depending on the process parameters. These Cu2O thin films deposited with too much or too less oxygen would transform into the CuO or Cu phase. Cu2O had the highest transmittance and crystallinity when the oxygen flow rate was set at 13.5% and the anode current increased to 0.2A. However, too much ion bombardment may disrupt the film structure, which resulted in lower transmission. The optical spectra of the ion beam were examined using OES. It was found the O*/Ar* ratio peaked with the increase of anode current, then, decreased. This trend was consistent with the variation of optical and electrical properties.
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