ICMCTF2010 Session H4/C4: Thin Films for Photovoltaics: Synthesis and Characterization

Thursday, April 29, 2010 1:30 PM in Room Royal Palm 4-6

Thursday Afternoon

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1:30 PM H4/C4-1 The Characteristics of Zinc Oxide, Cadium Oxide and SnO2 Prepared by RF Magnetron Sputtering
Yanwen Zhou, Fayu Wu, Chunyan Zheng (University of Science & Technology Liaoning, China)
Pure ZnO, CdO and SnO2 films were prepared under closed-field unbalanced magnetron from powder target, by varying RF power and deposition time. The thicknesses of the films were measured by Alpha-Step IQ surface profile and therefore deposition rates of the three materials were calculated. The CdO has much higher deposition rate than SnO2 and ZnO. The SEM and XRD graphs show that the films have the dense columnar structures, and the preferred orientations ZnO, SnO2 and CdO films are (0002), (200), (200), respectively. Vacuum or controlled atmosphere annealing help the intensities of the diffraction peaks grow and FWHM narrow according to XRD results, therefore the mobility of the free charged carriers are increased, showed agreement with Hall Effect measurement. Also, the resistivities of the films decreased, from too higher to be measured to 10-4 Ωcm, and the concentrations of the free charged carriers increased, from 1019 to 1021, after vacuum annealing, but the contrary results after controlled atmosphere annealing. The optical transmittances of these three films are: ZnO, 90%; SnO2, 88%; and CdO, 85%, within the visible wavelength. Annealing treatment did not affect the transmittances of the films, but showed the blue shift and red shift after vacuum and controlled atmosphere annealing, respectively.
1:50 PM H4/C4-2 Three-Terminal Microcrystalline Silicon Solar Cell
Cheng-Hung Tai, Chu-Hsuan Lin (National Dong Hwa University, Taiwan)

Like amorphous silicon, the microcrystalline silicon (μc-Si) can be demonstrated by plasma enhanced chemical vapor deposition. Hence, fabrication of μc-Si solar cells could be based on equipment for amorphous silicon (a-Si) solar cells. In addition, μc-Si has other advantages over a-Si. For example, the absorption coefficient of μc-Si is higher than a-Si in red light and infrared wavelengths, and the carriers mobility in μc-Si is also larger than a-Si. But for μc-Si, there are still a lot of defects inside it. These defects will lead to recombination of photo-generated carriers and the efficiency of μc-Si solar cells is limited. We have designed a new structure – the three-terminal μc-Si solar cell, a back-to-back pin-nip solar cell by the simulation tool, ISE. As compared with the typical μc-Si pin solar cells, the three-terminal μc-Si solar cell can increase the average electric field in the device. The electric field can help separation of photo-generated electron-hole-pairs and decrease the recombination velocity efficaciously. The comparison between the typical cell and the three-terminal μc-Si cell will be shown in this conference. The efficiency of the three-terminal μc-Si solar cell larger than 10 % can be expected.

2:10 PM H4/C4-6 Intergranular Microstructure and Residual Stress Investigation by EBSD on Laser-Crystallized Polycrystalline Si Thin Films on Glass Substrates for Photovoltaic Applications
Xavier Maeder, Christoph Niederberger (Empa, Sweden); Silke Christiansen (Max-Planck-Institute of Microstructure Physics, Germany); Arne Bochmann, Gudrun Andrä, Annett Gawlik, Fritz Falk (Institute for Photonic Technology, Germany); Johann Michler (Empa, Switzerland)
The combined process of diode laser crystallization of an amorphous Si seed layer and solid phase epitaxy (SPE) are used to produce polycrystalline silicon thin films on glass substrates for solar cells. The laser crystallization process is capable of producing large grains of several 100 µm in size while heating the temperature-sensitive substrate only for a very short duration. Grain size, orientation distribution, grain boundary population and lattice defects of polycrystalline silicon thin films are investigated by electron backscatter diffraction analyses (EBSD). The laser crystallization process caused a systematic and strong intergranular lattice twisting in the larger grains, with rotation axes parallel to the growth direction. This progressive lattice rotation is generally between 10 and 25° from one side of the grain to the other and can be up to 50° in the strongest cases. An intergranular misorientation rate higher than 0.2° per micron, constant for several hundred microns, has been observed. The intergranular misorientation is associated both with geometrically necessary dislocations and low angle boundaries which can serve as recombination centre for electron-hole pairs. The dislocation arrays associated with the lattice twisting can be observed by EBIC measurements. Since the lateral grain size is up to two orders of magnitude larger than the film thickness, these dislocations and low angle grain boundaries are an important factor in the degradation of the solar cell performance. An EBSD cross correlation technique has also been used to assess the residual stress in the grains that can influence the mechanical integrity of the device. The calculations show residual stresses values on the order of several GPa inside the grains with strong intergranular misorientation. The main component of stress is perpendicular to the grain growth direction.
2:30 PM H4/C4-7 Addition of Na into CuInS2 Thin Film via Co-Evaporation
Wen-Zen Tsai, Chia-Hung Tsai, Chih-Hui Chang, Jyh-Ming Ting (National Cheng Kung University, Taiwan)

The performance of CuInS2 (CIS) thin film solar cells can be enhanced through the addition of Na into the CIS layer. In almost all of the cases, Na originates from substrate glass or a separate NaF layer that is deposited before, during, or after the growth of CIS, followed by thermal annealing. In the study, we have used an alternative approach by which NaF is incorporated into the CIS layer through co-evaporation. Cu, In, and NaF were first co-evaporated at desired ratios to allow the formation of precursor films having various nominal concentrations of Na. The composition of the precursor films was determined using inductively coupled plasma-mass spectrometer. The precursor films were then sulfurized to form CIS absorber layers in the same evaporation chamber. During the sulfurization, samples were removed at different temperatures for analysis in order to determine the desired sulfurization schedules. The morphology of Na-doped CIS layers was characterized using scanning electron microscopy and the crystalline structure was investigated using grazing incident X-ray diffraction. Secondary ion mass spectrometry was used to determine the concentration profiles along the film thickness. The optical and electrical properties of the absorber layers were investigated using UV-Visible spectroscopy and Hall measurement system, respectively. Effects of Na concentration on the absorber layer characteristics are addressed and discussed.

2:50 PM H4/C4-8 Fabrication of Densely Distributed Silver Indium Selenide Nanorods by Ag+ Ion Irradiation
Dinesh Pathak, Ratish Kumar (Guru Nanak Dev University, India); Davinder Kaur (IIT Roorkee, India); Ravi Kumar (Inter University Accelerator Centre, India)

We prepared polycrystalline AgInSe2 thin films by vacuum evaporation on Si(100) substrate at a high temperature using the stochiometric powder. The thin films were characterized by X-ray diffraction and Uv-vis-NIR spectroscopy .For the fabrication of densely distributed one dimensional nanostructures of Silver Indium selenide on Si substrates, the thermally evaporated films of AIS on Si (1 0 0) substrate were irradiated by incident 200MeV Ag+ ions at a fluence of 5 X 1011 Ion/cm2. At elevated substrate temperatures AIS were featured by the nanorods -like structure. The optical and structural properties of the irradiated films were studied using UV–visible absorption spectroscopy , atomic force microscopy (AFM) , Field emission scanning electron microscopy (FESEM ) and XRD .The controlled fabrication of such densely distributed one dimensional nanorods on Si substrate using ion beam technique, we believe, would open up a variety of applications such as nanoelectronics and optoelectronics devices.

3:10 PM H4/C4-10 Impregnation of Nano-Particles in Glancing-Angle Deposited Titania Films for Efficiency Enhancement in Dye-Sensatized Solar Cells
Ching-Lun Chen, Chia-Hua Huang, Ming-Show Wong (National Dong Hwa University, Taiwan)
Sculptured porous nano-columnar titanium oxide films used as photoanode in dye-sensitized solar cell (DSSC) were prepared on ITO glasses by glancing-angle deposition (GLAD) method using an electron-beam evaporation system. The as-deposited TiO2 films are comprised of helical nano-columns and assembled in an orderly manner with open pores in between. The films were then partially impregnated with titania nanoparticles by spin coating method to increase their internal surface area for dye absorption. The modified porous nanostructured titania films provide a synergetic effect of high surface area, effective route for electron transfer, tight interfaces, and enhanced light trapping, which are all beneficial for higher cell efficiency. The DSSCs incorporated with the nanoparticles-impregnated GLAD films of 4 μm thick exhibited an increase of ~20% in light conversion efficiency over those with the as-deposited films.
3:30 PM H4/C4-11 Nano-Structured TiO2 Films by Plasma Electrolytic Oxidation of Ti Combined with Chemical and Thermal Post-Treatments for Dye-sensitized Solar Cell Applications
Po-Jen Chu (University of Sheffield, United Kingdom); Shu-Yuan Wu, Keh-Chang Chen, Ju-Liang He (Feng Chia University, Taiwan); Yerokhin Aleksey, Allan Matthews (University of Sheffield, United Kingdom)

Porous TiO2 layers are known to be produced on titanium by the plasma electrolytic oxidation (PEO) process. Such coatings can be considered as potential candidates to use as surface electrode materials in photovoltaic devices, e.g. dye-sensitized solar cells (DSSCs), where the specific surface area of the TiO2 electrode is required to be as large as possible for efficient dye absorption. However as shown in the literature and our previous work [1], the as-formed PEO layer does not provide a large enough specific area and thus the photovoltaic efficiency of the assembled device is low. The aim of this study is therefore to develop a nano-structured TiO2 surface layer based on PEO treated titanium by using alkaline and thermal annealing post-treatment procedures. The specific surface area is expected to be increased due to re-formation of the original PEO layer in NaOH solution and the anatase content to be enhanced due to crystallisation during subsequent annealing. Microstructure of the post-treated TiO2 and the photovoltaic efficiency of the assembled device are examined as a function of alkali concentration, bath temperature, and soaking time.

Experimental results show that, after the alkaline post-treatment, a ’nano-flaky’ morphology was developed over the oxide surface. Higher alkali concentration, bath temperature and soaking time enhanced the roughening of the PEO treated surface and at the same time a thicker reformed layer can be obtained. However, a possibility of crack development in the oxide layer increases, compromising the photovoltaic efficiency. Following the alkaline post-treatment in 1.25 M NaOH solution at 40oC for 12 h, the assembled device had an ultimate photovoltaic efficiency of 0.329% in contrast to that of 0.061% presented by the as-formed PEO TiO2. Further annealing at temperatures above 300oC significantly enhanced the formation of the anatase phase in the oxide layer and a maximum photovoltaic efficiency of 2.194% can be achieved when annealed at 400oC.

[1] P-J Chu, A Yerokhin, A Leyland, A Matthews, J-L He, Through-thickness Microstructural Characterization of the Plasma Electrolytic Oxidized Titanium Oxide Fabricated on Metal Titanium, Abstracts of ICMCTF 2009, paper GP-6, p 99.

3:50 PM H4/C4-12 Depth Profile Analysis of Thin Layers on Conductive or Nonconductive Substrates by Rf GD-OES (Semiconductor, Photovoltaic and PVD/CVD Applications)
Philippe Hunault (HORIBA Jobin Yvon Inc., USA); Célia Tauziède, Patrick Chapon, Agnès Tempez (HORIBA Jobin Yvon, France); Mihai Ganciu (NILPRP, Romania); Philippe Guillot (University JF Champollion, France); Philippe Belenguer (Laplace CNRS, France)
Radio Frequency Glow Discharge-Optical Emission Spectrometry (RF GD-OES) is an established technique capable of Ultra Fast Elemental Depth Profiling of thin films down to < 1 nanometer.

The application of the technique to the characterization of thin layers on conductive substrates or non-conductive substrates such as glasses and ceramics is investigated. Issues related to heat and thermal damage as well as coupling efficiency are shown and solutions to overcome these issues are presented resulting from theoretical and experimental characterizations of the RF GD plasma and its interaction with the material’s surface.

The new RF coupler allows sputtering of up to 5mm thick glasses or ceramics. It provides more than adequate performance for useful analysis as examples from solar cells and coated ceramics will illustrate. Other Semiconductor, Photovoltaic and PVD/CVD applications will be presented.

Time Period ThA Sessions | Abstract Timeline | Topic H Sessions | Time Periods | Topics | ICMCTF2010 Schedule