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指導 老師 :林克默 副教授 學生:陳信誠 學號: m9710246 ...
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Transcript of 指導 老師 :林克默 副教授 學生:陳信誠 學號: m9710246 ...
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太陽能材料與模組製造實驗室
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指導老師:林克默 副教授 學生:陳信誠 學號: m9710246 班級:碩機械一甲
Low-temperature growth of highly crystallized transparent conductive fluorine-doped tin oxide films by intermittent spray pyrolysis deposition
Tatsuo Fukano, Tomoyoshi Motohiro
Solar Energy Materials & Solar Cells 82 (2004) 567–575
Toyota Central Research and Development Laboratories Inc., Nagakute, Aichi 480-1192, Japan
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太陽能材料與模組製造實驗室
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大綱摘要前言實驗結果與討論結論
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摘要 Following the procedure by Sawada et al. (Thin Solid
Films 409 (2002) 46), high-quality SnO2:F films were grown on glass substrates at relatively low temperatures of 325–340℃ by intermittent spray pyrolysis deposition using a perfume atomizer for cosmetics use.
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前言 These techniques require simple apparatuses, are low in
cost but high in throughput, the necessary conditions for commercial production of solar cells.
Sawada et al. succeeded in producing high-quality ITO films by spray pyrolysis at relatively low temperatures. Highly conductive films of ITO, 1.9×10-4Ωcm in resistivity,were fabricated on glass substrates at 350℃ using a ‘perfume atomizer’, available in cosmetics shops.
We will demonstrate that the SnO2:F films thus produced are heatresistant, showing that the various properties change little after a heat treatment.
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太陽能材料與模組製造實驗室
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實驗 The solution for SnO2:F film growth was prepared as
follows. NH4F (50m mol) was dissolved in 50 ml of 2M HCl. This mixture was diluted to 1 l with C2H5OH. Then SnCl2 0.86H2O (0.1 mole) was dissolved into the mixture.
Sprayed the solution in air with the use of a perfume atomizer on Corning #7059 glass substrates (20×30×0.5mm3 in size),cleaned ultrasonically in organic solvents.
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實驗NH4F HCl C2H5OH SnCl2 .
0.86H2O
Spraying
Heating
Measurement and analysis
2 hr. Ultrasonic agitation for 10 min
air
~340℃325–330℃
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結果與討論 X-ray diffraction XPS and EDX UV-VIS-NIR FE-SEM Hall
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XRD
Fig. 1. XRD patterns of as-prepared SnO2:F films of various thicknesses. Standard powder peak intensities derived from the JCPDS file [22] are shown in the bottom diagram as vertical bars for single phase SnO2 rutile.
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Fig. 2. XRD patterns of 420nm thick SnO2:F films on the glass substrate before and after the heattreatment.
450 -60min℃
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XPS and EDX We confirmed the presence of Sn, O, F and Cl in the 420
nm-thick SnO2:F film by XPS. Before the heat treatment, the F/Sn, O/Sn and Cl/Sn atomic ratios on the film surface were approximately 0.0074, 1.75 and 0.0033, respectively. The F/Sn ratio is surprisingly low when compared with the value (=0.5) in the solution. One may suspect that the film surface is depleted of F since the detection depth of the XPS is only 3 nm. However, an EDX investigation, with a 300nm detection depth, supported this low F concentration throughout the film. After the heat treatment, the atomic ratios changed to F/Sn=0.0067, O/Sn=1.66, and Cl/Sn=0.0005. The Cl/Sn ratio was slightly decreased, but the F/Sn and O/Sn ratios were virtually unaffected.
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UV
Fig. 3. Optical transmittance spectrum of 420nm thick SnO2:F film on the glass substrate before and after the heat treatment.
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FE-SEM
Fig. 4. FE-SEM images of (a) the surface morphology and (b) cross-sectional image of SnO2:F film before the heat treatment.
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Hall
Fig. 5. Electrical properties of the SnO2:F films on the substrate for different thickness before heattreatment. ●: resistivity, ■ : carrier density, : Hall mobility.◇
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G. Haacke, J. Appl. Phys. 47 (1976) 4086
Haacke ΦTC=T10 / Rsh ΦTC–Ts
We find ΦTC=0.031 (Ω/sq.)-1 for our 420-nm-thick SnO2:F films using the sheet resistance of 14.0Ω/sq.
The F/Sn value of 0.0074 means that the F-ion density is ~2.0 ×1020 cm-3
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Fig. 6. Figure of merits for SnO2:F films fabricated in this work (●), and the previous works (○) in which SnO2:F films fabricated at relatively low synthesis temperature were obtained by spray pyrolysis depositions [1–5, 8, 9, 11, 12, 14, 15] as a function of synthesis temperature. A numeric symbol at the side of each datum point shows a reference number.
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結論 Even though the substrate temperature is low, as-
deposited films show a high optical transmittance of 92% in the visible range, a low electric resistivity of 5.8×10-4Ωcm and a high Hall mobility of 28 cm2/V s. The F/Sn atomic ratio (0.0074) in the films is low in comparison with the value (0.5) in the sprayed solution.
The carrier density in the film is approximately equal to the F-ion density, suggesting that most of the F-ions effectively function as active dopants.
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They are quite heat resistant, showing little change in transmittance and resistivity during a 450 –60 min ℃heat treatment in the atmosphere. The obtained films break the ΦTC–Ts limit achieved by the previous films.
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Thanks for your attention!