三明治結構透明導電層於可撓式銅銦鎵硒太陽能電池的製備及分析

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研究生：	蔡文錡 Tsai , Wen Chi
論文名稱：	三明治結構透明導電層於可撓式銅銦鎵硒太陽能電池的製備及分析 Fabrication of Sandwich Films as Alternative Transparent Conducting Layer on Flexible CIGS Solar Cells
指導教授：	闕郁倫 Chueh , Yu Lun 沈昌宏 Shen , Chang Hong
口試委員:	謝東坡呂宗昕闕郁倫沈昌宏 Hsieh , Tung Po Lu , Chung Hsin
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2015
畢業學年度：	103
語文別：	英文
論文頁數：	66
中文關鍵詞：	太陽能電池、銅銦鎵硒、透明導電層、銀奈米線
外文關鍵詞：	solar cell, CIGS, transparent conducting layer, silver nanowires
相關次數：	點閱：2 下載：0
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三明治結構用於太陽能電池上是近來發展的趨勢，以往的研究即有使用過摻鋁氧化鋅(Ag doped ZnO, AZO)當作透明導電層，但AZO本身電阻率並不佳，以致於目前市面上仍以ITO為大宗，所以漸漸地發展出三明治結構，起先是於兩層透明導電層中夾入金屬層以幫助導電，以銅為例：其在16 nm以上電阻率可降至1.6×10-3 Ω-cm，18 nm以上更可降至5.0×10-4 Ω-cm以下，但其最高穿透率卻僅在65 %左右(波長600 nm處)，這樣的表現是不符合太陽能電池的期待的，如果以銀作為金屬層的話，雖然電阻率更低，但在低厚度的情況下會有銀聚集的現象，這使得我們所要的透明導電層表面不連續，提高電阻進而影響其電流表現，另外，AZO的可撓性是較ITO差的，其電阻上升的狀況隨著彎曲次數愈多愈嚴重。
本論文以導入銀奈米線於低溫透明導電層製程，保持奈米線之連續性，亦可達到高穿透率與低電阻之目的，可以加入金屬奈米線後，能夠有效在膜之間形成金屬網絡，在起始彎曲時或有介面及表面不平整的問題，但當彎曲次數超過特定次數後，奈米線即扮演有效的介面連結處以確保其導電特性；在選定特定奈米線參數後以達到高穿透率 (80 %) 及足夠低的片電阻 (20 Ω/sq.)。加入上層AZO情況下的透明導電層其表面粗糙度可降低，另外，也利用摻鋁氧化鋅/銀金屬奈米線/摻鋁氧化鋅三明治結構透明導電層於可撓式銅銦鎵硒太陽能電池之製備，開發出簡易及迅捷的軟式CIGS太陽能電池，在原本玻璃基板上有接近10 %的效率，可在軟性基板上換得至少6 % 以上的表現。此方法於未來能源及行動裝置應用上必有十分龐大之潛力及前景。

Due to an impending energy shortage, renewable and clean energy should be considered as a next generation energy resource. CIGS is the best thin film solar cell technology among the second generation solar cells owing to its various outstanding characteristics, such as highest absorption coefficient, ease of integration with Si-based technology, and the highest efficiency in thin film solar cell form. As a result, it has already attracted tremendous attention in academic and industrial fields. To date, the highest efficiency of ~21.7 % has been demonstrated by ZSW in Germany. But there is still little research toward CIGS flexible devices for applications on specific building shapes or curve designs on mobile devices.

In stacked structures used in solar cells AZO has been used as transparent conducting oxide (TCO) before, but its intrinsic resistivity is high so industrial applications prefer to use ITO as alternative. This inspired the development of sandwich structures. Initially, metal layers are embedded between TCOs to enhance conductivity. For example, Cu film over 16 nm can reach 1.6×10-3 Ω-cm or even below 5.0×10-4 Ω-cm when over 18 nm. But the maximum transmittance is just around 65 % (at wavelength of 600 nm) which isn’t good for solar cell applications. In the case of Ag as a metal layer, it has lower resistivity but there’s aggregation when the thickness is too thin that makes the surface of the film discontinuous and leads to higher resistance and worse current. This thesis focuses on a low temperature TCO process using Ag NWs embedded to maintain their optical transparency and electrical conductivity.

In our research, flexibility of AZO is worse than ITO and that the resistance increases with the number of bending cycles. We can see from in SEM images that AZO has a wider crack seam and line-shaped structure after bending. It’s expected that after Ag NWs are embedded, they can form metal networks between films effectively. There might be interface or surface roughness issues in the beginning of bending but when it reaches certain bending cycles, nanowires can act as effective interface connections to ensure its conductive characteristics are maintained. Finally, we fix the parameters of the Ag NWs with using a figure of merit (FOM) that can be applied on devices. SEM images show the great qualities of Ag NWs clad with AZO continuously. We observe better roughness in AZO/Ag NWs/AZO than for AZO/Ag NWs from AFM measurements. IV plot shows CIGS with sandwich structure TCO has similar performance with one with ITO due to its lower series resistance. Cell with single layer AZO shows lower efficiency than single layer ITO.

We have already developed a simple and fast production method for flexible CIGS solar cells improving efficiency from 4.4 % to 6 % CIGS solar cells. It’s believed such an approach can further improve future performance and developments for energy and mobile applications based on chalcopyrite photovoltaics.

摘要    I
Abstract (English)    II
Acknowledgement (Chinese)    IV
Contents    V
Figure Caption    VII
Table Caption    IX
Chapter 1    Introduction    1
1    Background    1
2    Basic principle and characteristic of solar cell    3
3    CIGS solar cell introduction    8
3.1    CIGS introduction and development potential    8
3.2    CIGS device structure    9
4    Transparent Conducting Oxide Development    14
4.1    ITO Demands    14
4.2    AZO technology development and application    15
4.3    Silver Nanowires Characteristics and Applications    18
Chapter 2    Experiment and Analysis Instrument    20
1    Fabrication Instrument    20
1.1    Ultrasonic Cleaner    20
1.2    In-line Sputter System    21
1.3    Large Selenization Furnace    21
1.4    Chemical Bath Equipment    22
2    Analysis Instrument    24
2.1    4-point Probe    24
2.2    UV-Visible spectrometer    25
2.3    Hall Effect Measurement    25
2.4    Scanning Election microscope (SEM)    27
2.5    Energy Dispersive Spectrometers (EDS)    27
2.6    X-Ray Diffraction (XRD)    28
2.7    Atomic Force Microscope (AFM)    29
2.8    Solar Cell Simulator System    30
2.9    External Quantum Efficiecy (EQE)    33
Chapter 3    Experimental    37
1    Silver nanowires synthesis and coating    37
1.1    Synthesis of silver nanowires    37
1.2    Fabrication of sandwich films, pure AZO and Ag NWs    37
2    Flexible CIGS solar cell fabrication    39
2.1    Stainless steel cleaning    39
2.2    TaN blocking layer deposition    40
2.3    Mo back electrode deposition    40
2.4    CuInGa precursor sputtering    41
2.5    Post-selenization process    41
2.6    CdS buffer layer deposition    43
2.7    ZnO/AZO window layer and Al top electrode sputtering    44
Chapter 4    Results and Discussion    46
1    Optimization of ITO and AZO Films    46
1.1    Indium Tin Oxide (ITO)    47
1.2    Aluminum Doped Zinc Oxide (2wt %Al:ZnO)    49
2    Discussion and Analysis of Sandwich Structures    51
2.1    Density of Ag NWs    51
2.2    Roughness of Sandwich Structures    55
2.3    Electrical Measurement of CIGS With Sandwich Films    57
2.4    Flexibility of Transparent Conducting Layers    59
2.5    Cell Performance Decay after Bending    60
Chapter 5    Conclusion    64
1    Conclusion    64
Reference    65

                                

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