高壓輔助熱退火製程改善全無機鈣鈦礦太陽能電池之研究

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林啟玄(CI-SYUAN LIN) 查詢紙本館藏

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機械工程學系

論文名稱

高壓輔助熱退火製程改善全無機鈣鈦礦太陽能電池之研究
(The Study of Pressure-Assisted Annealing Process to Enhance All Inorganic Perovskite Solar Cell)

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摘要(中)

新世代鈣鈦礦太陽能電池在近年發展迅速，有機-無機鈣鈦礦太陽能電池的效率已
經來到了 25.7%，步步進逼傳統的矽基太陽能電池的光轉換效率，但是有機陽離子的
存在使得它對水氧的敏感性很高，容易在長時間的使用下發生降解，是有機-無機鈣鈦
礦太陽能電池的致命缺點，令它難以應用在商業用途，所以越來越多的科學家轉而對
相對穩定的全無機系列的鈣鈦礦太陽能電池進行研究，在這之中又屬 CsPbBr3 材料具
有最佳的穩定性。
現今對於 CsPbBr3太陽能電池的研究仍是以溶液法為大宗，雖然其成本低廉，但
無法兼顧薄膜均勻性和進行大面積的製作，且對於再現性的掌控也不佳，不利於產品
的商業化進展。所以兼顧製程穩定性與大面積製作的熱蒸鍍法便展現其優勢，其中單
源熱蒸鍍法製程簡單，不需調控太過繁瑣的參數，且對設備要求較低，也可製備出高
品質的鈣鈦礦薄膜。
在本研究，以先前實驗室研究單源熱蒸鍍鈣鈦礦太陽能電池元件結構為基礎，利
用 SEM、UV-vis、XRD 等儀器分析進行薄膜成分的優化，再探討厚度對電流密度的影
響，並以壓力輔助的方式進行熱退火製程以及調整退火時間，來提升薄膜品質與增加
晶粒尺寸，成功使電池元件的 Jsc 大幅增加﹐最終在 FTO/c-TiO2/m-TiO2/CsPbBr3/C 的
元件結構之下獲得了: PCE=10.80%、Voc=1.49V、Jsc=9.55mA/cm2、FF=75.83%的成
果，並在存放 30 天後仍具備原始效率的 87%，並在電極面積放大了四倍的元件上具有
原先最佳效率元件的 85%，展現出色的耐候性與薄膜品質。

摘要(英)

The new generation of perovskite solar cells has been developed rapidly in recent years.
The efficiency of organic-inorganic perovskite solar cells has reached 25.7%, which is close to
traditional silicon-based solar cells. However, the organic cations makes it highly sensitive to
water and oxygen, and it is easy to degrade under long-term using. It is the disadvantage of
organic-inorganic perovskite solar cells, making it difficult to apply in commercial applications.
Therefore, more and more scientists turn to research on relatively stable all-inorganic series of
perovskite solar cells. Among them, CsPbBr3 material has the best stability.
At present, the research on CsPbBr3 solar cells is still based on the solution process.
Although its cost is low, it cannot take into account the uniformity of the film and the production
of a large area, and the control of reproducibility is also poor, which is not conducive to the
commercialization of the product. Therefore, the vacuum deposition process shows its
advantages. Among them, the single-source vacuum deposition has a simple process, does not
need to master too complicated parameters, and requires less equipment. High-quality
perovskite films can also be prepared.
In this study, we build on previous studies on the structure of single-source vacuum
deposition perovskite solar cell device. Using SEM, UV-vis, XRD and other equipment analysis
to optimize the composition of the film, and then discuss the influence of thickness on the
current density. And then we use pressure-assisted annealing process to improve the film quality
and increase grain size. Successfully increased the Jsc of the device. Finally, we obtained
PCE=10.80%, Voc=1.49V, Jsc=9.55mA/cm2
, FF=75.83% under the structure of FTO/cTiO2/m-TiO2/CsPbBr3/C.
After 30 days of storage, it still has 87% of the original efficiency. And has 85% of the bestefficiency device with four times the electrode area. Shows great environment resistance and
film quality

關鍵字(中)

★ 鈣鈦礦
★ 太陽能電池
★ 高壓輔助熱退火

關鍵字(英)

★ CsPbBr3
★ Solar Cell
★ Pressure-Assisted Annealing Process

論文目次

目錄
摘要.............................................................................................................................................i
Abstract.......................................................................................................................................ii
誌謝...........................................................................................................................................iii
目錄...........................................................................................................................................iv
圖目錄......................................................................................................................................vii
表目錄.......................................................................................................................................xi
第 1 章緒論............................................................................................................................1
1-1 前言.............................................................................................................................1
1-2 太陽能電池分類介紹.................................................................................................2
1-2-1 矽太陽能電池 .................................................................................................2
1-2-2 化合物太陽能電池 .........................................................................................3
1-2-3 有機太陽能電池 .............................................................................................4
1-3 鈣鈦礦太陽能電池.....................................................................................................4
1-3-1 有機-無機鈣鈦礦太陽能電池發展................................................................5
1-3-2 無機鈣鈦礦太陽能電池發展 .........................................................................8
1-4 鈣鈦礦太陽能製程方法...........................................................................................10
1-4-1 溶液法 ...........................................................................................................10
1-4-2 熱蒸鍍法 .......................................................................................................12
1-5 無機鈣鈦礦太陽能電池改善...................................................................................18
1-5-1 電子傳輸層之改善 .......................................................................................18
1-5-2 熱退火製程之改善 .......................................................................................19
1-5-3 摻雜離子改善薄膜品質 ...............................................................................22
1-5-4 電洞傳輸層匹配改善 ...................................................................................23
1-5-5 電極改善 .......................................................................................................27
v
1-6 研究動機...................................................................................................................31
第 2 章實驗方法..................................................................................................................32
2-1 實驗材料與儀器.......................................................................................................32
2-1-1 實驗材料 .......................................................................................................32
2-1-2 實驗儀器 .......................................................................................................32
2-2 實驗步驟...................................................................................................................34
2-2-1 FTO 導電玻璃清洗.......................................................................................34
2-2-2 二氧化鈦(TiO2)緻密層的合成與塗佈 .........................................................34
2-2-3 二氧化鈦(TiO2)介孔層的合成與塗佈 .........................................................34
2-2-4 CsPbBr3 蒸鍍..................................................................................................34
2-2-5 薄膜熱處理 ...................................................................................................35
2-2-6 碳膠刮塗 .......................................................................................................35
2-3 實驗儀器分析介紹...................................................................................................36
2-3-1 XRD 量測原理...............................................................................................36
2-3-2 UV-vis 量測原理............................................................................................36
2-3-3 SEM 量測原理 ...............................................................................................36
2-3-4 UPS 量測原理................................................................................................36
2-3-5 太陽光能模擬器量測原理 ...........................................................................37
第 3 章結果與討論..............................................................................................................38
3-1 熱蒸鍍 CsPbBr3 薄膜 ...............................................................................................38
3-1-1 CsPbBr3 薄膜分段分析..................................................................................38
3-2 CsPbBr3 電池元件製作 .............................................................................................40
3-2-1 添加 CsBr ......................................................................................................40
3-2-2 電池主動層最佳厚度 ...................................................................................42
3-3 提升電流密度...........................................................................................................44
3-3-1 高溫高壓製程改善薄膜品質 .......................................................................44
vi
3-3-2 UPS 分析........................................................................................................46
3-3-3 高溫高壓製程元件應用 ...............................................................................48
3-3-4 不同壓力下退火對 CsPbBr3 太陽能電池的影響........................................49
3-3-5 退火時間增長 ...............................................................................................53
3-4 最佳參數電池分析...................................................................................................56
3-4-1 UV-vis 與 XRD 分析......................................................................................58
3-4-2 IPCE 測試.......................................................................................................60
3-4-3 耐候性測試 ...................................................................................................61
3-4-4 元件面積增加 ...............................................................................................61
第 4 章結論..........................................................................................................................63
參考文獻..................................................................................................................................64

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指導教授

詹佳樺(Chia-Hua Chan)

審核日期

2022-8-23

推文