臺灣博碩士論文加值系統

目前市售白光發光二極體(White Light-Emitting Diode, WLED)以藍光晶片加黃色釔鋁石榴石(Y3Al5O12:Ce3+, YAG)螢光粉為主，製備方法簡易且成本低廉，但電致激發光譜圖中缺乏紅光波段，導致元件演色性(Color Rendering Index, CRI)較低(約60-70)，可藉由添加紅色螢光粉或使用多色螢光粉進行改善，讓放射光譜可涵蓋廣的可見光範圍，藉此提高演色性。然而，因螢光粉容易造成光散射現象，會嚴重降低元件效率。而將量子點(Quantum dots, QD)封裝成WLED，因本身為奈米尺寸不會有散射現象，且量子點具有波長可調性及激發範圍廣等優點，使近年來的研究朝向以純量子點為主之WLED。
由於環保意識提高，鎘重金屬對環境及人體皆有害，窄峰含鎘量子點逐漸被取代，而使用發光二極體(Light-Emitting Diode, LED)激發單一寬峰量子點，既無散射且能避免自吸收效應，成為研究趨勢。而CuInS2 (CIS)量子點因本身為缺陷放光，半高寬相較其他量子點寬廣，因此，本研究選用CIS無鎘寬峰量子點進行研究，但由於CIS本身量子效率(Quantum yield, QY)極低(<1%)，半高寬仍不夠寬廣(68 nm)，因此本研究透過摻雜不同價數陽離子(Zn2+, Al3+)，創造缺陷能階使再結合路徑增加，寬化量子點的半高寬，以提高WLED之演色性。
結果顯示二硫化鋅銅銦((ZnCuIn)S2, ZCIS)與二硫化鋅鋁銅銦((ZnAlCuIn)S2, ZACIS) 量子點之半高寬分別增廣至120及238 nm，並透過X射線光電子能譜儀(XPS)及感應耦合電漿光學發射光譜儀(ICP-MS)分析證實了鋅離子(Zn2+)進入核心，大部分取代銦離子(In3+)，並與表面硫離子(S2-)形成硫化鋅(ZnS)，使ZCIS的QY提升至21%。而ZACIS 量子點熱穩定性最好，因鋁離子(Al3+)在表面形成緻密Al2O3保護層，能有效提高穩定性，QY僅下降13%。
將量子點(20 wt%)混合環氧樹脂封裝成WLED，ZCIS與ZACIS量子點因寬廣的半高寬，包含大部分的可見光範圍，可獲得使用單一發光材料封裝，CRI高達85之暖白光元件。

The current commercially available white light-emitting diodes (WLEDs) primarily use blue chips combined with yellow yttrium aluminum garnet (Y3Al5O12:Ce3+, YAG) phosphors. This preparation method is simple and cost-effective, but the lack of red light in the electroluminescence spectrum results in a lower color rendering index (CRI) of around 60-70. This deficiency can be addressed by adding red phosphors or using multi-color phosphors to broaden the emitted spectrum, thereby improving color rendering. However, the use of phosphors often leads to light scattering, significantly reducing the efficiency of the device. In contrast, the encapsulation of quantum dots (QDs) in WLEDs avoids scattering issues due to their nano-sized dimensions. QDs offer advantages such as tunable wavelengths and a broad excitation range, leading recent research to predominantly focus on WLEDs that primarily utilize a single type of QD for efficient light emission.
Due to the heightened environmental awareness and the harmful nature of cadmium heavy metals to both the environment and human health, narrow-band cadmium-containing QDs are gradually being replaced. The emerging trend in research involves utilizing LED excitation of single broad-band QDs, eliminating scattering and avoiding self-absorption effects. Copper indium disulfide (CuInS2, CIS) QDs are chosen for this study due to their defect-induced emission. However, CIS QDs have a relatively low quantum yield (QY) (<1%) and insufficiently broad full width at half maximum (FWHM) of 68 nm. To address these limitations, this research incorporates doping with different valence cations (Zn2+, Al3+) to create defect energy levels, increasing the recombination pathway and broadening the FWHM of QDs. This approach aims to enhance the color rendering properties of WLEDs.
The results indicate that the FWHM of zinc copper indium sulfide ((ZnCuIn)S2, ZCIS) and zinc aluminum copper indium sulfide ((ZnAlCuIn)S2, ZACIS) QDs has broadened to 120 and 238 nm, respectively. Analysis through X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectrometry (ICP-MS) has confirmed the incorporation of zinc ions (Zn2+) into the core, predominantly replacing indium ions (In3+), and forming zinc sulfide (ZnS) with surface sulfur ions (S2-), resulting in an enhanced QY of 21% for ZCIS. Notably, ZACIS QDs exhibit superior thermal stability attributed to the formation of a dense aluminum oxide (Al2O3) protective layer on the surface, effectively enhancing stability with only a 13% decrease in QY.
QDs (20 wt%) were mixed and encapsulated in epoxy resin to create WLEDs. Due to their broad FWHM, ZCIS and ZACIS QDs cover a significant portion of the visible spectrum. This allows the use of a single emissive material in the encapsulation process, resulting in a warm WLED with a high CRI of up to 85.

摘要...i
Abstract...ii
誌謝...iv
目錄...v
表目錄...vii
圖目錄...viii
第一章 前言...1
1.1白光LED...1
1.2量子點...1
第二章 文獻回顧...5
2.1 І-ІІІ-VІ族量子點...5
2.2二硫化銅銦( CuInS2, CIS)量子點...10
2.3 二硫化銅銦(CuInS2)量子點晶體結構...22
2.4 二硫化銅銦(CuInS2)量子點放光機制...26
2.5 I-III-VI族量子點之白光元件...30
2.6研究動機...32
第三章 實驗方法與步驟...33
3.1實驗藥品與材料...33
3.2量子點製備...35
3.2.1二硫化銅銦(CuInS2, CIS)核心量子點...35
3.2.2二硫化銅銦/硫化鋅(CIS/ZnS)量子點...35
3.2.3二硫化鋅銅銦(ZCIS)量子點...35
3.2.4二硫化鋅銅銦/硫化鋅(ZCIS/ZnS)量子點...35
3.2.5二硫化鋅鋁銅銦(ZnAlCuInS2, ZACIS)量子點...36
3.2.6二硫化鋅鋁銅銦/硫化鋅(ZACIS/ZnS)...36
3.2.7量子點純化...36
3.2.8白光發光二極體(WLED)元件製備...36
3.3量子點與發光二極體(LED)之特性分析...37
第四章 結果與討論...47
4.1 CIS量子點之性質分析...47
4.1.1 CIS量子點...47
4.1.2 ZCIS量子點...49
4.1.3 ZACIS量子點...64
4.1.4 CIS、ZCIS、ZACIS量子點...64
4.1.5 CIS/ZnS、ZCIS/ZnS、ZACIS/ZnS量子點...69
4.1.6 CIS、CIS/ZnS、Zn2量子點...75
4.1.7晶粒形貌與粒徑分布...75
4.2 WLED元件之製備及量測...79
4.2.1 Znx-WLED元件...79
4.2.2不同Zn2+-WLED元件之製備...79
4.2.3 CIS/ZnS-、Zn2-及Al0.1-WLED元件...80
第五章 結論...85
參考文獻...86
Extended Abstract...95

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