臺灣博碩士論文加值系統

白光發光二極體(WLED)具有體積小、高效能、低耗能及壽命長等優勢，在固態照明(SSL)應用中為新一代的技術。而半導體量子點(QD)具有波長可調性、高量子效率(QY)及寬廣的激發波段，因此在發光奈米材料中具有較大優勢。而目前市面上較為常見的QD主要為鎘基，但是由於有害物質的限制越來越多，且目前並沒有LED可回收再利用的方法，因此環保是至關重要的課題。而CuInS2(CIS)為I-III-VI2型半導體無鎘量子點，在未來中有望應用於白光LED，符合全球提倡環保的趨勢。但是CIS量子點具有較低的QY，而文獻指出在CIS核心外層包覆ZnS可有效提升量子效率。
本研究透過調控ZnS殼層中[Zn2+] 的濃度，探討其對CIS QD光學性能的影響，藉此改善CIS QD的QY。我們透過熱注射法合成QD，使用來自CuI的Cu++及In(AC)3的In3+作為金屬陽離子，以及1-十二烷硫醇(DDT)的陰離子S2-進行成核和生長核心CuInS2 (CIS)。結果顯示，當反應溫度及時間分別為240 oC及120分鐘時，CIS QDs放射波長及量子效率分別為626 nm及2 %。而利用不同莫耳比的[Zn2+]作為ZnS殼層前驅物進行包覆後，CIS/ZnS QD的放射波長從626 nm藍移至534 nm，而QY最高為107 %，粒徑尺寸為3.2±0.5 nm。
接著將於QD外層包覆二氧化矽進行表面改質，透過調控MPS及 APTES兩種矽前驅物比例提高QD的穩定性。 結果顯示，CIS/ZnS量子點在包覆二氧化矽後放射波長從578紅移至585 nm，而PPL QY從32提升至48 %。後續將QD與環氧樹脂均勻混合後，以藍色LED晶片激發得到白光LED元件，並探討白光元件之特性。結果顯示，CIS/ZnS QDs-LED的CIE色度座標為(0.32, 0.26)、演色性(CRI)為75、發光效率(LE)為103 lm/W、相關色溫(CCT)為6412 K，而在長時間穩定性測試250 h後LE降低至原始的85 %。另一方面，CIS/ZnS@SiO2-LED的CIE色度座標為(0.33, 0.29)、CRI為73、LE為89 lm/W及CCT為6374 K，而在長時間穩定性測試250小時後，LE僅降低至原始的11 %，其性能優於CIS/ZnS QDs-LED。
因此，從以上結果可知，本研究可製備出具有高QY的無鎘量子點，且QD在包覆二氧化矽之後可得到高穩定性及發光效率之白光元件，為未來的光源開發新一代的量子點技術。

White light-emitting diodes (WLEDs) are the most exciting advancement for new generation technologies of solid-state lighting (SSL) industry instead of traditional incandescent light and fluorescent lamps due to their small size but incredibly energy efficient, low consumption energy, and long lifetime. Semiconductor quantum dots (QDs) are outstanding luminescent nanomaterial owing to they exhibit excellent wavelength tunability, high quantum yield (QY), and broad excitation range. The most popular QDs material made by Cd-based semiconductors. However, environmental friendly has an essential point to concern due to the increasing restriction of hazardous substances since now no LED recycle methods are usable. I-III-VI2 type semiconductors QDs-CuInS2 (CIS), are promising new material for WLEDs as they compatible with global trends to regulate toxic materials with no Cd ions containing. However, CIS QDs has been shown the low QY. In this case, many works reported that this problem can be enhanced by overcoating with ZnS shell.
Therefore, in this work we investigate and improving the QY of CIS QDs by studying the effect of concentration of ZnS shell coating on their optical property. Herein, we synthesized QDs by hot injection method using Cu+ from CuI and In3+ from In(AC)3 as cation and anion S2- from 1-dodecanethiol (DDT) for nucleation and growth core CIS. The result shows that the CIS QDs exhibit the wavelength of 626 nm and the QY of 2 % and then overcoating ZnS shell with varying [Zn2+] in different mole ratios, the reaction temperature sets at 240 oC and reacts for 120 mins. CIS/ZnS QDs showed the emission wavelength significantly blue shift from 626 to 534 nm with maximum QY of 107 % and the particles size 3.2 ±0.5 nm.
Furthermore, we modified the preparation method to embedded QDs in silica matrix with directly surface modification for enhanced their stability by varying ratios of silica precursors MPS/APTES. Powder photoluminescence (PPL) analysis result showed that the emission wavelength significantly red shift after coating with silica from 578 nm with QY of 32 % of CIS/ZnS QD to 585 nm with QY 48 % of CIS/ZnS@SiO2 QD. After that, we fabricated QDs to WLED devices by mixed QDs particles with thermal curable epoxy-based AB gel and stack on a blue LED chip to investigate the device performance. The result indicated that CIS/ZnS QDs-LED showed CIE coordinates (0.32, 0.26), color rendering index (CRI)=75, luminous efficacy (LE) =103 lm/W, and correlated color temperature (CCT)= 6412 K with 85 % decreasing of LE after 250 h working time. On the other hand, CIS/ZnS@SiO2-LED has CIE coordinates (0.33, 0.29), CRI=73, LE=89 lm/W, and CCT=6374 K. Moreover, the stability of QDs@SiO2-LED device was excellent and higher than that of bare QDs-LED after working time 250 h by reduced only 11 %.
Thus, from the above results indicated that we can fabricate a high QY of Cd-free QDs successfully and high device stability after silica coating. A high luminous efficacy of device also can be obtained as regards to development of next generation quantum technology for the future lighting source.

English Abstract ……………………………………………………….………………………………………………… i
Chinese Abstract ……………………………………………………….………………………………………………… iii
Acknowledgment ……………………………………………………….……….………………………........................... v
Table of Contents ……………………………………………………….….…………………………….......................... vi
List of Tables ……………………………………………………….…….………………………….......................... vii
List of Figures ……………………………………………………….…….………………………….......................... viii
List of Abbreviations ……………………………………………………………………….............................................……. x
Chapter 1 Introduction ………………………………………………............................................……… 1
1.1 LEDs…………………………………………................................................……………………. 1
1.2 WLEDs………………………………………................................................…………………… 2
Chapter 2 Background and Related Works……………………...…………………................... 6
2.1 Semiconductor quantum dots…………………………………………………………. 6
2.2 QD-WLED……………………………………………………………………………………… 8
2.3 CuInS2/ZnS QDs…………………………………………………………………………….. 15
2.4 CuInS2/ZnS@SiO2 QDs……………………………………………………..................... 21
2.5 Research motivation………………………………………………………………………. 26
Chapter 3 Experimental…………………………………………………………………………………... 30
3.1 Material…………………………………………………………………………………………... 30
3.2 Methodology.………………………………………………………………………………….. 33
3.2.1 Synthesis of CIS/ZnS QD………………………………………………………………. 33
3.2.2 Preparation of the silica-coated QDs……………………………………………… 34
3.2.3 Fabrication of QDs-based whites LEDs…………………………………………. 34
3.2.4 Characterization……………………………………………………………………………… 34
Chapter 4 Results and Discussion…………………………………………………………………... 43
4.1 CIS/ZnSxQDs……….…………………………………............................................................. 43
4.1.1 The effect of Zn2+ concentration on CIS/ZnSxQDs………………………... 43
4.1.2 The morphologies and crystal structure…..……………………………………... 50
4.2 CIS/ZnSx@SiO2,y QDs……………………………………………………………………. 52
4.2.1 The optical properties of CIS/ZnSx@SiO2,y QDs…………........................... 52
4.2.2 The morphologies and crystal structure…..……………………........................... 57
4.3 CIS/ZnSx@SiO2,y QDs LED…………………………………………………............... 62
Chapter 5 Conclusions………………..………………………………….…………………...................... 72
References …………………………………………………….……………………………………...................... 73
Extended abstract …………………………………………………………………………………………..................... 86

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