臺灣博碩士論文加值系統

本文成功地藉由預先合成的晶種進行製備異質結構量子點。其反應機制利用
Ag2S 或是Cu2S 奈米晶體當作晶種，後續加入第二種金屬陽離子在晶種表面進行
沉積或離子交換反應，藉以合成出多種異質結構量子點。
在實驗表現上，因表面活性劑有穩定反應程序、減少表面缺陷特點，我們發
現搭配表面活性劑所合成出之異質結構量子點，其螢光量子產率有不錯的提升。
另一方面也利用Ag2S-CdS 異質結構的實驗原理成功合成出Cu2S-CdS 異質
結構量子點，並討論其反應生成機制。
接著再利用共同成長法順利合成過渡金屬摻雜CdS 量子點。CdS 量子點為
本實驗之主體量子點，並以Ag(OAc)、Cu(OAc)作為摻雜物，藉以調控量子點的
物理性質。於實驗表現中發現，在Cu 及Ag 摻雜時CdS 量子點擁有極易達成之
光學可調性；當Cu 摻雜時，CdS 量子可由黃綠光調控至橘紅光，而在Ag 摻雜
時，CdS 量子點可由黃綠光調控至橘黃光。
在分析鑑定上，我們利用TEM、XRD、EDS、XPS、UV、PL 及ICP 對上
述各種實加以分析與鑑定，並就其光學性質上的變化加以探討。

In this work, we have successfully synthesized the heterostructure quantum dots
(HNS QDs) by the preformed seeded approaches. Cu2S or Ag2S nanocrystals was
utilized as the seed crystals in the synthesis process of HNS QDs, and the secondary
cation ion precursor was introduced into the preformed seed solution, followed by the
cation exchange reaction.
A number of capping agents have demonstrated good surface modification for
the preparation of QDs. For example, capping agents could reduce the surface trap
sites of QDs, avoid QDs’ aggregation and so on. For these insights, we adapted the
various capping agents in the reaction system. The results revealed that a good optical
performance of HNS QDs such as high quantum yields. Additionally, we also utilized
the same formation mechanism to generate Cu2S-CdS HNS QDs and studied the
related reaction mechanism.
Furthermore, we synthesized the cation doped QDs by the common growth
method. In this stage, CdS QDs was employed as the host QDs which could be doped
with Cu (or Ag) cation. The results demonstrated that CdS host QDs did not initially
show good optical tunable, however, Cu (or Ag) doped CdS QDs exhibit red-shift
emission, showing from green (or yellow) to red orange (or orange) color. The
structure and composition of the as-prepared QDs were characterized by the use of
TEM, XRD, EDS, XPS, UV, PL, and ICP.

摘要................................................................................................................................1
Abstract .......................................................................................................................... 3
總目錄............................................................................................................................4
圖目錄............................................................................................................................7
表目錄..........................................................................................................................13
第一章緒論..............................................................................................................14
1.1 前言............................................................................................................... 14
1.2 研究動機....................................................................................................... 15
第二章 理論基礎與文獻回顧..................................................................................16
2.1 奈米材料之基本特性................................................................................... 16
2.1.1 小尺寸效應 (Size Effect) .................................................................. 16
2.1.2 量子尺寸效應 (The Quantum Size Effect) ....................................... 19
2.1.3 表面效應 (Surface Effect) ................................................................. 20
2.1.4 宏觀量子隧道效應(Macroscopic Quantum Tunneling, MQT) ....... 22
2.1.5 奈米材料之能隙與量子侷限效應..................................................... 22
2.1.6 奈米半導體材料光致發光(Photoluminescence)與電子躍遷機制 ... 27
2.2 奈米晶體發展與製備................................................................................... 29
2.2.1 量子點之發展.................................................................................... 29
2.3 摻雜奈米晶體簡介........................................................................................ 34
2.3.1 摻雜量子點的晶體成長方法與機制................................................ 35
2.4 銅原子摻雜於量子點介紹........................................................................... 40
2.4.1 銅摻雜量子點簡介............................................................................ 40
2.4.2 銅摻雜量子點概況............................................................................ 41
2.5 鋅原子摻雜於量子點介紹........................................................................... 45
2.5.1 鋅摻雜量子點簡介............................................................................ 45
2.5.2 鋅摻雜合金結構量子點概況............................................................ 45
2.6 銀原子摻雜於量子點介紹........................................................................... 49
2.6.1 銀摻雜量子點簡介............................................................................ 49
2.6.2 銀摻雜量子點概況............................................................................ 50
2.7 異質結構奈米晶體....................................................................................... 55
2.7.1 異質結構奈米晶體介紹.................................................................... 55
2.7.2 異質結構奈米晶體生長機制............................................................ 55
2.7.3 異質結構奈米晶體合成方法............................................................ 66
第三章 實驗儀器與方法..........................................................................................70
3.1 實驗架構....................................................................................................... 70
3.2 實驗藥品與儀器........................................................................................... 72
6
3.2.1 實驗藥品............................................................................................ 72
3.2.2 實驗儀器............................................................................................ 73
3.3 實驗步驟....................................................................................................... 74
3.3.1 CdS 量子點合成 ................................................................................. 74
3.3.2 Cu 摻雜於CdS 量子點合成 .............................................................. 75
3.3.3 Ag 摻雜於CdS 量子點合成 .............................................................. 75
3.3.4 Ag2S 量子點合成 ............................................................................... 76
3.3.5 Ag2S-CdS 量子點合成 ....................................................................... 76
3.3.6 Cu2S 量子點合成 ............................................................................... 77
3.3.7 Cu2S-CdS 量子點合成 ....................................................................... 77
3.4 樣品分析....................................................................................................... 78
第四章 實驗結果與討論..........................................................................................91
4.1.1 Ag2S-CdS 異質結量子點合成與光學特性的調控 ........................... 91
4.1.2 Cu2S-CdS 異質結量子點的合成 ..................................................... 109
4.2.1 CdS 量子點合成合成介紹 ............................................................... 113
4.2.2 Cu 摻雜CdS 量子點合成合成介紹 ................................................ 115
4.2.3 Ag 摻雜CdS 量子點合成合成介紹 ................................................ 122
第五章 結論與未來展望........................................................................................130
第六章參考文獻....................................................................................................131
6.1 摻雜量子點參考文獻................................................................................. 141
6.2 異質結構量子點參考文獻......................................................................... 144

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