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姓名 賴建融(Jian-rung Lai) 查詢紙本館藏 畢業系所 化學工程與材料工程學系 論文名稱 ZnS:Mn2+量子點合成與水性分散無 相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 本實驗的目的在開發一種高產量的水溶性ZnS:Mn2+量子點製程。我們將高濃
度的氯化鋅與硫化鈉水溶液逐滴加入當作緩衝溶液的乙二醇中，並控制反應時的
pH 值，會得到白色不透明的硫化鋅。將沉澱物用去離子水清洗後，離心取出沉
澱物，進行XRD 作晶體鑑定，可以確定產物為硫化鋅的閃鋅礦(zinc-blend)結構。
從結晶峰的半高寬估計其晶粒大小在2~4nm 之間。我們也發現在酸性中合下的
產物，粒子粒徑分佈較窄且小。
將上述清洗過之硫化鋅產物，再利用MPA 於水溶劑中進行改質，可得到
ZnS:Mn2+@MPA 水溶性量子點。此一量子點可分散在pH=6~11 的水中呈現透明狀。
由UV-abs 的起始吸收波長可計算出結晶大小在4~7nm 之間。而TEM 觀察的結果
也顯示出單顆結晶大小在5~7nm。
我們也嘗試了在不同的鋅硫比例下進行反應，發現在硫原子過量的情況下，
結晶會變大且會降低420nm 的藍光放射。另外，也試著將MPA 在合成的過程中加
入。使MPA 不僅當做改質劑，也當作保護劑使用。在鹼性合成(pH>10.8)下，MPA
的硫醇基團會解離，而與鋅有較強鍵結能力。但添加有MPA 並且在鹼性下進行反
應者，硫化鋅產物之結晶性會大幅降低。同樣先添加MPA 而在酸性下合成者，XRD
繞射強度較高，且UV-abs 也有相當明顯的吸收峰。從起始吸收波長計算出的結
晶大小為3.7nm。所以整體而言，應該在酸性條件下進行硫化鋅沉澱才可以獲得
較小及較整齊之結晶。
摘要(英) The purpose of this research is to develop a low-cost, low environmental impact,
and high yield of ZnS: Mn2 + QDs process. ZnS: Mn2 + QD were successfully prepared
by neutralizing aqueous solution of zinc chloride and sodium sulfide under controlled
the pH value. Using XRD to identify the crystal shows that the product was ZnS
sphalerite (zinc-blend) structure, whose domain size is only 2~3nm calculated from
the power XRD peak width.
ZnS: Mn2 + QD was washed by deionized water, centrifuged out the sediment,
and modified by MPA aqueous. The obtained ZnS: Mn2 +@ MPA QDs can be
dispersed in water. The transparent dispersed solution crystal size also calculated by
on-set of the UV-abs absorption, it shows that crystal size was between 4 ~ 7nm.
TEM observation also showed that the size of a single crystal in 5 ~ 7nm.
We also tried to add different ratio of Zn/S. We found that when sulfur atoms
were excess, it will cause crystal size became larger and reduces the 420nm blue light
radiation. We not only use the MPA as a modifier, but also try to add it as a protective
agent during synthesis process.
Although the pH value of synthesis under the alkaline (pH> 10.8), MPA will
dissociate its thiol groups and enhance its bonding ability. However, we found that
will significantly reduce the crystallization of zinc sulfide. But under acid synthesis,
XRD showed that the larger diffraction intensity. UV-abs also had quite obvious
absorption peak, calculated by on-set of the UV-abs absorption, crystal size was
3.7nm.
關鍵字(中) ★ 硫化鋅
★ 量子點
★ 水性分散關鍵字(英) ★ ZnS
★ QDs
★ water-soluble論文目次 摘要...............................................................................................................................I
ABSTRACT.................................................................................................................. II
目錄.............................................................................................................................III
圖目錄..........................................................................................................................V
表目錄....................................................................................................................... VII
第一章 緒論.................................................................................................................1
1.1 前言....................................................................................................................1
1-1.1 硫化鋅材料簡介..........................................................................................1
1-1.2 奈米粒子與量子點......................................................................................3
1-1.3 量子點之應用..............................................................................................4
1-2 文獻回顧.............................................................................................................5
1-2.1 量子點的合成..............................................................................................5
1-2.2 量子點發展史..............................................................................................6
1-2.3 硫化鋅量子點..............................................................................................7
1-2.4 親水性量子點..............................................................................................9
1.3 研究目的............................................................................................................12
第二章 硫化鋅製備與改質.......................................................................................14
2-1 硫化鋅製備前言...............................................................................................14
2-2 硫化鋅製備.......................................................................................................15
2.3 硫化鋅表面改質...............................................................................................17
2.4 直接在合成過程中加入MPA 的嘗試...............................................................19
2.5 實驗藥品...........................................................................................................20
2-6 儀器分析...........................................................................................................21
第三章 結果與討論...................................................................................................24
IV
3-1 合成硫化鋅條件之選擇...................................................................................24
3-1.1 緩衝液、加熱時間及清洗方式的選擇....................................................24
3-1.2 反應pH 值的選擇.....................................................................................28
3-1.3MPA 改質方法的比較................................................................................32
3-1.4 鋅硫比的影響...........................................................................................46
3.2 直接在合成過程中加入MPA 的嘗試............................................................48
第四章 結論與建議...................................................................................................51
Reference……………………………………………………………………...……...53
附錄ㄧ 實驗步驟整理...............................................................................................57
不同的PH 下進行中和(水、乙二醇)....................................................................57
使用乙二醇當作緩衝溶液......................................................................................57
中和液改質MPA(酸性改質)...................................................................................59
中和液水洗產物改質MPA(酸性改質)...................................................................59
中和液水洗產物改質MPA(鹼性改質)...................................................................59
鋅硫添加比例..........................................................................................................61
將MPA 放入緩衝液中使用......................................................................................61
將MPA 放入鋅源中使用..........................................................................................62
參考ZHUANG 的做法13 ..........................................................................................62
附錄二 實驗使用之藥品...........................................................................................64
附錄三 實驗使用之分析儀器...................................................................................65
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