TWI619856B - 高量子產率之ＩｎＰ／ＺｎＳ奈米結晶的連續合成 - Google Patents
高量子產率之ＩｎＰ／ＺｎＳ奈米結晶的連續合成 Download PDFInfo
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- TWI619856B TWI619856B TW101144901A TW101144901A TWI619856B TW I619856 B TWI619856 B TW I619856B TW 101144901 A TW101144901 A TW 101144901A TW 101144901 A TW101144901 A TW 101144901A TW I619856 B TWI619856 B TW I619856B
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- Prior art keywords
- inp
- mixing chamber
- indium
- zns
- shell
- Prior art date
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- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/701—Chalcogenides
- C09K11/703—Chalcogenides with zinc or cadmium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
- C30B29/48—AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/68—Crystals with laminate structure, e.g. "superlattices"
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Abstract
本發明係關於一種連續流合成方法，其用以在包含連接至一反應室之至少一混合室的微反應系統中進行高品質磷化銦/硫化鋅之核/殼半導電奈米結晶尤其是量子點(QD)之製備。
Description
本發明係關於用以製備高品質磷化銦/硫化鋅核/殼半導電奈米結晶尤其是量子點(QD)的連續合成方法。
近20年來由於膠狀半導體奈米結晶的獨特化學、物理、電子特性以及此些特性在生物標籤、LED、雷射、光伏技術與感測器等領域中的許多潛在技術應用，使得膠狀半導體奈米結晶倍受矚目。在所有的II-VI族與III-V族半導體中，InP可能是能提供匹配性或甚至提供比CdSe系系統更廣之發光範圍但卻免除了本質毒性(因為InP既不包含A類元素(Cd,Hg,Pb)也不包含B類元素(例如As,Se))的唯一系統(Xie et al.J.AM.CHEM.SOC.,2007,129,15432；Reiss et al.J.AM.CHEM.SOC.,2008,130,11588)。然而，高品質InP的合成仍有許多挑戰。已存在的問題尤其包含：低光致發光量子產率、較差的尺寸分佈、敏感的前驅物以及穩定性的控制不良。相較於CdSe系OD，InP的合成程序亦較精緻，一部分是因為膦前驅物係高度敏感(Nann et al.J.AM.CHEM.SOC.,2006,128,1054；Nann et al.J.Mater.Chem.,2008,18,2653)。
利用基於微反應技術的連續合成設備；吾人追求此些問題的解決
方案。近年來，由於微反應技術所提供的下列優點，使得微反應技術已躍升為用以合成高品質奈米粒子的替代方案：反應參數如溫度輪廓的精準控制、微型化的反應體積、快速的反應速度以及其平行操作的可能性，使其成為各種奈米粒子之規模可縮放的製造方法(Blackmond et al.Angew.Chem.Int.Ed.2010,49,2478；WO2008061632,WO2002053810)。此外，微管道中的較佳熱傳導以及混合效率可在極短的時間內將前驅物反應物的濃度提升至成核臨界值以上並藉由提高溫度而促進強烈成核，在為了達成較佳粒子尺寸分佈的加熱階段期間提供分離成核與成長相的可靠策略。
雖然WO2008061632與WO2002053810提到，製備InP奈米粒子應可應用利用微反應技術來連續地製備二元半導電奈米粒子的技術，但此些方法只用Cd系之核來作為實例，當利用此些方法於包含InP之核之奈米粒子的製備時，仍需修改此些方法來解決特定的問題。
因此需要InP奈米結晶的製備方法，雖然使用敏感的前驅物，但其能導致高光致發光量子產率、較窄的尺寸分佈以及較佳的穩定性。
利用保護性之ZnS殼來穩定InP奈米粒子已知能增進環境穩定性、化學與光化學穩定性、減少自消光特性等。尤其Peng等人[J.Am.Chem.Soc.,2007,12,15432-15433]揭露了InP/ZnS核殼奈米粒子的「單鍋」製備，其中一反應所能達到的尺寸範圍可輕易地藉由下列者來加以調整：胺類的濃度、脂肪酸尤其是用以溶解In(Ac)3前驅物之肉豆蔻酸及反應溫度(低於200℃)。調整尺寸的最方便方法為改變脂肪酸的濃度。
已知半導電奈米結晶的螢光特性取決於表面缺陷的數量與品質。已知覆蓋表面之配位體對於達成高量子產率奈米結晶是極關鍵的。富金屬的表面亦有利於表面缺陷的良好飽和。II-VI族半導體奈米結晶
的典型覆蓋配位體如三辛基膦氧化物(TOPO)與三辛基膦(TOP)對於銦比例如對於鎘具有更強的配位強度。已發現，在此些配位體的存在下InP奈米團簇會在高於200ºC的溫度下快速溶解，導致不穩定的初始核、更多本質缺陷與較慢的結晶過程。Nann等人教示，只有將弱或非配位的配位體添加至核反應混合物能夠避免強配位體的負面影響，且由於缺乏表面配位體所以需要過量的銦前驅物來避免奈米結晶團聚。研究顯示，過量的銦前驅物不僅僅能支持會快成核且能夠提供具有較少表面缺陷的富銦表面[Nann et al.J.Mater.Chem.,2008,18,2653]。Nann等人亦教示，由於相較於合成中所涉及之其他試劑，羧酸鋅具有本質上的低反應性，因此添加穩定的羧酸鋅至反應混合物中不會產生晶格摻雜但鋅會藉由耦合至膦懸鍵而鈍化InP表面，因此大幅增加InP的光致發光量子產率。又，研究顯示添加羧酸鋅能穩定QD的表面，且隨著初始羧酸鋅的濃度增加而光致發光之發光波長轉變為藍色所示，添加羧酸鋅能降低關鍵核的尺寸[Nann et al.J.Mater.Chem.,2008,18,2653]。通常使用三(三甲基矽)膦(TTSP)作為製備InP核的P前驅物[Nann et al.J.Mater.Chem.,2008,18,2653]。然而，TTSP對於氧化反應敏感且在使用之前以及整個反應期間需要在惰性環境下進行強烈除氣，故在批次製造期間需小心處理且成本昂貴。
需要一種InP/ZnS核/殼奈米結晶的製備方法，雖然使用敏感的前驅物，但其能導致高光致發光量子產率、較窄的尺寸分佈以及較佳的穩定性，且其製造成本較低。
在包含連接至一反應室之至少一混合室的微反應系統中進行InP/ZnS奈米粒子之製備的連續流方法可解決問題，此方法包含下列步驟：
(1)在無水與無氧的環境下藉著混合銦鹽、作為弱或非配位之配位體的脂肪族質子性烷基胺與脂肪族烷基酸及羧酸鋅與惰性溶劑，選擇性地將其加熱上至50-200ºC較佳地至80-150℃以得到澄清溶液，而製備銦的前驅物溶液，(2)在無水與無氧的環境下於惰性溶劑中製備包含三(三甲基矽)膦之膦的前驅物溶液，(3)在混合室中較佳地以0.1 ml/min至10 ml/min的流量將過量的該銦的前驅物溶液注射至該膦前驅物溶液中以獲得反應混合物，其中該混合室為磁性微混合室，(4)在160至320℃較佳地200至280℃的溫度下加熱該反應混合物並使其較佳地前饋至反應室中直到獲得InP之核懸浮液，(5)將該核懸浮液前饋至一混合室中並將包含Zn源與S源的殼前驅物溶液注射至該核懸浮液，較佳地將覆蓋配位體加入該混合室中，(6)在160至320ºC較佳地200至280℃的溫度下前饋並加熱該懸浮液以在該反應室內製備殼，(7)冷卻之。
在一較佳的實施例中，在圖3中所示的微反應系統中進行本發明的方法。
發現前驅物的高效率混合是有利的且可藉由在較佳地自30-70 mm3至10-1000 mm3體積之微型聚四氟乙烯(PTFE)混合室中所產生的紊流來達成，後續將其稱為混合設備。
通常QD的成核與成長係於作為反應室的聚四氟乙烯(PTFE)毛細管中於20-320ºC較佳地120-280℃的溫度下進行，此毛細管係連接至具有0.1-2.0 mm較佳地0.2-1.0 mm之內直徑與0.5至20 m長度的
混合室。將流量較佳地調整為0.1 ml/min至10 ml/min。
發現所用的微反應系統尤其是磁性微混合室係適合用來製備InP/Zns奈米結晶，因為其能提供高效率的混合且容易製造與擴產。
加熱油提供了簡易的加熱源以達到不同反應階段所期望的溫度。或者可使用微加熱設備。
無氧的環境通常是氮或氬。
較佳的溶劑為在室溫下為非配位或弱配位的液體較佳地為非極性或低極性者。根據極性量表，以水的極性指數為9為基準，極性指數的變化範圍介於4至0較佳地介於1.5至0最較佳地介於0.8至0(V.J.Barwick,Trends in Analytical Chemistry,vol.16,no.6,1997,p.293ff,Table 5)。有機溶液在反應溫度下應穩定且儘量不退化。有機化合物的較佳沸點應高於200℃更較佳地高於240℃。尤其適合的溶劑為十八烯(ODE)或肉豆蔻酸甲酯、癸二酸二丁酯、1-十六烯、1-二十烯、石蠟、二苯基醚、苄醚、二辛基醚、鯊烷、三辛基胺、熱傳導流體或其任何溶劑混合物。最較佳的是ODE。
銦鹽通常是氯化銦(III)、乙酸銦(III)、溴化銦(III)、硝酸銦(III)、硫酸銦(III)、高氯酸銦(III)或氟化銦(III)。最較佳的是氯化銦(III)與乙酸銦(III)。
使用脂肪族質子性烷基胺與脂肪族烷基酸的混合物作為弱配位或非配位配位體，以在銦的前驅物溶液中形成穩定的銦-配位體錯合物。適合的脂肪羧酸例如是硬脂酸、油酸、肉豆蔻酸。脂肪族烷基胺通常為十六烷基胺、二辛基胺或油胺。
用以鈍化InP表面的適合羧酸鋅為十一烯酸鋅與硬脂酸鋅。
最較佳的是油酸與油胺與硬脂酸鋅的混合物。由於已知配位體的濃度會對具有獨特吸收峰之奈米結晶的精確反應控制與製備有強烈的
影響，因此仔細地選擇配位體(脂肪族胺與脂肪族酸)的量並使胺/酸比約為4.0-1.0以避免銦的氧化或還原並形成可控制之成核與結晶成長程序用的穩定銦錯合物[Peng,X.G.et al.Nano Lett.2002,2,1027-1030]。
藉著改變羧酸、羧酸鋅及/或烷基胺的濃度，能調整InP的粒子尺寸且對應的發光可自藍改變為紅。在一較佳的實施例中，藉著改變羧酸鋅的濃度來控制InP QD的尺寸。
一般而言，將銦的前驅物溶液添加至三(三甲基矽)膦(TTSP)與ODE的混合物中，然後加熱上至150-300ºC較佳地至200-260℃。
所得產物為外覆有Zn的InP核懸浮液，其中獲得平均直徑為2至10 nm的InP量子點(QD)。
在另一步驟中，將ZnS殼沈積於外覆有Zn的InP核上。一般而言，在無水與無氧的環境下製備包含分離之Zn前驅物與S-前驅物(複數源)或者包含同時提供Zn與S之單一源前驅物的殼前驅物溶液，然後在反應溫度下或先冷卻之然後將其直接注射至粗製的核粒子懸浮液中。注射通常在第二混合室較佳地為磁性微混合室中進行。
二乙基二硫胺基甲酸鋅(ZDC)為ZnS殼用之較佳單一源前驅物。殼前驅物溶液通常更包含半導體奈米結晶用的覆蓋配位體如上述惰性溶劑中的油酸、油胺與三辛基膦(TOP)。
反應懸浮液能在反應溫度下反應直到形成厚度為0.2至4 nm的ZnS殼為止。
一般而言，根據最先進的已知程序添加抗溶液如甲醇、乙醇、異丙醇、丁醇或丙酮而純化所獲得的QD，然後利用例如UV-Vis光譜術、螢光光譜術與穿透式電子顯微鏡來量測特性。利用本發明之方法可製備具有藍至紅之PL發光範圍的InP QD。
已製備之QD的特性係由下列方法所測定：
--根據“A Guide to Recording Fluorescence Quantum Yields”,Jobin Yvon Horiba中所揭露的方法與硫若丹明B比較以量測量子產率
http：//www.horiba.com/fileadmin/uploads/Scientific/Documents/Fluorescence/quantumyieldstrad.pdf,retrieved October 5th,2011.
--奈米粒子的光致發光係藉由UV/VIS吸收(Jena Analytics,Specord)以及光致發光光譜術(Fluorolog 3,Jobin Yvon)所測試。
相較於已知的製備路徑，本發明之方法具有下列優點：
1.在最先進的微反應系統中藉由相較於穩定混合設備能提供更佳混合效率的磁性攪拌產生微室中的新活性混合。已顯示較佳的混合能導致較高的粒子品質。
2.配位分子羧酸鋅與十六烷基胺的已知用途有助於鈍化奈米結晶表面，因此增加量子產率。所獲得的富鋅奈米結晶表面幫助InP核上之額外高能隙ZnS殼的進一步成長。
結合方案能得到具有較佳光致發光與光穩定性的InP/ZnS QD。
3.本發明之方法為基於毛細微反應系統之用以合成高品質InP與InP/ZnS奈米結晶的簡單、快速且規模可縮放的連續流方法。
4.本發明為用以合成具有高量子產率之高度發光之InP與核/殼InP/ZnS的簡單連續方法。本發明能在少於一小時之時間內快速地合成InP核QD以及ZnS殼外罩兩者。
所獲得的InP/ZnS QD對於長時間的光漂白具有極佳的穩定性且具有至少40%的量子產率。半高寬(FWHM)係介於60至150 nm。剛製備好的核/殼InP/ZnS在氮氣環境下儲存了數禮拜甚至數月後具有少的光
致發光消光。圖1顯示了InP/ZnS QD之核/殼結構的概圖，以及在此報告中所製備之InP/ZnS QD的不同發光顏色。顏色範圍係自藍-綠至紅(500-610 nm)。
因此本發明的另一目的為，可由本發明之方法所獲得的InP/ZnS奈米粒子。
本發明的另一目的為包含本發明之半導電核-殼奈米粒子的配製物或裝置尤其是電子裝置。
圖3
I‧‧‧泵(前驅物1)
II‧‧‧泵(前驅物2)
III‧‧‧混合設備
IV‧‧‧毛細管反應器
V‧‧‧量子點
圖4A
I‧‧‧微型混合室50mm3
II‧‧‧攪拌子直徑2x2mm
III‧‧‧PTEE(POM)
IV‧‧‧攪拌子直徑2x2mm
V‧‧‧微型混合室50mm3
圖4B
VI‧‧‧微型混合室50mm3
VII‧‧‧攪拌子直徑2x2mm
圖1顯示InP/ZnS QD之核/殼結構的概圖，以及在UV燈光下已製備之InP/ZnS QD具有不同發光顏色的QD樣本的照片。顏色範圍自藍-綠至紅(500-610 nm)。
圖2為InP/ZnS核/殼QD之UV-VIS光譜與螢光光譜。
圖3為毛細管系之微反應系統的概圖。
圖4A與4B為微型化混合室的結構圖。
下面的實例為本發明之方法的例證但本發明不限於此。
製備前驅物溶液：在手套箱於氮氣環境下製備膦前驅物的儲備溶液：在玻璃瓶中混合0.2 mmol的三(三甲基矽膦)(TTSP)與2 ml的1-十八烯(ODE)。以超音波震盪分散在15 mL三辛基膦(TOP)中0.5 g的ZDC數分鐘直到獲得白色混濁懸浮液以製備二乙基二硫胺基甲酸鋅(ZDC)儲備溶液。
在50 ml的三頸燒瓶中將22 mg(0.1 mmol)的氯化銦、28.2 mg(0.1 mmol)的油酸、63.2 mg(0.1 mmol)的硬脂酸鋅與53.5 mg(0.2 mmol)
的油胺(OLA)與4 ml ODE混合。利用氮氣重覆地排空並再充填燒瓶以提供無水與無氧的反應環境(120ºC，持續約30分鐘)。接著，在強烈攪拌下快速地將溶液加熱至230ºC。當溶液溫度變得穩定時，快速地注入以上述方式製備之0.5 ml的TTSP-ODE(在2 mL的ODE中有0.2 mmol的TTSP)儲備溶液2)。將溶液維持在230ºC幾分鐘直到達到期望尺寸的InP核。在5、10、15等分鐘後取樣(0.5 mL的反應溶液，將每一者皆溶解於2 mL的甲苯中，藉由UV/Vis光譜術與螢光術來量測特性)。接著將反應溶液冷卻降溫至室溫以繼續進行殼外罩的步驟。藉著調整硬脂酸鋅與HAD的初始濃度亦可獲得不同尺寸的奈米結晶。
將上述之InP QD溶液冷卻至室溫。將1 mL TOP儲備溶液中的ZDC與1 mL的OLA添加至反應混合物。利用氮氣重覆地排空並再充填燒瓶以提供無水與無氧的反應環境。將溶液加熱至150ºC持續20 min。亦藉由UV/Vis與螢光光譜來獲得樣本的特性。基於強度估算與螢光光譜術的量測，相較於沒有外罩之InP，剛製備好之InP/ZnS的光致發光增加了3-10倍。沒有外罩之InP的光致發光在普通環境下儲存幾天後便消光但InP/ZnS的光致發光穩定地持續了幾個月。
在250 ml的三頸燒瓶中利用30 ml的ODE混合220 mg(1 mmol)的氯化銦、282.5 mg(1 mmol)的油酸與695.5 mg(2.6 mmol)的油胺(OLA)以製備銦-儲備溶液。利用氮氣重覆地排空並再充填燒瓶以提供無水與無氧的反應環境。然後在強烈攪拌下快速將溶液加熱至120-150ºC直到固體樣本被完全分散。接著將前驅物溶液冷卻降溫至室溫以供後續使用。在手套箱於氮氣環境下製備膦-儲備溶液：在玻璃瓶中混合三(三甲
基矽膦)與1-十八烯(ODE)。以超音波震盪分散在15mL ODE中0.5g的硬脂酸鋅數分鐘以製備碳酸鋅儲備溶液。所獲得的混合物為白色混濁懸浮液。以超音波震盪分散在15mL TOP中0.5g的ZDC數分鐘以製備ZDC-儲備溶液(殼前驅物溶液)。所獲得的混合物也是白色混濁懸浮液。
以1.0mL/min的流量將核前驅物溶液的儲備溶液(例如3mL的銦儲備溶液+1.2mL的膦儲備溶液+1mL的硬脂酸鋅儲備溶液+4.5mL的ODE)泵抽至體積為50mm3的混合設備中，然後通過毛細管系統(4米的PTFE管，在油浴中加熱上至230ºC)。在數分鐘後出現具有顏色(及螢光)的第一樣本，然後在獲得第一種顏色之懸浮液後以玻璃瓶收集InP樣本1-2分鐘。將上述的InP QD溶液冷卻至室溫。以ODE沖洗連續系統。藉著改變膦及/或硬脂酸鋅溶液的量來達成InP的其他尺寸(光致發光的其他顏色)：增加膦的量會產生較大尺寸的InP核，因此光致發光紅移；降低硬脂酸鋅的量也會產生較大尺寸的InP核，因此光致發光紅移。
為了ZnS外罩，以1.0mL/min的流量將2.5mL的InP粗製溶液與0.75mL的ZDC儲備溶液與4mL的ODE皆泵抽至相同的連續系統(50mm3體積的混合設備與4公尺的PTFE毛細管，在油浴中加熱上至220ºC)。收集所獲得的樣本並也藉由UV/Vis與螢光光譜來量測特性。圖2顯示根據實例2藉由改變膦及/或硬脂酸鋅溶液之量的連續方法所獲得之InP/ZnS核/殼QD的UV-VIS光譜以及螢光光譜。
Claims (6)
- 一種用以製備InP/ZnS奈米粒子之連續流方法，係在包含連接至一反應室之至少一混合室的微反應系統中進行InP/ZnS奈米粒子的製備，此方法包含下列步驟：a. 在無水與無氧的環境下藉著混合銦鹽、脂肪族質子性烷基胺、脂肪族烷基酸及羧酸鋅與惰性溶劑並加熱至50-200℃以得到澄清溶液，而製備銦的前驅物溶液，b. 在無水與無氧的環境下於惰性溶劑中製備包含三(三甲基矽)膦之膦的前驅物溶液，c. 在混合室中將過量的該銦的前驅物溶液注射至該膦前驅物溶液中以獲得反應混合物，其中該混合室為磁性微混合室，且其中注射流量為0.1ml/min至10ml/min，d. 於反應室中在160至320℃的溫度下前饋與加熱該反應混合物直到獲得InP之核懸浮液，e. 將該核懸浮液前饋至一混合室中並將包含Zn源與S源的殼前驅物溶液注射至該核懸浮液，將覆蓋配位體加入該混合室中，f. 在160至320℃的溫度下前饋並加熱該懸浮液以在該反應室內製備殼，g. 冷卻之。
- 如申請專利範圍第1項之方法，其中步驟f中，懸浮液被前饋及在200至280℃之溫度下加熱以在該反應室中製備殼。
- 如申請專利範圍第1項之方法，其中Zn源與S源為單一源。
- 一種InP/ZnS奈米粒子，可由如申請專利範圍第1至3項之方法所獲得。
- 一種配製物，包含如申請專利範圍第4項之奈米粒子，應用在生物標記、LEDs、雷射、光伏技術與感測器。
- 一種裝置，包含如申請專利範圍第4項之奈米粒子，應用在生物標記、LEDs、雷射、光伏技術與感測器。
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Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5568305B2 (ja) | 2006-09-29 | 2014-08-06 | ユニバーシティ オブ フロリダ リサーチ ファンデーション インコーポレーティッド | 赤外線検出および表示のための方法および装置 |
| BR112013033122A2 (pt) | 2011-06-30 | 2017-01-24 | Nanoholdings Llc | método e aparelho para detectar radiação infravermelha com ganho |
| US20150315721A1 (en) * | 2012-12-10 | 2015-11-05 | Xinhua Zhong | One step synthesis of core/shell nanocrystal quantum dots |
| US9627200B2 (en) * | 2013-07-29 | 2017-04-18 | US Nano LLC | Synthesis of CdSe/ZnS core/shell semiconductor nanowires |
| US12215266B2 (en) | 2013-09-26 | 2025-02-04 | Samsung Electronics Co., Ltd. | Nanocrystal particles and processes for synthesizing the same |
| US11746290B2 (en) | 2013-09-26 | 2023-09-05 | Samsung Electronics Co., Ltd. | Nanocrystal particles and processes for synthesizing the same |
| US9666768B2 (en) | 2014-02-07 | 2017-05-30 | Nanoco Technologies Ltd. | Quantum dot nanoparticles having enhanced stability and luminescence efficiency |
| JPWO2015156226A1 (ja) | 2014-04-08 | 2017-04-13 | Ｎｓマテリアルズ株式会社 | 量子ドット及びその製造方法、並びに、前記量子ドットを用いた成形体、シート部材、波長変換部材、発光装置 |
| EP3271063B1 (en) * | 2015-03-19 | 2019-12-25 | Universiteit Gent | Size-tunable nanoparticle synthesis |
| US9899575B2 (en) * | 2015-04-30 | 2018-02-20 | Nano And Advanced Materials Institute Limited | Method of continuous flow synthesis and method of correcting emission spectrum of light emitting device |
| EP3308113A4 (en) | 2015-06-11 | 2019-03-20 | University of Florida Research Foundation, Incorporated | MONODISPERSES, IR ABSORBENT NANOPARTICLES AND RELATED METHODS AND DEVICES |
| CN106564931B (zh) * | 2015-09-22 | 2018-05-29 | 苏州星烁纳米科技有限公司 | 一种纳米晶体制备方法 |
| EP3168278B2 (en) | 2015-10-28 | 2022-02-09 | Samsung Electronics Co., Ltd. | Quantum dots, production methods thereof, and electronic devices including the same |
| KR102498798B1 (ko) | 2015-12-22 | 2023-02-09 | 삼성전자주식회사 | 양자점 및 이를 포함하는 소자 |
| US10585228B2 (en) | 2015-12-29 | 2020-03-10 | Samsung Electronics Co., Ltd. | Quantum dots, production methods thereof, and electronic devices including the same |
| US10369538B2 (en) | 2015-12-31 | 2019-08-06 | Kuantag Nanoteknolojiler Gelistirme Ve Uretim A.S. | Flow system and process for photoluminescent nanoparticle production |
| US20180273844A1 (en) * | 2015-12-31 | 2018-09-27 | Dow Global Technologies Llc | Continuous flow syntheses of nanostructure materials |
| US10815424B2 (en) | 2015-12-31 | 2020-10-27 | Kuantag Nanoteknolojiler Gelistirme Ve Uretim A.S. | One-step process for synthesis of core shell nanocrystals |
| KR101789986B1 (ko) | 2016-07-18 | 2017-11-20 | 한국생산기술연구원 | 다층쉘 구조의 양자점 제조 방법 및 이에 의하여 제조되는 양자점 |
| KR101799479B1 (ko) | 2016-07-18 | 2017-12-20 | 한국생산기술연구원 | 양자점 제조 장치 및 이에 의하여 제조되는 비구형 양자점 |
| US20180067121A1 (en) * | 2016-09-06 | 2018-03-08 | Nanoco Technologies Ltd. | Exosome-conjugated quantum dot nanoparticles and methods of detecting exosomes and cancer using same |
| WO2018155009A1 (ja) * | 2017-02-21 | 2018-08-30 | 富士フイルム株式会社 | コアシェル粒子、コアシェル粒子の製造方法およびフィルム |
| US10510922B2 (en) * | 2017-04-12 | 2019-12-17 | Zhejiang University | Group III-V quantum dot and manufacturing method thereof |
| EP3694951B1 (en) | 2017-10-13 | 2023-12-13 | Merck Patent GmbH | Semiconducting light emitting material |
| CN110028948B (zh) | 2018-01-11 | 2024-07-26 | 三星电子株式会社 | 无镉量子点、其制造方法、包括其的组合物、量子点-聚合物复合物和显示器件 |
| EP3511393B1 (en) * | 2018-01-11 | 2021-04-28 | Samsung Electronics Co., Ltd. | A population of quantum dots, a method of making the same and a composition including the same |
| KR20190126597A (ko) * | 2018-05-02 | 2019-11-12 | 주식회사 라미나 | 양자점 제조장치 및 양자점 제조방법 |
| KR102165671B1 (ko) * | 2018-05-03 | 2020-10-14 | 한국과학기술원 | 인화인듐결정 제조방법 |
| CN110819347B (zh) * | 2018-08-09 | 2022-10-04 | 纳晶科技股份有限公司 | 无镉量子点及其制备方法 |
| CN109456764B (zh) * | 2018-12-12 | 2023-09-12 | 广东工业大学 | 一种基于微流控的钙钛矿量子点的制备方法 |
| CN111849483B (zh) * | 2019-04-26 | 2022-09-02 | 纳晶科技股份有限公司 | 一种蓝光无镉量子点及其制备方法、量子点光电器件 |
| CN111690401B (zh) * | 2019-12-30 | 2022-08-05 | 上海大学 | 增大磷化铟量子点发光核尺寸的制备方法 |
| GB2596809A (en) | 2020-07-06 | 2022-01-12 | King S College London | Production of luminescent particles |
| CN115193349B (zh) * | 2022-06-17 | 2023-09-26 | 佳木斯大学 | 一种多孔空心碳纳米球的制备方法 |
| KR102734074B1 (ko) * | 2022-10-14 | 2024-11-25 | 성균관대학교산학협력단 | Iii-v 족 양자점 합성용 전구체 소재 및 이의 제조 방법 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100068522A1 (en) * | 2008-08-07 | 2010-03-18 | Nanoco Technologies Limited | Surface Functionalised Nanoparticles |
| CN102031110A (zh) * | 2010-11-29 | 2011-04-27 | 天津大学 | 一种InP/ZnS核壳结构量子点及制备方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020083888A1 (en) * | 2000-12-28 | 2002-07-04 | Zehnder Donald A. | Flow synthesis of quantum dot nanocrystals |
| JP4269842B2 (ja) * | 2003-08-08 | 2009-05-27 | 日油株式会社 | 半導体ナノ微結晶の製造方法 |
| DE102006055218A1 (de) | 2006-11-21 | 2008-05-29 | Bayer Technology Services Gmbh | Kontinuierliches Verfahren zur Synthese von nanoskaligen metallhaltigen Nanopartikel und Nanopartikeldispersion |
-
2011
- 2011-12-01 EP EP11191589.8A patent/EP2599898A1/en active Pending
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2012
- 2012-11-26 EP EP12790906.7A patent/EP2785897A1/en not_active Withdrawn
- 2012-11-26 WO PCT/EP2012/073552 patent/WO2013079423A1/en not_active Ceased
- 2012-11-26 AU AU2012344013A patent/AU2012344013B2/en not_active Ceased
- 2012-11-26 US US14/361,862 patent/US9577149B2/en active Active
- 2012-11-30 TW TW101144901A patent/TWI619856B/zh not_active IP Right Cessation
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2017
- 2017-02-17 US US15/436,454 patent/US20170166808A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100068522A1 (en) * | 2008-08-07 | 2010-03-18 | Nanoco Technologies Limited | Surface Functionalised Nanoparticles |
| CN102031110A (zh) * | 2010-11-29 | 2011-04-27 | 天津大学 | 一种InP/ZnS核壳结构量子点及制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| Size Controlled Synthesis of Blue Emitting Core/Shell Nanocrystals via Microreaction, J. Phys. Chem. C, 2011, 115 (5), pp 1569–1575 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20170166808A1 (en) | 2017-06-15 |
| TW201341605A (zh) | 2013-10-16 |
| AU2012344013B2 (en) | 2017-03-02 |
| US9577149B2 (en) | 2017-02-21 |
| WO2013079423A1 (en) | 2013-06-06 |
| EP2599898A1 (en) | 2013-06-05 |
| EP2785897A1 (en) | 2014-10-08 |
| AU2012344013A1 (en) | 2014-06-19 |
| US20140326921A1 (en) | 2014-11-06 |
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