CN109104868A - 用于生产封装的量子点的方法 - Google Patents
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Abstract
一种用于封装量子点的方法。所述方法包含以下步骤：(a)混合量子点与聚合物和溶剂以形成混合物，所述聚合物的分子量为1,000至200,000并且溶解度参数为14至18.75(J/cm3)1/2；和(b)喷雾干燥所述混合物以产生封装的量子点粉末。
Description
技术领域
本发明涉及一种用于生产封装的量子点的方法。
背景技术
半导体量子点(QD)提供与块体材料的特性显著不同的光学吸收和发射(光致发光PL或电致发光EL)特性。随着粒径减小，有效能带隙(Eg)或可用能级会增加并产生蓝移的PL光谱。在相同材料内通过粒径依赖性量子限制效应得到的这种光谱可调性是相对于传统块体半导体的关键优势。由于其独特的光学特性，QD在许多显示和照明应用中引起了极大的兴趣。大多数QD具有使用较大带隙材料的无机壳，以将电子和空穴对限制在核心区域内并防止任何表面电荷态。然后外壳被有机配体覆盖以减少壳的陷阱态，陷阱态可能导致量子产率(QY)降低。有机配体有助于QD分散在有机/含水溶剂中。包围QD的典型有机配体具有相对长的烷基链，其可以在非极性溶剂或单体中提供高溶解度。不幸的是，QD在光吸收/转换过程中非常容易光氧化。并且，当配体与溶剂或单体不相容时，湿度会有类似的影响。QD通常封装在聚合物基质中以保护它们免受水和氧气的不利影响。例如，US8859442公开了在聚合物基质中封装的量子点。然而，这一参考文献未公开本文所描述的方法。
发明内容
本发明提供一种用于封装量子点的方法。所述方法包含以下步骤：(a)将量子点与聚合物和溶剂混合以形成混合物，所述聚合物的分子量为1,000至200,000并且溶解度参数为14至18.75(J/cm3)1/2；(b)喷雾干燥所述混合物以产生粒径为1-10微米的封装的量子点粉末
具体实施方式
除非另有说明，否则百分比是重量百分比(重量％)并且温度是以℃计。除非另有说明，否则操作在室温(20-25℃)下进行。沸点在大气压(约101kPa)下测量。术语″(甲基)丙烯酸酯″意味着丙烯酸酯或甲基丙烯酸酯。量子点在本领域中是众所周知的，参见例如，US2012/0113672。分子量以道尔顿(Daltons)为单位测量，并且是单体化合物的原子量和混合物(例如，低聚或聚合化合物)的重均分子量(Mw)的总和。
优选地，聚合物的酸值为0至500mg KOH/g；优选不大于350，优选不大于200。优选地，聚合物的分子量为至少2,000，优选至少3,000；优选不超过200,000，优选不超过175,000，优选不超过150,000。优选地，聚合物的溶解度参数为至少15(J/cm3)1/2；优选至少15.5；优选不大于18.5，优选不大于18.25。聚合物的玻璃化转变温度(Tg)或熔融温度优选为至少50℃，优选至少60℃；优选不大于200℃，优选不大于150℃。
优选地，聚合物包含有包含至少一个易于聚合的乙烯基的化合物；优选所述化合物的分子量为至少28，优选至少为72，优选至少为86；优选不超过500，优选不超过400。优选地，包含至少一个易于聚合的乙烯基的化合物具有一个或两个易于聚合的乙烯基，优选一个；即使当这一化合物仅含有一个易于聚合的乙烯基时，也可以存在具有更高官能度的其他单体。当包含至少一个易于聚合的乙烯基的化合物是低聚物时，乙烯基的数目是分布的数均值。优选地，易于聚合的乙烯基是(甲基)丙烯酸酯基团(CH2＝C(R)C(O)O-，其中R是H或CH3；也称为(甲基)丙烯酰氧基)。优选地，包含至少一个易于聚合的乙烯基的化合物不具有除碳、氢、氧和氮原子之外的原子；优选碳、氢和氧(这不排除来自杂质的痕量水平)；
优选地，溶剂的溶解度参数为14.5至18.5(J/cm3)1/2；优选至少14.75，优选至少15.0；优选不大于18.25，优选不大于18.0。优选地，溶剂是C6-C12烃或醚溶剂，优选C6-C10烃或醚溶剂，优选C6-C10烃溶剂。优选地，溶剂是芳香族的，即它含有至少一个芳环。如果使用超过一种溶剂，则溶剂混合物的溶解度参数是个别溶剂的溶解度参数的重均值。
优选的聚合物是不合任何酸性官能度的高Tg无定形聚合物。特别优选的聚合物包括基于烯烃的(共)聚合物、基于烷基苯乙烯的(共)聚合物和基于(甲基)丙烯酸酯的(共)聚合物。特别优选的包含至少一个易于聚合的乙烯基的化合物包括(甲基)丙烯酸异冰片酯、(甲基)丙烯酸C2-C18烷基酯(例如，(甲基)丙烯酸异丁酯、丙烯酸3，5，5-三甲基己酯、丙烯酸十二烷基酯、丙烯酸癸酯、丙烯酸十三烷基酯和丙烯酸异癸酯)、L-丙烯酸薄荷基酯、丙烯酸三环[5.2.1.02，6]癸基甲酯、C1-C6烷基苯丙烯、甲基丙烯酸3，3，5-三甲基环己酯和甲基丙烯酸3，3，5-三甲基环己酯。
优选地，喷雾干燥的材料，即量子点和溶剂和聚合物的混合物，包含0.001至2.4重量％的量子点；优选至少0.0025重量％，优选至少0.005重量％；优选不超过1.6重量％，优选不超过0.8重量％。优选地，喷雾干燥的材料包含1至30重量％的第一聚合物；优选至少3重量％，优选至少5重量％；优选不超过25重量％，优选不超过20重量％。优选地，喷雾干燥的材料包含50至99重量％的溶剂；优选至少60重量％，优选至少70重量％；优选不超过97重量％，优选不超过95重量％。
优选地，喷雾干燥在惰性气氛下进行，出口温度＜100℃，优选＜80℃；优选＜60℃。优选地，喷雾干燥器配备有双流体雾化器。优选地，干粉的平均粒径为0.1-10微米，优选至少0.5微米，优选至少1微米；优选不超过8微米，优选不超过6微米。
将封装的QD的喷雾干燥粉末与散射剂和光引发剂一起分散在液体单体中并固化成固体膜。树脂是物理稳定的，并且可以更易于进行测试。
实例
实例中使用的缩写：
PiBOMA是来自Scientific Polymer Products的聚甲基丙烯酸异冰片酯(Mw＝100kg/mol，Tg＝110℃)
PTBS：来自Scientific Polymer Products的聚(对-叔丁基苯乙烯)(Tg＝132℃)
COC 5013是来自TOPAS的乙烯-降冰片烯共聚物(Mw＝80.5kg/mol，Tg＝140℃)
SMA EF-60是来自Cray Valley的苯乙烯-马来酸酐共聚物(Mw＝11.5kg/mol，酸值＝156KOH/g)
HEA是来自西格玛奥德里奇公司(Sigma-Aldrich，Inc.)的丙烯酸2-羟乙酯。
SR494是来自Sartomer，Inc.的C{CH2OCH2CH2OC(O)CH＝CH2}4。
I-819是来自汽巴-嘉基公司(Ciba-Geigy Corp.)的光起始剂(IRGACURE)光活性聚合引发剂。
FINEX 30S LP2是来自堺化学工业株式会社(Sakai Chemical Industry Co.)的超细氧化锌。
通过喷雾干燥制备封装的QD
除非另有说明，否则典型的喷雾干燥条件描述于下文中。在MOBILE MINOR喷雾干燥器(基伊埃工程技术有限公司(GEA Process Engineering Inc.))上配备喷泉双流体喷嘴雾化器。使用蠕动泵(MASTERFLEX L/S)将聚合物/QD溶液进料到喷雾干燥器中。入口温度80℃，出口温度55℃。液体进料速率＝10mL/min(设定)并且喷嘴雾化器的N2流速＝1巴60％流量。喷雾干燥过程产生自由流动的QD聚合物粉末，其控制良好的粒径为～5微米，其中QD均匀分散在聚合物基质中而没有聚集
PLQY测量
PLQY是使用绝对PL量子产率分光仪测量(日本滨松公司的Quantaurus(C11347-01)(QUANTAURUS(C11347-01)，Hamamatsu，Japan))。积分球允许在350～1600nm内的～99％反射。入射和发射的光子都必须进行多次反射以到达检测器(这在量子产率测量中有助于消除光学各向异性)激发波长设定在450nm，并且PL的波长是在460和950nm之间溶液样品放置在积分球的中心(透射)；膜样品放置在底部。绝对PLQY的直接度量是发射光子数与被吸收光子数的比。
制备QD树脂膜
膜配制物在无氧环境中(例如在手套工作箱中)制备
1.使单体在真空下脱气1小时
2.使用速度混合器(南卡莱罗纳州兰德拉姆市(Landrum，SC)的FlackTek Inc)制备50重量％的FINEX 30S LP2在上述单体中的溶液。
3.通过在室温下搅拌所述混合物制备1.75重量％I-819在上述单体中的溶液
4.将I-819/单体引入到QD样品中
6.使用速度混合器将FINEX 30S LP2/单体溶液混合到上述溶液中
7.在UV(UVA，～400mJ/cm2)下使被两个用于QY测试的i-组分阻挡膜夹在中间的单体固化来制备～100μm的QD膜
实例1
聚合物与绿色QD在甲苯中的溶液PLQY
*将0.2g每种溶液(0.77mg QD/mL)加到1mL小瓶中，然后使用滨松公司绝对PL QY设备在450nm激发下测量PL QY、PWL、FWHM
实例2：HEA/CN104单体中的
含红色QD的甲苯：Manc11_Z A1(151.2OD/ml(450nm激发)
PTBS：Mw＝50-100kg/mol，Tg＝144℃
QD粉末规格
PTBS粉末1∶0.5重量％红色QD(8.75OD/g)
PtBSt粉末2：2.5重量％红色QD(43.75OD/g)
对照样品含QD的IBOA
含2.098g的BOA+QD的0.5mL甲苯溶液(0.5×151.2/2.098＝35OD/g)
实例3-HEA/SR-494单体中的含的PIBOMA
PiBOMA/QD封装的粉末：2重量％绿色QD
封装的QD树脂膜：
*两种配制物均含有1.5重量％I-819和2.125重量％Finex 30S LP2
SR494的结构
封装的QD展示了更好的在极性基质中的QY保持力和更低的发射峰红移在60℃/95％RH下使QD树脂膜老化
含有封装QD的膜在老化条件下展示出更好的QY保持力。
Claims (8)
1.一种用于封装量子点的方法；所述方法包含以下步骤：
(a)混合量子点与聚合物和溶剂以形成混合物，所述聚合物的分子量为1,000至200,000并且溶解度参数为14至18.75(J/cm3)1/2；和
(b)喷雾干燥所述混合物以产生封装的量子点粉末。
2.根据权利要求1所述的方法，其中所述聚合物的Tg为60至200℃。
3.根据权利要求2所述的方法，其中所述聚合物包含以下化合物的聚合单元，所述化合物包含一个或两个易于聚合的乙烯基并且分子量为44至400。
4.根据权利要求3所述的方法，其中所述溶剂的溶解度参数为14.5至18.5(J/cm3)1/2。
5.根据权利要求4所述的方法，其中所述喷雾干燥是在配备有双流体喷嘴雾化器的喷雾干燥器中进行。
6.根据权利要求5所述的方法，其中所述聚合物的溶解度参数为14.5至18.5(J/cm3)1/2。
7.根据权利要求6所述的方法，其中所述的量子点和溶剂和聚合物的混合物包含0.001至2.4重量％的量子点。
8.根据权利要求7所述的方法，其中所述包含至少一个易于聚合的乙烯基的化合物不合有除碳、氢和氧原子之外的原子。
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| CN113619204A (zh) * | 2021-08-04 | 2021-11-09 | 南京贝迪新材料科技股份有限公司 | 一种新型无阻隔量子点膜及其制备方法 |
| CN114426841A (zh) * | 2020-10-29 | 2022-05-03 | 歆炽电气技术股份有限公司 | 光波长转换复合材料及其制备方法、以及光波长转换结构 |
| WO2022089617A1 (zh) * | 2020-10-30 | 2022-05-05 | 致晶科技（北京）有限公司 | 钙钛矿量子点/聚合物复合粉体材料及其制备方法、应用 |
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| WO2023068664A1 (ko) * | 2021-10-19 | 2023-04-27 | (주)이노큐디 | 양자점 복합체를 포함하는 양자점 필름, 및 디스플레이용 파장변환 시트 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560633A (zh) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | 用作生物医学荧光探针的量子点微球的制备方法 |
| CN103228983A (zh) * | 2010-11-10 | 2013-07-31 | 纳米系统公司 | 量子点薄膜、照明器件及照明方法 |
| US20150083970A1 (en) * | 2013-09-25 | 2015-03-26 | Samsung Electronics Co., Ltd. | Quantum dot-resin nanocomposite and method of preparing same |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07332847A (ja) * | 1994-06-03 | 1995-12-22 | Mitsubishi Chem Corp | 噴霧乾燥方法 |
| WO1997041160A1 (en) * | 1996-04-26 | 1997-11-06 | N V Raychem S A | Alkyl methacrylate polymers |
| US7645436B1 (en) * | 2003-01-07 | 2010-01-12 | Aps Laboratory | Tractable metal oxide sols and nanocomposites therefrom |
| US6838486B2 (en) * | 2003-01-07 | 2005-01-04 | Aps Laboratory | Preparation of metal nanoparticles and nanocomposites therefrom |
| JP2007117937A (ja) * | 2005-10-31 | 2007-05-17 | Konica Minolta Medical & Graphic Inc | 微粒子粉末、その製造方法および製造装置 |
| WO2007114468A1 (ja) * | 2006-04-04 | 2007-10-11 | Mitsubishi Rayon Co., Ltd. | 噴霧乾燥器、噴霧乾燥方法及び重合体粉体 |
| US20100119697A1 (en) * | 2006-05-10 | 2010-05-13 | 3M Innovative Properties Company | Compositions and coatings containing fluorescent, inorganic nanoparticles |
| GB0916700D0 (en) * | 2009-09-23 | 2009-11-04 | Nanoco Technologies Ltd | Semiconductor nanoparticle-based materials |
| GB201005601D0 (en) | 2010-04-01 | 2010-05-19 | Nanoco Technologies Ltd | Ecapsulated nanoparticles |
| KR101574842B1 (ko) * | 2012-03-16 | 2015-12-08 | 세종대학교산학협력단 | 양자점- 고분자 복합체 입자, 상기 복합체 입자를 포함하는 광학요소, 및 상기 광학요소의 제조방법 |
| US9443998B2 (en) * | 2013-03-14 | 2016-09-13 | Nanoco Technologies Ltd. | Multi-layer-coated quantum dot beads |
| CN104418972B (zh) * | 2013-08-26 | 2017-04-05 | 中国科学院化学研究所 | 光子晶体胶囊颜料及其制备方法和应用 |
| JP2017520643A (ja) * | 2014-06-03 | 2017-07-27 | スリーエム イノベイティブ プロパティズ カンパニー | 量子ドットを含む粒子及びその製造方法 |
| EP3184602B1 (en) * | 2015-12-23 | 2018-07-04 | Avantama AG | Luminescent component |
-
2017
- 2017-03-16 TW TW106108791A patent/TWI774664B/zh active
- 2017-04-03 KR KR1020187030991A patent/KR102182236B1/ko active IP Right Grant
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560633A (zh) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | 用作生物医学荧光探针的量子点微球的制备方法 |
| CN103228983A (zh) * | 2010-11-10 | 2013-07-31 | 纳米系统公司 | 量子点薄膜、照明器件及照明方法 |
| US20150083970A1 (en) * | 2013-09-25 | 2015-03-26 | Samsung Electronics Co., Ltd. | Quantum dot-resin nanocomposite and method of preparing same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426841A (zh) * | 2020-10-29 | 2022-05-03 | 歆炽电气技术股份有限公司 | 光波长转换复合材料及其制备方法、以及光波长转换结构 |
| WO2022089617A1 (zh) * | 2020-10-30 | 2022-05-05 | 致晶科技（北京）有限公司 | 钙钛矿量子点/聚合物复合粉体材料及其制备方法、应用 |
| CN114437710A (zh) * | 2020-10-30 | 2022-05-06 | 致晶科技（北京）有限公司 | 钙钛矿量子点/聚合物复合粉体材料及其制备方法、应用 |
| CN114437710B (zh) * | 2020-10-30 | 2024-05-07 | 致晶科技（北京）有限公司 | 钙钛矿量子点/聚合物复合粉体材料及其制备方法、应用 |
| CN113619204A (zh) * | 2021-08-04 | 2021-11-09 | 南京贝迪新材料科技股份有限公司 | 一种新型无阻隔量子点膜及其制备方法 |
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| JP6766173B2 (ja) | 2020-10-07 |
| JP2019519621A (ja) | 2019-07-11 |
| KR20180123566A (ko) | 2018-11-16 |
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