CN114891504A - 锶掺杂钙钛矿量子点/介孔二氧化硅复合材料及其制备 - Google Patents
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Abstract
本发明公开了一种锶掺杂钙钛矿量子点/介孔二氧化硅复合材料及其制备,该复合材料为CsPb1‑xSrxBr3@SBA‑15。将油酸、1‑十八烯和碳酸铯混合搅拌加热得油酸铯前驱体;介孔二氧化硅、油酸、油胺、1‑十八烯、溴化铅和六水合溴化锶一起搅拌加热,得前驱体溶液;将油酸铯前驱体迅速注入前驱体溶液中,反应一定时间后进行冰水浴,自然冷却至室温,离心,所得一次沉淀分散在正己烷中静置,将静置得到的二次沉淀真空干燥,制得锶掺杂钙钛矿量子点/介孔二氧化硅复合材料。本发明制备方法用介孔二氧化硅孔道隔绝钙钛矿量子点与外界环境的接触,锶离子掺杂提高钙钛矿量子点结构稳定性,两种策略共同作用提高钙钛矿量子点光热稳定性。
Description
技术领域
本发明属于发光材料技术领域,涉及一种可被蓝光激发的高亮度、高稳定性的基于锶(Sr)掺杂钙钛矿(CsPbBr3)量子点/介孔二氧化硅复合材料及其制备方法。
背景技术
随着显示技术的迅速发展以及人们对显示色彩和实用性的追求,现代显示器件正朝着高密度、高分辨率、节能化、高亮度、彩色化的方向发展。而Micro-LED具有良好的色彩还原性、更高的亮度、色彩饱和度和响应速度等特点。相较于传统的荧光粉,量子点发光材料具有颗粒尺寸小、发光峰位可调、发射波长窄、色彩饱和度高、量子效率高等诸多优点,这些卓越的特性使量子点发光材料成为Micro-LED用发光材料的首选。
全无机钙钛矿量子点材料拥有量子产率高、色域覆盖范围广、缺陷耐受性高和半峰宽窄等特点。但是其形成能很低,对光照和温度等环境条件较为敏感,而且高度离子性的内部结构也导致钙钛矿量子点容易分解和发生离子交换反应。所以,CsPbX3钙钛矿量子点的稳定性依然是一个亟待解决的科学难题,也是限制钙钛矿基发光器件走向应用的关键。
专利申请《钙钛矿量子点与介孔二氧化硅复合发光材料及其制备》(申请号202111546621.6,公开日2022.02.24)公开了一种量子产率有巨大提升的红色荧光钙钛矿复合材料,使用了碘化锶,成本较高。
发明内容
本发明的目的是提供一种具有高亮度、高稳定性的Sr2+掺杂CsPbBr3量子点/介孔二氧化硅复合材料。
本发明的另一个目的是提供一种上述复合发光材料的制备方法。
为实现上述目的,本发明所采用的技术方案是:一种锶掺杂钙钛矿量子点/介孔二氧化硅复合材料,化学式为CsPb1-xSrxBr3@SBA-15,其中,0.05≤x≤0.4;钙钛矿量子点组成为CsPb1-xSrxBr3,介孔二氧化硅的类型为SBA-15。
本发明所采用的另一个技术方案是:一种上述复合材料的制备方法,具体按以下步骤进行:
1)油酸铯前驱体的制备:
将0.102~0.814g碳酸铯、5~40mL的1-十八烯和0.5~2.5mL油酸加入50mL三颈烧瓶中,在氮气气氛下以600rpm转速搅拌,并以5℃/min的升温速率升温至110~130℃,然后进行抽真空通氮气过程三次(因为空气会对反应造成影响,所以抽真空通氮气三次是为了尽可能保证反应过程中没有空气的参与),保温1~1.5h,保温期间观察溶液变化情况,待碳酸铯完全溶解,溶液澄清透明时,升温至140~160℃,得油酸铯前驱体;
2)按体积比1︰1︰10,分别取油酸、油胺和1-十八烯,再按0.5mL油酸需用0.147g介孔二氧化硅的比例,取介孔二氧化硅;再取钙钛矿材料(溴化铅)和六水合溴化锶;
介孔二氧化硅中硅(Si)与钙钛矿材料中铅(Pb)的摩尔质量比为1︰6~15;水合溴化锶中锶(Sr)与钙钛矿材料中铅(Pb)的摩尔质量比为1︰1~20。
将介孔二氧化硅、油酸、油胺和1-十八烯加入三口烧瓶中;在氮气氛围下搅拌,并以5℃/min的升温速率升温至120~130℃,抽真空30 min;加入溴化铅和六水合溴化锶,在氮气氛围和120~130℃温度下保温1~1.5h,保温期间抽真空通氮气三次,待反应物完全溶解后,升温至180℃保温10~20min,在介孔二氧化硅内部合成铅、锶前驱体,得前驱体溶液;
3)钙钛矿量子点与介孔二氧化硅复合材料的合成:
按体积比1︰12,分别取温度140~160℃的油酸铯前驱体和温度180℃的前驱体溶液,将油酸铯前驱体迅速加入前驱体溶液中,反应5~10s后,迅速进行冰水浴,自然冷却至室温,得绿色浑浊溶液;
4)复合材料后续纯化:
将绿色浑浊溶液在离心机中,3000rpm离心3min,弃去上清液,得一次沉淀,一次沉淀分散在正己烷溶液中,静置,再次沉淀后,弃去上层清液,得二次沉淀,二次沉淀在真空干燥箱中温度45~55℃真空干燥20~30h,制得干燥的锶掺杂钙钛矿量子点/介孔二氧化硅复合材料(CsPb1-xSrxBr3@SBA-15复合材料)。
本发明制备方法采用热注入法,将掺锶离子的钙钛矿量子点原位生长在介孔二氧化硅的孔道中,所得固体复合材料具有很高的量子产率、良好的光热稳定性。
本发明复合材料可应用于Micro-LED显示、白光LED照明、光电探测器和可见光通讯等领域。
本发明固体绿色CsPb0.8Sr0.2Br3@SBA-15复合材料的量子产率可达到82%,而作为对比的固态CsPbBr3量子点的量子产率仅为21%;当环境温度升高到120℃时CsPb0.8Sr0.2Br3@SBA-15复合材料荧光强度下降为初始强度的46%,固态CsPbBr3量子点荧光强度下降为初始强度的8%。将复合样品在紫外灯下照射72h之后,本发明复合材料的荧光强度保留初始强度的96%,而固态CsPbBr3量子点荧光强度下降为初始强度的17%。量子产率和稳定性提高的原因为锶离子掺杂后钙钛矿容忍因子改善,结构更加稳定;介孔二氧化硅孔道将量子点分隔开来避免了重吸收现象以及隔绝了量子点与外部环境的直接接触。掺杂和包覆两种策略共同作用得到了高亮度、高稳定性的CsPb0.8Sr0.2Br3@SBA-15复合材料。
本发明CsPb1-xSrxBr3@SBA-15复合材料具有以下优点:
1、锶离子部分取代铅离子,在降低钙钛矿量子点毒性的同时,改善了量子点容忍因子和八面体因子,进而得到更加稳定的结构,提升钙钛矿量子点的稳定性。
2、将介孔二氧化硅孔道作为原位反应的微反应器制备复合样品,孔道可以分隔开相邻的量子点,避免量子点互相聚集长大和重吸收现象的发生,提升钙钛矿量子点的光学稳定性;同时孔道作为钙钛矿量子点的保护层,隔绝了外界环境,有效提升了环境稳定性。
3、在钙钛矿量子点结构内部进行掺杂,得到更好的结构稳定性;再将其原位生长在介孔二氧化硅孔道中,得到更好的环境稳定性;双重策略同时作用,得到高亮度、高稳定性的CsPb1-xSrxBr3@SBA-15复合样品。
4、在提升绿色固体钙钛矿量子点复合材料的量子产率的同时,大幅提升了其紫外光照稳定性和热稳定性。
5、采用六水合溴化锶,相较于碘化锶,制备成本大幅下降。
附图说明
图1是实施例1制得复合材料的X射线衍射谱。
图2是实施例1制得复合材料的紫外吸收和发射光谱图。
图3是实施例1制得复合材料的透射电子显微镜图。
图4是本发明所得复合材料的光稳定性测试图。
图5是本发明所得复合材料的热稳定性测试图。
具体实施方式
下面结合附图和具体实施例,对本发明做进一步详细说明。
实施例1
将0.102g碳酸铯、5mL的1-十八烯和0.5mL油酸加入50mL三口烧瓶中,在氮气氛围下以600rpm转速搅拌,并以5℃/min的升温速率升温至120℃,进行抽真空通氮气过程三次,保温1h,至碳酸铯完全溶解,澄清透明时,升温至150℃,得油酸铯前驱体;将0.147g介孔二氧化硅、0.5mL油酸、0.5mL油胺和5mL的1-十八烯加入25mL三口烧瓶中,在氮气氛围下搅拌,并以5℃/min的升温速率升温至120℃,抽真空30 min;然后加入0.055g溴化铅和0.013g六水合溴化锶,在氮气氛围和120℃温度下继续保温1h,在此期间重复抽真空通氮气步骤三次,待反应物完全溶解后升温至180℃保温10min,得前驱体溶液;将0.5mL温度150℃的油酸铯前驱体快速注入6m L前驱体溶液中,反应10s后进行冰水浴,自然冷却至室温,得绿色浑浊溶液;将绿色浑浊溶液在离心机中3000rpm离心3min,得一次沉淀,将一次沉淀分散在14mL正己烷中静置2h,得二次沉淀,将二次沉淀置于真空干燥箱45℃干燥20h,制得CsPb0.8Sr0.2Br3@SBA-15复合材料粉末(样品1)。
实施例2
将0.208g碳酸铯、10mL的1-十八烯和1mL油酸加入50mL三口烧瓶中,在氮气氛围下以600rpm转速搅拌,并以5℃/min的升温速率升温110℃,重复抽真空通氮气步骤三次,保温1.5h,直至碳酸铯完全溶解,溶液澄清透明时,升温至140℃,得油酸铯前驱体;将0.147g介孔二氧化硅、0.5mL油酸、0.5mL油胺和5mL的1-十八烯加入25mL三口烧瓶中,在氮气氛围下搅拌,并以5℃/min的升温速率升温加热至130℃,重复抽真空通氮气步骤三次;然后加入0.066g溴化铅和0.003g六水合溴化锶,继续保温1.5h,在此期间重复抽真空通氮气步骤三次,待反应物完全溶解后,升温至180℃保温20min,得前驱体溶液。将0.5mL温度140℃的油酸铯前驱体快速注入6mL前驱体溶液中,反应5s后进行冰水浴,自然冷却至室温,得绿色浑浊溶液;将绿色浑浊溶液在离心机中3000rpm离心3min得到一次沉淀,将一次沉淀分散在14mL正己烷中静置2h,得二次沉淀,二次沉淀置于真空干燥箱55℃干燥25h,制得CsPb0.95Sr0.05Br3@SBA-15复合材料粉末(样品2)。
实施例3
将0.208g碳酸铯、10mL的1-十八烯和1mL油酸加入50mL三口烧瓶中,在氮气氛围下以600rpm转速搅拌,并以5℃/min的升温速率升温至130℃,重复抽真空通氮气步骤三次,保温1h,至碳酸铯完全溶解,溶液澄清透明时,升温至160℃,得油酸铯前驱体;将0.147g介孔二氧化硅、0.5mL油酸、0.5mL油胺和5mL的1-十八烯加入25mL三口烧瓶中,在氮气氛围下搅拌,并以5℃/min的升温速率升温至125℃,保温期间重复抽真空通氮气步骤三次;然后加入0.048g溴化铅和0.02g六水合溴化锶,继续保温1.5h,在此期间重复抽真空通氮气步骤三次,待反应物完全溶解后,升温至180℃保温15min,得前驱体溶液;将0.5mL油酸铯前驱体快速注入6mL前驱体溶液中,反应7.5s后进行冰水浴,自然冷却至室温,得绿色浑浊溶液;将绿色浑浊溶液在离心机中3000rpm离心3min,得一次沉淀,将一次沉淀分散在14mL正己烷中静置2h,得二次沉淀,将二次沉淀置于真空干燥箱50℃干燥30h,制得CsPb0.7Sr0.3Br3@SBA-15复合材料粉末(样品3)。
实施例1所得复合材料的X射线衍射谱图,如图1。可以在15~30°处观察到介孔二氧化硅的宽化衍射峰,说明其为非晶态的二氧化硅。在图中可以观察到与立方相CsPbBr3量子点(PDF #54-0752)相对应的衍射峰,这表明制备得到的CsPb0.8Sr0.2Br3@SBA-15复合材料中的钙钛矿量子点均为立方晶体,且晶相单一。从图中没有观测到由于掺入锶离子而引起的衍射峰偏移,原因为掺入的锶离子半径(118pm)与铅离子半径(119pm)几乎相同。
实施例1制得复合材料的紫外吸收和荧光发射光谱图,如图2。从图中可以看出样品的吸收峰位于510nm,荧光发射峰具有良好的对称性,峰位位于528nm处,半峰宽为21nm。
实施例1所得样品的透射电子显微镜图,如图3。从图中可以看出钙钛矿量子点分布在介孔二氧化硅孔道中。
表1为实施例1~3制备的复合材料的发射峰位、量子产率以及在120℃温度下保留的初始荧光强度。
表1 样品1-3的基本信息
如表1所示,三个样品均有很高的量子产率,当锶离子的掺杂浓度为20%时,复合样品拥有最高的量子产率和最佳热稳定性。
稳定性测试结果
1)为了测试CsPbBr3量子点和实施例1制得CsPb0.8Sr0.2Br3@SBA-15复合样品的光稳定性。进行以下测试:将两种样品同时置于发射波长为365nm的紫外灯下,分别辐照0h、3h、7h、11 h、24 h、48 h和72 h后测试其PL光谱,通过PL光谱强度的变化来确定CsPbBr3量子点和CsPb0.8Sr0.2Br3@SBA-15复合样品的光稳定性。参阅图4,随着光照时间的增加,实施例1制得CsPb0.8Sr0.2Br3@SBA-15复合样品的荧光发射强度呈先上升,之后略微下降的趋势,当光照时间达到72h时,其荧光发射强度下降至初始强度的96%。与之对比,CsPbBr3量子点在紫外光照72h后荧光发射强度仅保留17%。因此,本发明制备的复合材料在紫外光照下表现出良好的稳定性。
2)为了测试CsPbBr3量子点和CsPb0.8Sr0.2Br3@SBA-15复合样品的热稳定性。进行以下测试:首先将两种样品分别放置于光谱仪外接加热台上,温度每升高20℃测试一次光谱,最终通过样品荧光发射强度的变化来判断其热稳定性变化情况。参阅图5,CsPb0.8Sr0.2Br3@SBA-15复合样品的荧光发射强度随温度上升逐渐下降,当温度升高至120℃时保留初始强度的46%;作为对比,CsPbBr3量子点随着温度升高,荧光发射强度迅速下降,当温度升高至120℃时仅保留初始强度的8%。因此,本发明制备的复合材料在高温下依旧保持良好的发光性能和稳定性。
本发明通过热注入法将锶离子掺杂到CsPbBr3量子点中,然后再将其原位生长在介孔二氧化硅孔道中,最终所得的CsPb0.8Sr0.2Br3@SBA-15复合样品具有稳定的晶体结构以及良好的光热稳定性。
Claims (5)
1.一种锶掺杂钙钛矿量子点/介孔二氧化硅复合材料,其特征在于,该复合材料的化学式为CsPb1-xSrxBr3@SBA-15,其中0.05≤x≤0.4。
2.如权利要求1所述的锶掺杂钙钛矿量子点/介孔二氧化硅复合材料,其特征在于,钙钛矿量子点组成为CsPb1-xSrxBr3,介孔二氧化硅的类型为SBA-15。
3.一种权利要求1所述锶掺杂钙钛矿量子点/介孔二氧化硅复合材料的制备方法,其特征在于,该制备方法具体为:
1)将0.102~0.814g碳酸铯、5~40mL的1-十八烯和0.5~2.5mL油酸加入三颈烧瓶中,在氮气气氛下搅拌,并升温至110~130℃,然后抽真空通氮气过程三次,保温至碳酸铯完全溶解,溶液澄清透明时,升温至140~160℃,得油酸铯前驱体;
2)按体积比1︰1︰10,分别取油酸、油胺和1-十八烯,再按0.5mL油酸需用0.147g介孔二氧化硅的比例,取介孔二氧化硅;再取溴化铅和六水合溴化锶;
将介孔二氧化硅、油酸、油胺和1-十八烯加入三口烧瓶中;在氮气氛围下搅拌,并升温至120~130℃,抽真空30 min;加入溴化铅和六水合溴化锶,在氮气氛围和120~130℃温度下保温,保温期间抽真空通氮气三次,待反应物完全溶解后,升温至180℃保温10~20min,得前驱体溶液;
3)按体积比1︰12,分别取温度140~160℃的油酸铯前驱体和温度180℃的前驱体溶液,将油酸铯前驱体迅速加入前驱体溶液中,反应5~10s后,迅速进行冰水浴,自然冷却至室温,得绿色浑浊溶液;
4)将绿色浑浊溶液在离心机中,离心,弃去上清液,得一次沉淀,一次沉淀分散在正己烷溶液中,静置,再次沉淀后,弃去上层清液,得二次沉淀,二次沉淀真空干燥,制得干燥的锶掺杂钙钛矿量子点/介孔二氧化硅复合材料。
4.如权利要求3所述的锶掺杂钙钛矿量子点/介孔二氧化硅复合材料的制备方法,其特征在于,所述步骤2)中,介孔二氧化硅中硅与钙钛矿材料中铅的摩尔质量比为1︰6~15;六水合溴化锶中锶与钙钛矿材料中铅的摩尔质量比为1︰1~20。
5.如权利要求3所述的锶掺杂钙钛矿量子点/介孔二氧化硅复合材料的制备方法,其特征在于,所述步骤4)中,二次沉淀在真空干燥箱中,温度45~55℃真空干燥20~30h。
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