CN113583654B - 一种热致变色薄膜的制备方法及其应用 - Google Patents
一种热致变色薄膜的制备方法及其应用 Download PDFInfo
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Abstract
本发明提供一种钙钛矿结构的可逆热致变色薄膜的制备方法。该薄膜是经过溶液旋涂或刮涂再退火得到的,溶液溶质为ABIxBryCl3‑x‑y,其中A为Cs+、CH3NH3 +(MA+)或CH(NH2)2 +(FA+),B为Sn2+,溶剂为由N,N‑二甲基甲酰胺(DMF)和二甲基亚砜(DMSO)的混合液,添加剂为亚磷酸酯类包括亚磷酸三乙酯(TEP)和亚磷酸三苯酯(TPPi),添加量为5%;将溶质和溶剂按照1.0mol/L浓度配制完成后形成的前驱体溶液经旋涂或刮涂再退火后即可获得热致变色薄膜。本方案制备的薄膜在空气中呈现可逆的热致变色现象,根据x、y取值和退火温度的不同,薄膜呈现不同的颜色,且不同颜色薄膜之间在空气中可以发生可逆转变,即低温下的薄膜加热之后其颜色变为高温相的颜色,而在冷却之后又可以转变为原先的颜色,此过程可重复。
Description
技术领域
本发明属于热致变色薄膜领域,尤其涉及一种可逆热致变色薄膜的制备方法及应用。
背景技术
热致变色材料是指一些化合物或混合物在受热或冷却时可见吸收光谱发生变化的功能材料,它具有颜色随温度改变而变化的特性,发生颜色变化的温度称为变色温度。这种材料是一种热记忆功能材料,广泛应用于工业、纺织、军事、印刷、医疗保健、诊断、建筑、防伪标记、日用装饰、航空航天等各个领域。
随着研究的深入,热致变色功能薄膜的原料以及制备方法也在不断地发展,目前常用的可逆热致变色薄膜的材料主要分为无机和有机两大类,其中无机类材料主要为金属和金属卤化物、金属氧化物和多种金属氧化物的多晶,有机类材料主要三芳甲烷苯酞类、吲哚啉苯酞类、荧烷类、三苯甲烷类、螺吡喃类、席夫碱类、螺环类、双蒽酮类、α-萘醌衍生物、聚合物类(如聚二炔、聚硅烷、聚锗烷、聚噻吩)、生物大分子类等;相对于材料的两大种类来说,薄膜的制备方法就相对较多,主要有蒸镀法、溅射法、溶胶凝胶法、化学气相沉积法、分子自组装法等,虽然总体上来说,热致变色薄膜材料的种类和制备方法都有其特点,但从一定程度上来说薄膜原材料种类较少且这些制备方法都相对繁杂。
例如CN106711338A涉及一种锡基钙钛矿薄膜、方法及其太阳能电池器件;一种锡基钙钛矿薄膜,由DMF和DMSO中的一种或两种的混合液作为溶剂、钙钛矿和磷酸三苯酯作为溶质组成的溶液经旋涂并热处理后获得。该方法着重于钙钛矿薄膜的光电特性未涉及热致变色相关内容,且制备薄膜工艺范围不准确,薄膜均一性及重复率较差。
因此,寻找更多种类的热致变色材料以及开发更多薄膜制备的方法成为目前研究热致变色薄膜的一个重要方向。
发明内容
本发明的目的在于提供一种新型的热致变色材料以及简单的薄膜制备方法,旨在解决现有薄膜材料种类少且制备方法较为复杂的问题;同时薄膜具有优异的光电转换特性,可用于光电器件的制备。
本发明获得的薄膜颜色会随着ABIxBryCl3-x-y中的x、y值的变化而产生转变,其中x的值越大也就是I的含量越高,高温下薄膜颜色越黑。
本发明通过以下技术方案来实现:
一种热致变色薄膜的制备方法,该方法包括以下步骤:
步骤A:ABIxBryCl3-x-y作为溶质溶解在有机混合溶剂中,再加入液体添加剂制备前驱体溶液;
步骤B:通过旋涂和刮涂的办法将前驱体溶液制备成均匀薄膜;
步骤C:对制备好的薄膜进行热处理即可得到热致变色薄膜。将上述旋涂或刮涂后的薄膜在适当温度下进行退火,可以使热致变色薄膜结晶程度提高,质量变好。
作为本发明的一种优选技术方案,步骤A中所配制的前驱体溶液其溶质为ABIxBryCl3-x-y,其中A为Cs+、CH3NH3 +(MA+)或CH(NH2)2 +(FA+), B为Sn2+,来源于A和B的卤素化合物,选自CsI、FABr、SnCl2等,其中0≤x+y≤3。
作为本发明的一种优选技术方案,步骤A中液体添加剂为亚磷酸酯类包括亚磷酸三乙酯(TEP)和亚磷酸三苯酯(TPPi),其纯度需 95%以上,加入含量为体积比5%。
作为本发明的一种优选技术方案,步骤A中所配制的前驱体溶液其溶剂由与DMF和DMSO混合液组成,DMF和DMSO体积比例为9:1。
作为本发明的一种优选技术方案,步骤A中所述ABIxBryCl3-x-y的浓度为1.0mol/L。
前述步骤A中各材料配比的具体选择依据是热致变色薄膜的质量,经过实验优化将各原料配比以及添加剂含量稳定在固定范围,利于实验现象的重复也利于将来规模化生产;同时,本发明主要强调薄膜的变色特性及其应用范围,并对添加剂种类进行了完善。然而,如果材料组成及比例不在前述选择范围,则薄膜质量差异较大,重复率较低。
作为本发明的一种优选技术方案,所述步骤B中旋涂时转度为 2000-5000rpm,刮涂薄膜的厚度为1-10μm。
作为本发明的一种优选技术方案,所述步骤C中热处理温度为 40-130℃。所述步骤C中热处理时间为5-10分钟。
作为本发明的一种优选技术方案,所述方法包括:采用 ABIxBryCl3-x-y作为溶质;体积比例为9:1的DMF和DMSO的混合液作为溶剂;5%体积比含量的亚磷酸酯类(TEP或TPPi)作为添加剂;将三者充分搅拌混合后组成的前驱体溶液经旋涂或刮涂后获得该薄膜。
具体工艺包括:旋涂工艺,在2000-5000rpm的转速下,旋涂得到热致变色薄膜;刮涂工艺,将溶液或乳液滴加到衬底上,使用刮刀或玻璃棒刮涂出均匀薄膜。
作为本发明的一种优选技术方案,其中前驱体溶液浓度为1.0 mol/L,旋涂制备时转速为2000-5000rpm,加热温度为40-130℃,热处理时间为5-10分钟。
本发明进一步提供了一种可逆的热致变色薄膜,通过所述的热致变色薄膜的制备方法制备得到。
本发明相对于现有技术的有益效果包括:
本发明提供了一种利用新型材料制备热致变色薄膜的方法,不仅增加了一类热致变色原材料还引入了较为简单的制备方法,降低制备时间;其应用还包含各种基于此发明的成膜方法获得热致变色薄膜的器件,如传感器、智能窗、太阳能电池、光探测器等。
本发明采用新型材料制备热致变色薄膜,可以在短时间内获得较高质量的薄膜,为变色薄膜制备增加新的材料选择,同时可用于柔性电子、智能光电设备等的开发及制备。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。
图1是本发明中热致变色薄膜成膜方法的流程图。
其中11----加入亚磷酸酯类的N.N-二甲基甲酰胺(DMF)与二甲基亚砜(DMSO)的混合溶液,12----CsX粉末(X为卤素元素), 13----SnX2(X为卤素元素),14----CsSnIxBryCl3-x-y前驱体溶液,15----基于14溶液的热致变色薄膜,16----基于15薄膜冷却后的变色薄膜,17----基于16薄膜加热后的变色薄膜,其中17薄膜恢复到 15薄膜。
图2和3系本发明中实施例1内通过本发明的方法制备的 FASnI0.5Br0.5Cl2热致变色薄膜。
其中图2是FASnI0.5Br0.5Cl2前驱体溶液在40℃下退火形成薄膜后的变色情况,其中,211是薄膜在40℃下退火完成时的颜色状态, 212是211中的薄膜在空气中冷却10分钟后的颜色状态,213是212 的薄膜在40℃条件下加热10分钟后的颜色状态。图3是图2FASnI0.5Br0.5Cl2薄膜在变色前后的可见光吸收光谱,其中,A1是薄膜在40℃下退火完成时的可见光吸收光谱,A2薄膜在空气中冷却10 分钟变色之后的可见吸收光谱,A3是变色后的薄膜在40℃条件下加热10分钟后的可见吸收光谱。
图4和5系本发明中实施例2内通过本发明的方法制备的 MASnIBr0.5Cl1.5热致变色薄膜
其中图4是MASnIBr0.5Cl1.5前驱体溶液在70℃下退火形成薄膜后的变色情况,其中,311是薄膜在70℃下退火完成时的颜色状态, 312是311中的薄膜在空气中冷却10分钟后的颜色状态,313是312 中的薄膜在70℃条件下加热10分钟后的颜色状态。图5是图4MASnIBr0.5Cl1.5薄膜在变色前后的可见光吸收光谱,其中,B1是薄膜在70℃下退火完成时的可见光吸收光谱,B2薄膜在空气中冷却10 分钟变色之后的可见吸收光谱,B3是变色后的薄膜在70℃条件下加热10分钟后的可见吸收光谱。
图6和7系本发明中实施例3内通过本发明的方法制备的 CsSnIBrCl热致变色薄膜
其中图6是CsSnIBrCl前驱体溶液在110℃下退火形成薄膜后的变色情况,411是薄膜在110℃下退火完成时的颜色状态,412 是411中的薄膜在空气中冷却10分钟后的颜色状态,413是412中的薄膜在110℃条件下加热10分钟后的颜色状态。图7是图6中 CsSnIBrCl薄膜在变色前后的可见光吸收光谱,其中,C1是薄膜在 110℃下退火完成时的可见光吸收光谱,C2薄膜在空气中冷却10分钟变色之后的可见吸收光谱,C3是变色后的薄膜在110℃条件下加热10分钟后的可见吸收光谱。
图8和9系本发明中实施例4制备的电池器件结构及电池工作时的J-V曲线示意图。
图10、11和12系本发明中对比实施例1热致变色薄膜形貌示意图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
实施例1
参照图1所示,制备FASnIBr0.5Cl1.5变色薄膜:将FAI、SnBr2、 SnCl2按照摩尔比例1:0.25:0.75称取按照1mol/L的浓度溶解在0.9 mL DMF和0.1mL DMSO的混合溶剂中并添加5%TEP(纯度为98%) 经过搅拌获得澄清的前驱体溶液;取50uL前驱体溶液滴在玻璃片上在4000rpm转速下获得均匀薄膜;然后在40℃下退火10分钟即可得到热致变色薄膜,对薄膜加热和冷却状态下分别进行可见光吸收测试,测试结果如图2和图3所示。
实施例2
参照图1所示,制备MASnI0.5Br0.5Cl2变色薄膜:将MAI、SnBr2、 SnCl2按照摩尔比例0.5:0.25:1称取按照1mol/L的浓度溶解在0.9 mL DMF和0.1mL DMSO混合溶剂中并添加5%TPPi(纯度为98%)经过搅拌获得澄清的前驱体溶液;取50uL前驱体溶液滴在玻璃片上在3000rpm转速下获得均匀薄膜;然后在70℃下退火10分钟即可得到热致变色薄膜,对薄膜加热和冷却状态下分别进行可见光吸收测试,测试结果如图4和图5所示。
实施例3
参照图1所示,制备CsSnIBrCl变色薄膜:将CsI、SnBr2、SnCl2按照摩尔比例1:0.5:0.5称取按照1mol/L的浓度溶解在0.9mL DMF 和0.1mL DMSO混合溶剂中并添加5%TPPi(纯度为98%)经过搅拌获得澄清的前驱体溶液;取50uL前驱体溶液滴在玻璃片上在2000 rpm转速下获得均匀薄膜;然后在100℃下退火10分钟即可得到热致变色薄膜,对薄膜加热和冷却状态下分别进行可见光吸收测试,测试结果如图6和图7所示。
实施例4
参照实施例3配方制备基于CsSnIBrCl薄膜的智能变色太阳能电池器件;如图8所示为电池器件结构,其中511层为ITO电极,512 层为空穴传输层PEDOT:PSS,513层为CsSnIBrCl变色薄膜活性层, 514层为电子传输层PCBM+BCP(浴铜灵),515层为银电极;图9所示为电池工作时的J-V曲线,其中D1曲线为高温情况下薄膜为黑色时器件的工作状态,短路电流可以达到22.15mA/cm2,开路电压为 0.544V,效率可达8.55%;D2曲线为低温情况下薄膜为黑色时器件的工作状态,短路电流可以达到3.70mA/cm2,开路电压为0.496V,效率可达1.24%;D3曲线为重新加热后高温情况下薄膜为黑色时器件的工作状态,短路电流可以达到21.68mA/cm2,开路电压为0.582V,效率可达8.83%。这类温度变色太阳能器件可用于智能窗制备,低温下增强室内透光性,高温下可以降低光的透过并同时将光能转化为电能;此外温度与薄膜颜色的相关性还可用于温度及光探测方向。
对比实施例1
参照图1所示,制备CsSnIBrCl变色薄膜:将CsI、SnBr2、SnCl2按照摩尔比例1:0.5:0.5称取按照2.0mol/L的浓度溶解在1mL DMF 溶剂中并添加10%TEP(纯度为98%)经过搅拌获得前驱体溶液;取50uL前驱体溶液在2000rpm转速下获得均匀薄膜;然后在100℃下退火10分钟即可得到热致变色薄膜,薄膜形貌如图10、图11和图12所示,与实施例3相比,对比实施例1(本例)中溶液的浓度由1.0mol/L提高到2.0mol/L,添加剂从5%TPPi变成10%TEP,其他条件不变,薄膜质量从图10中看出高温下薄膜呈现均匀黑色,但低温相(612)呈现非均匀相分布,这与薄膜浓度和添加剂含量息息相关;从图11中可以看到实施例3中的变色薄膜在微观尺度下晶粒分布均匀,而本对比实施例薄膜微观形貌如图12所示,其薄膜覆盖率较差,晶粒分布不均使得薄膜低温相分布较差,影响薄膜整体质量也会进一步影响薄膜的实际应用。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.一种钙钛矿结构的热致变色薄膜的制备方法,包括以下步骤:
制备CsSnIBrCl变色薄膜:将CsI、SnBr2、SnCl2按照摩尔比例1:0.5:0.5称取按照1mol/L的浓度溶解在0.9mL DMF和0.1mL DMSO混合溶剂中并添加5%TPPi,TPPi纯度为98%,经过搅拌获得澄清的前驱体溶液;取50uL前驱体溶液滴在玻璃片上在2000rpm转速下获得均匀薄膜;然后在100℃下退火10分钟即可得到热致变色薄膜。
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