CN115571906B - 一种硫化亚锡量子点薄膜及其制备方法和应用 - Google Patents
一种硫化亚锡量子点薄膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种可见光响应型硫化亚锡(SnS)量子点薄膜及其制备方法。本发明的制备方法可获得高质量的SnS量子点,具有较窄的尺寸分布和高的单分散性,比常规添加油酸的热注入法制备得到的可见光响应型SnS量子点薄膜太阳能电池的导电性能提高2~3倍;并利用旋涂法制备SnS量子点薄膜,降低了对工艺流程设备的要求,为设计其他实验路径提供便捷,对室温可见光太阳能电池应用领域具有重要意义。
Description
技术领域
本发明属于量子点合成技术领域,具体涉及一种可见光响应型硫化亚锡(SnS)量子点光电薄膜及其制备方法。
背景技术
太阳能因其可持续性、可用性、可普及性、成本效益、能源转换率等,被认为是最可能满足未来需求的可再生能源。太阳能电池是一种通过光电效应或光化学效应将光能直接转化为电能的半导体光伏器件,其发展经历了三个阶段。以硅片为基础的第一代太阳能电池其技术发展已经成熟,但高昂的生产成本催生了开发新一代太阳能电池的需求。第二代太阳能电池是基于薄膜材料的太阳能电池,其市场规模受限于薄膜太阳能电池较差的稳定性和制备该类器件的高技术难度。第三代太阳能电池被定义为“高性能、低成本”的光伏器件,胶体半导体量子点是满足上述需求的一种颇具潜力的材料,利用量子点的软化学法制备方法,可有效降低太阳能电池的生产成本,同时可兼容其他设计工艺,为第三代太阳能电池的设计与应用提供了具有潜力的发展思路。
半导体量子点发展至今,优异的光电特性使得它们在光电、热电等领域有着广泛的研究,大多数窄带隙半导体纳米材料通过调节尺寸和组分可实现在0.5到1.5eV之间的带隙调节。SnS是一种IV-VI族半导体材料,Sn的浓度决定其表现出p型或n型的导电性。制备SnS胶体量子点,通过调节其表面配体、反应温度、反应时间、形貌等可以调控量子点的光谱特性,可实现可见光波段良好的光电转化效率。同时,利用量子点材料制备薄膜,可以拓宽柔性光伏器件方面的应用,适配更多应用场景。
目前SnS胶体量子点的制备方法主要是溶液化学沉淀法,其典型步骤为:将一定量的SnCl2溶解在乙二醇单甲醚(C3H8O2)和正丁醇的混合溶剂中,最后在室温下将(NH4)2S溶解到10ml乙醇中来制备SnS胶体量子点(参见Materials Science in SemiconductorProcessing,36(2015):65-70.),但是该方法很难控制量子点的尺寸分布。热注入法可以通过控制反应时间调节胶体量子点的尺寸分布,使用SnCl2、TOP、正十八烷、硫代乙酰胺作反应原料,在120℃的注入温度下反应10s可以得到尺寸可控的SnS胶体量子点,但是所合成的量子点需要利用油酸作为钝化剂,且表面缺陷多(参见Acs Applied Energy Materials,2019,2(5):3822-3829.)。
发明内容
为了克服现有技术中的不足,本发明提供一种可见光响应型硫化亚锡(SnS)量子点光电薄膜及其制备方法,解决了现有的外延生长的薄膜对设备工艺要求苛刻、且现有制备SnS量子点的方法存在分散性差、尺寸分布不均、胶体稳定性差等问题。
为实现以上目的,本发明通过以下技术方案实现:
第一方面,本发明提供了一种硫化亚锡量子点薄膜的制备方法,包括如下步骤:
步骤(1)、在氮气保护下,将第一配体溶剂分散在容器中,在100-150℃下加热一段时间以去除所述第一配体溶剂中的水分,然后加入锡源,将温度控制在130-200℃,搅拌溶解至溶液澄清,得到锡前驱体溶液;
步骤(2)、在手套箱内,室温下将硫源分散在第二配体溶剂中搅拌溶解至溶液澄清,得到硫前驱体溶液;
步骤(3)、在氮气保护下,将步骤2所得的硫前驱体溶液注入至步骤1所得的锡前驱体溶液中,在100-170℃下生长0.5-60min,然后加入1-十二烷基硫醇进行配体置换,最后利用反溶剂离心并分散至合适的溶剂中,得到SnS量子点胶体溶液;
步骤(4)、在手套箱内,将步骤3所得的SnS量子点胶体溶液以一定转速和时间旋涂在清洗过的FTO玻璃上,然后加热退火一段时间;随后在所得的量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,即得到硫化亚锡量子点薄膜。
传统外延生长SnS工艺为分子束外延,使用该方法获得表面落差小于200μm、致密度高无孔洞的SnS薄膜技术要求极高且造价昂贵(参见J.Appl.Phys.111,093520)。通过制备SnS量子点来制造SnS薄膜是更经济且具发展潜力的选择,但现有制备SnS量子点的技术因依赖油酸这一长链配体,通常存在下述问题:量子点分散性差,胶体溶液中量子点发生团聚,不利于制备量子点薄膜(参见Surface&Coatings Technology 362(2019)78–83);尺寸分布不均,在6-14nm上广泛分布,影响量子点薄膜性能(参见ACS Appl.EnergyMater.2019,2,3822-3829)。因此,本发明的制备方法中不添加油酸,而另外加入烷基硫醇进行配体置换,优化量子点分散性,提高制备的硫化亚锡量子点薄膜的性能。
根据本发明的优选实施例,步骤(1)中,所述的第一配体溶剂为油胺或油胺和1-十八烯的混合物,所述锡源选自Sn[N(SiMe3)2]2和C3H9N3Sn中的至少一种。
根据本发明的优选实施例,步骤(2)中,所述的第二配体溶剂为三辛基膦。
根据本发明的优选实施例,步骤(3)中,所述锡源与所述硫源的摩尔比为1:0.2~5。
根据本发明的优选实施例,步骤(3)中,注入温度控制在100-170℃,所述反溶剂选自甲醇、乙醇和乙酸丁酯中的至少一种,所述分散溶剂选自氯苯和正己烷中的至少一种。
根据本发明的优选实施例,步骤(3)中,SnS量子点溶液的旋涂转速为1000-5000rpm,旋涂时间为10-60s;退火温度问60-150℃,退火时间为5-120min。
本发明采用热注入的方法制备SnS量子点,在一定温度下利用除水后的油胺溶解含锡前驱体,手套箱内在室温下用强配体溶解硫粉,随后将含硫前驱体溶液注入到含锡前驱体溶液中,在一定温度和反应时间的条件下得到理想粒径的SnS量子点。随后将SnS量子点旋涂在FTO玻璃上,蒸镀Cr/Au金属电极,得到一种可见光响应型SnS量子点薄膜。本发明的制备方法简单,重现性高,同时量子点的单分散性,窄尺寸分布,软化学法制备等特性均有利于降低薄膜制备成本,兼容其他设计工艺流程,为第三代量子点薄膜太阳能电池领域的应用提供了理想的发展思路。
第二方面,本发明还提供一种由上所述的制备方法制备的硫化亚锡量子点薄膜。
第三方面,本发明还提供一种如上所述的硫化亚锡量子点薄膜在太阳能电池中的应用。
与现有技术相比,本发明具有如下有益效果:
1、本发明提供了更多的反应原料供选择,且反应计量可以按照一定比例扩大进行实验,同时为了合成尺寸更大的SnS量子点,可直接在反应容器内加入额外的前驱体溶液进行生长,本发明提供的反应实现条件较温和,反应温度较低,操作简单;
2、本发明的方法可获得高质量的SnS量子点,具有较窄的尺寸分布和高的单分散性,比常规添加油酸的热注入法制备得到的可见光响应型SnS量子点薄膜太阳能电池的导电性能提高2~3倍;并利用旋涂法制备SnS量子点薄膜,降低了对工艺流程设备的要求,为设计其他实验路径提供便捷,对室温可见光太阳能电池应用领域具有重要意义。
附图说明
图1为本发明中实施例1中所制备的SnS量子点的透射电镜图像。
图2为本发明中实施例3中所制备的SnS量子点的透射电镜图像。
具体实施方式
以下结合具体实施例,对本发明做进一步说明。应理解,以下实施例仅用于说明本发明而非用于限制本发明的范围。
还应当理解,在本发明说明书中所使用的术语仅仅是出于描述特定实施例的目的而并不意在限制本发明。如在本发明说明书和所附权利要求书中所使用的那样,除非上下文清楚地指明其它情况,否则单数形式的“一”、“一个”及“该”意在包括复数形式。
实施例1:
一种可见光响应型硫化亚锡(SnS)量子点薄膜的制备方法,包括以下步骤:
在氮气保护作用下,在三颈烧瓶内加入15mL油胺,20mL 1-十八烯,在120℃下加热2小时,以去除配体和溶剂中存在的水分。称取0.5mmol(0.5mL)的Sn[N(SiMe3)2]2加入至三颈烧瓶内搅拌至溶液澄清。随后将温度维持在150℃,在手套箱内,室温下将0.5mmol(0.016g)硫粉,5mL三辛基膦,5mL1-十八烯搅拌至溶液澄清。将S-TOP溶液取出注入到含锡前驱体溶液中,此时生长温度控制在120℃,反应时间维持2min,冷水浴冷却至室温。然后加入5mL1-十二烷基硫醇进行配体置换,优化量子点分散性。随后加入30mL甲醇离心洗涤,重复两次离心步骤,最后分散至10mL氯仿中。
将FTO玻璃以洗洁精,乙醇,丙酮,水分别洗涤超声15min,随后利用等离子体臭氧清洗机清洗15min,氮气氛围下干燥。在手套箱内,于清洗过的FTO玻璃上,将SnS量子点以4000rpm的转速旋涂30s,随后在90℃下退火20min得到SnS量子点薄膜。随后在该量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,完成上述步骤后得到可见光响应型SnS量子点薄膜太阳能电池。
对实施例1制备得到的SnS量子点进行结构表征,如图1所得的透射电镜图像可以看出SnS量子点的形貌为球形。
实施例2:
一种可见光响应型硫化亚锡(SnS)量子点薄膜的制备方法,包括以下步骤:
在氮气保护作用下,在三颈烧瓶内加入15mL油胺,在130℃下加热3小时,以去除配体中存在的水分。称取0.5mmol(0.1030g)的C3H9N3Sn加入至三颈烧瓶内搅拌至溶液澄清。随后将温度维持在160℃,在手套箱内,室温下将0.5mmol(0.016g)硫粉,5mL三辛基膦,5mL1-十八烯搅拌至溶液澄清。将S-TOP溶液取出注入到含锡前驱体溶液中,此时生长温度控制在130℃,反应时间维持1.5min,冷水浴冷却至室温。然后加入5mL1-十二烷基硫醇进行配体置换,优化量子点分散性。随后加入30mL甲醇离心洗涤,重复两次离心步骤,最后分散至10mL正己烷中。
将FTO玻璃以洗洁精,乙醇,丙酮,水分别洗涤超声15min,随后利用等离子体臭氧清洗机清洗15min,氮气氛围下干燥。在手套箱内,在清洗过的FTO玻璃上,将SnS量子点以3500rpm的转速旋涂30s,随后在100℃下退火20min得到SnS量子点薄膜。随后在该量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,完成上述步骤后得到可见光响应型SnS量子点薄膜太阳能电池。
实施例3:
一种可见光响应型硫化亚锡(SnS)量子点薄膜的制备方法,包括以下步骤:
在氮气保护作用下,在三颈烧瓶内加入15mL油胺,20mL 1-十八烯,在120℃下加热2小时,以去除配体和溶剂中存在的水分。称取0.5mmol(0.5mL)的Sn[N(SiMe3)2]2加入至三颈烧瓶内搅拌至溶液澄清。随后将温度维持在150℃,在手套箱内,室温下将1mmol(0.032g)硫粉,8mL三辛基膦,2mL1-十八烯搅拌至溶液澄清。将S-TOP溶液取出注入到含锡前驱体溶液中,此时生长温度控制在110℃,反应时间维持2min,冷水浴冷却至室温。然后加入5mL1-十二烷基硫醇进行配体置换,优化量子点分散性。随后加入30mL甲醇离心洗涤,重复两次离心步骤,最后分散至10mL氯仿中。
将FTO玻璃以洗洁精,乙醇,丙酮,水分别洗涤超声15min,随后利用等离子体臭氧清洗机清洗15min,氮气氛围下干燥。在手套箱内,在清洗过的FTO玻璃上,将SnS量子点以3500rpm的转速旋涂40s,随后在80℃下退火25min得到SnS量子点薄膜。随后在该量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,完成上述步骤后得到可见光响应型SnS量子点薄膜太阳能电池。
对实施例3制备得到的SnS量子点进行结构表征,如图2所示,制备得到的SnS量子点在加长反应时间仍旧呈现出良好的单分散性。
实施例4:
一种可见光响应型硫化亚锡(SnS)量子点薄膜的制备方法,包括以下步骤:
在氮气保护作用下,三颈烧瓶内加入15mL油胺,20mL 1-十八烯,在120℃下加热2小时,以去除配体和溶剂中存在的水分。称取0.5mmol(0.5mL)的Sn[N(SiMe3)2]2加入至三颈烧瓶内搅拌至溶液澄清。随后将温度维持在150℃,在手套箱内,室温下将0.2mmol(0.0064g)硫粉,3mL三辛基膦,7mL1-十八烯搅拌至溶液澄清。将S-TOP溶液取出注入到含锡前驱体溶液中,此时生长温度控制在150℃,反应时间维持1.5min,冷水浴冷却至室温。然后加入5mL1-十二烷基硫醇进行配体置换,优化量子点分散性。随后加入30mL甲醇离心洗涤,重复两次离心步骤,最后分散至10mL正己烷中。
将FTO玻璃以洗洁精,乙醇,丙酮,水分别洗涤超声15min,随后利用等离子体臭氧清洗机清洗15min,氮气氛围下干燥。在手套箱内,在清洗过的FTO玻璃上,将SnS量子点以5000rpm的转速旋涂20s,随后在75℃下退火10min得到SnS量子点薄膜。随后在该量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,完成上述步骤后得到可见光响应型SnS量子点薄膜太阳能电池。
对比例:添加有油酸的常规热注入法制备量子点薄膜的工艺
SnS量子点的合成:在氮气保护下,将15mL油胺,20mL 1-十八烯、0.5mmol(0.5mL)的Sn[N(SiMe3)2]2加入至三颈烧瓶,升温到120℃并保持60min干燥反应物。通入氮气,2ml干燥的油胺,油酸,(0.016g)硫粉,等待溶液澄清透明后开始升温到165℃,迅速将2ml S-TOP溶液注入到锡前驱体溶液中,反应1min后冰水浴至室温结束反应。随后加入30mL甲醇离心洗涤,重复两次离心步骤,最后分散至10mL氯仿中。
将FTO玻璃以洗洁精,乙醇,丙酮,水分别洗涤超声15min,随后利用等离子体臭氧清洗机清洗15min,氮气氛围下干燥。在手套箱内,于清洗过的FTO玻璃上,将SnS量子点以3000rpm的转速旋涂30s,随后在90℃下退火20min得到SnS量子点薄膜。随后在该量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,完成上述步骤后得到可见光响应型SnS量子点薄膜太阳能电池。
实施例1~4和对比例制备的可见光响应型SnS量子点薄膜太阳能电池的导电性能比较请见表1所示。
表1
导电性能(cm2/(V·s) | |
实施例1 | 150 |
实施例2 | 130 |
实施例3 | 165 |
实施例4 | 155 |
对比例 | 50 |
由表1可以看出,本发明实施例1~4制备的可见光响应型SnS量子点薄膜太阳能电池的导电性能优于对比例制备的可见光响应型SnS量子点薄膜太阳能电池的导电性能2~3倍左右。说明本发明在常规热注入法的基础上不添加油酸、而加入烷基硫醇进行配体置换,可以使制备得到的可见光响应型SnS量子点薄膜太阳能电池的导电性能提高2~3倍。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (6)
1.一种硫化亚锡量子点薄膜的制备方法,其特征在于,包括如下步骤:
步骤(1)、在氮气保护下,将第一配体溶剂分散在容器中,在100-150°C下加热一段时间以去除所述第一配体溶剂中的水分,然后加入锡源,将温度控制在130-200°C,搅拌溶解至溶液澄清,得到锡前驱体溶液;所述的第一配体溶剂为油胺或油胺和1-十八烯的混合物,所述锡源选自Sn[N(SiMe3)2]2和C3H9N3Sn中的至少一种;
步骤(2)、在手套箱内,室温下将硫源分散在第二配体溶剂中搅拌溶解至溶液澄清,得到硫前驱体溶液;所述的第二配体溶剂为三辛基膦;
步骤(3)、在氮气保护下,将步骤2所得的硫前驱体溶液注入至步骤1所得的锡前驱体溶液中,在100-170°C下生长0.5-60min,然后加入1-十二烷基硫醇进行配体置换,最后利用反溶剂离心并分散至合适的溶剂中,得到SnS量子点胶体溶液;所述反溶剂选自甲醇、乙醇和乙酸丁酯中的至少一种,所述分散溶剂选自氯苯和正己烷中的至少一种;
步骤(4)、在手套箱内,将步骤3所得的SnS量子点胶体溶液以一定转速和时间旋涂在清洗过的FTO玻璃上,然后加热退火一段时间;随后在所得的量子点薄膜上通过真空蒸镀工艺蒸镀Cr/Au金属电极,即得到硫化亚锡量子点薄膜。
2.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,所述锡源与所述硫源的摩尔比为1:0.2~5。
3.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,注入温度控制在100-170°C。
4.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,SnS量子点溶液的旋涂转速为1000-5000rpm,旋涂时间为10-60s;退火温度问60-150°C,退火时间为5-120min。
5.一种由权利要求1-4任一项所述的制备方法制备的硫化亚锡量子点薄膜。
6.一种如权利要求5所述的硫化亚锡量子点薄膜在太阳能电池中的应用。
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