CN114591742A - 一种铜铟锡硒/硒化锌核壳量子点及其制备方法与应用 - Google Patents
一种铜铟锡硒/硒化锌核壳量子点及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种铜铟锡硒/硒化锌核壳量子点及其制备方法与应用，其制备方法包括以下步骤：将碘化亚铜、醋酸铟、二氯化锡、油胺和正十八烯混合后，于惰性气体氛围下、100～120℃下保温，再于170～190℃注入硒前驱体溶液，并保温，其后进行淬灭，再经纯化后，溶解于正十八烯与油胺中，得铜铟锡硒量子点溶液；将铜铟锡硒量子点溶液于惰性气体氛围下、140～160℃下保温，再逐滴注入锌前驱体溶液，其后逐滴注入硒前驱体溶液，再升温至210～230℃，并保温25‑35min，其后进行淬灭，即得。本发明的铜铟锡硒/硒化锌核壳量子点材料在近红外波段具有良好的光吸收能力，具有良好的光生载流子生成能力。
Description
技术领域
本发明属于光电材料与探测技术领域，具体涉及一种铜铟锡硒/硒化锌核壳量子点及其制备方法与应用。
背景技术
光电探测器是一种可以将光信号转换为电信号的光电子器件，目前已经被广泛用于工业检测、安防监控、医疗、交通等多个领域。随着探测技术的进一步发展，市场无疑将更多地从军用向民用转换，如无人驾驶车辆、便携/手持式诊断系统等领域，进一步加速市场增长。目前主流的光电探测器以III-VI族半导体材料为基础，且一般通过单晶生长或分子束外延来制备，其工艺成本高、器件组装复杂、不能满足大尺寸制备应用，且与传统硅基技术不兼容，这阻碍了器件的进一步片上集成。而半导体胶体量子点因其优异的光电特性而成为光电材料的不二选择，且其有基于溶液制备、大面积、低成本、可延展、兼容性强等特点，克服了传统材料在光电探测器件制备应用中的劣势。
然而，迄今为止，基于半导体胶体量子点的近红外光电探测器大多基于剧毒金属铅、汞等组分量子点制备而成，将不可避免地给自然环境以及人类健康带来问题，其阻碍了量子点近红外光电探测器的商业化。因此，开发环保型的红外半导体胶体量子点具有重要意义。
此外，在核量子点表面生长合适的壳层材料，可以有效地抑制表面相关缺陷/陷阱态，获得定制的量子点光响应(例如拓展光吸收、增强吸光能力等)。因此，合理设计生长核壳结构量子点是获得量子点高载流子生成效率的有效策略，进而最终实现高性能的量子点近红外光电探测器。
发明内容
针对上述现有技术，本发明提供一种铜铟锡硒/硒化锌核壳量子点及其制备方法与应用，以解决现有的红外量子点材料存在的重金属高毒性组分、表面缺陷/陷阱态、其制备工艺复杂、造价昂贵、工作耐久性差、暗电流高等问题。
为了达到上述目的，本发明所采用的技术方案是：提供一种铜铟锡硒/硒化锌核壳量子点的制备方法，包括以下步骤：
(1)将碘化亚铜、醋酸铟、二氯化锡、油胺和正十八烯混合后，于惰性气体氛围下、100～120℃下保温10-60min，再于170～190℃注入硒前驱体溶液，并保温8-12min，其后进行淬灭，得铜铟锡硒量子点；
(2)将铜铟锡硒量子点纯化后，溶解于正十八烯与油胺中，得铜铟锡硒量子点溶液；
(3)将铜铟锡硒量子点溶液于惰性气体氛围下、140～160℃下保温8-12min，再逐滴注入锌前驱体溶液，其后逐滴注入硒前驱体溶液，再升温至210～230℃，并保温25-35min，其后进行淬灭，即得。
在各种环保型量子点中，铜铟硒胶体量子点具有高吸收和窄带隙的特点，而将锡掺杂在铜铟硒量子点中，可以更进一步减小带隙，增强对近红外波段光的捕获，提高光电探测器在近红外波段的探测性能。该量子点材料在近红外波段的光激发下能够很好将量子点中产生的电子和空穴分离，通过外电路读出，从而实现高性能的近红外光电探测。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，步骤(1)中硒前驱体溶液由以下步骤制得：将单质硒超声分散于油胺和二苯基膦的混合溶液中，即得；步骤(3)中硒前驱体溶液由以下步骤制得：将单质硒超声分散于三辛基膦中，即得；锌前驱体溶液由以下步骤制得：将硬脂酸锌超声分散于正十八烯中，即得。
进一步，单质硒、油胺和二苯基膦的用量比为3mmol:5ml:3ml；单质硒、三辛基膦的用量比为3mmol:20ml；硬脂酸锌、正十八烯的用量比为3mmol:20ml。
进一步，步骤(1)中碘化亚铜、醋酸铟、二氯化锡、油胺、正十八烯、硒前驱体溶液的用量比为0.2mmol:0.2mmol:0.4mmol:2ml:2ml:0.8ml。
进一步，纯化包括以下步骤：将铜铟锡硒量子点与乙醇按体积比1：3混合，再以4000转/秒的速度离心2min，取沉淀加入体积为铜铟锡硒量子点体积2.5倍的甲苯中，再以4000转/秒的速度离心1min，取上清液加入体积为铜铟锡硒量子点体积4.5倍的乙醇中，再以4000转/秒的速度离心1min。
进一步，升温速度为2-4℃/min。
本发明还提供了上述制备方法制得的铜铟锡硒/硒化锌核壳量子点。
本发明还提供了上述铜铟锡硒/硒化锌核壳量子点在制备光电导材料中的应用。
本发明的有益效果是：
1、本发明制备的铜铟锡硒/硒化锌核壳结构量子点材料为一种新型的半导体量子点材料，在近红外波段具有良好的光吸收能力，通过定制硒化锌壳层材料构筑核壳结构，有效解决了现有的量子点材料存在的大量的表面缺陷/陷阱态等问题，提升了材料光生载流子的生成能力。
2、本发明提供了一种基于铜铟锡硒/硒化锌核壳结构量子点的光电探测器，该器件可以在光激发下将量子点中产生的载流子有效分离，并通过外电路读出，从而实现高性能的近红外光电探测，相比于传统近红外光电探测器，有效解决了其工艺复杂且造价昂贵、工作耐久性差、暗电流高、对自然环境和人类有害等问题。
附图说明
图1为本发明实施例1中铜铟锡硒/硒化锌核壳量子点的TEM形貌表征图；
图2为采用本发明实施例1中铜铟锡硒/硒化锌核壳量子点制得的光电探测器在790nm近红外波长辐照下测试的光暗电流示意图；
图3为采用本发明实施例1中铜铟锡硒/硒化锌核壳量子点制得的光电探测器在980nm近红外波长辐照下测试的光暗电流示意图。
具体实施方式
下面结合附图对本发明的具体实施方式做详细的说明。
实施例1
一种铜铟锡硒/硒化锌核壳量子点材料，其制备方法包括以下步骤：
(1)将0.2mmol碘化亚铜、0.2mmol醋酸铟、0.04mmol二氯化锡与2ml油胺、2ml正十八烯硫混合后加入到三颈烧瓶中，于氮气氛围下升温至120℃，并保温10min，再升温至190℃，注入硒前驱体溶液，并保温10min，最后注入10ml正己烷进行反应淬灭，得铜铟锡硒量子点；其中，硒前驱体溶液的制备方法为：将0.3mmol单质硒粉、0.5ml油胺和0.3ml二苯基膦混合后，超声分散，即得；
(2)将0.75mmol硬脂酸锌和5ml正十八烯混合后，超声分散至溶解，得锌前驱体溶液；将0.6mmol单质硒粉和4ml三辛基膦混合后，超声分散至溶解，得硒前驱体溶液；
(3)取2ml铜铟锡硒量子点于试管中，加入6ml乙醇，以4000转/秒的速度离心2min，取沉淀加入5ml甲苯，以4000转/秒的速度离心1min，取上清液，将上清液均分为14管，每个试管加入4.5ml乙醇，以4000转/秒的速度离心1min，得纯化的铜铟锡硒量子点；
(4)将纯化的铜铟锡硒量子点溶解于3ml正十八烯和5ml油胺中，再于氮气氛围下升温至160℃并保温10min，再向其中逐滴注入步骤(2)中的锌前驱体混合溶液1.2ml，再向其中逐滴注入步骤(2)中的硒前驱体混合溶液1.2ml，其后以3℃/min的速度升温至230℃并保温30min，最后进行淬灭，即得。
实施例2
一种铜铟锡硒/硒化锌核壳量子点材料，其制备方法包括以下步骤：
(1)将0.2mmol碘化亚铜、0.2mmol醋酸铟、0.04mmol二氯化锡与2ml油胺、2ml正十八烯硫混合后加入到三颈烧瓶中，于氮气氛围下升温至110℃，并保温30min，再升温至180℃，注入硒前驱体溶液，并保温8min，最后注入10ml正己烷进行反应淬灭，得铜铟锡硒量子点；其中，硒前驱体溶液的制备方法为：将0.3mmol单质硒粉、0.5ml油胺和0.3ml二苯基膦混合后，超声分散，即得；
(2)将0.75mmol硬脂酸锌和5ml正十八烯混合后，超声分散至溶解，得锌前驱体溶液；将0.6mmol单质硒粉和4ml三辛基膦混合后，超声分散至溶解，得硒前驱体溶液；
(3)取2ml铜铟锡硒量子点于试管中，加入6ml乙醇，以4000转/秒的速度离心2min，取沉淀加入5ml甲苯，以4000转/秒的速度离心1min，取上清液，将上清液均分为14管，每个试管加入4.5ml乙醇，以4000转/秒的速度离心1min，得纯化的铜铟锡硒量子点；
(4)将纯化的铜铟锡硒量子点溶解于3ml正十八烯和5ml油胺中，再于氮气氛围下升温至150℃并保温8min，再向其中逐滴注入步骤(2)中的锌前驱体混合溶液1.2ml，再向其中逐滴注入步骤(2)中的硒前驱体混合溶液1.2ml，其后以2℃/min的速度升温至220℃并保温25min，最后进行淬灭，即得。
实施例3
一种铜铟锡硒/硒化锌核壳量子点材料，其制备方法包括以下步骤：
(1)将0.2mmol碘化亚铜、0.2mmol醋酸铟、0.04mmol二氯化锡与2ml油胺、2ml正十八烯硫混合后加入到三颈烧瓶中，于氮气氛围下升温至100℃，并保温60min，再升温至170℃，注入硒前驱体溶液，并保温12min，最后注入10ml正己烷进行反应淬灭，得铜铟锡硒量子点；其中，硒前驱体溶液的制备方法为：将0.3mmol单质硒粉、0.5ml油胺和0.3ml二苯基膦混合后，超声分散，即得；
(2)将0.75mmol硬脂酸锌和5ml正十八烯混合后，超声分散至溶解，得锌前驱体溶液；将0.6mmol单质硒粉和4ml三辛基膦混合后，超声分散至溶解，得硒前驱体溶液；
(3)取2ml铜铟锡硒量子点于试管中，加入6ml乙醇，以4000转/秒的速度离心2min，取沉淀加入5ml甲苯，以4000转/秒的速度离心1min，取上清液，将上清液均分为14管，每个试管加入4.5ml乙醇，以4000转/秒的速度离心1min，得纯化的铜铟锡硒量子点；
(4)将纯化的铜铟锡硒量子点溶解于3ml正十八烯和5ml油胺中，再于氮气氛围下升温至140℃并保温12min，再向其中逐滴注入步骤(2)中的锌前驱体混合溶液1.2ml，再向其中逐滴注入步骤(2)中的硒前驱体混合溶液1.2ml，其后以4℃/min的速度升温至210℃并保温35min，最后进行淬灭，即得。
实验例
采用实施例1所得的铜铟锡硒/硒化锌核壳量子点材料制备光电探测器，具体制备过程如下：
制作光电探测器中叉指电极：使用线宽为50微米的激光对掺氟氧化锡导电玻璃(FTO)进行刻蚀，形成叉指对数为20对，指间距为50微米，指长4毫米，指宽度50微米，厚度为300纳米的叉指电极；将刻蚀好的电极依次放入丙酮、乙醇、去离子水溶液中并超声30分钟后取出，使用氮气枪吹干，通过流延法将二氧化钛浆料沉积在FTO玻璃基板上，然后在120℃的热板上加热6分钟，最后将FTO玻璃基板在500℃的炉中在空气中以5℃/min的升温速率烧结30分钟；
然后进行介孔TiO2薄膜中量子点的敏化：电泳沉积(EPD)过程：将具有彼此面对的TiO2膜的两个FTO玻璃基板垂直浸入量子点甲苯溶液中；FTO玻璃基板之间的距离保持1厘米；在两个FTO上施加200V的直流(DC)偏压源120分钟；然后用甲苯洗涤光电阳极数次以除去未结合的量子点并用N2气干燥；
然后将FTO保持在CTAB溶液(CTAB 0.2g溶在20mL甲醇中)中1分钟，随后用甲醇洗涤并用N2干燥；该过程重复两次；通过使用连续离子层吸附反应(SILAR)方法沉积ZnS覆盖层来对沉积量子点后的FTO进行表面处理；0.1M的Zn(Ac)2溶液(在甲醇中)充当Zn2+的来源，并且0.1M的Na2S溶液(甲醇：去离子水为1：1)充当S2-的来源；对于所有FTO，使用两个SILAR循环；一个SILAR循环包括在Zn2+溶液中连续的光电阳极浸涂涂层1分钟，在S2-溶液中1分钟；每次浸涂后，通过相应的溶剂(甲醇或甲醇：去离子水＝1:1)彻底冲洗FTO，以除去残留的化学物质并用N2干燥。
借助标准的790nm和980nm近红外激光探头，源表(Keithley 2450-EC)提供外置2V电压，对上述制备的光电探测器进行性能测试，具体结果如图1～3所示。
从图1可以看到，量子点截面投影多为三角形和四边形，这是因为我们合成的量子点具有金字塔形状。
从图2可以看到光电探测的响应速度比较快，稳定性良好。
图3中在980nm波段下依旧有响应，说明量子点光电探测器实现了近红外的光电探测。
虽然结合附图对本发明的具体实施方式进行了详细地描述，但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内，本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (8)
1.一种铜铟锡硒/硒化锌核壳量子点的制备方法，其特征在于，包括以下步骤：
(1)将碘化亚铜、醋酸铟、二氯化锡、油胺和正十八烯混合后，于惰性气体氛围下、100～120℃下保温10-60min，再于170～190℃注入硒前驱体溶液，并保温8-12min，其后进行淬灭，得铜铟锡硒量子点；
(2)将铜铟锡硒量子点纯化后，溶解于正十八烯与油胺中，得铜铟锡硒量子点溶液；
(3)将铜铟锡硒量子点溶液于惰性气体氛围下、140～160℃下保温8-12min，再逐滴注入锌前驱体溶液，其后逐滴注入硒前驱体溶液，再升温至210～230℃，并保温25-35min，其后进行淬灭，即得。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中硒前驱体溶液由以下步骤制得：将单质硒超声分散于油胺和二苯基膦的混合溶液中，即得；步骤(3)中硒前驱体溶液由以下步骤制得：将单质硒超声分散于三辛基膦中，即得；所述锌前驱体溶液由以下步骤制得：将硬脂酸锌超声分散于正十八烯中，即得。
3.根据权利要求2所述的制备方法，其特征在于：所述单质硒、油胺和二苯基膦的用量比为3mmol:5ml:3ml；所述单质硒、三辛基膦的用量比为3mmol:20ml；所述硬脂酸锌、正十八烯的用量比为3mmol:20ml。
4.根据权利要求3所述的制备方法，其特征在于：步骤(1)中碘化亚铜、醋酸铟、二氯化锡、油胺、正十八烯、硒前驱体溶液的用量比为0.2mmol:0.2mmol:0.4mmol:2ml:2ml:0.8ml。
5.根据权利要求1所述的制备方法，其特征在于，所述纯化包括以下步骤：将铜铟锡硒量子点与乙醇按体积比1：3混合，再以4000转/秒的速度离心2min，取沉淀加入体积为铜铟锡硒量子点体积2.5倍的甲苯中，再以4000转/秒的速度离心1min，取上清液加入体积为铜铟锡硒量子点体积4.5倍的乙醇中，再以4000转/秒的速度离心1min。
6.根据权利要求1所述的制备方法，其特征在于：所述升温速度为2-4℃/min。
7.根据权利要求1～6任一项所述的制备方法制得的铜铟锡硒/硒化锌核壳量子点。
8.根据权利要求7所述的铜铟锡硒/硒化锌核壳量子点在制备光电导材料中的应用。
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| CN116285994A (zh) * | 2023-03-17 | 2023-06-23 | 电子科技大学长三角研究院(湖州) | 一种金修饰的铜铝硫/硒化锌核壳量子点材料及其制备方法和应用 |
| CN116285994B (zh) * | 2023-03-17 | 2024-01-26 | 电子科技大学长三角研究院(湖州) | 一种金修饰的铜铝硫/硒化锌核壳量子点材料及其制备方法和应用 |
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