CN111129199A - 一种石墨烯/硫化铅/钙钛矿光电探测器及其制备方法 - Google Patents
一种石墨烯/硫化铅/钙钛矿光电探测器及其制备方法 Download PDFInfo
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Abstract
本发明提供一种石墨烯/硫化铅/钙钛矿光电探测器及其制备方法,其中,一种石墨烯/硫化铅/钙钛矿光电探测器,包括衬底,从所述衬底往上依次铺设有石墨烯薄膜、金属电极、硫化铅层、三维钙钛矿层、二维钙钛矿层;其中,所述石墨烯薄膜上两端各铺设有一个所述金属电极,且中间与所述硫化铅层接触。该石墨烯/硫化铅/钙钛矿光电探测器通过引入三维钙钛矿层钝化硫化铅层表面缺陷,抑制载流子的复合,提升载流子寿命;同时,硫化铅/三维钙钛矿复合结构可有效分离光生载流子,最终实现高增益的光电探测器;此外,覆盖二维钙钛矿薄膜,增强光电探测器的稳定性。该结构具有轻薄、增益高、稳定性好、易集成等优点,是一种实用性强的光电探测器。
Description
技术领域
本发明属于半导体光电子器件领域,具体涉及一种石墨烯/硫化铅/钙钛矿光电探测器及其制备方法。
背景技术
红外光电探测器是一种把红外光信号转换为电信号的器件,根据器件对红外光辐射响应方式的不同,红外光电探测器可分为光电导型、内建电场光伏型、光热电型和测辐射热计型。红外探测器是现代国防军事的重要技术,方便官兵在夜晚、烟雾、雾天中的观察作战。目前广泛应用的红外探测器技术包括制冷和非制冷两类,其中制冷型红外成像由于需要复杂的制冷设备,而导致系统笨重,不易于官兵作战。非制冷红外成像技术起步较晚,但是发展迅速,硫化铅红外光电探测器是一种典型的非制冷红外探测器。研究人员将石墨烯与硫化铅吸光层相结合,形成复合结构,石墨烯中的电子转移至近端吸光层,填充由光子吸收产生的吸光材料价带中的空态,使得吸光层中光激发产生的电子空穴对复合受到抑制,硫化铅中的电子保留在导带中而不会衰减。同时,石墨烯与硫化铅所形成的异质结可实现光生载流子的有效分离,使得载流子寿命增大,进而引起器件增益和响应度的协同增加。
在现有技术中,一般使用溶液法制备硫化铅纳米薄膜,这样得到的硫化铅纳米薄膜的表面存在较多缺陷,这些缺陷为载流子复合提供了可能,同时还将导致大的泄漏电流,影响探测器的增益、响应度和比探测率。为了实现高性能的石墨烯/硫化铅红外光电探测器,需要有效抑制硫化铅纳米薄膜的表面缺陷。
发明内容
有鉴于此,本发明的目的之一在于提供一种石墨烯/硫化铅/钙钛矿光电探测器,该光电探测器能有效抑制硫化铅纳米薄膜表面存在较多缺陷造成石墨烯/硫化铅红外光电探测器在使用时电流泄露、增益小的问题。
为实现上述目的,本发明的技术方案为:
一种石墨烯/硫化铅/钙钛矿光电探测器,包括衬底,从所述衬底往上依次铺设有石墨烯薄膜、金属电极、硫化铅层、三维钙钛矿层、二维钙钛矿层;其中,所述石墨烯薄膜上两端各铺设有一个所述金属电极,且所述石墨烯薄膜中间与所述硫化铅层接触。
优选地,所述衬底为带有二氧化硅层的硅片。
进一步地,所述金属电极与所述衬底间铺设1-3层石墨烯薄膜。
进一步地,所述金属电极包括金、银、铬/金、铬/银;优选地,含铬的复合金属电极,铬位于石墨烯薄膜之上,金或银薄膜位于铬之上。
进一步地,所述硫化铅层由粒径50-500nm的纳米晶粒或大小1-10nm的量子点构成。
进一步地,所述三维钙钛矿层厚度为100-300nm,包括PbI2/MAI、PbCl2/MAI、PbI2/FAI、PbI2/PbCl2/MAI、PbI2/MACl/MAI体系。
进一步地,所述二维钙钛矿层由多元环碘化胺和所述三维钙钛矿层中过量的PbI2反应生成,所述多元环碘化胺由多元环胺与氢碘酸通过酸碱成盐、旋蒸及重结晶得到;其中,所述多元环胺包括:环丁胺、环戊胺、环己胺、环庚胺、环辛胺。
有鉴于此,本发明的目的之二在于提供一种石墨烯/硫化铅/钙钛矿光电探测器的制备方法,该方法工艺流程简单,通过此方法制备出的光电探测器的硫化铅表面缺陷被钝化,增益大、稳定性高,具有很强的实用性。
为实现上述目的,本发明的技术方案为:
一种石墨烯/硫化铅/钙钛矿光电探测器的制备方法,包括以下步骤:
(1)制备单层石墨烯薄膜并将其转移至清洗干净的衬底上;
(2)在所述石墨烯薄膜表面沉积金属并图形化,形成金属电极;
(3)石墨烯薄膜的图形化;
(4)在图案化的石墨烯薄膜和所述金属电极表面依次制备硫化铅层、三维钙钛矿层和二维钙钛矿层。
进一步地,所述步骤(1)中采用化学气相沉积法在铜上制备石墨烯薄膜,通过PMMA将石墨烯薄膜从铜箔转移至衬底上。
进一步地,所述步骤(2)中通过磁控溅射得到连续金属薄膜,基于双层胶剥离工艺进行结构化得到所述金属电极,具体步骤如下:
首先在所述石墨烯薄膜旋涂双层光刻胶,曝光显影留下胶结构,然后溅射沉积金属薄膜,利用丙酮去除光刻胶,光刻胶表面的金属一并剥离掉,最终形成金属电极。
进一步地,所述步骤(3)中采用双层胶工艺进行光刻,随后通过等离子体刻蚀石墨烯薄膜,最后去胶完成石墨烯薄膜的图形化。
进一步地,所述步骤(4)中使用溶液法制备所述硫化铅层、三维钙钛矿层和二维钙钛矿层;其中,所述溶液法包括旋涂法、化学水浴法、狭缝涂布法、喷墨打印法。
有益效果
本发明提供一种石墨烯/硫化铅/钙钛矿光电探测器,引入三维钙钛矿层,三维钙钛矿结晶度高、晶粒大、表面平整,在硫化铅表面沉积后钝化硫化铅层表面缺陷,抑制载流子的复合,提升载流子寿命,同时,硫化铅/三维钙钛矿复合结构可有效分离光生载流子,最终实现高增益的光电探测器。在此基础之上,本发明的光电探测器还在三维钙钛矿层上覆盖二维钙钛矿薄膜,增强光电探测器的稳定性。从而获得增益高、响应度大、稳定性好的光电探测器。本发明提出的石墨烯/硫化铅/钙钛矿光电探测器,结构简单,工艺重复性好,可实现并联结构,能够进行规模化生产,是一种极具实用性的光电探测器。与此同时,本发明还提供了该石墨烯/硫化铅/钙钛矿光电探测器的制备方法。
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一简单地介绍。显而易见地,下面描述中的附图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性的前提下,还可以根据这些附图获得其它的附图。
图1为本发明一种石墨烯/硫化铅/钙钛矿光电探测器的制备方法的一实施例流程图;
图2为本发明一种石墨烯/硫化铅/钙钛矿光电探测器的一实施例结构示意图;
图3为本发明一种石墨烯/硫化铅/钙钛矿光电探测器中硫化铅层一实施例纳米晶薄膜的扫描电子显微镜图像;
图4为本发明一种石墨烯/硫化铅/钙钛矿光电探测器中硫化铅层一实施例量子点薄膜的扫描电子显微镜图像;
图5为本发明一种石墨烯/硫化铅/钙钛矿光电探测器中三维钙钛矿层一实施例MAPbIxCl3-x薄膜的扫描电子显微镜图像。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,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,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
所举实施例是为了更好地对本发明进行说明,但并不是本发明的内容仅局限于所举实施例。所以熟悉本领域的技术人员根据上述发明内容对实施方案进行非本质的改进和调整,仍属于本发明的保护范围。
实施例1
参考图1和图2,分别为一种石墨烯/硫化铅/钙钛矿光电探测器的制备方法的一实施例流程示意图和一种石墨烯/硫化铅/钙钛矿光电探测器的一实施例结构示意图。具体地,一种石墨烯/硫化铅/钙钛矿光电探测器的制备方法,包括以下步骤:
S10:制备石墨烯薄膜并将其转移至清洗干净的衬底上;然后执行步骤S20;
本实施例中,选用表面制有二氧化硅层的硅片作为衬底1。
本实施例中,在使用衬底1之前,分别用丙酮、酒精、去离子水超声清洗10分钟,然后用氮气吹干备用;然后在铜箔基底上,使用化学气相沉积法制备单层石墨烯薄膜2。
在本实施中,通过PMMA(聚甲基丙烯酸甲酯)将制备出的石墨烯薄膜2从铜箔转移至衬底1上,具体地,将石墨烯薄膜2切割成3cmx3cm尺寸大小,用胶带粘贴到铜箔下面的硅片上,将PMMA溶液旋涂至石墨烯薄膜2表面,转速为4000RPM,随后在烘箱中100度烘烤10分钟。将上述旋涂有PMMA的石墨烯薄膜2和铜箔从硅片上取下,先用氧等离子体刻蚀去除背面的石墨烯,然后用湿法腐蚀去除铜箔,以HCl+H2O2溶液(3:1)为刻蚀溶液,反应时间为3小时。溶铜完成后,利用去离子水反复漂洗,用衬底1捞出石墨烯薄膜2,将其放在空气中自然晾干,再放入丙酮中去除PMMA胶,完成石墨烯薄膜2的转移。
S20:在石墨烯薄膜表面沉积金属并图形化,形成金属电极;然后执行步骤S30;
本实施例中,金属电极3通过磁控溅射得到连续金薄膜,基于双层胶剥离工艺进行结构化得到。具体地,首先在石墨烯薄膜2上旋涂双层光刻胶,曝光显影留下胶结构,然后溅射沉积金薄膜,再利用丙酮去除光刻胶,此时将光刻胶表面的金一并剥离掉,最终形成金属电极3;此时,石墨烯薄膜2的两端分别存在一个金属电极3。
S30:石墨烯薄膜的图形化;然后执行步骤S40;
本实施例中,采用双层胶工艺对经过步骤S20的石墨烯薄膜2的空余表面进行光刻,随后通过等离子体刻蚀石墨烯薄膜2,最后去胶完成石墨烯薄膜2的图形化。
S40:在图案化的石墨烯薄膜和金属电极表面依次制备硫化铅层、三维钙钛矿层和二维钙钛矿层。
本实施例中,选择化学水浴法制备硫化铅层4,旋涂法制备三维钙钛矿层5和二维钙钛矿层6。首先将乙酸铅、硫脲、柠檬酸钠、氢氧化钠溶于水中,在40度水浴下制备得到100nm厚的纳米晶硫化铅层4用作吸光层,其表面形貌如图3所示。然后配置PbI2/FAI溶液用于制备三维钙钛矿层5,将PbI2/FAI溶液在硫化铅层4表面旋涂并退火得到280nm厚致密光滑的FAPbI3薄膜,即三维钙钛矿层5,最后旋涂环己碘化胺溶液,退火使得环己碘化胺和三维钙钛矿层5中过量的PbI2反应生成二维钙钛矿层6,其中过量的PbI2是PbI2/FAI溶液在制备三维钙钛矿层5残留下来的。
本实施例中,使用环己胺与氢碘酸通过酸碱成盐、旋蒸及重结晶得到环己碘化胺,当然,在其他实施例中,也可选用除环己胺外的其它多元环胺,如环丁胺、环戊胺、环己胺、环庚胺、环辛胺等通过相同方法制备出对应的多元环碘化胺,这些多元环碘化胺均可与过量的PbI2反应生成二维钙钛矿层6。
根据以上制备方法,可以得到如图2所示结构的石墨烯/硫化铅/钙钛矿光电探测器,具体包括衬底1,从衬底1往上依次铺设有石墨烯薄膜2、金属电极3、硫化铅层4、三维钙钛矿层5、二维钙钛矿层6;其中,石墨烯薄膜上两端各铺设有一个金属电极。
经测试,本实施例中得到的石墨烯/硫化铅/钙钛矿光电探测器在980nm入射光波长下,器件的响应度达到105A/W。在1550nm入射光波长下,光电探测器的响应度达到10A/W。
实施例2
在本实施例中,需制备出具有两层石墨烯薄膜2的石墨烯/硫化铅/钙钛矿光电探测器,其结构类似图2,不同的是,在本实施例中,石墨烯薄膜2为双层薄膜。
本实施例中,制备方法可参考实施例1,不同的是:
在本实施例中需要重复步骤S10中的转移石墨烯薄膜步骤一次,得到双层石墨烯薄膜2;
在本实施例中,使用旋涂法制备硫化铅层4,具体地,配置浓度为25mg/ml的硫化铅溶液,在3000RPM转速下,通过配体置换,制备得到5nm粒径的量子点薄膜硫化铅层4用作吸光层,其表面形貌如图4所示;然后选用PbI2/PbCl2/MAI溶液,将其在硫化铅层4表面旋涂并退火得到致密光滑的MAPbIxCl3-x薄膜,即本实施例中的三维钙钛矿层5,其表面形貌如图5所示,随后旋涂环辛碘化胺溶液,退火使得环辛碘化胺和三维钙钛矿层5中过量的PbI2反应生成二维钙钛矿层6。
通过上述描述以及参考实施例1中的步骤方法,可得到本实施例中的石墨烯薄膜2为双层薄膜、硫化铅层4为5nm粒径的量子点薄膜、三维钙钛矿层5为280nm厚的MAPbIxCl3-x,二维钙钛矿层6由环辛碘化胺与PbI2反应生成得到的石墨烯/硫化铅/钙钛矿光电探测器。
经测试,本实施例中得到的石墨烯/硫化铅/钙钛矿光电探测器在980nm入射光波长下,器件的响应度达到106A/W。在1550nm入射光波长下,光电探测器的响应度达到102A/W。
上面结合附图对本发明的实施例进行了描述,但是本发明并不局限于上述的具体实施方式,上述的具体实施方式仅仅是示意性的,而不是限制性的,本领域的普通技术人员在本发明的启示下,在不脱离本发明宗旨和权利要求所保护的范围情况下,还可做出很多形式,这些均属于本发明的保护之内。
Claims (10)
1.一种石墨烯/硫化铅/钙钛矿光电探测器,其特征在于,包括衬底,从所述衬底往上依次铺设有石墨烯薄膜、金属电极、硫化铅层、三维钙钛矿层、二维钙钛矿层;其中,所述石墨烯薄膜上两端各铺设有一个所述金属电极,且所述石墨烯薄膜中间与所述硫化铅层接触。
2.根据权利要求1所述的光电探测器,其特征在于,所述金属电极与所述衬底间铺设1-3层石墨烯薄膜。
3.根据权利要求1所述的光电探测器,其特征在于,所述金属电极包括金、银、铬/金、铬/银;其中,含铬的复合金属电极,铬位于石墨烯薄膜之上,金或银薄膜位于铬之上。
4.根据权利要求1所述的光电探测器,其特征在于,所述硫化铅层由粒径50-500nm的纳米晶粒或大小1-10nm的量子点构成。
5.根据权利要求1所述的光电探测器,其特征在于,所述三维钙钛矿层厚度为100-300nm,包括PbI2/MAI、PbCl2/MAI、PbI2/FAI、PbI2/PbCl2/MAI、PbI2/MACl/MAI体系。
6.根据权利要求1所述的光电探测器,其特征在于,所述二维钙钛矿层由多元环碘化胺和所述三维钙钛矿层中过量的PbI2反应生成,所述多元环碘化胺由多元环胺与氢碘酸通过酸碱成盐、旋蒸及重结晶得到;其中,所述多元环胺包括:环丁胺、环戊胺、环己胺、环庚胺、环辛胺。
7.一种石墨烯/硫化铅/钙钛矿光电探测器的制备方法,其特征在于,包括以下步骤:
(1)制备石墨烯薄膜并将其转移至清洗干净的衬底上;
(2)在所述石墨烯薄膜表面沉积金属并图形化,形成金属电极;
(3)石墨烯薄膜的图形化;
(4)在图案化的石墨烯薄膜和所述金属电极表面依次制备硫化铅层、三维钙钛矿层和二维钙钛矿层。
8.根据权利要求7所述的制备方法,其特征在于,所述步骤(2)中通过磁控溅射得到连续金属薄膜,基于双层胶剥离工艺进行结构化得到所述金属电极,具体步骤如下:
首先在所述石墨烯薄膜旋涂双层光刻胶,曝光显影留下胶结构,然后溅射沉积金属薄膜,利用丙酮去除光刻胶,光刻胶表面的金属一并剥离掉,最终形成金属电极。
9.根据权利要求7所述的制备方法,其特征在于,所述步骤(3)中采用双层胶工艺进行光刻,随后通过等离子体刻蚀石墨烯薄膜,最后去胶完成石墨烯薄膜的图形化。
10.根据权利要求7所述的制备方法,其特征在于,所述步骤(4)中使用溶液法制备所述硫化铅层、三维钙钛矿层和二维钙钛矿层;其中,所述溶液法包括旋涂法、化学水浴法、狭缝涂布法、喷墨打印法。
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CN115985995B (zh) * | 2022-12-01 | 2023-08-08 | 暨南大学 | 一种二维钙钛矿掺杂过渡金属硫族化合物同质结光电探测器及其制备方法 |
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