CN110350045B - PbS量子点Si-APD红外探测器及其制备方法 - Google Patents
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Abstract
本发明提出一种PbS量子点Si‑APD红外探测器及其制备方法,所述探测器包括本征Si衬底(1)、减反膜区(4)、N+掺杂区(3)、P掺杂区(2)、P+掺杂区(6)、PbS量子点层(7)、上电极(5)和下电极(8),减反膜区(4)位于本征Si衬底(1)正上方、N+掺杂区(3)位于反射区(4)下方、P掺杂区(2)位于N+掺杂区(3)下方、P+掺杂区(6)位于本征Si衬底(1)下方、PbS量子点层(7)位于P+掺杂区(6)下方、上电极(5)位于反射区(4)上表面,以及下电极(8)位于PbS量子点层(6)下表面。本发明以PbS量子点层作为吸收层,采用纯电子注入的方式,使得本发明能够吸收近红外波段光波,具有光谱响应宽,响应度高,过噪声小,成本低,易于加工等优点。
Description
技术领域
本发明属于光电探测器技术领域,具体涉及一种PbS量子点Si-APD红外探测器及其制备方法,其涉及光电探测器结构和半导体纳米材料的硅基雪崩光电探测器技术。
背景技术
雪崩光电二极管(APD)是一种具有内部增益的光电探测器,工作在能使器件发生雪崩倍增效应的高反向偏压下,雪崩倍增效应造成了内部电流增益,使得APD器件比其他器件具有更高的响应度。因其具有灵敏度高、体积小、增益大灯一系列优点,实现对微弱信号的高校探测,被广泛的应用于光纤通讯、激光测距、激光引信、光谱测量、遥感测量、医学影像诊断、环境监测和军事侦察等方面。
光电探测器作为光纤通讯系统、红外成像系统、激光告警系统和激光测距系统等的重要组成部分,在民用和军用方面均得到了广泛的应用。目前商用的红外探测器主要包括HgCdTe材料APD和InGaAs-InP APD。HgCdTe材料根据Cd在HgCdTe材料中所占的比重调节材料禁带宽度(0eV-1.6eV),但是HgCdTe材料APD需要工作低温条件下,InGaAs单晶半导体材料存在价格昂贵、热机械性能差、晶体质量较差、且不易与现有硅微电子工艺兼容等缺陷。
Si材料具有易于提纯、易于掺杂、资源丰富、成本低、易于大规模集成和相关技术成熟等优点,是半导体行业应用最为广泛的一类材料。Si材料具有高得碰撞电离系数比,用于光探测时可使器件的信噪比得到提高。然而,由于其禁带宽度较大(1.1eV),即使在光敏区沉淀了增透膜,也无法探测波长大于1.1μm的光波信号。
发明内容
基于现有技术中存在的问题,本发明提供一种PbS量子点Si-APD红外探测器及其制备方法,其以PbS量子点层作为吸收层,采用纯电子注入的方式,使得红外探测器能够吸收近红外波段光波,具有光谱响应宽,响应度高,过噪声小,成本低,易于加工等优点。
依据本发明的技术方案,提供一种PbS量子点Si-APD红外探测器,其包括本征Si衬底1、减反膜区4、N+掺杂区3、P掺杂区2、P+掺杂区6、PbS量子点层7、上电极5和下电极8,其减反膜区4位于本征Si衬底1正上方、N+掺杂区3位于反射区4下方、P掺杂区2位于N+掺杂区3下方、P+掺杂区6位于本征Si衬底1下方、PbS量子点层7位于P+掺杂区6下方、上电极5位于反射区4上表面和下电极8位于PbS量子点层6下表面。
优选地,N+掺杂区3、P掺杂区2、P+掺杂区6在本征Si衬底1上形成;并且在俯视观察时,N+掺杂区3的面积大于位于N+掺杂区3下方的P掺杂区2。进一步地,N+掺杂区3掺杂浓度≥1ⅹ1020ion/cm3,结深为0.5μm~2μm,P掺杂区2掺杂浓度为4ⅹ1015ion/cm3~1ⅹ1017ion/cm3,结深为1.5μm~3.5μm,P+掺杂区6掺杂浓度≥1ⅹ1020ion/cm-3,结深为0.5μm~2μm;采用旋涂的方式涂覆在本征Si基底1的下表面形成PbS量子点层。
进一步地,PbS量子点层的层数为5层,PbS量子点直径大小为3-4nm;采用热注入法制造PbS量子点,注入温度为120℃,其中TMS为S源,PbO为Pb源。
可选择地,减反射膜为SiO2层,厚度在150-250nm,具有钝化和减少反射双重作用;在上电极5上蒸镀10nm厚的氧化钼和100nm银;在下电极8上旋涂在PbS量子点层表面的TiO2量子点层。
与现有技术相比,本发明具有以下有益效果:
一、器件工作时,被探测物质所激发出的光辐射或各种反射激光被PbS量子点Si-APD的PbS量子点层所吸收,产生光生载流子(电子空穴对),在反向偏压的作用下,空穴被TiO2电极吸收,电子在APD内部高电场的作用下,引发雪崩倍增效应,从而形成很大的光信号电流。PbS量子点Si-APD采用电子引发雪崩倍增效应,降低了器件噪声,提高了APD的探测度。
二、与传统Si-APD光电探测器相比,PbS量子点Si-APD采用PbS量子点层作为吸收层。PbS是直接带隙半导体材料,具有很高的吸收系数,块状体材料禁带宽度为0.45eV,能够吸收红外波段的光信号。PbS量子点吸收层不仅对入射光有良好的吸收效果,更在吸收入射光后能高效的产生光生载流子,对其能量进行有效的利用,使之转换为电能以提高器件的探测性能。
三、PbS量子点能带结构可调。PbS量子点的禁带宽度随着量子点半径的降低而增大。在制作过程中可通过控制反应温度、反应时间、反应物浓度制备具有不同禁带宽度的PbS量子点,以满足不同波段红外光电探测器的需求。
四、PbS量子点直径在1nm-10nm之间,表面原子占有相当大的比例,比表面积大,表面原子具有很高的活性,易于其他原子结合。PbS量子点层能有与Si表面完美配合,降低了传统Si基APD因表面配合不佳而产生的暗电流,提高了PbS量子点APD的探测性能。
五、本发明与传统的Si-APD光电探测器相比,器件的N+掺杂区比P掺杂区面积大,降低了APD的边缘击穿效应,减少横向暗电流的产生,从而大大提高器件的响应速度。
六、本发明采用TiO2量子点层作为阳极电极,TiO2量子点层能够高效的提取出PbS量子点层产生的光生空穴,降低了漂移电流,并与PbS量子点层形成良好的欧姆接触,提高了APD光电探测器的响应速度。
附图说明
图1是依据本发明的PbS量子点Si-APD红外探测器的剖面结构示意图;
图2是依据本发明的PbS量子点Si-APD红外探测器的俯视平面结构示意图
其中附图标记:1是本征Si衬底、2是P掺杂区、3是N+掺杂区、4是减反膜区、5是上电极、6是P+掺杂区、7是PbS量子点层、8是下电极。
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的一部分实施例,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做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。另外地,不应当将本发明的保护范围仅仅限制至下述具体实验方法或具体参数。
本申请人长期致力于红外探测器的研究,基于现有技术中存在的问题,本申请人针对于又可称为纳米晶的量子点进行研究,由于纳米晶一般由Ⅱ-Ⅵ族或Ⅳ-Ⅵ族元素组成的纳米颗粒,粒径一般介于1nm~10nm之间。当量子点的尺寸与材料的激子波尔半径相当时,受到量子效应的影响,禁带展宽,电子态密度出现分立量化能级结构,主要表现为量子尺寸效应,表面效应和多激子效应等。量子点的合成方法主要保罗外延生长、光刻、热注入等其中热注入法对设备的要求相对较低,操作简单,各种形貌的量子点可控,已成为量子点合成的主要方法。PbS量子点因为其较窄的块体带隙(0.41eV)及较大的激子波尔半径,所以很容易覆盖太阳光谱的近红外吸收,且具有独特的电学性能,很高的载流子收集效率。但是其存在HgCdTe APD必须工作在低温环境下;InGaAs-InP APD价格昂贵、热机械性能差、晶体质量较差、且不易与现有硅微电子工艺兼容;Si半导体材料由于禁带宽度较大,无法探测红外波段光信号,响应度低,光谱探测范围有限等不足的技术缺陷。
本申请人基于纳米晶的这一特性,提出一种PbS量子点Si-APD红外探测器,其包括本征Si衬底1、位于本征Si衬底1正上方的减反膜区4、位于反射区4下方的N+掺杂区3、位于N+掺杂区3下方的P掺杂区2、位于本征Si衬底1下方的P+掺杂区6、位于P+掺杂区6下方的PbS量子点层7、位于反射区4上表面的上电极5和位于PbS量子点层6下表面的下电极8。其中,N+区3为磷重扩散掺杂N型区,结深为0.5μm~2μm,掺杂浓度≥1ⅹ
1020ion/cm3。优选地,P区2为硼扩散掺杂P型区,结深为1.5μm~3.5μm,掺杂浓度为4ⅹ1015ion/cm3~1ⅹ1017ion/cm3;P+区6为硼重扩散掺杂P型区,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3。
可选择地,N+掺杂区3的面积大于所述P掺杂区2。减反膜层为SiO2层,厚度在150-250nm。PbS量子点层7的量子点层数为5层,PbS量子点直径大小为3-4nm,PbS量子点采用热注入法制备,TMS作为硫源,PbO为铅源。
进一步提出一种制备前述的PbS量子点层的制备方法,其包括以下步骤:
①在三颈瓶中分别加入2mmol氧化铅,4.8mmol的油酸和18ml的十八烯混合溶液作为制备PbS量子点的铅源前驱体;在烧杯中配置10ml含有200ul的TMS溶液,作为硫源前驱体溶液;
②将步骤①所得的铅源前驱体有机溶液在氩气条件下加热到120℃,溶液变为变为黄色澄清溶液;
③将10ml含有200ul TMS的十八烯溶液快速注入到以上前驱体溶液中,并停止加热,待溶液冷却到35℃时加入丙酮溶液去除反应副产物和提纯量子点,将制备好的PbS量子点保存在正辛烷溶液中;
④将步骤③所得的PbS量子点正辛烷溶液旋涂在P+区6的下表面,旋涂速度为2500rmp,时间为15秒,重复旋涂6层,制备PbS量子点层。
在上述制备方法中,通过在所述PbS量子点层旋涂TiO2胶体量子点溶液制备得到TiO2量子点层电极。
下面结合附图和实施例对本发明进一步的说明。如图1、图2、所示,PbS量子点Si-APD红外探测器包括本征Si衬底1、位于本征Si衬底1正上方的减反膜区4、位于反射区4下方的N+掺杂区3、位于N+掺杂区3下方的P掺杂区2、位于本征Si衬底1下方的P+掺杂区6、位于P+掺杂区6下方的PbS量子点层7、位于反射区4上表面的上电极5和位于PbS量子点层6下表面的下电极8
上述技术方案中:
所述N+区3为磷重扩散掺杂N型区,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3。
所述P区2为扩散掺杂P型区,结深为1.5μm~3.5μm,掺杂浓度为4ⅹ1015ion/cm3~1ⅹ1017ion/cm3,
所述P+区6为硼重扩散掺杂P型区,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3。
所述N+掺杂区3的面积大于所述P掺杂区2。
所述减反膜层为SiO2层,厚度在150-250nm。
所述PbS量子点层7的量子点层数为5层,PbS量子点直径大小为3-4nm,PbS量子点采用热注入法制备,TMS作为硫源,PbO为铅源。
制备前文所述的PbS量子点层,采用如下方法:
①在三颈瓶中分别加入2mmol氧化铅,4.8mmol的油酸和18ml的十八烯混合溶液作为制备PbS量子点的铅源前驱体;在烧杯中配置10ml含有200ul的TMS溶液,作为硫源前驱体溶液;
②将步骤①所得的铅源前驱体有机溶液在氩气条件下加热到120℃,溶液变为变为黄色澄清溶液;
③将10ml含有200ul TMS的十八烯溶液快速注入到以上前驱体溶液中,并停止加热,待溶液冷却到35℃时加入丙酮溶液去除反应副产物和提纯量子点,将制备好的PbS量子点保存在正辛烷溶液中;
④将步骤③所得的PbS量子点正辛烷溶液旋涂在P+区6的下表面,旋涂速度为2500rmp,时间为15秒,重复旋涂6层,制备PbS量子点层。
所述的TiO2量子点层电极通过在所述PbS量子点层旋涂TiO2胶体量子点溶液制备。
一种PbS量子点Si-APD红外探测器的制备方法包括以下步骤:
步骤1:在本征硅衬底1上表面氧化生长SiO2膜层。所用本征硅衬底为100晶向的低阻单晶硅衬底,SiO2膜层厚度为300nm~400nm,生长温度为1000℃。
步骤2:在SiO2膜层表面四周光刻出环形N+掺杂区3的图形,然后进行磷扩散掺杂;磷扩散掺杂形成N+掺杂区3时温度为1000℃~1100℃,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3。
步骤3:在SiO2膜层表面光刻出P型区2的图形,然后进行硼扩散掺杂形成P型区2;硼扩散掺杂形成P型区2时温度为1000℃,结深为1.5μm~3.5μm,掺杂浓度为4ⅹ1015ion/cm3~1ⅹ1017ion/cm3。
步骤4:对本征硅衬底1下表面进行硼重扩散掺杂形成P+掺杂区6;硼重扩散掺杂形成P+区6时温度为1000℃~1100℃,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3。
步骤5:在P+掺杂区6的下表面旋涂先前所述的PbS量子点正辛烷溶液,旋涂速度为2500rmp,时间为15秒,重复旋涂6层。
步骤6:在PbS量子层7的下表面旋涂TiO2量子点正辛烷溶液,旋涂速度为2500rmp,时间为15秒,重复旋涂6层。
步骤7:蒸镀上电极。
经过上述步骤制备出的PbS量子点Si-APD红外探测器,其相应波长为400nm~1200nm,相应度范围为40A/W~100A/W。
至此,已经结合附图对本发明实施例进行了详细的描述。需要说明的是,在附图或说明书正文中,未绘示或描述的实现方式,均为所属技术领域中普通技术人员所知的形式,并未进行详细说明。
本发明未详细阐述部分属于本领域技术人员的公知技术。以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种PbS量子点Si-APD红外探测器,其包括本征Si衬底(1)、减反膜区(4)、N+掺杂区(3)、P掺杂区(2)、P+掺杂区(6)、PbS量子点层(7)、上电极(5)和下电极(8),其特征在于,减反膜区(4)位于本征Si衬底(1)正上方,N+掺杂区(3)位于反射区(4)下方,P掺杂区(2)位于N+掺杂区(3)下方,P+掺杂区(6)位于本征Si衬底(1)下方,PbS量子点层(7)位于P+掺杂区(6)下方,上电极(5)位于反射区(4)上表面,以及下电极(8)位于PbS量子点层(7)下表面;
所述PbS量子点Si-APD红外探测器在俯视观察时,N+掺杂区(3)的面积大于位于N+掺杂区(3)下方的P掺杂区(2);PbS量子点层的层数为6层,PbS量子点直径大小为3-4nm;减反射膜为SiO2层,厚度在150nm-250nm;
PbS量子点采用热注入法制备,TMS作为硫源,PbO为铅源;
所述PbS量子点层采用以下制备方法来制备,所述制备PbS量子点层的制备方法包括以下步骤:
①在三颈瓶中分别加入2mmol氧化铅、4.8mmol的油酸和18ml的十八烯混合溶液作为制备PbS量子点的铅源前驱体;在烧杯中配置10ml含有200ul的TMS溶液,作为硫源前驱体溶液;
②将步骤①所得的铅源前驱体有机溶液在氩气条件下加热到120℃,溶液变为黄色澄清溶液;
③将10ml含有200ul TMS的十八烯溶液快速注入到步骤②得到的前驱体溶液中,并停止加热,待溶液冷却到35℃时加入丙酮溶液去除反应副产物和提纯量子点,将制备好的PbS量子点保存在正辛烷溶液中;
④将步骤③所得的PbS量子点正辛烷溶液旋涂在P+掺杂区的下表面,旋涂速度为2500rmp,时间为15秒,重复旋涂6层,制备PbS量子点层;
在制备PbS量子点层的制备方法中,通过在所述PbS量子点层旋涂TiO2胶体量子点溶液制备得到TiO2量子点层电极。
2.根据权利要求1所述的PbS量子点Si-APD红外探测器,其特征在于,N+掺杂区(3)掺杂浓度≥1ⅹ1020ion/cm3,结深为0.5μm~2μm;P掺杂区(2)掺杂浓度为4ⅹ1015ion/cm3~1ⅹ1017ion/cm3,结深为1.5μm~3.5μm;和/或P+掺杂区(6)掺杂浓度≥1ⅹ1020ion/cm3,结深为0.5μm~2μm。
3.根据权利要求2所述的PbS量子点Si-APD红外探测器,其特征在于,采用热注入法制造PbS量子点的注入温度为120℃。
4.根据权利要求1所述PbS量子点Si-APD红外探测器,其特征在于,在上电极(5)上蒸镀10nm厚的氧化钼和100nm银,在下电极(8)上旋涂在PbS量子点层表面的的TiO2量子点层。
5.一种PbS量子点Si-APD红外探测器的制备方法,其用于制备权利要求1-4之任一所述的PbS量子点Si-APD红外探测器,其包括以下步骤:
步骤1:在本征硅衬底上表面氧化生长SiO2膜层;本征硅衬底为100晶向的低阻单晶硅衬底,SiO2膜层厚度为300nm~400nm,生长温度为1000℃;
步骤2:在SiO2膜层表面四周光刻出环形N+掺杂区的图形,然后进行磷扩散掺杂;磷扩散掺杂形成N+掺杂区时温度为1000℃~1100℃,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3;
步骤3:在SiO2膜层表面光刻出P型区的图形,然后进行硼扩散掺杂形成P型区;硼扩散掺杂形成P型区时温度为1000℃,结深为1.5μm~3.5μm,掺杂浓度为4ⅹ1015ion/cm3~1ⅹ1017ion/cm3;
步骤4:对本征硅衬底下表面进行硼重扩散掺杂形成P+掺杂区;硼重扩散掺杂形成P+区时温度为1000℃~1100℃,结深为0.5μm~2μm,掺杂浓度≥1ⅹ1020ion/cm3;
步骤5:在P+掺杂区的下表面旋涂先前所述的PbS量子点正辛烷溶液,旋涂速度为2500rmp,时间为15秒,重复旋涂6层;
步骤6:在PbS量子层的下表面旋涂TiO2量子点正辛烷溶液,旋涂速度为2500rmp,时间为15秒,重复旋涂6层;
步骤7:蒸镀上电极。
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