CN109427923B - 一种半导体薄膜四象限光照传感器及其制备方法 - Google Patents

一种半导体薄膜四象限光照传感器及其制备方法 Download PDF

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CN109427923B
CN109427923B CN201710740273.3A CN201710740273A CN109427923B CN 109427923 B CN109427923 B CN 109427923B CN 201710740273 A CN201710740273 A CN 201710740273A CN 109427923 B CN109427923 B CN 109427923B
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刘生忠
秦炜
王辉
杜敏永
曹越先
张豆豆
李�灿
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明提供一种半导体薄膜四象限光照传感器及其制备方法。该传感器具有多层结构，从光入射面由表及里依次为光阑、衬底、顶电极、半导体薄膜光电转化层、背电极和保护层；所述传感器顶电极、半导体薄膜光电转化层、背电极具有阵列结构，其中每个单元所包含的顶电极、半导体薄膜光电转化层、背电极相互连通，单元之间的半导体薄膜光电转化层、背电极彼此不连通。本发明所述传感器的光电转化层为半导体薄膜材料，使器件阻抗显著增加，提高了测量稳定性。本发明所述制备方法，使器件加工精度显著增加，提高了测量精确度。

Description

一种半导体薄膜四象限光照传感器及其制备方法
技术领域
本发明属半导体传感器技术领域，具体涉及一种半导体薄膜光电转化层的四象限光照传感器及其制备方法。
背景技术
基于硅材料的四象限光电传感广泛应用于航天器姿态控制、激光瞄准、制导、跟踪、搜索以及精密测量等领域之中。传统的四象限传感器一般有四个单元，每一个单元为一个分立的光电二极管。传感器工作时，通过对各个单元二极管产生的光电信号进行比较，就可得到目标光源的位置信息，从而控制相应的机械传动部分使传感器对准目标。
四象限传感器的光阑、光电转化单元相对位置决定了传感器精度。四象限传感器包含光阑，用以在光电转化材料表面产生一个特定形状的光斑。当光源和传感器的相对位置变化时，光斑投射在各分立光电二极管的比例不同，各分立二极管输出不同的电流，可以根据其输出电流比例确定传感器与光源的相对位置。因此光阑与光电转化单元之间的相对位置精度决定了四象限传感器的定位精度。传统的四象限传感器光阑与光电转化材料彼此独立，难以精确控制其相对位置，从而影响传感器的定位精度。基于薄膜半导体薄膜光电转化层的四象限光照传感器具有光阑、光电转化层一体化结构，可以对上述两者的相对位置进行精确控制，从而使传感器具有高定位精度。
二极管单元的输出电流不仅受到光强的影响还收到两电极施加电压的影响，四象限传感器的阻抗决定了传感器的精度。目前传感器的信号分析电路可能在工作时无意地对传感器的二极管单元施加电压，从而对二极管单元的输出电流造成影响，造成测量误差。光电转化层的阻抗反映了二极管单元的抗外加电压干扰能力，低阻抗光电转化层的电流输出受外加电压影响大，高阻抗光电转化层的电流输出受外加电压影响小，其电流输出在有无外加电压时和光照强度保持相同的线性比例关系。基于薄膜半导体薄膜光电转化层的四象限光照传感器使用宽带隙半导体薄膜作为光电转化材料，可以使所述传感器的二极管单元具有极高的阻抗，从而使传感器具有稳定的定位精度。
发明内容
针对上述问题，本发明提供一种半导体薄膜四象限光照传感器及其制备方法。
一种基于半导体薄膜光电转化层的四象限光照传感器，该传感器具有多层结构，从光入射面由表至里由光阑、衬底、顶电极、半导体薄膜光电转化层、背电极和保护层组成；
所述光阑位于衬底上靠近光入射一侧，光阑设有开孔；所述顶电极位于衬底和半导体薄膜光电转化层之间，顶电极上设置顶电极有效区和顶电极无效区；
所述半导体薄膜光电转化层位于顶电极和背电极之间，半导体薄膜光电转化层与背电极具有一致的背电极有效区和背电极无效区；
所述顶电极有效区和背电极有效区部分重叠形成光电有效区；
所述保护层，位于背电极表面，覆盖光电有效区全部区域，覆盖顶电极有效区和背电极有效区部分区域，
所述传感器顶电极、半导体薄膜光电转化层、背电极具有阵列结构，其中每个单元所包含的顶电极、半导体薄膜光电转化层、背电极相互连通，单元之间的半导体薄膜光电转化层、背电极彼此不连通。
光照通过光阑开孔入射所述半导体薄膜光电转化层，角度不同的光照会在半导体薄膜光电转化层表面产生位置不同的阴影；半导体薄膜光电转化层具有阵列结构，光阑开孔的几何中心与光电转化单元交点重合。阴影会导致阵列中每个单元输出不同的电流；电流经过电极传输至外电路中，用于获得光照与所述传感器表面的相对位置。
所述光阑为位于衬底上靠近光入射一侧的挡光材料，其厚度为50nm～5mm。
所述衬底材质为石英、玻璃、有机玻璃、乙二醇酯(PEN)、聚对苯二甲酸乙二醇酯(PET)、聚醚酰亚胺(PEI)或聚酰亚胺(PI)中的一种或多种的组合。
所述顶电极为导电薄膜材料，厚度在50nm～5μm之间。
所述顶电极为材质为掺杂氧化锡、掺杂的氧化锌、掺杂氧化铟、掺杂氧化钨及其他半导体薄膜或钙、钛、钨、铬、金、银、铝、铜、钛、镉、铟、镓等金属薄膜中的一种或多种的组合。
所述半导体薄膜光电转化层厚度为10nm～10μm，所述半导体薄膜光电转化层由多层带隙在0.5～3.5eV之间的半导体薄膜组成，所述薄膜的暗态电导率介于10-10～105S/cm之间。
所述半导体薄膜的材质优选但不限于硅薄膜、砷化镓、镓铟磷、锗、晶体硅薄膜、碲化镉、硫化镉、铜铟镓硒系列材料、有机材料或有机-无机杂化钙钛矿材料；
所述硅薄膜为a-Si、a-SiGe、a-SiC、nc-Si或nc-SiOx；
所述铜铟镓硒系列材料为CIGS或CZTS；
所述有机材料为PDPP3T、PTB7、PCBM、Spiro-OMeTAD或PEDOT；
所述有机-无机杂化钙钛矿材料为MAPbI3、FAPbI3或MASnI3。
所述半导体薄膜光电转化层包含单个或多个PN结。
所述背电极为导电薄膜材料，厚度在50nm～5μm之间。
所述背电极其材质为掺杂氧化锡、掺杂的氧化锌、掺杂氧化铟、掺杂氧化钨等半导体薄膜或钙、钛、钨、铬、金、银、铝、铜、钛、镉、铟、镓等金属薄膜中的一种或多种的组合。
所述保护层其材质为有机物聚乙二醇酯(PEN)、聚对苯二甲酸乙二醇酯(PET)、聚醚酰亚胺(PEI)、聚酰亚胺(PI)、乙烯/乙酸乙烯酯共聚物(EVA)、乙烯/四氟乙烯共聚物(ETFE)中的一种或多种的组合，或为玻璃、不锈钢、铝、铜中的一种和上述有机物中一种或多种的组合。
一种基于半导体薄膜光电转化层的四象限光照传感器，制备方法按照以下步骤进行：
1)在衬底一侧制备顶电极并部分去除顶电极，形成顶电极有效区和顶电极无效区；
2)在顶电极表面制备半导体薄膜光电转化层和背电极，并使用激光部分去除半导体薄膜光电转化层和背电极，形成背电极有效区和背电极无效区；
3)所述顶电极有效区和背电极有效区部分重叠，重叠区域为光电有效区；
4)使用激光部分去除半导体薄膜光电转化层和背电极，在光电有效区内形成阵列结构；
5)在衬底表面无顶电极侧制备挡光材料并部分去除挡光材料，形成光阑。
通过激光切割或化学刻蚀的方式去除部分顶电极，去除宽度介于1μm～10cm之间。
通过激光切割或机械切割的方式去除部分挡光材料，形成光阑，去除宽度介于1μm～10cm之间。
所述激光波长为200～1200nm，激光功率为20mW～20W。
对于光电传感器而言，阻抗用于衡量二极管在有无外加电压下输出电流的偏差，是衡量光电传感器工作稳定性的重要指标。本发明所述传感器的使用半导体薄膜作为传感器的光电转化层材料，使器件阻抗可达120kΩ，与传统器件～30kΩ相比提高显著，这使得光电传感器的测量稳定性得到大幅提升。本发明所述器件的光阑和光电转化层具有一体化结构，因此传感器的特殊制备方法可使上述两者对齐的精度得到显著提升，由此使得光阑在传感器表面的阴影位置精度提高，使得器件的测量误差小于5‰。
附图说明
图1为所述四象限传感器俯视视图；
图2为图1中AA面的剖视图；
图3为图1中BB面的剖视图；
图4为所述四象限传感器区域示意图，
其中1为光阑、2为衬底、3为顶电极、4为半导体薄膜光电转化层、5为背电极、6为保护层；11为顶电极有效区、111为顶电极无效区，12为背电极有效区、121为背电极无效区，13为光电有效区。
图5为所述光照下四象限传感器中一个二极管单元的电压-电流密度曲线。
图6为所述光照下四象限传感器的四个二极管单元的电压-电流密度曲线。
具体实施方式
为了进一步阐明本发明内容，列举以下实施实例。
本发明的一种基于半导体薄膜光电转化层的四象限光照传感器，如图1～4所示，具有多层结构，从光入射面由表至里由光阑1、衬底2、顶电极3、半导体薄膜光电转化层4、背电极5和保护层6组成；
所述光阑1位于衬底2上靠近光入射一侧，光阑设有开孔；所述顶电极3位于衬底2和半导体薄膜光电转化层4之间，顶电极3上设置顶电极有效区11和顶电极无效区111；
所述半导体薄膜光电转化层4位于顶电极3和背电极5之间，半导体薄膜光电转化层与背电极具有一致的背电极有效区12和背电极无效区121；
所述顶电极有效区和背电极有效区部分重叠形成光电有效区13；
所述保护层6，位于背电极5表面，覆盖光电有效区全部区域，覆盖顶电极有效区和背电极有效区部分区域，
所述传感器顶电极3、半导体薄膜光电转化层4、背电极5具有阵列结构，其中每个单元所包含的顶电极3、半导体薄膜光电转化层4、背电极5相互连通，单元之间的半导体薄膜光电转化层4、背电极5彼此不连通。
光照通过光阑入射所述传感器，角度不同的光照会在半导体薄膜光电转化层表面产生位置不同的阴影；半导体薄膜光电转化层具有阵列结构，阴影会导致阵列中每个单元输出不同的电流；电流经过电极传输至外电路中，用于获得光照与所述传感器表面的相对位置。
实施例1
使用磁控溅射方法在玻璃表面制备氟掺杂氧化锡薄膜(FTO)材料，表面电导率约为10Ω/□，使用激光部分去除FTO薄膜顶电极，在衬底上形成顶电极有效区和顶电极无效区。
按照n型层、微晶硅本征层、p型层、n型层、非晶硅本征层、p型层的顺序制备双结a-Si/nc-Si光电转换层。首先将FTO玻璃衬底放入多腔室装置的n型层沉积室。将衬底温度控制在200℃，以7:1的比例通入硅烷和磷烷的混合气，将腔内气压稳定在约100Pa，开启射频等离子体源，待等离子体辉光稳定后打开样品挡板，沉积n型层约15nm后关闭等离子体。将衬底在真空中传输至本征层沉积室。衬底温度控制在200℃，以5:100的比例通入硅烷和氢气的混合气，将腔内气压稳定在约100Pa，开启射频等离子体源，待等离子体辉光稳定后打开样品挡板，沉积约1500nm本征微晶硅薄膜后关闭等离子体。将衬底在真空中传输至p型层沉积室，衬底温度控制在200℃，以6:2:1:10的比例通入硅烷、乙硼烷、氢气的混合气体，将腔内气压稳定在约100Pa，开启射频等离子体源，待等离子体辉光稳定后打开样品挡板，沉积p型层约10nm后关闭等离子体。衬底放入多腔室装置的n型层沉积室。将衬底温度控制在200℃，以7:1的比例通入硅烷和磷烷的混合气，将腔内气压稳定在约100Pa，开启射频等离子体源，待等离子体辉光稳定后打开样品挡板，沉积n型层约15nm后关闭等离子体。将衬底在真空中传输至本征层沉积室。衬底温度控制在200℃，以16:100的比例通入硅烷和氢气的混合气，将腔内气压稳定在约100Pa，开启射频等离子体源，待等离子体辉光稳定后打开样品挡板，沉积约120nm本征非晶硅薄膜后关闭等离子体。将衬底在真空中传输至p型层沉积室，衬底温度控制在200℃，以6:2:10的比例通入硅烷、乙硼烷、氢气的混合气体，将腔内气压稳定在约100Pa，开启射频等离子体源，待等离子体辉光稳定后打开样品挡板，沉积p型层约10nm后关闭等离子体。在p型层表面使用电阻蒸镀的方法沉积约150nm金属铝形成背电极。使用激光去除部分非晶硅薄膜和金属背电极形成多个二极管单元。
使用丝网印刷方法在玻璃衬底(无FTO薄膜)印刷黑色油墨挡光层，通过溶液浓度、刮板高度控制挡光层厚度为200μm。使用激光部分去除黑色油墨形成光阑。使用热压方式在背电极表面部分区域制备EVA保护层。
外电路连接顶电极和各二极管单元背电极，可以得到各二极管单元的电压-电流密度曲线(如图5、图6所示)。如图5所示，单个二极管单元在0～0.2V范围内阻抗大于120kΩ。如图6所示，当光照垂直入射所述四象限传感器时，各单元的短路电流密度差异小于5‰。根据四个二极管单元的输出电流密度差值，可以实现光照角度的精确测量。
实施例2
使用磁控溅射方法在玻璃表面制备氟掺杂氧化锡薄膜(FTO)材料，表面电导率约为10Ω/□，使用激光部分去除FTO薄膜顶电极，在衬底上形成顶电极有效区和顶电极无效区。
将PDPP3T和PC61BM溶于邻二氯苯(ODCB)中，80℃加热搅拌24小时，配成浓度为15mg/ml的PDPP3T:PC61BM-ODCB溶液(PDPP3T:PC61BM＝1:2w.t.)。在制备有顶电极的衬底表面旋涂聚3,4-乙撑二氧噻吩(PEDOT:PSS)溶液，得到PEDOT薄膜，在PEDOT薄膜表面旋涂上述溶液，得到PDPP3T:PC61BM有机光敏层薄膜。将衬底转移至真空蒸发系统中蒸镀电极钙、铝复合背电极。使用激光去除部分非晶硅薄膜和金属背电极形成多个二极管单元。
使用丝网印刷方法在玻璃衬底(无FTO薄膜)一侧印刷黑色油墨挡光层，通过溶液浓度、刮板高度控制挡光层厚度为200μm。使用激光部分去除黑色油墨形成光阑。使用热压方式在背电极表面部分区域制备EVA保护层。
外电路连接顶电极和各二极管单元背电极，可以实现光照角度的精确测量。
实施例3
使用磁控溅射方法在玻璃表面制备氟掺杂氧化锡薄膜(FTO)材料，表面电导率约为10Ω/□，使用激光部分去除FTO薄膜顶电极，在衬底上形成顶电极有效区和顶电极无效区。
将甲氨基碘和碘化铅溶于二甲基甲酰胺(DMF)和二甲基亚砜(DMSO)中，搅拌4小时，配成MAI:PbI2-DMF:DMSO溶液。在制备有顶电极的衬底表面旋涂聚3,4-乙撑二氧噻吩(PEDOT:PSS)溶液，得到PEDOT薄膜，在PEDOT薄膜表面旋涂上述溶液，得到MAPbI3光敏层薄膜。在MAPbI3薄膜表面旋涂PC61BM溶液。将衬底转移至真空蒸发系统中蒸镀金属铝背电极。使用激光去除部分非晶硅薄膜和金属背电极形成多个二极管单元。
使用丝网印刷方法在玻璃衬底(无FTO薄膜)一侧印刷黑色油墨挡光层，通过溶液浓度、刮板高度控制挡光层厚度为200μm。使用激光部分去除黑色油墨形成光阑。使用热压方式在背电极表面部分区域制备EVA保护层。
外电路连接顶电极和各二极管单元背电极，可以实现光照角度的精确测量。
实施例4
使用磁控溅射方法在玻璃表面制备铝掺杂氧化锌薄膜(AZO)材料，表面电导率约为15Ω/□，使用激光部分去除AZO顶电极，在衬底上形成顶电极有效区和顶电极无效区。
在顶电极表面制备CdS薄膜材料。以Cu1.5(In,Ga)Se为靶材，采用射频溅射法制备CIGS前驱体薄膜，溅射功率密度10W/cm2，靶间距20cm，气压为20Pa，通过溅射时间控制前驱体薄膜厚度为1500nm。在氮气气氛中对CIGS前驱体薄膜进行硒化处理，气氛为氮气，气压为5Pa，将固态单质硒加热到450℃，形成硒的饱和蒸气压。以100℃/分钟的升温速度将CIGS前驱体薄膜加热到600℃恒定10分钟，获得CIGS/CdS复合光电转化层。之后在将衬底转移至真空蒸发系统中蒸镀金属钼背电极。使用激光去除部分光电转化层和金属背电极形成多个二极管单元。
使用丝网印刷方法在玻璃衬底(无AZO薄膜)一侧印刷黑色油墨挡光层，通过溶液浓度、刮板高度控制挡光层厚度为200μm。使用激光部分去除黑色油墨形成光阑。使用热压方式在背电极表面部分区域制备EVA保护层。
外电路连接顶电极和各二极管单元背电极，可以实现光照角度的精确测量。

Claims (16)

1.一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于该传感器具有多层结构，从光入射面由表至里由光阑、衬底、顶电极、半导体薄膜光电转化层、背电极和保护层组成；
所述光阑位于衬底上靠近光入射一侧，光阑设有开孔；
所述顶电极位于衬底和半导体薄膜光电转化层之间，顶电极上设置顶电极有效区和顶电极无效区；
所述半导体薄膜光电转化层位于顶电极和背电极之间，半导体薄膜光电转化层与背电极具有一致的背电极有效区和背电极无效区；
所述顶电极有效区和背电极有效区部分重叠形成光电有效区；
所述保护层，位于背电极表面，覆盖光电有效区全部区域，覆盖顶电极有效区和背电极有效区部分区域，
所述传感器顶电极、半导体薄膜光电转化层、背电极具有阵列结构，其中每个单元所包含的顶电极、半导体薄膜光电转化层、背电极相互连通，单元之间的半导体薄膜光电转化层、背电极彼此不连通。
2.根据权利要求1所述的一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于光照通过光阑开孔入射所述半导体薄膜光电转化层，角度不同的光照会在半导体薄膜光电转化层表面产生位置不同的阴影；半导体薄膜光电转化层具有阵列结构，光阑开孔的几何中心与光电转化单元交点重合；阴影会导致阵列中每个单元输出不同的电流；电流经过电极传输至外电路中，用于获得光照与所述传感器表面的相对位置。
3.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述光阑为位于衬底上靠近光入射一侧的挡光材料，其厚度为50nm～5mm。
4.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述衬底材质为石英、玻璃、有机玻璃、乙二醇酯、聚对苯二甲酸乙二醇酯、聚醚酰亚胺或聚酰亚胺中的一种或多种的组合。
5.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述顶电极为导电薄膜材料，厚度在50nm～5μm之间。
6.根据权利要求5所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述顶电极为材质为掺杂氧化锡、掺杂的氧化锌、掺杂氧化铟或掺杂氧化钨半导体薄膜或钙、钛、钨、铬、金、银、铝、铜、钛、镉、铟、镓等金属薄膜中的一种或多种的组合。
7.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述半导体薄膜光电转化层厚度为10nm～10μm，所述半导体薄膜光电转化层由多层带隙在0.5～3.5eV之间的半导体薄膜组成，所述薄膜的暗态电导率介于10-10～105S/cm之间。
8.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述半导体薄膜的材质为硅薄膜、砷化镓、镓铟磷、锗、晶体硅薄膜、碲化镉、硫化镉、铜铟镓硒系列材料、有机材料或有机-无机杂化钙钛矿材料；
所述硅薄膜为a-Si、a-SiGe、a-SiC、nc-Si或nc-SiOx；
所述铜铟镓硒系列材料为CIGS或CZTS；
所述有机材料为PDPP3T、PTB7、PCBM、Spiro-OMeTAD或PEDOT；
所述有机-无机杂化钙钛矿材料为MAPbI3、FAPbI3或MASnI3。
9.根据权利要求7所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述半导体薄膜光电转化层包含单个或多个PN结。
10.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述背电极为导电薄膜材料，厚度在50nm～5μm之间。
11.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述背电极其材质为掺杂氧化锡、掺杂的氧化锌、掺杂氧化铟、掺杂氧化钨半导体薄膜或钙、钛、钨、铬、金、银、铝、铜、钛、镉、铟或镓金属薄膜中的一种或多种的组合。
12.根据权利要求1所述一种基于半导体薄膜光电转化层的四象限光照传感器，其特征在于所述保护层其材质为有机物聚乙二醇酯、聚对苯二甲酸乙二醇酯、聚醚酰亚胺、聚酰亚胺、乙烯/乙酸乙烯酯共聚物、乙烯/四氟乙烯共聚物中的一种或多种的组合，或为玻璃、不锈钢、铝、铜中的一种和上述有机物中一种或多种的组合。
13.根据权利要求1～12中任意权利要求所述的一种基于半导体薄膜光电转化层的四象限光照传感器，制备方法的特征在于按照以下步骤进行：
1)在衬底一侧制备顶电极并部分去除顶电极，形成顶电极有效区和顶电极无效区；
2)在顶电极表面制备半导体薄膜光电转化层和背电极，并使用激光部分去除半导体薄膜光电转化层和背电极，形成背电极有效区和背电极无效区；
3)所述顶电极有效区和背电极有效区部分重叠，重叠区域为光电有效区；
4)使用激光部分去除半导体薄膜光电转化层和背电极，在光电有效区内形成阵列结构；
5)在衬底表面无顶电极侧制备挡光材料并部分去除挡光材料，形成光阑。
14.根据权利要求13所述一种基于半导体薄膜光电转化层的四象限光照传感器的制备方法，其特征在于通过激光切割或化学刻蚀的方式去除部分顶电极，去除宽度为1μm～10cm。
15.根据权利要求13所述一种基于半导体薄膜光电转化层的四象限光照传感器的制备方法，其特征在于通过激光切割或机械切割的方式去除部分挡光材料，形成光阑，去除宽度为1μm～10cm。
16.根据权利要求13所述一种基于半导体薄膜光电转化层的四象限光照传感器的制备方法，其特征在于所述激光波长为200～1200nm，激光功率为20mW～20W。
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