CN110690322B - 一种自支撑高增益柔性硅基光电探测器的制备方法 - Google Patents
一种自支撑高增益柔性硅基光电探测器的制备方法 Download PDFInfo
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Abstract
本发明涉及一种自支撑高增益柔性硅基光电探测器的制备方法,通过化学腐蚀对单晶硅进行减薄使之具有柔韧性,并在柔性单晶硅表面制备具有准周期微锥结构的过饱和掺杂层,以此形成柔性黑硅。再经过退火处理激活黑硅层中的掺杂元素,极大提高了柔性单晶硅的吸收率并拓展了其光谱吸收范围。该柔性硅基光电探测器工作在反偏电压下,吸收光子产生光生电子‑空穴对,在外电场作用下分离,最终被电极收集后形成光电流,从而实现了光探测。本发明具有工艺简单,原材料易获取,易操控等优点,本发明所制备的柔性硅基光电探测器一方面实现了自支撑,另一方面实现了低偏压下高增益及宽谱的特性,并克服了有机柔性光电探测器响应时间较长的缺点。
Description
技术领域
本发明涉及柔性光电器件领域,具体涉及一种自支撑高增益柔性硅基光电探测器的制备方法。
背景技术
近几十年来,柔性光电探测器以其可弯曲、重量轻和便携等功能已引起广泛的关注,并具有开发下一代可穿戴电子器设备(如图像传感,光纤通信和环境监测等)的巨大潜力。迄今为止,已经探索了各种以有机电子材料作为光吸收层的柔性光电探测器,但确因这些材料中固有的缺陷和高度无序的晶体结构等所限,其载流子迁移率远远低于硅等无机半导体材料,导致器件的响应度及响应速度等光电性能依然不能与传统的硅基器件相比。
硅作为最重要的无机半导体材料之一,具有含量丰富、价格低廉、纯度高和缺陷少等优点,但它的硬度和脆性较大这一缺点限制了其在柔性电子领域的应用和发展。为了克服这一缺点,柔性硅开始替代传统无机半导体材料以满足新的光电探测要求。但目前以柔性硅薄膜制备的光电探测器响应度较低,难以满足柔性电子学的需求。此外,目前出现的柔性硅基光电探测器需与柔性基底结合,无法实现自支撑,降低了器件的热稳定性。
发明内容
为了解决上述问题,本发明人经过长期试验和研究,提出一种自支撑且具有高增益的柔性硅基光电探测器制备方法。一方面改进了柔性硅基光电探测器存在的需基底支撑和光电响应较低的不足,另一方面也弥补了有机柔性光电探测器响应速度较慢的缺点。
依据本发明的技术方案,提供一种自支撑高增益柔性硅基光电探测器的制备方法,包括如下步骤:
步骤1:选取单晶硅片,并对所选硅片进行预处理;
步骤2:采用一定浓度的氢氧化钾(KOH)溶液在加热条件下对单晶硅进行化学腐蚀以达到减薄的目的,使之具有柔韧性,即所谓的柔性单晶硅;
步骤3:采取相应工艺对腐蚀后的柔性单晶硅进行清洗;
步骤4:选取某一厚度的柔性单晶硅,通过飞秒激光在特定气氛中辐照其表面制备过饱和掺杂层,即获得柔性黑硅;
步骤5:对制备好的柔性黑硅材料进行退火处理,激活过饱和掺杂黑硅层中的杂质原子,并修复晶格,去除结构缺陷;
步骤6:在过饱和掺杂黑硅层表面上制备一正面接触电极;电极面积占黑硅层面积的1/9-1/3;
步骤7:在柔性单晶硅衬底背面制备一背面接触电极,覆盖整个单晶硅衬底背面;至此完成自支撑高增益柔性硅基光电探测器的制备;
其中所述的高增益柔性硅基光电探测器的响应波段为400nm-1200nm,在-2V偏压下响应度为0.8A/W-63A/W,其中峰值波长出现在840nm-900nm范围内,峰值响应度为63A/W;在-2V偏压下的上升和下降时间分别为68μs和172μs。其中各数学符号的具体含义为:nm:纳米,V:伏特,A/W:安培/瓦特,μs:微秒。
其中,步骤1中所述单晶硅衬底既可以是n型也可以是p型,厚度为100μm-500μm(微米),半导体晶片的晶向、电阻率和大小不限;单晶硅衬底要求表面平整,表面平整度即材料表面最高点和最低点的差值小于或等于10μm。
其中,上述步骤1中的预处理工艺为:(a)将单晶硅片切成一定尺寸的方块,依次用丙酮、乙醇、去离子水超声清洗10分钟;(b)将超声后的硅片放入5%的氢氟酸溶液中浸泡2分钟;(c)把浸泡后的硅片放浓硫酸和双氧水混合溶液中进行亲水性处理,浓硫酸和双氧水的体积比为7∶3,加热至100℃-130℃区间内,保持20分钟;(d)取出后用氮气流吹干,其中,在步骤(a)、(b)、(c)、(d)之间都需先用去离子水冲洗硅片。
进一步地,上述步骤2中所述氢氧化钾溶液浓度为30%-50%,所述加热温度为80-100℃,所述柔性单晶硅的厚度为10μm-50μm(微米)。
进一步地,上述步骤3中相应工艺的清洗步骤为:(a)用浓度为5%的稀盐酸将腐蚀后的硅片浸泡1小时,以去除残留的氢氧化钾;(b)用浓度为10%的氢氟酸再将其浸泡10分钟,去除反应生成的硅酸盐;(c)最后把柔性硅浸入浓盐酸、双氧水和去离子水混合溶液中,浓盐酸、双氧水和去离子水的体积比为1∶2∶7,并在80℃下水浴30分钟,去除钾、钠等金属污染;(d)将清洗后的硅片放入去离子水中存储备用,其中,在步骤(a)、(b)、(c)、(d)之间都需先用去离子水冲洗柔性硅片。
进一步地,步骤4中所述的飞秒激光辐照制备过饱和掺杂黑硅层的具体步骤如下:
(1)将清洗过的柔性硅固定在样品架上,并靠圆形磁铁的吸力固定在真空腔内的三维平移台上,在平移台的驱动下,样品在垂直于入射激光的平面上作二维运动,运动的范围取决于样品台与平移台之间的连接杆的可移动范围,移动的速度取决于平移台的设置,以此来制备大面积的黑硅层;
(2)抽真空,真空度为100-10-5Pa,然后,充入小于1个标准大气压的某种气体,如六氟化硫、氮气等;
(3)控制样品台的运动:通过控制加工面积和移动速度来控制掺杂的面积和扫描速度,即在垂直于入射激光方向的平面上作二维运动;并通过一个格兰-泰勒棱镜和一个半波片调节辐照到单晶硅表面激光功率大小,使柔性硅表面接收到的飞秒激光通量为1kJ/m2-8kJ/m2,单位面积上接收到的脉冲数为1-500个;
(4)扫描结束后,抽出真空腔内的气体,再充入氮气,即打开真空腔盖,取出样品硅片,检测加工过的区域(即黑硅层)呈黑色或深灰色;经过上述步骤处理的柔性硅材料表面形成了准周期排列的微纳结构,并掺入了大量的杂质元素。
优选地,步骤5所述的退火的方法可以选择但不限于:快速热退火,管式炉退火,纳秒激光熔融退火,飞秒激光退火等方法中的其中一种。
进一步地,步骤6或7所述正面或背面接触电极的制备方法为电阻热蒸发法、磁控溅射法或电子束蒸发法;电极材料是铝、金、银、铬、镍或铂中的一种或其组合;电极形状可制备为矩形或环状。
有益效果
与现有技术相比,本发明具有如下优点:
1.本发明所制备的柔性硅基光电探测器具有自支撑的优点,避免了光敏层与基底的不匹配性,提高了器件的稳定性。
2.本发明用飞秒激光直接辐照已制备的柔性单晶硅表面,与飞秒激光先辐照绝缘体上硅(SOI)再刻蚀中间层的两步法相比,有效避免了再次刻蚀对其结构的破坏,并简化了制备流程;
3.本发明所制备的柔性硅基光电探测器在400-1200nm波段范围内的响应度均大于0.8A/W(@-2V),实现低偏压下高增益及宽谱的特性;此外,本发明所制备的柔性硅基光电探测器在-2V偏压下的上升和下降时间分别为68μs和172μs,克服了有机柔性光电探测器响应时间较长的缺点。
4.本发明具有结构简单,工艺简单,原材料易获取,易加工和易保存等优点。
附图说明
附图1是依据本发明的柔性硅基光电探测器的剖面结构图。
附图2是依据本发明的柔性硅基光电探测器的制备流程示意图。
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结构或部件或具体参数。
本发明利用高浓度的氢氧化钾溶液在加热条件下对单晶硅进行腐蚀使之具有柔韧性,并在特定气氛中用飞秒激光辐照柔性单晶硅表面来制备过饱和掺杂黑硅层,以此形成柔性黑硅。其中,黑硅层表面具有准周期排列的微锥结构,且表面具有过饱和掺杂的杂质元素,经过后续退火处理激活黑硅掺杂层中的杂质元素,使其在宽谱段范围内(0.25μm-2.5μm)均有大于40%-60%的光吸收率,这极大提高了柔性单晶硅的吸收率并拓展了其光谱吸收范围。该柔性硅基光电探测器工作在反偏电压下,吸收光子产生光生电子-空穴对,并在电场的作用下分离分别向两边的电极运动,被电极收集后形成光电流,从而实现了光探测。
为使本发明的目的、技术方案和优点更加清楚明白,下面结合附图,对本发明的自支撑高增益柔性硅基光电探测器的制备方法进一步说明,包括如下具体步骤:
附图1是本发明提供的一种自支撑柔性硅基光电探测器的剖面结构图,其中,1-1是正面接触电极,1-2是飞秒激光过饱和掺杂的黑硅层,1-3是柔性单晶硅衬底,1-4是背面接触电极。
附图2是本发明提供的自支撑高增益柔性硅基光电探测器的制备方法流程示意图。
结合并参阅附图2,说明本发明提供的更详细的柔性硅基光电探测器的制备方法,其包括如下步骤:
步骤1:选取一表面洁净平整的单晶硅衬底;
步骤2:对所选取的单晶硅片进行预处理,包括切片、清洗、亲水性处理;
步骤3:将预处理后的硅片垂直放入一定浓度的氢氧化钾(KOH)溶液,在恒温加热条件下对单晶硅进行化学腐蚀以达到减薄的目的,使之具有柔韧性,即所谓的柔性单晶硅;
步骤4:将腐蚀至所需厚度的柔性单晶硅取出,并采用相应工艺清洗;
步骤5:将清洗过的柔性单晶硅放入真空腔中并将其固定在样品架上,使入射激光垂直照到样品表面;
步骤6:抽真空至100-10-5Pa,再充入低于1个大气压的特定气体;
步骤7:选取某一厚度的柔性单晶硅,通过飞秒激光在特定压强的气氛中辐照其表面制备表面微纳结构和过饱和掺杂层,辐照到柔性单晶硅表面的飞秒激光的中心波长为800nm,脉宽为120fs;并通过一个格兰-泰勒棱镜和一个半波片调节辐照到单晶硅表面的激光功率大小,使飞秒激光通量为1kJ/m2-8kJ/m2,单位面积上接收到的脉冲数为1-500个;样品在三维平移台的驱动下作二维平面扫描运动,通过控制扫描速度逐行扫描,可以加工大面积的黑硅层;
步骤8:加工完成后,抽走加工腔内的气体,再充入氮气,打开腔盖,取出样品,肉眼观察可见加工过的区域颜色为黑色或深灰色,经过上述步骤处理的柔性硅材料表面形成了准周期排列的微纳结构,并掺入了大量的杂质元素,由此获得了柔性黑硅;
步骤9:选用合适的退火方法对制备好的柔性黑硅材料做进一步处理,如快速热退火,管式炉退火,纳秒激光熔融退火或飞秒激光退火,调节好退火温度与退火时间等参数,激活黑硅层中的掺杂元素,同时去除缺陷,修复受损晶格;
步骤10:制备正面和背面接触电极,其中正面电极要留出吸光区域,背电极覆盖整个衬底背面;电极制备方法可以为电阻热蒸发、磁控溅射或电子束蒸发等;电极材料可以是铝、金、银、铬、镍或铂中的一种,或及其组合,电极形状可制备为矩形或环状;至此完成自支撑高增益柔性硅基光电探测器的制作。
其中,上述步骤2中预处理工艺为:(a)将单晶硅片切成一定尺寸的方块,依次用丙酮、乙醇、去离子水超声清洗10分钟;(b)将超声后的硅片放入5%的氢氟酸溶液中浸泡2分钟;(c)把浸泡后的硅片放浓硫酸和双氧水混合溶液中进行亲水性处理,浓硫酸和双氧水的体积比为7∶3,加热至100℃-130℃区间内,保持20分钟;(d)取出后用氮气流吹干。其中,在步骤(a)、(b)、(c)、(d)之间都需先用去离子水冲洗硅片。
其中,上述步骤4中相应工艺的清洗步骤为:(a)用浓度为5%的稀盐酸将腐蚀后的硅片浸泡1小时,以去除残留的氢氧化钾;(b)用浓度为10%的氢氟酸再将其浸泡10分钟,去除反应生成的硅酸;(c)最后把柔性硅浸入浓盐酸、双氧水和去离子水混合溶液中,浓盐酸、双氧水和去离子水的体积比为1∶2∶7,并在80℃下水浴30分钟,去除钾、钠等金属污染;(d)将清洗后的硅片放入去离子水中存储备用;其中,在步骤(a)、(b)、(c)、(d)之间都需先用去离子水冲洗柔性硅片。
所制作的柔性光电探测器响应波段为400nm-1200nm,在-2V偏压下响应度为0.8A/W-63A/W,其中峰值波长出现在840nm-900nm范围内,峰值响应度为63A/W;在-2V偏压下的上升和下降时间分别为68μs和172μs。其中各数学符号的具体含义为:nm:纳米,V:伏特,A/W:安培/瓦特,μs:微秒。
进一步地,步骤1中所述单晶硅衬底既可以是n型也可以是p型,厚度为100μm-500μm(微米),半导体晶片的晶向、电阻率和大小不限;单晶硅衬底要求表面平整,表面平整度即材料表面最高点和最低点的差值小于或等于10μm。
进一步地,步骤3所述氢氧化钾浓度为30%-50%,所述加热温度为80-100℃,所述柔性单晶硅的厚度为10μm-50μm(微米)。
根据上述柔性硅基光电探测器的制备方法所制备的柔性黑硅,兼具柔韧性和最优吸光性。该柔性黑硅层是利用飞秒激光在特定气氛中辐照柔性单晶硅制备而成,辐照通量为1kJ/m2-8kJ/m2,单位面积上接收到的脉冲数为1-500个,在0.25μm-2.5μm波长范围内的光学吸收率均大于40%-60%,在弥补硅减薄所带来的光损失的同时,极大提高了可见和近红外波段的吸收率。进一步地,由于表面掺入的大量的杂质元素扩展了硅的光谱吸收范围。
综上,使用上述制备方法制备的柔性硅基光电探测器包括-制备柔性单晶硅衬底;-制作在柔性硅基衬底上的过饱和掺杂黑硅层;-对制备好的柔性黑硅做退火处理;一制作在过饱和掺杂黑硅层表面上的正面接触电极;一制作在柔性硅衬底背面的背面接触电极。至此,柔性硅基光电探测器件制备完成。
实施示例1:
柔性硅基光电探测器的制备方法,包括如下步骤:
步骤1:选取2英寸n型(100)区熔单晶硅片,其电阻率为5000-8000Ω·cm,厚度为430±10μm;
步骤2:对所选取的单晶硅片进行预处理,具体步骤为:(a)将单晶硅片切成1x1cm2的方块,依次用丙酮、乙醇、去离子水依次超声清洗10分钟;(b)将超声后的硅片放入5%的氢氟酸溶液中浸泡2分钟;(c)把浸泡后的硅片放入浓硫酸和双氧水混合溶液中进行亲水性处理,浓硫酸和双氧水的体积比为7∶3,加热至100℃-130℃区间内,保持20分钟;(d)取出后用氮气流吹干。其中,在步骤(a)、(b)、(c)、(d)之间都先用去离子水冲洗硅片。
步骤3:将清洗干净的硅片垂直放入浓度为50%,温度为100℃的氢氧化钾溶液中,通过腐蚀制备20μm厚的柔性单晶硅;
步骤4:将已制得的柔性单晶硅采用相应工艺清洗,清洗步骤为:(a)用浓度为5%的稀盐酸将腐蚀后的硅片浸泡1小时,以去除残留的氢氧化钾;(b)用浓度为10%的氢氟酸再将其浸泡10分钟,去除反应生成的硅酸;(c)最后再把水浴后的硅片浸入浓盐酸、双氧水和去离子水混合溶液中,浓盐酸、双氧水和去离子水的体积比为1∶2∶7,使用80℃的水浴30分钟,去除钾、钠等金属污染;(d)将清洗后的硅片放入去离子水中存储备用;其中,在步骤(a)、(b)、(c)、(d)之间都需用去离子水冲洗柔性硅片;
步骤5:将清洗过的柔性单晶硅放入真空腔中并将其固定在样品架上,使入射激光垂直照到样品表面,样品架与一个三维移动台相连,在平移台的驱动下,样品可以在垂直于入射激光的平面上作二维运动;
步骤6:抽真空至10-5Pa,再充入0.67bar六氟化硫气体,最后在0.67bar的六氟化硫气氛下加工;
步骤7:入射飞秒激光的中心波长为800nm,脉宽为120fs,辐照到硅片表面的激光通量为1.2kJ/m2,样品在二维平移台的驱动下作二维扫描运动,逐行扫描,扫描一片面积为8mm×8mm的方形区域,扫描行间距为50μm,扫描速度为1mm/s;
步骤8:加工完成后,抽走加工腔内的气体至10-5Pa,再充入氮气,打开腔盖,取出样品,肉眼观察加工过的区域颜色为黑色或深灰色,即硫元素重掺杂黑硅层,掺杂层的厚度约为100nm;
步骤9:用快速热退火方法处理飞秒激光辐照过的样品,第一步升温,首先在10s内升温至240℃,再在5s内升温至600℃;第二步恒温,温度保持为600℃至600s;第三步自然降温;
步骤10:采用电阻热蒸发的方法在黑硅层边界之上制备铝电极作为正面接触电极,电极形状为一矩形,具体方法如下:在已退火的黑硅层上加一块掩膜版,掩膜版上的镂空区域与黑硅层上要镀电极的区域相对应,将贴好掩膜版的样品固定在蒸发镀膜机的钼舟正上方固定好,在钼舟中放入适量的铝条,抽真空至3×10-3Pa后蒸发镀电极;
步骤11:采用电阻热蒸发的方法在硅衬底背面制备铝电极作为背面接触电极,背电极覆盖整个衬底背面,至此完成器件制作。
经过以上步骤制备的柔性光电探测器响应波段为400nm-1200nm,在-2V工作偏压下响应度为0.8A/W-63A/W,峰值响应波长为860nm,峰值响应度为63A/W。该光电探测器克服了有机柔性光电探测器需基底支撑及响应度较低的缺点,并在低偏压下实现了高增益和宽谱的特性。此外,本发明所制备的柔性硅基光电探测在-2V偏压下的上升和下降时间分别为68μs和172μs,克服了有机柔性光电探测器响应时间较长的缺点。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。本领域普通的技术人员可以理解,在不背离所附权利要求定义的本发明的精神和范围的情况下,可以在形式和细节中做出各种各样的修改。
Claims (1)
1.一种自支撑高增益柔性硅基光电探测器的制备方法,其特征在于,包括如下步骤:
步骤1:选取单晶硅片,并对所选硅片进行预处理;
步骤2:采用浓度为50%的氢氧化钾(KOH)溶液在100℃的加热条件下对单晶硅片进行化学腐蚀以达到减薄的目的,使之具有柔韧性,即所谓的柔性单晶硅;
步骤3:采取相应工艺对腐蚀后的柔性单晶硅进行清洗;
步骤4:选取某一厚度为10μm-50μm(微米)的柔性单晶硅,通过飞秒激光在六氟化硫(SF6)气氛中辐照柔性单晶硅表面制备过饱和掺杂层,即获得柔性黑硅;
步骤5:对制备好的柔性黑硅材料进行退火处理,激活过饱和掺杂黑硅层中的杂质原子,并修复晶格,去除结构缺陷;
步骤6:在过饱和掺杂黑硅层表面上制备一正面接触电极,电极面积占黑硅层面积的1/9-1/3;
步骤7:在柔性单晶硅衬底背面制备一背面接触电极,覆盖整个单晶硅衬底背面,至此完成自支撑柔性硅基光电探测器的制备;
其中所述的高增益柔性硅基光电探测器的响应波段为400nm-1200nm,在-2V偏压下响应度为0.8A/W-63A/W,其中峰值波长出现在840nm-900nm,峰值响应度为63A/W;在-2V偏压下的上升和下降时分别为68μs和172μs; 在其中各数学符号的具体含义为:nm:纳米,V:伏特,A/W:安培/瓦特,μs:微秒;
其中步骤(1)中所述预处理工艺为:(a)将单晶硅片切成一定尺寸的方块,依次用丙酮、乙醇、去离子水超声清洗10分钟;(b)将超声后的硅片放入5%的氢氟酸溶液中浸泡2分钟;(c)把浸泡后的硅片放浓硫酸和双氧水混合溶液中进行亲水性处理,浓硫酸和双氧水的体积比为7∶3,加热至100℃-130℃区间内,保持20分钟;(d)取出后用氮气流吹干,其中,在步骤(a)、(b)、(c)、(d)之间都需先用去离子水冲洗硅片;
步骤(3)中所述相应工艺的清洗步骤为:(a)用浓度为5%的稀盐酸将腐蚀后的硅片浸泡1小时,以去除残留的氢氧化钾;(b)用浓度为10%的氢氟酸再将其浸泡10分钟,去除反应生成的硅酸;(c)最后把柔性硅浸入浓盐酸、双氧水和去离子水混合溶液中,浓盐酸、双氧水和去离子水的体积比为1∶2∶7,并在80℃下水浴30分钟,去除钾、钠等金属污染;(d)将清洗后的硅片放入去离子水中存储备用,其中,在步骤(a)、(b)、(c)、(d)之间都需先用去离子水冲洗柔性硅片。
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