CN113206168A - 可见光探测器及制备方法 - Google Patents
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Abstract
可见光探测器及制备方法，及电子信息材料与元器件技术，本发明的可见光探测器包括设置于Si(100)衬底上表面的Bi2O3层，所述Bi2O3层的上表面设置有Bi2(SeO3)3薄膜层，在Bi2O3层的上表面和Bi2(SeO3)3薄膜层的上表面设置有电极。本发明的探测器具有较低的暗电流和较快的光响应速度。
Description
技术领域
本发明涉及电子信息材料与元器件技术。
背景技术
光电探测器作为现代社会最重要的光电器件之一，已经于人类生活密不可分。该类器件可以将光信号精确地、快速地转换为电信号(通常是电流或者电压)，因而被广泛应用于图像传感、光通信、生物医学热成像、环境监测、国防技术和运动监测等领域。近几十年来，金属氧化物半导体材料由于其优异的物理性能，稳定的化学性能以及便于批量生产等优点而备受关注。
光电探测器根据太阳光的光谱范围，可简单分为紫外、可见和红外探测器。可见光的波长范围是390-780nm，可见光探测器即为探测到人眼可见的光。可见光探测器在光通信、遥感、光谱分析、监视、荧光生物医学成像等领域有着广泛的应用。因此，可见光电探测器的应用前景以及社会需求相对而言较大。
Bi2O3具有特殊的物理性质和晶体形态,现有的文献报道了其具有六种Bi2O3的多晶型，分别标记为α、β、γ、δ、ε、ω相。其中低温α-Bi2O3和高温δ-Bi2O3是稳定的；其他是高温亚稳相。每一种晶型都具有不同的晶体结构和物理性质，即电学、光学和光电等。氧化铋薄膜具有范围在2～3.96eV的直接带隙，同时具有高折射率、高介电常数以及显著的光电导和光致发光特性。这些特性使得Bi2O3材料作为可见光探测器材料使用有很大的潜力，但是相对于平时经常使用的可见光探测器又有所不足，如载流子迁移率较低，空穴-电子复合率较高，光生电流较小，为了进一步提升其性能和适应在可见光探测器的应用，选择制作Bi2(SeO3)3-Bi2O3异质结探测器。Bi2(SeO3)3是通过Se颗粒加热蒸发和Bi2O3颗粒电子打击溅射在Si(100)单晶基片表面反应生成。
发明内容
本发明所要解决的技术问题是，提供一种具有较低的暗电流和较快的光响应速度的可见光探测器及其制备方法。
本发明解决所述技术问题采用的技术方案是，可见光探测器，其特征在于，包括设置于Si衬底上表面的Bi2O3层，所述Bi2O3层的上表面设置有Bi2(SeO3)3薄膜层，在Bi2O3层的上表面和Bi2(SeO3)3薄膜层的上表面设置有电极，
本发明还提供一种可见光探测器的制备方法，包括下述步骤：
(S1)以Bi2O3为Bi和O源，以高纯的Se颗粒为Se源，利用分子束外延方法在Si衬底的表面依次生长Bi2O3薄膜和Bi2(SeO3)3薄膜；
(S2)在Bi2O3薄膜和Bi2(SeO3)3薄膜上利用掩模版生长Au/Ti电极。
进一步的，所述步骤(S1)为：
将Si衬底移入分子束外延设备中，使用机械泵和分子泵仪器腔内压强到4×10- 4Pa，调节衬底温度为200度，打开电子枪生长Bi2O3薄膜2小时。随后冷却到室温，取出样品在Bi2O3薄膜上放置预定的掩模版，然后在放入分子束外延仪器内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜；
所述步骤(S2)为：
使用电子枪仪器，将生长好的Bi2(SeO3)3薄膜上放置预定掩模版，随后放入电子束蒸发仪器中，通过机械泵和分子泵使腔内压强到3.6×10-4Pa，然后生长1分钟的Ti和生长5分钟的Au形成Au\Ti电极。
本发明使用分子束外延设备生长制备Bi2(SeO3)3-Bi2O3异质结可见光探测器，通过改变Se的蒸发温度，从而改变沉积的Bi2(SeO3)3薄膜的Se原子含量和晶体质量，优化Bi2(SeO3)3-Bi2O3异质结的光电性能，同时达到Bi2O3薄膜不分相，结晶性高、颗粒分布均匀等特点，进而使Bi2(SeO3)3-Bi2O3异质结可见光探测器具有较低的暗电流和较快的光响应速度，同时可工作在10V外加偏压下，并且具有较高的灵敏度，为研制高性能光电探测器件提供有效的解决方案。
附图说明
图1为本发明的可见光探测器的结构示意图；
图2为本发明的制备方法的流程示意图；
图3为本发明实施例1的电流-电压特性曲线图；
图4为本发明实施例1的电流-时间特性曲线图；
图5为本发明实施例2的电流-电压特性曲线图；
图6为本发明实施例2的电流-时间特性曲线图；
图7为本发明实施例3的电流-电压特性曲线图；
图8为本发明实施例3的电流-时间特性曲线图；
图9为本发明实施例4的电流-电压特性曲线图；
图10为本发明实施例4的电流-时间特性曲线图。
图11为本发明制备的Bi2O3薄膜测试的XRD数据
图12为本发明制备的Bi2(SeO3)3薄膜测试的XRD数据
图中，light表示光照下的电流-电压特性曲线，dark表示黑暗环境下的电流-电压特性曲线。
具体实施方式
为了扩展Bi2O3在可见光探测器的应用，同时提高所制作出来的Bi2(SeO3)3与Bi2O3薄膜的晶体质量、光电性能、光响应度等性质，本发明提供一种Bi2(SeO3)3与Bi2O3异质结可见光探测器及其制备方法，使用Bi2O3颗粒为Bi和O源，以高纯的Se颗粒为Se源，利用分子束外延方法在Si衬底的表面依次生长Bi2O3和Bi2(SeO3)3薄膜，使制备的Bi2O3薄膜具有结晶性高、颗粒分布均匀、薄膜稳定性好等特点，进而使Bi2(SeO3)3-Bi2O3异质结探测器具有较低的暗电流和较快的光响应速度。
本发明的可见光探测器包括从下至上依次叠加的Si衬底、Bi2O3薄膜、Bi2(SeO3)3薄膜，以及设置于Bi2O3薄膜和Bi2(SeO3)3薄膜上表面的Au/Ti电极。
所述Bi2O3薄膜为α-Bi2O3薄膜。
本发明的Bi2(SeO3)3-Bi2O3异质结可见光探测器吸收波长为200-800nm,Bi2(SeO3)3-Bi2O3异质结可见光探测器的光响应波长为200-800nm.
本发明还提供一种Bi2(SeO3)3-Bi2O3异质结可见光探测器的制备方法，包括如下步骤：
S1、以Bi2O3为Bi和O源，以高纯的Se颗粒为Se源，利用分子束外延方法在Si衬底的表面依次生长Bi2O3和Bi2(SeO3)3薄膜；
S2、在Bi2O3和Bi2(SeO3)3薄膜上利用特制的掩模版生长Au/Ti电极。
分子束外延设备使用的电子束流为12mA.
步骤S2中，采用电子束蒸发长电极时，先Ti生长1分钟，然后Au生长5分钟。
如图1所示，本发明提供的Bi2(SeO3)3-Bi2O3异质结可见光探测器，包括：按照从下至上的顺序依次叠加的Si衬底4、Bi2O3薄膜3、Bi2(SeO3)3薄膜2和电极1。
Bi2O3薄膜为α-Bi2O3，属于直接带隙半导体，禁带宽度在2～3ev之间，使Bi2O3通过掺Se能够更好的改变其光电性质，增强可见光区域的探测能力。
Bi2(SeO3)3-Bi2O3异质结可见光探测器的光吸收波长为200-800nm。
Bi2(SeO3)3-Bi2O3异质结可见光探测器的光响应波长为200-800nm.
Bi2(SeO3)3-Bi2O3异质结可见光探测器的制备方法为使用分子束外延设备仪器，Bi2O3作为Bi、O源和Se颗粒作为Se源，加热衬底到一定温度，在衬底上先生长Bi2O3薄膜、然后生长Bi2(SeO3)3薄膜。
电极的制备方法为：使用电子束蒸发仪器，同时在Bi2(SeO3)3-Bi2O3异质结上使用特制的掩模版，先生长1分钟的Ti，然后生长5分钟的Au.
上述内容详细说明了本发明提供的Bi2(SeO3)3-Bi2O3异质结可见光探测器的结构。与上述Bi2(SeO3)3-Bi2O3异质结可见光探测器相对应，本发明还提供一种Bi2(SeO3)3-Bi2O3异质结可见光探测器的制备方法.
图2示出了本发明提供的Bi2(SeO3)3-Bi2O3异质结可见光探测器的制备方法的流程。
如图2所示，本发明提供的Bi2(SeO3)3-Bi2O3异质结可见光探测器的制备方法，包括如下步骤：
S1、以Bi2O3为Bi和O源，以高纯的Se颗粒为Se源，利用分子束外延方法在Si衬底的表面依次生长Bi2O3和Bi2(SeO3)3薄膜；
将Si衬底移入分子束外延设备中，使用机械泵和分子泵仪器腔内压强到4×10- 4Pa，调节衬底温度为200度，打开电子枪生长Bi2O3薄膜2小时。随后冷却到室温，取出样品在Bi2O3薄膜上放置特定的掩模版，然后在放入分子束外延仪器内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜。
在步骤S1之前，还可以包括如下步骤：
S0、对衬底进行清洗。使用丙酮和乙醇依次在超声波仪器中清洗衬底5分钟，然后在重复操作清洗一次，最后用干燥的氮气吹干。
S0为可选步骤，如果衬底干净，可以不进行此步骤。
S2、在Bi2O3和Bi2(SeO3)3薄膜上利用掩模版生长Au/Ti电极。
使用电子枪仪器，将生长好的Bi2(SeO3)3薄膜上放置特制掩模版，随后放入电子束蒸发仪器中，通过机械泵和分子泵使腔内压强到3.6×10-4Pa，然后生长在1分钟的Ti和生长5分钟的Au形成Au\Ti电极。
下面以几个具体实施例对本发明提供的Bi2O3和Bi2(SeO3)3可见光探测器的制备方法及其性能进行详细说明。
实施例1
将清洗好的Si(100)衬底放入MBE设备的生长腔内，调节生长的衬底温度到200度，压强为4×10-4Pa。使用Bi2O3作为Bi源和O源，Se颗粒作为Se源。Se的蒸发温度为170度，电子枪的电子束流为12mA,生长2小时的Bi2O3薄膜。随后冷却到室温，取出样品在Bi2O3薄膜上放置特定的掩模版，然后在放入分子束外延设备的生长腔内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜。得到Bi2(SeO3)3-Bi2O3异质结。
使用电子枪仪器，将生长好的Bi2(SeO3)3-Bi2O3薄膜上放置特制掩模版，随后放入分子束外延仪器中，通过机械泵和分子泵仪器腔内压强到3.6×10-4Pa，然后生长在1分钟的Ti和生长5分钟的Au形成Au/Ti电极。
对实施例1中得到的Bi2(SeO3)3-Bi2O3异质结探测器进行暗态下和460nm光照下的电流-电压特性和I-T特性测试，得到其图谱分别如图3和图4所示。从图3和图4中可以看出，制备的Bi2(SeO3)3-Bi2O3异质结探测器在10V下的暗电流约为80nA，光电流为4.4μA，光暗电流比为55，且光响应速度较快，说明制备的Bi2(SeO3)3-Bi2O3异质结探测器具有较好的光电性能。
实施例2
将清洗好的Si(100)衬底放入MBE设备的生长腔内，调节生长的衬底温度到200度，压强为4×10-4Pa。使用Bi2O3作为Bi源和O源，Se颗粒作为Se源。Se的蒸发温度为180度，电子枪的电子束流为12mA,生长2小时的Bi2O3薄膜。随后冷却到室温，取出样品在Bi2O3薄膜上放置特定的掩模版，然后在放入分子束外延设备的生长腔内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜。得到Bi2(SeO3)3-Bi2O3异质结。
使用电子枪仪器，将生长好的Bi2(SeO3)3-Bi2O3薄膜上放置特制掩模版，随后放入分子束外延仪器中，通过机械泵和分子泵仪器腔内压强到3.6×10-4Pa，然后生长在1分钟的Ti和生长5分钟的Au形成Au/Ti电极。
对实施例1中得到的Bi2(SeO3)3-Bi2O3异质结探测器进行暗态下和460nm光照下的电流-电压特性和I-T特性测试，得到其图谱分别如图5和图6所示。从图5和图6中可以看出，制备的Bi2(SeO3)3-Bi2O3异质结探测器在10V下的暗电流约为400nA，光电流为8μA，光暗电流比为20，且光响应速度较快，说明制备的Bi2(SeO3)3-Bi2O3异质结探测器具有较好的光电性能。
实施例3
将清洗好的Si(100)衬底放入MBE设备的生长腔内，调节生长的衬底温度到200度，压强为4×10-4Pa。使用Bi2O3作为Bi源和O源，Se颗粒作为Se源。Se的蒸发温度为190度，电子枪的电子束流为12mA,生长2小时的Bi2O3薄膜。随后冷却到室温，取出样品在Bi2O3薄膜上放置特定的掩模版，然后在放入分子束外延设备的生长腔内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜。得到Bi2(SeO3)3-Bi2O3异质结。
使用电子枪仪器，将生长好的Bi2(SeO3)3-Bi2O3薄膜上放置特制掩模版，随后放入分子束外延仪器中，通过机械泵和分子泵仪器腔内压强到3.6×10-4Pa，然后生长在1分钟的Ti和生长5分钟的Au形成Au/Ti电极。
对实施例1中得到的Bi2(SeO3)3-Bi2O3异质结探测器进行暗态下和460nm光照下的电流-电压特性和I-T特性测试，得到其图谱分别如图7和图8所示。从图7和图8中可以看出，制备的Bi2(SeO3)3-Bi2O3异质结探测器在10V下的暗电流约为140nA，光电流为5.2μA，光暗电流比为13，且光响应速度较快，说明制备的Bi2(SeO3)3-Bi2O3异质结探测器具有较好的光电性能。
实施例4
将清洗好的Si(100)衬底放入MBE设备的生长腔内，调节生长的衬底温度到200度，压强为4×10-4Pa。使用Bi2O3作为Bi源和O源，Se颗粒作为Se源。Se的蒸发温度为200度，电子枪的电子束流为12mA,生长2小时的Bi2O3薄膜。随后冷却到室温，取出样品在Bi2O3薄膜上放置特定的掩模版，然后在放入分子束外延设备的生长腔内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜。得到Bi2(SeO3)3-Bi2O3异质结。
使用电子枪仪器，将生长好的Bi2(SeO3)3-Bi2O3薄膜上放置特制掩模版，随后放入分子束外延仪器中，通过机械泵和分子泵仪器腔内压强到3.6×10-4Pa，然后生长在1分钟的Ti和生长5分钟的Au形成Au/Ti电极。
对实施例1中得到的Bi2(SeO3)3-Bi2O3异质结探测器进行暗态下和460nm光照下的电流-电压特性和I-T特性测试，得到其图谱分别如图9和图10所示。从图9和图10中可以看出，制备的Bi2(SeO3)3-Bi2O3异质结探测器在10V下的暗电流约为120nA，光电流为12μA，光暗电流比为100，且光响应速度较快，说明制备的Bi2(SeO3)3-Bi2O3异质结探测器具有较好的光电性能。
Claims (4)
1.可见光探测器，其特征在于，包括设置于Si(100)衬底上表面的Bi2O3层，所述Bi2O3层的上表面设置有Bi2(SeO3)3薄膜层，在Bi2O3层的上表面和Bi2(SeO3)3薄膜层的上表面设置有电极。
2.如权利要求1所述的可见光探测器，其特征在于，所述电极为Ti/Au复合电极。
3.可见光探测器的制备方法，其特征在于，包括下述步骤：
(S1)以Bi2O3为Bi和O源，以高纯的Se颗粒为Se源，利用分子束外延方法在Si(100)衬底的表面依次生长Bi2O3薄膜和Bi2(SeO3)3薄膜；
(S2)在Bi2O3薄膜和Bi2(SeO3)3薄膜上利用掩模版生长Au/Ti电极。
4.如权利要求3所述的可见光探测器的制备方法，其特征在于，所述步骤(S1)为：
将Si衬底移入分子束外延设备中，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，打开电子枪生长Bi2O3薄膜2小时。随后冷却到室温，取出样品在Bi2O3薄膜上放置预定的掩模版，然后在放入分子束外延仪器内，使用机械泵和分子泵仪器腔内压强到4×10-4Pa，调节衬底温度为200度，同时蒸发Bi2O3源和Se源，生长2小时的Bi2(SeO3)3薄膜；
所述步骤(S2)为：
使用电子枪仪器，将生长好的Bi2(SeO3)3薄膜上放置预定掩模版，随后放入电子束蒸发仪器中，通过机械泵和分子泵使腔内压强到3.6×10-4Pa，然后生长Ti和Au形成Ti/Au电极。
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