CN113054050B - 一种V2O5-Ga2O3异质结自供电日盲光电探测器及制备方法 - Google Patents
一种V2O5-Ga2O3异质结自供电日盲光电探测器及制备方法 Download PDFInfo
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Abstract
本发明提供了一种V2O5‑Ga2O3异质结自供电日盲光电探测器及制备方法。所述探测器包括作为n型导电的Ga2O3材料和作为p型导电的V2O5材料形成的V2O5‑Ga2O3异质结，以及与上述材料欧姆接触的电极。本发明的制备方法通过对V2O5‑Ga2O3异质结进行二次退火，促进了平面异质结的形成和内建电场的产生，使异质界面可以有效分离激发态的电子‑空穴对，实现自供电工作模式。本发明提供的V2O5‑Ga2O3异质结自供电日盲光电探测器探测灵敏度高，响应速度快，其制备方法易于实现及有效，生产成本低，有利于生产和研究推广。
Description
技术领域
本发明涉及一种自供电日盲光电探测器及其制备方法，尤其涉及V2O5-Ga2O3异质结的自供电日盲光电探测器和其制备方法，属于半导体光电子器件领域。
背景技术
光电探测器可以实现光信号到电信号的转变，其本质是电子吸收光子后，从半导体材料的价带跃迁到导带进入电流循环。故光电探测器的信号识别能力由半导体材料的禁带宽度决定。比如，Si的带隙宽度为1.1eV，对应的响应光波段为1120nm左右。当光子能量大于Si的带隙宽度值，即
时，该光子可以激励Si材料的基态电子产生跃迁行为。基于半导体材料禁带宽度的不同，近年来不同紫外波段的探测器都逐渐被开发研究。AlN(6.2eV)用于真空紫外光谱(10～200nm)的感应；Ga2O3(4.9eV)用于UVC(200～280nm)波段的响应探测；ZnMgO(3.9eV)用于UVB(280～320nm)波段的响应探测；GaN(3.4eV)用于UVA(320～400nm)波段的响应探测。其中，由于Ga2O3所响应的波段正好覆盖太阳光的日盲波段，故基于Ga2O3制备的光电探测器也称为日盲紫外光电探测器。日盲探测器在紫外光检测、臭氧层空洞监测、火险预警等方面具有广阔的应用前景，近年来成为研究热点。
随着研究的深入和工艺技术的提高，光电探测器已具备高灵敏度、超快响应速度等优点，但需要额外供电工作的缺点依然制约着其进一步的发展。开发自供电模式的光电探测器，是未来节约型社会导向的必然趋势。通过构建异质结界面，产生内建电场，可以在无外部能量供应的情况下，实现电子-空穴对的自动分离，实现自供电工作模式。因此，发展基于Ga2O3异质结的自供电光电探测器，是开拓绿色无能耗日盲探测器的重要一步。
发明内容
针对传统日盲紫外探测器需要额外供电工作的问题，本发明旨在提供一种基于V2O5-Ga2O3异质结的自供电日盲光电探测器及其制备方法。通过Ga2O3和V2O5薄膜的平面异质结构建，实现了日盲紫外探测的自供电工作模式。
为了实现V2O5-Ga2O3异质结探测器的自供电日盲探测效果，本发明一方面提供一种V2O5-Ga2O3异质结自供电日盲光电探测器，包括：V2O5-Ga2O3异质结，该V2O5-Ga2O3异质结由作为n型导电的Ga2O3材料和作为p型导电的V2O5材料形成；与所述Ga2O3材料欧姆接触的第一电极；与所述V2O5材料欧姆接触的第二电极。
根据本发明的优选实施方式，所述Ga2O3材料为薄膜，薄膜厚度为10nm～5μm。
根据本发明的优选实施方式，所述V2O5材料为薄膜，薄膜的厚度为5nm～500nm。
根据本发明的优选实施方式，所述第一电极和第二电极的材料为铝、铜、银、铂、钛、镓、铟和金中的一种或多种组合。
本发明的另一方面还提供一种V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，包括如下步骤：
在衬底上制备Ga2O3薄膜；
在所述Ga2O3薄膜的部分区域覆盖形成V2O5薄膜，以形成V2O5-Ga2O3平面异质结；
在未覆盖V2O5薄膜的Ga2O3薄膜上，以及V2O5薄膜上，分别形成第一电极和第二电极。
根据本发明的优选实施方式，所述形成V2O5薄膜的步骤包括：
在Ga2O3薄膜的部分区域旋涂三异丙氧基氧化钒溶液；
加热蒸干所述溶液的溶剂，使所述三异丙氧基氧化钒分解获得钒的氧化物；
对所述钒的氧化物进行退火。
根据本发明的优选实施方式，其特征在于，所述三异丙氧基氧化钒溶液的溶剂为甲醇、乙醇、丙醇和异丙醇中的一种或多种组合。
根据本发明的优选实施方式，所述三异丙氧基氧化钒溶液中的溶质与溶剂的体积比为1:2～1:1000。
根据本发明的优选实施方式，所述退火温度为300～700℃。
根据本发明的优选实施方式，所述退火的退火时间为5～200min。
本发明的有益效果在于，通过构建V2O5-Ga2O3平面异质结，提供了一种V2O5-Ga2O3异质结自供电日盲光电探测器及制备方法。所构建的V2O5-Ga2O3异质结具备自供电工作模式。并且本发明提供的V2O5-Ga2O3异质结自供电日盲光电探测器，探测灵敏度高，响应速度快。
附图说明
图1是本发明的V2O5-Ga2O3平面异质结自供电日盲光电探测器结构示意图。
图2是本发明的实施例所制备的在Al2O3衬底上的V2O5-Ga2O3异质结的XRD图谱。
图3显示了本发明的实施例所制备的V2O5-Ga2O3异质结自供电日盲光电探测器在无光和254nm光照下的暗电流和光电流。
图4显示了本发明的实施例所制备的V2O5-Ga2O3异质结自供电日盲光电探测器在0V偏压和1mW/cm2光强的254nm光照下随光开关循环的光响应电流。
图5是本发明的实施例所制备的V2O5-Ga2O3异质结自供电日盲光电探测器在0V偏压下的光谱响应曲线。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
本发明提出的V2O5-Ga2O3异质结自供电日盲光电探测器包括V2O5-Ga2O3异质结，该V2O5-Ga2O3异质结由作为n型导电的Ga2O3材料和作为p型导电的V2O5材料形成。通常，该V2O5-Ga2O3异质结形成于衬底上。本发明所构建的V2O5-Ga2O3异质结，在平面界面处形成内建电场，无需外部电场也可以分离电子-空穴对。电子通过n型导电材料Ga2O3导出，空穴通过p型材料V2O5导出，实现日盲光信号到电信号的转变，从而使基于V2O5-Ga2O3异质结光电探测器具备自供电工作模式。
例如，可以在诸如蓝宝石(Al2O3)的衬底上形成Ga2O3薄膜，在所述Ga2O3薄膜的部分区域上，覆盖形成V2O5薄膜，由此形成V2O5-Ga2O3平面异质结。经发明人理论推算和实验测定，Ga2O3薄膜的厚度在10nm～5μm之间较为合适，更优选为200nm～500nm，而V2O5薄膜的厚度在5nm～500nm之间较为合适，更优选为10nm～50nm。
此外，该自供电日盲光电探测器还包括与所述Ga2O3材料欧姆接触的第一电极；与所述V2O5材料欧姆接触的第二电极。例如，可以在未覆盖V2O5薄膜的Ga2O3薄膜上形成第一电极，以及在V2O5薄膜上形成第二电极。铝、铜、银、铂、钛、镓、铟和金均以为作为单独电极材料，但也不排除其中多种材料的组合，或者上述材料的合金。
在制备上述V2O5-Ga2O3异质结自供电日盲光电探测器时，可以采用合适的方法在Ga2O3材料上形成V2O5材料，使之构成异质结。Ga2O3材料和V2O5材料都优选为形成薄膜，由此可形成平面异质结。Ga2O3薄膜可以通过金属有机物化学气象沉积(MOCVD)、脉冲激光沉积、分子束外延或磁控溅射中的一种或多种组合技术制备，如前所述，可以在诸如蓝宝石(Al2O3)的衬底上形成Ga2O3薄膜。
在形成了Ga2O3薄膜之后，可以在所述Ga2O3薄膜的部分区域覆盖形成V2O5薄膜，这样就形成了V2O5-Ga2O3平面异质结。作为具体实施方式的一种，形成V2O5薄膜的步骤如下：在Ga2O3薄膜的部分区域旋涂三异丙氧基氧化钒溶液，三异丙氧基氧化钒溶液的溶剂为甲醇、乙醇、丙醇和异丙醇中的一种或多种组合，溶液中的溶质与溶剂的体积比优选为1:2～1:1000，更优选为1:20～1:200；所选用的旋涂速度为1000～6000转/分钟，优选为2500～4000转/分钟。
接着，加热蒸干所述溶液的溶剂，使所述三异丙氧基氧化钒分解获得钒的氧化物(VOx)；最一对所述钒的氧化物进行退火，形成V2O5-Ga2O3平面异质结。退火气氛为空气、氧气、氩气、氮气中的一种或多种组合，退火温度为300℃～700℃，优选为400℃～600℃，退火时间为5min～200min，优选为30min～90min。
在上述步骤之后，为完成日盲光电探测器的制备，在未覆盖V2O5薄膜的Ga2O3薄膜上和V2O5薄膜上分别形成第一电极和第二电极。电极例如可通过电镀的方式形成。优选的，与Ga2O3材料欧姆接触的第一电极含有铟或钛，与V2O5材料欧姆接触的第二电极含有铟、铝或钛。以下通过一个具体实施例来更加清楚的解释本发明的结构和步骤。需要注意的是，下面的实施例仅仅是举例，本发明可以在上述方法和结构的基础上进行各种可能的实施。
具体实施例
在该实施中，通过金属有机物化学气象沉积(MOCVD)方法，在(0001)取向的蓝宝石(Al2O3)衬底上制备Ga2O3薄膜。镓源为三乙基镓，氧源为氧气，载气为氩气，制备温度为700～900℃，沉积速率为1～3μm/h。所制备的Ga2O3薄膜为β相，薄膜厚度为400nm。为了制备V2O5薄膜，将三异丙氧基氧化钒与异丙醇按照溶剂与溶质体积比为1:50的比率配置前驱体溶液。通过掩膜技术，将Ga2O3薄膜覆盖一半的面积，在未覆盖区域，以3000转/分钟的转速，旋涂三异丙氧基氧化钒与异丙醇的前驱体溶液。将覆盖均匀前驱体的Ga2O3薄膜放置于100℃的热平台，加热10min，蒸干溶剂并使三异丙氧基氧化钒分解，获得钒的氧化物(VOx)。去掉掩膜板，将初步获得的VOx-Ga2O3异质结进行二次退火，退火温度为500℃，退火气氛为空气，升温速度为5℃/min，高温保持时间为60min。退火后，形成V2O5-Ga2O3平面异质结，其XRD图谱如图2所示，Ga2O3为
取向的β相薄膜，V2O5为(001)取向。
为了构建V2O5-Ga2O3平面异质结光电探测器，通过掩膜板和磁控溅射技术，在V2O5薄膜和Ga2O3薄膜镀上钛金电极，其中与薄膜接触的金属为钛。所制备的V2O5-Ga2O3光电探测器的结构示意图如图1所示。图1中，01为Al2O3衬底，02为n型Ga2O3薄膜，03为p型V2O5薄膜，04为与Ga2O3材料欧姆接触的第一电极，05为与V2O5材料欧姆接触的第二电极
通过光电探测设备，测试的V2O5-Ga2O3光电探测器的暗电流如图3虚线所示，在-5V的偏压下，暗电流只有0.77pA。在254nm波段的光照下，光照强度1mW/cm2测得的光电流如图3实线所示。在-5V偏压下，光电流高达504nA，其光暗比高达6.55×105，显示了超高的光响应能力。同时，从电流-电压曲线还可以看出，所制备的异质结光电探测器具备自供电工作的能力，其光电流拥有0.3V的开路电压。
为了验证本发明提供的V2O5-Ga2O3光电探测器具备自供电工作能力，在1mW/cm2光强的254nm光照下，使器件在0偏压下工作，测得时间-电流曲线如图4所示。在无外部供电的情况下，所制备的V2O5-Ga2O3光电探测器依然可以对254nm光产生响应，电流高达27nA，说明V2O5-Ga2O3异质结光电探测器是一个自供电器件。
为了说明本发明制备的V2O5-Ga2O3异质结光电探测器是日盲紫外探测器，对器件进行了200～700nm波段的光谱响应测试，得到的光谱响应曲线如图5所示。本发明提供的V2O5-Ga2O3异质结光电探测器的主要响应波段在200～270nm，为日盲紫外区域，说明该探测器为日盲探测器。
根据实施例的实验结果，说明根据本发明制备的V2O5-Ga2O3异质结光电探测器探测灵敏度高，响应速度快，是一种性能优异的自供电日盲光电探测器。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，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 (10)
1.一种V2O5-Ga2O3异质结自供电日盲光电探测器，其特征在于，包括：
V2O5-Ga2O3异质结，该V2O5-Ga2O3异质结由作为n型导电的Ga2O3材料和作为p型导电的V2O5材料形成，且该V2O5-Ga2O3异质结是通过VOx-Ga2O3异质结退火形成；
与所述Ga2O3材料欧姆接触的第一电极；
与所述V2O5材料欧姆接触的第二电极。
2.根据权利要求1所述的V2O5-Ga2O3异质结自供电日盲光电探测器，其特征在于，所述Ga2O3材料为薄膜，薄膜厚度为10 nm~5 μm。
3.根据权利要求1所述的V2O5-Ga2O3异质结自供电日盲光电探测器，其特征在于，所述V2O5材料为薄膜，薄膜的厚度为5nm~500 nm。
4.根据权利要求1所述的V2O5-Ga2O3异质结自供电日盲光电探测器，其特征在于，所述第一电极和第二电极的材料为铝、铜、银、铂、钛、镓、铟和金中的一种或多种组合。
5.一种V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，其特征在于，包括如下步骤：
在衬底上制备Ga2O3薄膜；
在所述Ga2O3薄膜的部分区域覆盖形成VOx薄膜，再退火形成V2O5薄膜，以从VOx-Ga2O3异质结形成V2O5-Ga2O3平面异质结；
在未覆盖V2O5薄膜的Ga2O3薄膜上，以及V2O5薄膜上，分别形成第一电极和第二电极。
6.如权利要求5所述的V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，其特征在于，所述形成V2O5薄膜的步骤包括：
在Ga2O3薄膜的部分区域旋涂三异丙氧基氧化钒溶液；
加热蒸干所述溶液的溶剂，使所述三异丙氧基氧化钒分解获得钒的氧化物；
对所述钒的氧化物进行退火。
7.如权利要求6所述的V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，其特征在于，所述三异丙氧基氧化钒溶液的溶剂为甲醇、乙醇、丙醇和异丙醇中的一种或多种组合。
8.如权利要求7所述的V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，其特征在于，所述三异丙氧基氧化钒溶液中的溶质与溶剂的体积比为1:2~1:1000。
9.根据权利要求6所述的V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，其特征在于，所述退火的退火温度为300~700 ℃。
10.根据权利要求9所述的V2O5-Ga2O3异质结自供电日盲光电探测器的制备方法，其特征在于，所述退火的退火时间为5~200 min。
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