CN112186051B - 一种F-β-Ga2O3/CuGaO2紫外光电探测器及其制备方法 - Google Patents
一种F-β-Ga2O3/CuGaO2紫外光电探测器及其制备方法 Download PDFInfo
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Abstract
本发明属于光探测器技术领域，具体涉及一种F‑β‑Ga2O3/CuGaO2紫外光电探测器及其制备方法，该制备方法的步骤包括：先用乙酸铜、硝酸镓和NaOH反应制得CuGaO2纳米片，然后以硝酸镓为Ga源，辅以NaF分别制备负载在CuGaO2纳米片上的F‑β‑Ga2O3/CuGaO2和纯的F‑β‑Ga2O3；然后将两张材料先后涂在叉指电极上并用热蒸发在薄膜上制备Au电极，得到F‑β‑Ga2O3/CuGaO2紫外光电探测器。本发明所述紫外光电探测器具备高的的光敏度和响应度，探测器响应速度快。
Description
技术领域
本发明属于光探测器技术领域，具体涉及一种F-β-Ga2O3/CuGaO2紫外光电探测器及其制备方法。
背景技术
太阳光可以分为三个波段，紫外区、可见区，红外区；小于400nm波段的波段为紫外波段。除了在航空航天及军事领域，如太空中的辐射探测等对紫外探测技术有一定的要求外；在民用领域，由于紫外辐射会对人体内的维生素合成、紫外致癌等产生影响，也对紫外探测有一定的需求。
光电探测器是一种通过光电信号转变而实现感知探测的重要光电器件，光电探测主要通过以下步骤完成检测：首先在外界光辐射的情况下探测器产生光生载流子，然后光生载流子通过扩散和漂移的形式在半导体内部进行输运和倍增，最后光生载流子形成的光电流被两端电极收集，从而实现了对外界光辐射的检测。
传统上，紫外光的检测方式主要有光电倍增管、热探测器和窄带隙半导体光电二极管。光电倍增管虽然是对紫外光子十分敏感，但是它不仅体积和重量大，并且需要很高的工作电压；热探测器虽然检测效果较好，但是响应速度慢，且不具备波长选择性；窄带隙半导体光电二极管的带隙小，需要额外阻挡可见光和红外光子，进而导致系统的有效面积显著损失。因此制备具有高的响应度、量子效率、响应速度以及信噪比的紫外光电探测器十分必要。
发明内容
针对现有紫外光电探测器的光敏度不高、响应度低和响应速度慢的技术缺陷，本发明提供一种F-β-Ga2O3/CuGaO2紫外光电探测器及其制备方法。
为实现上述目的，本发明采用以下技术方案：
一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，包括以下步骤：
步骤一：将一定量的乙酸铜和适量硝酸镓先后加入去离子水中，室温下超声 15-20min后向溶液中缓慢的滴入适量NaOH溶液，并在50-60℃的水浴中搅拌20-30min，然后向混合溶液中滴入适量乙二醇溶液并在同样温度下继续搅拌 10-13min后静置1-2h，静置后将溶液置于反应釜内衬中在190-210℃下反应 36-48h，自然冷却至室温后用稀硝酸将产物离心洗涤至洗涤液呈中性，随后再用无水乙醇和去离子水交替洗涤4次，然后将产物放在65-70℃的真空干燥箱中烘干得到CuGaO2纳米片。
步骤二：将步骤一制备的CuGaO2纳米片和适量硝酸镓加入去离子水中，超声20-25min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入适量的NaF溶液和α-烯烃磺酸钠溶液，并快速搅拌10-15min；搅拌后将混合溶液置于170-190℃的反应釜中保温24-30h,冷却至室温后将产物用去离子水离子洗涤3次，然后放入60-70℃的干燥箱中18-22h，干燥后将产物放入管式炉中，在氩气气氛下以950℃煅烧2-3h制得F-β-Ga2O3/CuGaO2材料。
步骤三：采用步骤二的制备方法，但在硝酸镓的水溶液中不加入CuGaO2纳米片，制得F-β-Ga2O3材料。
步骤四：将F-β-Ga2O3/CuGaO2材料和F-β-Ga2O3材料分别置于无水乙醇中并超声40-50min；将叉指电极用无水乙醇和去离子水交替洗涤5次后置于60-70℃的干燥箱中烘干，然后将F-β-Ga2O3的无水乙醇溶液滴在叉指电极上，干燥后得到均匀的薄膜，然后在薄膜上滴加F-β-Ga2O3/CuGaO2的无水乙醇溶液并用刮刀涂抹均匀，随后把样品置于50-55℃的真空干燥箱中烘干，烘干后通过热蒸发在薄膜一侧制备Au电极，最后得到F-β-Ga2O3/CuGaO2紫外光电探测器。
所述步骤一中乙酸铜的添加量为20-35mmol，乙二醇的添加量为15-20ml；乙酸铜和硝酸镓的物质的量之比为1:0.8-1:1，乙酸铜和NaOH的物质的量之比为 1:6-1:8。
所述步骤二中硝酸镓和CuGaO2的质量比为0.76:1-1.12:1，NaF和硝酸镓的质量比为1:3.9-1:6.2，α-烯烃磺酸钠和CuGaO2的质量比为1:12-1:16。
所述步骤三中硝酸镓的添加量为40-50mmol，其他物质的用量比和步骤二相同。
优选地，所述步骤一中乙酸铜水溶液的浓度为0.08g/ml；NaOH溶液的浓度均为2.5mol/L，滴加速度均为3ml/min。
优选地，所述步骤二中硝酸镓水溶液的浓度为0.1g/ml；NaOH溶液的浓度均为2.5mol/L，滴加速度均为3ml/min；NaF水溶液的浓度为0.06g/ml；α-烯烃磺酸钠水溶液的浓度为0.03g/ml。
优选地，所述步骤二制备的复合材料中F-β-Ga2O3在CuGaO2纳米片上的负载量为28wt％-41wt％；所述步骤二和步骤三中F在β-Ga2O3的掺杂量为 10wt％-16wt％。
本发明的另一方面提供上述F-β-Ga2O3/CuGaO2紫外光电探测器制备方法制得的紫外光电探测器，本探测器在365nm紫外光、0.2mW/cm2的功率下的光敏度在2100以上，外加电压0V和10V下响应度分别最高可达0.27mA/W和32A/W，响应速度快，上升和下降所用时间分别为70ms和15ms左右。
有益效果：
(1)CuGaO2是形状均一的六角片状结构纳米片，属于大尺寸的二维材料，这样的形状提高了涂覆成膜后的取向，有利于异质结的形成。
(2)β-Ga2O3在F掺杂后成为了n型半导体，由于O和F的离子半径很接近，F十分容易取代O的位置；而且F的掺杂可以拓宽β-Ga2O3的占据态，从而提高材料的光学带隙；掺杂后的材料相对于未掺杂，在载流子密度上也有所提升，进而导致了导电性能的上升。
(3)本发明所述复合方法可以提供更多的空穴注入，提高两种半导体的接触面积，形成了许多局域的p-n结；这些局域p-n结及其附带的局域内建电场的存在影响了内部载流子传输，促进了电子-空穴的分离，提高了光电探测器的灵敏度。
附图说明
图1为实施例1中步骤二制得的F-β-Ga2O3/CuGaO2材料的XRD图；
图2为实施例1制得的紫外光电探测器的I-V曲线。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
步骤一：将3.99g乙酸铜和5.1g硝酸镓先后加入49.9ml去离子水中，室温下超声15min后向溶液中缓慢的滴入63.8ml的NaOH溶液，并在60℃的水浴中搅拌20min，然后向混合溶液中滴入15ml乙二醇溶液并在同样温度下继续搅拌 12min后静置1h，静置后将溶液置于反应釜内衬中在190℃下反应48h，自然冷却至室温后用稀硝酸将产物离心洗涤至洗涤液呈中性，随后再用无水乙醇和去离子水交替洗涤4次，然后将产物放在65℃的真空干燥箱中烘干得到CuGaO2纳米片。
步骤二：将3.3g的CuGaO2纳米片和3.69g硝酸镓加入36.9ml去离子水中，超声20min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入15.8ml的NaF溶液和10.2ml的α-烯烃磺酸钠溶液，并快速搅拌 10min；搅拌后将混合溶液置于190℃的反应釜中保温24h,冷却至室温后将产物用去离子水离子洗涤3次，然后放入60℃的干燥箱中18h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧3h制得F-β-Ga2O3/CuGaO2材料。
步骤三：将10.2g硝酸镓加入102ml去离子水中，超声20min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入43.6ml 的NaF溶液和28.3ml的α-烯烃磺酸钠溶液，并快速搅拌10min；搅拌后将混合溶液置于190℃的反应釜中保温24h,冷却至室温后将产物用去离子水离子洗涤3 次，然后放入60℃的干燥箱中18h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧3h制得F-β-Ga2O3材料。
步骤四：将F-β-Ga2O3/CuGaO2材料和F-β-Ga2O3材料分别置于无水乙醇中并超声50min；将叉指电极用无水乙醇和去离子水交替洗涤5次后置于60℃的干燥箱中烘干，然后将F-β-Ga2O3的无水乙醇溶液滴在叉指电极上，干燥后得到均匀的薄膜，然后在薄膜上滴加F-β-Ga2O3/CuGaO2的无水乙醇溶液并用刮刀涂抹均匀，随后把样品置于55℃的真空干燥箱中烘干，烘干后通过热蒸发在薄膜一侧制备Au电极，最后得到F-β-Ga2O3/CuGaO2紫外光电探测器。
实施例2
步骤一：将7g乙酸铜和7.2g硝酸镓先后加入87.5ml去离子水中，室温下超声20min后向溶液中缓慢的滴入84ml的NaOH溶液，并在50℃的水浴中搅拌 30min，然后向混合溶液中滴入20ml乙二醇溶液并在同样温度下继续搅拌13min 后静置2h，静置后将溶液置于反应釜内衬中在210℃下反应36h，自然冷却至室温后用稀硝酸将产物离心洗涤至洗涤液呈中性，随后再用无水乙醇和去离子水交替洗涤4次，然后将产物放在66℃的真空干燥箱中烘干得到CuGaO2纳米片。
步骤二：将5.78g的CuGaO2纳米片和4.39g硝酸镓加入43.9ml去离子水中，超声25min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入11.8ml的NaF溶液和9.1ml的α-烯烃磺酸钠溶液，并快速搅拌 15min；搅拌后将混合溶液置于170℃的反应釜中保温30h,冷却至室温后将产物用去离子水离子洗涤3次，然后放入70℃的干燥箱中21h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧3h制得F-β-Ga2O3/CuGaO2材料。
步骤三：将12.8g硝酸镓加入128ml去离子水中，超声25min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入34.4ml 的NaF溶液和26.6ml的α-烯烃磺酸钠溶液，并快速搅拌15min；搅拌后将混合溶液置于170℃的反应釜中保温30h,冷却至室温后将产物用去离子水离子洗涤3 次，然后放入70℃的干燥箱中21h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧3h制得F-β-Ga2O3材料。
步骤四：将F-β-Ga2O3/CuGaO2材料和F-β-Ga2O3材料分别置于无水乙醇中并超声47min；将叉指电极用无水乙醇和去离子水交替洗涤5次后置于70℃的干燥箱中烘干，然后将F-β-Ga2O3的无水乙醇溶液滴在叉指电极上，干燥后得到均匀的薄膜，然后在薄膜上滴加F-β-Ga2O3/CuGaO2的无水乙醇溶液并用刮刀涂抹均匀，随后把样品置于50℃的真空干燥箱中烘干，烘干后通过热蒸发在薄膜一侧制备Au电极，最后得到F-β-Ga2O3/CuGaO2紫外光电探测器。
实施例3
步骤一：将5.24g乙酸铜和5.76g硝酸镓先后加入65.5ml去离子水中，室温下超声18min后向溶液中缓慢的滴入68.2ml的NaOH溶液，并在53℃的水浴中搅拌28min，然后向混合溶液中滴入16ml乙二醇溶液并在同样温度下继续搅拌 10min后静置2h，静置后将溶液置于反应釜内衬中在200℃下反应40h，自然冷却至室温后用稀硝酸将产物离心洗涤至洗涤液呈中性，随后再用无水乙醇和去离子水交替洗涤4次，然后将产物放在69℃的真空干燥箱中烘干得到CuGaO2纳米片。
步骤二：将4.33g的CuGaO2纳米片和3.46g硝酸镓加入34.6ml去离子水中，超声23min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入12.1ml的NaF溶液和8.7ml的α-烯烃磺酸钠溶液，并快速搅拌 14min；搅拌后将混合溶液置于178℃的反应釜中保温26h,冷却至室温后将产物用去离子水离子洗涤3次，然后放入63℃的干燥箱中19h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧2h制得F-β-Ga2O3/CuGaO2材料。
步骤三：将11.3g硝酸镓加入113ml去离子水中，超声23min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入39.5ml 的NaF溶液和28.4ml的α-烯烃磺酸钠溶液，并快速搅拌14min；搅拌后将混合溶液置于178℃的反应釜中保温26h,冷却至室温后将产物用去离子水离子洗涤3 次，然后放入63℃的干燥箱中19h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧2h制得F-β-Ga2O3材料。
步骤四：将F-β-Ga2O3/CuGaO2材料和F-β-Ga2O3材料分别置于无水乙醇中并超声44min；将叉指电极用无水乙醇和去离子水交替洗涤5次后置于64℃的干燥箱中烘干，然后将F-β-Ga2O3的无水乙醇溶液滴在叉指电极上，干燥后得到均匀的薄膜，然后在薄膜上滴加F-β-Ga2O3/CuGaO2的无水乙醇溶液并用刮刀涂抹均匀，随后把样品置于52℃的真空干燥箱中烘干，烘干后通过热蒸发在薄膜一侧制备Au电极，最后得到F-β-Ga2O3/CuGaO2紫外光电探测器。
实施例4
步骤一：将6.32g乙酸铜和6.64g硝酸镓先后加入79ml去离子水中，室温下超声17min后向溶液中缓慢的滴入75.8ml的NaOH溶液，并在56℃的水浴中搅拌25min，然后向混合溶液中滴入18ml乙二醇溶液并在同样温度下继续搅拌 11min后静置1h，静置后将溶液置于反应釜内衬中在195℃下反应42h，自然冷却至室温后用稀硝酸将产物离心洗涤至洗涤液呈中性，随后再用无水乙醇和去离子水交替洗涤4次，然后将产物放在70℃的真空干燥箱中烘干得到CuGaO2纳米片。
步骤二：将5.22g的CuGaO2纳米片和3.96g硝酸镓加入39.6ml去离子水中，超声21min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入14.1ml的NaF溶液和11ml的α-烯烃磺酸钠溶液，并快速搅拌 12min；搅拌后将混合溶液置于184℃的反应釜中保温28h,冷却至室温后将产物用去离子水离子洗涤3次，然后放入67℃的干燥箱中22h，干燥后将产物放入管式炉中，在氮气气氛下以950℃煅烧2h制得F-β-Ga2O3/CuGaO2材料。
步骤三：将10.8g硝酸镓加入108ml去离子水中，超声21min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9左右，随后向溶液中加入38.5ml 的NaF溶液和30ml的α-烯烃磺酸钠溶液，并快速搅拌12min；搅拌后将混合溶液置于184℃的反应釜中保温28h,冷却至室温后将产物用去离子水离子洗涤3次，然后放入67℃的干燥箱中22h，干燥后将产物放入管式炉中，在氮气气氛下以 950℃煅烧2h制得F-β-Ga2O3材料。
步骤四：将F-β-Ga2O3/CuGaO2材料和F-β-Ga2O3材料分别置于无水乙醇中并超声40min；将叉指电极用无水乙醇和去离子水交替洗涤5次后置于68℃的干燥箱中烘干，然后将F-β-Ga2O3的无水乙醇溶液滴在叉指电极上，干燥后得到均匀的薄膜，然后在薄膜上滴加F-β-Ga2O3/CuGaO2的无水乙醇溶液并用刮刀涂抹均匀，随后把样品置于53℃的真空干燥箱中烘干，烘干后通过热蒸发在薄膜一侧制备Au电极，最后得到F-β-Ga2O3/CuGaO2紫外光电探测器。
表1
将实施例1-4制得的探测器置于365nm波长的紫外光、0.2mW/cm2功率下测试得出探测器对于光暗电流的光敏度、探测器的响应度和响应时间四项光电性能测试数据，具体如表1所示。从表1中可以得到本发明制备的F-β-Ga2O3/CuGaO2紫外光电探测器具有高的光敏度，实施例1-4的数值都在2100以上；对于365nm 的紫外光的响应度在0V时最高为0.27mA/W，在10V的外加电压下可达32A/W；探测器的响应时间为毫秒级别，上升时在65-75ms之间，下降时在13-16ms之间。以上数据证明了本发明提供的紫外光电探测器制备方法制得的探测器具有极佳的紫外光电探测性能。
图1是实施例1制备的F-β-Ga2O3/CuGaO2复合材料的XRD图，从图中可以看到F-β-Ga2O3和CuGaO2对应的衍射峰。其中CuGaO2的衍射峰较尖锐，这说明制备的CuGaO2纳米片的结晶性越好、粒径大。
图2是实施例1制得的紫外光电探测器在紫外灯照射和暗态下的I-V曲线。其中紫外灯发出的紫外光波长为300nm，功率密度为0.3mW/cm2。从光照和暗态两种情况下的IV特性曲线相对比可以看出，表现出良好的整流特性。光电流较暗态下电流大，光照下器件展现出显著的光响应。在-4V-0V的反向偏压部分，光电流与暗态下电流的变化更加显著；而在正向偏压的变化不如反向偏压的显著。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。
Claims (8)
1.一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，包括以下步骤：
步骤一：将乙酸铜和硝酸镓先后加入去离子水中，室温下超声15-20min后向溶液中缓慢的滴入NaOH溶液，并在50-60℃的水浴中搅拌20-30min，然后向混合溶液中滴入乙二醇溶液并在同样温度下继续搅拌10-13min后静置1-2h，静置后将溶液置于反应釜内衬中在190-210℃下反应36-48h，自然冷却至室温后用稀硝酸将产物离心洗涤至洗涤液呈中性，随后再用无水乙醇和去离子水交替洗涤4次，然后将产物放在65-70℃的真空干燥箱中烘干得到CuGaO2纳米片；
步骤二：将CuGaO2纳米片和硝酸镓加入去离子水中，超声20-25min，然后在室温下缓慢滴入NaOH溶液将溶液的pH值调至9，随后向溶液中加入NaF溶液和α-烯烃磺酸钠溶液，并快速搅拌10-15min；搅拌后将混合溶液置于170-190℃的反应釜中保温24-30h,冷却至室温后将产物用去离子水洗涤3次，然后放入60-70℃的干燥箱中18-22h，干燥后将产物放入管式炉中，在氩气气氛下以950℃煅烧2-3h制得F-β-Ga2O3/CuGaO2材料；
步骤三：采用步骤二的制备方法，但在硝酸镓的水溶液中不加入CuGaO2纳米片，制得F-β-Ga2O3材料；
步骤四：将F-β-Ga2O3/CuGaO2和F-β-Ga2O3分别置于无水乙醇中并超声40-50min；将叉指电极用无水乙醇和去离子水交替洗涤5次后置于60-70℃的干燥箱中烘干，然后将F-β-Ga2O3的无水乙醇溶液滴在叉指电极上，干燥后得到均匀的薄膜，然后在薄膜上滴加F-β-Ga2O3/CuGaO2的无水乙醇溶液并用刮刀涂抹均匀，随后把样品置于50-55℃的真空干燥箱中烘干，烘干后通过热蒸发在薄膜一侧制备Au电极，最后得到F-β-Ga2O3/CuGaO2紫外光电探测器。
2.根据权利要求1所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，步骤一中乙酸铜的添加量为20-35mmol，乙二醇的添加量为15-20ml；步骤三中硝酸镓的添加量为40-50mmol。
3.根据权利要求1所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，所述步骤一中乙酸铜和硝酸镓的物质的量之比为1:0.8-1:1，乙酸铜和NaOH的物质的量之比为1:6-1:8；所述步骤二中硝酸镓和CuGaO2的质量比为0.76:1-1.12:1，NaF和硝酸镓的质量比为1:3.9-1:6.2，α-烯烃磺酸钠和CuGaO2的质量比为1:12-1:16；所述步骤三中各种物质的用量比和步骤二相同。
4.根据权利要求1所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，所述步骤一中乙酸铜水溶液的浓度为0.08g/ml；NaOH溶液的浓度均为2.5mol/L，滴加速度均为3ml/min。
5.根据权利要求1所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，所述步骤二中硝酸镓水溶液的浓度为0.1g/ml；NaOH溶液的浓度均为2.5mol/L，滴加速度均为3ml/min；NaF水溶液的浓度为0.06g/ml；α-烯烃磺酸钠水溶液的浓度为0.03g/ml。
6.根据权利要求1所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，所述步骤二中F-β-Ga2O3在CuGaO2纳米片上的负载量为28wt％-41wt％。
7.根据权利要求1所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法，其特征在于，F在β-Ga2O3的掺杂量为10wt％-16wt％。
8.根据权利要求1-7任一项所述的一种F-β-Ga2O3/CuGaO2紫外光电探测器的制备方法制得的探测器在紫外线探测中的应用。
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