CN109378219B - 用于人工光合作用的氮化镓基器件及其制备方法 - Google Patents
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Abstract
本发明公开了一种用于人工光合作用的氮化镓基器件，自下而上有金属衬底(Cu、In、Sn、Ag、Au、Pb、Cd等)、n+‑GaN、InGaN层、其制备步骤如下：在n型重掺的GaN层上利用分子束外延技术生长InGaN层，再将获得的GaN基外延片用物理或者化学方法(如键合、倒装焊、导电胶等)与金属衬底上粘合在一起，使得GaN基电池中的电子可以顺利导入到金属基板上，获得用于人工光合作用的氮化镓器件。本发明的氮化镓器件具有吸收系数高、电子空穴分离效率高、电流均匀性好的优点，可作为光阳极材料用于人工光合作用中，对减少二氧化碳排放以及新能源的开发利用具有非常重要意义。
Description
技术领域
本发明涉及一种氮化镓基器件，尤其涉及一种用于人工光合作用的氮化镓基器件以及其制备方法。
背景技术
随着经济的迅速发展，煤炭、石油等不可再生资源大量燃烧，而消耗这些化石燃料的同时，也加重了环境的恶化，其中最重要的是温室效应，造成了全球气候变暖、海平面上升、病虫害增加等环境问题。
众所周知，植物和某些细菌可以将大气中的CO2固定，将CO2转化成有工业价值的有机物，并释放出氧气。早在20世纪90年代就有研究者提出了人工光合作用的概念。利用人工光合作用技术不仅能光解水，还可以将CO2还原为HCOOH、CH3OH、EtOH等。目前人工光合作用还原CO2的办法很多，有光还原、电还原、化学生物还原，以及将几种技术结合起来如生物化学还原、光电化学还原等，所应用的材料有无机和有机材料等，其中无机材料的应用更加广泛。
1972年，Fujishima和Honda等发现了本田藤岛效应：无机半导体TiO2单晶电极与Pt电极相连放入水中，在太阳光的照射下，水能分解成O2和H2。GaN及合金是直接带隙，光谱范围覆盖整个太阳光谱，合金GaN中掺杂InN可以对导带和价带位置进行调整，使得该材料同时满足CO2还原和H2O氧化条件，因此在光电还原CO2方面具有很大的研究潜力。
2011年Kazuhiro Ohkawa把GaN作为光阳极，铜片作为阴极，分别放在H型电解槽的两个槽室中反应，在光照条件下，光生电子由外电路传导阴极铜片上参与CO2还原，甲酸的法拉第效率可达2.59％。
2013年，Satoshi Yotsuhashi分别以蓝宝石和氮化镓为衬底，依次外延生长了高度掺杂GaN电传导层，AlGaN光吸收层作为光阳极，铟片作为阴极，分别放在H型电解槽的两个电解槽中进行反应，异质结使得光电转换效率提高，甲酸的能量转换效率为0.15％，几乎与自然界植物有相等的能量转换效率。
这些光阳极材料其响应的波长阈值最长为365nm，光谱范围利用太窄。且阳极表面上沉积的小面积欧姆接触使得器件上电子收集不均匀，电子由阳极传导致阴极效率不易提高。
发明内容
本发明的目的在于针对现有技术的不足，提供一种用于人工光合作用的氮化镓基器件及其制备方法，该器件可作为光阳极材料，异质结将光生电子与空穴有效分离，空穴在InGaN表面上发生氧化水的反应，电子迁移至金属基板上发生还原CO2的反应，实现高效人工光合作用。
本发明的用于人工光合作用的氮化镓基器件，依次包括金属衬底层、n+-GaN、InGaN层，n+-GaN/InGaN结构通过物理或者化学方法与金属衬底层粘合在一起，且接触电阻小于1x10-4Ωcm2。
上述技术方案中，优选的，所述的物理或化学方法包括键合、倒装焊、或采用导电胶。
优选的，所述的金属衬底层包括Cu、In、Sn、Ag、Au、Pb、Cd。
上述氮化镓基器件的制备方法，包括如下步骤：
在n型重掺GaN层上利用分子束外延技术生长InGaN层获得n+-GaN/InGaN结构，再通过键合、倒装焊、或采用导电胶将获得的n+-GaN/InGaN结构与金属衬底粘合在一起，使得n+-GaN与金属衬底层接触，且接触界面的接触电阻小于1x10-4Ωcm2，获得用于人工光合作用的氮化镓基器件。
本发明的氮化镓基器件采用独特的电池结构，具有吸收系数高、电子空穴分离效率高、电流均匀性好的优点。将该器件作为光阳极材料用于人工光合作用中，无需采用H型电解槽。氮化镓基器件产生的空穴在InGaN表面参与氧化水的反应，电子传到金属衬底上还原CO2。可实现将CO2转化为HCOOH、CH3OH、EtOH等有机物，对减少二氧化碳排放以及新能源的开发利用具有非常重要的意义。
附图说明
图1是本发明的氮化镓基器件的结构示意图。
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明。
参照图1，本发明的用于人工光合作用的氮化镓基器件，自下而上依次有金属衬底(可采用Cu、In、Sn、Ag、Au、Pb、或Cd等)、n+-GaN层、InGaN层。
其制备方法如下：
1)在洁净的n型重掺氮化镓层上采用分子束外延法生长InGaN外延层，获得n+-GaN/InGaN结构；
2)通过键合机将上述n+-GaN/InGaN结构键合在金属衬底上，或者采用倒装焊技术或采用导电胶将获得的n+-GaN/InGaN结构与金属衬底粘合在一起，使得n+-GaN与金属接触且接触界面的接触电阻小于1x10-4Ωcm2；获得器件。接触电阻过大不利于空穴和电子的传输，尤其不利于GaN基电池中的电子顺利导入到金属衬底上。
将上述氮化镓基器件作为光电极材料，电解质选用0.5M KHCO3，无需采用H型电解槽，可直接进行光合作用实验，该结构中空穴在InGaN表面参与氧化水的反应，电子传到金属衬底上还原CO2，可实现将CO2转化为HCOOH、CH3OH、EtOH。本发明的氮化镓器件具有吸收系数高、电子空穴分离效率高、电流均匀性好的优点，作为光阳极材料用于人工光合作用中，对减少二氧化碳排放以及新能源的开发利用具有非常重要意义。
Claims (3)
1.一种用于人工光合作用的氮化镓基器件，其特征在于，该器件依次包括金属衬底层、n+-GaN、InGaN层， n+-GaN/InGaN结构通过物理或者化学方法与金属衬底层粘合在一起，且接触电阻小于1x10-4Ωcm2；该氮化镓基器件作为光阳极材料用于人工光合作用，无需采用H型电解槽；所述的物理或化学方法为键合、倒装焊、或采用导电胶。
2.根据权利要求1所述的用于人工光合作用的氮化镓基器件，其特征在于，所述的金属衬底层为Cu、In、Sn、Ag、Au、Pb或Cd。
3.制备权利要求1所述的氮化镓基器件的方法，其特征在于，包括如下步骤：在n+-GaN层上利用分子束外延技术生长InGaN层获得n+-GaN/InGaN结构，再通过键合、倒装焊、或采用导电胶将获得的n+-GaN/InGaN结构与金属衬底粘合在一起，使得n+-GaN与金属衬底层接触，且接触界面的接触电阻小于1x10-4Ωcm2，获得用于人工光合作用的氮化镓基器件。
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