CN112951948B - 基于氧化镓能带调控的同质结光电探测器及其制备方法 - Google Patents
基于氧化镓能带调控的同质结光电探测器及其制备方法 Download PDFInfo
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Abstract
本发明提出了一种基于氧化镓能带调控的同质结光电探测器及其制备方法，同质结光电探测器包括绝缘的衬底，衬底(1)上依次设有无定形Ga2O3薄膜和β相Ga2O3薄膜，无定形Ga2O3薄膜和β相Ga2O3薄膜上均设有接触电极。本发明针对Ga2O3不能实现稳定p型掺杂限制同质结光电探测器制备的问题，提出了一种通过调控生长过程中氧气的量来改变氧化镓带隙，并利用两种不同带隙的氧化镓制备了同质结光电探测器，克服了制备同质结探测器时Ga2O3p型掺杂的难题，为Ga2O3的能带调控和高性能Ga2O3同质结光电探测器的制备和研究奠定基础。
Description
技术领域
本发明涉及光电器件制备领域，特别是指一种基于氧化镓能带调控的同质结光电探测器及其制备方法。
背景技术
氧化镓(Ga2O3)作为一种超宽带隙半导体，由于其具有高击穿场，高热稳定性和化学稳定性以及高巴利加优值等特性，因此在电力电子、日盲光电探测器和传感器等领域引起了广泛关注。此外，对在不同条件下制备的Ga2O3样品进行研究，发现其带隙在4.4-5.1eV之间变化，对应于日盲区域中234-280nm的波长，使其适合日盲光检测。已有文献报道了各种基于Ga2O3的电子和光电器件，然而，如何提高基于Ga2O3设备的性能是阻碍其未来应用最具挑战性的问题之一。带隙工程是制备高性能半导体器件的一种基本方法，且被广泛接受。但是，带隙工程涉及合金化或掺杂，合金化或者掺杂过程中通常会发生成成分波动和相分离，这对带隙工程的可重复性和可控性提出了巨大挑战。Ga2O3的带隙在某种程度上取决于合成技术和条件，这为合金化或掺杂之外的Ga2O3带隙工程提供了有效途径。同质结减少了制备过程中两种半导体材料的晶格失配问题，提高了薄膜的结晶质量，减少了材料的缺陷态。所以利用同质结制备的光电探测器通常具有较高的光响应，较快的响应速度和较高的灵敏度等。Ga2O3由于在生长过程中引入的氧空位是一种本征n型半导体材料，况且很难实现稳定的p型掺杂。这也是制备Ga2O3同质结光电探测器所面临的巨大挑战。如果可以通过调控氧化镓的带隙制备出不同导带性能的Ga2O3，利用他们的带隙和载流子浓度的差异可以制备同质结器件，这将为制备Ga2O3同质结光电探测器提供新的路径。
发明内容
本发明的目的在于针对Ga2O3不能实现稳定p型掺杂限制同质结光电探测器制备的问题，提出了一种通过调控生长过程中氧气的量来改变氧化镓带隙，并利用两种不同带隙的氧化镓制备了同质结光电探测器。
本发明的技术方案是这样实现的：基于氧化镓能带调控的同质结光电探测器，包括绝缘的衬底，衬底上依次设有无定形Ga2O3薄膜和β相Ga2O3薄膜，无定形Ga2O3薄膜和β相Ga2O3薄膜上均设有接触电极。利用不同带隙和不同导带性能的两种Ga2O3即可构建成同质结光电探测器。
进一步地，无定形Ga2O3薄膜氧空位为48％以上，电阻率为6×105Ω·m以下，厚度为100～200纳米。
进一步地，β相Ga2O3薄膜(3)氧空位为37％以下，电阻率为4×106Ω·m以上，厚度为30～60纳米。
进一步地，无定形Ga2O3薄膜氧空位为48～61％，电阻率为3×105～6×105Ω·m。
进一步地，β相Ga2O3薄膜(3)氧空位为18～37％，电阻率为4×106～4.5×107Ω·m。
进一步地，接触电极为钛金电极、铝银电极或者铝金电极。
进一步地，接触电极为钛金电极，钛金电极包括钛层和位于钛层上侧的金层，钛层和金层的厚度分别为20～30纳米和50～100纳米。
进一步地，无定形Ga2O3薄膜和β相Ga2O3薄膜上的接触电极的距离为0.5～1.5毫米。
进一步地，衬底为单面抛光的Al2O3衬底，衬底的厚度为300～400微米。
一种基于氧化镓能带调控的同质结光电探测器的制备方法，包括以下步骤：
(1)清洗衬底；
(2)采用等离子体增强化学气相沉积技术在衬底上沉积无定形Ga2O3薄膜；
(3)采用等离子体增强化学气相沉积技术在无定形Ga2O3薄膜上沉积β相Ga2O3薄膜；
(4)采用磁控溅射技术分别在无定形Ga2O3薄膜和β相Ga2O3薄膜上溅射接触电极；
(5)采用高温退火技术，让两个接触电极分别与无定形Ga2O3薄膜和β-Ga2O3薄膜形成欧姆接触。
进一步地，步骤(2)中，等离子体增强化学气相沉积所用的镓源为三乙基镓，生长所需的气体为氮气和氧气，气体流量分别为15和3～8sccm，生长温度为400～600℃，生长厚度为100～200纳米。
进一步地，步骤(3)中，等离子体增强化学气相沉积所用的镓源为三乙基镓，生长所需的气体为氮气和氧气，气体流量分别为15和20～10sccm，生长温度为400～600℃，生长厚度为30～60纳米。
优选的，步骤(5)中所用高温退火技术所需温度为300～400℃，时间为10～30分钟，通入的气体为氮气。
本发明的有益效果：
本发明通过改变生长过程中氧气的通入量来调控Ga2O3的结晶无序度，从而改变薄膜的电导率和带隙，无须复杂的掺杂和合金化过程，并利用两种不同带隙的Ga2O3制备了同质结光电探测器，克服了制备同质结探测器时Ga2O3 p型掺杂的难题，为Ga2O3的能带调控和高性能Ga2O3同质结光电探测器的制备和研究奠定基础。
本发明相对于无定形Ga2O3薄膜和β相Ga2O3薄膜同质结的配合，相比于ɑ-氧化镓和β-氧化镓或K-氧化镓和β-氧化镓等，可以实现零伏自驱动光电探测，无定形氧化镓带隙可调(4.1-5.1eV)，可以通过调节无定形氧化镓的带隙来调节探测范围。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明所述的调控氧化镓带隙范围示意图。
图2为本发明所述的调控氧化镓电阻率示意图。
图3为本发明所述的氧化镓同质结光电探测器的结构示意图。
图4为本发明所述的氧化镓同质结光电探测器的能带示意图。
图5为实施例1中无定形Ga2O3薄膜和β相Ga2O3薄膜的吸收光谱。
图6为实施例1中无定形Ga2O3薄膜和β相Ga2O3薄膜的X射线光电子能谱。
图7为实施例1中无定形Ga2O3薄膜和β相Ga2O3薄膜的X射线衍射能谱。
图8为实施例1中同质结光电探测器光电流和暗电流随电压变化曲线。
图9为实施例2中同质结光电探测器的光响应谱。
图10为实施例3中同质结光电探测器不同电压下的I-t曲线。
衬底1，无定形Ga2O3薄膜2，β相Ga2O3薄膜3，钛层4，金层5。
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付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。
使用等离子体增强化学气相沉积(PECVD)技术在蓝宝石衬底上生长Ga2O3膜。氧气(O2)和三乙基镓(TEGa)被用作生长的前体；氮气(N2)被用作载气将前驱物引入生长室。在沉积过程中，衬底温度保持在500℃，PECVD室中的压力设置为0.8Torr，N2流量保持在15sccm。通过将O2流量分别设置为20、15、10、8和5sccm，获得了一系列具有不同氧空位的Ga2O3膜，分别标记为样品1-5，图1为5个样品的吸收谱，插图为对应的带隙。5个样品的氧空位(Vo)分别为18％、26％、37％、48％和61％，图2为不同氧空位浓度的氧化镓电阻率的关系图，5个样品的电阻率如下表所示：
| 样品1 | 样品2 | 样品3 | 样品4 | 样品5 | |
| N<sub>2</sub>流量(sccm) | 15 | 15 | 15 | 15 | 15 |
| O<sub>2</sub>流量(sccm) | 20 | 15 | 10 | 8 | 5 |
| 氧空位V<sub>o</sub>(％) | 18 | 26 | 37 | 48 | 61 |
| 带隙(eV) | 5.1 | 4.9 | 4.7 | 4.5 | 4.4 |
| 电阻率(Ω·m) | 4.5×10<sup>7</sup> | 1.7×10<sup>7</sup> | 4×10<sup>6</sup> | 6×10<sup>5</sup> | 3×10<sup>5</sup> |
如图3所示，基于氧化镓能带调控的同质结光电探测器，包括绝缘的衬底1，衬底1的上端从下到上依次设有无定形Ga2O3薄膜2和β相Ga2O3薄膜3，无定形Ga2O3薄膜2和β相Ga2O3薄膜3的上端均设有接触电极，接触电极为钛金电极，钛金电极包括钛层4和位于钛层4上端的金层5。无定形Ga2O3薄膜氧空位为48％以上，电阻率为6×105Ω·m以下，厚度为100～200纳米。β相Ga2O3薄膜(3)氧空位为37％以下，电阻率为4×106Ω·m以上，厚度为30～60纳米。
所述衬底1为单抛的蓝宝石(Al2O3)衬底，衬底的厚度为300～400微米，优选为350微米左右。
所述钛金电极采用磁控溅射制备，钛层和金层的厚度分别为20～30纳米和50～100纳米。
所述基于氧化镓能带调控的同质结光电探测器的制备方法，包括以下步骤：
(1)清洗衬底；
(2)采用等离子体增强化学气相沉积技术在衬底上沉积无定形Ga2O3薄膜；
(3)在无定形Ga2O3薄膜上利用等离子体增强化学气相沉积技术在上面沉积β相Ga2O3薄膜；
(4)采用磁控溅射技术分别在两种Ga2O3薄膜上溅射钛金电极；
(5)采用高温退火技术，让两个电极分别与无定形Ga2O3和β-Ga2O3形成欧姆接触。
步骤(2)中等离子体增强化学气相沉积所用的镓源为三乙基镓，生长所需的气体为氮气和氧气，气体流量分别为15和3～8sccm，生长温度为400～600℃，生长厚度为100～200纳米。
步骤(3)中等离子体增强化学气相沉积所用的镓源为三乙基镓，生长所需的气体为氮气和氧气，气体流量分别为15和20～10sccm，生长温度为400～600℃，生长厚度为30～60纳米。
优选的，步骤(5)中所用高温退火技术所需温度为300～400℃，时间为10～30分钟，通入的气体为氮气。
本发明通过改变生长过程中氧气的通入量来调控Ga2O3的带隙和电导率，无须复杂的掺杂和合金化过程，并利用两种不同带隙的Ga2O3制备了同质结光电探测器，克服了制备同质结探测器时Ga2O3 p型掺杂的难题。
实施例1
步骤(2)和(3)，氧化镓制备过程中，通过通入氧气和氮气的量调控生长出来无定形Ga2O3薄膜和β相Ga2O3薄膜的带隙和导电性能，两种不同带隙的氧化镓薄膜接触后由于费米能级的不同，在界面出形成内建电场，能带图如4所示。
本实例中，步骤(2)中，无定形Ga2O3薄膜制备过程中氮氧流量分别为15和5sccm，生长温度为500℃，生长时间为1.5个小时，生长厚度为100纳米左右，步骤(3)中，β相Ga2O3薄膜制备过程中氮氧气体流量分别为15和15sccm，生长温度为500度，生长时间为1.0个小时，生长厚度为45纳米左右，无定形Ga2O3薄膜的带隙为4.4eV，β相Ga2O3薄膜的带隙为4.9eV，无定形Ga2O3薄膜和β相Ga2O3薄膜的吸收光谱如图3所示，强度随波长发生变化。由于生长过程中氧气量的不同，所制备的无定形Ga2O3薄膜和β相Ga2O3薄膜中氧空位的量也是不相同的，通过X射线光电子能谱技术分析可得，无定形Ga2O3薄膜和β相Ga2O3薄膜中的氧空位分别为61％和18％，如图4所示。通过测试X射线衍射分析可以看出，具有高氧空位的氧化镓为无定形相，具有少量氧空位的氧化镓为β相，如图5所示。
采用磁控溅射技术分别在无定形Ga2O3薄膜和β相Ga2O3薄膜上溅射钛金电极，然后放在高温管式炉中进行退火，退火温度和时间分别为400℃和10分钟。图6测试了本实例中同质结光电探测器的I-V曲线，从图中可以看出同质结光电探测器具有明显的整流特性，并且光电流远远大于暗电流，0下的开关比为8.9×102，且具有明显的开路电压和短路电流分别为0.6V和6nA，所以可以说明同质结已经完成，并且可以用于光电探测器的应用。
实施例2
本实例与实例1有所不同，改变了生长两次氧化镓过程中氮气和氧气的比例，本实例中生长无定形Ga2O3薄膜和β相Ga2O3薄膜过程中氮氧气体流量分别为15、3sccm和15、20sccm，带隙分别为4.1和5.1eV，按照上述器件制备过程制备出如图1所示的同质结光电探测器，制备完后把器件放在高温管式炉中进行退火，退火温度和时间分别为400℃和10分钟。通过对其进行零伏偏压下的光谱响应测试，响应曲线如图7所示。从图7中可以看出，在深紫外区域内的响应谱明显大于可见光区域，这说明在这个实例中此光电探测器也具有光伏效应，可以通过生长不同氧空位的氧化镓制备同质结光电探测器。
实施例3
本实例与实例1或2基本相同，不同之处在于：改变了电极的材料，把钛金电极换为铝银或者铝金电极，根据上述制备器件过程，在制备完电极后对器件进行高温退火，退火温度为300度，退火时间为5分钟，也可以得到氧化镓同质结光电探测器，通过测试器件的电流随时间的变化曲线，如图8所示，可以看出器件的光电流明显大于暗电流，且可以在三个测试电压下稳定运行，并且随着电压的增加，光电流也随着增加。这说明改变电极的材料也可以制备出氧化镓同质结光电探测器。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (4)
1.一种基于氧化镓能带调控的同质结光电探测器的制备方法，其特征在于，包括以下步骤：
（1）清洗衬底；
（2）采用等离子体增强化学气相沉积技术在衬底上沉积无定形Ga2O3薄膜；
（3）采用等离子体增强化学气相沉积技术在无定形Ga2O3薄膜上沉积β相Ga2O3薄膜；
（4）采用磁控溅射技术分别在无定形Ga2O3薄膜和β相Ga2O3薄膜上溅射接触电极；
（5）采用高温退火技术，让两个接触电极分别与无定形Ga2O3薄膜和β-Ga2O3薄膜形成欧姆接触；
步骤（2）中，等离子体增强化学气相沉积所用的镓源为三乙基镓，生长所需的气体为氮气和氧气，气体流量分别为15和3~8 sccm；无定形Ga2O3薄膜氧空位为48%以上；
步骤（3）中，等离子体增强化学气相沉积所用的镓源为三乙基镓，生长所需的气体为氮气和氧气，气体流量分别为15和20~10 sccm；β相Ga2O3薄膜（3）氧空位为37%以下。
2.根据权利要求1所述的制备方法，其特征在于，步骤（2）中，生长温度为400~600℃，生长厚度为100~200纳米。
3.根据权利要求1所述的制备方法，其特征在于，步骤（3）中，生长温度为400~600℃，生长厚度为30~60纳米。
4.根据权利要求1所述的制备方法，其特征在于，步骤（5）中所用高温退火技术所需温度为300~400℃，时间为10~30分钟，通入的气体为氮气。
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