CN104157721B - 基于石墨烯/硅/石墨烯的雪崩光电探测器及其制备方法 - Google Patents
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Abstract
本发明公开了一种基于石墨烯/硅/石墨烯的雪崩光电探测器及其制备方法,所述雪崩光电探测器包括n型硅衬底、二氧化硅隔离层、二氧化硅窗口、二氧化硅绝缘层、顶电极、石墨烯叉指电极薄膜和抗反射层。本发明以石墨烯作为透明叉指电极,与衬底硅形成MSM型结构光电探测器。该光电探测器可以进行宽光谱探测,解决了传统硅基PIN结对紫外光探测响应低的问题;抗反射层增强入射光的吸收,增强光生电流;在较大的反向偏压作用下,石墨烯叉指电极之间产生很强的电场,光生载流子与硅晶格易于产生碰撞离子化,获得很高的增益。本发明具有响应度高,响应速度快,内部增益大,开关比小,低功耗的特点。
Description
技术领域
本发明属于光电探测技术领域,涉及光电探测器件结构,尤其涉及一种基于石墨烯/硅/石墨烯的雪崩光电探测器及其制备方法。
背景技术
雪崩紫外光电探测器具有高灵敏度,高光学响应,响应速度快等优点,在高速调制和微弱信号监测方面有重要应用。对于硅基雪崩光电探测器达到雪崩条件需要高电压,功耗较大。因此,需要降低达到雪崩条件的电压。传统硅基PIN结型紫外探测器件需要热扩散或者离子注入工艺,而且对紫外光存在死层问题,响应随入射光波长的减小而迅速降低。因此,需要提高硅光探测器件对短波长可见光至紫外光的响应。
石墨烯是由单层sp2杂化碳原子构成的蜂窝状二维平面晶体薄膜,具有优异的力、热、光、电等性能。与普通金属不同,石墨烯是一种具有透明和柔性的新型二维导电材料。石墨烯和硅接触可以形成肖特基结,制备工艺简单,在光电探测领域有广泛应用。
与传统结型器件相比,金属/半导体/金属(MSM)结构对光生载流子的收集既可以沿着结的纵向上收集,还可以横向收集。该结构对在表面产生的光生载流子具有更强的收集作用;平面结构侧向电容小,RC时间常数小,可以缩短响应时间,提高信噪比;两个背靠背的肖特基结在施加偏压情况下,一个结处于正向偏置,另一个结处于反向偏置,可以获得较小的暗电流。
发明内容
本发明的目的在于针对现有技术的不足,提供一种基于石墨烯/硅/石墨烯的雪崩光电探测器及其制备方法。
本发明的目的是通过以下技术方案来实现的:一种基于石墨烯/硅/石墨烯的雪崩光电探测器,包括:n型硅衬底、二氧化硅隔离层、二氧化硅窗口、二氧化硅绝缘层、顶电极、石墨烯叉指电极薄膜和抗反射层;其中,所述n型硅衬底的上表面覆盖二氧化硅隔离层,在二氧化硅隔离层上开有二氧化硅窗口,使二氧化硅隔离层成凹形结构;在二氧化硅隔离层相对的两侧的上表面各覆盖一顶电极,两个顶电极不连通,且边界小于二氧化硅隔离层的边界;在二氧化硅窗口与n型硅衬底交界处覆盖二氧化硅绝缘层;在二氧化硅隔离层开口的内侧壁、顶电极和二氧化硅绝缘层的表面覆盖石墨烯叉指电极薄膜,石墨烯叉指电极薄膜的两翼分别放在两个顶电极上,顶电极上表面石墨烯叉指电极薄膜的覆盖范围小于顶电极的边界;在二氧化硅绝缘层和石墨烯叉指电极薄膜的表面覆盖抗反射层。
进一步地,所述的二氧化硅绝缘层厚度为1.5nm~2.5nm。
进一步地,所述的顶电极是金属薄膜电极,金属材料为铝、金或金铬合金。
进一步地,所述的抗反射层是透明薄膜,材料为二氧化硅、三氧化二铝或氧化钛。
制备上述基于石墨烯/硅/石墨烯的雪崩光电探测器的方法,包括以下步骤:
(1)在n型硅衬底的上表面氧化生长二氧化硅隔离层,所用n型硅衬底的电阻率为1~10Ω·cm;二氧化硅隔离层的厚度为100nm~500nm,生长温度为900~1200℃;
(2)在二氧化硅隔离层表面光刻出顶电极图形,然后采用电子束蒸发技术,首先生长厚度约为5nm的铬黏附层,然后生长50nm的金电极;
(3)在生长有顶电极的二氧化硅隔离层表面光刻出二氧化硅窗口图形,然后通过反应离子刻蚀技术,采用八氟环丁烷等离子体刻蚀二氧化硅隔离层并用缓冲氧化物刻蚀溶液去除残留的二氧化硅;其中,所述缓冲氧化物刻蚀溶液由NH4F、HF和水组成,NH4F:HF:H2O=60g:30ml:100ml;
(4)在二氧化硅窗口与n型硅衬底交界处采用快速热氧方法生长二氧化硅绝缘层;通入500sccm氮气和500sccm氧气,快速升温到900℃,反应30s;然后在500℃下退火10min;
(5)采用化学气相沉积方法在铜箔基底上制备石墨烯薄膜;
(6)在二氧化硅隔离层开口的内侧壁、顶电极和二氧化硅绝缘层的表面覆盖石墨烯薄膜;其中,石墨烯薄膜的转移方法为:将石墨烯薄膜表面均匀涂覆一层聚甲基丙烯酸甲酯薄膜,然后放入刻蚀溶液中4h腐蚀去除铜箔,留下由聚甲基丙烯酸甲酯支撑的石墨烯薄膜;将聚甲基丙烯酸甲酯支撑的石墨烯薄膜用去离子水清洗后转移到二氧化硅隔离层开口的内侧壁、顶电极和二氧化硅绝缘层的表面;最后用丙酮和异丙醇去除聚甲基丙烯酸甲酯;其中,所述刻蚀溶液由CuSO4、HCl和水组成,CuSO4:HCl:H2O=10g:50ml:50ml;
(7)对步骤(6)中转移后的石墨烯薄膜光刻出叉指电极图形,将光刻好的石墨烯薄膜放入反应离子刻蚀系统真空腔室,通入氧气对石墨烯薄膜进行刻蚀,获得石墨烯叉指电极薄膜;
(8)在二氧化硅绝缘层和石墨烯叉指电极薄膜的表面光刻出反射层图形,然后采用电子束蒸发技术生长30~200nm的三氧化二铝薄膜。
与现有技术相比,本发明具有以下有益效果:
一、入射光照射到本发明电探测器表面,被石墨烯和硅衬底吸收。反向偏压加到器件两端,产生的光生载流子(空穴电子对)在APD光电二极管表面和内部高电场作用下高速运动,在运动过程中通过碰撞电离效应,产生数量为初始电子空穴对的几十倍二次、三次新空穴电子对,从而形成很大的光信号电流,具有很高的增益。
二、石墨烯和硅形成肖特基浅结,产生的电子空穴对容易被电场分离,降低表面复合,消除死层。在紫外光区域,量子效率很高。
三、石墨烯作为透明电极,增强入射光吸收,提高光生电流,具有很高的光学响应。
四、叉指状的石墨烯电极之间可以形成很强的电场,更容易产生雪崩效应,降低能耗;相邻电极之间距离小,石墨烯的载流子迁移率很大,可以提高器件的时间响应。
四、二氧化硅钝化/绝缘层对多子形成很高的势垒,抑制硅衬底中的多子(电子)运动到石墨烯,大大降低暗电流,具有很高的开关比。
五、本发明提供的光电探测器所用材料以硅为基本材料,制备过程简单,成本低,易与现有半导体标准工艺兼容。
附图说明
图1为本发明基于石墨烯/硅/石墨烯的雪崩光电探测器的结构示意图;
图2为本发明基于石墨烯/硅/石墨烯的雪崩光电探测器的剖面结构示意图,其中剖开面经过其中一个石墨烯叉指电极;
图3为本发明中实施例所制备的MSM Si-APD光电探测器的石墨烯叉指电极光学显微镜图;
图中,n型硅衬底1、二氧化硅隔离层2、二氧化硅窗口3、二氧化硅绝缘层4、顶电极5、石墨烯叉指电极薄膜6、抗反射层7。
具体实施方式
本发明提供的基于石墨烯/硅/石墨烯的雪崩光电探测器的工作原理如下:
石墨烯与n型硅基底接触形成肖特基结,相邻石墨烯叉指电极与硅基底形成两个背靠背的肖特基结。两端电极加偏压后,一个肖特基结正向偏置,另一个肖特基结反向偏置。当入射光照射到石墨烯/硅界面,石墨烯和硅基底吸收入射光并产生电子-空穴对。在电场作用下,空穴流向正电极,电子流向负电极,形成光生电流。石墨烯和硅形成肖特基浅结,入射光产生的电子空穴很快被电场分离,减小表面复合,消除死层;叉指状的石墨烯电极之间可以形成很强的电场,更容易产生雪崩效应,降低能耗。
下面结合附图和实施例对本发明的具体实施方法作进一步的说明。
如图1和图2所示,基于石墨烯/硅/石墨烯的雪崩光电探测器,包括:n型硅衬底1、二氧化硅隔离层2、二氧化硅窗口3、二氧化硅绝缘层4、顶电极5、石墨烯叉指电极薄膜6和抗反射层7;其中,所述n型硅衬底1的上表面覆盖二氧化硅隔离层2,在二氧化硅隔离层2上开有二氧化硅窗口3,使二氧化硅隔离层2成凹形结构;在二氧化硅隔离层2相对的两侧的上表面各覆盖一顶电极5,两个顶电极5不连通,且边界小于二氧化硅隔离层2的边界;在二氧化硅窗口3与n型硅衬底1交界处覆盖二氧化硅绝缘层4;在二氧化硅隔离层2开口的内侧壁、顶电极5和二氧化硅绝缘层4的表面覆盖石墨烯叉指电极薄膜6,石墨烯叉指电极薄膜6的两翼分别放在两个顶电极5上,顶电极5上表面石墨烯叉指电极薄膜6的覆盖范围小于顶电极5的边界;在二氧化硅绝缘层4和石墨烯叉指电极薄膜6的表面覆盖抗反射层7。
所述的二氧化硅绝缘层4厚度为1.5nm~2.5nm。
所述的顶电极5是金属薄膜电极,金属材料为铝、金或金铬合金。
所述的抗反射层7是透明薄膜,材料为二氧化硅、三氧化二铝或氧化钛。
本实施例中制作基于石墨烯/硅/石墨烯的雪崩光电探测器的步骤具体如下:
(1)在n型硅衬底1的上表面氧化生长二氧化硅隔离层2,所用n型硅衬底1的电阻率为1~10Ω·cm;二氧化硅隔离层2的厚度为100nm~500nm,生长温度为900~1200℃;
(2)在二氧化硅隔离层2表面光刻出顶电极5图形,然后采用电子束蒸发技术,首先生长厚度约为5nm的铬黏附层,然后生长50nm的金电极;
(3)在生长有顶电极5的二氧化硅隔离层2表面光刻出二氧化硅窗口3图形,然后通过反应离子刻蚀技术,采用八氟环丁烷(C4F8)等离子体刻蚀二氧化硅隔离层2并用缓冲氧化物刻蚀(BOE)溶液去除残留的二氧化硅;其中,所述BOE溶液由氟化氨(NH4F)、氢氟酸(HF)和水组成,NH4F:HF:H2O=60g:30ml:100ml;
(4)在二氧化硅窗口3与n型硅衬底1交界处采用快速热氧方法生长二氧化硅绝缘层4;通入500sccm氮气和500sccm氧气,快速升温到900℃,反应30s;然后在500℃下退火10min;
(5)采用化学气相沉积方法(CVD)在铜箔基底上制备石墨烯薄膜;
(6)在二氧化硅隔离层2开口的内侧壁、顶电极5和二氧化硅绝缘层4的表面覆盖石墨烯薄膜;其中,石墨烯薄膜的转移方法为:将石墨烯薄膜表面均匀涂覆一层聚甲基丙烯酸甲酯(PMMA)薄膜,然后放入刻蚀溶液中4h腐蚀去除铜箔,留下由PMMA支撑的石墨烯薄膜;将PMMA支撑的石墨烯薄膜用去离子水清洗后转移到二氧化硅隔离层2开口的内侧壁、顶电极5和二氧化硅绝缘层4的表面;最后用丙酮和异丙醇去除PMMA;其中,所述刻蚀溶液由CuSO4、HCl和水组成,CuSO4:HCl:H2O=10g:50ml:50ml;
(7)对步骤(6)中转移后的石墨烯薄膜光刻出叉指电极图形,将光刻好的石墨烯薄膜放入反应离子刻蚀系统真空腔室,通入氧气(O2)对石墨烯薄膜进行刻蚀,获得石墨烯叉指电极薄膜6;
(8)在二氧化硅绝缘层4和石墨烯叉指电极薄膜6的表面光刻出反射层7图形,然后采用电子束蒸发技术生长30~200nm的三氧化二铝薄膜。
对上述石墨烯/硅/石墨烯的雪崩光电探测器加偏压,使其可以产生雪崩效应,实现增益。其中电压的正极和负极分别连接到两个顶电极5上,如图1所示。
图3为本发明中实施例所制备的石墨烯叉指电极光学显微镜图片。每根石墨烯叉指电极是连续的,相邻石墨烯叉指电极是断开的。通过本实施例可以获得较高质量的石墨烯叉指电极。
Claims (5)
1.基于石墨烯/硅/石墨烯的雪崩光电探测器,其特征在于,包括:n型硅衬底(1)、二氧化硅隔离层(2)、二氧化硅窗口(3)、二氧化硅绝缘层(4)、顶电极(5)、石墨烯叉指电极薄膜(6)和抗反射层(7);其中,所述n型硅衬底(1)的上表面覆盖二氧化硅隔离层(2),在二氧化硅隔离层(2)上开有二氧化硅窗口(3),使二氧化硅隔离层(2)成凹形结构;在二氧化硅隔离层(2)相对的两侧的上表面各覆盖一顶电极(5),两个顶电极(5)不连通,且边界小于二氧化硅隔离层(2)的边界;在二氧化硅窗口(3)与n型硅衬底(1)交界处覆盖二氧化硅绝缘层(4);在二氧化硅隔离层(2)开口的内侧壁、顶电极(5)和二氧化硅绝缘层(4)的表面覆盖石墨烯叉指电极薄膜(6),石墨烯叉指电极薄膜(6)的两翼分别放在两个顶电极(5)上,顶电极(5)上表面石墨烯叉指电极薄膜(6)的覆盖范围小于顶电极(5)的边界;在二氧化硅绝缘层(4)和石墨烯叉指电极薄膜(6)的表面覆盖抗反射层(7)。
2.根据权利要求1所述的基于石墨烯/硅/石墨烯的雪崩光电探测器,其特征在于,所述的二氧化硅绝缘层(4)厚度为1.5nm~2.5nm。
3.根据权利要求1所述的基于石墨烯/硅/石墨烯的雪崩光电探测器,其特征在于,所述的顶电极(5)是金属薄膜电极,金属材料为铝、金或金铬合金。
4.根据权利要求1所述的基于石墨烯/硅/石墨烯的雪崩光电探测器,其特征在于,所述的抗反射层(7)是透明薄膜,材料为二氧化硅、三氧化二铝或氧化钛。
5.制备如权利要求1所述的基于石墨烯/硅/石墨烯的雪崩光电探测器的方法,其特征在于,包括以下步骤:
(1)在n型硅衬底(1)的上表面氧化生长二氧化硅隔离层(2),所用n型硅衬底(1)的电阻率为1~10Ω·cm;二氧化硅隔离层(2)的厚度为100nm~500nm,生长温度为900~1200℃;
(2)在二氧化硅隔离层(2)表面光刻出顶电极(5)图形,然后采用电子束蒸发技术,首先生长厚度为5nm的铬黏附层,然后生长50nm的金电极;
(3)在生长有顶电极(5)的二氧化硅隔离层(2)表面光刻出二氧化硅窗口(3)图形,然后通过反应离子刻蚀技术,采用八氟环丁烷等离子体刻蚀二氧化硅隔离层(2)并用缓冲氧化物刻蚀溶液去除残留的二氧化硅;其中,所述缓冲氧化物刻蚀溶液由NH4F、HF和水组成,NH4F:HF:H2O=60g:30ml:100ml;
(4)在二氧化硅窗口(3)与n型硅衬底(1)交界处采用快速热氧方法生长二氧化硅绝缘层(4);通入500sccm氮气和500sccm氧气,快速升温到900℃,反应30s;然后在500℃下退火10min;
(5)采用化学气相沉积方法在铜箔基底上制备石墨烯薄膜;
(6)在二氧化硅隔离层(2)开口的内侧壁、顶电极(5)和二氧化硅绝缘层(4)的表面覆盖石墨烯薄膜;其中,石墨烯薄膜的转移方法为:将石墨烯薄膜表面均匀涂覆一层聚甲基丙烯酸甲酯薄膜,然后放入刻蚀溶液中4h腐蚀去除铜箔,留下由聚甲基丙烯酸甲酯支撑的石墨烯薄膜;将聚甲基丙烯酸甲酯支撑的石墨烯薄膜用去离子水清洗后转移到二氧化硅隔离层(2)开口的内侧壁、顶电极(5)和二氧化硅绝缘层(4)的表面;最后用丙酮和异丙醇去除聚甲基丙烯酸甲酯;其中,所述刻蚀溶液由CuSO4、HCl和水组成,CuSO4:HCl:H2O=10g:50ml:50ml;
(7)对步骤(6)中转移后的石墨烯薄膜光刻出叉指电极图形,将光刻好的石墨烯薄膜放入反应离子刻蚀系统真空腔室,通入氧气对石墨烯薄膜进行刻蚀,获得石墨烯叉指电极薄膜(6);
(8)在二氧化硅绝缘层(4)和石墨烯叉指电极薄膜(6)的表面光刻出反射层(7)图形,然后采用电子束蒸发技术生长30~200nm的三氧化二铝薄膜。
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