CN108878553B - 一种纤维状可穿戴紫外光电探测器及其制备方法 - Google Patents
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Abstract
本发明属于半导体光电器件技术领域,具体为一种纤维状可穿戴紫外光电探测器及其制备方法。该紫外探测器包括:纤维状碳纳米管电极,钛线电极,n型TiO2,p型CnZnS。其中p型CuZnS透明导电薄膜材料均匀保形覆盖于n型TiO2纳米管阵列上,碳纳米管电极螺旋状缠绕于p型材料之上,形成纤维状器件结构。本发明形成p‑CuZnS/n‑TiO2型紫外光探测器,有效促进光生载流子的分离,并提高响应速度,降低暗电流;p型材料沿纳米管结构均匀生长于n型材料表面,在保持紫外光透过率的同时增大p‑n结接触面积;碳纳米管和钛线作为p‑n结电极所形成的纤维状器件结构,最终实现光生载流子的有效收集和可穿戴的紫外探测应用。
Description
技术领域
本发明属于半导体光电探测器件技术领域,具体涉及一种纤维状可穿戴紫外光电探测器及其制备方法。
背景技术
受太阳光中紫外光过多的照射是皮肤癌的主要形成因素之一。目前,使用可穿戴式紫外光探测器对紫外光进行实时监测,是预防此种原因造成的皮肤癌的非常有效的手段。紫外光探测器有肖特基结、p-n结、p-i-n结等多种结构,是半导体光电器件的重要应用之一,其中p-n结型光电探测器可以有效抑制光生载流子的复合,降低暗电流,提高光响应速度及响应度、探测度等。为适应实际生活中对便携式可穿戴电子器件的需要,对紫外光探测器应提出良好的光谱选择性、适应各种人体活动的可弯折性、可与电源及数据采集系统集成以实现实时监测、可实现自驱动等要求,并要具有便携、质轻等特点。这可以从材料的选择和器件结构的设计等方面实现。TiO2是一种应用广泛的n型半导体材料,CuZnS是一种导电性良好的p型材料,利用p-n结的光电效应可以有效探测紫外光。阳极氧化法合成的TiO2可以生长于不同形状的Ti金属表面,化学浴法合成的CuZnS可保形覆盖于衬底表面增大接触面积,这些为纤维状器件的实现奠定了基础。
发明内容
本发明的目的在于提供一种响应速度快、暗电流低的纤维状可穿戴紫外光电探测器及其制备方法。
本发明提供的纤维状可穿戴紫外光电探测器,其结构参见图1所示;包括:
纤维状钛线电极;
在纤维状钛线电极外部包覆的n型TiO2纳米管阵列层;
在n型TiO2层表面的p型CuZnS透明导电薄膜层;
以螺旋状缠绕于p型层和n型层上的纤维状碳纳米管电极。
本发明中,探测器电极为纤维状碳纳米管和钛线。
本发明中,由n型TiO2纳米管阵列和p型CuZnS透明导电薄膜组成p-n结型探测器。
本发明中,所述n型TiO2纳米管阵列通过阳极氧化生长于钛线电极表面,p型CuZnS透明导电薄膜均匀保形覆盖生长于n型TiO2纳米管阵列层表面,纤维状碳纳米管电极以螺旋状缠绕于p-n结外部,形成纤维状器件。
本发明中,p型CuZnS与n型TiO2纳米管阵列层紧密接触,紫外光探测通过形成的p-n结光二极管实现。光生载流子的收集通过内部钛线电极和外部螺旋状碳纳米管电极实现。
进一步地,所述的n型TiO2层通过阳极氧化法形成纳米管阵列。
进一步地,所述的p型CuZnS层通过化学浴沉积的方式在n型TiO2层保形覆盖形成p-n结,促进紫外光生载流子的分离。
进一步地,所述的碳纳米管纤维电极螺旋状地缠绕在p-n结的表面,有效地收集光生载流子。
所述的紫外光电探测器具有以下三个优势:1,形成p-CuZnS/n-TiO2型紫外光探测器,有效促进光生载流子的分离,并提高响应速度,降低暗电流;2,p型材料沿纳米管结构均匀生长于n型材料表面,在保持紫外光透过率的同时增大p-n结接触面积;3,碳纳米管和钛线作为p-n结电极所形成的纤维状器件结构,最终实现了光生载流子的有效收集和可穿戴的紫外探测应用。
上述纤维状可穿戴紫外光电探测器的制备方法,包括如下步骤:
(1)TiO2纳米管阵列的制备:将钛线依次在丙酮、乙醇和去离子水中进行超声清洗,氮气吹干;电解液成分为包含0.2-0.5 wt% NH4F和1-10 vol% H2O的乙二醇溶液;将钛线置于电解液中,并作为阳极,铂丝作为阴极,在30-70 V直流电压下阳极氧化10-120 min;之后在450-500℃空气中退火1-2 h;
(2) p-n结的制备:采用化学浴法,预先准备3种溶液:(1)0.001-0.01 M CuSO4和0.001-0.01 M Zn(CH3COO)2混合液(20-80 mL),(2)0.001-0.01 M Na2EDTA (20-30 mL),(3)0.1-0.2 M C2H5NS (20-30mL);将阳极氧化后的钛线清洗并干燥;首先将溶液(1)和溶液(2)混合均匀,再将溶液(3)加入混合液中,反应立即开始,迅速将准备好的钛线置于溶液中,在50-70℃下反应0.5-2h;取出用去离子水冲净并在100-300℃下热处理5-15 min;
(3)碳纳米管纤维的制备:用化学气相沉积纺丝法,以二茂铁为催化剂,将乙醇/丙酮碳源和噻吩启动子在1200-1300℃氢气气氛下进行合成;
(4)探测器的组装:将碳纳米管纤维螺旋状缠绕于生长有p-n结的钛线上作为外部电极,钛线作为内部电极。
附图说明
图1:本发明的纤维状可穿戴紫外光探测器的结构示意图。
图2:CuZnS/TiO2纳米管p-n结的结构示意图。
图3:本发明的纤维状可穿戴紫外光探测器的扫描电镜(SEM)图。
图4:本发明的纤维状可穿戴紫外光探测器的光电测试结果:在暗态和350nm紫外光照下的电流-电压曲线。
图中标号:1为钛线电极,2为钛线表面的n型TiO2纳米管阵列层,3为n型TiO2层表面的p型CuZnS层,4为p-n结表面的碳纳米管纤维电极。
具体实施方式
实施例1,一种如图1所示的纤维状可穿戴紫外光电探测器,包括钛线电极1、钛线表面的n型TiO2层2、n型TiO2层表面的p型CuZnS层3、p-n结表面的碳纳米管纤维电极4。
本实施例采用阳极氧化和化学浴的方法生长,具体的制备方法如下:
(1)TiO2纳米管阵列的制备:钛线依次在丙酮、乙醇和去离子水中超声清洗,氮气吹干。电解液成分为包含0.27 wt% NH4F和5 vol% H2O的乙二醇溶液。将钛线置于电解液中,并作为阳极,铂丝作为阴极,在60V直流电压下阳极氧化30 min。之后在450℃空气中退火2h;
(2) p-n结的制备:采用化学浴法。预先准备3种溶液:(1)0.005 M CuSO4和0.06 MZn(CH3COO)2混合液(50 mL),(2)0.05 M Na2EDTA (25 mL),(3) 0.16 M C2H5NS (25 mL)。将阳极氧化后的钛线清洗并干燥。首先将溶液(1)和溶液(2)混合均匀,再将溶液(3)加入混合液中,反应立即开始,迅速将准备好的钛线置于溶液中,在80℃下反应1h。取出用去离子水冲净并在200℃下热处理10 min;
(3)碳纳米管纤维的制备:用化学气相沉积纺丝法,二茂铁催化剂、乙醇/丙酮碳源和噻吩启动子在1250℃氢气气氛合成;
(4)探测器的组装:将碳纳米管纤维螺旋状缠绕于生长有p-n结的钛线上作为外部电极,钛线作为内部电极。
实施例2,p-CuZnS/n-TiO2结采用阳极氧化和化学浴的方法生长,具体的制备方法如下:
(1)TiO2纳米管阵列的制备:钛线依次在丙酮、乙醇和去离子水中超声清洗,氮气吹干。电解液成分为包含0.5 wt% NH4F和8 vol% H2O的乙二醇溶液。将钛线置于电解液中,并作为阳极,铂丝作为阴极,在40V直流电压下阳极氧化30 min。之后在500℃空气中退火1h;
(2) p-n结的制备:采用化学浴法。预先准备3种溶液:(1)0.01 M CuSO4和0.05 MZn(CH3COO)2混合液(50 mL),(2)0.05 M Na2EDTA (25 mL),(3)0.16 M C2H5NS (25 mL)。将阳极氧化后的钛线清洗并干燥。首先将溶液(1)和溶液(2)混合均匀,再将溶液(3)加入混合液中,反应立即开始,迅速将准备好的钛线置于溶液中,在80℃下反应1h。取出用去离子水冲净并在200℃下热处理10 min;
(3)碳纳米管纤维的制备:用化学气相沉积纺丝法,二茂铁催化剂、乙醇/丙酮碳源和噻吩启动子在1200℃氢气气氛合成;
(4)探测器的组装:将碳纳米管纤维螺旋状缠绕于生长有p-n结的钛线上作为外部电极,钛线作为内部电极。
Claims (4)
1.一种纤维状可穿戴紫外光探测器,其特征在于,包括:
纤维状钛线电极;
在纤维状钛线电极外部包覆的n型TiO2纳米管阵列层;
在n型TiO2层表面的p型CuZnS透明导电薄膜层;
以螺旋状缠绕于p型层和n型层上的纤维状碳纳米管电极;
其中,由n型TiO2纳米管阵列和p型CuZnS透明导电薄膜组成p-n结型探测器。
2.根据权利要求1所述的纤维状可穿戴紫外光探测器,其特征在于,所述n型TiO2纳米管阵列通过阳极氧化生长于钛线电极表面;p型CuZnS透明导电薄膜均匀保形覆盖生长于n型TiO2纳米管阵列层表面,纤维状碳纳米管电极以螺旋状缠绕于p-n结外部,形成纤维状器件。
3.根据权利要求1所述的纤维状可穿戴紫外光探测器,其特征在于,p型CuZnS透明导电薄膜层与n型TiO2纳米管阵列层紧密接触,紫外光探测通过形成的p-n结光二极管实现;光生载流子的收集通过内部钛线电极和外部螺旋状碳纳米管电极实现。
4.根据权利要求1-3之一所述的纤维状可穿戴紫外光探测器的制备方法,其特征在于,步骤如下:
(1)TiO2纳米管阵列的制备:将钛线依次在丙酮、乙醇和去离子水中进行超声清洗,氮气吹干;电解液成分为包含0.2-0.5 wt% NH4F和1-10 vol% H2O的乙二醇溶液;将钛线置于电解液中,并作为阳极,铂丝作为阴极,在30-70 V直流电压下阳极氧化10-120 min;之后在450-500℃空气中退火1-2 h;
(2)p-n结的制备:采用化学浴法,预先准备3种溶液:(1)20-80 mL的0.001-0.01 MCuSO4和0.001-0.01 M Zn(CH3COO)2混合液,(2)20-30 mL 的0.001-0.01 M Na2EDTA,(3)20-30mL 的0.1-0.2 M C2H5NS;将阳极氧化后的钛线清洗并干燥;首先将溶液(1)和溶液(2)混合均匀,再将溶液(3)加入混合液中,反应立即开始,迅速将准备好的钛线置于溶液中,在50-70℃下反应0.5-2h;取出用去离子水冲净并在100-300℃下热处理5-15 min;
(3)碳纳米管纤维的制备:用化学气相沉积纺丝法,以二茂铁为催化剂,将乙醇/丙酮碳源和噻吩启动子在1200-1300℃氢气气氛下进行合成;
(4)探测器的组装:将碳纳米管纤维螺旋状缠绕于生长有p-n结的钛线上作为外部电极,钛线作为内部电极。
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