CN106409975B - 一种可定制的高增益ZnO纳米线阵列紫外探测器及其制备方法 - Google Patents
一种可定制的高增益ZnO纳米线阵列紫外探测器及其制备方法 Download PDFInfo
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Abstract
一种可定制的高增益ZnO纳米线阵列紫外探测器及其制备方法,涉及微电子工艺技术、纳米技术与紫外探测领域。本发明中,基于协同学理论,在涨落不稳定时,纳米线之间会彼此争夺反应溶质,在这种竞争机制下,种子层越薄,所需的溶质资源越少,生长时间由生长速率决定。基于此生长原理,本发明中,通过调整种子层厚度和溶液浓度、生长时间得到质量较高的纳米线,从而得到不同增益的紫外探测器件。本发明简单有效,定制不同增益的器件可适用于多种环境下的紫外光检测。
Description
技术领域
本发明涉及纳米技术与紫外探测技术领域,具体地说是利用ZnO对紫外响应的优良特性,将传统的微电子工艺技术与纳米线融合起来从而实现对紫外光的探测,利用器件结构的变化,实现较宽的探测范围,满足特定增益的探测器件的制备要求。
背景技术
随着环境污染日益严重,全球国际性的环境保护行动越来越频繁,其中,臭氧层是地球和人类的保护伞,能够过滤掉太阳光中99%的紫外光。由于人类广泛使用消耗臭氧层物质,使其遭到严重破坏,过量的紫外线会使人和动物免疫力下降,导致皮肤癌的发病率增高,动物和人眼睛失明;侵害生命安全,甚至破坏生态系统;引起气候变化等。早在1989年,国际社会通过了保护臭氧层的国际环保公约。臭氧层的破坏使人们对紫外探测表现出急迫的需求,与此同时,紫外传感技术引起了广泛关注,除了在空间和环境监测上的应用,紫外探测技术在在火焰传感和火灾预警、紫外通信,甚至包括医学的细胞癌变分析等许多领域都有着极其广泛的应用。近年来,纳米技术兴起,人们注意到纳米线大的长径比可显著提高探测器的灵敏度,不仅如此,纳米结构可以制备在柔性衬底上。其中,ZnO材料制备的纳米线具有良好的生物兼容性,容易应用于智能化的可穿戴设备,材料本身容易合成,器件制备成本低,适用于大量埋布在物联网中的多探测节点,实现对周围环境紫外强度的实时监测预警。其中,ZnO纳米线阵列以提高光响应信号的强度,和制备简单等优点,受到越来越多人的青睐。
从目前报道的研究成果看,大部分研究者都在追求更高的灵敏度和更快的响应速度,而忽略了器件在制备过程中的可靠性和稳定性。例如,比较常见的纵向纳米线阵列结构的紫外探测器件,用高温气相沉积或水热法在衬底上垂直向上生长。如果是上下电极,那么上电极的制备存在需要绝缘物质的填充和支撑的问题;如果是表面平行电极,可能会存在电流流经种子层过程中电子的散射问题。由于垂直结构的感光面积小,电极制备等的问题,横向平铺于两电极之间的纳米线阵列成为最适于紫外探测器应用的器件结构。横向结构的制备包括介电泳、纳米压印、直接侧向生长,其中,前两种方法由于需要人工的手法将纳米线挑出来排布在电极两端,容易损坏纳米线表面特性且无法保证纳米线与电极的牢固接触,导致器件性能降低。直接侧向生长纳米线直接通过自组织形成,且能够与电极牢固接触。因此直接在电极两端生长成为实现横向纳米线阵列的首选方法。
紫外探测要实用化,必须满足不同工作环境下的探测需求,这就要求器件有不同的增益范围。就目前横向结构的研究情况,由于固定的器件结构和制备方法,同一种器件的增益是相对稳定的,若想得到不同的增益,需要对电极做出改变,如增大电极的面积,这无异于新的工艺流程,周期长,成本高,影响器件的整体面积。水热法制备纳米线的方法在实现纳米线的桥接的基础上,且不改变电极的情况下,通过改变种子层的厚度及生长条件,如:生长溶液浓度和生长时间,来达到不同程度的纳米线分布的效果,从而实现不同的增益。通过不同厚度种子层与生长浓度和时间的匹配可以得到不同增益的紫外探测器件,满足不同环境下的紫外探测需求。如用于集成电路中,在探测要求不高的情况下,则可选择增益较低的,减少功耗;如运用到日常民用探测,低的紫外线密度则要求较高灵敏度的探测器。
在保证电极面积不变的前提下,同时实现不同灵敏度的紫外探测器,本发明公开了一种可定制的高增益ZnO纳米线阵列紫外探测器及其制备方法。基于生长过程中的资源竞争,调节生长浓度,种子层等条件可得到不同程度的横向纳米线阵列,调节有效参加工作的纳米线的数量及粗细,进而可以得到特定增益的紫外探测器件。
发明内容
本发明的目的在于,通过一种可定制的高增益ZnO纳米线阵列紫外探测器的制备方法,解决不同量级的光增益器件的实现,及纳米线生长方向方面的问题,突破技术瓶颈,实现制备出可定制的纳米探测器件。
本发明是通过以下工艺技术方法实现的:
一种制备可定制的高增益ZnO纳米线阵列紫外探测器的方法,其特征在于,包括以下步骤:
1.1.首先制备绝缘衬底,采用PECVD方法在硅衬底上生长二氧化硅绝缘层(如300纳米厚度的二氧化硅绝缘层);
1.2.用光刻的方法对步骤1.1.中所述的衬底进行图案化处理,具体的使用光刻胶AZ5214做反转图形,使得光刻胶AZ5214的图形的侧面具有梯形结构,光刻胶AZ5214与二氧化硅绝缘层接触的底面面积小于上部非接触的截面面积,光刻胶AZ5214图形的侧面具有坡度;
1.3.在步骤1.2.中得到二氧化硅绝缘层上通过磁控溅射的方法依次生长氧化锌种子层和Ti层、Au层金属电极(如100nm厚的氧化锌种子层);
1.4.剥离步骤1.3.的光刻胶,最终形成氧化锌种子层和金属电极的坡度或台阶衬底;
1.5.将等摩尔比例的六水合硝酸锌(Zn(NO3)2·6H2O)和六次甲基四胺(HMTA)溶于去离子水中,搅拌均匀,配制成0.1mmol/L-2.5mmol/L的硝酸锌溶液作为前体溶液;
1.6.步骤1.5所得前体溶液放入水热反应釜中,再将步骤1.4.中衬底Ti层、Au层电极面朝下浮于前体溶液表面,在80℃下反应生长ZnO纳米线,生长时间随种子层厚度和前体溶液浓度不同,纳米线生长速度不同,根据生长速度调节生长时间(如,100纳米种子层,1mmol/L的前体溶液浓度生长时间为16h);
1.7.将生长有ZnO纳米线的衬底取出,用去离子水反复冲洗,氮气吹干,此时,ZnO纳米线就以桥接的方式连接两个电极,就制备完成了ZnO纳米线阵列紫外探测器件的主要部分。
1.8.通过扫描电子显微镜观察纳米线的形貌和通过电学测试得到I-V特性,假设目标增益为G1以上,若当前实际增益GCN未达到G1,则返回步骤1.5.调整前体溶液的浓度和生长时间;
调整硝酸锌溶液的浓度使得与氧化锌种子层厚度相匹配,使得器件增益达到G1以上(此处G1是目标增益值,根据不同需求,取值可变,也可以是一个区间,如G2<GCN<G3)。
进一步优选,经过步骤1.8.后器件增益若能达到G1以上,说明当前浓度与种子层厚度较为匹配;若特性变差(增益为G1以下),则返回步骤1.3.调节种子层厚度,直到找到较为匹配值。
本发明制备的电极,见图1,进一步优选,两边电极完全对称,生长纳米线的两电极间相距5μm,竖条电极的宽度为150μm,长度为200μm;与竖条电极相连的横条电极,即纳米线生长处的电极宽度可改变,范围为25~100微米,纳米线的数量变化,可调控器件端口电学参数,在-1V~1V测试电压下,电流不同。
水热法生长纳米线过程存在溶质资源是否充分的问题,浓度高,即溶质资源充足时,纳米线的直径较大,降低浓度使纳米线变细,有利于提高器件特性。最终,浓度的改变起到调控器件的端口电学参数的作用。
与现有的制备氧化锌纳米线的技术相比,本发明具有如下优点:
本发明提供了一种可定制的高增益ZnO纳米线阵列紫外探测器的工艺方法,满足了特定增益器件的制备要求,解决了纳米线生长方向可控性问题。结合晶体生长原理,实现纳米线的方向可控,并且纳米线阵列的均匀性较高。当受到紫外光照射时,纳米线的电导发生变化,即光电导效应,实验上通过检测纳米线光电流来判定紫外光的强度,且获得103~106范围内的开关比。本发明简单有效,适用于军用及民用紫外光的检测。
附图说明
图1本发明的两种不同桥接宽度平面图;
图2本发明的剖面图;
图3本发明器件的制备流程;(a)-(d)为顺序步骤;
图4本发明增益的可定制方案流程图;
图5纳米线生长过程中资源竞争示意图;
图6不同放大比例的器件平面和截面SEM图;
图7器件I-V特性图。
图中:1-硅衬底 2-SiO2绝缘层 3-ZnO种子层 4-金属电极层 5-ZnO纳米线 6-紫外光源。
具体实施方式
为使本发明的目的、优点更加清楚明白,下面结合附图和具体实施方式对本发明做进一步的说明,但本发明并不限于以下实施例。
实施例1
本发明为一种可定制的高增益ZnO纳米线阵列紫外探测器件,具体地说是一种通过检测ZnO纳米线电导率的改变而检测紫外光的方法。
本发明公开的一种定制的高增益的ZnO纳米线阵列紫外探测器件的具体结构如下:
Si衬底表面有两部分完全对称的电极,每部分电极由一个200微米*100微米的矩形和一个150微米*200微米矩形连接组成,两电极间距为5微米。所有图形的组成部分是:100nmZnO种子层和115nmTi/Au电极。
所述的紫外探测器件,选择Si衬底作为本发明的衬底,为了保证各器件之间不存在相互影响,选择生长300nm的SiO2绝缘层。将台阶的侧面和表面制作电极后,再侧向生长ZnO纳米线。其具体制备方法如下:
(1)首先,将上述Si基衬底前烘之后,旋涂AZ-5214光刻胶,胶厚为1.5微米,经过后烘、曝光、反转烘、泛曝、显影、坚膜后将图形刻在衬表面,呈倒梯形(倒梯形下角范围在70°~80°之间),如附图3(a)所示。
(2)在(1)中图案化的衬底上依次溅射100nm厚ZnO种子层、15nm厚Ti、100nm厚Au,如附图3(b)所示。
(3)将(2)中溅射有种子层和电极的Si衬底中的AZ-5214进行剥离,该过程将衬底浸入剥离液或丙酮中,经过超声处理将光刻胶AZ-5214去掉,剥离好的Si衬底经过丙酮、乙醇、去离子水清洗干净,氮气吹干,剥离之后的衬底表面如附图3(c)所示。
(4)将等摩尔比例的六水合硝酸锌(Zn(NO3)2·6H2O)和六次甲基四胺(HMTA)溶于去离子水中,搅拌均匀,配制成1mmol/L的硝酸锌溶液作为前体溶液。
(5)取15mL前体溶液放入水热反应釜中,再将(3)中图案化Si衬底倒置浮于溶液表面,在80℃下反应生长ZnO纳米线,持续8h。
(6)将(5)中衬底取出,用去离子水反复冲洗干净后,放入新的溶液中。溶液浓度保持不变,生长时间持续8小时,实现纳米线桥接连接,器件制备完成,如附图3(d)所示。器件增益达到106以上。
实施例2
同实施例1相同的电极图案结构,Si衬底表面有两部分完全对称的电极,每部分电极由一个200微米*100微米的矩形和一个150微米*200微米矩形连接组成,两电极间距为5微米。所有图形的组成部分是:50nmZnO种子层和115nmTi/Au电极。
所述的紫外探测器件,选择Si衬底作为本发明的衬底,为了保证各器件之间不存在相互影响,选择生长300nm的SiO2绝缘层。将台阶的侧面和表面制作电极后,再侧向生长ZnO纳米线。其具体制备方法如下:
(1)首先,将上述Si基衬底前烘之后,旋涂AZ-5214光刻胶,胶厚为1.5微米,经过后烘、曝光、反转烘、泛曝、显影、坚膜后将图形刻在衬表面,呈倒梯形(倒梯形下角范围在70°~80°之间),如附图3(a)所示。
(2)在(1)中图案化的衬底上依次溅射50nm厚ZnO种子层、15nm厚Ti、100nm厚Au,如附图3(b)所示。
(3)将(2)中溅射有种子层和电极的Si衬底中的AZ-5214进行剥离,该过程将衬底浸入剥离液或丙酮中,经过超声处理将光刻胶AZ-5214去掉,剥离好的Si衬底经过丙酮、乙醇、去离子水清洗干净,氮气吹干,剥离之后的衬底表面如附图3(c)所示。
(4)将等摩尔比例的六水合硝酸锌(Zn(NO3)2·6H2O)和六次甲基四胺(HMTA)溶于去离子水中,搅拌均匀,配制成0.25mmol/L的硝酸锌溶液作为前体溶液。
(5)取15mL前体溶液放入水热反应釜中,再将(3)中图案化Si衬底倒置浮于溶液表面,在80℃下反应生长ZnO纳米线,持续8h,实现纳米线桥接连接,器件制备完成,如附图3(d)所示。器件增益达到106以上。
参见附图4本发明增益的可定制方案流程图。
本发明增益的可定制方案流程如下:
设定目标增益为G1,种子层厚度A为100纳米,前体液浓度B为2.5mmol/L,生长时间C为16h,按照设定参数制备种子层厚度和水热法生长条件制备器件,得到器件的I-V特性;若得到的增益在G1以下,则重新调整B、C的取值,种子层的厚度与生长的前体溶液浓度有直接关系,当种子层的厚度较厚时,生长纳米线所需的溶液浓度较高;当种子层较薄时,生长纳米线所需的溶液浓度较低。以本发明的器件结构为例,100nm的ZnO种子层对应1mmol/L的溶液浓度匹配度较好,50nm的ZnO种子层对应0.25mmol/L则匹配较好,因此,需要找到ZnO种子层和溶液浓度、生长时间的较优匹配值,在这个条件下的器件特性较优。经过这个循环过程,直到达到设定的目标增益。依据此流程图,可以得到不同量级增益的紫外探测器。此流程图可得到一系列种子层厚度和溶液浓度、生长时间、器件增益的对应关系,为制备特定器件提供实验参数支持。
参见附图5,本发明中纳米线生长过程中资源竞争示意图。
根据系统协同学理论,晶体生长过程中,非平衡系统涨落的不稳定带来竞争,在竞争过程中,大的成核点成为序参量吸附反应原子继续生长,当达到临界尺寸,晶核可以存在下去并向更稳定的方向发展,同时不断使新的反应原子参与纳米线的自组织生长。当系统发生涨落时,由于竞争关系系统出现序参量,在系统内部非线性作用下,序参数役使子系统按照晶格严格排列,最终出现不同的“宏观”结构,整个系统的中心环节是非线性相互作用和伺服机制。本发明中纳米线的生长就是小核长成大核,大核不断吸引反应原子复制自己的模式,进而完成纳米线的生长的过程。
Claims (5)
1.一种制备可定制的高增益ZnO纳米线阵列紫外探测器的方法,其特征在于,包括以下步骤:
1.1.首先制备绝缘衬底,采用PECVD方法在硅衬底上生长二氧化硅绝缘层;
1.2.用光刻的方法对步骤1.1.中所述的衬底进行图案化处理,具体的使用光刻胶AZ5214做反转图形,使得光刻胶AZ5214的图形的侧面具有梯形结构,光刻胶AZ5214与二氧化硅绝缘层接触的底面面积小于上部非接触的截面面积,光刻胶AZ5214图形的侧面具有坡度;
1.3.在步骤1.2.中得到二氧化硅绝缘层上通过磁控溅射的方法依次生长氧化锌种子层和Ti层、Au层金属电极;
1.4.剥离步骤1.3.的光刻胶,最终形成氧化锌种子层和金属电极的坡度或台阶衬底;
1.5.将等摩尔比例的六水合硝酸锌(Zn(NO3)2·6H2O)和六次甲基四胺(HMTA)溶于去离子水中,搅拌均匀,配制成0.1mmol/L-2.5mmol/L的硝酸锌溶液作为前体溶液;
1.6.步骤1.5所得前体溶液放入水热反应釜中,再将步骤1.4.中衬底Ti层、Au层电极面朝下浮于前体溶液表面,在80℃下反应生长ZnO纳米线,生长时间随种子层厚度和前体溶液浓度不同,纳米线生长速度不同,根据生长速度调节生长时间;
1.7.通过扫面电子显微镜观察纳米线的形貌和通过电学测试I-V特性,若器件特性超过设定值,直接进行步骤1.8.;
若器件特性不佳,则返回步骤1.5.调整前体溶液的浓度,重新进行制备;经过上述步骤后器件增益若能达到设定值以上,说明当前浓度与种子层厚度匹配;若特性变差即增益在设定值以下,则返回步骤1.3.调节种子层厚度,直到找到较为匹配值;
1.8.将生长有ZnO纳米线的衬底取出,用去离子水反复冲洗,氮气吹干,此时,ZnO纳米线就以桥接的方式连接两个电极,就制备完成了ZnO纳米线阵列紫外探测器件的主要部分。
2.按照权利要求1的方法,其特征在于,氧化锌种子层为小于100nm的薄种子层。
3.按照权利要求1的方法,其特征在于,两横条电极即桥接方式的两电极相对处电极宽度端部宽度可改变,范围为25~100微米。
4.按照权利要求1的方法,其特征在于,厚度在100nm以下ZnO种子层、15nm厚Ti、100nm厚Au。
5.按照权利要求1-4任一项方法制备得到的高增益ZnO纳米线阵列紫外探测器。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101319372A (zh) * | 2008-06-03 | 2008-12-10 | 中山大学 | 一种低温可控制备氧化锌纳米线的方法及其应用 |
CN103066154A (zh) * | 2012-12-31 | 2013-04-24 | 东华大学 | 一种ZnO/CdS/Cu2ZnSnS4 pn 结纳米棒阵列的制备方法 |
CN103227230A (zh) * | 2013-04-10 | 2013-07-31 | 中国科学院安徽光学精密机械研究所 | 一种侧向生长ZnMgO纳米线日盲区紫外探测器及其制备方法 |
CN105655442A (zh) * | 2016-01-12 | 2016-06-08 | 浙江大学 | 一种ZnO纳米晶薄膜晶体管型紫外探测器的制备方法 |
-
2016
- 2016-11-17 CN CN201611012268.2A patent/CN106409975B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101319372A (zh) * | 2008-06-03 | 2008-12-10 | 中山大学 | 一种低温可控制备氧化锌纳米线的方法及其应用 |
CN103066154A (zh) * | 2012-12-31 | 2013-04-24 | 东华大学 | 一种ZnO/CdS/Cu2ZnSnS4 pn 结纳米棒阵列的制备方法 |
CN103227230A (zh) * | 2013-04-10 | 2013-07-31 | 中国科学院安徽光学精密机械研究所 | 一种侧向生长ZnMgO纳米线日盲区紫外探测器及其制备方法 |
CN105655442A (zh) * | 2016-01-12 | 2016-06-08 | 浙江大学 | 一种ZnO纳米晶薄膜晶体管型紫外探测器的制备方法 |
Non-Patent Citations (1)
Title |
---|
《片上制备横向结构Zn0纳米线阵列紫外探测器件》;李江江 等;《物理学报》;20160605;第65卷(第11期);第2-4页 * |
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