CN109594044A - 氧化钨纳米颗粒和多孔硅复合结构气敏传感器及制备方法 - Google Patents

氧化钨纳米颗粒和多孔硅复合结构气敏传感器及制备方法 Download PDF

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CN109594044A
CN109594044A CN201811522818.4A CN201811522818A CN109594044A CN 109594044 A CN109594044 A CN 109594044A CN 201811522818 A CN201811522818 A CN 201811522818A CN 109594044 A CN109594044 A CN 109594044A
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porous silicon
solution
wolframic acid
tungsten oxide
gas sensor
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胡明
秦岳
强晓永
周立伟
赵博硕
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Tianjin University
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Abstract

本发明公开了一种氧化钨纳米颗粒和多孔硅复合结构气敏传感器及制备方法，依顺序利用钨酸钠和盐酸反应生成钨酸溶胶，利用热退火工艺在多孔硅顶部形成氧化钨纳米颗粒结构，利用半导体异质结效应实现多孔硅对二氧化氮气体灵敏度和选择性的提升，从而制备有良好二氧化氮探测能力的气敏传感器。本发明气敏传感器利用氧化钨与多孔硅间异质结的影响，提升了多孔硅的气敏性能，在室温下对二氧化氮气体具有较高的灵敏度和较好的选择性，适宜应用在气敏传感器的进一步开发中。同时，这种多孔硅氧化钨复合结构气敏传感器的制备工艺重复性高，具有大规模生产的潜力。

Description

氧化钨纳米颗粒和多孔硅复合结构气敏传感器及制备方法
技术领域
本发明涉及一种气敏传感器，具体涉及一种氧化钨纳米颗粒和多孔硅复合结构气敏传感器及制备方法。
背景技术
由于长期以来对发展中的环境因素考虑不足等因素，以及城市规模的不断扩大，我国空气质量明显恶化，常出现极端大气污染事件。我国空气环境的主要污染物包括PM2.5、PM10、臭氧(O3)、二氧化氮(NO2)、一氧化碳(CO)和二氧化硫(SO2)等。二氧化氮空气污染已被证实与人的健康有着密切相关的影响，长时间生活在二氧化氮污染物超标环境中会增加人罹患呼吸道、心血管等疾病的风险。近年来，人们对于空气质量的改善有强烈意愿，对于二氧化氮等有害气体的检测越发引起重视。因此，对二氧化氮气体具有良好选择性和灵敏度的气敏传感器有良好的发展前景。
多孔硅是一种硅基气敏材料，属于低维微米-纳米材料，具有极大的比表面积，能够在室温下探测多种气体，同时兼容集成电路工艺，被视为极具应用前景的气敏材料。当前多孔硅气敏材料的问题集中在其灵敏度不高、选择性较差这两方面。
多孔硅对二氧化氮的气敏响应机理在于：空气中的二氧化氮分子吸附在多孔硅表面，与多孔硅之间发生电子转移，使多孔硅表面电子浓度下降，从而引起多孔硅电阻的变化。传感器器件在空气中的电阻值定义为Ra，器件在二氧化氮环境中的电阻定义为Rg。半导体的载流子为半导体中可以自由移动的带有电荷的物质微粒，包括电子和空穴。载流子中较多的载流子多子为电子的多孔硅称为N型多孔硅，对二氧化氮响应时电阻上升，使得Rg>Ra；载流子多子为空穴的多孔硅为P型多孔硅，对二氧化氮响应时电阻下降，使得Rg<Ra。
氧化钨是一种金属氧化物半导体材料，可由对钨酸胶体进行高温热处理制备得来。
半导体异质结是指不同种类的半导体材料间形成电学接触后形成的一种结构。形成异质结的材料间会产生载流子迁移，使材料载流子浓度发生变化。
发明内容
为了解决现有技术中的问题，本发明提供一种氧化钨纳米颗粒和多孔硅复合结构气敏传感器及制备方法，解决现有技术中多孔硅对二氧化氮气体的灵敏度和选择性差的问题。
本发明的技术方案是：
一种氧化钨纳米颗粒和多孔硅复合结构气敏传感器，由以下方法制得：
(1)清洗硅基片：
将硅基片依次浸入以下清洗液中清洗：浓硫酸和双氧水混合溶液；氢氟酸溶液；丙酮；乙醇；清洗后的硅基片放入乙醇中备用；
(2)制备多孔硅：
采用双槽电化学腐蚀法对步骤(1)中硅基片进行腐蚀，以制备多孔硅层；腐蚀电源为恒流稳压电源，腐蚀中电流保持不变；腐蚀液为氢氟酸水溶液；
(3)制备钨酸：
将钨酸钠粉末溶于去离子水中，形成浓度为0.05mol/L的钨酸钠溶液；在钨酸钠溶液中滴加浓度为6mol/L的盐酸溶液，盐酸溶液与钨酸钠溶液的体积比为3-5:100，将溶液离心，形成黄色钨酸沉淀；
(4)制备钨酸溶胶：
将步骤(3)中钨酸沉淀中加入30％过氧化氢溶液，再加入80％乙醇溶液，搅拌生成钨酸溶胶；
(5)在多孔硅上旋涂钨酸：
在步骤(2)的样品基础上，通过匀胶机在多孔硅上旋涂钨酸；将步骤(4)中钨酸溶胶涂于步骤(2)的多孔硅表面，然后将多孔硅层朝上置于匀胶机上，调节转速，匀胶20-40秒；重复涂钨酸和匀胶一至多次；
(6)制备氧化钨纳米颗粒：
将步骤(5)中样品多孔硅层朝上置于马弗炉中，调节热处理温度、升温速率，温度保持时间；
(7)制备铂电极：
将步骤(6)中样品置于电极模版中，放置于磁控溅射机真空室内，多孔硅层朝外；调节磁控溅射机参数，设置所需的本体真空度、氩气流量、工作压强、溅射功率与溅射时间。
所述步骤(1)中硅基片为N型单面硅抛光片，电阻率0.01-0.02Ω·cm，晶向为<1 00>，厚度为390-410μm，尺寸为23-25mm×7-9mm。
所述步骤(2)腐蚀时间为2-10min。
所述步骤(3)离心条件为在5000ppm下离心15-60分钟。
所述步骤(4)钨酸与过氧化氢溶液的比例范围为：0.05mol钨酸：2-4ml过氧化氢溶液；每0.05mol钨酸溶于过氧化氢后，加入乙醇溶液配至50ml。
所述步骤(7)中磁控溅射机为JCP-200高真空磁控溅射镀膜机。
一种氧化钨纳米颗粒和多孔硅复合结构气敏传感器的制备方法，包括以下步骤：
(1)清洗硅基片：
将硅基片依次浸入以下清洗液中清洗：浓硫酸和双氧水混合溶液；氢氟酸溶液；丙酮；乙醇；清洗后的硅基片放入乙醇中备用；
(2)制备多孔硅：
采用双槽电化学腐蚀法对步骤(1)中硅基片进行腐蚀，以制备多孔硅层；腐蚀电源为恒流稳压电源，腐蚀中电流保持不变；腐蚀液为氢氟酸水溶液；
(3)制备钨酸：
将钨酸钠粉末溶于去离子水中，形成浓度为0.05mol/L的钨酸钠溶液；在钨酸钠溶液中滴加浓度为6mol/L的盐酸溶液，盐酸溶液与钨酸钠溶液的体积比为3-5:100，将溶液离心，形成黄色钨酸沉淀；
(4)制备钨酸溶胶：
将步骤(3)中钨酸沉淀中加入30％过氧化氢溶液，再加入80％乙醇溶液，搅拌生成钨酸溶胶；
(5)在多孔硅上旋涂钨酸：
在步骤(2)的样品基础上，通过匀胶机在多孔硅上旋涂钨酸；将步骤(4)中钨酸溶胶涂于步骤(2)的多孔硅表面，然后将多孔硅层朝上置于匀胶机上，调节转速，匀胶20-40秒；重复涂钨酸和匀胶一至多次；
(6)制备氧化钨纳米颗粒：
将步骤(5)中样品多孔硅层朝上置于马弗炉中，调节热处理温度、升温速率、温度保持时间；
(7)制备铂电极：
将步骤(6)中样品置于电极模版中，放置于磁控溅射机真空室内，多孔硅层朝外；调节磁控溅射机参数，设置所需的本体真空度、氩气流量、工作压强、溅射功率和溅射时间。
本发明的有益效果是：
(1)通过氧化钨纳米颗粒复合结构，使本发明中的氧化钨多孔硅复合结构传感器对高浓度二氧化氮表现反型的P型响应，对低浓度二氧化氮表现N型响应，形成复合结构前为N型响应。
(2)与多孔硅气敏传感器相比，本发明中的氧化钨纳米颗粒多孔硅复合结构传感器对二氧化氮有更高的灵敏度和更好的选择性。
(3)本发明中应用的双槽电化学腐蚀法、匀胶法和热处理工艺，具有可重复性好、适宜大规模生产的优势。
本发明方法依顺序利用钨酸钠和盐酸反应生成钨酸溶胶，利用热退火工艺在多孔硅顶部形成氧化钨纳米颗粒结构，利用半导体异质结效应实现多孔硅对二氧化氮气体灵敏度和选择性的提升，从而制备有良好二氧化氮探测能力的气敏传感器。本发明在室温工作的多孔硅氧化钨复合结构气敏传感器利用氧化钨与多孔硅间异质结的影响，提升了多孔硅的气敏性能，在室温下对二氧化氮气体具有较高的灵敏度和较好的选择性，适宜应用在气敏传感器的进一步开发中。同时，这种多孔硅氧化钨复合结构气敏传感器的制备工艺重复性高，具有大规模生产的潜力。
附图说明
图1为通过双槽电化学腐蚀法制备的多孔硅的形貌SEM图；(A)平面图(B)断面图；
图2为经过溅射热氧化制备的氧化钨纳米颗粒/多孔硅复合结构SEM图；
图3为氧化钨纳米颗粒/多孔硅复合结构EDS能谱；
图4氧化钨纳米颗粒/多孔硅复合结构传感器对不同浓度二氧化氮气体的室温动态响应恢复曲线图；
图5氧化钨纳米线/多孔硅传感器对不同气体选择性图。
具体实施方式
下面结合附图和实施例对本发明作进一步的详细说明，但本发明的实施方式不限于此。
本发明所用原料均采用市售材料，并确定的最佳实施方案如下：
(1)清洗硅基片
所用硅片为2吋直径，电阻率0.01-0.02Ω·cm，厚度390-410μm，晶向<1 0 0>的N型单面硅抛光片。将硅基片依次浸入以下溶液进行清洗：于浓硫酸和双氧水混合溶液(浓硫酸与双氧水体积比例3：1)中浸泡清洗30分钟，于氢氟酸溶液(氢氟酸与去离子水体积比例1：1)中浸泡清洗20分钟，于丙酮中超声清洗5分钟，于无水乙醇中超声清洗5分钟。清洗后的硅基片放入无水乙醇中浸泡备用。
(2)制备多孔硅
采用双槽电化学腐蚀法对步骤(1)中硅基片进行腐蚀，腐蚀电源为恒流稳压电源。腐蚀在室温无外加光源环境下进行。腐蚀液为氢氟酸水溶液，氢氟酸与去离子水的体积比例为1：5。腐蚀时间为2min，腐蚀电流密度控制为恒定的64mA/cm2。
(3)制备钨酸：
将钨酸钠粉末溶于去离子水中，形成钨酸钠溶液。在钨酸钠溶液中滴加盐酸，将溶液在5000ppm下离心30分钟，形成黄色钨酸沉淀。钨酸钠溶液浓度为0.05mol/L。所用盐酸为6mol/L的盐酸溶液。盐酸与钨酸钠溶液的体积比为3：100。
(4)制备钨酸溶胶：
将步骤(3)中钨酸沉淀中加入过氧化氢溶液，再加入乙醇溶液，搅拌生成钨酸溶胶。过氧化氢溶液浓度为30％。钨酸与过氧化氢溶液的比例为0.005mol钨酸：2ml过氧化氢溶液。乙醇溶液浓度为80％。0.005mol钨酸溶于2ml过氧化氢溶液后，加入乙醇溶液配至50ml。
(5)在多孔硅上旋涂钨酸：
在步骤(2)的样品基础上，通过匀胶机在多孔硅上旋涂钨酸。将步骤(4)中钨酸溶胶涂于步骤(2)的多孔硅表面，然后将多孔硅层朝上置于匀胶机上，调节转速1500rpm，匀胶30秒。涂钨酸和匀胶次数为一次。
(6)制备氧化钨纳米颗粒：
将步骤(5)中样品多孔硅层朝上置于马弗炉中，调节热处理温度450℃、升温速率2℃每分钟，温度保持时间1h。
(7)制备铂电极：
将步骤(6)中样品置于电极模版中，放置于磁控溅射机真空室内，多孔硅层朝外。调节磁控溅射机参数，设置所需的本体真空度为4×10-4Pa、氩气流量为24sccm、工作压强为2Pa、溅射功率为100W，溅射时间为2min。通过溅射在样品上沉积一对尺寸为2mm×2mm的方型铂电极，两电极间距为8mm。
如图4所示，传感器在室温下对0.25ppm，0.5ppm，1ppm浓度下表现N型响应，灵敏度分别为1.44，1.52，1.86。传感器在室温下对1.5ppm，2ppm，4ppm表现P型响应，灵敏度分别为2.10，4.00，9.75。本传感器相较多孔硅，对二氧化氮的响应有较大提升，本传感器对浓度为4ppm的二氧化氮气体灵敏度达到了多孔硅的6.02倍。
如图5所示，传感器(深灰色)对二氧化氮(4ppm)的灵敏度为对其他气体(200ppm氨气、200ppm甲烷、200ppm乙醇、200ppm丙酮)的两倍以上，表现出对二氧化氮的良好选择性。
以上所述仅为本发明的优选实施方式，凡是利用本发明说明书及附图内容所作的若干改进或变形，或直接或间接运用在其他相关的技术领域，也应视为在本发明的专利保护范围内。

Claims (7)

1.一种氧化钨纳米颗粒和多孔硅复合结构气敏传感器，其特征在于，由以下方法制得：
(1)清洗硅基片：
将硅基片依次浸入以下清洗液中清洗：浓硫酸和双氧水混合溶液；氢氟酸溶液；丙酮；乙醇；清洗后的硅基片放入乙醇中备用；
(2)制备多孔硅：
采用双槽电化学腐蚀法对步骤(1)中硅基片进行腐蚀，以制备多孔硅层；腐蚀电源为恒流稳压电源，腐蚀中电流保持不变；腐蚀液为氢氟酸水溶液；
(3)制备钨酸：
将钨酸钠粉末溶于去离子水中，形成浓度为0.05mol/L的钨酸钠溶液；在钨酸钠溶液中滴加浓度为6mol/L的盐酸溶液，盐酸溶液与钨酸钠溶液的体积比为3-5:100，将溶液离心，形成黄色钨酸沉淀；
(4)制备钨酸溶胶：
将步骤(3)中钨酸沉淀中加入30％过氧化氢溶液，再加入80％乙醇溶液，搅拌生成钨酸溶胶；
(5)在多孔硅上旋涂钨酸：
在步骤(2)的样品基础上，通过匀胶机在多孔硅上旋涂钨酸；将步骤(4)中钨酸溶胶涂于步骤(2)的多孔硅表面，然后将多孔硅层朝上置于匀胶机上，调节转速，匀胶20-40秒；重复涂钨酸和匀胶一至多次；
(6)制备氧化钨纳米颗粒：
将步骤(5)中样品多孔硅层朝上置于马弗炉中，调节热处理温度、升温速率，温度保持时间；
(7)制备铂电极：
将步骤(6)中样品置于电极模版中，放置于磁控溅射机真空室内，多孔硅层朝外；调节磁控溅射机参数，设置所需的本体真空度、氩气流量、工作压强、溅射功率与溅射时间。
2.根据权利要求1所述氧化钨纳米颗粒和多孔硅复合结构气敏传感器，其特征在于，所述步骤(1)中硅基片为N型单面硅抛光片，电阻率0.01-0.02Ω·cm，晶向为<1 0 0>，厚度为390-410μm，尺寸为23-25mm×7-9mm。
3.根据权利要求1所述氧化钨纳米颗粒和多孔硅复合结构气敏传感器，其特征在于，所述步骤(2)腐蚀时间为2-10min。
4.根据权利要求1所述氧化钨纳米颗粒和多孔硅复合结构气敏传感器，其特征在于，所述步骤(3)离心条件为在5000ppm下离心15-60分钟。
5.根据权利要求1所述氧化钨纳米颗粒和多孔硅复合结构气敏传感器，其特征在于，所述步骤(4)钨酸与过氧化氢溶液的比例范围为：0.05mol钨酸：2-4ml过氧化氢溶液；每0.05mol钨酸溶于过氧化氢后，加入乙醇溶液配至50ml。
6.根据权利要求1所述氧化钨纳米颗粒和多孔硅复合结构气敏传感器，其特征在于，所述步骤(7)中磁控溅射机为JCP-200高真空磁控溅射镀膜机。
7.一种权利要求1-6任意一项权利要求所述氧化钨纳米颗粒和多孔硅复合结构气敏传感器的制备方法，其特征在于，包括以下步骤：
(1)清洗硅基片：
将硅基片依次浸入以下清洗液中清洗：浓硫酸和双氧水混合溶液；氢氟酸溶液；丙酮；乙醇；清洗后的硅基片放入乙醇中备用；
(2)制备多孔硅：
采用双槽电化学腐蚀法对步骤(1)中硅基片进行腐蚀，以制备多孔硅层；腐蚀电源为恒流稳压电源，腐蚀中电流保持不变；腐蚀液为氢氟酸水溶液；
(3)制备钨酸：
将钨酸钠粉末溶于去离子水中，形成浓度为0.05mol/L的钨酸钠溶液；在钨酸钠溶液中滴加浓度为6mol/L的盐酸溶液，盐酸溶液与钨酸钠溶液的体积比为3-5:100，将溶液离心，形成黄色钨酸沉淀；
(4)制备钨酸溶胶：
将步骤(3)中钨酸沉淀中加入30％过氧化氢溶液，再加入80％乙醇溶液，搅拌生成钨酸溶胶；
(5)在多孔硅上旋涂钨酸：
在步骤(2)的样品基础上，通过匀胶机在多孔硅上旋涂钨酸；将步骤(4)中钨酸溶胶涂于步骤(2)的多孔硅表面，然后将多孔硅层朝上置于匀胶机上，调节转速，匀胶20-40秒；重复涂钨酸和匀胶一至多次；
(6)制备氧化钨纳米颗粒：
将步骤(5)中样品多孔硅层朝上置于马弗炉中，调节热处理温度、升温速率、温度保持时间；
(7)制备铂电极：
将步骤(6)中样品置于电极模版中，放置于磁控溅射机真空室内，多孔硅层朝外；调节磁控溅射机参数，设置所需的本体真空度、氩气流量、工作压强、溅射功率和溅射时间。
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