CN111285409A - 基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料、制备工艺及其应用 - Google Patents
基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料、制备工艺及其应用 Download PDFInfo
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Abstract
本发明公开了一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料、制备工艺及其应用。本发明先采用合成条件简单的硬模板法制备单层氧化锡纳米碗材料，后采用水热法制备支化氧化铁纳米棒，最终得到了单层氧化锡纳米碗支化氧化铁纳米棒多级异质结构。与现有制备工艺相比，本发明具有可重复性强，成品率高，制备效率高，可规模化生产，与硅集成电路工艺兼容等优点。本发明构建的基于异质结的多级复合纳米结构，其应用于气体传感时灵敏度大幅提升，响应时间和恢复时间大幅缩减，展现了更加优异的气敏性能；其能够对微量甲醛能实现超灵敏、高选择性探测，为气体监测领域开发高灵敏度、高稳定性的气体传感器提供了坚实的技术支持。
Description
技术领域
本发明涉及半导体纳米材料制备技术领域，具体指一种具有高比表面积、高灵敏度和优良稳定性的基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料、制备工艺及其应用。
背景技术
近年来，基于半导体纳米材料的电阻式气体传感器受到了极大的关注，已经广泛应用于气体泄漏警报、环境气体监测和工业气体分析等各个领域。研发各种拥有高比表面积、优异的气体吸附能力和高载流子迁移率的基于金属氧化物半导体材料的新型气体传感器已成为当前的研究热点。甲醛气体属于一类致癌物，广泛存在于室内装潢的材料中，生活中对人体的健康影响巨大。发展一种灵敏度高、响应-恢复快及低功耗的新型甲醛气体传感器可有效的保护人体免受甲醛的影响。当前，气体传感器的类型多种多样，包括有电化学式、半导体化学电阻式及PID等，其中，基于MEMS技术的化学
电阻式气体传感器受到了巨大的关注，由于其具有尺寸小、功耗低、可集成等优势。而开发一种高效的气体敏感材是决定MEMS基的气体传感器性能的关键。由于纳米材料具有超高的比表面积、小尺寸效应等，在用作气体敏感材料时往往会比其他材料表现出更加出色的气敏性能。
发明内容
为了克服现有技术的不足，本发明的目的在于提供一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料、制备工艺及其应用。本发明制备得到的单层有序氧化锡纳米碗支化氧化铁纳米棒材料作为气敏材料具有高比表面积、高灵敏度、高选择性和优良稳定性的特点，可以用于微量甲醛的选择性检测。
本发明提供一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构气敏纳米材料的制备工艺，其采用合成条件简单的硬模板法制备单层有序氧化锡纳米碗材料，采用水热法合成支化氧化铁纳米棒；具体步骤如下：
（1）取直径1 μm以下的PS球或PMMA球粉体，用去离子水超声分散，配制成质量分数为1~4 wt%的分散液，再加入无水乙醇将上述得到的分散液稀释1~2倍；
（2）配制用于制备单层氧化锡纳米碗的四氯化锡前驱体溶液，其中四氯化锡溶液浓度为0.05~0.20 mol/L；
（3）将步骤（1）中制备的无水乙醇稀释后的PS球或PMMA球分散液逐滴滴入步骤（2）中配制得到的四氯化锡前驱体溶液，再滴入几滴表面活性剂，得到漂浮于前驱体溶液表面的单层PS球或PMMA球；
（4）用清洗后的衬底捞取步骤（3）中漂浮于前驱体溶液表面的单层PS球或PMMA球，待室温下或烘箱中完全干燥后，将样品放入马弗炉中煅烧；煅烧结束后，自然冷却至室温，得到单层氧化锡纳米碗结构；
（5）将步骤（4）中得到的样品置于水热釜中，向水热釜中加入含有氯化铁和硝酸钠的混合溶液，经水热法生成支化氧化铁纳米棒结构，完成后用去离子水冲洗并烘干，得到单层氧化锡纳米碗支化氧化铁纳米棒的多级异质气敏纳米材料。
上述步骤（3）中，表面活性剂为十二烷基硫酸钠；滴入表面活性剂后，能够得到排列紧密（如六方密堆积）的漂浮于四氯化锡溶液表面的单层有序PS球或PMMA球。
上述步骤（4）中，可以按照需求选择不同的衬底，衬底为硅片、石英片或其它衬底。
上述步骤（4）中，采用烘箱干燥时，烘箱的设置温度不高于80℃，优选为60~80℃。
上述步骤（4）中，马弗炉的煅烧温度为450~600℃，煅烧时间为1~3 h。
上述步骤（5）中，混合溶液中，氯化铁的浓度为0.02~0.10 mol/L，硝酸钠的浓度为0.5~1.5 mol/L；水热生长温度为100~110℃，生长时间为15~60分钟。
本发明还提供一种上述制备工艺制得的基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料。本发明得到的单层有序氧化锡纳米碗支化氧化铁纳米棒结构的多级异质气敏纳米材料的平均孔径取决于硬模板PS球或PMMA球的直径，而支化纳米棒的平均直径约为100~500 nm。
本发明进一步提供一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料在检测有机挥发性气体方面的应用，特别的，在选择性检测甲醛方面的应用。
和现有技术相比， 本发明的有益效果在于：
1、构建了基于异质结的多级纳米结构，相比于单一氧化锡结构，其应用于气体传感时灵敏度大幅提升，响应时间和恢复时间大幅缩减，展现了更加优异的气敏性能。
2、单层有序纳米碗结构相比于薄膜结构已经有效增加了材料的比表面积，而支化纳米棒结构使得比表面积得到了进一步的增加，从而能够有效提升材料的气敏性能。
3、本发明的单层有序氧化锡纳米碗支化氧化铁纳米棒结构的多级异质气敏纳米材料能够对微量甲醛实现超灵敏、高选择性探测，同时能够对有机挥发性气体进行微量检测，为气体监测领域开发高灵敏度、高稳定性的气体传感器提供了坚实的技术支持。
4、本发明的制备工艺将水热法与合成条件简单的硬模板法相结合，并可在多种衬底上实现大规模制备，与传统制备工艺相比具有可重复性强，成品率高，制备效率高，适合规模化制备，与硅基兼容等优点。
附图说明
图1为本发明一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的多级异质气敏纳米材料制备工艺的流程框图。
图2为实施例1得到的单层有序氧化锡纳米碗的SEM表征图。
图3为实施例1得到的单层有序氧化锡纳米碗支化氧化铁纳米棒的SEM表征图。
图4为实施例1得到的单层有序氧化锡纳米碗支化氧化铁纳米棒的TEM表征图。
图5为实施例1得到的单层有序氧化锡纳米碗和单层有序氧化锡纳米碗支化氧化铁纳米棒这两个器件的微量甲醛气敏性能测试结果图。
图6为实施例1得到的单层有序氧化锡纳米碗支化氧化铁纳米棒对五种还原性气体的选择性气敏测试结果图。
图7为实施例2得到的单层有序氧化锡纳米碗支化氧化铁纳米棒的SEM表征图。
具体实施方式
以下结合附图和实施例对本发明作进一步详细描述。
本发明一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的多级异质气敏纳米材料制备工艺的流程框图如图1所示。
实施例1
（1）取直径为800 nm，质量分数为2 wt%的PS球分散液，加入无水乙醇稀释1倍；
（2）配制浓度为0.15 mol/L的四氯化锡溶液；
（3）将无水乙醇稀释后的PS球分散液逐滴滴入0.15 mol/L的四氯化锡溶液，再滴入1滴表面活性剂，得到漂浮于四氯化锡溶液表面的单层PS球；
（4）用带有叉指电极的硅片捞取单层PS球，待室温中完全干燥后，将样品放入马弗炉中500 ℃煅烧2小时；煅烧结束后，自然冷却至室温；
（5）将（4）中得到的样品在106 ℃下水热30分钟支化氧化铁纳米棒，完成后用去离子水冲洗并烘干。
上述步骤（4）中得到的样品呈单层有序氧化锡纳米碗结构，具体如图2所示；步骤（5）后得到的样品的结构如图3和图4所示，其结果显示，通过水热法在纳米碗周边生成支化的氧化铁纳米棒，纳米棒的平均直径在100~400nm之间。
利用上述步骤（5）得到的单层有序氧化锡纳米碗支化氧化铁纳米棒MP-SnO2@Fe2O3NRs和单层有序氧化锡纳米碗MP-SnO2对750~150 ppb的甲醛气体进行气体传感测试。对750ppb的甲醛气体，MP-SnO2@Fe2O3 NRs的响应值（定义为Ra/Rg，其中Ra是空气中电阻，Rg是待测气体中电阻）为1.62，而MP-SnO2的灵敏度为0.12，本发明的支化纳米棒结构将对750 ppb甲醛气体的传感灵敏度提高了5倍，对其它浓度下的甲醛气体其灵敏度也有不同程度的提升（如图5所示）。此外，对得到的MP-SnO2@Fe2O3 NRs进行了选择性测试，即分别对相同浓度（1ppm）的甲烷、二氧化氮、丙酮、甲苯、硫化氢和氨气进行了气敏传感测试。如图6所示，本发明的单层有序氧化锡纳米碗支化氧化铁纳米棒MP-SnO2@Fe2O3 NRs对甲醛气体展现了极其优异的选择性。
实施例2
与实施例1类似，其区别在于支化氧化铁纳米棒时的水热生长时间为60分钟。得到的单层有序氧化锡纳米碗支化氧化铁纳米棒的SEM表征图如图7所示。
以上实施例详细描述了本发明的实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
Claims (9)
1.一种基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料的制备工艺，其特征在于，具体步骤如下：
（1）取直径1 μm以下的PS球或PMMA球粉体，用去离子水超声分散，配制成质量分数为1~4 wt%的分散液，再加入无水乙醇将上述得到的分散液稀释1~2倍；
（2）配制用于制备单层氧化锡纳米碗的四氯化锡前驱体溶液，其中四氯化锡溶液浓度为0.05~0.20 mol/L；
（3）将步骤（1）中制备的无水乙醇稀释后的PS球或PMMA球分散液逐滴滴入步骤（2）中配制得到的四氯化锡前驱体溶液，再滴入几滴表面活性剂，得到漂浮于前驱体溶液表面的单层PS球或PMMA球；
（4）用清洗后的衬底捞取步骤（3）中漂浮于前驱体溶液表面的单层PS球或PMMA球，待室温下或烘箱中完全干燥后，将样品放入马弗炉中煅烧；煅烧结束后，自然冷却至室温，得到单层氧化锡纳米碗结构；
（5）将步骤（4）中得到的样品置于水热釜中，向水热釜中加入含有氯化铁和硝酸钠的混合溶液，经水热法生成支化氧化铁纳米棒结构，完成后用去离子水冲洗并烘干，得到单层有序氧化锡纳米碗支化氧化铁纳米棒的多级异质气敏纳米材料。
2.如权利要求1所述的制备工艺，其特征在于，步骤（3）中，表面活性剂为十二烷基硫酸钠。
3.如权利要求1所述的制备工艺，其特征在于，步骤（4）中，衬底为硅片或石英片。
4.如权利要求1所述的制备工艺，其特征在于，步骤（4）中，采用烘箱干燥时，烘箱的设置温度为60~80℃。
5.如权利要求1所述的制备工艺，其特征在于，步骤（4）中，马弗炉的煅烧温度为450~600 ℃，煅烧时间为1~3 h。
6.如权利要求1所述的制备工艺，其特征在于，步骤（5）中，混合溶液中，氯化铁的浓度为0.02~0.10 mol/L的氯化铁和0.5~1.5 mol/L的硝酸钠；水热生长温度为100~110℃，生长时间为15~60分钟。
7.一种如权利要求1所述的制备工艺制得的基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料。
8.如权利要求7所述的基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料，其特征在于，其包括单层有序纳米碗状的氧化锡和在其周围支化的氧化铁纳米棒；氧化铁纳米棒的平均直径在100~500nm 之间。
9.一种如权利要求7或8所述的基于单层有序氧化锡纳米碗支化氧化铁纳米棒结构的气敏纳米材料在检测甲醛方面的应用。
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