CN110941127B - 一种电致变色智能玻璃复合膜组及其制备方法 - Google Patents
一种电致变色智能玻璃复合膜组及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种微缺陷诱导的电致变色智能玻璃复合膜组及其制备方法，其特征在于：在FTO或ITO导电玻璃基底的FTO或ITO面上依次设有WO3层、电解质层、NiO层、电极层；其中WO3层和NiO层内均嵌有SiO2纳米微球；电解质层为LixGayO或者LixNbyO层；电极层为ITO层。本发明有益效果：通过在变色层中内嵌SiO2纳米粒子作为微缺陷，微缺陷纳米球与变色层会形成界面缺陷，促进电致变色过程中离子在微缺陷界面处的诱导聚集，达到提升薄膜变色效率的目的，包括着色时间的加快，光调制幅度的增大、提高变色均匀性等；采用一种常温溅射制备ITO电极层的方法，本方法通过常温溅射制备ITO薄膜在保证了薄膜性能的同时，避免了加热对膜系变色层、电解质层带来的可能的影响。
Description
技术领域
本发明涉及一种电致变色膜组的制备方法，具体地说是一种以纳米SiO2颗粒作为微缺陷内嵌变色层产生离子诱导的电致变色智能玻璃复合膜组及其制备方法。
背景技术
当下我们的世界正以前所未有的速度进入智能时代，这样的时代背景下，材料研究领域也掀起了智能化热潮，智能材料代表着未来材料研究的方向，其中电致变色材料是一种在诸多领域有着巨大的潜力与优势的智能材料。电致变色是指材料的光学性能（透射、反射和吸收等）可以在外加电场或电流的作用下产生稳定可逆的变化。电致变色材料作为一种新型智能材料，具有良好的物理化学性质以及可逆的光学性能，可用于制作显示器、调光玻璃、信息存储等器件，在信息、电子、能源、建筑以及国防等诸多领域有着广泛的应用前景，对于节能、环保具有重要意义。电致变色器件最核心的部分是电致变色材料。与所有材料分类相似，电致变色材料可分为无机和有机两大类。其中以WO3、NiO为代表的无机电致变色材料，由于较高的着色效率、较大的光调制范围、较好的电化学可逆性以及化学稳定性，成为研究最多并实现商业化的无机电致变色材料，但是其在电致变色器件中的应用和尺寸化等仍受到很多因素的制约，主要有变色速度慢、循环稳定性差和色彩变化单一等。以sage与view为代表的西方公司已经实现电致变色组件的投产与销售。国内尚没有电致变色组件企业实现稳定生产，面对相关存在的一些基础卡脖子技术难题、西方公司专利壁垒，还得继续攻关实现突破。例如在电致变色过程中，电致变色材料在外加电压下发生氧化还原的传荷反应，为了保证电中性，还会同时伴随着离子嵌入脱出的传质过程，伴随着离子嵌入脱出电致变色材料内部，材料晶格或者分子键会发生不可逆的破坏或者断裂，同时，电极、电解质层和电致变色材料之间的界面也会直接影响器件的传质过程，进而影响整体的反应速率，最终影响材料的变色时间；并且由于通常施加外加电场在器件四周，电致变色器件的变色过程通常会从四周向中间扩散，导致电致变色过程容易不均匀。
发明内容
本发明的目的是提供一种微缺陷诱导的电致变色智能玻璃复合膜组及其制备方法，本发明通过在变色层中内嵌SiO2纳米粒子作为微缺陷，微缺陷纳米球与变色层会形成界面缺陷，促进电致变色过程中离子在微缺陷界面处的诱导聚集，达到提升薄膜变色效率的目的。
为了实现上述目的，本发明采用的技术方案如下：
一种微缺陷诱导的电致变色智能玻璃复合膜组，包括FTO或ITO导电玻璃基底，其特征在于：在FTO或ITO导电玻璃基底的FTO或ITO面上依次设有WO3层、电解质层、NiO层、电极层；其中WO3层和NiO层内均嵌有SiO2纳米微球；电解质层为LixGayO或者LixNbyO层；电极层为ITO层。
进一步， WO3层厚度为60～450nm，电解质层厚度为50～400nm，NiO层厚度为60～400nm，电极层为方块电阻为3~50Ω/□的ITO电极层，SiO2纳米微球的直径为5～100nm。
一种微缺陷诱导的电致变色智能玻璃复合膜组的制备方法，其特征在于包括以下步骤：
（1）制备WO3层：在FTO或ITO导电玻璃基底的FTO或ITO面上，先以直流反应磁控溅射法制备厚度为10～100nm 的WO3层，其次采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在WO3层上，在WO3层上形成离散的SiO2微球，微球直径为5～100nm；再次以直流反应磁控溅射法制备厚度为50～350nm的WO3层，其中磁控溅射的靶材为金属平面钨靶，溅射压强为0.1～2.0Pa，溅射功率为100～2000W，溅射氩氧比为3:1～15:1；
（2）制备电解质层：在步骤（1）制得的WO3层上，以直流反应溅射法，制备一层厚度为50～400nm的LixGayO或者LixNbyO层，所用靶材为Li、Ga合金靶或Li、Nb合金靶，Li/Ga混合质量比为1:3～20，Li/Nb混合质量比为1:4～30；
（3）制备NiO层：在步骤（2）制得的电解质层上，先以直流反应磁控溅射法制备厚度为10～100nm的NiO层，采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在NiO层上，在NiO层上形成离散的SiO2微球层，微球直径为5～100nm；再次以直流反应磁控溅射法制备厚度为50～300nmNiO层，其中溅射NiO层靶材为金属平面镍靶，溅射压强为0.1～2.0Pa，溅射功率为100～2500W，溅射氩氧比为5:1～30:1；
（4）制备电极层: 采用常温直流反应溅射法制备方块电阻为3~50Ω/□的ITO电极层，溅射靶材为ITO靶，溅射功率为500～4000W，氩氧比为50:1～4:1。
本发明的有益效果：通过在变色层中内嵌SiO2纳米粒子作为微缺陷，微缺陷纳米球与变色层会形成界面缺陷，促进电致变色过程中离子在微缺陷界面处的诱导聚集，达到提升薄膜变色效率的目的，包括着色时间的加快，光调制幅度的增大、提高变色均匀性等；采用一种常温溅射制备ITO电极层的方法，通过常温溅射制备ITO薄膜在保证了薄膜性能的同时，避免了加热对膜系变色层、电解质层带来的可能的影响。
附图说明
图1为一种微缺陷诱导的电致变色智能玻璃复合膜组的结构示意图。
具体实施方式
一种微缺陷诱导的电致变色智能玻璃复合膜组的制备方法，具体实施步骤如下：
实施例1
（1）制备内嵌SiO2纳米微球的WO3层：在FTO或ITO导电玻璃基底的FTO或ITO面上，先以直流反应磁控溅射法制备厚度为20nm 的WO3层，其次采用刮涂镀膜的方式，将5%固含量的氧化硅纳米微球乳液涂制在WO3层上，在WO3层上形成离散的SiO2微球，微球直径为100nm；再次以直流反应磁控溅射法制备厚度为300nm的WO3层，其中磁控溅射的靶材为金属平面钨靶，溅射压强为0. 37Pa，溅射功率为800W，溅射氩气流量200sccm，氧气流量55sccm；
（2）制备电解质层：在步骤（1）制得的WO3层上，以直流反应溅射法，制备一层厚度为100nm的LixGayO层，所用靶材为Li、Ga合金靶，Li/Ga混合质量比为1:10，溅射功率为1000W，氩气流量200sccm，氧气流量20sccm；
（3）制备内嵌SiO2纳米微球的NiO层：在步骤（2）制得的电解质层上，先以直流反应磁控溅射法制备厚度为20nm的NiO层，采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在NiO层上，在NiO层上形成离散的SiO2微球层，微球直径为100nm；再次以直流反应磁控溅射法制备厚度为300nmNiO层，其中溅射NiO层靶材为金属平面镍靶，溅射压强为0.25Pa，溅射功率为1000W，溅射氩气流量200sccm，氧气流量25sccm；
（4）制备电极层: 采用常温直流反应溅射法制备方块电阻为40Ω/□的ITO电极层，溅射靶材为ITO平面靶，溅射功率为800W，氩气流量200sccm，氧气流量10sccm。
实施例2
（1）制备内嵌SiO2纳米微球的WO3层：在FTO或ITO导电玻璃基底的FTO或ITO面上，先以直流反应磁控溅射法制备厚度为50nm 的WO3层，其次采用刮涂镀膜的方式，将5%固含量的氧化硅纳米微球乳液涂制在WO3层上，在WO3层上形成离散的SiO2微球，微球直径为50nm；再次以直流反应磁控溅射法制备厚度为200nm的WO3层，其中磁控溅射的靶材为金属平面钨靶，溅射压强为1.0Pa，溅射功率为1000W，溅射氩气流量450sccm，氧气流量120sccm；
（2）制备电解质层：在步骤（1）制得的WO3层上，以直流反应溅射法，制备一层厚度为200nm的LixGayO层，所用靶材为Li、Ga合金靶，Li/Ga混合质量比为1:18，溅射功率为1250W，氩气流量250sccm，氧气流量25sccm；
（3）制备内嵌SiO2纳米微球的NiO层：在步骤（2）制得的电解质层上，先以直流反应磁控溅射法制备厚度为50nm的NiO层，采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在NiO层上，在NiO层上形成离散的SiO2微球层，微球直径为50nm；再次以直流反应磁控溅射法制备厚度为200nmNiO层，其中溅射NiO层靶材为金属平面镍靶，溅射压强为0.9Pa，溅射功率为1600W，溅射氩气流量450sccm，氧气流量35sccm；
（4）制备电极层: 采用常温直流反应溅射法制备方块电阻为20Ω/□的ITO电极层，溅射靶材为ITO平面靶，溅射功率为1500W，氩气流量200sccm，氧气流量12sccm。
实施例3
（1）制备内嵌SiO2纳米微球的WO3层：在FTO或ITO导电玻璃基底的FTO或ITO面上，先以直流反应磁控溅射法制备厚度为90nm 的WO3层，其次采用刮涂镀膜的方式，将5%固含量的氧化硅纳米微球乳液涂制在WO3层上，在WO3层上形成离散的SiO2微球，微球直径为20nm；再次以直流反应磁控溅射法制备厚度为150nm的WO3层，其中磁控溅射的靶材为金属平面钨靶，溅射压强为1.5Pa，溅射功率为1500W，溅射氩气流量450sccm，氧气流量50sccm；
（2）制备电解质层：在步骤（1）制得的WO3层上，以直流反应溅射法，制备一层厚度为300nm的LixNbyO层，所用靶材为Li、Nb合金靶，Li/Ga混合质量比为1:20，溅射功率为1500W，氩气流量250sccm，氧气流量30sccm；
（3）制备内嵌SiO2纳米微球的NiO层：在步骤（2）制得的电解质层上，先以直流反应磁控溅射法制备厚度为70nm的NiO层，采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在NiO层上，在NiO层上形成离散的SiO2微球层，微球直径为20nm；再次以直流反应磁控溅射法制备厚度为150nmNiO层，其中溅射NiO层靶材为金属平面镍靶，溅射压强为1.6Pa，溅射功率为2000W，溅射氩气流量450sccm，氧气流量20sccm；
（4）制备电极层: 采用常温直流反应溅射法制备方块电阻为8Ω/□的ITO电极层，溅射靶材为ITO平面靶，溅射功率为3000W，氩气流量200sccm，氧气流量15sccm。
Claims (1)
1.一种微缺陷诱导的电致变色智能玻璃复合膜组的制备方法，包括FTO或ITO导电玻璃基底，其特征在于：在FTO或ITO导电玻璃基底的FTO或ITO面上依次设有WO3层、电解质层、NiO层、电极层；其中WO3层和NiO层内均嵌有SiO2纳米微球；电解质层为LixGayO或者LixNbyO层；电极层为ITO层；
所述 WO3层厚度为60～450nm，电解质层厚度为50～400nm，NiO层厚度为60～400nm，电极层为方块电阻为3~50Ω/□ 的ITO电极层，SiO2纳米微球的直径为50～100nm；
包括以下步骤：
（1）制备WO3层：在FTO或ITO导电玻璃基底的FTO或ITO面上，先以直流反应磁控溅射法制备厚度为10～100nm 的WO3层，其次采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在WO3层上，在WO3层上形成离散的SiO2微球，微球直径为50～100nm；再次以直流反应磁控溅射法制备厚度为50～350nm的WO3层，其中磁控溅射的靶材为金属平面钨靶，溅射压强为0 .1～2.0Pa，溅射功率为100～2000W，溅射氩氧比为3:1～15:1；
（2）制备电解质层：在步骤（1）制得的WO3层上，以直流反应溅射法，制备一层厚度为50～400nm的LixGayO或者LixNbyO层，所用靶材为Li、Ga合金靶或Li、Nb合金靶，Li/Ga混合质量比为1:3～20，Li/Nb混合质量比为1:4～30；
（3）制备NiO层：在步骤（2）制得的电解质层上，先以直流反应磁控溅射法制备厚度为10～100nm的NiO层，采用刮涂镀膜的方式，将氧化硅纳米微球乳液涂制在NiO层上，在NiO层上形成离散的SiO2微球层，微球直径为50～100nm；再次以直流反应磁控溅射法制备厚度为50～300nmNiO层，其中溅射NiO层靶材为金属平面镍靶，溅射压强为0 .1～2 .0Pa，溅射功率为100～2500W，溅射氩氧比为5:1～30:1；
（4）制备电极层: 采用直流反应溅射法制备方块电阻为3~50Ω/□ 的ITO电极层，溅射靶材为ITO靶，溅射功率为500～4000W，氩氧比为50:1～4:1。
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