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一种新型电致变色薄膜的制作方法 【EN】A kind of production method of novel electrochromic film

申请(专利)号:CN201910144105.7国省代码:广东 44
申请(专利权)人:【中文】暨南大学 广东谛思纳为新材料科技有限公司【EN】Jinan University;Guangdong Texna New Material Technology Co., Ltd.
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摘要:
【中文】本发明属于电致变色无机薄膜技术,为电致变色薄膜的制作方法,步骤如下:洗净的透明导电材料置于磁控溅射腔室内,控制好溅射腔室的参数,控制好分子泵与真空溅射腔室之间的打通角度;对第一层膜生长的金属靶材进行预溅射处理,打开基片挡板进行第一层膜的溅射生长处理,控制溅射功率和时间,让第一层膜涨到合适厚度;在第一层无机电致变色薄膜的基础上进行第二层膜生长,对第二层膜溅射的金属靶材进行预溅射处理,控制让第二层膜涨到合适的厚度。本发明利用磁控溅射的方法,在第一层电致变色薄膜基础上涨一层具有电致变色性能的保护膜或良好离子传导能力的保护膜,以获得新型结构的电致变色薄膜,有效提高了单膜电致变色薄膜的电致变色性能。 【EN】Paragraph:The invention belongs to electrochromism inorganic thin film technologies, for the production method of electrochomeric films, steps are as follows: clean transparent conductive material is placed in magnetron sputtering chamber, controls the parameter of sputtering chamber, is controlled and is got through angle between molecular pump and vacuum sputtering chamber;Pre-sputtering processing is carried out to the metal targets of the first tunic growth, opens the sputtering growth process that substrate baffle plate carries out the first tunic, sputtering power and time is controlled, the first tunic is allowed to increase to suitable thickness;The second tunic growth is carried out on the basis of first layer inorganic electrochromic film, pre-sputtering processing is carried out to the metal targets of the second tunic sputtering, control allows the second tunic to increase to suitable thickness.The method that the present invention utilizes magnetron sputtering; in one layer of protective film with electrochromic property of first layer electrochomeric films basis rise or the protective film of good ionic conductivity; to obtain new structural electrochomeric films, the electrochromic property of monofilm electrochomeric films is effectively increased.Image:201910144105.GIF

主权项:
【中文】1.一种新型电致变色薄膜的制作方法,其特征在于,包括以下步骤: 步骤1:洗净的透明导电材料置于磁控溅射腔室内,管路抽真空,控制好溅射腔室里的气体总流量以及氧气与氩气的比例含量; 步骤2:将溅射腔室温度调节在所需范围内,控制好分子泵与真空溅射腔室之间的打通角度,将溅射腔室内气体压强控制在所需范围内; 步骤3:对所需要进行第一层膜生长的金属靶材进行预溅射处理,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第一层膜的溅射生长处理,控制溅射功率和溅射时间,让第一层膜涨到合适的厚度; 步骤4:将要生长的第二层膜的基片置于与第一层膜生长的基片同一个位置,在第一层所生长的无机电致变色薄膜的基础上进行第二层膜的生长; 步骤5:控制好第二次溅射腔室里的气体总流量以及氧气与氩气的比例含量,调节腔室温度,并控制好腔室内的气体压强; 步骤6:对所需要进行第二层膜溅射的金属靶材进行预溅射处理,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第二层膜的溅射生长处理,溅射时间控制到让第二层膜涨到合适的厚度; 所述第二层膜为具有电致变色性能的保护膜或良好离子传导能力的保护膜。 【EN】1. a kind of production method of novel electrochromic film, which comprises the following steps: Step 1: clean transparent conductive material is placed in magnetron sputtering chamber, and pipeline vacuumizes, and is controlled in sputtering chamber The proportional amount of total gas flow rate and oxygen and argon gas; Step 2: sputtering chamber temperature being adjusted within the required range, getting through between molecular pump and vacuum sputtering chamber is controlled Angle, within the required range by gas pressure intensity control in sputtering chamber; Step 3: pre-sputtering processing being carried out to the required metal targets for carrying out the first tunic growth, for removing original target table Then impurity on face opens the sputtering growth process that substrate baffle plate carries out the first tunic, controls sputtering power and sputtering time, The first tunic is allowed to increase to suitable thickness; Step 4: the substrate for the second tunic that will be grown is placed in the same position of substrate with the growth of the first tunic, in first layer The growth of the second tunic is carried out on the basis of the inorganic electrochromic film grown; Step 5: controlling the proportional amount of the total gas flow rate and oxygen and argon gas in second of sputtering chamber, adjust chamber Temperature, and control the indoor gas pressure intensity of chamber; Step 6: pre-sputtering processing being carried out to the required metal targets for carrying out the second tunic sputtering, for removing original target table Impurity on face, then opens the sputtering growth process that substrate baffle plate carries out the second tunic, and sputtering time control is to allowing the second layer Film increases to suitable thickness; Second tunic is the protective film of the protective film with electrochromic property or good ionic conductivity.


说明书

【中文】

一种新型电致变色薄膜的制作方法

技术领域

本发明涉及电致变色无机薄膜材料制备技术,具体为一种新型电致变色薄膜的制作方法。

背景技术

近些年以来,可持续性发展与节约能源、环境保护等这些新能源科学技术的领域已经成为当今时代最值得研究与最重要的课题。但是目前,人类的生活与生产方式还是主要以石油、煤、天然气等不可再生能源为主,在各种新能源尚未得到普及使用的时候,采取各种措施降低能源的消耗显得尤其重要。而每年建筑能耗逐年升高,通过采取有效的办法减少因为门、窗户等建筑用具而损失的能量显得尤其重要,而提高窗户所损失的能量,提高窗户的保温性能,遮光性逐渐成为一个人们关注的新焦点。

与此同时,节能玻璃、智能窗户的出现让人们看到了一个节能减排的新希望。电致变色智能窗户可以实现对室外照射进来的光的透射与吸收等光学性能的调整,以解决由于外来环境的影响对室内所造成的能源损耗的问题。除了用在建筑物的玻璃上,这些电致变色材料还可以应用于汽车的防弦后视镜,以减低交通事故的意外发生,应用于汽车的挡风玻璃、车窗玻璃上,以减低因为外来照射光线而导致车内保温性能的损失。电致变色材料还可以应用于各类型的显示器、衣物之类的随身物体。

电致变色是指在外加电场的作用下,材料的光学属性(反射率、透过率、吸收率等)发生稳定而且可逆的连续性变化,在外观上可以表现为材料的颜色、透明度发生可逆的连续性变化。无机电致变色材料多为过渡金属氧化物或其衍生物。由于无机电致变色材料的光吸收变化是由于离子和电子的双注入或抽取而引起的,在无机电致变色材料(如WO3、MoO3)中,电致变色薄膜具有着色效率高、稳定性好及无视盲角等优点,被广泛研究使用。但现有无机电致变色材料存在响应时间长,多次进行循环伏安特性后出现偏差的问题。

目前制备电致变色薄膜的技术主要有以下几类:

1、化学气相沉积

化学气相沉积法虽然薄膜的生长速度快,成膜质量好,容易控制掺杂,但缺点是设备较为复杂,而且需要的温度要求较高,对低温制备的薄膜并不适用,而且膜的结合力差,容易造成脱落。

2、溶胶-凝胶工艺

这种方法无需真空设备,工艺简单,可获得理想厚度和组分的薄膜,溶胶中通常含有水和醇类物质,其排除需经干燥和热处理;而在热处理过程中,薄膜的开裂是一个必须解决的问题。此外膜层与基底的附着力也较差,薄膜厚度均匀性难以控制,致密性较差。

3、真空蒸镀沉积

真空蒸镀法具有较长的历史,在实验室里研究得比较透彻,形成了许多成熟的工艺。这种方法沉积速率高、沉积面积大、生产效率高,另外设备和操作也比较简单,是实验室和工业生产中制备薄膜的主要技术手段。不过,真空蒸镀法的缺点也是非常突出的,用这种方法制备的薄膜有以下不足之处:

①聚集密度小,折射率比块体数值偏低。

②容易吸附残余气体和水汽,光学吸收大,时效性差。

③表面、界面不平整,体内散射、表面散射大。

④应力高,各向异性。

⑤硬度低,附着力小,牢固性差。

4、脉冲准分子激光瓣射沉积(PLD),是近年发展起来的新型蒸锭技术,具有成膜速度快的优点,但膜层与基底的结合力差,缺陷多,薄膜易受污染,薄膜的质量不佳。

发明内容

为了解决现有技术所存在的问题,本发明提供一种新型电致变色薄膜的制作方法,在透明导电材料衬底上利用磁控溅射的方法,通过控制腔室内的温度、压强、掺氧量以及溅射的变量,先在衬底上通过掺杂或不掺杂的方法生长一层合适厚度的无机电致变色薄膜;然后再改变涨膜的材料体系,在第一层电致变色薄膜的基础上,再涨一层具有良好离子传导能力的TaO2薄膜或具有电致变色性能TiO2薄膜,即获得本发明新型结构的电致变色薄膜,有效提高了单膜电致变色薄膜的电致变色性能。

为了达到以上目的,本发明提供以下技术方案:一种新型电致变色薄膜的制作方法,包括以下步骤:

步骤1:洗净的透明导电材料置于磁控溅射腔室内,管路抽真空,控制好溅射腔室里的气体总流量以及氧气与氩气的比例含量;

步骤2:将溅射腔室温度调节在所需范围内,控制好分子泵与真空溅射腔室之间的打通角度,将溅射腔室内气体压强控制在所需范围内;

步骤3:对所需要进行第一层膜生长的金属靶材进行预溅射处理,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第一层膜的溅射生长处理,控制溅射功率和溅射时间,让第一层膜涨到合适的厚度;

步骤4:将要生长的第二层膜的基片置于与第一层膜生长的基片同一个位置,在第一层所生长的无机电致变色薄膜的基础进行第二层膜的生长;

步骤5:控制好第二次溅射腔室里的气体总流量以及氧气与氩气的比例含量,调节腔室温度,并控制好腔室内的气体压强;

步骤6:对所需要进行第二层膜溅射的金属靶材进行预溅射处理,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第二层膜的溅射生长处理,溅射时间控制到让第二层膜涨到合适的厚度;

所述第二层膜为具有电致变色性能的保护膜或良好离子传导能力的保护膜。

优选地,步骤3对第一层膜生长的金属钨靶材进行预溅射处理,或对第一层膜生长的金属钨靶材与金属钛靶材进行共溅射的预溅射处理。当步骤3对第一层膜生长的金属钨靶材进行预溅射处理时,溅射功率控制在50w~200w之间,溅射时间在10min~1h之间,把要生长的WO3膜厚控制在100nm~400nm之间。当步骤3对第一层膜生长的金属钨靶材与金属钛靶材进行共溅射的预溅射处理时,金属钨靶材的溅射功率控制在150w,金属钛靶材的溅射功率控制在50w,溅射时间均为17min,把要生长的WO3掺杂TiO2的薄膜的膜厚控制在360nm。

步骤6中第二层膜溅射的金属靶材为金属钛靶材或金属钽靶材。步骤6中第二层膜的溅射生长处理,对于金属钛靶材功率控制在150w,溅射时间为11min,把要生长的TiO2的膜厚控制在100nm;而对于金属钽靶材功率控制在130w,溅射时间为30min,把要生长的TaO2的膜厚控制在100nm。

优选地,步骤1中管路真空抽至1.0x10-4pa~1.0x10-5pa,气体总流量控制在40sccm~100sccm,氧气与氩气的比例含量控制在20%~40%;步骤2中的腔室温度范围控制在30℃~150℃,溅射腔室内气体压强范围控制在0.5pa~3pa;步骤5中气体总流量控制在40sccm~100sccm,氧气与氩气的比例含量控制在20%~40%,腔室温度控制在30℃~150℃,腔室内的气体压强控制在0.5pa~3pa。

与现有技术相比,本发明具有如下有益效果:

1、本发明所制作的电致变色薄膜的衬底为透明导电的ITO玻璃或FTO玻璃。在透明导电材料衬底上利用磁控溅射的方法,通过控制腔室内的温度、压强、掺氧量以及溅射的变量,先在衬底上通过掺杂或不掺杂的方法生长一层合适厚度(如100-350nm)的无机电致变色薄膜;然后再改变涨膜的材料体系,第一层电致变色薄膜的基础上,再涨一层具有良好离子传导能力的TaO2薄膜或具有弱电致变色特性TiO2薄膜,即获得本发明新型结构的电致变色薄膜,有效提高了单膜电致变色薄膜的电致变色性能。

2、以无机电致变色薄膜为基础,通过在原有电致变色薄膜的基础上,叠加一层性能稳定,且能提升原本电致变色薄膜性能的相关电致变色材料体系的薄膜或具有良好离子传导能力的保护膜,通过利用不同无机电致变色材料或具有离子传导能力材料的不同特性来提高原本单一无机电致变色薄膜的电致变色性能,其工艺制作简便,在同一腔室内便能实现所需的要求。

附图说明

图1是本发明方法所制作的一种电制变色薄膜结构示意图;

图2是本发明方法所制作的另一种电制变色薄膜结构示意图;

图3是实施例1制作的电制变色薄膜结构示意图;

图4是实施例2制作的电制变色薄膜结构示意图;

图5是实施例3制作的电制变色薄膜结构示意图。

具体实施方式

下面结合实施例和附图对本发明作进一步详细的说明,但本发明的实施方式并不限于此。

本发明以透明导电材料ITO玻璃或FTO玻璃为电致变色薄膜的衬底,利用磁控溅射的方法,通过控制磁控溅射腔室内的温度、压强、掺氧量以及溅射变量等参数,先在透明导电材料衬底上通过掺杂或不掺杂的方法生长一层无机电致变色薄膜,然后在第一层电致变色薄膜的基础上,生长一层具有良好离子传导能力的TaO2薄膜或具有电致变色性性能TiO2薄膜,以最终完成本发明新型结构电致变色薄膜的制备,如图1所示。下面分别以不同的无机电致变色薄膜材料,对本发明的实施过程举例详细说明。

实施例1

步骤1:将洗净的ITO玻璃或FTO玻璃置于磁控溅射腔室内,管路真空抽至1.0x10-4pa~1.0x10-5pa,控制溅射腔室内的参数,控制好溅射腔室里的气体总量控制在40sccm~100sccm之间,例如将气体总量控制为80sccm,将氧气与氩气的比例含量控制在20%~40%之间,本实施例将氧气与氩气的比例控制在24sccm:56sccm。

步骤2:打开腔室内的温度装置,将溅射腔室的温度范围控制在30℃~150℃之间,例如将腔室温度调节在50℃;控制好分子泵与真空溅射腔室之间的打通角度,本实施例控制在18°的这个角度上,使溅射腔室内的压强达到0.5pa~3pa。本实施例可将腔室内压强控制在2pa。

步骤3:打开直流电源,对所需要进行第一层膜生长的金属钨靶材进行预溅射处理,处理的时间为10~15min,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第一层膜的溅射生长处理,溅射功率可控制在50w~200w之间,例如控制在150w,溅射时间可设置在10min~1h之间,本实施例可将溅射时间设为17min,把要生长的WO3薄膜厚度控制在100nm~400nm之间,最终生成的WO3薄膜厚度可以为360nm这个数值。

步骤4:将要生长的第二层膜的基片置于与第一层膜生长的基片同一个位置,在第一层所生长的WO3电致变色薄膜的基础上通过直流溅射Ti靶材的方式,进行第二层膜TiO2的溅射生长,使第二层膜TiO2覆盖在第一层膜WO3的表面,如图2所示。

步骤5:控制好第二次溅射腔室里的气体总量以及氧气与氩气的比例含量,其中氧气与氩气的比例含量控制在24sccm:56sccm,然后再打开温度装置,将腔室的温度范围调节在适合的温度范围内,例如将温度控制在50摄氏度。

步骤6:控制好分子泵与真空腔室之间的打通角度,本实施例控制在18°的这个角度上,使腔室内的压强达到2pa。然后打开直流电源,对所需要进行第二层膜生长的金属钛靶材进行预溅射处理,处理的时间为10~15min,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第二层膜的溅射生长处理,功率控制在150w,溅射时间为11min,把要生长的TiO2的膜厚控制在100nm这个数值上。

需说明的是,本实施例中第二次溅射生长时,腔室内气体总量、氧气与氩气的比例含量、腔室温度范围、腔室压强、预溅射处理时间、溅射时间、溅射功率等参数的数值范围,与第一次溅射生长时的基本相同,但是薄膜的生长厚度有所区别。

实施例2

本实施例与实施例1的溅射原理及工艺参数所选取的数值范围基本相同,所不同的主要是金属靶材。

步骤1:将洗净的ITO玻璃或FTO玻璃置于磁控溅射腔室内,管路真空抽至1.0x10-4pa~1.0x10-5pa,控制溅射腔室内的参数,控制好腔室里的气体总量为80sccm,其中氧气与氩气的比例控制在24sccm:56sccm。

步骤2:打开溅射腔室内的温度装置,将腔室温度调节在50℃,控制好分子泵与真空溅射腔室之间的打通角度,本实施例也控制在18°的这个角度上,使腔室内的压强达到2pa。

步骤3:打开直流电源,对所需要进行第一层膜生长的金属钨靶材进行预溅射处理,处理时间为10~15min,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第一层膜的溅射生长处理,功率控制在150w,溅射的时间为17min,把要生长的WO3膜厚控制在360nm这个数值。

步骤4:将要生长的第二层膜的基片置于与第一层膜生长的基片同一个位置,在第一层所生长的WO3电致变色薄膜的基础上通过直流溅射Ta靶材的方式,进行第二层膜TaO2的溅射生长,使第二层膜TaO2覆盖在第一层膜WO3的表面。

步骤5:控制好第二次溅射腔室里的气体总量以及氧气与氩气的比例含量,其中比例含量控制在24sccm:56sccm,然后再打开温度装置,将腔室的温度调节在适合的温度范围内,例如将温度控制在50摄氏度。

步骤6:控制好分子泵与真空溅射腔室之间的打通角度,控制在18°的这个角度上,使溅射腔室内的压强达到2pa。然后打开直流电源,对所需要进行第二层膜生长的金属钽Ta靶材进行预溅射处理,处理的时间为10~15min,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第二层膜的溅射生长处理,功率控制在130w,溅射的时间为30min,把要生长的TaO2的膜厚控制在100nm这个数值上。

实施例3:

本实施例与实施例1的溅射原理及工艺参数所选取的数值范围基本相同,所不同的主要是金属靶材。

步骤1:将洗净的ITO玻璃或FTO玻璃置于磁控溅射腔室内,管路真空抽至1.0x10-4pa~1.0x10-5pa,控制溅射腔室内的参数,控制好腔室里的气体总量为80sccm,其中氧气与氩气的比例控制在24sccm:56sccm。

步骤2:打开腔室内的温度装置,将腔室的温度调节在50℃,控制好分子泵与真空腔室之间的打通角度,控制在18°的这个角度上,使腔室内的压强达到2pa。

步骤3:打开直流电源,对所需要进行第一层膜生长的金属钨靶材与金属钛靶材进行共溅射的预溅射处理,处理时间为10~15min,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第一层膜的溅射生长处理,其中金属钨靶材的溅射功率控制在150w,而金属钛靶材的溅射功率控制在50w,溅射时间均为17min,把要生长的WO3掺杂TiO2的薄膜的膜厚控制在360nm这个数值。

步骤4:将要生长的第二层膜的基片置于与第一层膜生长的基片同一个位置,在第一层所生长的WO3掺杂TiO2电致变色薄膜的基础上通过直流溅射Ta靶材的方式,进行第二层膜TaO2的溅射生长,使第二层膜TaO2覆盖在第一层WO3掺杂TiO2薄膜的表面。

步骤5:控制好第二次溅射腔室里的气体总量以及氧气与氩气的比例含量,其中比例含量控制在24sccm:56sccm,然后再打开温度装置,将腔室的温度调节在适合的温度范围内,例如将温度控制在50摄氏度。

步骤6:控制好分子泵与真空腔室之间的打通角度,控制在18°的这个角度上,使腔室内的压强达到2pa。然后打开直流电源,对所需要进行第二层膜生长的金属钽Ta靶材进行预溅射处理,处理的时间为10~15min,用于去除原来靶材表面上的杂质,然后打开基片挡板进行第二层膜的溅射生长处理,功率控制在130w,溅射的时间为30min,把要生长的TaO2的膜厚控制在100nm这个数值量上。

由以上实施例可知,本发明采取的是磁控溅射的方法进行镀膜,因而膜与基片的粘附性极好。此外薄膜生长速率高、工艺参数易控制,能制备难熔材料薄膜,能实现大面积制膜,具有稳定性好、制备方便的优点。相对于单膜的纯电致变色薄膜来说,由于单膜的纯电致变色薄膜循环伏安稳定性等电致变色的性能尚有改进的空间,通过复合电致变色薄膜的制备,确实能够改善单膜的电致变色材料的稳定性能,提高电致变色的变色性能。

上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。

【EN】

A kind of production method of novel electrochromic film

Technical field

The present invention relates to electrochromism inorganic thin film material technology of preparing, specially a kind of system of novel electrochromic film

Make method.

Background technique

Since in recent years, the field of these new energy science and technology such as sustainable development and energy saving, environmental protection

Have become the most worth research of current era and most important project.But currently, the life of the mankind is still led with production method

It when universal use is not yet received in various new energy, to be taken based on the non-renewable energy resources such as petroleum, coal, natural gas

The consumption that various measures reduce the energy, which seems, to be even more important.And annual building energy consumption increases year by year, by adopting an effective means

The energy that reduction is lost because of the building appliances such as door, window, which seems, to be even more important, and improves the energy that window is lost, and improves

The thermal insulation property of window, light-proofness are increasingly becoming a new focus concerned by people.

At the same time, the appearance of energy-saving glass, intelligent window allows it is seen that the new hope of an energy-saving and emission-reduction.It is electroluminescent

Intelligent color-changing window may be implemented to outdoor shine in light transmission with absorb etc. optical properties adjustment, with solve due to

The problem of influence of external environment is to energy loss caused by interior.In addition to on the glass of building, these electroluminescent changes

Color material can also be applied to the anti-string rearview mirror of automobile, be occurred with lowering the unexpected of traffic accident, applied to keeping out the wind for automobile

On glass, glass for vehicle window, to lower the loss for leading to interior thermal insulation property because of external irradiation light.Electrochromic material is also

It can be applied to the carry-on object of all types of displays, clothing etc.

Electrochromism refers under the action of extra electric field, the optical properties (reflectivity, transmitance, absorptivity etc.) of material

Occur to stablize and reversible continuity changes, the color of material can be shown as in appearance, reversible company occurs for transparency

Continuous property variation.Inorganic electrochromic material is mostly transition metal oxide or derivatives thereof.Due to inorganic electrochromic material

Caused by light absorption variation is Dual Implantations or extraction due to ion and electronics, in inorganic electrochromic material (such as WO3

MoO3) in, electrochomeric films have many advantages, such as that coloration efficiency is high, stability is good and ignores blind angle, are widely studied use.But

Existing inorganic electrochromic material is long there are the response time, the problem of deviation occurs after repeatedly carrying out Cyclic voltamogram.

The technology for preparing electrochomeric films at present mainly has following a few classes:

1, chemical vapor deposition

Although the speed of growth of chemical vapour deposition technique film is fast, quality of forming film is good, is easy to control doping, the disadvantage is that setting

It is standby complex, and the temperature requirement needed is higher, and the film to low temperature preparation is simultaneously not suitable for, and the binding force of film is poor,

It is easy to cause and falls off.

2, sol-gel technology

This method is not necessarily to vacuum equipment, and simple process can get the film of ideal thickness and component, usually contain in colloidal sol

There are water and alcohols material, excluding need to be through dry and heat treatment;And during heat treatment, the cracking of film, which is one, to be solved

Certainly the problem of.This theca externa and the adhesive force of substrate are also poor, and film gauge uniformity is difficult to control, and compactness is poor.

3, vacuum evaporation deposits

Vacuum vapour deposition has longer history, studies relatively more thorough under lab, forms the work of many maturations

Skill.This method deposition rate is high, depositional area is big, high production efficiency, and it is laboratory that in addition equipment and operation are also fairly simple

With the technical way for preparing film in industrial production.But, be also the shortcomings that vacuum vapour deposition it is very outstanding, use is this

The film of method preparation has following shortcoming:

1. gather density is small, refractive index is more relatively low than block numerical value.

2. being easy absorption residual gas and steam, optical absorption is big, poor in timeliness.

3. surface, interface out-of-flatness, scattering, surface scattering are big in vivo.

4. stress is high, anisotropy.

5. hardness is low, adhesive force is small, and fastness is poor.

4, pulsed excimer laser valve penetrates deposition (PLD), is the Novel steam ingot technology that developed recently gets up, and has film forming speed

Fast advantage is spent, but the binding force of film layer and substrate is poor, defect is more, and the quality of film vulnerable to pollution, film is bad.

Summary of the invention

In order to solve the problems of prior art, the present invention provides a kind of production side of novel electrochromic film

Method, on transparent conductive material substrate utilize magnetron sputtering method, by the indoor temperature of control chamber, pressure, mix oxygen amount with

And the variable of sputtering, the inorganic electrochromic for first growing one layer of suitable thickness by doped or undoped method on substrate are thin

Film;Then the material system for changing the film that rises again, on the basis of first layer electrochomeric films, rising again one layer has good ion

The TaO of conducting power2Film has electrochromic property TiO2It is thin to obtain the new structural electrochromism of the present invention for film

Film effectively increases the electrochromic property of monofilm electrochomeric films.

In order to reach the goals above, the present invention is the following technical schemes are provided: a kind of production side of novel electrochromic film

Method, comprising the following steps:

Step 1: clean transparent conductive material is placed in magnetron sputtering chamber, and pipeline vacuumizes, and controls sputtering chamber

In total gas flow rate and oxygen and argon gas proportional amount;

Step 2: sputtering chamber temperature being adjusted within the required range, is controlled between molecular pump and vacuum sputtering chamber

Angle is got through, within the required range by gas pressure intensity control in sputtering chamber;

Step 3: pre-sputtering processing being carried out to the required metal targets for carrying out the first tunic growth, for removing original target

Then impurity on material surface opens the sputtering growth process that substrate baffle plate carries out the first tunic, controls sputtering power and sputtering

Time allows the first tunic to increase to suitable thickness;

Step 4: the substrate for the second tunic that will be grown is placed in the same position of substrate with the growth of the first tunic, the

The basis of one layer of inorganic electrochromic film grown carries out the growth of the second tunic;

Step 5: controlling the proportional amount of the total gas flow rate and oxygen and argon gas in second of sputtering chamber, adjust

Chamber temp, and control the indoor gas pressure intensity of chamber;

Step 6: pre-sputtering processing being carried out to the required metal targets for carrying out the second tunic sputtering, for removing original target

Impurity on material surface, then opens the sputtering growth process that substrate baffle plate carries out the second tunic, and sputtering time control is to allowing the

Two tunics increase to suitable thickness;

Second tunic is the protective film of the protective film with electrochromic property or good ionic conductivity.

Preferably, step 3 carries out pre-sputtering processing to the metal tungsten target material that the first tunic is grown, or grows to the first tunic

Metal tungsten target material and Titanium target carry out cosputtering pre-sputtering handle.When the tungsten that step 3 grows the first tunic

When target carries out pre-sputtering processing, sputtering power is controlled between 50w~200w, and sputtering time is between 10min~1h, wanting

The WO of growth3Film thickness monitoring is between 100nm~400nm.When the metal tungsten target material and Titanium that step 3 grows the first tunic

When target carries out the pre-sputtering processing of cosputtering, the sputtering power of metal tungsten target material is controlled in 150w, the sputtering of Titanium target

For power control in 50w, sputtering time is 17min, the WO to be grown3Adulterate TiO2Film film thickness monitoring in 360nm.

The metal targets that second tunic sputters in step 6 are Titanium target or metal tantalum target.Second tunic in step 6

Sputtering growth process, for Titanium target power control in 150w, sputtering time 11min, the TiO to be grown2's

Film thickness monitoring is in 100nm;And metal tantalum target power is controlled in 130w, sputtering time 30min, the TaO to be grown2

Film thickness monitoring in 100nm.

Preferably, pipeline vacuum is evacuated to 1.0x10 in step 1-4Pa~1.0x10-5Pa, total gas flow rate control exist

The proportional amount of 40sccm~100sccm, oxygen and argon gas is controlled 20%~40%;Chamber temp range control in step 2

System is at 30 DEG C~150 DEG C, and gas pressure intensity scope control is in 0.5pa~3pa in sputtering chamber;Total gas flow rate controls in step 5

In 40sccm~100sccm, the control of the proportional amount of oxygen and argon gas 20%~40%, chamber temp control 30 DEG C~

150 DEG C, the indoor gas pressure intensity control of chamber is in 0.5pa~3pa.

Compared with prior art, the invention has the following beneficial effects:

1, the substrate of the electrochomeric films made by the present invention is the ito glass or FTO glass of electrically conducting transparent.Transparent

The method that magnetron sputtering is utilized on conductive material substrate, passes through the indoor temperature of control chamber, pressure, the change for mixing oxygen amount and sputtering

Amount is first become by the inorganic electroluminescence that doped or undoped method grows one layer of suitable thickness (such as 100-350nm) on substrate

Color film;Then change the material system for the film that rises again, on the basis of first layer electrochomeric films, rise again one layer have well from

The TaO of sub- conducting power2Film has weak electrochromic property TiO2Film obtains the new structural electroluminescent change of the present invention

Color film effectively increases the electrochromic property of monofilm electrochomeric films.

2, based on inorganic electrochromic film, by the basis of original electrochomeric films, being superimposed one layer of property

It can stablize, and the film of the associated electrochromic material system of script electrochomeric films performance can be promoted or there is good ion

The protective film of conducting power, by utilizing different inorganic electrochromic materials or the different characteristics with ionic conductivity material

Improve the electrochromic property of single inorganic electrochromic film originally, technique is simple for production, just can in the same chamber

Requirement needed for realizing.

Detailed description of the invention

Fig. 1 is a kind of electricity optically variable films structural schematic diagram made by the method for the present invention;

Fig. 2 is another electricity optically variable films structural schematic diagram made by the method for the present invention;

Fig. 3 is the electricity optically variable films structural schematic diagram that embodiment 1 makes;

Fig. 4 is the electricity optically variable films structural schematic diagram that embodiment 2 makes;

Fig. 5 is the electricity optically variable films structural schematic diagram that embodiment 3 makes.

Specific embodiment

Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are not

It is limited to this.

The present invention utilizes magnetron sputtering using transparent conductive material ito glass or FTO glass as the substrate of electrochomeric films

Method, by the indoor temperature of control magnetron sputtering chamber, pressure, mix the parameters such as oxygen amount and sputtering variable, first led transparent

One layer of inorganic electrochromic film is grown by doped or undoped method on electric material substrate, then in the electroluminescent change of first layer

On the basis of color film, one layer of TaO with good ionic conductivity of growth2Film has electrochromism performance TiO2

Film, to be finally completed the preparation of new structure electrochomeric films of the present invention, as shown in Figure 1.Separately below with different nothings

Machine electrochromism thin-film material is illustrated to implementation process of the invention and is described in detail.

Embodiment 1

Step 1: clean ito glass or FTO glass being placed in magnetron sputtering chamber, pipeline vacuum is evacuated to 1.0x10-4Pa~1.0x10-5Pa, control the indoor parameter of sputtering chamber, control in sputtering chamber gas gross control 40sccm~

Between 100sccm, such as gas gross controlled as 80sccm, the proportional amount of oxygen and argon gas is controlled 20%~40%

Between, the present embodiment controls the ratio of oxygen and argon gas in 24sccm:56sccm.

Step 2: the indoor temperature device of chamber is opened, the temperature range of sputtering chamber is controlled between 30 DEG C~150 DEG C,

Such as chamber temp is adjusted at 50 DEG C;Control the angle of getting through between molecular pump and vacuum sputtering chamber, the present embodiment control

System makes the indoor pressure of sputtering chamber reach 0.5pa~3pa in 18 ° this angle.The present embodiment can control by force chamber inner pressure

System is in 2pa.

Step 3: opening DC power supply, the required metal tungsten target material for carrying out the first tunic growth is carried out at pre-sputtering

Reason, time of processing is 10~15min, for removing the impurity on original target material surface, then opens substrate baffle plate and carries out the

The sputtering growth process of one tunic, sputtering power are can be controlled between 50w~200w, such as control, in 150w, sputtering time can

It is arranged between 10min~1h, sputtering time can be set as 17min by the present embodiment, the WO to be grown3Plastics thickness control exists

Between 100nm~400nm, the WO that ultimately generates3Film thickness can be this numerical value of 360nm.

Step 4: the substrate for the second tunic that will be grown is placed in the same position of substrate with the growth of the first tunic, the

One layer of WO grown3On the basis of electrochomeric films by way of d.c. sputtering Ti target, the second tunic TiO is carried out2's

Sputtering growth, makes the second tunic TiO2It is covered on the first tunic WO3Surface, as shown in Figure 2.

Step 5: controlling the proportional amount of the gas gross and oxygen and argon gas in second of sputtering chamber, wherein oxygen

The proportional amount of gas and argon gas is controlled in 24sccm:56sccm, then opens temperature device again, and the temperature range of chamber is adjusted

It controls within the scope of suitable temperature, such as by temperature at 50 degrees Celsius.

Step 6: controlling the angle of getting through between molecular pump and vacuum chamber, this angle of the present embodiment control at 18 °

On degree, the indoor pressure of chamber is made to reach 2pa.Then DC power supply is opened, to the required Titanium for carrying out the second tunic growth

Target carries out pre-sputtering processing, and the time of processing is then 10~15min is beaten for removing the impurity on original target material surface

The sputtering growth process that substrate baffle plate carries out the second tunic is opened, power control is in 150w, sputtering time 11min, growing

TiO2Film thickness monitoring 100nm this numerically.

It should be noted that in the present embodiment when second of sputtering growth, the ratio of gas gross, oxygen and argon gas in chamber

The numberical range of the parameters such as content, chamber temp range, chamber pressure, pre-sputtering processing time, sputtering time, sputtering power,

It is essentially identical when being grown with first time sputtering, but the growth thickness different from of film.

Embodiment 2

Numberical range selected by sputtering principle and technological parameter of the present embodiment with embodiment 1 is essentially identical, and institute is different

Mainly metal targets.

Step 1: clean ito glass or FTO glass being placed in magnetron sputtering chamber, pipeline vacuum is evacuated to 1.0x10-4Pa~1.0x10-5Pa controls the indoor parameter of sputtering chamber, and controlling gas gross in chamber is 80sccm, wherein oxygen with

The ratio of argon gas is controlled in 24sccm:56sccm.

Step 2: opening the indoor temperature device of sputtering chamber, chamber temp is adjusted at 50 DEG C, control molecular pump and true

Angle is got through between empty sputtering chamber, the present embodiment also controls in 18 ° this angle, reaches the indoor pressure of chamber

2pa。

Step 3: opening DC power supply, the required metal tungsten target material for carrying out the first tunic growth is carried out at pre-sputtering

Reason, the processing time is 10~15min, for removing the impurity on original target material surface, then opens substrate baffle plate and carries out first

The sputtering growth process of tunic, power control is in 150w, and the time of sputtering is 17min, the WO to be grown3Film thickness monitoring exists

This numerical value of 360nm.

Step 4: the substrate for the second tunic that will be grown is placed in the same position of substrate with the growth of the first tunic, the

One layer of WO grown3On the basis of electrochomeric films by way of d.c. sputtering Ta target, the second tunic TaO is carried out2's

Sputtering growth, makes the second tunic TaO2It is covered on the first tunic WO3Surface.

Step 5: the proportional amount of the gas gross and oxygen and argon gas in second of sputtering chamber is controlled, wherein comparing

Then example content control opens temperature device again, the temperature of chamber is adjusted in suitable temperature range in 24sccm:56sccm

It is interior, such as temperature is controlled at 50 degrees Celsius.

Step 6: the angle of getting through between molecular pump and vacuum sputtering chamber is controlled, is controlled in 18 ° this angle,

The indoor pressure of sputtering chamber is set to reach 2pa.Then DC power supply is opened, to the required metal tantalum Ta for carrying out the second tunic growth

Target carries out pre-sputtering processing, and the time of processing is then 10~15min is beaten for removing the impurity on original target material surface

The sputtering growth process that substrate baffle plate carries out the second tunic is opened, for power control in 130w, the time of sputtering is 30min, giving birth to

Long TaO2Film thickness monitoring 100nm this numerically.

Embodiment 3:

Numberical range selected by sputtering principle and technological parameter of the present embodiment with embodiment 1 is essentially identical, and institute is different

Mainly metal targets.

Step 1: clean ito glass or FTO glass being placed in magnetron sputtering chamber, pipeline vacuum is evacuated to 1.0x10-4Pa~1.0x10-5Pa controls the indoor parameter of sputtering chamber, and controlling gas gross in chamber is 80sccm, wherein oxygen with

The ratio of argon gas is controlled in 24sccm:56sccm.

Step 2: opening the indoor temperature device of chamber, the temperature of chamber is adjusted at 50 DEG C, molecular pump and vacuum are controlled

Angle is got through between chamber, controls in 18 ° this angle, the indoor pressure of chamber is made to reach 2pa.

Step 3: open DC power supply, to it is required carry out the first tunic growth metal tungsten target material and Titanium target into

The pre-sputtering of row cosputtering is handled, and the processing time is then 10~15min is beaten for removing the impurity on original target material surface

The sputtering growth process that substrate baffle plate carries out the first tunic is opened, wherein the sputtering power of metal tungsten target material is controlled in 150w, and golden

The sputtering power for belonging to titanium target material is controlled in 50w, and sputtering time is 17min, the WO to be grown3Adulterate TiO2Film film

Thickness control is in this numerical value of 360nm.

Step 4: the substrate for the second tunic that will be grown is placed in the same position of substrate with the growth of the first tunic, the

One layer of WO grown3Adulterate TiO2On the basis of electrochomeric films by way of d.c. sputtering Ta target, the second layer is carried out

Film TaO2Sputtering growth, make the second tunic TaO2It is covered on first layer WO3Adulterate TiO2The surface of film.

Step 5: the proportional amount of the gas gross and oxygen and argon gas in second of sputtering chamber is controlled, wherein comparing

Then example content control opens temperature device again, the temperature of chamber is adjusted in suitable temperature range in 24sccm:56sccm

It is interior, such as temperature is controlled at 50 degrees Celsius.

Step 6: controlling the angle of getting through between molecular pump and vacuum chamber, control in 18 ° this angle, make chamber

Indoor pressure reaches 2pa.Then DC power supply is opened, the required metal tantalum Ta target for carrying out the second tunic growth is carried out

The time of pre-sputtering processing, processing is 10~15min, for removing the impurity on original target material surface, then opens substrate gear

Plate carries out the sputtering growth process of the second tunic, and power control is in 130w, and the time of sputtering is 30min, the TaO to be grown2

Film thickness monitoring in this numerical quantities of 100nm.

As seen from the above embodiment, what the present invention took is that the method for magnetron sputtering carries out plated film, thus film and substrate

Adhesiveness is fabulous.Furthermore film growth rate is high, technological parameter is easy to control, can prepare refractory material film, be able to achieve large area

Film, has the advantages that stability is good, it is convenient to prepare.It is pure due to monofilm for the pure electrochomeric films of monofilm

The electrochromic performances such as electrochomeric films cyclic voltammetric stability still have improved space, pass through compound electrochromic membrane

Preparation, the stability of the electrochromic material of monofilm can actually be improved, improve electrochromic discoloration.

The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment

Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,

It should be equivalent substitute mode, be included within the scope of the present invention.

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