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一种利用磁控溅射制备高光电稳定性透明导电膜的方法 【EN】Method for preparing transparent conductive film with high photoelectric stability by magnetron sputtering

申请(专利)号:CN202010384746.2国省代码:黑龙江 23
申请(专利权)人:【中文】哈尔滨工业大学【EN】HARBIN INSTITUTE OF TECHNOLOGY
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摘要:
【中文】一种利用磁控溅射制备高光电稳定性透明导电膜的方法,本发明涉及制备透明导电膜的方法。本发明要解决现有Ag基多层薄膜在长期或高温条件下会发生光电性能劣化的问题。方法:一、将AZO靶材、Ni靶材及Ag靶材安装在多靶磁控溅射设备的靶位上,抽真空;二、AZO靶材溅射直至第一AZO层厚度为25nm~55nm,Ag靶材溅射直至Ag层厚度为6nm~10nm,Ni靶材溅射直至Ni层厚度为2nm~4nm,AZO靶材溅射直至第二AZO层厚度为25nm~55nm;三、关闭所有电源,取样。本发明可用于太阳能电池的电极、平板显示器等对透明导电薄膜有高光电性能及优异稳定性需求的领域。 【EN】The invention discloses a method for preparing a transparent conductive film with high photoelectric stability by utilizing magnetron sputtering, and relates to a method for preparing a transparent conductive film. The invention aims to solve the problem that the existing Ag-based multilayer film can be degraded in photoelectric performance for a long time or under a high-temperature condition. The method comprises the following steps: firstly, mounting an AZO target material, a Ni target material and an Ag target material on a target position of multi-target magnetron sputtering equipment, and vacuumizing; secondly, sputtering the AZO target until the thickness of the first AZO layer is 25 nm-55 nm, sputtering the Ag target until the thickness of the Ag layer is 6 nm-10 nm, sputtering the Ni target until the thickness of the Ni layer is 2 nm-4 nm, and sputtering the AZO target until the thickness of the second AZO layer is 25 nm-55 nm; and thirdly, turning off all power supplies and sampling. The invention can be used in the fields of electrodes of solar cells, flat panel displays and the like which have high photoelectric property and excellent stability requirements on transparent conductive films.

主权项:
【中文】1.一种利用磁控溅射制备高光电稳定性透明导电膜的方法,其特征在于它是按照以下步骤进行的: 一、将AZO靶材、Ni靶材及Ag靶材安装在多靶磁控溅射设备的靶位上,将清洗干净的衬底固定在托盘上,放入腔室中,然后开启设备,真空度抽至1×10Pa~5×10Pa; 二、在室温下通入氩气,并调节氩气流量为15sccm~40sccm,首先对AZO靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.6Pa~2Pa、氩气流量为15sccm~40sccm及功率为100W~150W的条件下,AZO靶材溅射直至第一AZO层厚度为25nm~55nm,其次对Ag靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.5Pa~1Pa、氩气流量为15sccm~40sccm及功率为40W~80W的条件下,Ag靶材溅射直至Ag层厚度为6nm~10nm,再对Ni靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.5Pa~1Pa、氩气流量为15sccm~40sccm及功率为40W~80W的条件下,Ni靶材溅射直至Ni层厚度为2nm~4nm,最后在室温、真空气压为0.6Pa~2Pa、氩气流量为15sccm~40sccm及功率为100W~150W的条件下,AZO靶材溅射直至第二AZO层厚度为25nm~55nm; 三、关闭所有电源,打开放气阀直至真空腔室气压恢复至大气压,然后打开腔室取样,得到AZO/Ni/Ag/AZO薄膜,即完成利用磁控溅射制备高光电稳定性透明导电膜的方法。 【EN】1. A method for preparing a transparent conductive film with high photoelectric stability by utilizing magnetron sputtering is characterized by comprising the following steps: firstly, mounting an AZO target material, a Ni target material and an Ag target material on a target position of a multi-target magnetron sputtering device, fixing a cleaned substrate on a tray, putting the tray into a chamber, then starting the device, and pumping the vacuum degree to 1 × 10Pa~5×10Pa; Secondly, introducing argon gas at room temperature, adjusting the argon gas flow to be 15 sccm-40 sccm, firstly carrying out pre-sputtering on the AZO target for 3 min-15 min, then carrying out pre-sputtering on the Ag target for 3 min-15 min under the conditions of room temperature, vacuum pressure of 0.6 Pa-2 Pa, argon gas flow of 15 sccm-40 sccm and power of 100W-150W until the thickness of the first AZO layer is 25 nm-55 nm, then carrying out pre-sputtering on the Ag target for 3 min-15 min, then carrying out pre-sputtering on the Ni target for 3 min-15 min under the conditions of room temperature, vacuum pressure of 0.5 Pa-1 Pa, argon gas flow of 15 sccm-40 sccm and power of 40W-80W until the thickness of the Ag layer is 6 nm-10 nm, then carrying out pre-sputtering on the argon target for 3 min-15 min, and then carrying out pre-sputtering on the AZO target under the conditions of room temperature, vacuum pressure of 0.5 Pa-1 Pa, argon gas flow of 15 sccm-40 sccm and power of 40W, sputtering the Ni target until the thickness of the Ni layer is 2 nm-4 nm, and finally sputtering the AZO target until the thickness of the second AZO layer is 25 nm-55 nm under the conditions of room temperature, vacuum pressure of 0.6 Pa-2 Pa, argon flow of 15 sccm-40 sccm and power of 100W-150W; and thirdly, closing all power supplies, opening a vent valve until the air pressure of the vacuum chamber is restored to the atmospheric pressure, then opening the chamber for sampling to obtain the AZO/Ni/Ag/AZO film, and finally completing the method for preparing the transparent conductive film with high photoelectric stability by utilizing magnetron sputtering.


说明书

【中文】

一种利用磁控溅射制备高光电稳定性透明导电膜的方法

技术领域

本发明涉及制备透明导电膜的方法。

背景技术

目前在显示器件、太阳能电池、低辐射(low-E)玻璃、电磁屏蔽窗等多个领域都对透明导电薄膜(TCF)有广泛的应用需求。当前产业化的TCF主要是一种透明导电氧化物(TCO)——掺锡氧化铟(Indium-doped Tin Oxide,ITO),但是随着行业发展其应用越来越受到TCO这种物质本身质脆、力学性能差,高光电性能需要经高温制程来获得以及制备成本相对较高等限制,此外铟(In)易被还原、易扩散、具有毒性等问题亦不可忽略,因此ITO薄膜无法同时满足相关领域对高透过率、高电导率、稳定性以及制作工艺和成本等要求。金属薄膜具有电阻率低,延展性能好的优点,但透光性和耐热性较差,长时间在空气中容易氧化和磨损。通过将其与适合的金属氧化物结合得到电介质/金属/电介质(DMD)结构复合薄膜,可以将金属膜与电介质层的优势互补:中间的夹层金属可以保证整体薄膜的高导电性,且其优异的延展性可以保证DMD薄膜的两侧电介质被弯折破坏时仍保持优异的导电性能,两侧的电介质可以对金属层起到一定的保护作用,使其不容易被磨损或者氧化,并抑制金属层对光的反射,提高整体薄膜的性能。由于金属层的存在,DMD结构薄膜与单层TCO相比还具有室温下制备即可获得高光电性能的优点,可以节约能耗和简化工艺,更利于实现大面积低成本的制备,在满足各领域的需求方面具有巨大的潜力。

目前研究者针对DMD多层薄膜结构的光电性能已展开大量研究并取得了显著的成果,但在实际应用中,太阳能电池、平板显示、其他各类光电器件及电磁屏蔽涂层、透明隔热玻璃等诸多领域中在涉及透明导电薄膜的制备和使用过程中都对其稳定性提出了高要求,研制具有良好稳定性的薄膜对相关光电器件及涂层的制备工艺简化以及使用寿命和环境适应性的提高意义重大。当前DMD结构中常用的金属夹层是银(Ag),这是由于Ag与其他金属相比导电性优异,且在可见光波段的消光系数低,对光的吸收和反射少,因此Ag基多层薄膜光电性能优异,但实际使用时由于电介质对Ag膜的保护不彻底,不能抑制在长期或高温条件下Ag原子的扩散、团聚和Ag层的氧化,导致薄膜会发生光电性能的劣化,无法满足相关产业对透明导电薄膜在长期条件下或高温环境中保持正常性能的要求。经研究证明,以光电性能优、成本低廉的掺铝氧化锌(AZO)作为Ag基多层薄膜的电介质材料得到的AZO/Ag/AZO薄膜在真空条件下处理温度高于300℃后性能即发生明显下降。

由此可知,现有Ag基多层薄膜在长期或高温条件下会发生光电性能劣化的问题。

发明内容

本发明要解决现有Ag基多层薄膜在长期或高温条件下会发生光电性能劣化的问题,而提供一种利用磁控溅射制备高光电稳定性透明导电膜的方法,在保证具有同样优异的光电性能的同时,达到在空气中的高温稳定性与现有同结构薄膜相比大幅提升的效果。

一种利用磁控溅射制备高光电稳定性透明导电膜的方法,它是按照以下步骤进行的:

一、将AZO靶材、Ni靶材及Ag靶材安装在多靶磁控溅射设备的靶位上,将清洗干净的衬底固定在托盘上,放入腔室中,然后开启设备,真空度抽至1×10-4Pa~5×10-4Pa;

二、在室温下通入氩气,并调节氩气流量为15sccm~40sccm,首先对AZO靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.6Pa~2Pa、氩气流量为15sccm~40sccm及功率为100W~150W的条件下,AZO靶材溅射直至第一AZO层厚度为25nm~55nm,其次对Ag靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.5Pa~1Pa、氩气流量为15sccm~40sccm及功率为40W~80W的条件下,Ag靶材溅射直至Ag层厚度为6nm~10nm,再对Ni靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.5Pa~1Pa、氩气流量为15sccm~40sccm及功率为40W~80W的条件下,Ni靶材溅射直至Ni层厚度为2nm~4nm,最后在室温、真空气压为0.6Pa~2Pa、氩气流量为15sccm~40sccm及功率为100W~150W的条件下,AZO靶材溅射直至第二AZO层厚度为25nm~55nm;

三、关闭所有电源,打开放气阀直至真空腔室气压恢复至大气压,然后打开腔室取样,得到AZO/Ni/Ag/AZO薄膜,即完成利用磁控溅射制备高光电稳定性透明导电膜的方法。

原理:为克服实际使用中Ag基多层薄膜的功能退化,本发明提出引入阻挡层Ni来阻止Ag原子的扩散和进一步团聚,同时Ni发生氧化时形成的氧化膜致密,可以有效防止内层Ag的进一步氧化,且Ni的导电性优异,氧化膜通常为p型半导体,将其引入后得到的薄膜既可以保持高光电性能,还获得了优异的稳定性(在更易出现氧化扩散等现象的空气气氛中500℃处理后性能仍保持稳定),而且这种薄膜的制备工艺简单,耗时短,能耗少,在太阳能电池、平板显示器、导电涂层等领域都具有很高的应用价值。

本发明的有益效果是:

本发明采用磁控溅射法在衬底上制备了AZO/Ni/Ag/AZO薄膜,工艺操作简单方便,所需设备和材料成本较低,制备过程中不产生污染,制备的AZO/Ni/Ag/AZO薄膜具有优异的光电性能,可见光透过率可达78%以上,平均透过率大约74%,对应的载流子浓度可达1022cm-3数量级,电阻率数量级为10-5Ω·cm,面电阻仅6.352Ω/sq,平均透过率与同样条件下得到的AZO/Ag/AZO相比下降约6%,但面电阻值下降约32%,电学性能明显优化,薄膜综合光电性能优异。经过在空气中进行高温处理实验发现,该薄膜经过500℃处理后仍可以保持与室温沉积样品相差不多的面电阻值,且透光性得到了改善,与AZO/Ag/AZO薄膜相比光电稳定性大幅提升。本发明制备的高光电稳定性透明导电膜在保证具有同样优异的光电性能的同时,达到在空气中的高温稳定性,与现有同结构薄膜相比大幅提升的效果。此种薄膜材料的研制实现了对透明导电薄膜高光电性能及稳定性的要求,为透明导电薄膜材料的设计思路开拓了一个新方向,有利于后续更深入的应用研究。

本发明用于一种利用磁控溅射制备高光电稳定性透明导电膜的方法。

附图说明

图1为AZO/Ni/Ag/AZO薄膜的透光率曲线,1为实施例一制备的AZO/Ni/Ag/AZO薄膜,2为实施例二制备的AZO/Ni/Ag/AZO薄膜,3为实施例三制备的AZO/Ni/Ag/AZO薄膜,4为实施例四制备的AZO/Ni/Ag/AZO薄膜,5为实施例五制备的AZO/Ni/Ag/AZO薄膜;

图2为实施例一至五制备的AZO/Ni/Ag/AZO薄膜的平均透光率和面电阻值变化曲线;

图3为实施例一至五制备的AZO/Ni/Ag/AZO薄膜的电性能曲线;

图4为实施例四高温处理后的AZO/Ni/Ag/AZO薄膜的平均透光率和面电阻的变化曲线。

具体实施方式

本发明技术方案不局限于以下所列举的具体实施方式,还包括各具体实施方式之间的任意组合。

具体实施方式一:本实施方式为一种利用磁控溅射制备高光电稳定性透明导电膜的方法,它是按照以下步骤进行的:

一、将AZO靶材、Ni靶材及Ag靶材安装在多靶磁控溅射设备的靶位上,将清洗干净的衬底固定在托盘上,放入腔室中,然后开启设备,真空度抽至1×10-4Pa~5×10-4Pa;

二、在室温下通入氩气,并调节氩气流量为15sccm~40sccm,首先对AZO靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.6Pa~2Pa、氩气流量为15sccm~40sccm及功率为100W~150W的条件下,AZO靶材溅射直至第一AZO层厚度为25nm~55nm,其次对Ag靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.5Pa~1Pa、氩气流量为15sccm~40sccm及功率为40W~80W的条件下,Ag靶材溅射直至Ag层厚度为6nm~10nm,再对Ni靶材进行预溅射,预溅射时间为3min~15min,然后在室温、真空气压为0.5Pa~1Pa、氩气流量为15sccm~40sccm及功率为40W~80W的条件下,Ni靶材溅射直至Ni层厚度为2nm~4nm,最后在室温、真空气压为0.6Pa~2Pa、氩气流量为15sccm~40sccm及功率为100W~150W的条件下,AZO靶材溅射直至第二AZO层厚度为25nm~55nm;

三、关闭所有电源,打开放气阀直至真空腔室气压恢复至大气压,然后打开腔室取样,得到AZO/Ni/Ag/AZO薄膜,即完成利用磁控溅射制备高光电稳定性透明导电膜的方法。

本实施方式步骤一中使用机械泵和分子泵抽真空,真空度抽至1×10-4Pa~5×10-4Pa。

本实施方式步骤一由于Ni靶材具有铁磁性,使得溅射过程中大部分磁场几乎完全从靶材内部通过,无法形成有效的电子束缚区域,使得磁控溅射不能进行,因此,Ni靶材需要安装在强磁靶位以使得靶材表面的磁场达到正常磁控溅射时要求的磁场强度。

本实施方式为提高薄膜的稳定性,防止Ag层的性能退化,本实施方式在Ag基DMD结构中引入镍(Ni)层,Ni可以阻挡金属原子扩散,且电导率高,耐腐蚀和耐氧化性好(Ni层被氧化后形成的镍的氧化物十分稳定,可以有效保护银原子不被氧化)。电介质层选用AZO,这种氧化物与ITO相比,具有无毒,原材料广泛,成本低廉,透光性高(可见光消光系数几乎为0)等优势。通过设计制备AZO/Ni/Ag/AZO薄膜,使薄膜在实现优异光电性能的同时,优化其在使用环境中的光电稳定性,并满足生产中对低成本和环保方面的要求。

本实施方式的有益效果是:本实施方式采用磁控溅射法在衬底上制备了AZO/Ni/Ag/AZO薄膜,工艺操作简单方便,所需设备和材料成本较低,制备过程中不产生污染,制备的AZO/Ni/Ag/AZO薄膜具有优异的光电性能,可见光透过率可达78%以上,平均透过率大约74%,对应的载流子浓度可达1022cm-3数量级,电阻率数量级为10-5Ω·cm,面电阻仅6.352Ω/sq,平均透过率与同样条件下得到的AZO/Ag/AZO相比下降约6%,但面电阻值下降约32%,电学性能明显优化,薄膜综合光电性能优异。经过在空气中进行高温处理实验发现,该薄膜经过500℃处理后仍可以保持与室温沉积样品相差不多的面电阻值,且透光性得到了改善,与AZO/Ag/AZO薄膜相比光电稳定性大幅提升。本实施方式制备的高光电稳定性透明导电膜在保证具有同样优异的光电性能的同时,达到在空气中的高温稳定性,与现有同结构薄膜相比大幅提升的效果。此种薄膜材料的研制实现了对透明导电薄膜高光电性能及稳定性的要求,为透明导电薄膜材料的设计思路开拓了一个新方向,有利于后续更深入的应用研究。

具体实施方式二:本实施方式与具体实施方式一不同的是:步骤一中所述的清洗干净的衬底形状为边长为1cm~2cm的方形。其它与具体实施方式一相同。

具体实施方式三:本实施方式与具体实施方式一或二之一不同的是:步骤一中所述的清洗干净的衬底的清洗过程为:将衬底置于无水乙醇溶液中超声清洗10min,再用去离子水冲洗。其它与具体实施方式一或二相同。

具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第一AZO层厚度为30nm~55nm;步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第二AZO层厚度为30nm~55nm。其它与具体实施方式一至三相同。

具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第一AZO层厚度为35nm~55nm;步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第二AZO层厚度为35nm~55nm。其它与具体实施方式一至四相同。

具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第一AZO层厚度为40nm~55nm;步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第二AZO层厚度为40nm~55nm。其它与具体实施方式一至五之一相同。

具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第一AZO层厚度为45nm~55nm;步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第二AZO层厚度为45nm~55nm。其它与具体实施方式一至六相同。

具体实施方式八:本实施方式与具体实施方式一至七之一不同的是:步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第一AZO层厚度为50nm~55nm;步骤二中在室温、真空气压为1Pa~1.2Pa、氩气流量为19sccm~20sccm及功率为120W~130W的条件下,AZO靶材溅射直至第二AZO层厚度为50nm~55nm。其它与具体实施方式一至七相同。

具体实施方式九:本实施方式与具体实施方式一至八之一不同的是:步骤二中在室温、真空气压为0.5Pa~0.6Pa、氩气流量为19sccm~20sccm及功率为40W~50W的条件下,Ag靶材溅射直至Ag层厚度为8nm~9nm。其它与具体实施方式一至八相同。

具体实施方式十:本实施方式与具体实施方式一至九之一不同的是:步骤二中在室温、真空气压为0.5Pa~0.6Pa、氩气流量为19sccm~20sccm及功率为40W~50W的条件下,Ni靶材溅射直至Ni层厚度为3nm~4nm。其它与具体实施方式一至九相同。

采用以下实施例验证本发明的有益效果:

实施例一:

一种利用磁控溅射制备高光电稳定性透明导电膜的方法,它是按照以下步骤进行的:

一、将AZO靶材、Ni靶材及Ag靶材安装在多靶磁控溅射设备的靶位上,将清洗干净的衬底固定在托盘上,放入腔室中,然后开启设备,真空度抽至4.5×10-4Pa;

二、在室温下通入氩气,并调节氩气流量为20sccm,首先对AZO靶材进行预溅射,预溅射时间为5min,然后在室温、真空气压为1Pa、氩气流量为20sccm及功率为120W的条件下,AZO靶材溅射直至第一AZO层厚度为30nm,其次对Ag靶材进行预溅射,预溅射时间为3min,然后在室温、真空气压为0.5Pa、氩气流量为20sccm及功率为40W的条件下,Ag靶材溅射直至Ag层厚度为8nm,再对Ni靶材进行预溅射,预溅射时间为3min,然后在室温、真空气压为0.5Pa、氩气流量为20sccm及功率为40W的条件下,Ni靶材溅射直至Ni层厚度为4nm,最后在室温、真空气压为1Pa、氩气流量为20sccm及功率为120W的条件下,AZO靶材溅射直至第二AZO层厚度为30nm;

三、关闭所有电源,打开放气阀直至真空腔室气压恢复至大气压,然后打开腔室取样,得到AZO/Ni/Ag/AZO薄膜,即完成利用磁控溅射制备高光电稳定性透明导电膜的方法。

步骤一中所述的清洗干净的衬底形状为边长为1cm的方形。

步骤一中所述的清洗干净的衬底的清洗过程为:将衬底置于无水乙醇溶液中超声清洗10min,再用去离子水冲洗。

所述的衬底为玻璃衬底。

步骤一中所述的AZO靶材即掺铝的氧化锌,其中ZnO与Al2O3的质量比为98:2。

本实施例制备的AZO/Ni/Ag/AZO薄膜总厚度约为72nm。

实施例二:本实施例与实施例一不同的是:步骤二中AZO靶材溅射直至第一AZO层厚度为35nm;步骤二中AZO靶材溅射直至第二AZO层厚度为35nm。其它与实施例一相同。

本实施例制备的AZO/Ni/Ag/AZO薄膜总厚度约为82nm。

实施例三:本实施例与实施例一不同的是:步骤二中AZO靶材溅射直至第一AZO层厚度为40nm;步骤二中AZO靶材溅射直至第二AZO层厚度为40nm。其它与实施例一相同。

本实施例制备的AZO/Ni/Ag/AZO薄膜总厚度约为92nm。

实施例四:本实施例与实施例一不同的是:步骤二中AZO靶材溅射直至第一AZO层厚度为45nm;步骤二中AZO靶材溅射直至第二AZO层厚度为45nm。其它与实施例一相同。

本实施例制备的AZO/Ni/Ag/AZO薄膜总厚度约为102nm。

实施例五:本实施例与实施例一不同的是:步骤二中AZO靶材溅射直至第一AZO层厚度为50nm;步骤二中AZO靶材溅射直至第二AZO层厚度为50nm。其它与实施例一相同。

本实施例制备的AZO/Ni/Ag/AZO薄膜总厚度约为112nm。

实施例一至五制备的AZO/Ni/Ag/AZO薄膜中Ni层厚度均为4nm,Ag层厚度均为8nm,实施例一中第一AZO层及第二AZO层厚度均为30nm、实施例二中第一AZO层及第二AZO层厚度均为35nm、实施例三中第一AZO层及第二AZO层厚度均为40nm、实施例四中第一AZO层及第二AZO层厚度均为45nm、实施例五中第一AZO层及第二AZO层厚度均为50nm。

图1为AZO/Ni/Ag/AZO薄膜的透光率曲线,1为实施例一制备的AZO/Ni/Ag/AZO薄膜,2为实施例二制备的AZO/Ni/Ag/AZO薄膜,3为实施例三制备的AZO/Ni/Ag/AZO薄膜,4为实施例四制备的AZO/Ni/Ag/AZO薄膜,5为实施例五制备的AZO/Ni/Ag/AZO薄膜。由图可知,在人眼敏感的550nm波长处,随着AZO层厚度的增加,透过率逐渐增加。AZO层厚度为50nm对应的样品最高透过率高于其他样品,达到大约80%。

图2为实施例一至五制备的AZO/Ni/Ag/AZO薄膜的平均透光率和面电阻值变化曲线。由图可知,可见光透过率平均值随着AZO层厚度的增加先增大后减小,当AZO膜厚为45nm时,薄膜的平均透光率最高(大约74%),同时面电阻达到最低,仅有6.352Ω/sq,光电性能优异,平均透过率与同样条件下得到的AZO/Ag/AZO相比下降约6%,但面电阻值下降约32%。

图3为实施例一至五制备的AZO/Ni/Ag/AZO薄膜的电性能曲线。图中载流子浓度Nb对应左边坐标轴,载流子迁移率μ、面电阻Rs分别对应于右边第一、第二条坐标轴。由图可知,AZO厚度为40nm时,薄膜的载流子迁移率μ最高;AZO厚度为45nm时薄膜中载流子浓度Nb最高,可达1022/cm3数量级,不同AZO厚度下薄膜的电阻率均达到了10-5Ω·cm数量级,导电性优异。

将实施例四制备的AZO/Ni/Ag/AZO薄膜在300℃、400℃、500℃及600℃的条件下,分别进行高温处理,具体如下:

将实施例四制备的AZO/Ni/Ag/AZO薄膜置于管式炉中,在空气气氛下,以升温速率为8℃/min,将温度升温至300℃,在温度为300℃的条件下,高温处理0.5h,得到高温处理后的AZO/Ni/Ag/AZO薄膜;

将实施例四制备的AZO/Ni/Ag/AZO薄膜置于管式炉中,在空气气氛下,以升温速率为8℃/min,升温至400℃,在温度为400℃的条件下,高温处理0.5h,得到高温处理后的AZO/Ni/Ag/AZO薄膜;

将实施例四制备的AZO/Ni/Ag/AZO薄膜置于管式炉中,在空气气氛下,以升温速率为8℃/min,升温至500℃,在温度为500℃的条件下,高温处理0.5h,得到高温处理后的AZO/Ni/Ag/AZO薄膜;

将实施例四制备的AZO/Ni/Ag/AZO薄膜置于管式炉中,在空气气氛下,以升温速率为8℃/min,升温至600℃,在温度为600℃的条件下,高温处理0.5h,得到高温处理后的AZO/Ni/Ag/AZO薄膜。

图4为实施例四不同高温处理后的AZO/Ni/Ag/AZO薄膜的平均透光率和面电阻的变化曲线。由曲线可知,薄膜在可见光波段平均透过率随处理环境温度的升高逐渐上升,直至600℃出现大幅提升,达到大约82%;薄膜的面电阻经300℃和400℃处理后持续下降,导电性得到优化,500℃时略有增加,电学性能基本保持稳定,直至600℃处理后面电阻才发生明显增大,导电性变差。

【EN】

Method for preparing transparent conductive film with high photoelectric stability by magnetron sputtering

Technical Field

The present invention relates to a method for producing a transparent conductive film.

Background

At present, Transparent Conductive Films (TCFs) are widely applied in the fields of display devices, solar cells, low-emissivity (low-E) glass, electromagnetic shielding windows and the like. Currently, the industrialized TCF is mainly a Transparent Conductive Oxide (TCO) -Indium-doped Tin Oxide (ITO), but the application of the TCF is increasingly limited by the fact that the TCO is brittle, has poor mechanical properties, requires a high-temperature process for obtaining high photoelectric properties, has relatively high preparation cost, and the like as the industry develops, and In addition, the problems of easy reduction, easy diffusion, toxicity and the like of Indium (In) are not negligible, so that the ITO film cannot simultaneously meet the requirements of related fields on high transmittance, high conductivity, stability, manufacturing process, cost and the like. The metal thin film has the advantages of low resistivity and good ductility, but has poor light transmittance and heat resistance, and is easily oxidized and worn in the air for a long time. The advantages of the metal film and the dielectric layer can be complemented by combining it with a suitable metal oxide to obtain a dielectric/metal/dielectric (DMD) structured composite film: the middle interlayer metal can ensure high conductivity of the whole film, excellent ductility of the middle interlayer metal can ensure that dielectric media on two sides of the DMD film still keep excellent conductivity when being bent and damaged, the dielectric media on the two sides can play a certain protection role on the metal layer, so that the metal layer is not easily abraded or oxidized, reflection of the metal layer on light is inhibited, and the performance of the whole film is improved. Compared with single-layer TCO, the DMD structure film has the advantage that high photoelectric property can be obtained by preparation at room temperature due to the existence of the metal layer, so that energy consumption can be saved, the process can be simplified, large-area and low-cost preparation can be realized, and the DMD structure film has great potential in meeting the requirements of various fields.

At present, researchers have carried out a great deal of research on the photoelectric properties of a DMD multilayer film structure and obtained remarkable results, but in practical application, in the fields of solar cells, flat panel displays, other various photoelectric devices, electromagnetic shielding coatings, transparent heat-insulating glass and the like, high requirements are put on the stability of the transparent conductive film in the preparation and use processes of the transparent conductive film, and the research of the film with good stability has great significance for simplifying the preparation process of the related photoelectric devices and coatings and improving the service life and the environmental adaptability. The silver (Ag) interlayer commonly used in the current DMD structure has excellent conductivity compared with other metals, has low extinction coefficient in a visible light band, and has less absorption and reflection of light, so that the Ag-based multilayer film has excellent photoelectric performance, but in actual use, because the Ag film is not completely protected by a dielectric, the diffusion and agglomeration of Ag atoms and the oxidation of the Ag layer under a long-term or high-temperature condition cannot be inhibited, the photoelectric performance of the film can be degraded, and the requirement of related industries on the maintenance of normal performance of the transparent conductive film under a long-term or high-temperature environment cannot be met. Researches prove that the performance of the AZO/Ag/AZO film obtained by taking aluminum-doped zinc oxide (AZO) with excellent photoelectric performance and low cost as the dielectric material of the Ag-based multilayer film is obviously reduced after the processing temperature is higher than 300 ℃ under the vacuum condition.

It is known from the above that the conventional Ag-based multilayer thin film has a problem of deterioration of photoelectric properties over a long period of time or under high temperature conditions.

Disclosure of Invention

The invention aims to solve the problem that the existing Ag-based multilayer film can be deteriorated in photoelectric property for a long time or under a high-temperature condition, and provides a method for preparing a transparent conductive film with high photoelectric stability by utilizing magnetron sputtering, so that the same excellent photoelectric property is ensured, and simultaneously, the effect of greatly improving the high-temperature stability in the air compared with the existing film with the same structure is achieved.

A method for preparing a transparent conductive film with high photoelectric stability by magnetron sputtering is carried out according to the following steps:

firstly, mounting an AZO target material, a Ni target material and an Ag target material on a target position of a multi-target magnetron sputtering device, fixing a cleaned substrate on a tray, putting the tray into a chamber, then starting the device, and pumping the vacuum degree to 1 × 10-4Pa~5×10-4Pa;

Secondly, introducing argon gas at room temperature, adjusting the argon gas flow to be 15 sccm-40 sccm, firstly carrying out pre-sputtering on the AZO target for 3 min-15 min, then carrying out pre-sputtering on the Ag target for 3 min-15 min under the conditions of room temperature, vacuum pressure of 0.6 Pa-2 Pa, argon gas flow of 15 sccm-40 sccm and power of 100W-150W until the thickness of the first AZO layer is 25 nm-55 nm, then carrying out pre-sputtering on the Ag target for 3 min-15 min, then carrying out pre-sputtering on the Ni target for 3 min-15 min under the conditions of room temperature, vacuum pressure of 0.5 Pa-1 Pa, argon gas flow of 15 sccm-40 sccm and power of 40W-80W until the thickness of the Ag layer is 6 nm-10 nm, then carrying out pre-sputtering on the argon target for 3 min-15 min, and then carrying out pre-sputtering on the AZO target under the conditions of room temperature, vacuum pressure of 0.5 Pa-1 Pa, argon gas flow of 15 sccm-40 sccm and power of 40W, sputtering the Ni target until the thickness of the Ni layer is 2 nm-4 nm, and finally sputtering the AZO target until the thickness of the second AZO layer is 25 nm-55 nm under the conditions of room temperature, vacuum pressure of 0.6 Pa-2 Pa, argon flow of 15 sccm-40 sccm and power of 100W-150W;

and thirdly, closing all power supplies, opening a vent valve until the air pressure of the vacuum chamber is restored to the atmospheric pressure, then opening the chamber for sampling to obtain the AZO/Ni/Ag/AZO film, and finally completing the method for preparing the transparent conductive film with high photoelectric stability by utilizing magnetron sputtering.

The principle is as follows: in order to overcome the function degradation of an Ag-based multilayer film in practical use, the invention provides that a barrier layer Ni is introduced to prevent Ag atoms from diffusing and further agglomerating, an oxidation film formed when Ni is oxidized is compact, the further oxidation of inner-layer Ag can be effectively prevented, the conductivity of Ni is excellent, the oxidation film is usually a p-type semiconductor, the film obtained after the introduction of the Ni can keep high photoelectric property, and excellent stability is obtained (the performance is still stable after the treatment at 500 ℃ in an air atmosphere in which phenomena such as oxidation diffusion and the like are more likely to occur), and the film has the advantages of simple preparation process, short time consumption, low energy consumption and high application value in the fields of solar cells, flat panel displays, conductive coatings and the like.

The invention has the beneficial effects that:

the invention adopts a magnetron sputtering methodThe AZO/Ni/Ag/AZO film is prepared on the substrate, the process operation is simple and convenient, the cost of required equipment and materials is low, no pollution is generated in the preparation process, the prepared AZO/Ni/Ag/AZO film has excellent photoelectric property, the visible light transmittance can reach over 78 percent, the average transmittance is about 74 percent, and the corresponding carrier concentration can reach 10 percent22cm-3Of the order of 10 resistivity-5Omega cm, the surface resistance is only 6.352 omega/sq, the average transmittance is reduced by about 6% compared with AZO/Ag/AZO obtained under the same conditions, but the surface resistance is reduced by about 32%, the electrical property is obviously optimized, and the comprehensive photoelectric property of the film is excellent. The experiment of high-temperature treatment in the air shows that the film can still keep the surface resistance value which is not much different from that of a room-temperature deposition sample after being treated at 500 ℃, the light transmittance is improved, and the photoelectric stability is greatly improved compared with an AZO/Ag/AZO film. The transparent conductive film with high photoelectric stability, prepared by the invention, has the same excellent photoelectric property, achieves high-temperature stability in air, and greatly improves the effect compared with the existing film with the same structure. The development of the film material realizes the requirements on the high photoelectric property and stability of the transparent conductive film, develops a new direction for the design idea of the transparent conductive film material, and is beneficial to the subsequent deeper application research.

The invention provides a method for preparing a transparent conductive film with high photoelectric stability by magnetron sputtering.

Drawings

FIG. 1 is a graph of transmittance of AZO/Ni/Ag/AZO films, where 1 is the AZO/Ni/Ag/AZO film prepared in example one, 2 is the AZO/Ni/Ag/AZO film prepared in example two, 3 is the AZO/Ni/Ag/AZO film prepared in example three, 4 is the AZO/Ni/Ag/AZO film prepared in example four, and 5 is the AZO/Ni/Ag/AZO film prepared in example five;

FIG. 2 is a graph showing the variation of the average transmittance and the sheet resistance of the AZO/Ni/Ag/AZO thin films prepared in examples one to five;

FIG. 3 is an electrical property curve of AZO/Ni/Ag/AZO thin films prepared in examples one to five;

FIG. 4 is a graph showing the average transmittance and the area resistance of the AZO/Ni/Ag/AZO thin film after the four high temperature treatments of example.

Detailed Description

The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.

The first embodiment is as follows: the embodiment is a method for preparing a transparent conductive film with high photoelectric stability by magnetron sputtering, which is carried out according to the following steps:

firstly, mounting an AZO target material, a Ni target material and an Ag target material on a target position of a multi-target magnetron sputtering device, fixing a cleaned substrate on a tray, putting the tray into a chamber, then starting the device, and pumping the vacuum degree to 1 × 10-4Pa~5×10-4Pa;

Secondly, introducing argon gas at room temperature, adjusting the argon gas flow to be 15 sccm-40 sccm, firstly carrying out pre-sputtering on the AZO target for 3 min-15 min, then carrying out pre-sputtering on the Ag target for 3 min-15 min under the conditions of room temperature, vacuum pressure of 0.6 Pa-2 Pa, argon gas flow of 15 sccm-40 sccm and power of 100W-150W until the thickness of the first AZO layer is 25 nm-55 nm, then carrying out pre-sputtering on the Ag target for 3 min-15 min, then carrying out pre-sputtering on the Ni target for 3 min-15 min under the conditions of room temperature, vacuum pressure of 0.5 Pa-1 Pa, argon gas flow of 15 sccm-40 sccm and power of 40W-80W until the thickness of the Ag layer is 6 nm-10 nm, then carrying out pre-sputtering on the argon target for 3 min-15 min, and then carrying out pre-sputtering on the AZO target under the conditions of room temperature, vacuum pressure of 0.5 Pa-1 Pa, argon gas flow of 15 sccm-40 sccm and power of 40W, sputtering the Ni target until the thickness of the Ni layer is 2 nm-4 nm, and finally sputtering the AZO target until the thickness of the second AZO layer is 25 nm-55 nm under the conditions of room temperature, vacuum pressure of 0.6 Pa-2 Pa, argon flow of 15 sccm-40 sccm and power of 100W-150W;

and thirdly, closing all power supplies, opening a vent valve until the air pressure of the vacuum chamber is restored to the atmospheric pressure, then opening the chamber for sampling to obtain the AZO/Ni/Ag/AZO film, and finally completing the method for preparing the transparent conductive film with high photoelectric stability by utilizing magnetron sputtering.

In the first step of the present embodiment, a mechanical pump and a molecular pump are used to pump vacuumThe void degree is pumped to 1 × 10-4Pa~5×10-4Pa。

In the first step of the present embodiment, since the Ni target has ferromagnetism, most of the magnetic field almost completely passes through the inside of the target during sputtering, and an effective electron confinement region cannot be formed, so that magnetron sputtering cannot be performed.

In order to improve the stability of the film and prevent the performance degradation of the Ag layer, the nickel (Ni) layer is introduced into the Ag-based DMD structure, Ni can prevent metal atoms from diffusing, and the Ag-based DMD structure has high conductivity, good corrosion resistance and good oxidation resistance (the oxide of the nickel formed after the Ni layer is oxidized is very stable, and can effectively protect the silver atoms from being oxidized). The dielectric layer is AZO, and compared with ITO, the oxide has the advantages of no toxicity, wide raw materials, low cost, high light transmittance (the extinction coefficient of visible light is almost 0) and the like. Through the design and preparation of the AZO/Ni/Ag/AZO film, the film realizes excellent photoelectric performance, optimizes the photoelectric stability in the use environment and meets the requirements on low cost and environmental protection in production.

The beneficial effects of the embodiment are as follows: the method adopts the magnetron sputtering method to prepare the AZO/Ni/Ag/AZO film on the substrate, the process operation is simple and convenient, the cost of the required equipment and materials is lower, no pollution is generated in the preparation process, the prepared AZO/Ni/Ag/AZO film has excellent photoelectric property, the visible light transmittance can reach more than 78 percent, the average transmittance is about 74 percent, and the corresponding carrier concentration can reach 10 percent22cm-3Of the order of 10 resistivity-5Omega cm, the surface resistance is only 6.352 omega/sq, the average transmittance is reduced by about 6% compared with AZO/Ag/AZO obtained under the same conditions, but the surface resistance is reduced by about 32%, the electrical property is obviously optimized, and the comprehensive photoelectric property of the film is excellent. The experiment of high-temperature treatment in the air shows that the film can still keep the surface resistance value which is not much different from that of a room-temperature deposition sample after being treated at 500 ℃, the light transmittance is improved, and the photoelectric stability is greatly improved compared with an AZO/Ag/AZO film. The present embodimentThe transparent conductive film with high photoelectric stability can achieve high-temperature stability in the air while ensuring the same excellent photoelectric property, and compared with the existing film with the same structure, the film with the high photoelectric stability has the greatly improved effect. The development of the film material realizes the requirements on the high photoelectric property and stability of the transparent conductive film, develops a new direction for the design idea of the transparent conductive film material, and is beneficial to the subsequent deeper application research.

The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the shape of the cleaned substrate in the step one is a square with the side length of 1 cm-2 cm. The rest is the same as the first embodiment.

The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the cleaning process of the cleaned substrate in the first step is as follows: and (3) placing the substrate in an absolute ethyl alcohol solution, ultrasonically cleaning for 10min, and then washing with deionized water. The other is the same as in the first or second embodiment.

The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the second step, the AZO target is sputtered under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W until the thickness of the first AZO layer is 30 nm-55 nm; and in the second step, the AZO target is sputtered until the thickness of the second AZO layer is 30 nm-55 nm under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W. The others are the same as the first to third embodiments.

The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the second step, the AZO target is sputtered under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W until the thickness of the first AZO layer is 35 nm-55 nm; and in the second step, the AZO target is sputtered until the thickness of the second AZO layer is 35nm to 55nm under the conditions of room temperature, the vacuum pressure of 1Pa to 1.2Pa, the argon flow of 19sccm to 20sccm and the power of 120W to 130W. The rest is the same as the first to fourth embodiments.

The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the second step, the AZO target is sputtered under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W until the thickness of the first AZO layer is 40 nm-55 nm; and in the second step, the AZO target is sputtered until the thickness of the second AZO layer is 40 nm-55 nm under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W. The other is the same as one of the first to fifth embodiments.

The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the second step, the AZO target is sputtered under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W until the thickness of the first AZO layer is 45 nm-55 nm; and in the second step, the AZO target is sputtered until the thickness of the second AZO layer is 45nm to 55nm under the conditions of room temperature, vacuum pressure of 1Pa to 1.2Pa, argon flow of 19sccm to 20sccm and power of 120W to 130W. The others are the same as the first to sixth embodiments.

The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: sputtering the AZO target material until the thickness of the first AZO layer is 50 nm-55 nm under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W; and in the second step, the AZO target is sputtered under the conditions of room temperature, vacuum pressure of 1 Pa-1.2 Pa, argon flow of 19 sccm-20 sccm and power of 120W-130W until the thickness of the second AZO layer is 50 nm-55 nm. The rest is the same as the first to seventh embodiments.

The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and in the second step, the Ag target is sputtered under the conditions of room temperature, the vacuum pressure of 0.5-0.6 Pa, the argon flow of 19-20 sccm and the power of 40-50W until the thickness of the Ag layer is 8-9 nm. The other points are the same as those in the first to eighth embodiments.

The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and in the second step, the Ni target is sputtered under the conditions of room temperature, the vacuum pressure of 0.5 Pa-0.6 Pa, the argon flow of 19 sccm-20 sccm and the power of 40W-50W until the thickness of the Ni layer is 3 nm-4 nm. The other points are the same as those in the first to ninth embodiments.

The following examples were used to demonstrate the beneficial effects of the present invention:

the first embodiment is as follows:

a method for preparing a transparent conductive film with high photoelectric stability by magnetron sputtering is carried out according to the following steps:

firstly, mounting an AZO target, a Ni target and an Ag target on a target position of a multi-target magnetron sputtering device, fixing a cleaned substrate on a tray, putting the tray into a chamber, then starting the device, and pumping the vacuum degree to 4.5 × 10-4Pa;

Secondly, introducing argon gas at room temperature, adjusting the argon gas flow to be 20sccm, firstly carrying out pre-sputtering on an AZO target for 5min, then carrying out pre-sputtering on an Ag target for 3min under the conditions of room temperature, vacuum pressure of 1Pa, argon gas flow of 20sccm and power of 120W until the thickness of a first AZO layer is 30nm, then carrying out pre-sputtering on an Ag target for 3min, then carrying out pre-sputtering on an Ni target for 3min under the conditions of room temperature, vacuum pressure of 0.5Pa, argon gas flow of 20sccm and power of 40W until the thickness of the Ag layer is 8nm, then carrying out pre-sputtering on the Ni target for 4nm under the conditions of room temperature, vacuum pressure of 1Pa, argon gas flow of 20sccm and power of 40W, finally carrying out pre-sputtering on the conditions of room temperature, vacuum pressure of 1Pa, argon gas flow of 20sccm and power of 120W, sputtering the AZO target until the thickness of the second AZO layer is 30 nm;

and thirdly, closing all power supplies, opening a vent valve until the air pressure of the vacuum chamber is restored to the atmospheric pressure, then opening the chamber for sampling to obtain the AZO/Ni/Ag/AZO film, and finally completing the method for preparing the transparent conductive film with high photoelectric stability by utilizing magnetron sputtering.

The shape of the cleaned substrate in the step one is a square with the side length of 1 cm.

The cleaning process of the cleaned substrate in the first step is as follows: and (3) placing the substrate in an absolute ethyl alcohol solution, ultrasonically cleaning for 10min, and then washing with deionized water.

The substrate is a glass substrate.

The AZO target material in the step one is aluminum-doped zinc oxide, wherein ZnO and Al2O3In a mass ratio of 98: 2.

The total thickness of the AZO/Ni/Ag/AZO film prepared in the example is about 72 nm.

Example two: the difference between the present embodiment and the first embodiment is: sputtering the AZO target until the thickness of the first AZO layer is 35 nm; and sputtering the AZO target in the second step until the thickness of the second AZO layer is 35 nm. The rest is the same as the first embodiment.

The total thickness of the AZO/Ni/Ag/AZO film prepared in the example is about 82 nm.

Example three: the difference between the present embodiment and the first embodiment is: sputtering the AZO target until the thickness of the first AZO layer is 40 nm; and sputtering the AZO target in the second step until the thickness of the second AZO layer is 40 nm. The rest is the same as the first embodiment.

The total thickness of the AZO/Ni/Ag/AZO film prepared in the example is about 92 nm.

Example four: the difference between the present embodiment and the first embodiment is: sputtering the AZO target until the thickness of the first AZO layer is 45 nm; and sputtering the AZO target in the second step until the thickness of the second AZO layer is 45 nm. The rest is the same as the first embodiment.

The total thickness of the AZO/Ni/Ag/AZO film prepared in the example is about 102 nm.

Example five: the difference between the present embodiment and the first embodiment is: sputtering the AZO target until the thickness of the first AZO layer is 50 nm; and sputtering the AZO target in the second step until the thickness of the second AZO layer is 50 nm. The rest is the same as the first embodiment.

The total thickness of the AZO/Ni/Ag/AZO film prepared in the example is about 112 nm.

The thickness of the Ni layer and the thickness of the Ag layer in the AZO/Ni/Ag/AZO thin films prepared in examples one to five were all 4nm, the thickness of the Ag layer was 8nm, the thickness of the first AZO layer and the second AZO layer was 30nm in example one, the thickness of the first AZO layer and the second AZO layer was 35nm in example two, the thickness of the first AZO layer and the second AZO layer was 40nm in example three, the thickness of the first AZO layer and the second AZO layer was 45nm in example four, and the thickness of the first AZO layer and the second AZO layer was 50nm in example five.

FIG. 1 is a graph of transmittance of AZO/Ni/Ag/AZO films, where 1 is the AZO/Ni/Ag/AZO film prepared in example one, 2 is the AZO/Ni/Ag/AZO film prepared in example two, 3 is the AZO/Ni/Ag/AZO film prepared in example three, 4 is the AZO/Ni/Ag/AZO film prepared in example four, and 5 is the AZO/Ni/Ag/AZO film prepared in example five. As can be seen, at a wavelength of 550nm, at which the human eye is sensitive, the transmittance gradually increases with increasing AZO layer thickness. The highest transmission of the sample with an AZO layer thickness of 50nm is higher than that of the other samples, reaching about 80%.

FIG. 2 is a graph showing the average transmittance and the sheet resistance of the AZO/Ni/Ag/AZO thin films prepared in examples one to five. It can be seen from the figure that the average value of the visible light transmittance increases and then decreases with the increase of the thickness of the AZO layer, and when the thickness of the AZO layer is 45nm, the average light transmittance of the film is the highest (about 74%), the sheet resistance reaches the lowest and is only 6.352 Ω/sq, the photoelectric performance is excellent, and the average transmittance is reduced by about 6% compared with the AZO/Ag/AZO obtained under the same conditions, but the sheet resistance is reduced by about 32%.

FIG. 3 is a graph of the electrical properties of AZO/Ni/Ag/AZO films prepared in examples one through five. Concentration of carriers N in the figurebCarrier mobility mu, sheet resistance R corresponding to the left coordinate axissCorresponding to the right first and second coordinate axes, respectively. As can be seen from the figure, when the AZO thickness is 40nm, the carrier mobility mu of the film is the highest; when the thickness of AZO is 45nm, the concentration of current carriers N in the film is NbUp to 1022/cm3The order of magnitude, the resistivity of the film under different AZO thicknesses reaches 10-5The order of Ω · cm, and excellent conductivity.

The AZO/Ni/Ag/AZO film prepared in the fourth example was subjected to high temperature treatment at 300 deg.C, 400 deg.C, 500 deg.C and 600 deg.C, respectively, as follows:

placing the AZO/Ni/Ag/AZO film prepared in the fourth embodiment into a tube furnace, heating the AZO/Ni/Ag/AZO film to 300 ℃ at the heating rate of 8 ℃/min in the air atmosphere, and performing high-temperature treatment for 0.5h at the temperature of 300 ℃ to obtain the AZO/Ni/Ag/AZO film subjected to high-temperature treatment;

placing the AZO/Ni/Ag/AZO film prepared in the fourth embodiment into a tube furnace, heating to 400 ℃ at a heating rate of 8 ℃/min in an air atmosphere, and performing high-temperature treatment for 0.5h at the temperature of 400 ℃ to obtain the AZO/Ni/Ag/AZO film subjected to high-temperature treatment;

placing the AZO/Ni/Ag/AZO film prepared in the fourth embodiment into a tube furnace, heating to 500 ℃ at a heating rate of 8 ℃/min in an air atmosphere, and performing high-temperature treatment for 0.5h at the temperature of 500 ℃ to obtain the AZO/Ni/Ag/AZO film subjected to high-temperature treatment;

and (3) placing the AZO/Ni/Ag/AZO film prepared in the fourth embodiment into a tube furnace, heating to 600 ℃ at the heating rate of 8 ℃/min in the air atmosphere, and carrying out high-temperature treatment for 0.5h at the temperature of 600 ℃ to obtain the AZO/Ni/Ag/AZO film subjected to high-temperature treatment.

FIG. 4 is a graph showing the average transmittance and the area resistance of the AZO/Ni/Ag/AZO thin films after four different high temperature treatments of examples. The curve shows that the average transmittance of the film in the visible light wave band gradually increases along with the increase of the temperature of the treatment environment until the temperature is greatly increased to 600 ℃, and reaches about 82%; the surface resistance of the film is continuously reduced after being treated at 300 ℃ and 400 ℃, the conductivity is optimized, the surface resistance is slightly increased at 500 ℃, the electrical property is basically kept stable, the resistance is obviously increased until being treated at 600 ℃, and the conductivity is deteriorated.

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