CN108461368B - 一种ZnO/PdO复合表面传导电子发射膜及其制备方法 - Google Patents
一种ZnO/PdO复合表面传导电子发射膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种ZnO/PdO复合表面传导电子发射膜及其制备方法，发射膜包括PdO膜层，PdO膜层上设置有ZnO籽晶层，ZnO籽晶层上生长有方向能够调控的ZnO纳米线层，ZnO纳米线层经过电形成过程能够产生具有许多发射尖端的纳米裂缝，使纳米裂缝处的电场增强。制备方法包括以下步骤：1)通过射频反应磁控溅射法在经过抛光处理的Si基片上沉积PdO膜层；2)通过射频反应磁控溅射法在沉积有PdO膜层的Si基片上沉积ZnO籽晶层；3)通过低温水浴法在ZnO籽晶层上按照电子发射方向生长ZnO纳米线。本发明能够有效提高发射效率，提升器件的显示质量及寿命，降低功耗和成本。
Description
技术领域
本发明涉及表面传导电子发射领域，具体涉及一种ZnO/PdO复合表面传导电子发射膜及其制备方法，能应用于表面传导电子发射显示器，提升显示质量和寿命，降低功耗和成本。
背景技术
SED(Surface-conduction Electron-emitter Display，表面传导电子发射显示器)属于高真空器件，对经过电形成过程和激活过程制备完成的表面传导电子发射源(SCE，Surface-conduction Electron-emitter)薄膜两端施加一定的器件电压Vf，SCE薄膜的纳米缝隙表面附近形成超高电场，促使SCE薄膜的内部电子因量子遂穿效应而越过固体表面势垒，形成一定的场致发射电流，称为器件电流If。在阳极高压Va的作用下，部分遂穿电子向上运动到达阳极形成一定的有效发射电流Ie，高动能的电子轰击阳极板上的荧光粉发出可见光，从而完成场致发射和电致发光的过程。由此可见，SCE上使用的表面传导电子发射膜是SED器件的核心，提高表面传导电子发射膜的发射效率，能够有效降低SED器件的功耗和成本、提高表面传导电子发射显示器的显示质量和寿命，故而对表面传导电子发射膜的研究具有重要意义。
发明内容
本发明的目的在于针对上述现有技术中的问题，提供一种ZnO/PdO复合表面传导电子发射膜及其制备方法，能够有效提高发射效率，提升器件的显示质量及寿命，降低功耗和成本。
为了实现上述目的，本发明ZnO/PdO复合表面传导电子发射膜，包括PdO膜层，PdO膜层上设置有ZnO籽晶层，ZnO籽晶层上生长有方向能够调控的ZnO纳米线层，ZnO纳米线层经过电形成过程能够产生具有许多发射尖端的纳米裂缝，使纳米裂缝处的电场增强。
本发明ZnO/PdO复合表面传导电子发射膜的制备方法，包括以下步骤：
1)通过射频反应磁控溅射法在经过抛光处理的Si基片上沉积PdO膜层；
2)通过射频反应磁控溅射法在沉积有PdO膜层的Si基片上沉积ZnO籽晶层；
3)通过低温水浴法在ZnO籽晶层上按照电子发射方向生长ZnO纳米线。
所述的步骤1)在沉积PdO膜层时：
溅射温度为25℃，本底真空低于5×10-4Pa，将纯度均为99.99％的氩气与氧气制成混合气体与纯度为99.99％的金属Pd靶反应溅射，混合气体中的氧气所占比例为25％～75％，溅射气压为0.3Pa～0.5Pa，Pd靶的溅射功率为80～100W，沉积时间为40s～100s。
所述的步骤2)在沉积ZnO籽晶层时：
溅射温度为25℃，本底真空低于5×10-4Pa，将纯度均为99.99％的氩气与氧气制成混合气体与纯度为99.99％的金属Zn靶反应溅射，混合气体中氧气所占的比例为25％～75％，溅射气压为0.3Pa～0.5Pa，Zn靶溅射功率为120～180W，沉积时间为100s～1000s。
射频反应磁控溅射法采用的仪器为ULVAC制造的ACS-4000-C4型多功能磁控溅射仪。
将经过步骤2)得到的基片放入生长液中再进行低温水浴加热生长ZnO纳米线，所述的生长液为5mM分析纯的乙酸锌溶液与5mM分析纯的六次甲基四胺溶液组成的混合溶液。
步骤3)中的水浴温度为60℃～100℃。
步骤3)中的水浴时间为3000s～8000s。
与现有技术相比，本发明具有如下的有益效果：ZnO/PdO复合表面传导电子发射膜经过电形成过程能够产生纳米裂缝，纳米裂缝处具有许多纳米线发射尖端，继而使得纳米裂缝处的电场加强，复合表面传导电子发射膜的电子发射系数提高，应用于表面传导电子发射显示器时，能够降低器件的功耗及成本，也使得器件显示质量和工作寿命得到提升。通过高真空电子发射测试平台对使用本发明制备得到的SED器件样品进行电形成，即电子发射性能测试，得出具有ZnO纳米线层的复合表面传导电子发射膜具有高的电子发射效率。
与现有技术相比，本发明的制备方法操作简单，通过射频反应磁控溅射法完成PdO膜层与ZnO籽晶层的沉积，再通过低温水浴法在ZnO籽晶层上按照电子发射方向生长ZnO纳米线即可，射频反应磁控溅射法与低温水浴法实施过程易控，制备成品率高。
附图说明
图1应用本发明ZnO/PdO复合表面传导电子发射膜的SED测试器件结构示意图；
图2本发明ZnO/PdO复合表面传导电子发射膜纳米裂缝的发射示意图；
具体实施方式
下面结合附图对本发明做进一步的详细说明。
参见图1-2，本发明ZnO/PdO复合表面传导电子发射膜包括PdO膜层，PdO膜层上设置有ZnO籽晶层，ZnO籽晶层上生长有方向能够调控的ZnO纳米线层，ZnO纳米线层经过电形成过程能够产生具有许多发射尖端的纳米裂缝，使纳米裂缝处的电场增强。
实施例1
本发明ZnO/PdO复合表面传导电子发射膜的制备方法，包括以下步骤：
采用日本真空(ULVAC)的ACS-4000-C4型多功能磁控溅射仪沉积PdO膜层，靶材为Pd靶。溅射本底真空度为1×10-4Pa，溅射过程中的工作气体为Ar和O2的混合气体，纯度均为99.999％，通入的气体流量比为Ar：O2＝4：1，工作气压为0.3Pa；Pd靶溅射功率为射频100W，预溅射时间为15min，沉积时间为60s。之后利用日本真空(ULVAC)的ACS-4000-C4型多功能磁控溅射仪沉积ZnO籽晶层，靶材为Zn靶。溅射本底真空度为1×10-4Pa，溅射过程中的工作气体为Ar和O2混合气体，纯度均为99.999％，通入的气体流量比为Ar：O2＝4：1，工作气压为0.3Pa；Zn靶溅射功率为射频150W，预溅射时间为15min，沉积时间分别为60s。最后将沉积了ZnO籽晶层的基片放入装生长液(生长液为5mM的乙酸锌(Zn(CH3COO)2·2H2O)(分析纯)和5mM的六次甲基四胺(C6H12N4)(分析纯)的混合溶液)的烧杯中，然后对烧杯水浴加热，水浴温度为80℃，水浴时间为3600s，获得ZnO纳米线层。所得PdO膜层的厚度为6nm，ZnO籽晶层的厚度为9nm，所述ZnO纳米线层的厚度为81nm。本发明采用ZnO/PdO复合表面传导电子发射膜的SED测试器件包括有若干SCE单元1。SCE单元1由器件电极2(其材质为金属Ni-Cu-Ni复合薄膜)和ZnO/PdO复合表面传导电子发射膜3构成，其中，ZnO/PdO复合表面传导电子发射膜3的各层构成及厚度如上所述。电形成的流程如下：将SED器件样品放入真空度高于6*10-6的真空室内，在电极两端施加幅值渐增的三角脉冲电压，使得器件电流If逐渐减小至零，此时电子发射膜内部形成纳米裂缝。当SED器件纳米裂缝形成后，在真空测试***中进行电子发射特性的测试。
实施例2
本发明ZnO/PdO复合表面传导电子发射膜的制备方法，包括以下步骤：
采用日本真空(ULVAC)的ACS-4000-C4型多功能磁控溅射仪沉积PdO膜层，靶材为Pd靶。溅射本底真空度为9.5×10-5Pa，溅射过程中的工作气体为Ar和O2混合气体，纯度均为99.999％，通入的气体流量比为Ar：O2＝4：1，工作气压为0.33Pa；Pd靶溅射功率为射频100W，预溅射时间为15min，沉积时间为60s。之后利用日本真空(ULVAC)的ACS-4000-C4型多功能磁控溅射仪沉积ZnO籽晶层，靶材为Zn靶。溅射本底真空度为1.2×10-4Pa，溅射过程中的工作气体为Ar和O2混合气体，纯度均为99.999％，通入的气体流量比为Ar：O2＝4：1，工作气压为0.31Pa；Zn靶溅射功率为射频150W，预溅射时间为15min，沉积时间分别为180s。最后将沉积了ZnO籽晶层的基片放入装生长液(生长液为5mM的乙酸锌(Zn(CH3COO)2·2H2O)(分析纯)和5mM的六次甲基四胺(C6H12N4)(分析纯)的混合溶液)的烧杯中，然后对烧杯水浴加热，水浴温度为80℃，水浴时间为5400s，以此获得ZnO纳米线层。所得PdO膜层的厚度为6nm，ZnO籽晶层的厚度为27nm，ZnO纳米线层的厚度为120nm。采用ZnO/PdO复合表面传导电子发射膜的SED测试器件包括若干SCE单元1。SCE单元1由器件电极2(其材质为金属Ni-Cu-Ni复合薄膜)和ZnO/PdO复合表面传导电子发射膜3构成，其中，ZnO/PdO复合表面传导电子发射膜3的各层构成及厚度如上所述。电形成的流程如下：将SED器件样品放入真空度高于6*10-6的真空室内，在电极两端施加幅值渐增的三角脉冲电压，使得器件电流If逐渐减小至零，此时电子发射膜内部形成纳米裂缝。当SED器件纳米裂缝形成后，在真空测试***中进行电子发射特性的测试。
实施例3
本发明ZnO/PdO复合表面传导电子发射膜的制备方法，包括以下步骤：
采用日本真空(ULVAC)的ACS-4000-C4型多功能磁控溅射仪沉积PdO膜层，靶材为Pd靶。溅射本底真空度为9.8×10-5Pa，溅射过程中的工作气体为Ar和O2混合气体，纯度均为99.999％，通入的气体流量比为Ar：O2＝4：1，工作气压为0.32Pa；Pd靶溅射功率为射频100W，预溅射时间为15min，沉积时间为60s。之后利用日本真空(ULVAC)的ACS-4000-C4型多功能磁控溅射仪沉积ZnO籽晶层，靶材为Zn靶。溅射本底真空度为1.1×10-4Pa，溅射过程中的工作气体为Ar和O2混合气体，纯度均为99.999％，通入的气体流量比为Ar：O2＝4：1，工作气压为0.3Pa；Zn靶溅射功率为射频150W，预溅射时间为15min，沉积时间分别为600s。最后将沉积了ZnO籽晶层的基片放入装生长液(生长液为5mM的乙酸锌(Zn(CH3COO)2·2H2O)(分析纯)和5mM的六次甲基四胺(C6H12N4)(分析纯)的混合溶液)的烧杯中，然后对烧杯水浴加热，水浴温度为80℃，水浴时间为7200s，以此获得ZnO纳米线层。所得PdO膜层的厚度为6nm，ZnO籽晶层的厚度为54nm，ZnO纳米线层的厚度为170nm。采用ZnO/PdO复合表面传导电子发射膜的SED测试器件包括若干SCE单元1。SCE单元1由器件电极2(其材质为金属Ni-Cu-Ni复合薄膜)和ZnO/PdO复合表面传导电子发射膜3构成，其中，ZnO/PdO复合表面传导电子发射膜3的各层构成及厚度如上所述。电形成的流程如下：将SED器件样品放入真空度高于6*10-6的真空室内，在电极两端施加幅值渐增的三角脉冲电压，使得器件电流If逐渐减小至零，此时电子发射膜内部形成纳米裂缝。当SED器件纳米裂缝形成后，在真空测试***中进行电子发射特性的测试。
表1.不同样品的发射效率对比
| 样品 | ZnO纳米线厚度 | ZnO籽晶层厚度 | 发射效率 | 测试器件电压 |
| 对比样品 | 无 | 9nm | 0.15 | 17.5V |
| 实施例1 | 81nm纳米线厚度 | 9nm | 0.35 | 17.5V |
| 实施例2 | 120nm纳米线厚度 | 27nm | 0.65 | 17.5V |
| 实施例3 | 170nm纳米线厚度 | 54nm | 1.125 | 17.5V |
通过对生长有不同厚度ZnO纳米线层的ZnO/PdO复合表面传导电子发射膜与未生长ZnO纳米线层的发射膜测试数据比较，得知：1、随着ZnO籽晶层沉积时间增加，薄膜平均厚度和ZnO籽晶层的平均厚度均逐渐增加。2、利用高真空电子发射测试平台对ZnO/PdO复合表面传导电子发射膜制备的SED器件样品进行电形成，即电子发射性能测试，可见具有ZnO纳米线层的复合表面传导电子发射膜具有高的电子发射效率。
Claims (6)
1.一种ZnO/PdO复合表面传导电子发射膜，其特征在于：包括PdO膜层，PdO膜层上设置有ZnO籽晶层，ZnO籽晶层上生长有方向能够调控的ZnO纳米线层，ZnO纳米线层经过电形成过程能够产生具有许多发射尖端的纳米裂缝，使纳米裂缝处的电场增强；
所述纳米裂缝的形成过程为：采用ZnO/PdO复合表面传导电子发射膜的SED测试器件包括有若干SCE单元，SCE单元由器件电极和ZnO/PdO复合表面传导电子发射膜构成，器件电极材质为金属Ni-Cu-Ni复合薄膜；电形成过程如下：
将SED测试器件放入真空度高于6*10-6的真空室内，在电极两端施加幅值渐增的三角脉冲电压，使得器件电流If逐渐减小至零，此时电子发射膜内部形成纳米裂缝。
2.一种如权利要求1所述ZnO/PdO复合表面传导电子发射膜的制备方法，其特征在于，包括以下步骤：
1)通过射频反应磁控溅射法在经过抛光处理的Si基片上沉积PdO膜层；
溅射温度为25℃，本底真空低于5×10-4Pa，将纯度均为99.99％的氩气与氧气制成混合气体与纯度为99.99％的金属Pd靶反应溅射，混合气体中的氧气所占比例为25％～75％，溅射气压为0.3Pa～0.5Pa，Pd靶的溅射功率为80～100W，沉积时间为40s～100s；
2)通过射频反应磁控溅射法在沉积有PdO膜层的Si基片上沉积ZnO籽晶层；
溅射温度为25℃，本底真空低于5×10-4Pa，将纯度均为99.99％的氩气与氧气制成混合气体与纯度为99.99％的金属Zn靶反应溅射，混合气体中氧气所占的比例为25％～75％，溅射气压为0.3Pa～0.5Pa，Zn靶溅射功率为120～180W，沉积时间为100s～1000s；
3)通过低温水浴法在ZnO籽晶层上按照电子发射方向生长ZnO纳米线。
3.根据权利要求2所述的制备方法，其特征在于：射频反应磁控溅射法采用的仪器为ULVAC制造的ACS-4000-C4型多功能磁控溅射仪。
4.根据权利要求2所述的制备方法，其特征在于：将经过步骤2)得到的基片放入生长液中再进行低温水浴加热生长ZnO纳米线，所述的生长液为5mM分析纯的乙酸锌溶液与5mM分析纯的六次甲基四胺溶液组成的混合溶液。
5.根据权利要求2所述的制备方法，其特征在于：步骤3)中的水浴温度为60℃～100℃。
6.根据权利要求2所述的制备方法，其特征在于：步骤3)中的水浴时间为3000s～8000s。
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