CN108642460A - 网状复合结构薄膜及增韧合成方法 - Google Patents
网状复合结构薄膜及增韧合成方法 Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/28—Vacuum evaporation by wave energy or particle radiation
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Abstract
本发明实施公开了一种网状复合结构薄膜及增韧合成方法。通过溅镀金属纳米薄层、金属表层氧化、以复合粒子为基点生长纳米晶三个步骤，形成网状结构复合薄膜。发明实施的复合结构薄膜中金属颗粒为韧性相，能提高薄膜塑性变形能力，纳米晶须可改善薄膜中应力集中问题。
Description
技术领域
本发明涉及氧化物复合结构薄膜及生长合成技术领域，特别是涉及网状复合结构薄膜及增韧合成方法。
背景技术
氧化物薄膜具有良好的光电特性、强机械性能、高致密及环境稳定性等特点，在光电器件领域应用广泛。现代信息技术发展对器件的柔性显示提出更高要求，而氧化物材料固有力学脆性，制约了它在柔性电子器件的应用发展。
基于石墨烯、碳纳米管、纳米纤维等新兴透明导电薄膜材料存在薄膜面电阻、器件兼容性、工艺结构稳定性等诸多问题，使得其在光电器件及大面积显示的应用缓慢。
目前应用最广泛的透明导电薄膜仍是铟、锡、锌、铝等金属氧化物薄膜，氧化铟锡（Indium tin oxide ITO）薄膜，不管是在玻璃还是在触控面板电子器件领域都仍是主流导电材料。改善传统ITO薄膜材料柔韧性并保持低阻高透光电性是透明薄膜光电器件中亟待解决的问题。
发明内容
氧化物材料没有金属塑性变形能力，断裂过程中只需要克服断裂面表面能，材料结构可改善氧化物薄膜的脆性。
本发明通过结构改善传统薄膜韧性，提供一种网状复合结构薄膜及原位增韧合成方法，金属纳米粒子经过表层氧化后，形成复合粒子基体，以复合基体粒子为基点生长纳米晶，纳米晶连接形成网状复合结构薄膜。
金属纳米粒子为基点网状复合结构薄膜，薄膜中金属粒子比例、微结构形状大小、薄膜厚度及纳米晶尺寸、晶型结构等会对薄膜的机械性能有所改善。金属粒子为韧性相，能提高薄膜的塑性变形能力。以金属复合粒子为基点原位生长的纳米晶，作为应力分散结构可改善薄膜应力集中问题。
纳米晶一般为韧性相金属粒子的同源氧化物或其掺杂氧化物。如铟/氧化铟，锡/氧化锡，锌/氧化锡，锌/氧化铟锌等。
复合结构薄膜主体为以金属粒子为基点原位生长的纳米晶，纳米晶为氧化物网状结构可分散薄膜应力。
根据上述网状复合结构薄膜特征，提供一种网状ITO/SnO2/Sn复合结构薄膜及其原位增韧合成方法。
ITO属氧化物陶瓷材料，本身没有金属塑性变形能力，共价键和离子键的决定材料脆性，通过在ITO材料中置入同源金属Sn纳米粒子以提高薄膜塑性变形能力。
Sn是一种柔软易弯曲熔点232 ℃银白色光泽的金属，化学性质稳定，不易被氧化，常温下展性非常好，高温下会熔成水银般的液体。鉴于金属Sn物理性质且ITO材料Sn掺杂，考虑到金属相塑性和ITO单晶生长催化液核的需要，以金属Sn复合粒子为基点可降低纳米晶生长门槛，容易形成共熔剂。
金属Sn纳米粒子经过表层氧化后，形成SnO2/Sn复合粒子基体，以Sn复合基体粒子为基点生长ITO纳米晶，纳米晶无序交错形成网状ITO/SnO2/Sn复合结构薄膜。
根据本发明实施例网状ITO/SnO2/Sn复合结构薄膜的第一方面，对玻璃基底进行金属粒子修饰。
在基底上沉积金属Sn纳米薄层，热处理薄层团聚成金属纳米颗粒。调整温度、气体氛围，对薄层材料进行热处理，金属Sn表面氧化出SnO2薄层，获得Sn/SnO2复合颗粒结构。
优选利用磁控溅射镀金属Sn厚度10～20nm薄层，120～150 oC温度空气氛围热处理，金属薄层团聚成金属纳米颗粒，表面氧化出SnO2薄层，获得Sn/SnO2复合颗粒结构。磁控溅射金属薄层与基底粘附力强，薄膜纯度高厚度均匀可控。
共熔性金属Sn液滴，在液滴中浓度远高于ITO中掺杂浓度，金属Sn蒸汽压低不会影响ITO组成，过程没有副反应，体系温度恒定。
根据本发明实施例网状ITO/SnO2/Sn复合结构薄膜的第二方面，复合粒子修饰后ITO纳米晶原位增韧合成。
采用电子束蒸发技术，控制工艺条件以纳米SnO2/Sn复合粒子为催化基点，生长ITO纳米晶枝，合成网状ITO/SnO2/Sn复合结构薄膜。复合结构薄膜合成是以SnO2/Sn复合粒子为基点生长ITO纳米晶，液相催化剂能降低晶核形成门槛，控制条件保证液相催化生成及气相成分饱和溶解以合成薄膜。
优选以ITO（SnO2质量分数: 5～10%）靶材为蒸发源料，设置温度280～350 oC、压力1╳10-4～1╳10-3 m Torr、功率600～800KW、速率0.5～1 Å/s，以金属复合粒子为基点气液固生长ITO纳米晶，纳米晶连接成网状ITO/SnO2/Sn复合结构薄膜。
复合粒子修饰后ITO纳米晶原位增韧合成，提供具体实施步骤如下：
（1）市售纯度4N的ITO （In2O3:SnO2 = 95%:5%）靶材为源料，设置压强10-4 mTorr，温度300 oC，速率1A/s，高压3000V。
（2）开启真空泵，以N2置换炉内气氛，形成炉腔缺氧氛围，开加热至设定温度，稳定20分钟后，开电子束高压3000KV调整束斑电流，轰击ITO靶材蒸镀。
（3）ITO源料在高压下分解挥发In2O3和SnO2蒸汽，部分氧化物源会分解成氧和金属Sn、In蒸汽。真空泵抽动腔体压强保持10-4 mTorr，气相源被泵抽动带动至腔体上方，高温金属源蒸汽遇行星架300oC低温基底冷凝成金属液滴，成为晶体生长催化液滴。氧化物气相源蒸汽透过液滴界面熔解到其中，气氛源被液滴吸附溶解，当其过饱和时，会有亚稳相晶核析出，晶核越过生长壁垒，不断生长成一维ITO纳米晶。
腔室温度300oC高于金属Sn熔点，保证催化液相合金形成。金属Sn粒子提供液相催化剂，同时保证ITO/SnO2/Sn复合结构薄膜中金属内核，为薄膜应力分散提供消耗点。
金属催化剂是物理吸附和气相传输成固相的媒介，同时有效降低气相反应物裂解活化能，在晶体成核过程中接纳气相分子，活化反应，提供结晶场所，使得结晶过程远低于二维成核的临界条件。ITO/SnO2/Sn复合薄膜具有完整的ITO晶体结构、SnO2和ITO异质结构，界面处能带结构不连续，材料力学性能好。
粒子多相复合及多层结构可提高薄膜材料机械韧性，ITO/SnO2/Sn复合结构薄膜中金属Sn粒子起韧性相作用，多级结构微纳化和多晶界密度可提高裂纹钝化以及界面开裂应力分散能力，通过ITO薄膜结构改善薄膜柔性。
本发明实施提供的ITO/SnO2/Sn复合材料由金属和氧化物复合而成，具有比单一金属氧化物更优机械性能，可改善传统ITO薄膜柔性差问题，具有很好的产业前景。
由以上技术方案可见，本发明提供的一种网状复合结构薄膜及其原位增韧合成方法，以韧性相金属纳米粒子及其表层氧化后复合粒子为基体，在上述复合粒子上原位生长同源氧化物纳米晶，进而构成具有塑性变形能力和应力分散结构的网状复合薄膜。
需要说明的是，本发明实施例提供的复合结构薄膜不局限于氧化铟锡材料成分，本发明方法实施例中仅是以氧化铟锡纳米晶为例进行陈述，需要说明的是，本发明实施所述提供的复合结构薄膜及其合成方法还可以用于无机有机金属、非金属、氧化物、硅化物和碳化物等材料的生长，其中具体的生长过程在此不再赘述。本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本发明的实施例，并与说明书一起用于解释本发明的原理。
图1为本发明实施例提供的一种网状复合结构薄膜结构示意图。
图2为本发明实施例提供的网状ITO/SnO2/Sn复合结构薄膜示意图。
图3为本发明实施例提供的网状ITO/SnO2/Sn复合结构薄膜的制备流程示意图。
附图说明：1. 金属粒子，2. 氧化薄层，3. 纳米晶；4. 金属Sn颗粒，5. SnO2薄层，6. ITO 纳米晶。
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。以下示例性实施例中所描述的实施方式并不代表与本发明相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本发明的一些方面相一致的装置和结构的例子。
针对传统氧化物薄膜柔性差问题，本发明实施例给出通过结构改善薄膜机械性能思路，网状ITO/SnO2/Sn复合结构薄膜及其原位增韧合成方法。
图3为本发明实施例提供的网状结构ITO/SnO2/Sn复合结构薄膜的流程示意图。该方法具体包括如下步骤：
步骤S110：在基底材料上，溅镀金属Sn纳米薄层。
具体的，将清洗干净的基底材料或基板置入磁控溅射设备中，开启设备设置氩气流量，溅镀高纯4N金属锡靶于基底材料上，金属薄层厚度10～30nm。
步骤S120：金属纳米Sn薄层在一定温度氛围下，团聚并表层氧化成SnO2/Sn复合粒子。
具体的，将上述S110中溅镀金属Sn薄层的基板，至于快速退火炉中，开启N2：O2=1:4气体流量比例，温度设置120～200 oC，时间400～600 s。使溅镀金属Sn薄层软化团聚，并表层氧化出SnO2薄层。基底被复合SnO2/Sn粒子修饰。
步骤S130：载有SnO2/Sn复合粒子基底置于电子束蒸发设备中，调整工艺条件，使其满足ITO纳米晶生长方式，以复合粒子为基点原位生长纳米晶，形成网状ITO/SnO2/Sn 复合结构薄膜。
具体的，将市售4N 的ITO（SnO2 ：In2O3= 5% ：95%）靶材置入坩埚中，设置腔体温度300 oC、压力4╳10-3m Torr、功率500KW、速率1 Å/s，以金属复合粒子为基点VLS气液固生长ITO纳米晶，纳米晶连接成网状ITO/SnO2/Sn复合结构薄膜。
ITO靶源在电子束高压下挥发In2O3和SnO2蒸汽，部分氧化物源会分解成氧和金属Sn、In蒸汽。气相源被泵抽动带动至腔体上方，金属源蒸汽遇行星架300 oC低温基底冷凝成金属液滴，与基底材料复合粒子成为晶体生长催化液滴。气相源蒸汽不断熔解到液滴中，当其过饱和时会有亚稳相晶核析出，晶核越过生长壁垒，不断生长成一维ITO纳米晶。金属催化剂是物理吸附和气相传输成固相的媒介，能有效降低气相反应物裂解活化能，在晶体成核过程中接纳气相分子，活化反应，提供结晶场所，使得结晶过程远低于二维成核的临界条件。
腔室温度300oC高于金属Sn熔点，保证催化液相合金形成。金属Sn粒子提供液相催化剂，同时保证ITO/SnO2/Sn复合结构薄膜中金属内核，为薄膜应力分散提供消耗点。
粒子多相复合及多层结构可提高薄膜材料机械韧性，ITO/SnO2/Sn复合薄膜具有完整的ITO晶体结构、SnO2和ITO异质结构，界面处能带结构不连续，材料力学性能好。复合结构薄膜中金属Sn粒子起韧性相作用，多级结构微纳化和多晶界密度可提高裂纹钝化以及界面开裂应力分散能力。
Claims (6)
1.一种网状复合结构薄膜及原位增韧合成方法，其特征包括：
金属纳米粒子经过表层氧化后，形成复合粒子基体，以复合基体粒子为基点生长纳米晶，纳米晶连接形成网状复合结构薄膜；
金属粒子为韧性相，能提高薄膜的塑性变形能力；以金属粒子为基点原位生长的纳米晶，作为薄膜应力分散结构可改善应力集中问题。
2.根据权利要求1所述的方法，其特征在于，纳米晶一般为韧性相金属粒子的同源氧化物或其掺杂氧化物；如铟/氧化铟，锡/氧化锡，锌/氧化锡，锌/氧化铟锌等。
3.根据权利要求1所述的方法，其特征在于，薄膜主体结构为氧化物纳米晶网状薄膜。
4.根据权利要求1所述的网状复合结构薄膜，提供一种网状ITO/SnO2/Sn复合结构薄膜。
5.根据权利要求4所述，网状ITO/SnO2/Sn复合结构薄膜，其特征在于：
金属Sn纳米粒子经过表层氧化后，形成SnO2/Sn复合粒子基体，复合基体粒子为基点生长ITO纳米晶，纳米晶无序交错形成网状ITO/SnO2/Sn复合结构薄膜。
6.根据权利要求5所述的方法：
利用磁控溅射镀金属Sn厚度10～20nm薄层，120～150 oC温度空气氛围热处理，金属薄层团聚成金属纳米颗粒，且表面氧化出SnO2薄层，获得Sn/SnO2复合颗粒结构；
金属Sn柔软易弯曲展性好物理性质，且ITO材料为Sn掺杂氧化铟，纳米晶生长过程中易形成共熔剂；
将金属Sn纳米粒子修饰后的基底，置于电子束蒸发设备中，以ITO（SnO2质量分数: 5～10%）靶材为蒸发源料，设置温度280～350 oC、压力1╳10-4～1╳10-3m Toor、功率600～800KW、速率0.5～1 Å/s，以金属复合粒子为基点气液固模式生长ITO纳米晶，纳米晶连接成网状ITO/SnO2/Sn复合结构薄膜。
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