氧化物薄膜晶体管及其制备方法 Oxide thin film transistor and preparation method thereof
技术领域 Technical field
本发明涉及半导体技术领域， 特别涉及一种氧化物薄膜晶体管及其制备方法。 本 申请是以申请号为 201310249839.4、申请日为 2013年 6月 21 日的中国发明专利申请为 基础的。 The present invention relates to the field of semiconductor technology, and in particular, to an oxide thin film transistor and a method of fabricating the same. This application is based on the Chinese invention patent application with the application number 201310249839.4 and the application date of June 21, 2013.
背景技术 说 Background art
薄膜晶体管（TFT， Thin Film Transistor)主要应用于控制和驱动液晶显示器（LCD, Liquid Crystal Display )、 有机发光二极管 ( OLED, Organic Light-Emitting Diode) 显示 器的子像素， 是平板显示领域中最重要的电子器件之一。 Thin Film Transistors (TFTs) are mainly used to control and drive sub-pixels of Liquid Crystal Display (LCD), Organic Light-Emitting Diode (OLED) displays, and are the most important in the field of flat panel display. One of the electronic devices.
书 Book
在平板显示方面， 目前主要使用氢化非晶硅（a-Si:H)或多晶硅等材料的薄膜晶体 管， 然而氢化非晶硅材料的局限性主要表现在对光敏感、 电子迁移率低（<lcm2/Vs) 以 及电学参数稳定性差等方面， 而多晶硅薄膜的局限性主要体现在电学性质均匀性差、制 备温度高以及成本高等方面。In terms of flat panel display, thin film transistors of hydrogenated amorphous silicon (a-Si:H) or polysilicon are mainly used. However, the limitations of hydrogenated amorphous silicon materials are mainly sensitive to light and low electron mobility (<lcm).2 /Vs) and poor stability of electrical parameters, and the limitations of polysilicon film are mainly reflected in the poor uniformity of electrical properties, high preparation temperature and high cost.
基于氧化物的薄膜晶体管电子迁移率高 （l〜100cm2/Vs)、 制备温度低 （<400°C， 远低于玻璃的熔点）、 成本低 （只需要普通的溅射工艺即可完成） 以及持续工作稳定性 好的特点，基于金属氧化物的薄膜晶体管在平板显示领域尤其是有机发光显示（OLED) 领域有替代传统的硅材料工艺薄膜晶体管的趋势， 受到学术界和业界的关注和广泛研 究。Oxide-based thin film transistors have high electron mobility (1~100cm2 /Vs), low preparation temperature (<400°C, much lower than the melting point of glass), and low cost (only need ordinary sputtering process) And the characteristics of continuous work stability, metal oxide-based thin film transistors have a tendency to replace traditional silicon material process thin film transistors in the field of flat panel display, especially organic light-emitting display (OLED), which has attracted the attention and extensiveness of the academic community and the industry. the study.
然而， 由于氧化物半导体稳定性差， 容易造成氧化物薄膜晶体管的电学稳定性差， 表现在器件的正扫和回扫的转移特性曲线之间磁滞回线较大， 阈值电压容易发生漂移 等。 However, due to the poor stability of the oxide semiconductor, the electrical stability of the oxide thin film transistor is likely to be poor, and the hysteresis loop is large between the forward sweep and the retrace transfer characteristic curve of the device, and the threshold voltage is liable to drift.
因此， 针对现有技术不足， 提供一种电学稳定性好的氧化物薄膜晶体管及其制备 方法以克服现有技术不足甚为必要。 Therefore, in view of the deficiencies of the prior art, it is necessary to provide an oxide thin film transistor having good electrical stability and a preparation method thereof to overcome the disadvantages of the prior art.
发明内容 Summary of the invention
本发明的目的之一是提供一种氧化物薄膜晶体管，该氧化物薄膜晶体管具有稳定性 好的特点。 SUMMARY OF THE INVENTION An object of the present invention is to provide an oxide thin film transistor which is characterized by good stability.
本发明的上述目的通过如下技术手段实现。 一种氧化物薄膜晶体管， 设置有表面自主装单分子层， 所述表面自主装单分子层 固定设置于氧化物半导体层的裸露面表面。The above object of the present invention is achieved by the following technical means. An oxide thin film transistor provided with a surface self-assembled monolayer, the surface self-assembled monolayer It is fixedly disposed on the exposed surface of the oxide semiconductor layer.
上述表面自主装单分子层是通有机溶剂或无机溶剂处理所述氧化物半导体层的表 面获得的； The surface self-loading monolayer is obtained by treating the surface of the oxide semiconductor layer with an organic solvent or an inorganic solvent;
当通过有机溶剂处理时， 所述有机溶剂为甲醇、 甲苯、 二甲苯、 二甲基甲酰胺 (DMF), 二甲基亚砜 （DMSO)、 六甲基磷酰三胺 (HMPA)、 氧化吡啶或酮类中的任意一 种； When treated by an organic solvent, the organic solvent is methanol, toluene, xylene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), pyridine oxide. Or any of the ketones;
当通过无机溶剂处理时， 所述无机溶剂为双氧水。 When treated by an inorganic solvent, the inorganic solvent is hydrogen peroxide.
另一优选的， 上述表面自主装单分子层是通过垸烃硫醇处理所述氧化物半导体层 的表面获得的。 In another preferred embodiment, the surface-independent monolayer is obtained by treating the surface of the oxide semiconductor layer with a mercapto mercaptan.
另一优选的， 上述表面自主装单分子层通过垸基或苯基取代的三乙氧基硅垸处理 所述氧化物半导体层的表面获得的。 Alternatively, the surface-independent monolayer is obtained by treating the surface of the oxide semiconductor layer with a mercapto group or a phenyl-substituted triethoxysilane.
以上的， 上述氧化物薄膜晶体管还设置有基板、 栅极、 绝缘层、 源极和漏极； 所述栅极位于所述基板之上， 所述绝缘层位于所述栅极之上， 所述氧化物半导体 层、所述源极和所述漏极位于所述绝缘层之上， 所述表面自主装单分子层位于所述氧化 物半导体层的上表面，所述源极和所述漏极相互间隔并分别与所述氧化物半导体层或所 述表面自主装单分子层的两端电性相接。 In the above, the oxide thin film transistor is further provided with a substrate, a gate, an insulating layer, a source and a drain; the gate is located on the substrate, and the insulating layer is located on the gate, An oxide semiconductor layer, the source and the drain are located on the insulating layer, and the surface-independent monolayer is located on an upper surface of the oxide semiconductor layer, the source and the drain They are electrically spaced apart from each other and electrically connected to the two ends of the oxide semiconductor layer or the surface self-assembled monolayer.
上述氧化物半导体层的材料为 ZnO。 The material of the above oxide semiconductor layer is ZnO.
上述氧化物半导体层的材料为 ZnO中掺入 In、 Ga、 Sn、 Cd、 Al、 Si、 Ni、 Ta、 W、 Hf、 Y、 Ti、 La、 Nd、 Ce、 Pr、 Pm、 Sm、 Eu中的任意一种或两种以上元素。 The material of the above oxide semiconductor layer is ZnO doped with In, Ga, Sn, Cd, Al, Si, Ni, Ta, W, Hf, Y, Ti, La, Nd, Ce, Pr, Pm, Sm, Eu Any one or two or more elements.
本发明的氧化物薄膜晶体管， 设置有表面自主装单分子层， 所述表面自主装单分 子层固定设置于氧化物半导体层的裸露面表面。通过设置表面自主装单分子层， 该表面 自主装单分子层能在不损伤氧化物半导体层的前提下有效修饰氧化物表面以降低氧化 物半导体的表面能， 减少水、 氧吸附和解吸附现象， 从而提高器件的稳定性。 表面自主 装单分子层还能填充氧化物半导体上的悬挂键和一些结构缺陷， 提高载流子的迁移率。 此外，表面自主装单分子层还能提高氧化物半导体的抗蚀性， 减少后续镀膜或刻蚀对其 造成的损伤。 故本发明的氧化物薄膜晶体管具有稳定性好、制备工艺简单、 成本低廉的 特点。 The oxide thin film transistor of the present invention is provided with a surface-independent monolayer which is fixedly disposed on the exposed surface of the oxide semiconductor layer. By providing a surface-independent monolayer, the surface-independent monolayer can effectively modify the oxide surface without damaging the oxide semiconductor layer to reduce the surface energy of the oxide semiconductor and reduce water, oxygen adsorption and desorption. Thereby improving the stability of the device. The surface autonomously mounted monolayer can also fill dangling bonds on the oxide semiconductor and some structural defects, improving carrier mobility. In addition, the surface-independent monolayer can also improve the corrosion resistance of the oxide semiconductor and reduce the damage caused by subsequent coating or etching. Therefore, the oxide thin film transistor of the present invention has the characteristics of good stability, simple preparation process, and low cost.
本发明的另一目是提供一种氧化物薄膜晶体管的制备方法，所制备的氧化物薄膜晶 体管具有稳定性好的特点。 Another object of the present invention is to provide a method for producing an oxide thin film transistor which has a stable stability.
本发明的上述目的通过如下技术手段实现。 一种氧化物薄膜晶体管的制备方法， 通过旋涂、 滴涂或浸泡的方法在氧化物半导 体层的裸露面表面制备表面自主装单分子层。The above object of the present invention is achieved by the following technical means. A method for preparing an oxide thin film transistor, comprising preparing a surface-independent monolayer on a surface of an exposed surface of an oxide semiconductor layer by spin coating, drop coating or immersion.
具体的， 使用有机溶剂或者无机溶剂或者垸烃硫醇或者通过垸基或苯基取代的三 乙氧基硅垸处理所述氧化物半导体层的裸露面表面制备表面自主装单分子层； Specifically, a surface-independent monolayer is prepared by treating an exposed surface of the oxide semiconductor layer with an organic solvent or an inorganic solvent or a terpene hydrocarbon thiol or a triethoxysilane substituted with a mercapto group or a phenyl group;
当通过有机溶剂处理时， 所述有机溶剂为甲醇、 甲苯、 二甲苯、 二甲基甲酰胺 (DMF), 二甲基亚砜 （DMSO)、 六甲基磷酰三胺 (HMPA)、 氧化吡啶或酮类中的任意一 种； When treated by an organic solvent, the organic solvent is methanol, toluene, xylene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), pyridine oxide. Or any of the ketones;
当通过无机溶剂处理时， 所述无机溶剂为双氧水。 When treated by an inorganic solvent, the inorganic solvent is hydrogen peroxide.
进一步的， 氧化物薄膜晶体管还设置有基板、 栅极、 绝缘层、 源极和漏极； 所述栅极位于所述基板之上， 所述绝缘层位于所述栅极之上， 所述氧化物半导体 层、所述源极和所述漏极位于所述绝缘层之上， 所述表面自主装单分子层位于所述氧化 物半导体层的上表面，所述源极和所述漏极相互间隔并分别与所述氧化物半导体层或所 述表面自主装单分子层的两端电性相接； Further, the oxide thin film transistor is further provided with a substrate, a gate, an insulating layer, a source and a drain; the gate is located on the substrate, the insulating layer is located on the gate, and the oxidation a semiconductor layer, the source and the drain are located on the insulating layer, the surface self-assembled monolayer is located on an upper surface of the oxide semiconductor layer, and the source and the drain are mutually Intersecting and electrically contacting the two ends of the oxide semiconductor layer or the surface self-assembled monolayer;
氧化物薄膜晶体管的制备顺序为： The order of preparation of the oxide thin film transistor is:
在基板上依次制备栅极、 绝缘层、 氧化物半导体层、 源极漏极层和表面自主装单 分子层； 或者为 Preparing a gate electrode, an insulating layer, an oxide semiconductor layer, a source drain layer, and a surface autonomously mounted molecular layer on the substrate; or
在基板上依次制备栅极、 绝缘层、 氧化物半导体层、 表面自主装单分子层和源极 漏极层； 或者为 Preparing a gate electrode, an insulating layer, an oxide semiconductor layer, a surface-independent monolayer, and a source drain layer on the substrate; or
制备顺序为： 在基板上依次制备栅极、 绝缘层、 源极漏极层、 氧化物半导体层和 表面自主装单分子层； The preparation sequence is: sequentially preparing a gate electrode, an insulating layer, a source drain layer, an oxide semiconductor layer and a surface autonomous monolayer on the substrate;
所述栅极是在所述基板上通过溅射的方法制备一层厚度为 100〜500nm 的导电薄 膜， 并通过遮挡掩膜或光刻的方法图形化制备而成； The gate electrode is prepared by sputtering on the substrate to prepare a conductive film having a thickness of 100~500 nm, and is formed by patterning by masking or photolithography;
所述绝缘层是通过阳极氧化法、 热氧化法、 物理气相沉积法或化学气相沉积法制 备厚度为 100〜1000nm的薄膜， 并通过遮挡掩膜或光刻法图形化制备而成； The insulating layer is prepared by anodizing, thermal oxidation, physical vapor deposition or chemical vapor deposition to prepare a film having a thickness of 100 to 1000 nm, and is formed by masking or photolithography;
所述氧化物半导体层是通过溅射法或溶胶 -凝胶法制备厚度为 10〜100nm的薄膜， 并通过遮挡掩膜法或光刻法图形化制备而成； The oxide semiconductor layer is prepared by a sputtering method or a sol-gel method to form a film having a thickness of 10 to 100 nm, and is formed by masking or photolithography;
所述源极和漏极是采用真空蒸镀或溅射的方法制备一层厚度为 100〜1000nm的导 电层， 并采用遮挡掩膜或光刻的方法图形化同时制备所述源极和漏极。 The source and the drain are prepared by vacuum evaporation or sputtering to prepare a conductive layer having a thickness of 100 to 1000 nm, and patterned by masking or photolithography to simultaneously prepare the source and drain. .
本发明提供的氧化物薄膜晶体管的制备方法， 通过旋涂、 滴涂或浸泡的方法在氧 化物半导体层的裸露面表面制备表面自主装单分子层。 通过制备表面自主装单分子层， 该表面自主装单分子层能在不损伤氧化物半导体层的前提下有效修饰氧化物表面以降 低氧化物半导体的表面能， 减少水、 氧吸附和解吸附现象， 从而提高器件的稳定性。 表 面自主装单分子层能填充氧化物半导体上的悬挂键和一些结构缺陷，提高载流子的迁移 率。此外， 这层表面自主装单分子层还能提高氧化物半导体的抗蚀性， 减少后续镀膜或 刻蚀对其造成的损伤。 故本发明方法具有工艺简单、成本低廉的特点， 所制备的氧化物 薄膜晶体管稳定性好。The invention provides a method for preparing an oxide thin film transistor by means of spin coating, dripping or immersion in oxygen The exposed surface of the semiconductor layer is prepared to prepare a surface-independent monolayer. By preparing a surface-independent monolayer, the surface-independent monolayer can effectively modify the oxide surface without damaging the oxide semiconductor layer to reduce the surface energy of the oxide semiconductor and reduce water, oxygen adsorption and desorption. Thereby improving the stability of the device. The surface-independent monolayer can fill the dangling bonds on the oxide semiconductor and some structural defects, improving the mobility of carriers. In addition, the surface of the self-installed monolayer can also improve the corrosion resistance of the oxide semiconductor and reduce the damage caused by subsequent coating or etching. Therefore, the method of the invention has the characteristics of simple process and low cost, and the prepared oxide thin film transistor has good stability.
附图说明DRAWINGS
图 1是本发明氧化物薄膜晶体管的实施例 3的结构示意图； 1 is a schematic structural view of Embodiment 3 of an oxide thin film transistor of the present invention;
图 2是本发明氧化物薄膜晶体管的实施例 4的结构示意图； Figure 2 is a schematic view showing the structure of Embodiment 4 of the oxide thin film transistor of the present invention;
图 3是本发明氧化物薄膜晶体管的实施例 5的结构示意图； Figure 3 is a schematic view showing the structure of Embodiment 5 of the oxide thin film transistor of the present invention;
图 4是本发明氧化物薄膜晶体管实施例 6的转移特性曲线； Figure 4 is a transfer characteristic curve of Example 6 of the oxide thin film transistor of the present invention;
图 5是本发明氧化物薄膜晶体管实施例 Ί的转移特性曲线； Figure 5 is a transfer characteristic curve of an oxide thin film transistor of the present invention;
图 6是本发明氧化物薄膜晶体管实施例 8的转移特性曲线； Figure 6 is a transfer characteristic curve of Example 8 of the oxide thin film transistor of the present invention;
图 7是本发明氧化物薄膜晶体管实施例 9的转移特性曲线； Figure 7 is a transfer characteristic curve of Embodiment 9 of the oxide thin film transistor of the present invention;
图 8是本发明氧化物薄膜晶体管实施例 10的转移特性曲线； Figure 8 is a transfer characteristic curve of Example 10 of the oxide thin film transistor of the present invention;
图 9是本发明氧化物薄膜晶体管实施例 11的转移特性曲线； Figure 9 is a transfer characteristic curve of Example 11 of the oxide thin film transistor of the present invention;
图 10是本发明氧化物薄膜晶体管实施例 12的转移特性曲线。 Figure 10 is a graph showing the transfer characteristics of Example 12 of the oxide thin film transistor of the present invention.
具体实施方式 detailed description
下面结合附图和实例对本发明做进一步的说明， 但本发明要求保护的范围并不局 限于实施例的范围。 The invention will be further described with reference to the drawings and examples, but the scope of the invention is not limited to the scope of the embodiments.
实施例 1。 Example 1.
一种氧化物薄膜晶体管， 设置有表面自主装单分子层， 表面自主装单分子层固定 设置于氧化物半导体层的裸露面表面。该氧化物薄膜晶体管主要用于有机发光显示、液 晶显示、 电子纸的有源驱动， 也可以用于传感器或集成电路。 An oxide thin film transistor is provided with a surface-independent monolayer, and a surface-independent monolayer is fixedly disposed on an exposed surface of the oxide semiconductor layer. The oxide thin film transistor is mainly used for organic light-emitting display, liquid crystal display, active driving of electronic paper, and can also be used for a sensor or an integrated circuit.
本发明的氧化物薄膜晶体管， 具体还设置有基板、 栅极、 绝缘层、 源极和漏极， 栅极位于基板之上， 绝缘层位于栅极之上， 氧化物半导体层、源极和漏极位于绝缘层之 上，表面自主装单分子层位于氧化物半导体层的上表面， 源极和漏极相互间隔并分别与 氧化物半导体层或表面自主装单分子层的两端电性相接。 需要说明的是， 本发明上、 下位置关系是以基板作为下层的参照位置关系。The oxide thin film transistor of the present invention is further provided with a substrate, a gate, an insulating layer, a source and a drain, a gate on the substrate, an insulating layer on the gate, an oxide semiconductor layer, a source and a drain. The pole is located above the insulating layer, and the surface self-assembled monolayer is located on the upper surface of the oxide semiconductor layer, and the source and the drain are spaced apart from each other and electrically connected to the two ends of the oxide semiconductor layer or the surface self-assembled monolayer respectively. . It should be noted that the upper and lower positional relationship of the present invention is a reference positional relationship in which the substrate is the lower layer.
需要说明的是， 本发明 "相对应"关系是指相应的薄膜层的对称轴或对称中心在 基板上的投影重合。 It should be noted that the "corresponding" relationship of the present invention refers to the coincidence of the projection of the axis of symmetry or the center of symmetry of the corresponding film layer on the substrate.
需要说明的是， 作为本领域的公知常识， 氧化物薄膜晶体管的基板、 栅极、 绝缘 层、源极和漏极等层状结构是依次设置附着于各个功能层表面的， 因此相邻两层之间固 定连接， 在此不再赘述。 It should be noted that, as common knowledge in the art, a layered structure of a substrate, a gate, an insulating layer, a source, and a drain of an oxide thin film transistor is sequentially attached to the surface of each functional layer, and thus two adjacent layers are provided. There is a fixed connection between them, and will not be described here.
需要说明的是， 本发明的氧化物薄膜晶体管可以为仅包括基板、 栅极、 绝缘层、 氧化物半导体层、源极和漏极、表面自主装单分子层的封闭结构， 也可以进一步包括钝 化层、 刻蚀阻挡层或像素定义层等， 还可以与其它器件集成等结构。 It should be noted that the oxide thin film transistor of the present invention may be a closed structure including only a substrate, a gate electrode, an insulating layer, an oxide semiconductor layer, a source and a drain, and a surface-independent monolayer, and may further include a blunt structure. Layers, etch barriers or pixel definition layers, etc., can also be integrated with other devices.
也就是说， 本发明是在现有技术的氧化物薄膜晶体管的基础上设置了表面自主装 单分子层， 其适用于现有技术中所有氧化物薄膜晶体管结构。 That is, the present invention is based on the prior art oxide thin film transistor in which a surface autonomous monolayer is provided which is suitable for use in all oxide thin film transistor structures of the prior art.
具体的， 表面自主装单分子层可通过有机溶剂或者无机溶剂或者垸烃硫醇或者通 过垸基或苯基取代的三乙氧基硅垸处理处理氧化物半导体层的表面获得的。 Specifically, the surface-independent monolayer can be obtained by treating the surface of the oxide semiconductor layer with an organic solvent or an inorganic solvent or a terpene hydrocarbon thiol or a triethoxysilane which is substituted with a mercapto group or a phenyl group.
当通过有机溶剂处理时， 有机溶剂为甲醇、 甲苯、 二甲苯、 二甲基甲酰胺 (DMF)、 二甲基亚砜（DMSO)、 六甲基磷酰三胺 (HMPA)、 氧化吡啶或酮类等。 当通过无机溶剂 处理时， 无机溶剂为双氧水等。 When treated by an organic solvent, the organic solvent is methanol, toluene, xylene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), pyridine oxide or ketone. Classes, etc. When treated by an inorganic solvent, the inorganic solvent is hydrogen peroxide or the like.
氧化物半导体被这些有机溶剂处理后， 能使原先吸附在氧化物半导体表面的氧被 吸附， 并且形成一层单分子层阻止外界的氧重新吸附在氧化物半导体上。 When the oxide semiconductor is treated with these organic solvents, oxygen which is originally adsorbed on the surface of the oxide semiconductor is adsorbed, and a monomolecular layer is formed to prevent external oxygen from being re-adsorbed on the oxide semiconductor.
甲醇结构最为简单的饱和一元醇， 在醇类中极性最强， 它容易被氧化成酸， 甲醇 处理后氧化物半导体表面的氧的解吸附的化学式如下： The most simple saturated monohydric alcohol in methanol structure is the most polar in alcohols. It is easily oxidized to acid. The chemical formula for desorption of oxygen on the surface of oxide semiconductor after methanol treatment is as follows:
CH30H + 0"2 (¾Ρίί )→ HCOOH + Η20 + e" 。 酮类为羰基碳直接与两个碳原子相连的有机物， 如丙酮、 乙酰丙酮、 环己酮等。 以丙酮为例， 丙酮较易进一步氧化成酸根离子， 丙酮处理后氧化物半导体表面的氧的解 吸附的化学式如下：CH30H + 0"2 (3⁄4Ρίί ) → HCOOH + Η2 0 + e" . A ketone is an organic substance in which a carbonyl carbon is directly bonded to two carbon atoms, such as acetone, acetylacetone, cyclohexanone, and the like. Taking acetone as an example, acetone is more easily oxidized to acid ion, and the chemical formula of oxygen desorption on the surface of the oxide semiconductor after acetone treatment is as follows:
CH3COCH3 + (；吸附）→ CH3COOH + H20 + C02 + 2e -。CH3COCH3 + (adsorption) → CH3COOH + H2 0 + C02 + 2e -.
甲苯、 二甲苯在某些条件下也能被氧化成苯甲酸。 Toluene and xylene can also be oxidized to benzoic acid under certain conditions.
二甲基甲酰胺 (DMF)、 二甲基亚砜（DMSO)、六甲基磷酰三胺 (HMPA)、氧化吡啶 都是极性很强的非质子溶剂， 非质子极性溶剂能使阳离子， 特别是金属阳离子溶剂化。 因此， 用这类溶剂处理氧化物半导体表面后， 能形成含有金属氧离子的单分子层。 无机溶剂中的双氧水处理后氧化物半导体表面的氧的解吸附的化学式如下：Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), and pyridine oxide are all highly polar aprotic solvents. Aprotic polar solvents can make cations. , especially the cationization of metal cations. Therefore, after treating the surface of the oxide semiconductor with such a solvent, a monomolecular layer containing metal oxygen ions can be formed. The chemical formula for the desorption of oxygen on the surface of the oxide semiconductor after the hydrogen peroxide treatment in the inorganic solvent is as follows:
H202 + 0"(¾Pii)→H20 + 02 + e" ; 双氧水还可以进一步氧化未饱和的氧离子， 减少氧空位缺陷。H2 02 + 0" (3⁄4Pii) → H2 0 + 02 + e"; Hydrogen peroxide can further oxidize unsaturated oxygen ions and reduce oxygen vacancy defects.
表面自主装单分子层也可以通过垸烃硫醇处理得到。 垸烃硫醇的化学式为 CH3(CH2)nSH, n^O), 这类有机物能饱和氧化物半导体的悬挂键， 形成 M-S-(CH2)n CH3, 其中 M为氧化物半导体中的金属氧离子如 Zn、 In, Ga或 Sn等。 这样便在氧化 物半导体表面形成一层自主装单分子层。The surface self-assembled monolayer can also be obtained by treatment with a mercapto mercaptan. The chemical formula of the terpene hydrocarbon thiol is CH3(CH2)n SH, n^O). Such an organic substance can saturate the dangling bond of the oxide semiconductor to form MS-(CH2)n CH3, where M is the metal oxygen in the oxide semiconductor. Ions such as Zn, In, Ga or Sn. This forms a self-assembled monolayer on the surface of the oxide semiconductor.
表面自主装单分子层还可以通过垸基或苯基取代的三乙氧基硅垸处理得到。 垸基 或 苯 基 取 代 的 三 乙 氧 基 硅 垸 的 化 学 式 为 R-(OCH2CH3)3 ， 包 括 n-C12H25Si(OCH2CH3)3、 C6H5Si(OCH2CH3)3等， 它们能在氧化物半导体表面形成很 强的 Si-0-M键， 从而形成自主装的单分子层。 The surface-independent monolayer can also be obtained by treatment with a mercapto or phenyl-substituted triethoxysilane. The fluorenyl or phenyl substituted triethoxysilane has the chemical formula R-(OCH2CH3)3, including n-C12H25Si(OCH2CH3)3, C6H5Si(OCH2CH3)3, etc., which can form a strong surface on the oxide semiconductor. The Si-0-M bond forms a self-assembled monolayer.
与其它界面材料如十八垸基三氯硅氧垸（Octadecyltrichlorosilane, OTS)或六甲基 二硅胺 （hexamethyldisilazene, HMDS) 等相比， 上述的溶剂、 垸烃硫醇和垸基或苯基 取代的三乙氧基硅垸不具有酸性， 处理氧化物半导体时不会腐蚀氧化物半导体， 从而不 会破坏氧化物半导体层。 Compared with other interface materials such as Octadecyltrichlorosilane (OTS) or hexamethyldisilazene (HMDS), the above solvents, terpene thiols and mercapto or phenyl substituted Triethoxysilane does not have an acidity, and the oxide semiconductor is not corroded when the oxide semiconductor is processed, so that the oxide semiconductor layer is not destroyed.
氧化物半导体层的材料为 ZnO， 也可以是 ZnO中掺入 In、 Ga、 Sn、 Cd、 Al、 Si、 Ni、 Ta、 W、 Hf、 Y、 Ti、 La、 Nd、 Ce、 Pr、 Pm、 Sm、 Eu中的任意一种或两种以上原 素。 The material of the oxide semiconductor layer is ZnO, and ZnO may be doped with In, Ga, Sn, Cd, Al, Si, Ni, Ta, W, Hf, Y, Ti, La, Nd, Ce, Pr, Pm, Any one or two or more of Sm and Eu.
该氧化物薄膜晶体管， 通过在氧化物半导体层的裸露面表面设置表面自主装单分 子层，相比原有的氧化物薄膜晶体管器件结构多了一层表面自主装单分子层， 该表面自 主装单分子层能在不损伤氧化物半导体层的前提下有效修饰氧化物表面以降低氧化物 半导体的表面能， 减少水、 氧吸附和解吸附现象， 从而提高器件的稳定性。 The oxide thin film transistor has a surface self-loading monolayer which is disposed on the exposed surface of the oxide semiconductor layer by a surface, and the surface of the oxide thin film transistor device is self-assembled. The monolayer can effectively modify the surface of the oxide without damaging the oxide semiconductor layer to reduce the surface energy of the oxide semiconductor, reduce the adsorption of water and oxygen, and desorb the phenomenon, thereby improving the stability of the device.
同时，这层表面自主装单分子层能填充氧化物半导体上的悬挂键和一些结构缺陷， 提高载流子的迁移率。 At the same time, this surface self-loading monolayer can fill the dangling bonds on the oxide semiconductor and some structural defects, and improve the mobility of carriers.
此外， 这层表面自主装单分子层还能提高氧化物半导体的抗蚀性， 减少后续镀膜 或刻蚀对其造成的损伤，可以不必另外制备保护层，简化了制备工艺，降低了制备成本。 In addition, the surface of the self-installed monolayer can also improve the corrosion resistance of the oxide semiconductor, reduce the damage caused by subsequent coating or etching, and can eliminate the need to separately prepare a protective layer, simplify the preparation process, and reduce the manufacturing cost.
可见， 本发明的氧化物薄膜晶体管具有稳定性好、 制备工艺简单和成本低廉等特 点。 It can be seen that the oxide thin film transistor of the present invention has characteristics of good stability, simple preparation process, and low cost.
实施例 2。 制备实施例 1的氧化物薄膜晶体管的制备方法， 除了常规结构部分的制备工艺外， 还包括通过旋涂、滴涂或浸泡的方法在氧化物半导体层的裸露面表面制备表面自主装单 分子层的工序。Example 2. The preparation method of the oxide thin film transistor of the preparation example 1, in addition to the preparation process of the conventional structural part, further comprises preparing a surface self-assembled monolayer on the exposed surface of the oxide semiconductor layer by spin coating, drop coating or immersion. Process.
具体使用有机溶剂如甲醇、 甲苯、 二甲苯、 二甲基甲酰胺 (DMF)、 二甲基亚砜 (DMSO)、六甲基磷酰三胺 (HMPA)、氧化吡啶或酮类或者无机溶剂如双氧水或者垸烃 硫醇或者通过垸基或苯基取代的三乙氧基硅垸处理所述氧化物半导体层的裸露面表面 制备表面自主装单分子层。 Specifically, an organic solvent such as methanol, toluene, xylene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), pyridine oxide or ketone or an inorganic solvent such as A surface-independent monolayer is prepared by treating the exposed surface of the oxide semiconductor layer with hydrogen peroxide or a terpene hydrocarbon thiol or triethoxysilane having a mercapto or phenyl group.
本发明的制备方法， 由于设置了在氧化物半导体层的裸露面表面设置表面自主装 单分子层的工艺，该表面自主装单分子层能在不损伤氧化物半导体层的前提下有效修饰 氧化物表面以降低氧化物半导体的表面能， 减少水、氧吸附和解吸附现象， 从而提高器 件的稳定性。 In the preparation method of the present invention, since a process of disposing a surface-independent monolayer on the exposed surface of the oxide semiconductor layer is provided, the surface-independent monolayer can effectively modify the oxide without damaging the oxide semiconductor layer. The surface reduces the surface energy of the oxide semiconductor, reduces water, oxygen adsorption and desorption, thereby improving the stability of the device.
同时，这层表面自主装单分子层能填充氧化物半导体上的悬挂键和一些结构缺陷， 提高载流子的迁移率。 At the same time, this surface self-loading monolayer can fill the dangling bonds on the oxide semiconductor and some structural defects, and improve the mobility of carriers.
此外， 这层表面自主装单分子层还能提高氧化物半导体的抗蚀性， 减少后续镀膜 或刻蚀对其造成的损伤，可以不必另外制备保护层，简化了制备工艺，降低了制备成本。 In addition, the surface of the self-installed monolayer can also improve the corrosion resistance of the oxide semiconductor, reduce the damage caused by subsequent coating or etching, and can eliminate the need to separately prepare a protective layer, simplify the preparation process, and reduce the manufacturing cost.
可见， 本发明的氧化物薄膜晶体管的制备方法具有工艺简单和成本低廉等特点， 所制备的氧化物薄膜晶体管也具有稳定性好的特点。 It can be seen that the preparation method of the oxide thin film transistor of the invention has the characteristics of simple process and low cost, and the prepared oxide thin film transistor also has the characteristics of good stability.
实施例 3。Example 3.
一种氧化物薄膜晶体管， 如图 1所示， 设置有基板 10、 栅极 11、 绝缘层 12、 氧化 物半导体层 13、 源极 14a、 漏极 14b和表面自主装单分子层 15。 An oxide thin film transistor, as shown in Fig. 1, is provided with a substrate 10, a gate electrode 11, an insulating layer 12, an oxide semiconductor layer 13, a source electrode 14a, a drain electrode 14b, and a surface-independent monolayer 15.
栅极 11位于基板 10之上， 绝缘层 12位于基板 10和栅极 11之上， 氧化物半导体 层 13覆盖在绝缘层 12的上表面并与栅极 11对应， 源极 14a和漏极 14b相互间隔并与 氧化物半导体层 13的两端电性相连， 表面自主装单分子层 15位于氧化物半导体层 13 的上表面未被源极 14a和漏极 14b覆盖的区域。 The gate electrode 11 is located on the substrate 10, the insulating layer 12 is located on the substrate 10 and the gate electrode 11. The oxide semiconductor layer 13 covers the upper surface of the insulating layer 12 and corresponds to the gate electrode 11. The source electrode 14a and the drain electrode 14b are mutually connected. The spacers are electrically connected to both ends of the oxide semiconductor layer 13, and the surface-independent monolayer 15 is located in a region where the upper surface of the oxide semiconductor layer 13 is not covered by the source 14a and the drain 14b.
基板 10为玻璃、 塑料、 硅片、 不锈钢、 石英等衬底材料中的一种， 也可以进一步 包括覆盖在衬底上面的缓冲层或水氧阻隔层等。 The substrate 10 is one of a substrate material such as glass, plastic, silicon wafer, stainless steel, quartz, etc., and may further include a buffer layer or a water-oxygen barrier layer or the like covering the substrate.
栅极 11的材料为金属、 合金、 掺杂硅、 导电金属氧化物、 导电聚合物等， 或是由 以上材料的任意组合构成的两层以上的叠层薄膜。 The material of the gate electrode 11 is a metal, an alloy, doped silicon, a conductive metal oxide, a conductive polymer or the like, or a laminated film of two or more layers composed of any combination of the above materials.
绝缘层 12为二氧化硅、 氮化硅、 氧化铝、 氧化镱、 氧化钛、 氧化铪、 氧化钽、 氧 化锆、 聚酰亚胺、 光刻胶、 苯丙环丁烯或聚甲基丙烯酸甲酯等构成的单层薄膜， 或是由 以上材料的任意组合构成的两层以上的叠层薄膜。The insulating layer 12 is silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, titanium oxide, hafnium oxide, tantalum oxide, oxygen. A single-layer film composed of zirconium, polyimide, photoresist, styrene-butadiene or polymethyl methacrylate, or a laminated film of two or more layers composed of any combination of the above materials.
氧化物半导体层 13的材料可以为 ZnO， 也可以是 ZnO中掺入 In、 Ga、 Sn、 Cd、 Al、 Si、 Ni、 Ta、 W、 Hf、 Y、 Ti、 La、 Nd、 Ce、 Pr、 Pm、 Sm、 Eu中的任意一种以上 或两种以上元素。 The material of the oxide semiconductor layer 13 may be ZnO, or ZnO may be doped with In, Ga, Sn, Cd, Al, Si, Ni, Ta, W, Hf, Y, Ti, La, Nd, Ce, Pr, Any one or more of Pm, Sm, and Eu.
源极 14a和漏极 14b的材料为金属、 合金、 导电金属氧化物、 导电聚合物等的单 层薄膜， 或是由以上材料的任意组合构成的两层以上的叠层薄膜。 The material of the source electrode 14a and the drain electrode 14b is a single-layer film of a metal, an alloy, a conductive metal oxide, a conductive polymer or the like, or a laminated film of two or more layers composed of any combination of the above materials.
表面自主装单分子层 15可通有机溶剂或者无机溶剂或者垸烃硫醇或者通过垸基或 苯基取代的三乙氧基硅垸处理处理氧化物半导体层 13的表面获得的， 其处理方式与实 施例 1相同， 在此不再赘述。 The surface-independent monolayer 15 can be obtained by treating the surface of the oxide semiconductor layer 13 with an organic solvent or an inorganic solvent or a terpene hydrocarbon thiol or a triethoxysilane substituted by a mercapto or phenyl group. The embodiment 1 is the same and will not be described again.
该氧化物薄膜晶体管的制备工序为： 在基板 10上依次制备栅极 11、 绝缘层 12、 氧化物半导体层 13、 源极 14a漏极 14b层和表面自主装单分子层 15。 The oxide thin film transistor is prepared by sequentially preparing a gate electrode 11, an insulating layer 12, an oxide semiconductor layer 13, a drain electrode 14b layer of the source electrode 14a, and a surface-molding single molecular layer 15 on the substrate 10.
具体的步骤如下： The specific steps are as follows:
( 1 ) 在基板 10上通过溅射的方法制备一层厚度为 100〜500nm的导电薄膜， 并 通过遮挡掩膜或光刻的方法图形化制备栅极 11 ; (1) preparing a conductive film having a thickness of 100 to 500 nm by sputtering on the substrate 10, and patterning the gate 11 by masking or photolithography;
(2)再通过阳极氧化法、热氧化法、物理气相沉积法或化学气相沉积法在栅极 11 层上部制备厚度为 100〜1000nm的薄膜， 并通过遮挡掩膜或光刻的方法图形化制备绝 缘层 12; (2) preparing a film having a thickness of 100 to 1000 nm on the upper portion of the gate 11 layer by anodization, thermal oxidation, physical vapor deposition or chemical vapor deposition, and patterning by masking or photolithography Insulation layer 12;
(3 )接着， 通过溅射或溶胶-凝胶的方法制备厚度为 10〜100nm的薄膜， 并通过 掩膜或光刻的方法图形化制得氧化物层； (3) Next, a film having a thickness of 10 to 100 nm is prepared by sputtering or a sol-gel method, and an oxide layer is patterned by masking or photolithography;
(4) 采用真空蒸镀或溅射的方法制备一层厚度为 100〜1000nm 的导电层， 采用 掩膜或光刻的方法图形化同时得到源极 14a和漏极 14b;(4) A conductive layer having a thickness of 100 to 1000 nm is prepared by vacuum evaporation or sputtering, and a source 14a and a drain 14b are simultaneously obtained by masking or photolithography;
(5 )通过旋涂、滴涂或浸泡的方法制得表面自主装单分子层 15: 旋涂是将上述的 溶剂、垸烃硫醇、垸基或苯基取代的三乙氧基硅垸中的任意一种滴至氧化物薄膜晶体管 的氧化物半导体层 13上， 然后通过旋涂甩干； 滴涂是将上述的溶剂、 垸烃硫醇、 垸基 或苯基取代的三乙氧基硅垸中的任意一种滴至氧化物薄膜晶体管的氧化物半导体层 13 上， 然后让其自然干燥、 吹干或烘干； 浸泡是将含有氧化物半导体层 13的器件浸泡在 上述的溶剂、垸烃硫醇、垸基或苯基取代的三乙氧基硅垸中的任意一种中， 浸泡过程可 以伴随室温至 150°C的加热， 然后将其取出甩干、 吹干、 烘干或自然干燥。 需要说明的是， 步骤（5 )可以选取任意几种处理剂按任意顺序多次处理制得表面 自主装单分子层 15。(5) Surface self-loading monolayer 15 is obtained by spin coating, dripping or immersion: spin coating is performed by using the above solvent, terpene thiol, mercapto or phenyl substituted triethoxysilane. Any one of which is dropped onto the oxide semiconductor layer 13 of the oxide thin film transistor, and then dried by spin coating; the dropwise coating is a solvent, a mercaptan thiol, a mercapto group or a phenyl-substituted triethoxysilane. Any one of the crucibles is dropped onto the oxide semiconductor layer 13 of the oxide thin film transistor, and then allowed to be naturally dried, dried or dried; the immersion is to soak the device containing the oxide semiconductor layer 13 in the above solvent, hydrazine In any one of a hydrocarbon thiol, a mercapto group or a phenyl-substituted triethoxysilane, the soaking process can be carried out with heating from room temperature to 150 ° C, and then taken out, dried, dried, dried or naturally dry. It should be noted that step (5) may select any of several treatment agents to be processed in any order for multiple times to obtain a surface self-assembled monolayer 15.
需要说明的是， 通过步骤 （5 ) 得表面自主装单分子层 15后可以进一步对其进行 热处理， 以使反应更充分、 性能更稳定。 It should be noted that the surface of the monolayer 15 can be further heat-treated by the step (5) to further make the reaction more complete and the performance more stable.
该氧化物薄膜晶体管及其制备方法，通过在氧化物半导体层 13的裸露面表面制备 表面自主装单分子层 15， 相比原有的氧化物薄膜晶体管器件结构多了一层表面自主装 单分子层 15， 该表面自主装单分子层 15能在不损伤氧化物半导体层 13的前提下有效 修饰氧化物表面以降低氧化物半导体的表面能， 减少水、氧吸附和解吸附现象， 从而提 高器件的稳定性。 The oxide thin film transistor and the method for fabricating the same, by preparing a surface-independent monolayer 15 on the exposed surface of the oxide semiconductor layer 13, a surface self-loading single molecule is added to the original oxide thin film transistor device structure The layer 15 , the surface self-loading monolayer 15 can effectively modify the oxide surface without damaging the oxide semiconductor layer 13 to reduce the surface energy of the oxide semiconductor, reduce water and oxygen adsorption and desorption, thereby improving the device. stability.
同时，这层表面自主装单分子层 15能填充氧化物半导体上的悬挂键和一些结构缺 陷， 提高载流子的迁移率。 At the same time, this surface self-assembled monolayer 15 can fill the dangling bonds on the oxide semiconductor and some structural defects, improving the mobility of carriers.
此外， 这层表面自主装单分子层 15还能提高氧化物半导体的抗蚀性， 减少后续镀 膜或刻蚀对其造成的损伤， 可以不必另外制备保护层， 简化了制备工艺， 降低了制备成 本。 In addition, the surface of the self-assembled monolayer 15 can also improve the corrosion resistance of the oxide semiconductor, reduce damage caused by subsequent coating or etching, and can eliminate the need to separately prepare a protective layer, simplify the preparation process, and reduce the manufacturing cost. .
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备工艺简单、 成本低廉。 实施例 4。 It can be seen that the oxide thin film transistor of the invention has good stability, simple preparation process and low cost. Example 4.
一种氧化物薄膜晶体管， 与实施例 3的不同之处在于： 源极 25a和漏极 25b相互 间隔并与表面自主装单分子层 24的上表面的两端电性相连， 如图 2所示。 An oxide thin film transistor is different from the third embodiment in that the source electrode 25a and the drain electrode 25b are spaced apart from each other and electrically connected to both ends of the upper surface of the surface self-assembled monolayer 24, as shown in FIG. .
其制备工序为， 在基板 20上依次制备栅极 21、 绝缘层 22、 氧化物半导体层 23、 表面自主装单分子层 24， 最后制备源极 25a和漏极 25b。 The preparation process is such that the gate electrode 21, the insulating layer 22, the oxide semiconductor layer 23, and the surface-independent monolayer 24 are sequentially formed on the substrate 20, and finally the source electrode 25a and the drain electrode 25b are prepared.
本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本低廉。 实施例 5。 The oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost. Example 5.
一种氧化物薄膜晶体管， 与实施例 3的不同之处在于： 氧化物半导体层 34覆盖在 源极 33a、 漏极 33b以及绝缘层 32的上表面并与栅极 31相对应， 表面自主装单分子层 35位于氧化物半导体层 34的上表面， 如图 3所示。 An oxide thin film transistor is different from Embodiment 3 in that an oxide semiconductor layer 34 covers the upper surfaces of the source 33a, the drain 33b, and the insulating layer 32 and corresponds to the gate 31, and the surface is self-assembled. The molecular layer 35 is located on the upper surface of the oxide semiconductor layer 34 as shown in FIG.
其制备工序为， 在基板 30上依次制备栅极 31、 绝缘层 32、 源极 33a漏极 33b、 氧 化物半导体层 34和表面自主装单分子层 35。 The preparation process is such that a gate electrode 31, an insulating layer 32, a drain electrode 33b of the source electrode 33a, an oxide semiconductor layer 34, and a surface-matrix monolayer 35 are sequentially formed on the substrate 30.
本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本低廉。 实施例 6。 本实施例的氧化物薄膜晶体管的结构如图 1所示， 其具体制备方法是： 首先在玻璃基板 10上通过溅射的方法制备一层厚度为 300nm的铝-钕合金薄膜，并 通过光刻的方法图形化得到栅极 11。The oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost. Example 6. The structure of the oxide thin film transistor of this embodiment is as shown in FIG. 1 , and the specific preparation method is as follows: First, an aluminum-germanium alloy film having a thickness of 300 nm is prepared by sputtering on the glass substrate 10, and photolithography is performed. The method is graphically obtained to obtain the gate 11.
绝缘层 12通过阳极氧化法制备， 阳极氧化中使用的电解质溶液为酒石酸铵和乙二 醇的混合液， 将制备好栅极 11的基片和不锈钢板放入电解质溶液中分别作为阳极和阴 极， 先在阳极和阴极之间加恒定的电流， 阳极和阴极之间的电压将随时间线性升高， 当 电压达到 100V 时保持电压恒定 100V, 直至阳极和阴极之间的电流减小至约为 0.001 mA/cm2时， 铝钕合金表面便形成一层厚度为 200nm的氧化铝钕绝缘层 12。The insulating layer 12 is prepared by anodizing, and the electrolyte solution used in the anodizing is a mixture of ammonium tartrate and ethylene glycol, and the substrate on which the gate 11 is prepared and the stainless steel plate are placed in an electrolyte solution as an anode and a cathode, respectively. First, a constant current is applied between the anode and the cathode. The voltage between the anode and the cathode will rise linearly with time. When the voltage reaches 100V, the voltage is kept constant at 100V until the current between the anode and the cathode is reduced to about 0.001. At mA/cm2 , an aluminum tantalum insulating layer 12 having a thickness of 200 nm is formed on the surface of the aluminum-niobium alloy.
氧化物半导体层 13的材料为 IGZO ( ln203、 Ga203和 ZnO的摩尔比为 1： 1： 2)， 氧化物半导体层 13是通过射频磁控溅射法制备厚度为 40nm的薄膜并通过遮挡掩膜的 方法进行图形化制备而成。The material of the oxide semiconductor layer 13 is IGZO (molar ratio of ln2 O3 , Ga2 O3 , and ZnO is 1: 1: 2), and the oxide semiconductor layer 13 is prepared by RF magnetron sputtering to a thickness of 40 nm. The film is prepared by patterning by masking the mask.
源极 14a和漏极 14b的材料为 ITO， 通过溅射法制备厚度为 280nm的 ITO薄膜， 通过遮挡掩膜的方法同时制备源极 14a和漏极 14b，使得形成宽度和长度分别为 ΙΟΟΟμηι 和 300μηι、 宽长比为 10:3的沟道。 The material of the source 14a and the drain 14b is ITO, and an ITO film having a thickness of 280 nm is prepared by a sputtering method, and the source 14a and the drain 14b are simultaneously prepared by masking the mask so that the width and length are ΙΟΟΟμηι and 300μη, respectively. A channel with a width to length ratio of 10:3.
表面自主装单分子层 15通过丙酮处理得到，具体是将丙酮滴在上述制备好的器件 的上表面， 然后以 2000r/min的转速旋涂 40s制得。 The surface-independent monolayer 15 is obtained by acetone treatment, specifically, dropping acetone on the upper surface of the above-prepared device, and then spin-coating at a rate of 2000 r/min for 40 s.
再将整个器件在空气中加热至 120°C保持 10min。 The entire device was then heated to 120 ° C in air for 10 min.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。 图 4是实施例 6的氧化物 薄膜晶体管测得的转移特性曲线， 即漏极 14b电流与栅极 11 电压之间的关系。 曲线的 测试条件为： 源极 14a电压 ( Vs ) 为 0V， 漏极 14b电压 （ϊ¾) 恒定为 5V， 栅极 11电 压 （ϊ¾) 先从 -10V到 10V正向扫描， 再从 -10V到 10V反向扫描， 测试漏极 14b电流 (7D) o 图 4中还示意了丙酮处理前器件的转移特性曲线。 从图 4的两组曲线的对比中 可以看出， 甲醇处理后的氧化物薄膜晶体管的磁滞效应明显减小， 意味着氧吸附 -解吸 附效应明显减小； 同时亚阈值摆幅明显增大， 迁移率明显增高， 意味着缺陷的减少。The properties of the prepared oxide thin film transistor device were tested in air. 4 is a transfer characteristic curve measured by the oxide thin film transistor of Example 6, that is, a relationship between the current of the drain 14b and the voltage of the gate electrode 11. The test conditions of the curve are: source 14a voltage (Vs ) is 0V, drain 14b voltage (ϊ3⁄4) is constant at 5V, and gate 11 voltage (ϊ3⁄4) is first scanned from -10V to 10V, then from -10V to 10V reverse scan, test drain 14b current (7D ) o Figure 4 also shows the transfer characteristics of the device before acetone treatment. It can be seen from the comparison of the two sets of curves in Fig. 4 that the hysteresis effect of the oxide thin film transistor after methanol treatment is significantly reduced, which means that the oxygen adsorption-desorption effect is significantly reduced; and the subthreshold swing is significantly increased. The apparent increase in mobility means a reduction in defects.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
实施例 7。 Example 7.
本实施例的氧化物薄膜晶体管的结构如图 2所示， 其制备方法具体如下： 首先在玻璃基板 20上通过溅射法制备一层厚度为 300nm的铝-钕合金薄膜，并通过 光刻的方法图形化得到栅极 21。The structure of the oxide thin film transistor of this embodiment is as shown in FIG. 2, and the preparation method thereof is as follows: First, an aluminum-bismuth alloy thin film having a thickness of 300 nm is prepared by sputtering on the glass substrate 20, and passed through The method of photolithography is patterned to obtain the gate 21.
绝缘层 22和氧化物半导体层 23的材料为和制备方法分别与实施例 6中的绝缘层 12和氧化物半导体层 13的相同。 The material of the insulating layer 22 and the oxide semiconductor layer 23 and the preparation method are the same as those of the insulating layer 12 and the oxide semiconductor layer 13 in Embodiment 6, respectively.
表面自主装单分子层 24通过丙酮处理得到， 将丙酮滴在上述制备的器件的上部， 然后以 2000r/min的转速旋涂 40s制得。 再将器件在空气中加热 120°C 10min。 The surface-independent monolayer 24 was obtained by acetone treatment, and acetone was dropped on the upper portion of the device prepared above, and then spin-coated at 2000 r/min for 40 s. The device was then heated in air at 120 ° C for 10 min.
然后在表面自主装单分子层 24上面制备源极 25a和漏极 25b， 其材料和制备方法 与实施例 6的源极 14a和漏极 14b的相同。 Then, a source electrode 25a and a drain electrode 25b are formed on the surface-independent monolayer 24, and the material and preparation method are the same as those of the source electrode 14a and the drain electrode 14b of the embodiment 6.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。 图 5是实施例 7的氧化物 薄膜晶体管测得的转移特性曲线， 图中还画出了未设置表面自主装单分子层 24的器件 的转移特性曲线。从图 5的两组曲线的对比中可以看出， 虽然源极 25a和漏极 25b区域 的接触电阻变大了，但是丙酮处理后的氧化物薄膜晶体管的磁滞效应明显减小， 意味着 氧吸附 -解吸附效应明显减小。 The properties of the prepared oxide thin film transistor device were tested in air. Fig. 5 is a transfer characteristic curve measured by the oxide thin film transistor of Example 7, and the transfer characteristic curve of the device in which the surface-independent monolayer 24 is not provided is also shown. It can be seen from the comparison of the two sets of curves of FIG. 5 that although the contact resistance of the source 25a and the drain 25b regions becomes larger, the hysteresis effect of the oxide-treated oxide thin film transistor is remarkably reduced, which means oxygen. The adsorption-desorption effect is significantly reduced.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
实施例 8。 Example 8.
本实施例的氧化物薄膜晶体管的结构如图 3所示， 其制备方法如下： The structure of the oxide thin film transistor of this embodiment is as shown in FIG. 3, and the preparation method thereof is as follows:
首先在玻璃基板 30上通过溅射的方法制备一层厚度为 300nm的铝-钕合金薄膜，通 过光刻的方法图形化得到栅极 31。 First, an aluminum-niobium alloy thin film having a thickness of 300 nm was formed by sputtering on the glass substrate 30, and the gate electrode 31 was patterned by photolithography.
绝缘层 32的制备方法分别与实施例 6中的绝缘层 12的相同。 The manufacturing method of the insulating layer 32 is the same as that of the insulating layer 12 in the embodiment 6, respectively.
源极 33a和漏极 33b的材料为 ITO， 通过溅射法制备在绝缘层 32上制备厚度为 280nm的薄膜， 再通过遮挡掩膜的方法同时制备源极 33a和漏极 33b， 使得形成宽度和 长度分别为 ΙΟΟΟμηι和 300μηι、 宽长比为 10:3的沟道。 The material of the source 33a and the drain 33b is ITO, a film having a thickness of 280 nm is prepared on the insulating layer 32 by a sputtering method, and the source 33a and the drain 33b are simultaneously prepared by masking the mask, so that the width and the width are formed. The lengths are ΙΟΟΟμηι and 300μηι, and the channel has a width to length ratio of 10:3.
氧化物半导体层 34的材料为和制备方法分别与实施例 6中的氧化物半导体层 13的 相同，制备在源极 33a和漏极 33b的上表面以及绝缘层 32的上表面并与栅极 31相对应。 The material of the oxide semiconductor layer 34 and the preparation method are the same as those of the oxide semiconductor layer 13 in Embodiment 6, respectively, and the upper surfaces of the source 33a and the drain 33b and the upper surface of the insulating layer 32 and the gate 31 are prepared. Corresponding.
表面自主装单分子层 35通过丙酮处理得到，具体是将丙酮滴在上述制备的器件的 上部， 然后以 2000r/min的转速旋涂 40s制得。 The surface self-assembled monolayer 35 was obtained by acetone treatment, specifically, acetone was dropped on the upper portion of the device prepared above, and then spin-coated at 2000 r/min for 40 s.
最后再将器件在空气中加热 120°C 10min。 Finally, the device was heated in air at 120 ° C for 10 min.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。 图 6是实施例 8的氧化物 薄膜晶体管测得的转移特性曲线， 图中还画出了未经甲醇处理的器件的转移特性曲线。 从图 6的两组曲线的对比中可以看出，丙酮处理后的氧化物薄膜晶体管的磁滞效应明显 减小， 意味着氧吸附-解吸附效应明显减小。The properties of the prepared oxide thin film transistor device were tested in air. Fig. 6 is a graph showing the transfer characteristic of the oxide thin film transistor of Example 8, and the transfer characteristic curve of the device which was not treated with methanol was also shown. It can be seen from the comparison of the two sets of curves in Fig. 6 that the hysteresis effect of the oxide thin film transistor after acetone treatment is remarkably reduced, which means that the oxygen adsorption-desorption effect is remarkably reduced.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
实施例 9。 Example 9.
本实施例的氧化物薄膜晶体管的结构以及制备方法除表面自主装单分子层 15 以外 均与实施例 6中的相同。 所不同的是采用对二甲苯处理得到表面自主装单分子层 15， 具体是将对二甲苯滴在上述制备的器件的上部，然后以 2000r/min的转速旋涂 40s制得， 所制备的氧化物薄膜晶体管未经进一步热处理。 The structure and preparation method of the oxide thin film transistor of this embodiment are the same as those in the embodiment 6 except for the surface-independent monolayer 15. The difference is that the surface is self-assembled monolayer 15 by p-xylene treatment, specifically, the paraxylene is dropped on the upper part of the device prepared above, and then spin-coated at 2000 r/min for 40 s, and the prepared oxidation is performed. The thin film transistor was not further heat treated.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。 图 7是实施例 9的氧化物 薄膜晶体管测得的转移特性曲线， 图中还画出了对二甲苯处理前器件的转移特性曲线。 从图 7的两组曲线的对比中可以看出，对二甲苯处理后的氧化物薄膜晶体管的磁滞效应 明显减小， 意味着氧吸附-解吸附效应明显减小； 同时亚阈值摆幅明显减小， 迁移率明 显增高， 意味着缺陷的减少。 The properties of the prepared oxide thin film transistor device were tested in air. Fig. 7 is a transfer characteristic curve measured by the oxide thin film transistor of Example 9, and the transfer characteristic curve of the device before para-xylene treatment is also shown. It can be seen from the comparison of the two sets of curves in Fig. 7 that the hysteresis effect of the p-xylene treated oxide thin film transistor is significantly reduced, which means that the oxygen adsorption-desorption effect is significantly reduced; and the subthreshold swing is obvious. Decrease, the mobility is significantly increased, which means the reduction of defects.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
实施例 10。 Example 10.
本实施例的氧化物薄膜晶体管的结构以及制备方法除表面自主装单分子层 15 以外 均与实施例 6中的相同。 所不同的是采用垸烃硫醇处理得到表面自主装单分子层 15， 选用化学式为 CH3CCH2)12SH的垸烃硫醇， 将器件浸泡在 CH3CCH2)12SH溶液中 48小 时， 并同时伴随加热 50°C。The structure and preparation method of the oxide thin film transistor of the present embodiment are the same as those in the embodiment 6 except for the surface-independent monolayer 15. The difference is that the surface self-assembled monolayer 15 is obtained by treatment with anthracene thiol, and the hydrazine thiol of the formula CH3CCH2)12 SH is selected, and the device is immersed in CH3CCH2)12 SH solution for 48 hours, accompanied by heating 50. °C.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。图 8是实施例 10的氧化物 薄膜晶体管测得的转移特性曲线， 图中还画出了 CH3(CH2)12SH处理前器件的转移特性 曲线。 从图 8的两组曲线的对比中可以看出， CH3(CH2)12SH处理后的氧化物薄膜晶体 管的磁滞效应明显减小， 意味着氧吸附-解吸附效应明显减小； 同时亚阈值摆幅明显减 小， 迁移率明显增高， 意味着缺陷的减少。The properties of the prepared oxide thin film transistor device were tested in air. Figure 8 is a graph showing the transfer characteristics of the oxide thin film transistor of Example 10, and also shows the transfer characteristics of the device before CH3(CH2)12 SH treatment. It can be seen from the comparison of the two sets of curves in Fig. 8 that the hysteresis effect of the oxide thin film transistor after CH3(CH2)12 SH treatment is significantly reduced, which means that the oxygen adsorption-desorption effect is significantly reduced; and the subthreshold value The swing is significantly reduced and the mobility is significantly increased, which means a reduction in defects.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
实施例 11。 本实施例的氧化物薄膜晶体管的结构以及制备方法除表面自主装单分子层 15 以外 均与实施例 6中的相同，所不同的是采用垸基或苯基取代的三乙氧基硅垸处理得到表面 自主装单分子层 15。 具体是选用苯基取代的三乙氧基硅垸 （化学式为 C6H5Si(OCH2CH3)3 ), 将器件浸泡在 C6H5Si(OCH2CH3)3溶液中 1小时， 并同时伴随 加热 45°C。 所制备的器件再经后退火 100°C。Example 11. The structure and preparation method of the oxide thin film transistor of this embodiment are the same as those in the embodiment 6 except for the surface-independent monolayer 15 except that the ruthenium group or the phenyl group-substituted triethoxysilane is used. A surface-independent monolayer 15 is obtained. Specifically, a phenyl-substituted triethoxysilane (chemical formula: C6H5Si(OCH2CH3)3) was used, and the device was immersed in a C6H5Si(OCH2CH3)3 solution for 1 hour with heating at 45 °C. The prepared device was post-annealed at 100 °C.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。 图 9是实施例 11的氧化物 薄膜晶体管测得的转移特性曲线， 图中还画出了 C6H5Si(OCH2CH3)3处理前器件的转 移特性曲线。 从图 9 的两组曲线的对比中可以看出， C6H5Si(OCH2CH3)3处理后的氧 化物薄膜晶体管的磁滞效应明显减小， 意味着氧吸附-解吸附效应明显减小； 同时亚阈 值摆幅明显减小， 迁移率明显增高， 意味着缺陷的减少。 The properties of the prepared oxide thin film transistor device were tested in air. Fig. 9 is a transfer characteristic curve measured by the oxide thin film transistor of Example 11, and the transfer characteristic curve of the device before the treatment of C6H5Si(OCH2CH3)3 is also shown. It can be seen from the comparison of the two sets of curves in Fig. 9 that the hysteresis effect of the oxide thin film transistor treated by C6H5Si(OCH2CH3)3 is significantly reduced, which means that the oxygen adsorption-desorption effect is significantly reduced; and the subthreshold pendulum The width is significantly reduced and the mobility is significantly increased, which means a reduction in defects.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
实施例 12。 Example 12.
本实施例的氧化物薄膜晶体管的结构如图 1所示， 其具体制备方法如下： 首先在玻璃基板 10上通过溅射的方法制备一层厚度为 300nm的金属钼薄膜， 通过 光刻的方法图形化得到栅极 11。 The structure of the oxide thin film transistor of this embodiment is as shown in FIG. 1 , and the specific preparation method is as follows: First, a metal molybdenum thin film having a thickness of 300 nm is prepared by sputtering on the glass substrate 10, and the pattern is formed by photolithography. The gate 11 is obtained.
绝缘层 12是通过等离子增强型化学气相沉积 （PECVD) 法制备的 SiNx/Si02双层 复合薄膜， SiNx和 Si02的厚度均为 100nm。The insulating layer 12 is a SiNx/SiO2 double-layer composite film prepared by a plasma enhanced chemical vapor deposition (PECVD) method, and the thickness of both SiNx and SiO2 is 100 nm.
氧化物半导体层 13的材料为 NAIZO (Nd203、 A1203、 ln203、 Ga203和 ZnO的摩尔 比为 0.05: 0.1： 1： 1 )， 是通过射频磁控溅射法制制备的厚度为 30nm的薄膜， 并通过 光刻的方法进行图形化。The material of the oxide semiconductor layer 13 is NAIZO (Nd2 03 , A12 03 , ln2 03 , Ga2 03 and ZnO molar ratio is 0.05: 0.1: 1: 1 ), which is by RF magnetron sputtering. A film having a thickness of 30 nm prepared by a firing method was patterned and patterned by photolithography.
源极 14a和漏极 14b的材料为 ITO，是通过溅射的方法制备厚度为 280nm的薄膜， 并通过光刻剥起 （lift-off) 的方法同时制得源极 14a和漏极 14b， 形成沟道的宽度和长 度分别为 ΙΟΟμηι禾口 30μηι、 宽长比为 10:3。 The material of the source 14a and the drain 14b is ITO, and a film having a thickness of 280 nm is prepared by a sputtering method, and a source 14a and a drain 14b are simultaneously formed by a photolithography lift-off method to form a source 14a and a drain 14b. The width and length of the channel are respectively ΙΟΟμηι and 30μηι, and the aspect ratio is 10:3.
表面自主装单分子层 15 通过双氧水处理得到， 具体将器件浸泡在双氧水溶液中 lOmin取出， 再用去离子水清洗烘干。 The surface self-installed monolayer 15 is obtained by hydrogen peroxide treatment, and the device is specifically immersed in an aqueous solution of hydrogen peroxide for 10 minutes, and then washed and washed with deionized water.
最后再将整个器件在空气中加热 150°C 10min。 Finally, the entire device was heated in air at 150 ° C for 10 min.
将所制备的氧化物薄膜晶体管器件性能在空气中测试。 图 10是实施例 12的氧化 物薄膜晶体管测得的转移特性曲线， 图中还画出了双氧水处理前器件的转移特性曲线。 从图 10的两组曲线的对比中可以看出， 双氧水处理后的氧化物薄膜晶体管的磁滞效应 明显减小， 意味着氧吸附-解吸附效应明显减小。The properties of the prepared oxide thin film transistor device were tested in air. Fig. 10 is a graph showing the transfer characteristic of the oxide thin film transistor of Example 12, and the transfer characteristic curve of the device before the hydrogen peroxide treatment is also shown. It can be seen from the comparison of the two sets of curves in Fig. 10 that the hysteresis effect of the oxide thin film transistor after the hydrogen peroxide treatment is remarkably reduced, which means that the oxygen adsorption-desorption effect is remarkably reduced.
可见， 本发明的氧化物薄膜晶体管具有稳定性好， 制备方法具有工艺简单、 成本 低廉。 It can be seen that the oxide thin film transistor of the invention has good stability, and the preparation method has the advantages of simple process and low cost.
最后应当说明的是， 以上实施例仅用以说明本发明的技术方案而非对本发明保护 范围的限制，尽管参照较佳实施例对本发明作了详细说明， 本领域的普通技术人员应当 理解， 可以对本发明的技术方案进行修改或者等同替换， 而不脱离本发明技术方案的实 质和范围。 It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those skilled in the art The technical solutions of the present invention are modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201310249839.4 | 2013-06-21 | ||
| CN201310249839.4ACN103311313B (en) | 2013-06-21 | 2013-06-21 | Oxide thin film transistor and preparation method thereof |
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| WO2014201816A1true WO2014201816A1 (en) | 2014-12-24 |
| Application Number | Title | Priority Date | Filing Date |
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| PCT/CN2013/089151WO2014201816A1 (en) | 2013-06-21 | 2013-12-12 | Oxide thin-film transistor and preparation method therefor |
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