技术领域technical field
本发明属于光电器件领域，具体涉及一种可揭式任意图形化的透明导电薄膜及其应用。The invention belongs to the field of photoelectric devices, and in particular relates to a detachable transparent conductive film with arbitrary patterns and an application thereof.
背景技术Background technique
以掺锡氧化铟(ITO)、掺氟氧化锡(FTO)和掺铝氧化锌(AZO)薄膜为代表的透明导电氧化物(TCO)通常具有禁带宽、可见光谱区光透射率高和电阻率低等共同光电特性，被广泛地应用于太阳能电池、平面显示、特殊功能窗口涂层、抗电磁波干扰及其它光电器件领域。近年，氧化物-金属-氧化物(如ITO|Ag|ITO，AZO|Ag|AZO，NiO|Ag|NiO等)和金属纳米结构基透明导电复合膜等研制的透明导电薄膜也逐步应用到太阳能电池、显示和抗电磁干扰等领域。在太阳能电池、显示等光电领域通常要求至少一面电极是透明导电薄膜，要求高透光率和高导电率。但有些特殊领域，如半透明太阳能电池或者全透明显示，要求上下电极都有透明要求。在防电磁干扰的场所，使用非透明的镍银金属复合涂层或者金属薄膜通常都具有良好电磁抗干扰能力，但既要高透光性又要强抗电磁干扰能力的窗口材料和窗口薄膜仍有很强应用领域，如军用飞机窗口、仪表仪器窗口以及要求良好电磁屏蔽场场所的观察窗口等。高透光和高导电薄膜通常是相互制约和矛盾对立的，通常增加薄膜厚度可以提高薄膜导电能力，但会降低透光率。在太阳能电池中，增加透光性可提高电池光吸收，但薄膜方块电阻增加导致高的串联电阻，降低了电池效率。在发光显示如有机发光器件(OLED)中，高透光电极能提高OLED器件的光逸出，但高阻值电极需要更高驱动电压和导致更高能量耗散。在防电磁波干扰场所，低电阻薄膜有利于提高防电磁干扰能力，高阻值透明窗口将降低防电磁波干扰能力。实际应用中为了降低其负面影响，尽量减少高阻值透明薄膜覆盖面积，增加低阻值薄膜的覆盖面积，通常是一种可行办法。目前常用透明导电薄膜如ITO、FTO和AZO，氧化物-金属-氧化物导电薄膜如AZO|Ag|AZO，金属纳米结构基组成透明导电复合膜等在衬底上制备透明导电薄膜后，现有技术手段在后续应用中就很难根据需要灵活的进行图形化调整，这为后期应用带来不便和提高应用成本。Transparent conductive oxides (TCO) represented by tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO) and aluminum-doped zinc oxide (AZO) films usually have a band gap, high light transmittance in the visible spectrum, and resistivity. Low common optoelectronic properties are widely used in solar cells, flat panel displays, special function window coatings, anti-electromagnetic interference and other optoelectronic devices. In recent years, transparent conductive films developed by oxide-metal-oxide (such as ITO|Ag|ITO, AZO|Ag|AZO, NiO|Ag|NiO, etc.) and metal nanostructure-based transparent conductive composite films have also been gradually applied to solar energy. Battery, display and anti-electromagnetic interference and other fields. In optoelectronic fields such as solar cells and displays, at least one electrode is usually required to be a transparent conductive film, requiring high light transmittance and high conductivity. However, in some special fields, such as semi-transparent solar cells or fully transparent displays, both upper and lower electrodes are required to be transparent. In the place of anti-electromagnetic interference, the use of non-transparent nickel-silver metal composite coating or metal film usually has good electromagnetic anti-interference ability, but there are still window materials and window films that require high light transmission and strong anti-electromagnetic interference ability. Very strong application fields, such as military aircraft windows, instrumentation windows, and observation windows that require good electromagnetic shielding fields. High light transmission and high conductivity films are usually mutually restrictive and contradictory. Generally, increasing the film thickness can improve the conductivity of the film, but will reduce the light transmittance. In solar cells, increasing the light transmission can improve the light absorption of the cell, but the increased sheet resistance of the sheet leads to high series resistance, which reduces the cell efficiency. In light-emitting displays such as organic light-emitting devices (OLEDs), high-transmittance electrodes can improve light escape from OLED devices, but high-resistance electrodes require higher driving voltages and result in higher energy dissipation. In the anti-electromagnetic interference place, the low-resistance film is beneficial to improve the anti-electromagnetic interference ability, and the high-resistance transparent window will reduce the anti-electromagnetic interference ability. In order to reduce its negative impact in practical applications, it is usually a feasible way to minimize the coverage area of high-resistance transparent films and increase the coverage area of low-resistance films. Currently commonly used transparent conductive films such as ITO, FTO and AZO, oxide-metal-oxide conductive films such as AZO|Ag|AZO, transparent conductive composite films composed of metal nanostructure bases, etc. After preparing transparent conductive films on the substrate, the existing It is difficult for technical means to be flexibly adjusted graphically according to needs in subsequent applications, which brings inconvenience to later applications and increases application costs.
发明内容Contents of the invention
本发明克服现有技术的上述缺点，提出了一种可揭式任意图形化的透明导电薄膜，在实际使用中可以根据需要剥离上层导电薄膜而露出下层透明导电薄膜窗口，而其他未剥离部分仍保持具有良好导电性的薄膜，本发明可揭式任意图形化的透明导电薄膜在使用中具有很强灵活性和可操作性。The present invention overcomes the above-mentioned shortcomings of the prior art, and proposes a detachable arbitrarily patterned transparent conductive film. In actual use, the upper conductive film can be peeled off to expose the window of the lower transparent conductive film, while other unpeeled parts remain Maintaining a film with good conductivity, the peelable arbitrary patterned transparent conductive film of the present invention has strong flexibility and operability in use.
本发明提出了一种可揭式任意图形化的透明导电薄膜，其包括衬底、以及在所述衬底上从下至上依次沉积的透明导电薄膜和导电薄膜层。其中，所述衬底与透明导电薄膜层之间的附着力大于透明导电薄膜层与导电薄膜层之间的附着力；所述导电薄膜层可剥离。The invention provides a detachable arbitrary patterned transparent conductive film, which includes a substrate, a transparent conductive film and a conductive film layer deposited sequentially from bottom to top on the substrate. Wherein, the adhesion between the substrate and the transparent conductive film layer is greater than the adhesion between the transparent conductive film layer and the conductive film layer; the conductive film layer can be peeled off.
本发明中，可根据需要剥离导电薄膜层。由于衬底与透明导电薄膜层之间的附着力明显大于透明导电薄膜层与导电薄膜层之间的附着力，因此，在剥离导电薄膜层时，透明导电薄膜层与衬底之间不发生剥离现象，从而形成任意图形化的透明导电薄膜。In the present invention, the conductive thin film layer may be peeled off as needed. Because the adhesive force between the substrate and the transparent conductive film layer is significantly greater than the adhesive force between the transparent conductive film layer and the conductive film layer, therefore, when the conductive film layer is peeled off, no peeling occurs between the transparent conductive film layer and the substrate phenomenon, thereby forming an arbitrary patterned transparent conductive film.
本发明可揭式任意图形化的透明导电薄膜进一步包括中间层。通过在所述透明导电薄膜层与所述导电薄膜层之间引入中间层，从而来弱化所述透明导电薄膜层与所述导电薄膜层之间的附着力。优选地，所述中间层包括LiF、氯化纳、碳膜、有机小分子、聚合物材料、氧化钼、硅烷等。The peelable arbitrary patterned transparent conductive film of the present invention further includes an intermediate layer. The adhesion between the transparent conductive film layer and the conductive film layer is weakened by introducing an intermediate layer between the transparent conductive film layer and the conductive film layer. Preferably, the intermediate layer includes LiF, sodium chloride, carbon film, small organic molecules, polymer materials, molybdenum oxide, silane and the like.
本发明可揭式任意图形化的透明导电薄膜进一步包括超薄界面修饰层。所述超薄界面修饰层是通过采用对透明导电薄膜层的界面修饰方式而形成的，从而来弱化所述透明导电薄膜层与导电薄膜层之间的附着力。其中，对透明导电薄膜层的界面修饰为采用氮气、氧气、Ar、甲烷、乙炔、氢气、水汽等进行表面等离子处理，或者通入硅烷气体等方法，从而形成自组装超薄界面修饰层等，弱化所述透明导电薄膜层与导电薄膜层之间的附着力。The detachable arbitrary patterned transparent conductive film of the present invention further includes an ultra-thin interface modification layer. The ultra-thin interface modification layer is formed by modifying the interface of the transparent conductive film layer, so as to weaken the adhesion between the transparent conductive film layer and the conductive film layer. Among them, the interface modification of the transparent conductive film layer is to use nitrogen, oxygen, Ar, methane, acetylene, hydrogen, water vapor, etc. for surface plasma treatment, or to introduce silane gas, etc., so as to form a self-assembled ultra-thin interface modification layer, etc., Weakening the adhesion between the transparent conductive film layer and the conductive film layer.
本发明可揭式任意图形化的透明导电薄膜进一步包括衬底界面修饰层。通过在衬底表面进行化学或物理修饰以形成衬底界面修饰层，从而来加强所述衬底与透明导电薄膜层之间的附着力。其中，所述在衬底表面进行化学或物理修饰是包括在衬底表面沉积缓冲层、衬底表面粗化，通入气体进行表面等离子处理等方法，形成衬底界面修饰层。优选地，所述衬底界面修饰层为在衬底表面涂覆的功能性硅胶层。优选地，在衬底表面上涂覆功能性硅胶层，用氧气/氩气表面等离子处理或者用NaOH等碱溶液处理在衬底表面形成羟基。所述“功能性硅胶层”是指硅胶层里含有硅烷偶联剂，通过“功能性硅胶层”作用使透明导电薄膜与衬底通过共价键或者离子键连接；“硅烷偶联剂”是指含有烷氧基团的硅烷，典型的硅烷偶联剂如：甲基丙烯酰氧丙基三甲基硅烷，正硅酸乙脂，氨丙基三甲基硅烷和1，2-二(三乙氧基甲硅烷基)乙烷等。The detachable arbitrary patterned transparent conductive film of the present invention further includes a substrate interface modification layer. The surface of the substrate is chemically or physically modified to form a substrate interface modification layer, thereby strengthening the adhesion between the substrate and the transparent conductive film layer. Wherein, the chemical or physical modification on the surface of the substrate includes methods such as depositing a buffer layer on the surface of the substrate, roughening the surface of the substrate, and introducing gas for surface plasma treatment to form a substrate interface modification layer. Preferably, the substrate interface modification layer is a functional silica gel layer coated on the surface of the substrate. Preferably, a functional silica gel layer is coated on the surface of the substrate, and a surface plasma treatment with oxygen/argon gas or an alkali solution such as NaOH is used to form hydroxyl groups on the surface of the substrate. The "functional silica gel layer" means that the silica gel layer contains a silane coupling agent, and the transparent conductive film is connected to the substrate through a covalent bond or an ionic bond through the action of the "functional silica gel layer"; the "silane coupling agent" is Refers to silanes containing alkoxy groups, typical silane coupling agents such as: methacryloxypropyltrimethylsilane, tetraethylorthosilicate, aminopropyltrimethylsilane and 1,2-bis(trimethylsilane) Ethoxysilyl)ethane, etc.
本发明中，衬底可以是玻璃、塑料、石英和蓝宝石等任意透明材料之任意一种。In the present invention, the substrate can be any one of any transparent material such as glass, plastic, quartz and sapphire.
本发明中，透明导电薄膜层是金属或金属合金构成的透明金属薄膜，可以是透明导电氧化物薄膜，还可以是透明导电氧化物/金属/透明导电氧化物(O/M/O)组成的复合薄膜。In the present invention, the transparent conductive film layer is a transparent metal film made of metal or metal alloy, which can be a transparent conductive oxide film, or can also be made of transparent conductive oxide/metal/transparent conductive oxide (O/M/O) Composite film.
其中，金属或金属合金构成的透明金属薄膜为铝、钛、铬、镍、铁、铜、银、金、钛铬、银铝、镁铝、钛银、镁银、镍银、银铜锌等一元或者多元合金形成的透明金属薄膜之任意一种。Among them, the transparent metal film composed of metal or metal alloy is aluminum, titanium, chromium, nickel, iron, copper, silver, gold, titanium chromium, silver aluminum, magnesium aluminum, titanium silver, magnesium silver, nickel silver, silver copper zinc, etc. Any one of the transparent metal films formed by one-element or multi-element alloys.
其中，透明导电氧化物薄膜为掺铝氧化锌(AZO)、掺镓氧化锌(GZO)、掺铟氧化锌(IZO)、掺锡氧化铟(ITO)、掺氟氧化锡(FTO)等形成的透明导电薄膜之任意一种。Among them, the transparent conductive oxide film is formed by aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), etc. Any kind of transparent conductive film.
其中，透明导电氧化物/金属/透明导电氧化物(O/M/O)多层复合体系形成的透明导电薄膜为AZO|Ag|AZO，ZnO|Ag|ZnO，GZO|Ag|GZO等体系的任意一种。Among them, the transparent conductive film formed by the transparent conductive oxide/metal/transparent conductive oxide (O/M/O) multilayer composite system is AZO|Ag|AZO, ZnO|Ag|ZnO, GZO|Ag|GZO and other systems. any kind.
本发明中，导电薄膜层是金属或金属合金如铝、钛、铬、镍、铁、铜、银、钛铬、银铝、镁铝、钛银、镁银、镍银、银铜锌等一元或者多元合金的形成的半透明或者不透明金属薄膜之任意一种。In the present invention, the conductive thin film layer is metal or metal alloy such as aluminum, titanium, chromium, nickel, iron, copper, silver, titanium chromium, silver aluminum, magnesium aluminum, titanium silver, magnesium silver, nickel silver, silver copper zinc, etc. Or any one of translucent or opaque metal films formed by multi-element alloys.
本发明中，中间层用于减弱透明导电薄膜和导电薄膜层的附着性。中间层可以选用LiF、氯化纳、碳膜等形成一层物理薄膜。In the present invention, the intermediate layer is used to weaken the adhesion between the transparent conductive film and the conductive film layer. The middle layer can use LiF, sodium chloride, carbon film, etc. to form a physical film.
本发明中，减弱透明导电薄膜和导电薄膜层之间的附着性，还可以采用物理化学方法如等离子体处理、硅烷修饰处理透明导电薄膜界面，例如，通入氮气、氧气、Ar、甲烷、乙炔、氢气或水汽进行表面等离子体处理、或通入硅烷气体形成超薄界面修饰层，从而减弱透明导电薄膜与导电薄膜层之间化学键联系，弱化透明导电薄膜与导电薄膜层之间的附着性。In the present invention, to weaken the adhesion between the transparent conductive film and the conductive film layer, physical and chemical methods such as plasma treatment and silane modification can also be used to process the transparent conductive film interface, for example, feed nitrogen, oxygen, Ar, methane, acetylene , hydrogen or water vapor for surface plasma treatment, or pass through silane gas to form an ultra-thin interface modification layer, thereby weakening the chemical bond between the transparent conductive film and the conductive film layer, and weakening the adhesion between the transparent conductive film and the conductive film layer.
本发明还提出了上述可揭式任意图形化的透明导电薄膜的制备方法，真空热蒸发镀膜、磁空溅射沉积、化学气相沉积(CVD)、溶液法旋涂、印刷、刮图成膜等，得到可揭式任意图形化的透明导电薄膜。The present invention also proposes the preparation method of the above-mentioned detachable arbitrary patterned transparent conductive film, vacuum thermal evaporation coating, magnetic space sputtering deposition, chemical vapor deposition (CVD), solution method spin coating, printing, scraping pattern film formation, etc. , to obtain a transparent conductive film that can be peeled off and patterned arbitrarily.
在一个具体实施方案中，本发明制备方法包括如下具体步骤：选用高透明玻璃、先用清洁工艺把玻璃表面清晰干净，接着用NaOH溶液或者HF溶液对玻璃进行表面粗化和羟基化，然后烘干。把准备好的玻璃放入真空热蒸发系统抽真空，接着蒸度TiCr或者NiCr合金透明导电薄膜，然后蒸发LiF薄膜和Ag层。In a specific embodiment, the preparation method of the present invention includes the following specific steps: select high-transparency glass, first clear and clean the glass surface with a cleaning process, then use NaOH solution or HF solution to roughen and hydroxylate the glass surface, and then bake Dry. Put the prepared glass into the vacuum thermal evaporation system to evacuate, then evaporate TiCr or NiCr alloy transparent conductive film, and then evaporate LiF film and Ag layer.
优选的，金属或金属合金薄膜、透明导电氧化物以及中间层可通过磁控溅射、真空热蒸发、电子束蒸发和激光沉积等方式制备，也可用打印、印刷和旋涂等方式制备。如用热蒸发制备透明导电薄膜，先在衬底上沉积透明导电薄膜、接着沉积中间层和导电薄膜层。为了提高衬底与透明导电薄膜附着力，衬底表面可通过等离子体处理、硅烷化学修饰、化学清洗粗化以及加衬底温度等提高与透明导电薄膜附着力。如采用磁控溅射沉积透明导电层、中间层以及导电薄膜层，在衬底上依次溅射透明导电薄膜层、中间层和导电薄膜层。衬底表面清洗、物理化学处理以及衬底温度和偏压等参数对提高衬底与透明导电薄膜附着力密切相关，溅射参数如功率、气压、溅射速率、氧氩比、各层薄膜厚度、靶材与衬底间距和角度等可根据需要进行调整。衬底与透明导电薄膜之间的附着力要明显大于透明导电薄膜与导电薄膜层之间附着力，便于后续用粘性工具剥离导电薄膜时，只剥离上层导电薄膜而下层透明导电薄膜不受剥离影响。本发明中，所述透明导电薄膜层与导电薄膜层之间的附着力明显低于所述衬底与透明导电薄膜之间的附着力。在中间层插入LiF、有机小分子层、非功能化硅烷层等。这里指得“非功能化硅烷层”指得形成的中间硅烷层与下层的透明导电薄膜层和上层导电薄膜层之间主要以范德华力作用，共价键和离子键作用数量较少或较弱。Preferably, the metal or metal alloy thin film, transparent conductive oxide and intermediate layer can be prepared by magnetron sputtering, vacuum thermal evaporation, electron beam evaporation and laser deposition, and can also be prepared by printing, printing and spin coating. If the transparent conductive film is prepared by thermal evaporation, the transparent conductive film is first deposited on the substrate, and then the intermediate layer and the conductive film layer are deposited. In order to improve the adhesion between the substrate and the transparent conductive film, the surface of the substrate can be improved by plasma treatment, silane chemical modification, chemical cleaning and roughening, and increasing the substrate temperature to improve the adhesion with the transparent conductive film. For example, the transparent conductive layer, the intermediate layer and the conductive thin film layer are deposited by magnetron sputtering, and the transparent conductive thin film layer, the intermediate layer and the conductive thin film layer are sequentially sputtered on the substrate. Parameters such as substrate surface cleaning, physical and chemical treatment, substrate temperature and bias are closely related to improving the adhesion between substrate and transparent conductive film. Sputtering parameters such as power, air pressure, sputtering rate, oxygen-argon ratio, and film thickness of each layer , distance and angle between target and substrate can be adjusted as needed. The adhesion between the substrate and the transparent conductive film is significantly greater than the adhesion between the transparent conductive film and the conductive film layer, so that when the conductive film is peeled off with an adhesive tool, only the upper conductive film is peeled off and the lower transparent conductive film is not affected by the peeling. . In the present invention, the adhesion between the transparent conductive film layer and the conductive film layer is obviously lower than the adhesion between the substrate and the transparent conductive film. Insert LiF, organic small molecule layer, non-functional silane layer, etc. in the middle layer. The "non-functional silane layer" here refers to the interaction between the formed intermediate silane layer and the lower transparent conductive film layer and the upper conductive film layer mainly by Van der Waals force, and the number of covalent bonds and ionic bonds is small or weak. .
本发明还提出了可揭式任意图形化的透明导电薄膜在作为光电器件的透明电极或抗电磁波干扰的透明窗口等各方面的应用。The invention also proposes the application of the detachable arbitrary patterned transparent conductive film as a transparent electrode of a photoelectric device or a transparent window against electromagnetic interference.
本发明中，衬底与透明导电薄膜之间的附着力明显大于透明导电薄膜层与导电薄膜层之间的附着力是指剥离上层导电薄膜时，上层导电薄膜能彻底剥离而下层透明导电薄膜层不会任何脱落。本发明中，只要衬底与透明导电薄膜之间的附着力要明显大于透明导电薄膜层与导电薄膜层之间的附着力，透明导电薄膜不受导电薄膜层剥离影响，中间层和/或超薄界面修饰层可以省略。In the present invention, the adhesive force between the substrate and the transparent conductive film is obviously greater than the adhesive force between the transparent conductive film layer and the conductive film layer. Won't have any shedding. In the present invention, as long as the adhesion between the substrate and the transparent conductive film is significantly greater than the adhesion between the transparent conductive film layer and the conductive film layer, the transparent conductive film will not be affected by the stripping of the conductive film layer, and the intermediate layer and/or super The thin interface modification layer can be omitted.
本发明创新在于，在透明导电薄膜层与导电薄膜层之间引入中间层或对透明导电薄膜层进行界面修饰，从而弱化透明导电薄膜层与导电薄膜层之间的附着力，而透明导电薄膜层与衬底之间保持足够附着力，在剥离上层导电薄膜时下层透明导电薄膜不受影响。根据需要透明导电窗口的位置，灵活剥离上层导电薄膜而完好保留下层透明导电薄膜，从而形成图形可任意设计的透明导电薄膜窗口。The innovation of the present invention lies in that an intermediate layer is introduced between the transparent conductive film layer and the conductive film layer or the interface modification is carried out on the transparent conductive film layer, thereby weakening the adhesion between the transparent conductive film layer and the conductive film layer, and the transparent conductive film layer Maintain sufficient adhesion with the substrate, and the lower transparent conductive film will not be affected when the upper conductive film is peeled off. According to the position of the transparent conductive window, the upper conductive film is flexibly peeled off while the lower transparent conductive film is kept intact, thereby forming a transparent conductive film window with arbitrarily designed graphics.
本发明创新在于，通过在衬底表面进行化学或者物理修饰，使得透明导电薄膜层与衬底之间具有很强的附着力，而透明导电薄膜与导电薄膜层之间引入中间层或者对透明导电薄膜层的界面修饰，透明导电薄膜层与导电薄膜层之间附着力明显低于衬底与透明导电薄膜之间的附着力，用粘性胶带和图章剥离上层导电薄膜时下层透明导电薄膜不受影响，由此获得可以任意设计的图形化的透明导电薄膜窗口，而未剥离的全结构薄膜仍与图形化的透明导电薄膜窗口连接成一体化的导电薄膜。以上述构思获得的图形化的透明导电薄膜结构，均应属于本发明保护范围。The innovation of the present invention lies in that, by chemically or physically modifying the surface of the substrate, the transparent conductive film layer and the substrate have strong adhesion, and an intermediate layer is introduced between the transparent conductive film and the conductive film layer or the transparent conductive film layer The interface modification of the film layer, the adhesion between the transparent conductive film layer and the conductive film layer is significantly lower than the adhesion between the substrate and the transparent conductive film, and the lower transparent conductive film is not affected when the upper conductive film is peeled off with an adhesive tape and a stamp , thereby obtaining a patterned transparent conductive film window that can be designed arbitrarily, and the unpeeled full-structure film is still connected with the patterned transparent conductive film window to form an integrated conductive film. The patterned transparent conductive thin film structure obtained by the above-mentioned idea should all belong to the protection scope of the present invention.
附图说明Description of drawings
图1是实施例1中的本发明可揭式任意图形化的透明导电薄膜的截面示意图。FIG. 1 is a schematic cross-sectional view of the detachable arbitrary patterned transparent conductive film in embodiment 1 of the present invention.
图2是实施例2中的本发明可揭式任意图形化的透明导电薄膜的截面示意图。FIG. 2 is a schematic cross-sectional view of the detachable arbitrary patterned transparent conductive film in embodiment 2 of the present invention.
图3是实施例3中的本发明可揭式任意图形化透明导电薄膜的截面示意图。FIG. 3 is a schematic cross-sectional view of the detachable arbitrary patterned transparent conductive film in embodiment 3 of the present invention.
图4是实施例4中的本发明可揭式任意图形化透明导电薄膜的截面示意图。FIG. 4 is a schematic cross-sectional view of the detachable arbitrary patterned transparent conductive film in embodiment 4 of the present invention.
具体实施方式Detailed ways
结合以下具体实施例和附图，对本发明作进一步的详细说明，本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制。The present invention will be described in further detail in conjunction with the following specific examples and accompanying drawings, and the protection content of the present invention is not limited to the following examples. Without departing from the spirit and scope of the inventive concept, changes and advantages conceivable by those skilled in the art are all included in the present invention, and the appended claims are the protection scope. The process, conditions, reagents, experimental methods, etc. for implementing the present invention are common knowledge and common knowledge in the art except for the content specifically mentioned below, and the present invention is not particularly limited.
如图1-图4，1表示衬底，10表示衬底界面修饰层，2表示透明导电薄膜层，21表示超薄界面修饰层，3表示中间层，4表示导电薄膜层。As shown in Figures 1-4, 1 represents the substrate, 10 represents the substrate interface modification layer, 2 represents the transparent conductive film layer, 21 represents the ultra-thin interface modification layer, 3 represents the intermediate layer, and 4 represents the conductive film layer.
如图1(a)和(b)所示，本发明可揭式任意图形化的透明导电薄膜，从下至上依次包括衬底1、透明导电薄膜层2、中间层3和导电薄膜层4。所述衬底1与透明导电薄膜层2之间的附着力大于透明导电薄膜层2与导电薄膜层4之间的附着力。As shown in Figure 1 (a) and (b), the transparent conductive film of the present invention that can be peeled off and patterned arbitrarily includes a substrate 1, a transparent conductive film layer 2, an intermediate layer 3 and a conductive film layer 4 from bottom to top. The adhesion between the substrate 1 and the transparent conductive film layer 2 is greater than the adhesion between the transparent conductive film layer 2 and the conductive film layer 4 .
其中，衬底1是玻璃，衬底1还可以是塑料、石英或蓝宝石之任意一种。透明导电薄膜层2是铝形成的透明金属薄膜；还可以是铝、钛、铬、镍、铁、铜、银、金、钛铬、银铝、镁铝、钛银、镁银、镍银、银铜锌等一元或者多元合金形成的透明金属薄膜之任意一种；亦可以是AZO透明导电氧化物形成的透明导电薄膜，还可以是AZO、GZO、IZO、ITO、FTO等透明导电氧化物形成的透明导电薄膜之任意一种。导电薄膜层4是铝、钛、铬、镍、铁、铜、银、钛铬、银铝、镁铝、钛银、镁银、镍银、银铜锌等一元或者多元合金形成的透明、半透明或者不透明金属薄膜之任意一种。中间层3为LiF；还可以选用LiF、氯化纳、碳膜、有机小分子、聚合物材料、氧化钼、硅烷等之任意一种。Wherein, the substrate 1 is glass, and the substrate 1 can also be any one of plastic, quartz or sapphire. The transparent conductive film layer 2 is a transparent metal film formed by aluminum; it can also be aluminum, titanium, chromium, nickel, iron, copper, silver, gold, titanium chromium, silver aluminum, magnesium aluminum, titanium silver, magnesium silver, nickel silver, Any one of the transparent metal films formed by single or multi-element alloys such as silver, copper and zinc; it can also be a transparent conductive film formed by AZO transparent conductive oxides, and can also be formed by transparent conductive oxides such as AZO, GZO, IZO, ITO, and FTO Any of the transparent conductive films. The conductive thin film layer 4 is a transparent, semi-conductive film formed by a single or multiple alloy such as aluminum, titanium, chromium, nickel, iron, copper, silver, titanium chromium, silver aluminum, magnesium aluminum, titanium silver, magnesium silver, nickel silver, silver copper zinc, etc. Either transparent or opaque metal film. The middle layer 3 is LiF; any one of LiF, sodium chloride, carbon film, small organic molecules, polymer materials, molybdenum oxide, silane, etc. can also be selected.
在具体实施方式中，还可以采用对透明导电薄膜层2进行界面修饰的方法等形成一层弱化透明导电薄膜2和导电薄膜层4附着力的过渡层，即超薄界面修饰层21，如图2所示。所述对透明导电薄膜层2的界面修饰方法包括采用通入氮气、氧气、Ar、甲烷、乙炔、氢气或水汽进行表面等离子体处理、或通入硅烷气体形成自组装超薄界面修饰层。In a specific embodiment, the method of modifying the interface of the transparent conductive film layer 2 can also be used to form a transition layer that weakens the adhesion of the transparent conductive film 2 and the conductive film layer 4, that is, the ultra-thin interface modification layer 21, as shown in the figure 2. The method for modifying the interface of the transparent conductive film layer 2 includes introducing nitrogen, oxygen, Ar, methane, acetylene, hydrogen or water vapor for surface plasma treatment, or introducing silane gas to form a self-assembled ultra-thin interface modification layer.
本发明还可以通过在透明导电薄膜层2与导电薄膜层4之间引入中间层3，使得透明导电薄膜层2与导电薄膜层4之间附着力明显低于透明导电薄膜层2和衬底1之间的附着力，接着采用粘性胶带或者图形化图章把上层的导电薄膜层4部分剥离，而下层的透明导电薄膜层2不受剥离影响，获得图形化的透明导电薄膜。The present invention can also introduce the intermediate layer 3 between the transparent conductive film layer 2 and the conductive film layer 4, so that the adhesion between the transparent conductive film layer 2 and the conductive film layer 4 is significantly lower than that of the transparent conductive film layer 2 and the substrate 1 Adhesion between them, and then use adhesive tape or patterned stamp to partially peel off the upper conductive film layer 4, while the lower transparent conductive film layer 2 is not affected by the peeling, and obtain a patterned transparent conductive film.
本发明还可能通过在衬底1表面进行化学或物理修饰形成衬底界面修饰层10，其加强所述衬底1与透明导电薄膜层2之间的附着力。例如，包括在衬底1表面涂覆功能性硅胶层或者功能性硅烷层。In the present invention, it is also possible to form a substrate interface modification layer 10 by chemically or physically modifying the surface of the substrate 1 , which strengthens the adhesion between the substrate 1 and the transparent conductive film layer 2 . For example, it includes coating a functional silica gel layer or a functional silane layer on the surface of the substrate 1 .
本发明中，只要衬底1与透明导电薄膜2之间的附着力要明显大于透明导电薄膜层3与导电薄膜层4之间的附着力，透明导电薄膜2不受导电薄膜层4剥离影响，中间层3和/或超薄界面修饰层21可以省略。本发明中，衬底1与透明导电薄膜2之间的附着力明显大于透明导电薄膜层3与导电薄膜层4之间的附着力是指剥离上层导电薄膜时，上层导电薄膜能彻底剥离而下层透明导电薄膜层不会任何脱落。由于衬底与透明导电薄膜层之间的附着力明显大于透明导电薄膜层与导电薄膜层之间的附着力，因此，在剥离导电薄膜层4时，透明导电薄膜层2与衬底1之间不发生剥离现象。在本发明可揭式任意图形化的透明导电薄膜中，导电薄膜层4可以通过胶带或者粘性图章剥离，而透明导电薄膜层2不受剥离影响，获得任意图形化的透明导电薄膜。In the present invention, as long as the adhesion between the substrate 1 and the transparent conductive film 2 is significantly greater than the adhesion between the transparent conductive film layer 3 and the conductive film layer 4, the transparent conductive film 2 is not affected by the stripping of the conductive film layer 4, The intermediate layer 3 and/or the ultra-thin interface modification layer 21 can be omitted. Among the present invention, the adhesive force between substrate 1 and transparent conductive film 2 is obviously greater than the adhesive force between transparent conductive film layer 3 and conductive film layer 4. The transparent conductive film layer will not fall off in any way. Because the adhesive force between the substrate and the transparent conductive film layer is obviously greater than the adhesive force between the transparent conductive film layer and the conductive film layer, therefore, when the conductive film layer 4 is peeled off, the transparent conductive film layer 2 and the substrate 1 Peeling did not occur. In the detachable arbitrary patterned transparent conductive film of the present invention, the conductive film layer 4 can be peeled off by adhesive tape or adhesive stamp, while the transparent conductive film layer 2 is not affected by peeling, and an arbitrary patterned transparent conductive film can be obtained.
实施例1Example 1
如图1(a)所示，本实施例中可揭式任意图形化的透明导电薄膜包括由下到上依次的衬底1、透明导电薄膜层2、中间层3、和导电薄膜层4。其中，衬底1为玻璃，透明导电薄膜层2是银铝合金膜，中间层3为LiF，导电薄膜层4为银膜。导电薄膜层4部分剥离后的留下的透明导电薄膜如图1(b)所示。本实施例中给出单一具体材料，并不限定其它材料选择，只是举例说明本发明。衬底1玻璃表面经过表面粗化和表面等离子体处理，热蒸镀上透明导电银铝合金膜2，接着热蒸发中间层3LiF过渡层，最后热蒸发上导电薄膜层4银膜。上述本实施例制备得到的产品的结构为Glass/AgAl/LiF/Ag，玻璃与银铝合金膜的附着力明显大于银铝合金膜与银膜之间的附着力，通过粘性胶带或者图形化的图章，银膜剥离过程中下层的银铝膜不受影响，剥离之后形成由Glass/AgAl或者Glass/AgAl/LiF结构组成的图形化透明导电薄膜。本实施例制得的透明导电薄膜可以作为光电器件的透明阴极或者透明阳极，未剥离的导电薄膜可作为光电器件中无需透明要求的阻值更低的连接导线。本实施例透明导电薄膜还可以用作抗电磁波干扰的透明窗口，即要求透明的位置用粘性胶带剥离导电薄膜，剥离之后形成Glass/AgAl或者Glass/AgAl/LiF组成的图形化的透明导电薄膜作为观察窗口，未剥离的薄膜为全结构薄膜Glass/AgAl/LiF/Ag，实现更高等级的抗电磁干扰能力。As shown in FIG. 1( a ), the removable patterned transparent conductive film in this embodiment includes a substrate 1 , a transparent conductive film layer 2 , an intermediate layer 3 , and a conductive film layer 4 sequentially from bottom to top. Wherein, the substrate 1 is glass, the transparent conductive thin film layer 2 is a silver aluminum alloy film, the intermediate layer 3 is LiF, and the conductive thin film layer 4 is a silver film. The remaining transparent conductive film after the conductive film layer 4 is partially peeled off is shown in FIG. 1( b ). A single specific material is given in this embodiment, which does not limit the choice of other materials, but is just an example to illustrate the present invention. The glass surface of the substrate 1 undergoes surface roughening and surface plasma treatment, and a transparent conductive silver-aluminum alloy film 2 is thermally evaporated, followed by thermally evaporating the middle layer 3LiF transition layer, and finally thermally evaporating the conductive film layer 4 silver film. The structure of the product prepared in the above-mentioned embodiment is Glass/AgAl/LiF/Ag, and the adhesion between glass and silver-aluminum alloy film is obviously greater than that between silver-aluminum alloy film and silver film. Stamp, the lower silver aluminum film is not affected during the stripping process of the silver film, and a patterned transparent conductive film composed of Glass/AgAl or Glass/AgAl/LiF structure is formed after stripping. The transparent conductive film prepared in this embodiment can be used as a transparent cathode or transparent anode of a photoelectric device, and the unstripped conductive film can be used as a connecting wire with a lower resistance in a photoelectric device that does not require transparency. The transparent conductive film of this embodiment can also be used as a transparent window against electromagnetic wave interference, that is, the conductive film is peeled off with an adhesive tape at a transparent position, and a patterned transparent conductive film composed of Glass/AgAl or Glass/AgAl/LiF is formed after peeling as The observation window, the unstripped film is a full-structure film Glass/AgAl/LiF/Ag, which achieves a higher level of anti-electromagnetic interference.
实施例2Example 2
如图2所示，本实施例透明导电薄膜包括由下到上依次的衬底1、透明导电薄膜层2、和导电薄膜层4，以及在透明导电薄膜层2上界面修饰所形成的超薄界面修饰层21。其中，衬底1为玻璃或者PET塑料，透明导电薄膜层2为NiCr合金膜，导电薄膜层4为银膜层。本实施例给出单一具体材料，并不限定其它材料选择，只是为了举例说明本发明。制作过程同实施例1。衬底1经粗化和表面等离子体处理后，NiCr透明导电薄膜层2与衬底1具有很强附着力。采用水汽方式对NiCr膜2进行表面等离子体处理，在NiCr膜2上形成超薄界面修饰层21，导致银膜4与NiCr膜2之间的附着力在水汽作用下能快速下降，因此用胶带可以很好把剥离Ag层而获得图形化的Glass/NiCr或者PET/NiCr透明导电薄膜。对NiCr膜2的界面修饰还可以通入硅烷气体形成自组装超薄界面修饰层，或通入氮气、氧气、Ar、甲烷、乙炔、氢气进行表面等离子体处理。本实施例透明导电薄膜可以用作抗电磁波干扰的透明窗口，即用图形化的Glass/NiCr或者PET/NiCr透明导电薄膜作为观察窗口，未剥离的薄膜Glass/NiCr/Ag或者PET/NiCr/Ag作为更高等级的抗电磁干扰防护薄膜。透明导电薄膜窗口与未剥离的导电薄膜一起形成连续的一体化电磁波干扰防护膜。As shown in Figure 2, the transparent conductive film of this embodiment includes a substrate 1, a transparent conductive film layer 2, and a conductive film layer 4 from bottom to top, and an ultra-thin film formed by interface modification on the transparent conductive film layer 2. Interface modification layer 21. Wherein, the substrate 1 is glass or PET plastic, the transparent conductive film layer 2 is a NiCr alloy film, and the conductive film layer 4 is a silver film layer. This embodiment gives a single specific material, does not limit the choice of other materials, and is just to illustrate the present invention. Manufacturing process is with embodiment 1. After the substrate 1 is roughened and treated with surface plasma, the NiCr transparent conductive thin film layer 2 has strong adhesion to the substrate 1 . The surface plasma treatment of the NiCr film 2 is carried out by means of water vapor, and an ultra-thin interface modification layer 21 is formed on the NiCr film 2, which causes the adhesion between the silver film 4 and the NiCr film 2 to decrease rapidly under the action of water vapor. The Ag layer can be peeled off to obtain a patterned Glass/NiCr or PET/NiCr transparent conductive film. The interface modification of the NiCr film 2 can also be fed with silane gas to form a self-assembled ultra-thin interface modification layer, or fed with nitrogen, oxygen, Ar, methane, acetylene, and hydrogen for surface plasma treatment. The transparent conductive film of this embodiment can be used as the transparent window of anti-electromagnetic wave interference, promptly uses patterned Glass/NiCr or PET/NiCr transparent conductive film as observation window, unpeeled thin film Glass/NiCr/Ag or PET/NiCr/Ag As a higher level of anti-electromagnetic interference protective film. The transparent conductive film window and the unpeeled conductive film together form a continuous integrated electromagnetic wave interference protection film.
实施例3Example 3
如图3所示，本实施例透明导电薄膜包括由下到上依次的衬底1、衬底界面修饰层10、透明导电薄膜层2和导电薄膜层4。其中，衬底1为玻璃或者PET塑料，衬底界面修饰层10为透明硅胶层，透明导电薄膜层2为TiCr合金膜，导电薄膜层4为银膜层。本实施例给出单一具体材料，并不限定其它材料选择，只是为了更好地说明本发明。制作过程同实施例1。衬底1经粗化处理后涂覆一层透明硅胶层10，TiCr透明导电薄膜层2与经透明硅胶层修饰后的衬底1之间具有很强附着力。采用水汽方式对TiCr透明导电薄膜层2进行表面等离子体处理，在TiCr透明导电薄膜层2上形成超薄界面修饰层，导致银膜4与TiCr膜2之间附着力在水汽作用下能快速下降，因此用胶带可以很好把剥离Ag层而获得图形化的Glass/硅胶层/TiCr或者PET/硅胶层/TiCr透明导电薄膜。还可以在衬底1表面涂覆透明硅烷层。对TiCr透明导电薄膜层2的界面修饰还可以通入硅烷气体形成自组装超薄界面修饰层，或通入氮气、氧气、Ar、甲烷、乙炔、氢气进行表面等离子体处理。本实施例的透明导电薄膜可以用作抗电磁波干扰的透明窗口，即用图形化的Glass/硅胶层/TiCr或者PET/硅胶层/TiCr透明导电薄膜作为观察窗口，未剥离的薄膜作为更高等级的抗电磁干扰防护薄膜，并且两者薄膜仍然连续的。As shown in FIG. 3 , the transparent conductive film of this embodiment includes a substrate 1 , a substrate interface modification layer 10 , a transparent conductive film layer 2 and a conductive film layer 4 in sequence from bottom to top. Wherein, the substrate 1 is glass or PET plastic, the substrate interface modification layer 10 is a transparent silica gel layer, the transparent conductive film layer 2 is a TiCr alloy film, and the conductive film layer 4 is a silver film layer. This embodiment gives a single specific material, and does not limit other material choices, just for better illustrating the present invention. Manufacturing process is with embodiment 1. The substrate 1 is roughened and coated with a layer of transparent silica gel layer 10, and the TiCr transparent conductive film layer 2 has strong adhesion to the substrate 1 modified by the transparent silica gel layer. Surface plasma treatment is carried out on the TiCr transparent conductive film layer 2 by means of water vapor, and an ultra-thin interface modification layer is formed on the TiCr transparent conductive film layer 2, resulting in a rapid decline in the adhesion between the silver film 4 and the TiCr film 2 under the action of water vapor , so the Ag layer can be peeled off with adhesive tape to obtain a patterned Glass/silica gel layer/TiCr or PET/silica gel layer/TiCr transparent conductive film. A transparent silane layer can also be coated on the surface of the substrate 1 . The interface modification of the TiCr transparent conductive film layer 2 can also be conducted by introducing silane gas to form a self-assembled ultra-thin interface modification layer, or by injecting nitrogen, oxygen, Ar, methane, acetylene, and hydrogen for surface plasma treatment. The transparent conductive film of this embodiment can be used as a transparent window against electromagnetic interference, that is, use patterned Glass/silica gel layer/TiCr or PET/silica gel layer/TiCr transparent conductive film as the observation window, and the unpeeled film is used as a higher grade The anti-electromagnetic interference protective film, and the two films are still continuous.
实施例4Example 4
如图4所示，本实施例透明导电薄膜包括由下到上依次的衬底1、衬底界面修饰层10、透明导电薄膜层2、中间层3和导电薄膜层4。其中，衬底1为玻璃，衬底界面修饰层10为透明硅胶层，透明导电薄膜层2为AgAl合金膜，中间层3为LiF层，导电薄膜层4为银膜层。此处给出单一具体材料，并不限定其它材料选择，只是为了更好地说明本发明。制作过程同实施例1。衬底1经粗化处理后涂覆一层透明硅胶层10，AgAl透明导电薄膜层2与经透明硅胶层修饰后的衬底1具有很强附着力，银膜4与AgAl膜2之间附着力经中间层3LiF间隔后能快速下降，因此用胶带可以很好把剥离Ag层而获得图形化的Glass/硅胶层/AgAl或者Glass/硅胶层/AgAl/LiF结构的透明导电薄膜。本实施例的透明导电薄膜可以用作抗电磁波干扰的透明窗口，也可以用光电器件的透明电极，即剥离导电薄膜层Ag后，用图形化的Glass/硅胶层/AgAl或者Glass/硅胶层/AgAl/LiF作为器件的透明导电电极，未剥离的薄膜可作为串联电阻更低的光电器件间的连接导线。As shown in FIG. 4 , the transparent conductive film of this embodiment includes a substrate 1 , a substrate interface modification layer 10 , a transparent conductive film layer 2 , an intermediate layer 3 and a conductive film layer 4 from bottom to top. Wherein, the substrate 1 is glass, the substrate interface modification layer 10 is a transparent silica gel layer, the transparent conductive film layer 2 is an AgAl alloy film, the intermediate layer 3 is a LiF layer, and the conductive film layer 4 is a silver film layer. A single specific material is given here, without limiting the selection of other materials, but for better illustrating the present invention. Manufacturing process is with embodiment 1. The substrate 1 is roughened and coated with a layer of transparent silica gel layer 10, the AgAl transparent conductive film layer 2 has strong adhesion to the substrate 1 modified by the transparent silica gel layer, and the silver film 4 and the AgAl film 2 are attached The force can drop rapidly after passing through the middle layer of 3LiF, so the Ag layer can be peeled off with adhesive tape to obtain a patterned Glass/silica gel layer/AgAl or Glass/silica gel layer/AgAl/LiF transparent conductive film. The transparent conductive film of this embodiment can be used as a transparent window against electromagnetic wave interference, and can also be used as a transparent electrode of an optoelectronic device, that is, after stripping off the conductive film layer Ag, use patterned Glass/silica gel layer/AgAl or Glass/silica gel layer/ AgAl/LiF is used as a transparent conductive electrode of the device, and the unstripped film can be used as a connecting wire between optoelectronic devices with lower series resistance.
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。The above is only the preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the inventive concept of the present invention, some modifications and improvements can also be made, and these all belong to the present invention. protection scope of the invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273143.XACN105185843B (en) | 2014-06-18 | 2014-06-18 | A kind of detachable arbitrarily patterned transparent conductive film and its application |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273143.XACN105185843B (en) | 2014-06-18 | 2014-06-18 | A kind of detachable arbitrarily patterned transparent conductive film and its application |
| Publication Number | Publication Date |
|---|---|
| CN105185843Atrue CN105185843A (en) | 2015-12-23 |
| CN105185843B CN105185843B (en) | 2017-07-25 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410273143.XAExpired - Fee RelatedCN105185843B (en) | 2014-06-18 | 2014-06-18 | A kind of detachable arbitrarily patterned transparent conductive film and its application |
| Country | Link |
|---|---|
| CN (1) | CN105185843B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107393979A (en)* | 2017-06-09 | 2017-11-24 | 中国科学院宁波材料技术与工程研究所 | A kind of transparency electrode based on ultrathin metallic film and its preparation method and application |
| CN109545979A (en)* | 2018-10-19 | 2019-03-29 | 杭州电子科技大学 | The organic photovoltaic cell of metallic transparent electrode and preparation method and composition |
| CN109830545A (en)* | 2019-02-14 | 2019-05-31 | 中国科学院半导体研究所 | A kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery |
| CN111816365A (en)* | 2019-04-10 | 2020-10-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for transferring conductive polymers to flexible substrates and flexible electrodes |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6040521A (en)* | 1996-11-08 | 2000-03-21 | Showa Shell Sekiyu K.K. | N-type window layer for a thin film solar cell and method of making |
| CN201302999Y (en)* | 2009-02-02 | 2009-09-02 | 信义玻璃工程（东莞）有限公司 | Transparent conductive film glass |
| CN103151394A (en)* | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | Thin film solar cell and manufacturing method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6040521A (en)* | 1996-11-08 | 2000-03-21 | Showa Shell Sekiyu K.K. | N-type window layer for a thin film solar cell and method of making |
| CN201302999Y (en)* | 2009-02-02 | 2009-09-02 | 信义玻璃工程（东莞）有限公司 | Transparent conductive film glass |
| CN103151394A (en)* | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | Thin film solar cell and manufacturing method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107393979A (en)* | 2017-06-09 | 2017-11-24 | 中国科学院宁波材料技术与工程研究所 | A kind of transparency electrode based on ultrathin metallic film and its preparation method and application |
| CN107393979B (en)* | 2017-06-09 | 2019-07-16 | 中国科学院宁波材料技术与工程研究所 | A kind of transparent electrode based on ultra-thin metal film and its preparation method and application |
| CN109545979A (en)* | 2018-10-19 | 2019-03-29 | 杭州电子科技大学 | The organic photovoltaic cell of metallic transparent electrode and preparation method and composition |
| CN109830545A (en)* | 2019-02-14 | 2019-05-31 | 中国科学院半导体研究所 | A kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery |
| CN111816365A (en)* | 2019-04-10 | 2020-10-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for transferring conductive polymers to flexible substrates and flexible electrodes |
| Publication number | Publication date |
|---|---|
| CN105185843B (en) | 2017-07-25 |
| Publication | Publication Date | Title |
|---|---|---|
| CN104979037B (en) | A kind of transparent conductive film with enhanced thermal stability and its preparation method and application | |
| CN107393979B (en) | A kind of transparent electrode based on ultra-thin metal film and its preparation method and application | |
| CN102779944B (en) | Transparent conductive thin film | |
| CN105449106B (en) | A kind of transparent electrode and preparation method thereof based on super thin metal | |
| CN103730194B (en) | The preparation method of the compound transparent electricity conductive film of a kind of nano silver wire Quito Rotating fields | |
| CN107254664B (en) | A kind of ultra-thin silver-based film, MULTILAYER COMPOSITE transparent conductive film and the preparation method and application thereof | |
| US20130040516A1 (en) | Transparent electrode based on combination of transparent conductive oxides, metals and oxides | |
| CN111244229B (en) | A flexible transparent thin-film solar cell fabrication method | |
| CN105185843B (en) | A kind of detachable arbitrarily patterned transparent conductive film and its application | |
| CN1979695A (en) | Flexible composite transparent conductive film and mfg. method | |
| KR19980048999A (en) | Transparent conductive laminate and EL light emitting device using same | |
| CN103730195B (en) | Compound transparent electricity conductive film of a kind of copper nano-wire Quito Rotating fields and preparation method thereof | |
| CN108074991A (en) | A kind of composite transparent conductive film | |
| JP2005108467A (en) | Transparent conductive sheet, and photosensitive solar cell | |
| CN101497992A (en) | Method for preparing pile face zinc oxide transparent conductive film coating glass by plasma bombardment | |
| WO2014064939A1 (en) | Transparent conductor | |
| JP3725908B2 (en) | Conductive laminate | |
| CN106887274A (en) | A kind of flexible transparent conductive film and preparation method thereof | |
| JPH06136159A (en) | Transparent conductive film and its production | |
| CN104377261B (en) | One prepares CdTe thin film solar panel method | |
| TW201040299A (en) | Layer system having barrier properties and a structured conductive layer, method for producing the same, and use of such a layer system | |
| CN105039911B (en) | A kind of transparent conductive film and preparation method thereof | |
| CN105039910A (en) | Flexible transparent conducting thin film | |
| CN102544388B (en) | Flexible electrode based on carbon nano tube/ silver/ zinc aluminium oxide structure | |
| CN102195006A (en) | Flexible electrode based on AZO/graphene/AZO structure and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20170725 Termination date:20200618 |