CN105289588A - Palladium alloy catalytic membrane material and preparation method thereof - Google Patents
Palladium alloy catalytic membrane material and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及一种催化薄膜材料及其制备方法，具体涉及一种能够催化氢气解离、可应用于调光玻璃的钯合金催化薄膜材料及其制备方法。The invention relates to a catalytic thin film material and a preparation method thereof, in particular to a palladium alloy catalytic thin film material capable of catalyzing hydrogen gas dissociation and applicable to dimming glass and a preparation method thereof.
背景技术Background technique
随着社会的发展，能源与环境问题日益突出，节能与环保是会可持续发展的必然要求。据报道，我国建筑能耗占社会总能耗的34％，与发达国家相比，我国建筑不仅能源消耗大，而且能源利用效率低。玻璃门窗是建筑与外界热量交换的主要通道，门窗节能是建筑节能的关键。目前已经应用的Low-E玻璃不能调节光学状态的改变，单个季节；基于WO3的节能窗是吸收型，它的调光机理是通过吸收阳光实现的，存在向室内再放热现象。镁合金调光镜是一种反射型节能窗，节能效率很高，因而调光镜应用于建筑玻璃具有很大的节能效益。With the development of society, energy and environmental issues have become increasingly prominent, and energy conservation and environmental protection are inevitable requirements for sustainable development. According to reports, my country's building energy consumption accounts for 34% of the total energy consumption of the society. Compared with developed countries, my country's buildings not only consume a lot of energy, but also have low energy utilization efficiency. Glass doors and windows are the main channel for heat exchange between buildings and the outside world, and energy saving of doors and windows is the key to building energy conservation. The Low-E glass that has been applied at present cannot adjust the change of optical state, a single season; the energy-saving window based on WO 3 is an absorption type, and its dimming mechanism is realized by absorbing sunlight, and there is a phenomenon of heat release to the room. Magnesium alloy dimming mirror is a reflective energy-saving window with high energy-saving efficiency, so the dimming mirror applied to architectural glass has great energy-saving benefits.
1996年，荷兰阿姆斯特丹自由大学Huiberts等人研究了Y、La和其氢化物，发现在氢的连续吸收过程中，这些材料可以实现金属态(YH2或LaH2)到半导体(YH3或LaH3)的可逆变化，其光学性质也从金属镜面变为淡黄色透明。在其表面镀一层可以使氢原子扩散的Pd层，具有催化和保护材料不被氧化作用。这种材料被称为“调光镜”。此后，又发现了镁与稀土金属(如：Y、La等)、过渡金属(如：Ni、Ti、Nb、Zr等)以及碱土金属(如：Ca、Sr、Ba等)合金在氢气中光学性质以及电学性质的转变。这些材料配合钯催化层制成的调光镜可以应用于气质变色窗(建筑节能，汽车节能)，氢气传感器或光电开关等。关于调光镜中气致变色层的研究很多，但是关于催化层的研究很少。而调光镜的制造成本、响应速率以及寿命都与催化层的性质有关。这些调光薄膜在多次吸放氢后催化层受到破坏，表面出现很多火山状的突起，导致下层镁合金的氧化从而导致调光薄膜的劣化。因而催化层的研究对于调光镜寿命的提高具有重大意义。In 1996, Huiberts et al. studied Y, La and their hydrides at the Free University of Amsterdam, and found that these materials can achieve a reversible change from a metallic state (YH2 or LaH2) to a semiconductor (YH3 or LaH3) during the continuous absorption of hydrogen. , and its optical properties also changed from metal mirror to light yellow transparent. A layer of Pd that can diffuse hydrogen atoms is plated on its surface, which has the function of catalysis and protection of materials from oxidation. This material is called a "light-adjustable mirror". Since then, it has been found that magnesium and rare earth metals (such as: Y, La, etc.), transition metals (such as: Ni, Ti, Nb, Zr, etc.) and alkaline earth metals (such as: Ca, Sr, Ba, etc.) properties and changes in electrical properties. The dimming mirror made of these materials combined with the palladium catalytic layer can be applied to temperament color windows (building energy saving, automobile energy saving), hydrogen sensors or photoelectric switches, etc. There are many studies on aerochromic layers in light-switching mirrors, but few studies on catalytic layers. The manufacturing cost, response rate, and lifetime of the dimming mirror are all related to the properties of the catalytic layer. The catalytic layer of these light-adjusting films is damaged after repeated hydrogen absorption and desorption, and many volcanic protrusions appear on the surface, which leads to the oxidation of the underlying magnesium alloy and the deterioration of the light-adjusting film. Therefore, the research on the catalytic layer is of great significance to the improvement of the lifetime of the dimming mirror.
目前，用于调光薄膜催化层的材料主要是钯(Pd)，Pd比较贵重，增加了调光玻璃的制备成本；并且在吸放氢过程中由于氢化物的体积膨胀造成Pd表面层裂开出现空洞现象，容易受到破坏，致使调光镜寿命低。因而，该领域迫切需要制备出一种具有优良性能的催化层。At present, palladium (Pd) is the main material used for the light-adjusting thin film catalytic layer. Pd is relatively expensive, which increases the preparation cost of light-adjustable glass; and the Pd surface layer is cracked due to the volume expansion of the hydride during the hydrogen absorption and desorption process. Cavitation occurs and is easily damaged, resulting in a low service life of the dimming mirror. Therefore, there is an urgent need in this field to prepare a catalytic layer with excellent performance.
发明内容Contents of the invention
本发明旨在进一步提高催化氢气解离领域、可应用调光玻璃领域中催化层的性能，本发明提供了一种能够催化氢气解离、可应用调光玻璃的钯合金催化薄膜材料及其制备方法。The present invention aims to further improve the performance of the catalytic layer in the field of catalyzing hydrogen gas dissociation and the field of applicable dimming glass. The present invention provides a palladium alloy catalytic thin film material capable of catalyzing hydrogen dissociation and applicable to dimming glass and its preparation method.
本发明提供了一种钯合金催化薄膜材料，所述催化薄膜材料的化学组成是PdMx，其中M为Ti或Ni，0﹤x﹤0.5。The invention provides a palladium alloy catalytic thin film material. The chemical composition of the catalytic thin film material is PdM x , wherein M is Ti or Ni, and 0<x<0.5.
本发明还提供一种包括钯合金催化薄膜材料的复合薄膜，所述复合薄膜包括：The present invention also provides a kind of composite film comprising palladium alloy catalytic film material, and described composite film comprises:
沉积在基材表面的镁合金薄膜；Magnesium alloy film deposited on the surface of the substrate;
以及沉积在所述镁合金薄膜上的钯合金催化薄膜，所述钯合金催化薄膜的化学组成是PdMx，其中M为Ti或Ni，0﹤x﹤0.5。And a palladium alloy catalytic film deposited on the magnesium alloy film, the chemical composition of the palladium alloy catalytic film is PdM x , wherein M is Ti or Ni, 0<x<0.5.
较佳地，所述催化薄膜材料的厚度可为1nm-10nm。Preferably, the thickness of the catalytic thin film material may be 1nm-10nm.
较佳地，所述镁合金薄膜的厚度为10nm-200nm。Preferably, the thickness of the magnesium alloy thin film is 10nm-200nm.
较佳地，所述复合薄膜的基材包括玻璃、柔性基片、金属薄片、和硅基板。Preferably, the base material of the composite film includes glass, flexible substrate, metal foil, and silicon substrate.
较佳地，所述镁合金薄膜的组成为二元镁合金Mg1-aAa、或三元镁合金Mg1-a-bAaBb，其中A为Ni、Ti、V、Nb、Y、Zr、Mo、Cu、V、Co、Mn、W、Fe、Y、La、Ca、Sr或Ba，B为Ni、Ti、V、Nb、Y、Zr、Mo、Cu、V、Co、Mn或W，0﹤a﹤1，0﹤b﹤1，1-a-b﹥0。Preferably, the composition of the magnesium alloy thin film is a binary magnesium alloy Mg 1-a A a or a ternary magnesium alloy Mg 1-ab A a B b , wherein A is Ni, Ti, V, Nb, Y, Zr, Mo, Cu, V, Co, Mn, W, Fe, Y, La, Ca, Sr or Ba, B is Ni, Ti, V, Nb, Y, Zr, Mo, Cu, V, Co, Mn or W, 0﹤a﹤1, 0﹤b﹤1, 1-ab﹥0.
又，本发明还提供了一种制备上述复合薄膜的方法，所述方法包括：Again, the present invention also provides a kind of method for preparing above-mentioned composite thin film, and described method comprises:
1)通过物理沉积法，在基材表面沉积镁合金薄膜；以及1) Depositing a magnesium alloy film on the surface of the substrate by physical deposition; and
2)通过物理沉积法，在位于基材表面的镁合金薄膜上沉积所述钯合金催化薄膜。2) Depositing the palladium alloy catalytic film on the magnesium alloy film on the surface of the substrate by physical deposition.
较佳地，步骤1)和/或2)中所述物理沉积法包括磁控溅射、脉冲激光溅射、蒸发镀膜。Preferably, the physical deposition method in step 1) and/or 2) includes magnetron sputtering, pulsed laser sputtering, and evaporation coating.
较佳地，步骤1)中，以纯Mg、所述镁合金薄膜中的其他纯金属靶材为溅射靶材，采用磁控溅射在基材表面上共溅射，磁控溅射的参数为：本底真空度≦1×10-5Pa，氩气的工作压力0.3—1.5Pa，溅射功率10—60W，溅射时间30—180秒，靶基距10—20cm。Preferably, in step 1), pure Mg and other pure metal targets in the magnesium alloy thin film are used as sputtering targets, and magnetron sputtering is used to co-sputter on the surface of the substrate, and the parameters of magnetron sputtering It is: background vacuum degree ≦1×10 -5 Pa, working pressure of argon gas 0.3-1.5 Pa, sputtering power 10-60W, sputtering time 30-180 seconds, target base distance 10-20cm.
较佳地，步骤2)中，以纯Pd、纯金属M为溅射靶材，采用磁控溅射在镁合金薄膜上共溅射，磁控溅射的参数为：本底真空度≦1×10-5Pa，氩气的工作压力0.3—1.5Pa，溅射功率4—30W，溅射时间30—120秒，靶基距10—20cm。Preferably, in step 2), pure Pd and pure metal M are used as sputtering targets, and magnetron sputtering is used to co-sputter on the magnesium alloy film. The parameters of magnetron sputtering are: background vacuum degree≦1× 10 -5 Pa, working pressure of argon gas 0.3-1.5Pa, sputtering power 4-30W, sputtering time 30-120 seconds, target base distance 10-20cm.
本发明的有益效果：Beneficial effects of the present invention:
本发明公开了一种钯合金催化薄膜材料及其制备方法。通过光性能测试表明，本发明所制备的钯合金催化层调光薄膜的放氢速率快；能提高催化层韧性和调光镜的寿命；并且降低了调光薄膜的制备成本，对于调光玻璃大规模生产具有很大的经济效益。The invention discloses a palladium alloy catalytic film material and a preparation method thereof. Show by optical performance test, the hydrogen desorption rate of palladium alloy catalytic layer dimming thin film prepared by the present invention is fast; Can improve the life-span of catalytic layer toughness and dimming mirror; And reduce the preparation cost of dimming thin film, for dimming glass Large-scale production has great economic benefits.
附图说明Description of drawings
图1示出了包含本发明的一个实施方式中制备的钯合金催化薄膜材料的调光玻璃结构示意图，其中1-基板，2-镁合金层，3-钯合金催化层；Fig. 1 shows the structure schematic diagram of the dimming glass comprising the palladium alloy catalytic film material prepared in one embodiment of the present invention, wherein 1-substrate, 2-magnesium alloy layer, 3-palladium alloy catalytic layer;
图2示出了对本发明的一个实施方式中制备的钯合金催化薄膜材料进行调光速度与寿命测试的装置图，4-镀有镁合金调光层的玻璃片，5-玻璃，6-硅橡胶密封垫，7-氢气质量流量计，8-670nm激光器，9-检测光电流用硅光电二极管，10-计算机控制系统(信号处理系统)；Fig. 2 shows the device figure that the palladium alloy catalytic thin film material prepared in one embodiment of the present invention carries out dimming speed and life test, 4-glass sheet coated with magnesium alloy dimming layer, 5-glass, 6-silicon Rubber seal, 7-hydrogen mass flowmeter, 8-670nm laser, 9-silicon photodiode for detecting photocurrent, 10-computer control system (signal processing system);
图3示出了本发明的一个实施方式中制备的PdTi/Mg4Ni调光镜与Pd/Mg4Ni调光镜在670nm下的透光率及响应速度示意图，其中PdNi/Mg4Ni调光镜中Ti与Pd的原子比分别为0.08、0.10以及0.12；Fig. 3 shows a schematic diagram of light transmittance and response speed at 670nm of the PdTi/Mg 4 Ni dimming mirror and the Pd/Mg 4 Ni dimming mirror prepared in one embodiment of the present invention, wherein the PdNi/Mg 4 Ni dimming The atomic ratios of Ti and Pd in the light microscope are 0.08, 0.10 and 0.12, respectively;
图4示出了本发明的一个实施方式中制备的PdNi/Mg4Ni调光镜与Pd/Mg4Ni调光镜在670nm下的透光率及响应速度示意图，其中PdNi/Mg4Ni调光镜中Ni与Pd的原子比分别为0.13、0.195以及0.26；Figure 4 shows a schematic diagram of the light transmittance and response speed at 670nm of the PdNi/Mg 4 Ni dimming mirror and the Pd/Mg 4 Ni dimming mirror prepared in one embodiment of the present invention, wherein the PdNi/Mg 4 Ni dimming mirror The atomic ratios of Ni and Pd in the light microscope are 0.13, 0.195 and 0.26, respectively;
图5示出了本发明的一个实施方式中制备的PdTi/Mg4Ni调光镜与Pd/Mg4Ni调光镜在670nm下的循环寿命示意图，其中PdNi/Mg4Ni调光镜中Ti与Pd的原子比分别为0.08、0.10以及0.12；Figure 5 shows a schematic diagram of the cycle life of the PdTi/Mg 4 Ni light-adjustable mirror and the Pd/Mg 4 Ni light-adjustable mirror prepared in one embodiment of the present invention at 670nm, wherein the Ti in the PdNi/Mg 4 Ni light-adjustable mirror The atomic ratios to Pd are 0.08, 0.10 and 0.12, respectively;
图6示出了本发明的一个实施方式中制备的PdNi/Mg4Ni调光镜与Pd/Mg4Ni调光镜在670nm下的循环寿命示意图，其中PdNi/Mg4Ni调光镜中Ni与Pd的原子比分别为0.13、0.195以及0.26；Figure 6 shows a schematic diagram of the cycle life of the PdNi/Mg 4 Ni light-adjustable mirror and the Pd/Mg 4 Ni light-adjustable mirror prepared in one embodiment of the present invention at 670nm, wherein Ni in the PdNi/Mg 4 Ni light-adjustable mirror The atomic ratios to Pd are 0.13, 0.195 and 0.26, respectively;
图7示出了本发明的一个实施方式中制备的具有PdTi0.10合金催化层的调光薄膜在250～2600nm波长光范围的金属态和氢化态透射率；Fig. 7 shows the metal state and hydrogenation state transmittance of the dimming film with PdTi 0.10 alloy catalytic layer prepared in one embodiment of the present invention in the light range of 250-2600nm wavelength;
图8示出了本发明的一个实施方式中制备的具有PdTi0.10合金催化层的调光薄膜在250～2600nm波长光范围的金属态和氢化态反射率；Figure 8 shows the metal state and hydrogenation state reflectance of the dimming film with PdTi 0.10 alloy catalyst layer prepared in one embodiment of the present invention in the 250-2600nm wavelength light range;
图9示出了本发明的一个实施方式中制备的具有PdNi0.13合金催化层的调光薄膜在250～2600nm波长光范围的金属态和氢化态透射率；Fig. 9 shows the metal state and hydrogenation state transmittance of the dimming film with PdNi 0.13 alloy catalyst layer prepared in one embodiment of the present invention in the light range of 250-2600nm wavelength;
图10示出了本发明的一个实施方式中制备的具有PdNi0.13合金催化层的调光薄膜在250～2600nm波长光范围的金属态和氢化态反射率；Figure 10 shows the metal state and hydrogenation state reflectance of the dimming film with PdNi 0.13 alloy catalytic layer prepared in one embodiment of the present invention in the light range of 250-2600nm wavelength;
图11示出了本发明中一个实施方式中制备的PdTi薄膜催化层与Pd薄膜催化层的X线衍射示意图；Fig. 11 shows the X-ray diffraction schematic diagram of the PdTi thin film catalyst layer and the Pd thin film catalyst layer prepared in one embodiment of the present invention;
图12示出了本发明中一个实施方式中制备的PdNi薄膜催化层与Pd薄膜催化层的X线衍射示意图。Fig. 12 shows a schematic diagram of X-ray diffraction of a PdNi thin film catalytic layer and a Pd thin film catalytic layer prepared in an embodiment of the present invention.
具体实施方式detailed description
以下结合附图和下述实施方式进一步说明本发明，应理解，附图及下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below in conjunction with the drawings and the following embodiments. It should be understood that the drawings and the following embodiments are only used to illustrate the present invention rather than limit the present invention.
本发明公开了一种钯合金催化薄膜材料及其制备方法。该薄膜材料能催化氢气裂解，覆盖在镁合金薄膜上所形成的调光镜，能提高其寿命，降低调光镜的制备成本。该钯合金薄膜可用于调光玻璃(建筑节能窗，汽车玻璃)，氢气传感器以及分离氢及提纯氢气膜，能提高其寿命，具有保护镁合金不被氧化和催化的功能，降低其制备成本。The invention discloses a palladium alloy catalytic film material and a preparation method thereof. The thin-film material can catalyze hydrogen cracking, and the light-adjustable mirror formed on the magnesium alloy thin film can improve the service life of the light-adjustable mirror and reduce the preparation cost of the light-adjustable mirror. The palladium alloy thin film can be used for dimming glass (building energy-saving window, automobile glass), hydrogen sensor, hydrogen separation and hydrogen purification film, can improve its service life, has the function of protecting magnesium alloy from oxidation and catalysis, and reduces its preparation cost.
本发明提供了一种钯合金催化薄膜材料，基于钯而形成的Pd-M合金薄膜，M为金属Ti或Ni。本发明中，提出在钯催化层薄膜材料中掺入了其他的金属如：Ni或Ti，不仅能提高催化层的韧性，提高放氢速率和寿命，同时也降低调光薄膜的制备成本。The invention provides a palladium alloy catalytic thin film material, which is a Pd-M alloy thin film formed based on palladium, and M is metal Ti or Ni. In the present invention, it is proposed that other metals such as Ni or Ti are mixed into the palladium catalytic layer film material, which can not only improve the toughness of the catalytic layer, improve the hydrogen desorption rate and life, but also reduce the preparation cost of the dimming film.
所述的薄膜材料覆盖在镁合金薄膜上方形成的调光镜可用于调光玻璃(节能玻璃)和氢气传感器。The dimming mirror formed on the magnesium alloy thin film covered by the thin film material can be used for dimming glass (energy-saving glass) and hydrogen sensor.
所述薄膜材料，PdTi合金薄膜成分是PdTix，其中0<x<0.5；或Pd-Ni合金薄膜成分是PdNiy，其中0<y<0.5。For the thin film material, the composition of the PdTi alloy thin film is PdTi x , where 0<x<0.5; or the composition of the Pd-Ni alloy thin film is PdNi y , where 0<y<0.5.
所述薄膜材料，薄膜的厚度在1nm-10nm之间。As for the thin film material, the thickness of the thin film is between 1nm-10nm.
所述薄膜材料，钯合金能催化氢气裂解，保护镁合金不被氧化。The thin film material, palladium alloy, can catalyze hydrogen cracking and protect magnesium alloy from oxidation.
所述的薄膜材料，镁合金薄膜材料可以为稀土材料Y、La掺杂的镁合金、镁二元合金材料Mg1-xMx或镁三元合金材料Mg1-x-yMyNz其中M为Ni、Ti、V、Nb、Y、Zr、Mo、Cu、V、Co、Mn、W、Fe稀土金属(Y、La)、碱土金属(Ca、Sr、Ba)，N为Ni、Ti、V、Nb、Y、Zr、Mo、Cu、V、Co、Mn、W。The thin film material, the magnesium alloy thin film material can be rare earth material Y, La-doped magnesium alloy, magnesium binary alloy material Mg 1-x M x or magnesium ternary alloy material Mg 1-xy M y N z where M Ni, Ti, V, Nb, Y, Zr, Mo, Cu, V, Co, Mn, W, Fe rare earth metals (Y, La), alkaline earth metals (Ca, Sr, Ba), N is Ni, Ti, V, Nb, Y, Zr, Mo, Cu, V, Co, Mn, W.
所述的薄膜材料中，镁合金薄膜的厚度在10nm-200nm之间。Among the thin film materials, the thickness of the magnesium alloy thin film is between 10nm and 200nm.
本发明提供了一种调光镜用钯合金催化薄膜的制备方法，通过物理气相沉积的方法在基片上沉积镁合金薄膜后，接着沉积钯合金薄膜，获得调光镜薄膜材料。The invention provides a method for preparing a palladium alloy catalytic thin film for a dimming mirror. After depositing a magnesium alloy thin film on a substrate by a physical vapor deposition method, the palladium alloy thin film is then deposited to obtain a dimming mirror thin film material.
所述的制备方法中，所述物理沉积法为磁控溅射法，脉冲激光溅射，蒸发镀膜。In the preparation method, the physical deposition method is magnetron sputtering, pulsed laser sputtering, and evaporation coating.
所述的制备方法，制备步骤如下：Described preparation method, preparation steps are as follows:
(1)镁合金薄膜层的制备：在室温下，将清洗过的基片放入溅射室内，通入气体，调节沉积压力利用直流磁控溅射法共溅射沉积镁合金和其他纯金属靶材，通过改变溅射功率来控制形成不同组分的合金薄膜，通过调节溅射时间来控制沉积薄膜的厚度，在基片上沉积一层镁合金薄膜；(1) Preparation of magnesium alloy thin film layer: at room temperature, put the cleaned substrate into the sputtering chamber, introduce gas, adjust the deposition pressure, and co-sputter deposit magnesium alloy and other pure metals by DC magnetron sputtering The target material, by changing the sputtering power to control the formation of alloy films of different components, by adjusting the sputtering time to control the thickness of the deposited film, depositing a layer of magnesium alloy film on the substrate;
(2)催化层的制备：制备出镁合金层后，接着调节适当压力，共溅射沉积纯金属Pd与Ni、Ti，通过改变溅射功率来控制形成不同组分的合金薄膜。通过调节溅射时间来控制沉积薄膜的厚度。(2) Preparation of the catalytic layer: after preparing the magnesium alloy layer, adjust the appropriate pressure, co-sputter deposit pure metal Pd, Ni, Ti, and control the formation of alloy films with different components by changing the sputtering power. The thickness of the deposited film was controlled by adjusting the sputtering time.
所述的制备方法中，所述基片可以是玻璃、柔性基片(高分子膜)、导电玻璃、金属薄片、硅基板等。In the preparation method, the substrate may be glass, flexible substrate (polymer film), conductive glass, metal sheet, silicon substrate and the like.
本发明克服现有调光薄膜的不足，获得制备成本较低，韧性好，吸放氢速率快，且能提高调光镜寿命的催化层薄膜材料。The invention overcomes the shortcomings of the existing dimming films, and obtains a catalyst layer thin film material with low preparation cost, good toughness, fast hydrogen absorption and desorption rate, and improved service life of dimming mirrors.
本发明中提供了一种调光镜的制备方法，是通过在基片上共溅射金属镁和其他金属(如：Ni，Ti、Nb、Zr、Ca等)制备出镁合金薄膜材料，再接着共溅射沉积金属钯和其他过渡金属(如Ni、Ti)而获得的钯合金催化层薄膜材料。其特征是在氢气中会从镜态转变成透明态，在氧气或空气中又变回镜态。在可逆吸放氢过程中电阻也会发生可逆变化。The present invention provides a method for preparing a dimming mirror, which is to prepare a magnesium alloy film material by co-sputtering metal magnesium and other metals (such as: Ni, Ti, Nb, Zr, Ca, etc.) on a substrate, and then Palladium alloy catalytic layer film material obtained by co-sputtering deposition of metal palladium and other transition metals (such as Ni, Ti). Its characteristic is that it will change from a mirror state to a transparent state in hydrogen, and change back to a mirror state in oxygen or air. The resistance will also change reversibly during the reversible hydrogen absorption and desorption process.
本发明提供了一中催化层薄膜材料的制备方法：在室温下，利用磁控溅射法共溅射沉积纯金属Pd与Ni或Ti，通过改变溅射功率来控制形成不同组分的合金薄膜。通过调节溅射时间来控制沉积薄膜的厚度，以满足应用要求。The invention provides a method for preparing a catalytic layer thin film material: at room temperature, use magnetron sputtering to co-sputter deposit pure metal Pd and Ni or Ti, and control the formation of alloy thin films with different components by changing the sputtering power . The thickness of the deposited film is controlled by adjusting the sputtering time to meet the application requirements.
本发明调光镜所用镁合金薄膜及钯合金催化层是在系统真空小于10-5Pa下，在氩气分工作压力为0.5Pa下采用磁控溅射沉积法制备而得。The magnesium alloy thin film and palladium alloy catalytic layer used in the dimming mirror of the present invention are prepared by magnetron sputtering deposition method under the vacuum of the system less than 10 -5 Pa, and the working pressure of argon gas is 0.5 Pa.
本发明中，制备方法为物理气相沉积法包括：磁控溅射方法，脉冲激光溅射，蒸发镀膜；本发明中所叙述的催化层可应用于气致变色窗(建筑节能窗，汽车玻璃)、氢气传感器、透氢薄膜。通过光性能测试表明，本发明所制备的钯合金催化层调光薄膜的放氢速率快；能提高催化层韧性和调光镜的寿命；并且降低了调光薄膜的制备成本，对于调光玻璃大规模生产具有很大的经济效益。In the present invention, the preparation method is a physical vapor deposition method including: magnetron sputtering method, pulse laser sputtering, and evaporation coating; the catalytic layer described in the present invention can be applied to aerochromic windows (building energy-saving windows, automotive glass) , hydrogen sensor, hydrogen permeable film. Show by optical performance test, the hydrogen desorption rate of palladium alloy catalytic layer dimming thin film prepared by the present invention is fast; Can improve the life-span of catalytic layer toughness and dimming mirror; And reduce the preparation cost of dimming thin film, for dimming glass Large-scale production has great economic benefits.
以下进一步列举出一些示例性的实施例以更好地说明本发明。应理解，本发明详述的上述实施方式，及以下实施例仅用于说明本发明而不用于限制本发明的范围，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。另外，下述工艺参数中的具体配比、时间、温度等也仅是示例性，本领域技术人员可以在上述限定的范围内选择合适的值。Some exemplary embodiments are further enumerated below to better illustrate the present invention. It should be understood that the above-mentioned embodiments described in detail in the present invention and the following examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention, and those skilled in the art may make some non-essential improvements and improvements according to the above-mentioned contents of the present invention All adjustments belong to the protection scope of the present invention. In addition, the specific proportions, time, temperature, etc. in the following process parameters are only exemplary, and those skilled in the art can select appropriate values within the range defined above.
实施例1：Example 1:
1)镁合金薄膜的制备1) Preparation of magnesium alloy film
薄膜的制备采用磁控溅射法，利用直流磁控溅射仪。靶材组分分别为纯Mg金属、纯Ni金属和纯Pd金属。将清洗过的普通玻璃基片、石英玻璃、ITO玻璃或单晶硅基片(基片选取取决于所采用的测试)放入真空室内，溅射室本底真空度达10-5数量级以下，通入高纯氩气，流量40sccm；调节转速为15r/min；沉积压力为0.5Pa，待稳定后，在基片上共溅射Mg和Ni功率分别是40W和16W，时间110s。X射线分析其成分为Mg4Ni；The preparation of the thin film adopts the magnetron sputtering method and utilizes a DC magnetron sputtering apparatus. The target components are pure Mg metal, pure Ni metal and pure Pd metal, respectively. Put the cleaned ordinary glass substrate, quartz glass, ITO glass or single crystal silicon substrate (substrate selection depends on the test used) into the vacuum chamber, the background vacuum of the sputtering chamber is below the order of 10 -5 , Introduce high-purity argon gas with a flow rate of 40 sccm; adjust the rotation speed to 15 r/min; and deposit pressure to 0.5 Pa. After stabilization, co-sputter Mg and Ni on the substrate with powers of 40 W and 16 W, respectively, for 110 s. X-ray analysis of its composition is Mg 4 Ni;
2)钯合金催化层的制备2) Preparation of palladium alloy catalytic layer
①PdTi合金薄膜的制备①Preparation of PdTi alloy film
制备好镁合金薄膜后，接着继续共溅射Pd和Ti，在镁合金薄膜上制备PdTi合金催化层，功率分别是30W和8W、10W、12W，时间分别为43s、42s、41s,沉积压力为0.5Pa。X射线荧光分析其成分，薄膜为PdTi0.08/Mg4Ni，PdTi0.10/Mg4Ni、PdTi0.120/Mg4Ni；After preparing the magnesium alloy thin film, continue to co-sputter Pd and Ti to prepare a PdTi alloy catalytic layer on the magnesium alloy thin film. 0.5Pa. X-ray fluorescence analysis of its composition, the film is PdTi 0.08 /Mg 4 Ni, PdTi 0.10 /Mg 4 Ni, PdTi 0.120 /Mg 4 Ni;
②PdNi合金薄膜的制备② Preparation of PdNi alloy film
制备好镁合金薄膜后，接着继续共溅射Pd和Ni，在镁合金薄膜上制备PdNi合金催化层，功率分别是30W和4W、6W、8W，时间分别为43s、42s、41s，沉积压力为0.5Pa。X射线荧光分析其成分，薄膜为PdNi0.13/Mg4Ni，PdNi0.195/Mg4Ni、PdNi0.26/Mg4Ni；After preparing the magnesium alloy thin film, continue to co-sputter Pd and Ni to prepare a PdNi alloy catalytic layer on the magnesium alloy thin film. 0.5Pa. X-ray fluorescence analysis of its composition, the film is PdNi 0.13 /Mg 4 Ni, PdNi 0.195 /Mg 4 Ni, PdNi 0.26 /Mg 4 Ni;
所制备薄膜结构图如图1所示，1为基片，2为Mg4Ni，3为钯合金，其中基片可以是玻璃、石英、ITO玻璃或单晶硅。钯合金可以为PdTi合金或PdNi合金；The structure diagram of the prepared thin film is shown in Figure 1, 1 is the substrate, 2 is Mg4Ni, 3 is the palladium alloy, wherein the substrate can be glass, quartz, ITO glass or single crystal silicon. Palladium alloy can be PdTi alloy or PdNi alloy;
制备的薄膜具有金属光泽处于金属态；当在其表面通4％H2和Ar混合气体时，薄膜变为透明态；当表面通空气或氧气时，薄膜恢复金属态。The prepared film has a metallic luster and is in a metallic state; when the mixed gas of 4% H 2 and Ar is passed on the surface, the film becomes transparent; when air or oxygen is passed on the surface, the film returns to the metallic state.
实施例2：Example 2:
调光速度性能测试采用图2所示的装置进行评价，将镀有镁镍合金薄膜的玻璃片4与一普通玻璃片5相对设置，使镀有镁镍合金薄膜的一面面向普通玻璃片5，在两玻璃片之间用硅胶垫片6隔开，形成一可通入氢气或氘气的空腔，利用气体流量检测器7来控制气体，将半导体激光器8和硅光电二极管9分别设置在镀有镁镍合金薄膜的玻璃片4和普通玻璃片5的外侧，将信号处理系统10串联在硅光电二极管9和半导体激光器8之间。测试时，向两层玻璃板之间通入氢气的体积分数为4％氢氩混合气体，再用670nm的激光照射两玻璃板，测量其在670nm的调光速度，结果如图3、图4所示。图3示出了一些PdTi/Mg4Ni/普通玻璃调光速度图，图4也示出了一些PdNi/Mg4Ni/普通玻璃调光速度图。从图中可以看出与具有纯钯催化层的调光薄膜相比，具有PdTi合金催化层的调光薄膜不影响调光薄膜的吸放氢速率；具有PdNi合金催化层的调光薄膜具有更快的吸放氢速率。The dimming speed performance test is evaluated using the device shown in Figure 2. A glass sheet 4 coated with a magnesium-nickel alloy film is set opposite to an ordinary glass sheet 5, so that the side coated with a magnesium-nickel alloy film faces the ordinary glass sheet 5. Separate the two glass sheets with a silica gel gasket 6 to form a cavity that can pass into hydrogen or deuterium gas, and use a gas flow detector 7 to control the gas, and a semiconductor laser 8 and a silicon photodiode 9 are respectively arranged on the plated A signal processing system 10 is connected in series between the silicon photodiode 9 and the semiconductor laser 8 on the outside of the glass sheet 4 with the magnesium-nickel alloy thin film and the common glass sheet 5 . During the test, a hydrogen-argon mixed gas with a volume fraction of 4% was introduced between the two glass plates, and then a 670nm laser was used to irradiate the two glass plates, and the dimming speed at 670nm was measured. The results are shown in Figure 3 and Figure 4 shown. Figure 3 shows some PdTi/Mg4Ni/common glass dimming speed diagrams, and Figure 4 also shows some PdNi/Mg4Ni/common glass dimming speed diagrams. It can be seen from the figure that compared with the dimming film with pure palladium catalytic layer, the dimming film with PdTi alloy catalytic layer does not affect the hydrogen absorption and desorption rate of dimming film; the dimming film with PdNi alloy catalytic layer has a higher Fast hydrogen absorption and desorption rate.
实施例3：Example 3:
循环寿命测试采用图3所示装置进行评价，测试时，设置4％氢氩混合气体流量为50sccm，气体开30s，关300s，即调光薄膜每330s进行一次吸放氢循环。图5示出了一些PdTi/Mg4Ni/普通玻璃循环寿命图，由图可见与具有纯钯催化层的调光玻璃相比，具有PdTi0.08、PdTi0.10、PdTi0.120的调光玻璃循环寿命都有所增加。图6也示出了一些PdNi/Mg4Ni/普通玻璃循环寿命图，由图可见与具有纯钯催化层的调光玻璃相比，PdNi0.13、PdNi0.195、PdNi0.26的调光玻璃循环寿命都有所增加。纯钯催化层的调光玻璃循环寿命大约110次，PdTi合金催化层可达130次，PdNi可达170次。The cycle life test is evaluated using the device shown in Figure 3. During the test, the flow rate of 4% hydrogen-argon mixed gas is set to 50 sccm, the gas is turned on for 30s and turned off for 300s, that is, the dimming film undergoes a hydrogen absorption and desorption cycle every 330s. Figure 5 shows some cycle life diagrams of PdTi/Mg4Ni/common glass. It can be seen from the figure that compared with the switchable glass with pure palladium catalyst layer, the cycle life of the switchable glass with PdTi 0.08 , PdTi 0.10 , and PdTi 0.120 is significantly improved. Increase. Figure 6 also shows some PdNi/Mg4Ni/ordinary glass cycle life diagrams. It can be seen from the figure that compared with the dimming glass with pure palladium catalytic layer, the cycle life of the dimming glass of PdNi 0.13 , PdNi 0.195 , and PdNi 0.26 has a significant difference. Increase. The cycle life of dimming glass with pure palladium catalytic layer is about 110 times, that of PdTi alloy catalytic layer can reach 130 times, and that of PdNi can reach 170 times.
实施例4：Example 4:
调光薄膜透光率图谱采用HITACHIU-4100分光光度计进行测试。首先对光度计做基线的扫描，然后设置测试参数：起始波长:2600nm,终止波长:250nm,扫描速度:600nm/min，测试模式：T％，最后分别依次将各合金薄膜放进测试箱内，扫描出透光率图谱；The light transmittance spectrum of the dimming film is tested with a HITACHIU-4100 spectrophotometer. First do a baseline scan on the photometer, then set the test parameters: start wavelength: 2600nm, stop wavelength: 250nm, scan speed: 600nm/min, test mode: T%, and finally put each alloy film into the test box in turn , scan out the transmittance spectrum;
反射率图谱采用HITACHIU-4100分光光度计进行测试。首先对光度计做基线的扫描，然后设置测试参数：起始波长:2600nm,终止波长:250nm,扫描速度:600nm/min，测试模式：R％，最后分别依次将各合金薄膜放进测试箱内，扫描出反射率图谱；The reflectance spectrum is tested by HITACHIU-4100 spectrophotometer. First do a baseline scan on the photometer, then set the test parameters: start wavelength: 2600nm, end wavelength: 250nm, scan speed: 600nm/min, test mode: R%, and finally put each alloy film into the test box in turn , scan the reflectance map;
各样品氢化态光谱是在通入氢气体积分数为4％的氢氩混合气体时测得的；The hydrogenation state spectrum of each sample was measured when a hydrogen-argon mixed gas with a hydrogen gas fraction of 4% was introduced;
测试PdTi0.10/Mg4Ni/石英玻璃，金属态和氢化态透射率结果如图7所示，反射率如图8所示；测试PdNi0.13/Mg4Ni/石英玻璃，金属态和氢化态透射率结果如图9所示，反射率如图10所示。所有的合金在金属态时对光有非常高的反射率，只存在极少的吸收，证实其是一种反射型调光薄膜。在氢化物态时具有较高的透光率，是一种透明状态。Test PdTi 0.10 /Mg 4 Ni/quartz glass, metal state and hydrogenated state transmittance results are shown in Figure 7, reflectivity is shown in Figure 8; test PdNi 0.13 /Mg 4 Ni/quartz glass, metal state and hydrogenated state transmittance The results of the ratio are shown in Figure 9, and the reflectance results are shown in Figure 10. All the alloys have very high reflectivity to light in the metal state, and there is only very little absorption, which proves that it is a reflective dimming film. It has a high light transmittance in the hydride state and is a transparent state.
实施例5：Example 5:
与实施例1中方案相同，采用Pd溅射，功率30W、时间35s，制备Pd催化层；The same scheme as in Example 1, using Pd sputtering, power 30W, time 35s, to prepare a Pd catalytic layer;
采用Pd与Ti共溅射，功率10W、12W，时间42s、41s，制备PdTi0.1催化层、PdTi0.2催化层；Using Pd and Ti co-sputtering, power 10W, 12W, time 42s, 41s, prepare PdTi 0.1 catalytic layer, PdTi 0.2 catalytic layer;
采用Pd与Ni共溅射，功率4W、8W，时间43s、41s，制备PdNi0.13催化层、PdNi0.26催化层；Using Pd and Ni co-sputtering, power 4W, 8W, time 43s, 41s, prepare PdNi 0.13 catalytic layer, PdNi 0.26 catalytic layer;
图11制备的PdTi薄膜催化层与Pd薄膜催化层的X线衍射示意图，从图中可以看出，在室温沉积条件下，2θ在40o附近只有Pd(111)面的衍射峰，未出现其它新的衍射峰，说明非晶态Pd-Ti的形式存在；Figure 11 is a schematic diagram of the X-ray diffraction of the PdTi thin film catalytic layer and the Pd thin film catalytic layer. It can be seen from the figure that under room temperature deposition conditions, there are only diffraction peaks of the Pd(111) plane at 2θ around 40o, and no other new ones appear. Diffraction peaks, indicating that the form of amorphous Pd-Ti exists;
图12示出了本发明中一个实施方式中制备的PdTi薄膜催化层与Pd薄膜催化层的X线衍射示意图，从图中可以看出，2θ在40o附近有Pd(111)面的衍射峰，由于Ni()的晶格常数小于Pd()的晶格常数，所以Ni含量的提高向大角度方向迁移，说明Pd-Ni合金催化层是一个固溶体。Fig. 12 shows the X-ray diffraction schematic diagram of the PdTi film catalyst layer and the Pd film catalyst layer prepared in one embodiment of the present invention, as can be seen from the figure, 2θ has a diffraction peak of Pd (111) plane near 40°, Since Ni( ) has a lattice constant smaller than that of Pd( ) lattice constant, so the increase of Ni content migrates to the large angle direction, indicating that the Pd-Ni alloy catalytic layer is a solid solution.
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