CN109154078A - 薄层沉积过程 - Google Patents

薄层沉积过程 Download PDF

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CN109154078A
CN109154078A CN201780032099.5A CN201780032099A CN109154078A CN 109154078 A CN109154078 A CN 109154078A CN 201780032099 A CN201780032099 A CN 201780032099A CN 109154078 A CN109154078 A CN 109154078A
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titanium
thickness
layer
substrate
coating
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N.瓦纳库勒
C.马涅
C.博托瓦
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Abstract

本发明涉及一种获得包含涂覆有光催化涂层的基材的材料的方法,所述方法包括通过溅射在所述基材上沉积叠薄层叠层的步骤,其依次包括第一钛金属层,厚度为1至3nm,至少部分氧化的钛的中间层,厚度为0.5至5nm,和第二钛金属层,厚度为2至5nm;借助于通过激光辐射的热处理氧化步骤,其中该叠层与氧化气氛接触。

Description

薄层沉积过程
本发明涉及获得包含涂覆有光催化涂层的基材的材料的方法,和还涉及以这种方式获得的涂覆有光催化涂层的基材。
工业规模通常用于沉积薄层(特别地在玻璃基材上)的方法是溅射方法,特别地通过磁场增强,在这种情况下称为“磁控管”方法。在该方法中,在包括待沉积的化学元素的靶附近在高真空下产生等离子体。在轰击靶时,等离子体的活性实体撕掉沉积在基材上的所述元素,形成所需的薄层。当该层由从靶标撕裂的元素和等离子体中包含的气体之间的化学反应产生的材料组成时,该方法被称为“反应性”。该方法的主要优点在于,可以通过相继地(successive)使基材在各种靶下运行,通常在同一个装置中,在同一条生产线上沉积非常复杂的层叠层。
然而,氧化物层(例如氧化钛)的沉积速率通常远低于金属的沉积速率,这限制了生产速率,这增加了包括通过溅射沉积的氧化物层的叠层的生产成本。申请WO2011 /039488描述了一种薄层沉积方法,其包括沉积金属,氮化物或碳化物的中间层的步骤和使用快速热处理,特别是通过激光辐射氧化该中间层的步骤。该方法可以获得具有更高生产率的金属氧化物层。
如WO2011 / 039488中所述的激光处理使得可以将薄涂层加热到约几百度的高温,同时保留下面的基材。处理速度当然优选尽可能高,有利地至少为每分钟几米。为了能够高速处理大宽度的基材,例如“巨型”尺寸(6 mx 3.21 m)的平板玻璃板,离开浮法工艺,必须使激光线本身非常长(> 3 m)。由于不能想到制造对于这样长度的能够获得单个激光线的单片光学器件,因此通常将较小尺寸(几十厘米)的各个激光器线组合在一起以形成足够长的激光器线。
在激光处理期间必须被氧化的金属层通常必须具有最小厚度,以便能够在氧化之后实现所需的产品规格。例如,为了使钛层一旦被氧化,具有所需的光催化和光学性质,该层有利地在氧化之前具有至少5nm的厚度。然后难以对该层进行完全和/或均匀氧化,特别是在高运行速度下。具体地,激光的强度变化可能导致某些区域中的氧化差异,特别是在各个激光线的重叠区域。这种被称为拼叠的现象,在高处理速率下特别恶化,可能在最终产品上产生可见的缺陷,例如在基材长度上的不均匀条带,这从美学观点来看是不可接受的。此外,从生产成本的观点来看,所需的高处理速率可能导致待处理层的不完全氧化,这具有增加处理后涂层的残余光吸收的效果。
本发明的目的是克服上述缺点。申请人已经证明,通过激光处理,特别是在高处理速率下,通过将待处理层分离(通过至少部分氧化的钛的层分离)成两层相等总厚度的钛,可以改善钛层的氧化。
因此,本发明涉及获得包含涂覆有光催化涂层的基材的材料的方法,所述方法包括:
- 在所述基材上沉积薄层叠层的步骤,所述薄层依次包括厚度为1至3nm的第一钛金属层,至少部分氧化的钛的中间层,厚度为0.5至5nm,第二钛金属层,厚度为2-5nm;和
- 借助于通过激光辐射的热处理氧化的步骤,其中所述叠层与氧化气氛接触。
根据本发明的方法使得可以减少拼叠(stitching)现象和/或残余光吸收,特别是在高处理速率下,通常大于2米/分钟,或大于3米/分钟,或甚至大于4米/分钟,或大于5米/分钟。在两个金属层之间存在部分氧化的中间层使得金属层的氧化更完全和/或更均匀。
根据本发明的方法包括在基材上沉积薄层叠层的第一步骤,所述薄层包括在两层钛金属层之间的至少部分氧化的钛的中间层。钛金属层与至少部分氧化的钛的中间层直接接触。第一钛金属层可以与基材直接接触。然而,在某些实施方案中,可以在基材和第一钛金属层之间沉基材积其他层,例如基于氧化硅的碱金属阻挡层。通常,在第二钛金属层上没有沉积其它层,使得在根据本发明的方法结束时获得的氧化钛光催化层是与大气接触的最后一层涂层。
基材优选是玻璃板,玻璃陶瓷板或聚合有机材料板。它优选是透明的,无色的(然后是透明或超透明玻璃)或着色的,例如蓝色,绿色,灰色或青铜色。玻璃优选为钠钙硅酸盐类型,但也可以是硼硅酸盐或铝硼硅酸盐类型的玻璃。优选的聚合有机材料是聚碳酸酯或聚甲基丙烯酸甲酯或聚对苯二甲酸乙二醇酯(PET)。基材有利地具有至少一个大于或等于1米,或实际上2米甚至3米的尺寸。基材的厚度通常在0.5mm至19mm之间,优选在0.7至9mm之间,特别是在2至8mm之间,或实际在4至6mm之间变化。基材可以是平的或弯曲的,或者实际上是柔性的。
玻璃基材优选为浮法玻璃类型,也就是说能够通过包括将熔融玻璃浇注到熔融锡浴(“浮法”浴)的方法获得。在这种情况下,待处理的层可以沉积在基材的“锡”面和“气氛”面两者上。术语“气氛”面和“锡”面应理解为是指基材的表面,其分别与浮法浴中存在的气氛接触和与熔融锡接触。锡侧含有表面少量的锡,其扩散到玻璃结构中。玻璃基材也可以通过在两个辊之间滚动来获得,该技术使得尤其可以在玻璃表面上印刷图案。
通过溅射沉积第一和第二钛金属层。与氧化物层的沉积相比,金属层的沉积具有允许非常高的沉积速率的优点。也可以通过溅射沉积中间层。由于该层非常薄,所以叠层的生产速率仅受到氧化钛层沉积的轻微影响。中间层也可以通过第一钛金属层的部分氧化来获得,例如通过在沉积第一钛金属层之后将基材暴露于空气或氧化等离子体。
第一钛金属层的厚度为1-3nm,优选1-2nm,和第二钛金属层的厚度为2-5nm,优选2-4nm。具体地,第一钛金属层太厚会导致在热处理过程中涂层显著分层。此外,太厚的第二钛金属层可能损害第一钛金属层的氧化效果。第一和第二钛金属层的厚度之和优选大于或等于4nm,或者实际上大于或等于5nm,以便在热处理后获得具有令人满意的活性的光催化涂层。
至少部分氧化的钛的中间层优选具有0.5至3nm的厚度,更优选0.5至2nm的厚度。
至少部分氧化的钛的中间层可以是任选亚化学计量的氧化钛层。后者将由TiOx表示。根据一个具体实施方案,x的值优选小于或等于1.8。在这种情况下,中间层参与激光辐射的吸收,和因此可以改善最终光催化层的活化。根据另一具体实施方案,值x优选大于或等于1.8,特别是至少部分氧化的钛层是氧化钛TiO2层。该实施方案具有能够使叠层更完全氧化并因此减少其残余吸收的优点。
根据本发明的方法还包括氧化叠层的步骤。叠层的氧化,特别是钛金属层的氧化通过使用激光的热处理来进行,该叠层与氧化气氛接触。氧化气氛优选为空气,特别是在大气压下。如果需要,可以增加气氛的氧含量以进一步促进中间层的氧化。
热处理使得可以在单个步骤中将金属钛氧化成氧化钛并获得光催化层,因此光催化层至少部分地结晶。在热处理后获得的氧化钛层(优选呈锐钛矿相)至少部分结晶,也可任选地存在金红石相。
通过激光辐射进行的热处理具有非常高的热交换系数的优点,通常大于400W/(m²·s)。中间层处激光辐射的每单位面积功率甚至优选大于或等于20或30 kW/cm²。这种非常高的能量密度使得可以在中间层非常快速地达到所需温度(通常在小于或等于1秒的时间内)并因此相应地限制处理的持续时间,然后产生的热量没有时间在基材内扩散。
因此,叠层的每个处理点优选地经受热处理一段时间,通常小于或等于1秒,或实际上0.5秒。由于与根据本发明的方法相组合的非常高的热交换系数,即使位于距中间层0.5mm的玻璃部分通常也不经受高于100℃的温度。优选地,在热处理期间基材的温度不超过100℃,特别是50℃。这尤其是与沉积中间层的面相对的面上的温度。该温度可以例如通过高温测定法(pyrometry)测量。
该方法还使得可以在现有的连续生产线上结合激光处理装置。因此,激光可以结合到层沉积生产线中,例如磁场增强(磁控管工艺)溅射沉积生产线。通常,该生产线包括用于处理基材的装置,沉积单元,光学控制装置和叠层装置。基材例如在传送辊上连续地在每个装置或每个单元的前面运行。激光优选地紧接在层沉积单元之后,例如在沉积单元的出口处。因此,在沉积层之后,在沉积单元的出口处和光学控制装置之前,或在光学控制装置之后和在基材叠层装置之前,可以在线处理涂覆的基材。在某些情况下,还可以在真空沉积室内进行根据本发明的热处理。然后将激光结合到沉积单元中。例如,可以将激光引入溅射沉积单元的一个腔室中。
无论激光是在沉积单元之外还是并入其中,这些“在线”或“连续”方法优于涉及离线操作的方法,其中有必要在沉积步骤和热处理之间叠层玻璃基材。
然而,涉及离线操作的方法在根据本发明的热处理在与进行沉积的地方不同的地方进行(例如在玻璃转化的地方进行)的情况下具有优势。因此,辐射装置可以结合到除层沉积生产线之外的生产线中。例如,它可以结合到用于制造多层玻璃制品(特别是双层或三层玻璃制品)的生产线中或者用于制造层压玻璃制品的生产线中。在这些不同的情况下,根据本发明的热处理优选在生产多层或层压玻璃制品之前进行。
激光辐射优选地由至少一个形成线的激光束(在文本的延续部分中称为“激光线”)产生,该激光束同时辐射基材的整个宽度。特别地,可以使用聚焦光学系统获得在线(en ligne)激光束。为了能够同时辐射非常宽的基材(>3m),通常通过组合多个单独的激光线来获得激光线。各个激光线的厚度优选地在0.01至1mm之间。它们的长度通常在5毫米至1米之间。各个激光线通常并排并置,以便形成单个激光线,使得叠层的整个表面得到处理。每个单独的激光线优选垂直于基材的运行方向定位。
激光源通常是激光二极管或光纤激光器,特别是光纤,二极管或盘式激光器。激光二极管使得可以经济地实现相对于电源功率的高功率密度,以满足小的空间需求。光纤激光器的空间要求甚至更小,并且获得的线性功率密度可以更高,但是成本更高。术语“光纤激光器”应理解为激光器,其中产生激光的位置在空间上从其传送的位置移除,激光通过至少一根光纤传送。在盘式激光器的情况下,激光在谐振腔中产生,其中已发现发射介质呈盘形式,例如由Yb:YAG制成的薄盘(约0.1mm厚)。由此产生的光耦合在至少一个指向处理的地方的光纤中。激光器也可以是光纤激光器,只要放大介质本身是光纤即可。优选使用激光二极管光学任选地泵浦光纤或盘式激光器。由激光源产生的辐射优选是连续的。
激光辐射的波长以及处理波长优选在800至1300nm,特别是800至1100nm的范围内。已经证明,发射选自808nm,880nm,915nm,940nm或980nm的一种或多种波长的高功率激光二极管特别适合。在盘式激光器的情况下,处理波长例如是1030nm(Yb:YAG激光器的发射波长)。对于光纤激光器,处理波长通常为1070nm。
优选地,叠层在激光辐射波长下的吸收大于或等于20%,特别是30%。吸收定义为等于100%的值,从中减去层的透射率和反射率。
为了处理涂覆基材的整个表面,在一方面,在涂覆有该层的基材和激光线之间产生相对运动。因此,基材可以移动,特别是使其平移地经过固定激光线,通常在激光线下方但可选地在激光线上方。该实施方案对于连续处理特别有利。优选地,基材和激光器的相应速度之间的差值大于或等于2米/分钟,实际上3米甚至4,5,8或10米/分钟,以确保高处理速率。
可以使用任何机械传送装置(例如使用平移移动的带,辊或托盘)移动基材。输送系统可以控制和调节运动速度。如果基材由柔性聚合有机材料制成,则可以使用一系列辊子形式的薄膜推进系统移动基材。
当然,只要可以适当地辐射基材的表面,基材和激光的所有相对位置都是可能的。通常,基材将水平放置,但也可以垂直放置或根据任何可能的倾斜放置。当基材水平放置时,通常定位激光以辐射基材的上表面。激光还可以辐射基材的下表面。在这种情况下,基材的支撑系统,任选地用于在基材移动时传送基材的系统,必须允许辐射在待辐射的区域中通过。例如,当使用输送辊时就是这种情况:由于辊是分开的实体,因此可以将激光定位在位于两个相继(successive)的辊之间的区域中。
当要处理基材的两个面时,可以采用位于基材两侧的多个激光器,无论后者处于水平,垂直还是任何倾斜位置。
本发明还涉及涂覆有薄层叠层的基材,该薄层依次包括厚度为1-3nm,优选1-2nm的第一钛金属层,具有至少部分氧化的钛的中间层,其厚度为0.5至5nm,优选0.5至3nm,或实际0.5至2nm,和第二钛金属层,其厚度为2至5nm,优选2至4nm。该基材旨在通过激光辐射的热处理进行氧化,该叠层与氧化气氛接触,以获得涂覆有光催化涂层的基材。
本发明还涉及涂覆有光催化涂层的基材,其能够通过本发明的方法获得。根据本发明获得的基材优选结合至玻璃制品中。玻璃制品可以是单层或多层(特别是双层或三层),只要它可以包括提供充气空间的多个玻璃板。玻璃制品也可以被层压和/或回火和/或硬化和/或弯曲。
与沉积叠层的面相对的基材的面,或者在适当的情况下,多层玻璃制品的另一基材的面可以涂覆有另一个功能层或功能层叠层。它尤其可以是具有热功能的层或叠层,特别是太阳能保护层或低发射率层或叠层,例如包括由介电层保护的银层的叠层。它也可以是镜面层,特别是基于银的镜面层。它最终可能是一种漆或搪瓷,用于使玻璃制品不透光,以便从中制造墙面板(a wall cladding panel),称为拱肩玻璃(spandrel glass)。拱肩玻璃位于非不透明玻璃制品侧面的墙壁上,和从美学的角度来看,可以获得完全上釉和均匀的墙壁。
位于基材的与沉积氧化物层的面相对的面上的其他层或叠层可以看到由于根据本发明的热处理而改善了它们的性能。这些尤其可以是与功能层(例如银层)的更好结晶相关的性质。因此,已经观察到,特别是在由厚度为至多6mm的玻璃制成的基材的情况下,根据本发明的氧化热处理也能够降低包含至少一个银层的低发射率叠层的发射率和/或电阻率。
根据本发明的一个实施方案,包括如上所述的包括在两层钛金属层之间的至少部分氧化的钛的中间层的薄层叠层因此沉积在基材的一个面上,并且在所述基材的另一面上沉积包括至少一个银层的低发射率层的叠层,然后使用至少一个激光辐射处理所述中间层,使得低发射率叠层的发射率或电阻率降低至少3% 。发射率或电阻率的降低至少为3%,或实际为5%甚至10%。因此,可以使用单一热处理来改善低发射率叠层的发射率性质并获得光催化层。这是因为激光辐射仅部分地被叠层的钛层和基材吸收,使得位于另一面上的低发射率叠层接收辐射能量的一部分,其可用于改善银或每个银层的结晶性质。所获得的产品在一个面上具有自清洁的光催化功能,因此倾向于朝向建筑物的外部,并且在另一个面上具有隔热功能,因此倾向于朝向建筑物内部。
借助于以下非限制性示例性实施例说明本发明。
实施例
如下制备通过根据本发明的方法获得的包含光催化涂层的三个样品(I1至I3)。
在透明的钠-钙-硅玻璃基材上沉积薄层叠层,其依次由第一钛金属层,氧化钛TiO2中间层,和第二钛金属层构成。
使用氩等离子体中的钛靶通过溅射沉积钛金属层。还使用在氩等离子体中的TiO2靶通过溅射沉积氧化钛TiO2的中间层。
使用在线激光处理样品,所述在线激光通过并列多条单独的线获得,发射波长为1030nm的辐射,涂覆的基材平移经过该辐射。样品I1和I2以2m / min的运行速度处理,而样品I3以3m / min的运行速度处理。
作为比较,制备包括通过激光处理涂层而获得的光催化涂层的样品(R1至R3),所述涂层分别由单个5nm的钛金属层,覆盖有4nm的钛金属层的6nm的氧化钛层,和覆盖有6nm氧化钛层的6nm钛金属层构成。以2m / min的运行速度处理样品(R1至R3)。
对于每个处理的样品,观察者以在黑色背景上的反射和在白色背景上的透射评估“拼叠”现象。
下面的表1总结了每个样品的特征和“拼叠”现象的评估结果。“拼叠”现象的观察结果表示如下:“×”表示可见标记,“○”表示搜索后可见的非常浅的标记,和“◎”表示没有可见标记。
还测量了每种样品的光催化活性。根据本发明的样品具有与参照物R1和R2相当的光催化活性。

Claims (15)

1.获得材料的方法,所述材料包含涂覆有光催化涂层的基材,所述方法包括:
- 通过溅射在所述基材上沉积薄层叠层的步骤,其依次包括厚度为1至3nm的第一钛金属层,厚度为0.5至5nm的至少部分氧化的钛的中间层,和厚度为2至5nm的第二钛金属层;和
- 借助于通过激光辐射的热处理氧化的步骤,其中所述叠层与氧化气氛接触。
2.如权利要求1所述的方法,其特征在于,基材是玻璃板材。
3.如权利要求1或2所述的方法,其特征在于至少部分氧化的钛的中间层是TiOx层,x大于或等于1.8。
4.如权利要求1至3中任一项所述的方法,其特征在于至少部分氧化的钛的中间层是TiO2层。
5.如权利要求1至4中任一项所述的方法,其特征在于至少部分氧化的钛的中间层的厚度为0.5至2nm。
6.如权利要求1至5中任一项所述的方法,其特征在于第一钛金属层和第二钛金属层各自具有1至5nm的厚度。
7.如权利要求1至6中任一项所述的方法,其特征在于第一钛金属层的厚度为1-2nm和第二钛金属层的厚度为2-4nm。
8.如权利要求1至7中任一项所述的方法,其特征在于在通过激光辐射进行热处理期间,基材的运行速度大于或等于2m/min。
9.根据权利要求1至8中任一项所述的方法,其特征在于所述激光辐射的波长为800至1300nm,特别是800至1100nm。
10.如权利要求1至9中任一项所述的方法,其特征在于中间层处激光辐射的每单位面积功率大于或等于20kW/cm²,优选大于或等于30kW/cm²。
11.根据权利要求1至10中任一项所述的方法,其特征在于所述激光辐射由至少一个激光束进行,所述激光束是形成同时辐射所述基材宽度的全部或部分的线的激光束。
12.包含涂覆有薄层叠层的基材的材料,其依次包括厚度为1至3nm的第一钛金属层,厚度为0.5至5nm的至少部分氧化的钛的中间层,和厚度为2至5nm的第二钛金属层。
13.如权利要求12所述的材料,其特征在于至少部分氧化的钛的中间层的厚度为0.5至2nm。
14.如权利要求12或13所述的材料,其特征在于第一钛金属层的厚度为1-2nm和第二钛金属层的厚度为2-4nm。
15.如权利要求12-14中任一项所述的材料,其特征在于至少部分氧化的钛的中间层是TiO2层。
CN201780032099.5A 2016-05-24 2017-05-22 薄层沉积过程 Pending CN109154078A (zh)

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