CN102795790A - 具有热致变色膜的后热处理的基板 - Google Patents

具有热致变色膜的后热处理的基板 Download PDF

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CN102795790A
CN102795790A CN2012101124905A CN201210112490A CN102795790A CN 102795790 A CN102795790 A CN 102795790A CN 2012101124905 A CN2012101124905 A CN 2012101124905A CN 201210112490 A CN201210112490 A CN 201210112490A CN 102795790 A CN102795790 A CN 102795790A
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CN102795790B (zh
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郑永秀
文东建
沈勉基
柳翔炼
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Corning Precision Materials Co Ltd
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Abstract

一种具有热致变色膜的后热处理的基板。所述后热处理的基板包括基底基板、涂布在基底基板上的热致变色膜、形成于热致变色膜的上表面和下表面中至少一面上的辅助膜以及位于热致变色膜与辅助膜间的牺牲膜。所述牺牲膜由金属制成。因此，防止了热致变色材料在对基板进行后热处理的过程中结块。辅助膜防止氧和氮扩散到热致变色膜中，这样可对基板进行后热处理，如对基板进行回火的过程、对基板进行热增强的过程和使基板弯曲的过程。

Description

具有热致变色膜的后热处理的基板
交叉引用
本申请要求于2011年4月18日递交的韩国专利申请号10-2011-0035790的优先权，该申请的全部内容通过引用合并于此以用于全部目的。
技术领域
本发明涉及具有热致变色膜的后热处理的基板，更具体地，涉及具有热致变色膜的后热处理的基板，其在热致变色膜的上层和下层中的至少一层上具有牺牲膜。
背景技术
针对化学能源如石油的价格飞涨，对开发新能源的需求正在增加。另外，节能技术的重要性也正在与新能源的需求同等增加。事实上，普通住宅中至少60％的能耗归因于制热和/或制冷。尤其是普通住宅和建筑通过窗户损失24％的能量。
因此，人们已进行多种尝试，以在保证窗户的基本功能如美观和观看功能的同时减少透过窗户消耗的能量。举例来说，代表性的方法包括改变窗户的尺寸及配置高保温窗。
高保温窗玻璃的种类包括在一对玻璃板间布置氩(Ar)气、氪(Kr)气等以防止热交换的注气双层玻璃，涂有传导材料以防止热量由室内辐射到外部的低辐射玻璃等。也正在研究一种涂有具有特定的热特性的层以调节太阳能传入的玻璃。
具体地，低辐射玻璃在其表面上涂有金属或金属氧化物的薄层，该薄层可允许入射到窗户上的大部分可见光进入，这样可保持室内的明亮，同时又阻挡了红外(IR)范围内的辐射。这种玻璃的功能在于，它防止了由加热产生的热量耗散到外部，还防止了来自建筑物外部的热能，因此减少了制冷和制热开销。然而，这种玻璃由于其反射除可见光以外波长的光的特性而具有以下缺点。具体地，它不允许IR范围的阳光进入室内，这尤其在冬天是一个缺点，而且也不能根据季节(温度)调解阳光的透光率。
因此，正在进行设计通过用热致变色材料涂布玻璃来节约制冷和/或制热能量的技术开发。这种热致变色材料可选择性地透过或阻挡具有强热作用的IR光线。
热致变色涂层涂布于房屋的外部玻璃、车辆的天窗、侧窗和后窗等时，该涂层在夏季可通过阻挡来自外部的太阳能热量而节约制冷能量，并在冬季通过允许来自外部的太阳能进入而节约制热能量。
然而，上述涂层玻璃需要进行后热处理。具体地，当这种玻璃用于建筑业时，被用作钢化或热增强玻璃。当这种玻璃用于车辆时，它必须经历将其变弯曲的过程以符合车辆的流线型。考虑到涂层玻璃的特性，当在约700℃的温度对其进行后热处理时，其特征常常会劣化。由于后热处理，热致变色涂层也具有质量缺陷的问题，如变色、出现小孔、混浊、产生裂缝及图像失真。
发明背景部分公开的信息仅用来增强对发明背景的理解，并不是承认或以任何形式暗示所述信息形成为本领域中技术人员已知的现有技术。
发明内容
本发明的多种方面提供了一种由于存在由布置在热致变色膜的上层或下层中的至少一层上的金属形成的牺牲膜而能够进行后热处理的基板。
在本发明的一个方面中，提供了一种后热处理(post-heat-treatable)的基板，所述基板包括基底基板、涂布在所述基底基板上的热致变色膜、以及在所述热致变色膜的上表面和下表面中的至少一面上形成的牺牲膜，所述牺牲膜由金属制成。
在一个实施方式中，所述热致变色膜由二氧化钒(VO2)制成。
在一个实施方式中，所述后热处理的基板可进一步包括在所述热致变色膜的上表面和下表面的至少一面上形成的辅助膜。所述牺牲膜可位于所述热致变色膜和所述辅助膜之间。所述辅助膜可以是氧化物膜或氮化物膜。
所述金属可为选自由钛(Ti)、镍铬合金(NiCr)、铬(Cr)、镍(Ni)、铝(Al)、铌(Nb)、锌(Zn)、锡(Sn)及其合金组成的组中的至少一种。
在一个实施方式中，所述辅助膜可由二氧化钛(TiO2)制成，而所述牺牲膜可由钛(Ti)制成。
在一个实施方式中，牺牲膜的厚度可在1nm至5nm的范围内。
根据本发明的实施方式，由金属制成、布置在热致变色膜的上表面和下表面中至少一面上的牺牲膜可在基板的后热处理过程中防止热致变色材料结块，并防止相邻层中或空气中的氧气和氮气扩散到热致变色膜，这样就可以对基板进行高温热处理，如对基板进行回火的过程、对基板进行热增强的过程及使基板变弯曲的过程。
被合并于此的附图和以下对本发明的详细说明可使得本发明的方法和设备的其它特征和优点更为显而易见，它们一起也可解释本发明的特定原理。
附图说明
图1为表示根据本发明实施方式的后热处理的基板的横截面示意图。
图2为表示相关领域中的基板被后热处理之后的状态的概念图。
图3为表示根据本发明的实施方式的基板被后热处理之后的状态的概念图。
具体实施方式
现在将详细引用本发明的各实施方式，其实施例示于附图并说明以下，从而与本发明相关的领域中的技术人员可以很容易将本发明付诸实践。
在本发明的以下说明中，当对合并于此的已知功能和元件会使得本发明的主题不清楚时，将会省略其细节说明。
图1为表示根据本发明的实施方式的后热处理的基板的横截面示意图。
参照图1，后热处理的基板包括基底基板100、在基底基板100上形成的热致变色膜200、在热致变色膜200的上表面和下表面中的至少一面上形成的辅助膜300、以及在热致变色膜200及辅助膜300之间形成的牺牲膜400，牺牲膜400由金属制成。
基底基板100为具有预定面积和预定厚度的透明或有色基板。优选基底基板100为钠钙玻璃基板。
热致变色膜200是通过将可发生热致变色现象的材料涂布基板100而形成，并用于控制在基板100上入射的阳光量。
热致变色材料在特定温度下改变颜色。具体地，由于热致变色现象，热致变色材料的晶体结构变化至其物理性能(如导电性和红外(IR)透光率)快速改变。因此，用热致变色材料涂布基底基板可实现使可见光在特定温度或更高温度下进入的同时阻挡IR射线的效果。
这里，热致变色膜200可由选自二氧化钒(VO2)、氧化钛(III)(Ti2O3)、二氧化铌(NbO2)和硫化镍(NiS)中的一种材料制成，但不限于此。优选热致变色膜200由VO2制成。
辅助膜300可形成于热致变色膜200的上表面和下表面的至少一面上，并可具有改善热致变色膜的光学性能等的功能。举例来说，辅助膜可作为提供低反射率性能的层使用。另外，它还可以用于通过防止热致变色膜直接暴露于空气或基板而最初阻挡漫射。辅助膜300可实施为氧化物膜或氮化物膜。举例来说，辅助膜300可由选自二氧化硅(SiO2)、五氧化铌(Nb2O5)、氧化铝(Al2O3)、二氧化钛(TiO2)和氮化硅(Si3N4)中的一种材料制成，但不限于此。
辅助膜300包括形成于热致变色膜的下表面的辅助膜310以及形成于热致变色膜的上表面上的辅助膜320。取决于它们各自的功能，辅助膜310和320可由相同或不同材料制成。例如，形成于热致变色膜下表面的辅助膜310可由用于调节热致变色膜的透光率和颜色的材料制成，而形成于热致变色膜上表面上的辅助膜320可由用于保护热致变色膜的材料制成。形成于基底基板上的辅助膜可用作钠扩散阻挡膜，它防止基底基板中的钠(Na)离子在350℃或更高温度下扩散到热致变色膜中，否则这将会使热致变色膜丧失其性能。
牺牲膜400(410、420)形成于热致变色膜200和辅助膜300(310、320)之间。
牺牲膜400可由金属制成，优选由选自钛(Ti)、镍铬合金(NiCr)、铬(Cr)、镍(Ni)、铝(Al)、铌(Nb)、锌(Zn)、锡(Sn)及其合金中的一种制成，但不限于此。
牺牲层400用于防止热致变色材料中的原子扩散到上和下辅助膜310和320中，并用于防止构成辅助膜300的元素如氧和氮扩散到热致变色膜200中。牺牲层400还可以防止丧失热致变色特性并防止热致变色材料结块。
图2为表示相关领域中的基板被后热处理之后的状态的概念图，而图3为表示根据本发明实施方式的基板被后热处理之后的状态的概念图。
参照图2和图3，当热致变色膜200为VO2薄膜，辅助膜300为氧化物膜时，牺牲膜40用于防止VO2原子扩散到氧化物膜中，而通过吸收由氧化物膜扩散的氧被氧化，从而转化为氧化物膜。然而，VO2膜仍可作为能够保持氧化速率的氧阻挡层。
因此，可解决相关领域的如下问题，包括VO2薄膜和氧化物膜的基板无法保持其作为产品的质量水平，这是因为通过对VO2的进一步氧化使得VO2转化为V2O5从而丧失其相变特性，或者由于其受热而导致的VO2的结块，从相邻层中分层，或由于在例如对基板进行回火的过程、对基板进行热增强的过程和使基板变弯曲的过程等的后热处理过程中因物质扩散而导致的变色。
表1示出了在进行后热处理之后涂层膜的质量变化，如Ra(粗糙度)、雾度和缺陷。
后热处理条件：普通竖炉(设备)、700℃-10分钟(条件)、大气压
表1
  膜结构   Ra(nm)   雾度(％)   缺陷
  1   玻璃/VO2   122   7   小孔、裂缝、混浊
  2   玻璃/TiO2/VO2/TiO2   103   5   裂缝、混浊
  3   玻璃/TiO2/Ti/VO2/TiO2   41   2.1   小孔
  4   玻璃/TiO2/VO2/Ti/TiO2   29   2.3   小孔
  5   玻璃/TiO2/Ti/VO2/Ti/TiO2   15   0.9   -
  6   玻璃/TiO2/NiCr/VO2/NiCr/TiO2   21   1.2   -
  7   玻璃/TiO2/Al/VO2/Al/TiO2   24   1.5   轻微混浊
参照表1，在后热处理后，在玻璃基底基板上只有VO2薄膜的基板表现出122nm的粗糙度，并具有如小孔、裂缝和混浊的缺陷。
另外，在后热处理后，在玻璃基底基板上具有TiO2辅助膜、VO2薄膜和TiO2辅助膜的基板表现出103nm的粗糙度，并具有如裂缝和混浊的缺陷。
相比之下，在后热处理后，具有TiO2辅助膜、Ti牺牲膜、VO2薄膜、Ti牺牲膜和TiO2辅助膜的基板表现出15nm的粗糙度，并且没有缺陷。
因此，应理解的是，在对涂层基板进行后热处理的过程中，牺牲膜降低了VO2薄膜的粗糙度(结块)并防止产生缺陷。
优选牺牲膜具有在1nm至5nm范围内的厚度。
由于薄牺牲膜的厚度在1nm至5nm的范围内，因此它在后热处理过程中被全部氧化或氮化。因此，牺牲膜可并入位于其上或其下的氧化物膜或氮化物膜中，从而由于提供牺牲膜而使光干涉最小化。
以上参照特定的实施方式和附图对本发明的具体的示例性实施方式进行了说明。它们并非意在穷举，或不应将本发明局限于所公开的特定形式中，显然本领域中技术人员可根据上述教导做出多种修改和变更。
因此，本发明的范围并不局限于上述实施方式，而是由所附的权利要求及其等效方案限定。

Claims (12)

1.一种后热处理的基板，包括：
基底基板；
涂布所述基底基板的热致变色膜；和
在所述热致变色膜的上表面和下表面的至少一面上形成的牺牲膜，所述牺牲膜由金属制成。
2.如权利要求1所述的后热处理的基板，其中所述热致变色膜包含二氧化钒(VO2)。
3.如权利要求1所述的后热处理的基板，进一步包括在所述热致变色膜的上表面和下表面的至少一面上形成的辅助膜，
其中所述牺牲膜位于所述热致变色膜和所述辅助膜之间。
4.如权利要求3所述的后热处理的基板，其中所述辅助膜包括氧化物膜或氮化物膜。
5.如权利要求3所述的后热处理的基板，其中所述牺牲膜包含金属，且所述辅助膜包含所述金属的氧化物或所述金属的氮化物。
6.如权利要求5所述的后热处理的基板，其中所述牺牲膜包含钛(Ti)，且所述辅助膜包含二氧化钛(TiO2)。
7.如权利要求1所述的后热处理的基板，其中所述金属包括选自由钛(Ti)、镍铬合金(NiCr)、铬(Cr)、镍(Ni)、铝(Al)、铌(Nb)、锌(Zn)、锡(Sn)及其合金组成的组中的至少一种。
8.如权利要求1所述的后热处理的基板，其中所述牺牲膜具有在1nm至5nm范围内的厚度。
9.一种制造涂布热致变色膜的基板的方法，包括对后热处理的基板进行后热处理，
所述后热处理的基板包括：
基底基板；
涂布所述基底基板的热致变色膜；和
在所述热致变色膜的上表面和下表面的至少一面上形成的牺牲膜，所述牺牲膜由金属制成。
10.如权利要求9所述的方法，其中所述后热处理包括对所述后热处理的基板进行回火，对所述后热处理的基板进行热增强，或者使所述后热处理的基板变弯曲。
11.如权利要求9所述的方法，其中辅助膜形成在所述热致变色膜的上表面和下表面中的至少一面上，其中：
所述牺牲膜位于所述热致变色膜与所述辅助膜之间，且
通过所述后热处理，所述牺牲膜具有与所述辅助膜相同的组成。
12.如权利要求9所述的方法，其中所述后热处理在空气中进行。
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Address before: Gyeongbuk, South Korea

Applicant before: Samsung Corning Precision Materials Co., Ltd.

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