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CN107074636B - 被提供有具有热性质和亚化学计量中间层的堆叠体的基材 - Google Patents

被提供有具有热性质和亚化学计量中间层的堆叠体的基材 Download PDF

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CN107074636B
CN107074636B CN201580053011.9A CN201580053011A CN107074636B CN 107074636 B CN107074636 B CN 107074636B CN 201580053011 A CN201580053011 A CN 201580053011A CN 107074636 B CN107074636 B CN 107074636B
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CN107074636A (zh
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N.梅卡迪耶
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Abstract

本发明涉及一种在一个面(11)上涂覆有在红外中和/或在太阳辐射中具有反射性质的薄层堆叠体(14)的基材(10)，该堆叠体包含单个金属功能层(140)，特别地基于银或基于含银金属合金的金属功能层，和两个抗反射涂层(120,160)，所述涂层每个包括至少一个电介质层(122,164)，所述功能层(140)被设置于两个抗反射涂层(120,160)之间，特征在于所述抗反射涂层(120,160)中的至少一个包含中间层，所述中间层包含氧化锌锡SnxZnyOz，其中比例为0.1≤x/y≤2.4并且0.75(2x+y)≤z≤0.95(2x+y)，并具有为2nm‑25nm，甚至2nm‑12nm的物理厚度。

Description

被提供有具有热性质和亚化学计量中间层的堆叠体的基材
本发明涉及一种多层窗玻璃，其包含至少两个玻璃基材类型的基材，它们通过框架结构保持在一起，所述窗玻璃实现在外部空间和内部空间之间的间隔，其中至少一个中间气体腔被设置于两个基材之间。
已知地，所述基材之一可以在与中间气体腔接触的内表面上涂覆有在红外中和/或在太阳辐射中具有反射性质的薄层堆叠体，其包含单个金属功能层，特别是基于银或含银金属合金的功能层，以及两个抗反射涂层，所述涂层每个包含至少一个电介质层，所述功能层被设置于两个抗反射涂层之间。
本发明更具体地涉及这种基材用于制造绝热和/或太阳保护窗玻璃的用途。这种窗玻璃可用于装备建筑物，特别是为了减少空调负载和/或防止过度加热(称为“太阳控制”窗玻璃)和/或减少由于在建筑中不断增加的玻璃表面尺寸所导致的耗散到外部的能量(称为“低发射”窗玻璃)。
此外，这些窗玻璃可以被集成到具有特定功能的玻璃窗，例如加热玻璃窗或电致变色玻璃窗中。
已知用于赋予基材这种性质的一种类型的层堆叠体包含在红外中和/或在太阳辐射中具有反射性质的金属功能层，特别是基于银或基于含银金属合金的金属功能层。
在这种类型的堆叠体中，功能层因此被设置在两个抗反射涂层之间，每个抗反射涂层通常包括多个层，所述层中的每个由氮化物类型的电介质材料，特别是氮化硅或氮化铝，或者氧化物制成。从光学角度来看，这些围绕所述一个或多个金属功能层的涂层的目的是使该金属功能层“抗反射”。
然而，阻挡涂层有时被插入在一个或每个抗反射涂层和金属功能层之间；设置于功能层下方的阻挡涂层(在基材的方向上)在任选的弯曲和/或淬火类型的高温热处理期间保护功能层，和设置于功能层上方的阻挡涂层(在与基材相反的一侧上)在上抗反射涂层的沉积期间以及在任选的弯曲和/或淬火类型的高温热处理期间保护该功能层免受任何降解。
本发明更特别地涉及中间层在堆叠体内的使用，以及借助于产生辐射，特别地红外辐射的源来实施对整个薄层堆叠体的处理。
特别是从国际专利申请WO2010/142926已知，提供堆叠体的吸收中间层，并且在沉积堆叠体之后施加处理以便降低发射率或改善低发射性堆叠体的光学性能。该处理允许改善金属功能层的质量，并因此降低发射率(其与薄层电阻直接相关)，并且吸收中间层的使用允许增加在该处理期间堆叠体的吸收，以使该处理是短时但有效的。由于该吸收中间层在处理期间变得透明的，在处理之后的堆叠体的光学特征是有利的(特别地可以获得高的光透射率)。
然而，这种解决方案对于某些应用并不是完全令人满意的，因为有时需要该处理的功率是高的和/或使其持续相对长的时间(即，对于在通常固定的辐射源下方行进的基材的速度是慢的)。
在现有技术中，从国际专利申请WO2007/101964已知具有单个功能层的薄层堆叠体，其中在功能层下方下伏的抗反射涂层包含由混合氧化物，优选混合氧化锌锡制成的非结晶的平滑电介质层。
由于该层是介电的，这意味着期望的是，材料被充分氧化以便不是吸收性的。
本发明的目的是通过开发一种新型的具有单个功能层的层堆叠体能够克服现有技术的缺点，该堆叠体在处理后具有低的薄层电阻(因此具有低的发射率)、高的光透射率，并且该处理可以以更低的功率和/或以更高的速度进行实施。
因此，本发明的一个主题，在其最广泛的意义中，是根据权利要求1的在一个面上涂覆有在红外中和/或在太阳辐射中具有反射性质的薄层堆叠体的基材。这种堆叠体包含单个金属功能层，特别地基于银或基于含银金属合金的金属功能层，和两个抗反射涂层，所述涂层每个包括至少一个电介质层，所述功能层被设置于两个抗反射涂层之间。
根据本发明，所述抗反射涂层中的至少一个包括中间层，所述中间层包含氧化锌锡SnxZnyOz，其中比例为0.1≤x/y≤2.4，并且0.75(2x+y)≤z≤0.95(2x+y)，并具有为2nm-25nm，甚至2nm-12nm的物理厚度。
该中间层因此包含亚化学计量的混合氧化锌锡，并且这种混合氧化物是吸收性的。
在本发明的意义中，中间层包含锌和锡的氧化物的事实意味着这两种元素占该层的金属元素的98至100重量％，即金属靶的金属元素的98至100重量％，如果金属靶用于沉积中间层的话；不排除该层可以包含一种或多种金属元素，例如铝和/或锑，作为用于改善靶的导电性的掺杂剂，或作为杂质。
实际上，已经发现，这种包含SnxZnyOz并且是亚化学计量的层需要比金属层在被完全氧化时更少的氧供应，并且在该处理之前它已经引起的吸收的上升通过该处理将消失。在处理期间，这种氧通过一个或两个相邻的电介质层和/或通过在该处理的气氛中存在的氧被提供给它。
因此，为了使该处理引起中间层的温度升高所需的功率可以除以1.5至3的系数；替代地或组合地，处理速度可以提高1.2至2.5倍，以便提高生产率。
在处理之后，堆叠体具有已经经受高温弯曲、淬火或退火热处理的堆叠体的性质，所述堆叠体的所有氧化物层具有其稳定的化学计量，但是基材不表现出已经经受高温弯曲、淬火或退火热处理的基材的状态。
根据本发明的所述中间层不是堆叠体的末端层，即不是最远离的基材的面(堆叠体所位于该面上)的堆叠体的层。
术语“涂层”在本发明意义中应当理解为在涂层内可以具有单个层或多个不同材料的层。
通常，术语“电介质层”在本发明的意义上应被理解为从其性质的角度来看，该层的材料是“非金属的”，即不是金属。在本发明的上下文中，该术语表示在整个可见光的波长范围(380nm至780nm)中具有等于或大于5的n/k比的材料。
术语“吸收层”在本发明意义中应当理解为是指该层是在整个可见光波长范围(从380nm至780nm)上具有大于0.5的平均k系数的材料，并且具有大于10-6Ω.cm的体积电阻率(如从文献中已知)。
回顾的是，n表示材料在给定波长处的真实折射指数，和系数k表示在给定波长处的折射指数的虚部，n/k比在对于n和k相同的给定波长下进行计算。
根据本发明的中间层是在上述含义内的吸收层。
在本文件中指示的折射指数的值是如通常在550nm的波长处测量的值。
在本发明的意义上表述“基于...的层”应当理解是指该层包括大于50at％的所述材料。
在本发明的一个特定版本中，所述中间层包含氧化锌锡SnxZnyOz，其中比率为0.55≤x/y≤0.83。
在一个特定版本中，所述中间层由氧化锌锡SnxZnyOz组成，并且不包含任何其它元素。
所述中间层优选位于所述设置于所述金属功能层下方(在基材的方向上)的抗反射涂层中，直接在基于氮化物的电介质层的上方并且直接在包含氧化锌的润湿层的下方，所述基于氮化物的电介质层优选具有为10至50nm的物理厚度，并且优选基于氮化硅Si3N4。
替代地或组合地，所述中间层可位于在功能层上方上伏的抗反射涂层中(与基材相反的一侧)，优选直接位于上阻挡涂层上方，该上阻挡涂层直接位于所述功能层上方。
所述金属功能层的物理厚度优选在6nm至16nm之间，包括这些值，并且旨在实现小于5％的发射率。
在本发明的另一特定版本中，功能层被直接沉积设置在该功能层和电介质涂层(在功能层下方下伏)之间的下阻隔涂层的上方和/或该功能层被直接沉积在上阻挡涂层下方，该上阻挡涂层被设置在功能层和在功能层上方上伏的电介质涂层之间，并且该上阻挡涂层和/或下阻挡涂层包含基于镍或钛的薄层，该薄层具有物理厚度e'，使得0.2nm≤e'≤2.5nm。
在本发明的另一个特定版本中，下伏的电介质涂层的最终层(离基材最远的层)基于氧化物，优选以亚化学计量进行沉积，特别是基于氧化钛(TiOx)。
因此，该堆叠体可以包括优选以亚化学计量沉积的最终层(英文为“overcoat”)，即保护层。在沉积之后，这种层在堆叠体中大部分以化学计量地被氧化。
本发明还涉及一种用于获得在一个面上涂覆有根据本发明的在红外线中和/或在太阳辐射中具有反射性质的薄层堆叠体的基材的方法，该薄层堆叠体包含单个金属功能层，特别是基于银或基于含银金属合金的金属功能层，和两个抗反射涂层，以如下顺序包括以下步骤：
-在所述基材的一个面上沉积根据本发明的在红外中和/或在太阳辐射中具有反射性质的薄层叠堆体，该堆叠体包含单个金属功能层，特别是基于银或基于含银金属合金的金属功能层，和两个抗反射涂层；
-在优选地包含氧的气氛下，借助于产生辐射，特别是红外辐射的源来处理所述薄层堆叠体。
还可以预期到使用根据本发明的包含氧化锌锡SnxZnyOz的层，其中比率为0.1≤x/y≤2.4，0.75(2x+y)≤z≤0.95(2x+y)并且具有介于2nm至25nm之间，甚至介于2nm至12nm之间的物理厚度作为在根据本发明的在红外中和/或中太阳辐射中具有反射性质的薄层堆叠体的中间层，该堆叠体包含单个金属功能层，特别是基于银或含银金属合金的金属功能层，以及两个抗反射涂层。
本发明还涉及包括至少两个通过框架结构保持在一起的基材的多层窗玻璃，所述窗玻璃实现在外部空间和内部空间之间的间隔，其中至少一个中间气体腔被设置于所述两个基材之间，其中一个基材是根据本发明的。
优选地，包括至少两个基材的多层窗玻璃的一个基材或包括至少三个基材的多层窗玻璃的一个基材在与中间气体腔接触的内表面上涂覆有在红外中和/或在太阳辐射中具有反射性质的薄层堆叠体。
根据本发明的窗玻璃这时至少包括根据本发明的承载该堆叠体的基材，该基材任选地与至少一个其它基材结合。每个基材可以是透明的或有色的。基材中的一个至少特别地可以由在体积中着色的玻璃制成。着色类型的选择将取决于一旦完成窗玻璃的制造，对于该窗玻璃所期望的光透射水平和/或比色外观。
根据本发明的窗玻璃可以具有层压结构，特别是将至少两个玻璃类型的刚性基材通过至少一个热塑性聚合物片材进行组合，以具有以下类型的结构：玻璃/薄层堆叠体/片材/玻璃/中间气体腔/玻璃片材。聚合物特别地可以基于聚乙烯醇缩丁醛PVB、乙烯-乙酸乙烯酯EVA、聚对苯二甲酸乙二醇酯PET、聚氯乙烯PVC。
有利地，本发明因此允许制备具有单个功能层的薄层堆叠体，该沉积在透明基材上的堆叠体在使用产生辐射的源进行处理之后具有高于80％的高的在可见光中的光透射率 TL和小于4欧姆/平方的低薄层电阻，所述处理需要更少的功率和/或能够更快地进行。
有利地，借助于辐射源的处理不是对由基材和堆叠体构成的整个组件的高温热处理；因此该基材不通过这种借助于辐射源的处理进行热处理(不进行弯曲、淬火或退火)。
本发明的细节和有利特征将借助于以下使用附图示出的非限制性实施例中显现，附图图示：
-在图1中，根据本发明的具有单个功能层的堆叠体，所述功能层直接沉积在下阻挡涂层上方并且直接在上阻挡涂层下方，在借助于产生辐射的源的处理期间图示所述堆叠体；和
-在图2中，包括具有单个功能层的堆叠体的双层玻璃的方案。
在这些图中，没有严格遵守不同层或不同要件的厚度之间的比例，以便更容易观察它们。
图1示出了具有沉积在透明玻璃基材10的面11上的根据本发明的具有单个功能层的堆叠体14的结构，其中唯一功能层140，特别是基于银或基于含银金属合金的功能层，被设置于两个抗反射涂层(位于功能层140下方(在基材10的方向上)的下伏抗反射涂层120和位于功能层140上方(在与基材10相反一侧)的上伏抗反射涂层160)之间。
这两个抗反射涂层120，160各自包括至少一个电介质层122，124，128；162，164。
任选地，一方面，功能层140可以被直接沉积在下阻挡涂层130的上方，该下阻挡涂层130设置于下伏抗反射涂层120和功能层140之间，另一方面，功能层140可以被直接沉积在上阻挡涂层150的下方，该上阻挡涂层150被设置于功能层140和上伏抗反射涂层160之间。
下阻挡层和/或上阻挡层虽然以金属形式进行沉积并呈现为金属层，但在实践中有时是氧化层，因为它们的功能之一(特别是对于上阻挡层)是在堆叠体的沉积期间进行氧化以保护功能层。
位于金属功能层上方的抗反射涂层160由末端层168终止，该末端层168是该堆叠体的最远离面11的层。
当具有单个功能层的堆叠体用于具有双层窗玻璃结构的多层窗玻璃100中时，如图2所示，这种窗玻璃包括两个基材10,30，它们通过框架结构90保持在一起并且通过中间气体腔15彼此分隔。
该窗玻璃因此实现在外部空间ES和内部空间IS之间的分隔。
堆叠体可以被设置于面2上(当考虑进入建筑物的阳光的入射方向时，位于最接近建筑物外部的片材上并且在其朝向气体腔的面上)。
图2示出了位于与中间充气空间15接触的基材10的内面11上的薄层堆叠体14在面2上的这种定位(进入建筑物中的太阳光的入射方向由双箭头表示)，基材10的另一个面9与外部空间ES接触。
然而，也可以设想，在这种双层窗玻璃结构中，基材之一具有层压结构。
基于在图1中示出的堆叠体结构进行了两个实施例。
对于这两个实施例，在功能层140下方下伏的抗反射涂层120包括三个电介质层122,124,128，层122(该堆叠体的第一层并与面11接触)是具有中等折射指数的层；它由氮化物Si3N4:Al制成并且使用掺杂有8重量％的铝的金属靶进行沉积。它具有为1.9至2.1的折射指数，并且其在这里精确地为2.0。
第二电介质层126是中间层，其在下面将进行更详细描述。
抗反射涂层120的第三电介质层是设置于金属功能层140正下方的润湿层128。
在所述实施例中，不存在下阻挡涂层130。
对于这些实施例，抗反射层128被称为“润湿层”，因为它允许改善金属功能层140的结晶，该金属功能层140在这里由银制成，这改善了其导电性。该抗反射层128由铝掺杂的氧化锌ZnO:Al制成(从掺杂有2重量％的铝的锌构成的金属靶进行沉积)。
在所述实施例中，不存在上阻挡涂层150。
上伏抗反射涂层160包含由铝掺杂的氧化锌ZnO:Al制成的电介质层162(由与用于润湿层128的靶相同的靶并且在相同条件下进行沉积)，然后形成具有中等折射指数的电介质层164，由与电介质层122相同的材料制成。
该电介质涂层160可以用任选的保护层168来终止，该保护层特别是基于氧化物，特别是亚化学计量氧的氧化物。
对于下面的所有实施例，层的沉积条件是：
层 使用的靶 沉积压力 气体
Si<sub>3</sub>N<sub>4</sub>:Al 为92:8wt%的Si:Al 1.5×10<sup>-3</sup>mbar 为45%的Ar/(Ar+N<sub>2</sub>)
TiO<sub>x</sub> TiO<sub>x</sub> 2×10<sup>-3</sup>mbar 为90%的Ar/(Ar+O<sub>2</sub>)
TiO<sub>2</sub> Ti 2×10<sup>-3</sup>mbar 为35%的Ar/(Ar+O<sub>2</sub>)
Ti Ti 7×10<sup>-3</sup>mbar 为100%的Ar
ZnO:Al 为98:2wt%的Zn:Al 2×10<sup>-3</sup>mbar 为52%的Ar/(Ar+O<sub>2</sub>)
Sn<sub>x</sub>Zn<sub>y</sub>O<sub>z</sub> 为30:68:2wt%的Sn:Zn:Sb 3×10<sup>-3</sup>mbar 为64%的Ar/(Ar+O<sub>2</sub>)
Ag Ag 2×10<sup>-3</sup>mbar 为100%的Ar
因此，沉积的层可分为四类：
i-由具有在整个可见光的波长范围内大于5的n/k比率的抗反射/电介质材料制成的层：Si3N4:Al，TiO2，ZnO:Al，
ii-吸收性材料制成的中间层，其在整个可见光波长范围内具有大于0.5的中等ķ系数，和大于10-6Ω.cm的体积电阻率：TiOx和SnxZnyOz，
iii-由在红外中和/或在太阳辐射中具有反射性质的材料制成的金属功能层：Ag，
iv-上阻挡层和下阻挡层，用于在堆叠体的沉积期间保护功能层抵抗其性质的改变；它们对光学和能量性质的影响通常被忽略。
观察到银在整个可见光的波长范围内具有0<n/k<5的比率，但是其体积电阻率小于10-6Ω.cm。
对于这两个实施例，将薄层堆叠体沉积在由SAINT-GOBAIN公司分销的4mm厚的Planilux牌的透明钠钙玻璃制成的基材上。
对于这两个实施例，
-ε表示从堆叠体的薄层电阻R(其以欧姆/平方为单位进行测量)根据下式进行计算的标准发射率：ε=0.0106R
-AL表示在使用D65光源在2°测量的在可见光中的光吸收率(%)；
-A980表示在2°在D65光源下测量的在980nm的波长下特定测量的吸收(%)，；
-TL表示使用D65光源在2°测量的在可见光中的光透射率(%)；
-FS指示太阳因子，即以百分比表示的穿过窗玻璃进入房间的总太阳能与总入射太阳能的比率；该因子通过考虑带有堆叠体的基材被结合到具有以下结构的双层玻璃中进行计算：4-16-4(Ar-90%)，即，两个各自厚度为4mm的玻璃基材通过由90%氩气和10%空气组成的厚度为16mm的气体腔隔开。
根据在图1中所示的堆叠体结构实施两个实施例，但没有下阻挡涂层130。
下表1示出了该两个实施例的每个层的以纳米计的几何或物理厚度(而不是光学厚度)：
Figure 91030DEST_PATH_IMAGE001
表1。
下面的表2总结了这两个实施例的主要光学和能量特征，分别地当仅考虑单个基材10(对于发射率，两种吸收和光透射)，和当其作为双层窗玻璃组装时，在面2(F2)上，如在图2中(对于分别为在处理前(BT)和处理后(AT)的太阳因子FS)。
Figure DEST_PATH_IMAGE003
表2。
因此，根据本发明的实施例2的光学和能量性质基本上与参考实施例1的相同。
对于两个实施例，堆叠的处理包括在沉积所有层之后，使堆叠在二极管激光帘20下方通过，使二极管定位于堆叠体的上方(参考图1)并且在堆叠的方向上发射(由直黑色箭头示出的发射)。二极管在980nm的波长发射，每个二极管在12mm的长度和45μm的宽度上进行发射。
然而，对于实施例1，涂覆有完整堆叠体的基材的运行速度为11m /分钟，而对于实施例2为22m /分钟。
特别令人惊讶的是，位于设置在所述金属功能层140下方的所述电介质涂层120中的中间层可以通过借助于产生辐射，特别是红外辐射的源对完整堆叠体的后处理进行“再氧化”。
当该中间层，如在上述实施例的情况下，直接在具有10至50nm的物理厚度的基于氮化物的电介质层的上方并且直接在包含氧化锌的润湿层的下方时，这时该中间层还可以具有平滑效果，如在国际专利申请WO 2007/101964中公开的那样。
还测试了由56.5:43.5重量％的Sn:Zn制成的靶沉积的中间层，并得到类似的结果。
重要的是，注意根据本发明的中间层可以从包含为了达到目标化学计量氧所需的氧的陶瓷靶并在无氧气氛中进行沉积，或者可以从不包含为了达到目标化学计量氧所需的氧的陶瓷靶并在含氧气氛中进行沉积。
本发明通过实施例在前文中进行了描述。理解的是，本领域技术人员将能够实现本发明的不同变型，而不脱离由权利要求限定的本专利的范围。

Claims (8)

1.在具有在红外和/或太阳辐射中的反射性质的薄层堆叠体(14)内的中间层的用途，该中间层用于通过使用产生红外辐射的源对该堆叠体进行热处理，其中该薄层堆叠体(14)被涂覆在基材(10)的一个面(11)上，该薄层堆叠体包含单个基于银或基于含银金属合金的金属功能层(140)，和两个抗反射涂层(120,160)，所述涂层每个包含至少一个电介质层(122,164)，所述功能层(140)被设置于两个抗反射涂层(120,160)之间，特征在于所述抗反射涂层(120,160)中的至少一个包含该中间层，所述中间层包含氧化锌锡SnxZnyOz，其中比率为0.1≤x/y≤2.4并且0.75(2x+y)≤z≤0.95(2x+y)，并具有为2nm-25nm的物理厚度。
2.根据权利要求1所述的用途，其特征在于，所述中间层包含氧化锌锡SnxZnyOz，其中比率为0.55≤x/y≤0.83。
3.根据权利要求1或2所述的用途，其特征在于，所述中间层位于所述设置在所述金属功能层(140)的下方的电介质涂层(120)中，直接地在基于氮化物的电介质层的上方并且直接在包含氧化锌的润湿层的下方，所述基于氮化物的电介质层具有为10至50nm的物理厚度，并且基于氮化硅Si3N4。
4.根据权利要求1至2中任一项所述的用途，其特征在于，所述中间层位于在功能层(140)上方上伏的抗反射涂层(160)中。
5.根据权利要求4所述的用途，其特征在于，所述中间层直接在上阻挡涂层(150)的上方，该上阻挡涂层直接位于所述功能层(140)的上方。
6.根据权利要求1至2中任一项所述的用途，其特征在于，所述包含氧化锌锡SnxZnyOz的中间层具有为2nm-12nm的物理厚度。
7.一种多层窗玻璃(100)，其包含至少两个通过框架结构(90)保持在一起的基材(10,30)，所述窗玻璃实现在外部空间(ES)和内部空间(IS)之间的间隔，其中至少一个中间气体腔(15)被设置于两个基材之间，基材(10)具有位于朝向所述气体腔(15)的面（11）上的薄层堆叠体(14)，并且在薄层堆叠体(14)中的抗反射涂层(120,160)中至少一个包含中间层，所述中间层包含氧化锌锡SnxZnyOz，其中比率为0.1≤x/y≤2.4并且0.75(2x+y)≤z≤0.95(2x+y)，并具有为2nm-25nm的物理厚度。
8.一种用于获得在一个面(11)上涂覆有在红外中和/或在太阳辐射中具有反射性质的薄层堆叠体(14)的基材(10)的方法，该堆叠体包含单个基于银或含银金属合金的金属功能层(140)，和两个抗反射涂层(120,160)，该方法包括按以下顺序的以下步骤：
-在所述基材(10)的一个面(11)上沉积在红外中和/或在太阳辐射中具有反射性质的薄层堆叠体(14)，该堆叠体包含单个基于银或在基于含银金属合金的金属功能层(140)，和两个抗反射涂层(120,160)，其中所述抗反射涂层(120,160)中至少一个包含中间层，所述中间层包含氧化物SnxZnyOz，其中比率为0.1≤x/y≤2.4并且0.75(2x+y)≤z≤0.95(2x+y)，并具有为2nm-25nm的物理厚度；
-在包含氧的气氛中，借助于产生红外辐射的源处理所述薄层堆叠体(14)。
CN201580053011.9A 2014-09-30 2015-09-29 被提供有具有热性质和亚化学计量中间层的堆叠体的基材 Expired - Fee Related CN107074636B (zh)

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