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CN1852871A - 用于电磁屏蔽的有多个薄层的叠层的透明基材 - Google Patents

用于电磁屏蔽的有多个薄层的叠层的透明基材 Download PDF

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CN1852871A
CN1852871A CNA2004800267040A CN200480026704A CN1852871A CN 1852871 A CN1852871 A CN 1852871A CN A2004800267040 A CNA2004800267040 A CN A2004800267040A CN 200480026704 A CN200480026704 A CN 200480026704A CN 1852871 A CN1852871 A CN 1852871A
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CN1852871B (zh
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C·弗勒里
S·贝利奥
E·曼平
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Saint Gobain Glass France SAS
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Abstract

一种透明基材，特别地用玻璃制成的透明基材，它有多个薄层的叠层(20)，其中包括三个银层(Ag1、Ag2、Ag3)，以及在这种基材上交替排列的一个二氧化钛层(21)、一个金属氧化物层(22)，其中一个银层(Ag1、Ag2、Ag3)和一个涂层(23)，其特征在于金属氧化物是氧化锌；该涂层(23)是一种牺牲金属；以及在离基材最远的银层(Ag3)的涂层(23)上沉积含有至少一种金属氧化物的抗反射层(24)。

Description

用于电磁屏蔽的有多个薄层的叠层的透明基材
本发明的目的是一种用于电磁屏蔽的透明基材，特别是用玻璃制成的基材，其基材覆盖一个多个薄层的叠层，其中包括至少一个金属层。
本发明将更特别地描述这样一种基材在等离子体显示屏中的应用，但是本发明不限于这样一种应用，这种基材可以插入任何电磁屏蔽壁中。
一种等离子体显示屏有一种约束在两块玻璃板之间的等离子体气体混合物(Ne、Xe、Ar)，和置于显示屏后板内面上的荧光粉。在两块玻璃板之间等离子体放电时，等离子体气体混合物发射的紫外光辐射与该后板内面上的荧光粉相互作用，产生可见光辐射(红色、绿色、蓝色)。气体微粒去激发机制与发射紫外光竞争，这样产生800-1250nm红外辐射，其主要通过显示屏前面的传播，可能是非常棘手的干扰之源，特别是靠近红外控制设备，例如采用远程控制的设备的干扰之源。
另外，如同任何的电子装置，这些等离子体显示屏有一些寻址系统(驱动器)，它们可能产生一种对不应该干扰其它设备(例如微型计算机、移动电话等)的寄生辐射。
为了消除这些辐射传播和将这些辐射传播衰减至最低，一种解决办法是对着显示屏前面设置一个用于保证电磁屏蔽的窗口，也称之滤波器，它同时是透明的和金属化的。这个滤波器例如是一种覆盖多个银基薄层的透明基材，它们反射频率范围30MHz-1GHz的电磁波和超过800nm红外线。
因此，专利FR 2 641 272提出一种基材，它包括在一个透明下层与一个透明覆盖层之间呈夹层状的银反射层，该透明下层有至少一个金属氧化物层，该透明覆盖层有一个牺牲金属氧化物层、一个厚度不超过15nm的氧化锌层和一个金属氧化物覆盖上层。
该银层的厚度优选地是8-12nm。
该下层的金属氧化物层可以选自多种氧化物，是多种氧化物的混合物。一个优选实例是一个二氧化钛层和一个沉积在所述二氧化钛上的氧化锡层。
该牺牲金属氧化物的目的是防止银层受到氧化作用，特别是采用阴极溅射技术进行沉积时在其沉积期间发生的氧化作用。事实上，如果该银受到损害，这种覆盖基材会失去其低发射性，就大大降低其光透射率。通常优选的牺牲金属是钛，因为它能非常有效防止银受到氧化作用，还具有易氧化生成吸收能力非常低的氧化物的优点。
氧化锌层用作防止氧渗透到下层并有可能使牺牲金属厚度有一定减少，这时这种金属比较容易、比较完全和比较均匀地被氧化。这个文件要求将氧化锌层的厚度限制在15nm，主要使其层具有良好的光透射性能。
但是，这样一种只有一个金属层的基材还不适合于获得足够的电磁屏蔽，例如其每平方电阻(résistance par carré)小于1.8Ω/□。另外，其它的专利申请提出有多个金属层的叠层，特别是有多个银层的叠层。然而，人们知道增加这些层将减少光的透射率；因此应该找到层厚度与类型之间的一种折中，以便有可能使光透射率达到令人满意。
公开专利申请WO 01/81262提出一种有两个银层的叠层，其中最接近基材的银层厚度e1，而另一层厚度e2，牺牲金属氧化物，例如钛置于每个银层上面，保护其银层。一个顺序实例如下：
基材/Si3N4/ZnO/Ag/Ti/Si3N4/ZnO/Ag/Ti/ZnO/Si3N4。
为了达到每平方电阻小于1.8Ω/□，同时保持适当的光透射率，厚度比e1/e2是0.8-1.1，优选地0.9-1，金属层总厚度e1+e2是27.5-30nm，优选地是28-29.5nm。
欧洲专利申请EP 1 155 816描述了有三个，甚至四个银层的叠层，该叠层还交替排列了二氧化钛层和在波长550nm的折射指数小于2.4的层，例如像氧化锌层或优选地氮化硅层。最靠近基材的银层厚度与离基材最远的银层厚度优选地是其它银层厚度的0.5-1倍。一个每平方电阻等于1.5Ω/□与光透射率为67％的顺序实例是有三个掺杂钯的银层，每层厚度16nm。这个顺序如下：
基材/TiOx/SiNx/Ag/SiNx/TiOx/SiNx/Ag/SiNx/TiOx/SiNx/Ag/SiNx/TiOx
但是，人们总是希望对现有解决办法的性能作进一步改进，以达到每平方电阻更显著的降低，还不损害光透射率。
因此，本发明的目的是寻找一种滤波器的另外解决办法，特别是等离子体显示屏滤波器的另外解决办法，克服电磁波透射率问题，同时还达到令人满意的光学性能。
根据本发明，这种透明基材，特别地用玻璃制成的透明基材有一个多薄层的叠层，其中包括三个银层和在这种基材上交替排列的一个二氧化钛层、一个金属氧化物层、其中一个银层和一个涂层，其特征在于：
-该金属氧化物是氧化锌；
-该涂层是一种牺牲金属，和
-在离基材最远银层的涂层上沉积一个抗反射层，其中含有至少一种金属氧化物。
根据一个特征，每个银层的厚度是13nm-19nm。三个银层(Ag1、Ag2、Ag3)各自厚度(eAg1、eAg2、eAg3)是相同的，或它们按照比例0.8-1.2改变，并且是eAg1≤eAg3≤eAg2。
根据另一个特征，作为靠近基材银层(Ag1)的下层，二氧化钛层具有厚度10-20nm，优选地10-15nm，以及作为两个其它银层(Ag2、Ag3)的下层，二氧化钛层具有厚度35-55nm，优选地40-50nm。
优选地，氧化锌层的厚度大于15nm。
有利地，该牺牲金属层是铌、钛或锆，该层的厚度小于或等于2nm。
根据另一个特征，抗反射层的厚度是25-50nm，优选地25-35nm。这个抗反射层有利地包括至少一个二氧化钛层，它的厚度是15-35nm，优选地20-30nm，还可以包括另一个金属氧化物层，它沉积在所述的二氧化钛层上，它的厚度是5-15nm，优选地6-10nm。这个金属氧化物层优选地是氧化锡(SnO2)或氮化硅(Si3N4)。
本发明基材具有这样一些特征时的每平方电阻小于或等于1Ω/□，优选地0.7-0.9Ω/□。
这种基材可以用钢化或非钢化玻璃制成，或用塑料制成。
在例如应用于等离子体显示屏类显示荧光屏的电磁屏蔽滤波器中使用这样一种基材很有利。这种滤波器因此包括一块有本发明叠层的基材，连同一块或多块功能性塑料板(例如有颜料或着色剂)和/或另一块透明基材，它任选地覆盖一个抗反射层，以便具有下述光学性能：
-光透射率TL是45-55％，
-透射时纯度小于10％，
-光反射RL低于5％，优选地低于4％，
-反射时蓝-紫色主色(une couleur en réflexion àdominancebleu-violet)纯度低于20％，
-透射时蓝色主色(dominance bleue)。
现在对着附图描述本发明的其它特征和优点，其中：
-图1说明电磁屏蔽滤波器的第一个实施方式；
-图2说明电磁屏蔽滤波器的第二个实施方式；
-图3示意性说明本发明的叠层。
首先应该明确指出，为了便于阅读，这些附图没有按照本发明元件不同尺寸的相对比例，特别是厚度的相对比例绘制。
图1说明了透明结构1实施方式的第一个实例，打算将该结构装在等离子体显示屏的前面，构成光学和电磁屏蔽滤波器。
结构1包括例如第一个玻璃类透明基材10，但是作为变通它可以是用塑料制成的，打算将其放置在显示屏一侧；一个本发明的多个薄层叠层20，它放置在基材10内面上，向着该结构内部；第二个玻璃类基材30，借助塑料薄膜40(例如PVB薄膜)，将它与对着叠层20的第一个基材连接起来。有利地，这种功能性塑料薄膜可以含有一种无机颜料或一种有机着色剂，以便制成其中心波长590nm的橙色滤波器。人们可由法国专利申请FR 03/04636了解到这种塑料薄膜或该结构多个实施方案的更多细节。
向着该结构外面的基材10和30外面优选地有一个抗反射涂层50。
图2说明了结构1实施方式的第二个实例，在这里它包括一个基材10，其中与观测者相反的一个面有多个薄层的叠层20，和一个用塑料(例如PET)制成的基材60，打算将它放在显示屏一侧，并且使用塑料薄膜40(例如PVB)将其与对着叠层20的基材10连接起来，有利地，它可以加入如前面在第一个实施方式中描述的其它功能性。朝向结构外面的基材10外面优选地有一个抗反射涂层50。
因此，本发明涉及沉积在一个基材(例如基材10)上的叠层20。这个叠层包括三个用银制成的金属层，最靠近基材的Ag1、中间的Ag2和最远的Ag3，其功能是反射其频率为30MHz-1GHz的电磁波和超过800nm的红外波。
该叠层包括在这种基材上交替排列的一个二氧化钛层21、一个由氧化锌构成的金属氧化物层22，其中一个银层Ag1、Ag2和Ag3，和一个牺牲金属涂层23。在沉积在离基材最远银层Ag3上的牺牲金属层23上面沉积了由至少一种金属氧化物构成的抗反射层24。
每个银层Ag1、Ag2和Ag3的厚度是13-19nm。银层Ag1、Ag2和Ag3的各自厚度eAg1、eAg2和eAg3可以相同，或它们可以按照其比0.8-1.2改变，并且它们是eAg1≤eAg3≤eAg2。为了降低光反射，同时保持同样的每平方电阻，优选的是层厚度不平衡。
作为靠近基材银层Ag1的下层，二氧化钛层21的厚度是10-20nm，优选地10-15nm。
作为两个其它银层Ag2和Ag3的下层，二氧化钛层21的厚度是35-55nm，优选地40-50nm。
氧化锌层22的厚度优选地大于15nm，例如16或18nm。
该牺牲金属层23是铌、钛或锆，优选地是钛，它的厚度至多2nm，例如1.5nm。
这个牺牲金属层能够防止银受到氧化作用，还能够改进其电阻率。尽管钛的存在会损害光透射率，但它能够得到更低的每平方电阻，同时保持足够合理的光透射率。通过优选其屏蔽，同时还保持良好的光学质量，可保证在滤波器光学质量与屏蔽质量之间找到这种折中。因此，采用本发明的三个银层基顺序，每平方电阻降低直到0.8Ω/□，而不是该技术状况的1.5，这样不仅能够满足针对所谓“伟大公众”产品的标准EN55022的A类，而且还满足针对家庭电影放映机类特殊产品的B类。
远离基材银层Ag3的抗反射层24厚度是25-50nm，优选地25-35nm。它至少包括厚度15-35nm，优选地20-30nm的二氧化钛层。
有利地，在这个抗反射层的二氧化钛层上面沉积另一个厚度小的金属氧化物层，其厚度是5-15nm，优选地6-10nm。这种金属氧化物例如是氧化锡(SnO2)或氮化硅(Si3N4)，它能够改善反射与透射时的颜色纯度。
采用阴极溅射技术将该叠层的所有层沉积在这种基材上。
我们在下面表中给出五个本发明叠层20实施例(ex1至ex5)。列出了以nm表示的每层厚度，并且对于与基材10连接的每个叠层，光透射率TL(以％表示)、光反射RL率(以％表示)、T时透射纯度pe(以％表示)、R时反射纯度pe(以％表示)、透射和反射时各自主波长，T时λd和R时λd(以nm表示)以及每平方电阻(以Ω表示)。
这五个实施例能够得到低于1Ω/□的合适屏蔽。
实施例1、2和5的银层厚度是相同的，都是15nm，氧化锌的厚度则是不同的，厚度低于15nm，而实施例5的厚度严格等于10nm。对于每个实施例，二氧化钛层的厚度固定不变以优化叠层的光学性能。
这些结果表明，实施例1和2的氧化锌厚度比实施例5(6-8nm或更高)高，光透射率(与相对于该技术状况可能预料的相反)依然基本相同，甚至氧化锌厚度18nm的实施例1还要好些，其有好处，实施例1和2获得的反射好处比实施例5的少，这样对于观测者来说能够达到显示屏照明不太亮，刺激性也小。
实施例3和4对不同银层厚度进行了比较，实施例4还对SnO2基反射层25进行了比较。可以看到这种不平衡的优点是降低光反射，但是其缺陷是增加了透射与反射时的纯度；然而添加抗反射层能够克服这个缺陷，因此能够达到与实施例1、2和5相当或基本相当的透射纯度，与实施例3相比降低了反射纯度。
  实施例1   实施例2   实施例3   实施例4   实施例5
  TiO2   12   12   12   12   13
  ZnO   18   16   16   16   10
  Ag1   15   15   13.5   13.5   15
  Ti   1.5   1.5   1.5   1.5   1.6
  TiO2   43   43   43   43   48
  ZnO   18   16   16   16   10
  Ag2   15   15   16.5   16.5   15
  Ti   1.5   1.5   1.5   1.5   1.5
  TiO2   43   43   43   43   48
  ZnO   18   16   16   16   10
  Ag3   15   15   15   15   15
  Ti   1.5   1.5   1.5   1.5   1.5
  TiO2   25   25   25   25   25
  SnO2   0   0   0   7   0
  TL，％   62   61   62   65   61
  RL，％   5.8   5.0   4.7   4.7   6
  T时pe(％)   5   6   9   6   5
  T时λd(nm)   500   490   496   499   500
  R时pe(％)   30   20   50   40   30
  R时λd(nm)   -555   -560   -553   -547   -555
  R/□(Ω)   0.8   0.8   0.8   0.8   0.8
因此，通过控制沉积银和介电质层和根据本发明配制的厚度以及通过采用金属保护层，根据图1或图2得到的滤波器具有下述性能：
-每平方电阻低于1Ω/□，
-光透射率TL是45-55％，
-透射时纯度低于10％，
-光反射RL低于5％，优选地低于4％，
-反射时蓝-紫色主色纯度低于20％，
-透射时蓝色主色。
使用本发明基材的电磁屏蔽滤波器可以应用于显示荧光屏，特别是等离子体显示屏。它保证这种屏蔽有非常好的性能(每平方电阻低于1Ω/□)，因此特别地阻断了这些红外线，在900nm透射率不超过1％。这些滤波器还保证了良好的可视性-光透射率是45-55％-以及改善显示屏对比度。

Claims (15)

1.一种透明基材，特别地用玻璃制成的透明基材，它有多个薄层的叠层(20)，其中包括三个银层(Ag1、Ag2、Ag3)，以及在这种基材上交替排列的一个二氧化钛层(21)、一个金属氧化物层(22)，其中一个银层(Ag1、Ag2、Ag3)和一个涂层(23)，其特征在于：
-该金属氧化物是氧化锌；
-该涂层(23)是一种牺牲金属；以及
-在离基材最远的银层(Ag3)的涂层(23)上沉积含有至少一种金属氧化物的抗反射层(24)。
2.根据权利要求1所述的基材，其特征在于每个银层(Ag1、Ag2、Ag3)的厚度是13nm-19nm。
3.根据权利要求2所述的基材，其特征在于各个银层(Ag1、Ag2、Ag3)的厚度(eAg1、eAg2、eAg3)是相同的，或按照比例0.8-1.2改变，并且是eAg1≤eAg3≤eAg2。
4.根据权利要求1-3中任一权利要求所述的基材，其特征在于作为靠近基材银层(Ag1)的下层，二氧化钛层(21)的厚度是10-20nm，优选地是10-15nm，和作为两个其它银层(Ag2、Ag3)的下层，二氧化钛层(21)的厚度是35-55nm，优选地是40-50nm。
5.根据上述权利要求中任一权利要求所述的基材，其特征在于氧化锌层(22)的厚度大于15nm。
6.根据上述权利要求中任一权利要求所述的基材，其特征在于该牺牲金属层(23)是铌(Nb)、钛(Ti)或锆(Zr)。
7.根据上述权利要求中任一权利要求所述的基材，其特征在于该牺牲金属层(23)的厚度小于或等于2nm。
8.根据上述权利要求中任一权利要求所述的基材，其特征在于该抗反射层(24)的厚度是25-50nm，优选地是25-35nm。
9.根据权利要求8所述的基材，其特征在于该抗反射层(24)包括至少一个二氧化钛层，它的厚度是15-35nm，优选地是20-30nm。
10.根据权利要求8或9中任一权利要求所述的基材，其特征在于该抗反射层(24)包括一个二氧化钛层和另一个金属氧化物层，它沉积在所述的二氧化钛层上，其厚度是5-15nm，优选地是6-10nm。
11.根据权利要求10所述的基材，其特征在于该抗反射层(24)的金属氧化物层是氧化锡(SnO2)或氮化硅(Si3N4)。
12.根据上述权利要求中任一权利要求所述的基材，其特征在于它的每平方电阻小于或等于1Ω/□，优选地是0.7-0.9Ω/□。
13.根据上述权利要求中任一权利要求所述的基材，其特征在于它是用钢化或非钢化玻璃制成的，或是用塑料制成的。
14.包括上述权利要求中任一权利要求所述基材的电磁屏蔽滤波器，其特征在于它具有下述光学性能：
-光透射率TL是45-55％，
-透射时纯度小于10％，
-光反射RL低于5％，优选地低于4％，
-反射时蓝-紫色主色纯度低于20％，
-透射时蓝色主色。
15.等离子体显示类显示荧光屏，在其前面上加入至少一个如权利要求1-14中任一权利要求所述的基材或滤波器。
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US20060280951A1 (en) 2006-12-14
PL1663897T3 (pl) 2010-02-26
US20090015909A1 (en) 2009-01-15
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DE602004022955D1 (de) 2009-10-15
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ATE441624T1 (de) 2009-09-15
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