CN101080368A - 制造玻璃外壳的方法 - Google Patents
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Abstract
玻璃片的预先选定的区域的吸光系数被优先地增大。然后可使用密封激光器将所述玻璃片密封到基板上。在一个实施方式中,通过以波长约248纳米的光、优选透过掩模对玻璃片进行辐照来增大玻璃片的吸光系数,在玻璃片上形成具有预定形状的辐照过的图案。然后对所述玻璃片进行热处理,将其置于基板上,通过使辐照过的图案暴露于波长约355-532纳米的密封激光,将其密封在基板上,制得玻璃外壳。本文所揭示的方法可用来制造电致发光器件,例如发光二极管(LED)、特别是有机发光二极管(OLED)。
Description
发明背景
发明领域
本发明涉及密封玻璃制品的方法,更具体来说涉及用来包封电致发光元件的方法。
技术背景
人们对用于显示器应用中的OLED的需求在不断增加,而且将OLED用于普通照明的工作也在不断获得进展。使用OLED的一个缺点在于,OLED的使用寿命比更传统的发光二极管(LED)短。影响器件的寿命的因素包括可能进入器件的包封的电致发光元件中的水分和/或氧气。随着OLED器件使用次数的增加,由于电极氧化、电致发光层脱离或有机元件破裂造成的器件故障的可能性也随之增加。气密的玻璃外壳被认为是一种可以减轻这些影响的方法。但是,将玻璃包封层密封至基板所需的较高的温度可能会降低这些玻璃包封层之内或之上的器件的热敏有机层的性能。因此,工业中在进行广泛的努力以开发更好的将防护玻璃(cover glass)密封到基板上的方法,例如使用玻璃料或其它非玻璃粘合剂(例如紫外(UV)固化树脂)进行密封。不幸的是,由于非玻璃粘合剂可渗透水分,而且粘合剂材料还会放出气体,因此已经证明非玻璃粘合剂不能用于长使用寿命的器件。另一方面,设置在基板和玻璃罩之间的玻璃料必须同时具有低熔化温度和与防护玻璃和/或基板非常匹配的热膨胀系数(CTE)。
发明内容
简单来说,可以根据本文所述实施用来制造适用于电致发光器件(例如有机发光二极管(OLED)等)的方法的实施方式。
所述方法包括增大玻璃片的一部分在大约300-600纳米波长处的吸光性,将该玻璃片置于基板上方,使玻璃片的这个部分暴露于所述波长的光能之下,使玻璃片与基板熔合起来,形成玻璃外壳(envelope)。
在另一个实施方式中,可通过以下步骤形成玻璃外壳:提供第一玻璃片,该玻璃片具有第一面和第二面,掺杂有Ag或Au;用第一光能辐照所述玻璃片的一部分;在至少约480℃的温度下对所述玻璃片进行加热处理;将所述玻璃片置于基板上方;使所述玻璃片被辐照过的部分暴露于第二光能,使得该玻璃片与基板熔合,在其间形成空腔。
较佳的是,所述玻璃片具有均一的化学组成。所述玻璃片的第一面的至少一部分用波长约248纳米的光进行辐照,例如透过掩模进行辐照。较佳的是,所述玻璃片被辐照过的部分在该玻璃片的第一面上形成了预定的图案。所述预定的图案优选是闭合回路。较佳的是,对所述玻璃片进行至少约2分钟、更优选至少约10分钟的热处理。
在另一个实施方式中,一种制造玻璃外壳的方法包括:提供第一玻璃片,该第一玻璃片具有第一面和第二面,而且掺杂有Ag或Au;用波长约248纳米的光辐照所述玻璃片的第一面的一部分;在至少约480℃的温度下对所述玻璃片进行加热处理;将所述玻璃片置于基板上方;使所述辐照过的部分暴露于波长约300-600纳米的光能,使玻璃片与基板熔合,在其间形成空腔。常规的密封激光器可以是例如Nd:YAG激光器。
较佳的是,所述基板包含电致发光材料;更佳的是,所述电致发光材料是有机材料。
在本发明的另一个实施方式中,对玻璃片的第一面和第二面都进行辐照。然后可以根据上述的方法将所述玻璃片密封在基板上。可通过以下方法将第二玻璃片密封在第一玻璃片上:将第二玻璃片置于第一玻璃片上,用密封激光器辐照第一玻璃片的第二面上的预定图案,从而将第二玻璃片密封在第一玻璃片上。
参照附图,通过以下说明性的描述可以更容易理解本发明,更清楚地了解本发明的其它目的、特征、细节和优点,以下说明并不构成限制。另外的系统、方法特征和优点也都包括在本发明中,在本发明的范围之内,受到所附权利要求书的保护。
附图简述
图1是根据本发明方法的设备的截面侧视图,图中显示透过掩模对玻璃片进行辐照。
图2是根据本发明一个实施方式的玻璃片的俯视图,图中显示了透过掩模进行过辐照的玻璃片区域的轮廓。
图3是四种相同的玻璃样品在不同的工艺条件下的透光率(吸光率)曲线图,图中显示了根据本发明的方法的实施方式的有效性。
图4是已经根据本发明的一个实施方式进行辐照、热处理和用密封激光器曝光之后的玻璃表面的膨胀的量的曲线图。
图5是根据本发明一个实施方式形成的玻璃外壳的截面侧视图。
图6是根据本发明另一个实施方式形成的玻璃外壳的截面侧视图。
图7是根据本发明另一个实施方式的玻璃外壳的截面侧视图,其中一些玻璃片逐次叠置密封起来。
详述
在以下详述中,出于说明而非限制的目的,提供了描述特定细节的示例实施方式以帮助完全理解本发明。但是对于本领域普通技术人员显而易见的是,可以通过阅读本说明书,以不同于本文所揭示的具体细节的其它实施方式实施本发明。另外,众所周知的器件、方法和材料的描述将会省去,以免混淆本发明的描述。最后,在任何合适的情况下,相同的编号表示相同的元素。
广义上来说,根据本发明的一个实施方式,可以通过使光敏性玻璃片的一部分以预定的图案暴露于具有预定波长的光能(优选使用激光器),然后对玻璃进行热处理,从而选择性地提高这部分玻璃片的吸光度。然后可以使用密封激光器,发射一定波长的光能,该光能被玻璃片进行过辐照和热处理的一个或多个部分吸收,从而将玻璃片密封至基板。玻璃片进行过辐照和热处理的部分吸收光能,将所述辐照过的部分至少加热至玻璃的软化温度,从而将玻璃片与基板结合起来。
在图1所示的示例性实施方式中,掺杂有银(Ag)或金(Au)的玻璃片100暴露于波长约为248纳米的光能。在一些情况下,所述玻璃可包含卤化物以提高玻璃对曝光的敏感性。较佳的是,所述卤化物是氯(Cl)、溴(B)、碘(I)、氟或其组合。所述玻璃片优选是二氧化硅基的,所述玻璃片的主要(>50%)组分是SiO2。示例性的玻璃组成包含约60-70重量%的二氧化硅(SiO2),约14.5-17重量%的B2O3,约5重量%的ZnO,约1.7重量%的F,约0-2重量%的Sb2O3,约0.22-0.66重量%的Ag和约0.22重量%的Cl。例如,合适的玻璃片可包含约64.55重量%的SiO2,16.06重量%的B2O3,0.32重量%的Ag,0.21重量%的Cl,7.02重量%的Na2O,1.64重量%的F,0.96重量%的Sb2O3,4.81重量%的ZnO和2.89重量%的Al2O3。
如图1所示,可以将铬掩模之类的掩模102置于包括第一面104和第二面106的玻璃片100上方,然后用光源110发射的光108透过掩模102辐照玻璃片的第一面104,以优先地辐照玻璃片的辐照区域112。较佳的是,光108包括约为248纳米的波长。掩模102可以接触玻璃片100,但是优选与玻璃片隔开(偏移)距离d。通常的隔离距离d=0.2毫米。较佳的是,光源110包括以脉冲模式操作的KF准分子激光器。通常的辐照功率可约为20-40毫焦/厘米2。对玻璃片辐照约1-5分钟。当激光器在约10赫兹的脉冲重复频率下操作的时候,通常辐照时间约为1分钟。可以通过例如增大脉冲重复频率、延长总曝光时间或这二者的组合来调节区域112的曝光,从而控制区域112的深度。
掩模102包括开口114,用来仅对待辐照的玻璃片的选定区域112进行辐照。在图2中可以更清楚地显示,当使用玻璃片100制造玻璃外壳的时候,辐照过的区域112宜呈框架边缘区域116的形状,所述边缘区域116未进行辐照,该框架取决于玻璃片的形状,优选与玻璃片的周边相邻。应当意识到辐照过的区域112可为能够在玻璃片上形成所需辐照过的区域的任意合适形状,但是该形状优选形成闭合的回路;更优选是形成近似多边形的闭合回路。近似表示所述多边形可以有例如圆角部分。在优选的实施方式中,可以在单独的玻璃片上形成多个辐照过的区域112,然后将该玻璃片分成多个更小的玻璃片,每个更小的玻璃片具有一个或多个辐照过的区域。然后将各个具有辐照过的区域的玻璃片与基板相结合,形成玻璃外壳。
在另一种方法中,可以使用辐照激光器,使得会聚的激光束相对于玻璃片移动,从而在无需使用掩模的情况下在玻璃片上“写”下图案,但是在曝光时间成本很高的生产环境下,不太希望采用这些方法。
对玻璃片100进行辐照之后,立刻对玻璃片进行热处理。较佳的是,在至少约480℃、更优选约500-600℃的温度下对玻璃片进行热处理。较佳的是对玻璃片热处理至少约2分钟;更优选至少约10分钟。可持续热处理最多约2小时,但是热处理约超过2小时的话会减小辐照过的玻璃和没有辐照过的玻璃之间的对比度。也即是说,辐照过的玻璃部分和未辐照过的玻璃部分之间的吸收的变化可能变得比较不明显。
图3显示了四种玻璃样品在不同的工艺条件下的吸收光谱曲线(吸光度随波长的变化关系),其中吸光度表示为mm-1。所述玻璃片样品各自包含约64.55重量% SiO2,16.06重量% B2O3,0.32重量% Ag,0.21重量% Cl,7.02重量% Na2O,1.64重量% F,0.96重量% Sb2O3,4.81重量% ZnO以及2.89重量% Al2O3,0.01重量% CaO,0.01重量% SO3和1.52重量% H2O。
如图3所示,曲线118显示了用KF准分子激光器辐照之前的第一玻璃样品的吸光曲线。在波长大约为275纳米处可以看到尖锐的紫外(UV)吸收变化。也即是说,在大约275纳米处观察到玻璃的吸光率迅速减小。曲线120显示了进行过辐照、但是未进行热处理的玻璃样品的吸光曲线。观察到与曲线118所示类似的UV变化。曲线122显示了仅进行热处理的玻璃片样品的吸收曲线。观察到与曲线118和120类似的UV变化,但是观察到该样品在约大于350纳米波长处的吸光度增大(相对于曲线118),在波长约400纳米处具有最大的吸光度。最后,曲线124表示根据本发明进行处理的玻璃样品,该玻璃样品首先用波长约248纳米的光辐照约4分钟,然后在550℃的温度下热处理约1.5小时。曲线124显示在约325-600纳米波长范围内的吸光度显著增大,在大约400-500纳米波长范围内具有宽吸收峰。超过500纳米以后,玻璃样品的吸光度迅速减小。
在对玻璃片进行热处理之后,可以将热处理过的玻璃片置于基板上方,使得玻璃片的辐照过的第一面104朝向基板126。基板126通常包含玻璃或玻璃陶瓷,优选包括沉积在其上的一个或多个发光材料层128。例如所述发光材料可包括一个或多个有机发光层。还可包括其它的层,例如阳极层或阴极层。然后可以例如用合适的密封激光器,沿着之前辐照的区域112对玻璃片进行加热。较佳的是,所述密封激光器具有在约300-600纳米波长范围内的发射峰;较优选在大约355-532纳米内;更优选密封激光器的发射峰约为420纳米。例如Nd:YAG激光器是合适的密封激光器。较佳的是,可以如箭头130所示透过玻璃片的第二面106,使辐照过的区域暴露于密封激光而对该区域进行加热,或者如果基板在加热激光波长下基本是透明的,则可以如箭头132所示透过基板126将来自加热激光器的光能引导到辐照过的区域上而对该区域进行加热。这样,该实施方式从玻璃片的顶上或者从基板的底下将所述玻璃罩片密封到基板上。较佳的是,基板126可以具有与玻璃片100相同的玻璃组成,但是基板126并不进行首先在大约248纳米波长下辐照、然后热处理的操作,从而可以使用一种单独的玻璃组合物制造玻璃外壳,而无需在基板和玻璃片中使用不同的组合物。更简单来说,可以使用密封激光器从防护玻璃上方或下方将玻璃片密封在基板上。另外,与使用以其整体吸收光的玻璃片的现有技术方法不同,通过辐照和随后的热处理,使得根据本发明的玻璃片中仅有一个浅的表面区域会吸收光,通常该区域的深度D约小于300微米。使用本发明的方法可以显著改进将玻璃片密封到基板上的效果,例如仅需要优先地对所述防护玻璃和基板之间的密封界面处的浅的辐照过的玻璃区域112进行加热。另外,由于玻璃片100上仅有被辐照过的区域112的吸光度显著增大,玻璃片100余下的部分仍具有高透光率(例如>90%),使得电致发光器件可以透过防护玻璃和/或基板有效地透射。
当玻璃片100上的辐照过的区域112被密封激光器加热至软化温度的时候,辐照过的区域112相应地发生膨胀,形成用来容纳所述电致发光元件的空腔134,在辐照过的区域112使玻璃片100与基板126相结合。图5显示了具有以下组成的玻璃样品表现出的常规的膨胀距离:64.55重量% SiO2,16.06重量% B2O3,0.32重量% Ag,0.21重量% Cl,7.02重量% Na2O,1.64重量% F,0.96重量% Sb2O3,4.81重量% ZnO以及2.89重量% Al2O3,0.01重量% CaO,0.01重量% SO3和1.52重量% H2O。使用以10赫兹的频率运作的脉冲KF准分子激光器以248纳米的波长对所述样品辐照4分钟。然后在大约550℃的温度下对该样品加热处理约1.5小时,使用Nd:YAG密封激光器从与辐照过的区域相反的面对该样品的一部分进行加热。如本文所示,进行过辐照、热处理、然后用密封激光器加热过的玻璃片区域发生膨胀,使得玻璃片的辐照过的区域的表面延伸至高出没有在248纳米辐照过的玻璃片的表面大约10微米。
在另一个实施方式中,如图6所示,可以透过掩模以248纳米的波长的光优先地辐照第一玻璃片200,以制得具有上述预定形状的辐照过的区域212。在图6所示的实施方式中,可对玻璃片200的两个面进行优先辐照。然后如上文所述对玻璃片200进行热处理,同样如上文所述使用合适的密封激光器将第一面204密封到基板126上,从而形成空腔234。较佳的是,引导来自密封激光器的光通过基板而将玻璃片200密封到基板126上。然后可以将第二基板126(其上可沉积一个或多个电致发光层)类似地密封在第一玻璃片200的第二面206上,该密封操作优选通过引导来自密封激光器的光通过第二激光片或基板而进行。
在另一个实施方式中,通过常规的离子交换法对玻璃片的预定部分的吸光系数进行了改良。例如,可以根据预定的图案对玻璃片的预定部分进行离子交换,在玻璃中结合入铜离子。当玻璃片的预定部分发生吸光系数变化之后,使用能够发射该预定部分显著吸收的波长的光的密封激光器,依照与上文所述类似地方式将玻璃片密封在基板上。
应当强调的是,上述本发明的实施方式,特别是任意“优选的”实施方式仅仅是可能的实施的例子,仅仅是用来帮助清楚地理解本发明的原理。可以在不背离本发明精神和原理的前提下对上述本发明的实施方式进行许多的改变和改良。例如如图7所示,可以如前文所述仅在一面上对第一玻璃片100进行辐照,热处理,然后将其密封到基板上。还可对第二玻璃片100的一个面进行辐照,热处理,然后通过第二玻璃片100的辐照过的部分112将其密封在第一玻璃片100的第二面106上。通过这种方式,连续数量的玻璃片可以堆叠起来互相密封。第一玻璃片100可作为用于另外的电致发光元件的基板。所有这些改良和改变都包括在本文中,包括在本说明书和发明的范围之内,受到所附的权利要求书的保护。
Claims (18)
1.一种用来制造玻璃外壳的方法,该方法包括:
增大玻璃片的一部分在约300-600纳米波长范围内的吸光性;
将所述玻璃片置于基板上方;
使所述玻璃片的所述部分暴露于所述波长的光能下,使玻璃片与基板熔合形成玻璃外壳。
2.一种制造玻璃外壳的方法,该方法包括:
提供第一玻璃片,该第一玻璃片具有第一面和第二面,掺杂有Ag或Au;
用第一光能辐照所述玻璃片的一部分;
在至少约480℃的温度下对所述玻璃片进行加热处理;
将所述玻璃片置于基板上方;
使所述玻璃片的辐照过的部分暴露于第二光能,使玻璃片与基板熔合,在其间形成空腔。
3.如权利要求2所述的方法,其特征在于,所述第一光能的波长约为248纳米。
4.如权利要求2所述的方法,其特征在于,所述第二光能的波长约为300-600纳米。
5.如权利要求2所述的方法,其特征在于,所述辐照步骤包括透过掩模进行辐照。
6.如权利要求2所述的方法,其特征在于,所述辐照过的部分包括位于第一面上的闭合回路。
7.如权利要求2所述的方法,其特征在于,所述玻璃片包括多个辐照过的图案。
8.如权利要求2所述的方法,其特征在于,所述方法还包括设置在所述空腔中的电致发光层。
9.如权利要求8所述的方法,其特征在于,所述电致发光层包含有机材料。
10.如权利要求5所述的方法,其特征在于,所述第二光能的波长约为420纳米。
11.如权利要求2所述的方法,其特征在于,所述玻璃片的化学组成与所述基板的化学组成基本相同。
12.如权利要求2所述的方法,其特征在于,对所述玻璃片加热处理至少约2分钟。
13.如权利要求2所述的方法,其特征在于,对所述玻璃片加热处理至少约1小时。
14.如权利要求2所述的方法,其特征在于,所述玻璃片中Ag或Au的含量约为0.22-0.66重量%。
15.如权利要求2所述的方法,其特征在于,所述辐照过的部分的深度约小于300毫米。
16.一种用来制造玻璃外壳的方法,该方法包括:
提供第一玻璃片,该第一玻璃片具有第一面和第二面,并且掺杂有Ag或Au;
以大约248纳米的波长辐照所述玻璃片第一面的一部分;
在至少约480℃的温度下对所述玻璃片进行热处理;
将所述玻璃片置于基板上;
使所述辐照过的部分曝光于波长约为300-600纳米的光能,使得玻璃片与基板熔合,在其间形成空腔。
17.如权利要求16所述的方法,其特征在于,该方法还包括以波长约248纳米的光辐照第一玻璃片第二面的一部分。
18.如权利要求16所述的方法,其特征在于,该方法还包括将第二玻璃片密封到第一玻璃片上。
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-
2005
- 2005-12-12 CN CNA2005800435638A patent/CN101080368A/zh active Pending
- 2005-12-12 EP EP05826626A patent/EP1838635A2/en not_active Withdrawn
- 2005-12-12 KR KR1020077016563A patent/KR20070087167A/ko not_active Application Discontinuation
- 2005-12-12 JP JP2007548283A patent/JP2008524112A/ja not_active Withdrawn
- 2005-12-12 WO PCT/US2005/044952 patent/WO2006068869A2/en active Application Filing
- 2005-12-15 US US11/303,578 patent/US7565817B2/en not_active Expired - Fee Related
- 2005-12-19 TW TW094145688A patent/TW200633941A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
WO2006068869A2 (en) | 2006-06-29 |
JP2008524112A (ja) | 2008-07-10 |
KR20070087167A (ko) | 2007-08-27 |
TW200633941A (en) | 2006-10-01 |
WO2006068869A3 (en) | 2006-09-08 |
US20060130523A1 (en) | 2006-06-22 |
EP1838635A2 (en) | 2007-10-03 |
US7565817B2 (en) | 2009-07-28 |
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