CN105219149A - 遮光材料和包含遮光材料的显示装置 - Google Patents
遮光材料和包含遮光材料的显示装置 Download PDFInfo
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- CN105219149A CN105219149A CN201510405784.0A CN201510405784A CN105219149A CN 105219149 A CN105219149 A CN 105219149A CN 201510405784 A CN201510405784 A CN 201510405784A CN 105219149 A CN105219149 A CN 105219149A
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- 230000001590 oxidative effect Effects 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- MNMVKGDEKPPREK-UHFFFAOYSA-N trimethyl(prop-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=C MNMVKGDEKPPREK-UHFFFAOYSA-N 0.000 description 1
- UWAWYGLUQDYLTK-UHFFFAOYSA-N trimethylsilylmethyl prop-2-enoate Chemical compound C[Si](C)(C)COC(=O)C=C UWAWYGLUQDYLTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
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- H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
- H01L29/78633—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device with a light shield
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- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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Abstract
本发明涉及遮光材料和包含遮光材料的显示装置,所述显示装置可包含基板上的多个像素;和在所述基板上的限定或划分所述多个像素的遮光层,其中,所述遮光层包含多个纳米颗粒,每个纳米颗粒均具有芯和在所述芯外的壳,并且其中所述芯包含金属氧化物,并且所述壳包含绝缘材料。
Description
本申请要求于2014年6月30日递交的韩国专利申请第10-2014-0081278号和于2014年12月17日递交的韩国专利申请第10-2014-0181957号的优先权,并出于所有目的将它们如同完整阐述一样并入本文中。
技术领域
本发明涉及显示装置及其制造方法,更具体而言涉及包含遮光材料的显示装置。
背景技术
最近,平板显示器(FPD)随着多媒体的发展而变得更加重要。随着这一趋势,诸如液晶显示器(LCD)、等离子体显示面板(PDP)、场发射显示器(FED)和有机电致发光显示器(OLED)等多种类型的显示器正在商业化。OLED具有1ms以下的高响应速度和低能耗,属于自发光型。由于这些优越特征,OLED尤其凭借其优异的视角而成为下一代显示装置的关注焦点。
驱动显示装置的方法包括无源矩阵方法和利用薄膜晶体管的有源矩阵方法。在无源矩阵方法中,正极和负极相互交叉形成,对线进行选择和驱动。在有源矩阵方法中,薄膜晶体管连接至各像素电极,并响应于与薄膜晶体管的栅极连接的电容器所保持的电压而被驱动。
除了薄膜晶体管的基本特征(例如迁移率和漏泄电流)之外,与薄膜晶体管的长寿命和电气可靠性相关的耐久性也很重要。用于显示装置的薄膜晶体管的有源层通常由非晶硅或多晶硅制成。非晶硅的有利之处在于膜形成过程简单并且制造成本低,但可能不能确保电气可靠性。另一方面,多晶硅也具有以下问题:可能由于其高温过程和结晶的非均一性而难以在大型装置中应用。
如果有源层由氧化物制成,则能够在低温下获得高迁移率,而且因为能够根据氧含量控制其电阻而容易获得所需的性质。因此,氧化物作为薄膜晶体管的有源层材料最近备受关注。所使用的氧化物材料的实例为氧化锌(ZnO)、氧化铟锌(InZnO)、或氧化铟镓锌(InGaZnO4)。
包含氧化物有源层的薄膜晶体管有利地具有遮光层,以保护有源层免受外部光的影响。这是因为如果由外部光源在有源层中产生光电流,则有源层可能变得不稳定。
可将常规的遮光层配置为包括反射层。例如,常规遮光层可包括金属层和绝缘层,或者可包括表面与氧化物有源层接触的金属层。常规遮光层可还包括用于吸收光的绝缘层,并且可以由例如非晶硅或碳化硅(SiC)制成。
然而,作为薄膜晶体管的有源层材料,上述材料可能不满足耐热性、高电阻、低反射和低透光率等特性。特别而言,非晶硅具有约30%的高反射率,包含SiNx的多层具有约14%的高反射率,黑色系碳化硅具有约11%至25%的反射率。因此,显示装置的可靠性可能因薄膜晶体管有源层的劣化而变差,而薄膜晶体管有源层的劣化可归因于从LCD的背光侧或OLED的外侧引入有源层中的光。
发明内容
因此,本发明涉及遮光材料和包含该遮光材料的显示装置,其基本上消除了相关技术中的局限和缺陷所导致的一个或多个问题。
本发明的优点在于提供了具有改进的遮光特性的显示装置。
本发明的其他特点和优点将在后续描述中给出,并且部分地通过所述描述而变得显而易见,或者可以通过实施本发明而习得。通过书面说明书和其权利要求书以及附图中特别阐明的结构,将实现和获得本发明的各种优点。
为了实现本发明具体和广泛地描述的各种优点和目的,遮光材料例如可含有:多个纳米颗粒,每个纳米颗粒均具有芯和在所述芯外的壳;和粘合剂和溶剂,其中所述芯包含金属氧化物,并且所述壳包含绝缘材料。
在本发明的另一方面,显示装置例如可含有:基板上的多个像素;和在所述基板上的限定或划分所述多个像素的遮光层,其中,所述遮光层包含多个纳米颗粒,每个纳米颗粒均具有芯和在所述芯外的壳,并且其中所述芯包含金属氧化物,并且所述壳包含绝缘材料。
应当理解的是,以上一般描述和下文详细描述均是示例性和说明性的,目的是提供对所要求保护的发明的进一步解释。
附图说明
将附图包含在本文中以提供对本发明的进一步理解,并且将其并入本说明书构成本说明书一部分,附图图示了本发明的实施方式,其与说明书一同用于解释本发明的原理。附图中:
图1是图示本发明实施方式的显示装置的截面图;
图2是图示本发明另一实施方式的显示装置的截面图;
图3是图示本发明实施方式的纳米颗粒的图;
图4A和4B是显示根据本发明实施例1制造的纳米颗粒的图像;
图5A是显示根据本发明实施例2制造的遮光材料的热重分析结果的图,图5B是显示根据本发明实施例1制造的遮光材料的热重分析结果的图;
图6A是显示根据本发明实施例2制造的遮光材料的P&TMS测量结果的图,图6B是显示根据本发明实施例1制造的遮光材料的P&TMS测量结果的图;
图7是显示本发明实施方式的两种硅氧烷和两种倍半硅氧烷的P&TMS测量结果的图;
图8是显示根据本发明实施例3和实施例6制造的遮光材料的热重分析(TGA)结果的图;
图9是显示根据本发明实施例3和实施例6制造的遮光材料的P&TMS测量结果的图;
图10是对于本发明实施方式的掩模和遮光层图案用4倍放大和10倍放大的光学显微镜测量得到的图像;
图11是本发明实施方式的遮光层图案的SEM图像;和
图12是显示本发明实施方式的遮光层图案的反射率的图。
具体实施方式
现在将详细描述本发明的实施方式,其实例在附图中给出。在所有附图中可以使用相同的附图标记指示相同或相似的部分。
图1是图示本发明实施方式的显示装置的截面图,图2是图示本发明另一实施方式的显示装置的截面图。
作为本发明实施方式的显示装置的实例,下面描述有机发光显示器。然而,本发明不限于有机电致发光显示器,而是可应用于其他各种显示装置,例如液晶显示器和电泳显示装置。
参考图1,遮光层LS放置在基板105上。基板105由玻璃、塑料或金属制成。遮光层LS由能够遮光的遮光材料制成,并且包含具有芯-壳结构的纳米颗粒(下文将对此详细描述)。在其上已经形成有遮光层LS的基板105上,形成缓冲层110。缓冲层110的功能是保护将在后续工序中形成的薄膜晶体管免受杂质(例如可能从基板105中抽出的碱离子)的影响。缓冲层110由氧化硅(SiO2)或硅氮化物(SiNx)制成。
有源层120设置在缓冲层110上。有源层120可由非晶氧化锌系复合半导体或a-IGZO半导体形成。特别是,a-IGZO半导体可利用氧化镓(Ga2O3)、氧化铟(In2O3)和氧化锌(ZnO)的复合靶通过溅射或化学沉积法(例如化学气相沉积或原子层沉积(ALD))来形成。非晶氧化锌系复合半导体可利用镓(Ga)、铟(In)和锌(Zn)的原子比分别为1∶1∶1、2∶2∶1、3∶2∶1或4∶2∶1的复合氧化物靶进行沉积。在此情况中,如果使用镓(Ga)、铟(In)和锌(Zn)的原子比为2∶2∶1的复合氧化物靶,镓(Ga)、铟(In)和锌(Zn)的当量重量比可以为约2.8∶2.8∶1。源极区域120a和漏极区域120b通过在其中掺杂杂质而设置在有源层120的两侧上。沟道区域120c设置在源极区域120a和漏极区域120b之间。
栅极绝缘层125设置在有源层120上。栅极绝缘层125由硅氧化物(SiOx)层或硅氮化物(SiNx)层或者其多层结构体形成。栅极131设置在栅极绝缘层125上。栅极131由选自包括铜(Cu)、钼(Mo)、铝(Al)、铬(Cr)、金(Au)、钛(Ti)、镍(Ni)、钕(Nd)、钽(Ta)和钨(W)的组的任一种物质制成,并可具有单层或其多层结构。栅极131对应于有源层120的沟道区域120c放置。
在已形成有栅极131基板105上,设置层间介电绝缘层135。层间介电绝缘层135由硅氧化物(SiOx)层或硅氮化物(SiNx)层或其多层结构体形成。层间介电绝缘层135包括接触孔136a和136b,接触孔136a和136b暴露出有源层120,并根据有源层120的源极区域120a和漏极区域120b而设置。
源极141和漏极142设置在层间介电绝缘层135上。源极141和漏极142各自可由单层或多层形成。如果源极141和漏极142各自由单层形成,则该单层可由选自包括钼(Mo)、铝(Al)、铬(Cr)、金(Au)、钛(Ti)、镍(Ni)、钕(Nd)和铜(Cu)或它们的合金的组的任一种物质制成。如果源极141和漏极142各自由多层形成,则该多层可具有钼(Mo)/铝(Al)-钕(Nd)、钼(Mo)/铝(Al)、或钛(Ti)/铝(Al)的双层结构,或具有钼(Mo)/铝(Al)-钕(Nd)/钼(Mo)、钼(Mo)/铝(Al)/钼(Mo)、或钛(Ti)/铝(Al)/钛(Ti)的三层结构。源极141和漏极142通过形成在层间介电绝缘层135中的接触孔136a和136b分别连接至有源层120的源极区域120a和漏极区域120b。
在已形成有源极141和漏极142的基板105上,设置钝化层145。钝化层145由硅氧化物(SiOx)层或硅氮化物(SiNx)层或其多层结构体形成。钝化层145包括过孔147,过孔147暴露出漏极142,并设置在与漏极142对应的区域中。
滤色片CF设置在钝化层145上。红(R)、绿(G)和蓝(B)中任一种颜色形成在各滤色片CF像素中,但在本实施方式中,为了便于描述,已经图示了红(R)、绿(G)和蓝(B)所有颜色。在滤色片CF上设置保护层150。保护层150可以由无机材料(例如硅氧化物(SiOx)或硅氮化物(SiNx))制成,或者由有机材料(例如聚酰亚胺、苯并环丁烯系树脂、或丙烯酸酯)制成。
像素电极160设置在保护层150上。像素电极160由透明导电物质构成,例如氧化铟锡(ITO)或氧化铟锌(IZO)。像素电极160通过设置在钝化层145和保护层150中的过孔147连接至漏极142。在像素电极160上设置暴露出像素电极160的堤层165。堤层165限定了像素并使像素电极160绝缘。堤层165由有机物质制成,例如聚酰亚胺、苯并环丁烯树脂或丙烯酸酯。本发明实施方式的堤层165可以是能够遮光的黑色堤层。黑色堤层可以由能够遮光的遮光材料制成,并且包含具有芯-壳结构的纳米颗粒(下文将对此详细描述)。当堤层165由这种黑色堤层形成时,可有利地降低或防止相邻像素之间的颜色混合,并可改进对比度。
有机发光层170设置在像素电极160和堤层165上。有机发光层170至少包括发光层,并且还可包括空穴注入层、空穴输送层、电子输送层或电子注入层。在有机发光层170上设置反电极175。反电极175可以由具有低功函数的金属制成,例如银(Ag)、镁(Mg)或钙(Ca)。
在如上构造的显示装置中,有机发光层170发射光,并通过下层的滤色片实现红色、绿色和蓝色。通常,有机电致发光显示器在基板中包括偏光板,以降低由外部光引起的反射光,并且包括设置在反射光路线上的遮光层,以防止外部光被反射。本发明实施方式的有机电致发光显示器的有利之处在于可以省略在常见有机电致发光显示器中为了防止反射光而设置的这种偏光板。
图2是图示本发明另一实施方式的显示装置的截面图。将省略对与图1相同的部件的描述。
参考图2,本发明实施方式的显示装置可以是液晶显示器300。液晶显示器300包括彼此相对设置的薄膜晶体管(TFT)阵列基板310和滤色片基板370,而液晶层360位于二者之间。滤色片基板370包括经配置而划分像素的黑底(blackmatrix)375、在由黑底375划分的像素中形成的滤色片380、和设置在滤色片380上的共用电极385。滤色片380在由黑底375划分的像素区域中以R、G和B中的每一种形成,从而实现R、G和B色。还可以在滤色片380与共用电极385之间形成外包层。
栅极315设置在TFT阵列基板310上。使栅极315绝缘的栅极绝缘层320设置在栅极315上。与栅极315对应的有源层325设置在栅极绝缘层320上,源极330a和漏极330b设置在有源层325的两侧,由此形成薄膜晶体管(TFT)。保护层335设置在TFT上,与漏极330b连接的像素电极340设置在保护层335上。
在如上构造的液晶显示器300中,在像素电极340和共用电极385之间形成垂直电场,通过TFT向像素电极340供应像素信号,并向共用电极385供应参比电压,从而驱动液晶。在图2中,液晶显示器300具有TN结构,举例而言,其中,将像素电极340放置在TFT阵列基板310中,将共用电极385放置在滤色片基板370中。在一些实施方式中,可以实施其他类型的液晶显示器,例如,IPS结构,其中像素电极和共用电极均形成在TFT阵列基板310中。
在本发明另一实施方式的显示装置中,黑底375由能够遮光的遮光材料制成,并包含具有芯-壳结构的纳米颗粒(下文将对此详细描述)。由于本发明实施方式的显示装置包括遮光特性优异的黑底375,因此能够改进其对比度和显示品质。
已经描述了作为实施方式的有机电致发光显示器和液晶显示器。然而。本发明不限于这些显示器,本发明可应用于其他类型的显示装置,例如电解显示装置。
现将详细描述上述显示装置中所用的遮光材料。本发明实施方式的遮光材料包括:芯-壳结构的纳米颗粒,粘合剂,和分散纳米颗粒和粘合剂的溶剂。
图3是图示本发明实施方式的纳米颗粒的图。
参考图3,形成本发明实施方式的遮光材料的纳米颗粒200具有遮光功能并且具有芯-壳结构。纳米颗粒200具有由金属氧化物(有利的是黑色金属氧化物)制成的芯210以基本遮光。黑色金属氧化物可包含铬(Cr)或锰(Mn),例如,铜锰氧化物(CuMnOx)、铜(铬,锰)氧化物(Cu(Cr,Mn)xOy)、铜(铬,铁)氧化物(Cu(Cr,Fe)xOy)、或(铁,锰)(铁,锰)氧化物((Fe,Mn)(Fe,Mn)xOy)。纳米颗粒200的芯210的尺寸可以为数纳米至数微米,例如10nm至100nm。
壳220是使芯210绝缘并包围芯210的绝缘层。壳220由具有绝缘特性的无机物质制成,例如硅氧烷、硅氧化物(SiOx)、硅氮化物(SiNx)、氧化钛(TiO2)或硅烷。壳220可以以1至50nm的厚度包围芯210。在此情况下,如果壳220的厚度为1nm以上,则可以提高绝缘性并改进低反射效果。另外,如果壳220的厚度为50nm以下,可有利地降低或阻止表面粗糙度的增加和遮光效果的消失。然而,壳220的厚度不限于此,可以根据芯210的尺寸以各种方式进行设计。因此,包含芯210和壳220的纳米颗粒200的尺寸例如可以为150nm以下或100nm以下。
相对于100重量份的本发明实施方式的遮光材料,纳米颗粒200的含量可以为1至30重量份。如果纳米颗粒200的含量为1重量份以上,则可以改进光学尺寸(OD)特性。如果纳米颗粒200的含量为30重量份以下,则可以提高纳米颗粒200的分散稳定性。
在合成步骤中,纳米颗粒之间会形成物理和化学凝结。因此,可以对纳米颗粒进行表面处理,从而使纳米颗粒分散在本发明实施方式的遮光材料的溶剂中。
例如,如有需要,可以采用以下方法:将纳米颗粒加入到有机溶剂(例如1,2-二氯苯、N-甲基吡咯烷酮(NMP)或N,N-二甲基甲酰胺(DMF))中并进行超声处理的方法;利用离子型低聚物表面活性剂(例如十二烷基硫酸钠(SDS)、TritonX-100、十二烷基苯磺酸钠(NaDDBS)或***胶)和/或聚合物表面活性剂(例如二元或三元共聚物,如聚乙烯基吡咯烷酮(PVP))的方法;通过酸处理引入羧基从而增加在水和醇中的溶解性、并通过用烃选择性地取代羧基而获得芳香性有机溶剂(例如苯胺十八胺(ODA)或十四烷基苯胺)的分散液的方法;或利用离子液体(诸如1-丁基-3-甲基咪唑鎓四氟硼酸盐(BMIMBF4)或1-丁基-3-甲基咪唑鎓六氟磷酸盐(BMIMPF6)等离子液体)作为电解质并将离子液体再分散在有机溶剂中的方法。
形成本发明实施方式的遮光材料的粘合剂是交联键合的化合物,并且是具有至少一个硅醇基或硅氧烷基的单体化合物。所述化合物可通过热处理而形成交联键(下文将对此进行描述),从而能够形成聚硅氧烷。通过固化过程使所述化合物进行交联键合,并充当形成涂层基质的粘合剂。
属于交联键合化合物并且具有硅醇基的单体化合物可以包括例如:通过对含甲硅烷基的不饱和单体(例如乙烯基不饱和烷氧基硅烷型和乙烯基不饱和酰氧基硅烷型)进行水解而获得的含硅醇基的单体。乙烯基不饱和烷氧基硅烷可包括:例如,(1)丙烯酸酯基烷氧基硅烷型(例如,γ-丙烯酰氧基丙基-三甲氧基硅烷和γ-丙烯酰氧基丙基-三乙氧基硅烷)和(2)甲基丙烯酸酯基烷氧基硅烷型(例如,γ-甲基丙烯酰氧基丙基-三甲氧基硅烷、γ-甲基丙烯酰氧基丙基-三乙氧基硅烷和γ-甲基丙烯酰氧基丙基-三(2-甲氧基乙氧基)硅烷)。乙烯基不饱和酰氧基硅烷可包括:例如,丙烯酸酯基乙酰氧基硅烷、甲基丙烯酸酯基乙酰氧基硅烷和乙烯基不饱和乙酰氧基硅烷型(例如,丙烯酰氧基丙基三乙酰氧基硅烷、甲基丙烯酰氧基丙基三乙酰氧基硅烷)。
另外,能够通过水解而获得具有硅醇基的单体的含甲硅烷基不饱和化合物可包括例如:氯二甲基乙烯基硅烷、5-三甲基甲硅烷基-1,3-环戊二烯、3-三甲基甲硅烷基丙烯醇、三甲基甲硅烷基甲基丙烯酸酯、1-三甲基甲硅烷氧基-1,3-丁二烯、1-三甲基甲硅烷氧基环戊烯、2-三甲基甲硅烷氧基乙基甲基丙烯酸酯、2-三甲基甲硅烷氧基呋喃、2-三甲基甲硅烷氧基丙烯、烯丙氧基叔丁基二甲基硅烷和三烷氧基乙烯基硅烷,例如,烯丙氧基三甲基硅烷、三甲氧基乙烯基硅烷、三乙氧基乙烯基硅烷和三(甲氧基乙氧基)乙烯基硅烷。具有上述硅醇基的单体可以单独使用,也可以将两种以上单体组合使用。
另外,具有硅氧烷基的单体也可以用作交联键合化合物。具有这种硅氧烷基的单体可包括具有直链硅氧烷基的化合物、具有环硅氧烷基的化合物、具有四面体结构的硅氧烷基的化合物和倍半硅氧烷。
具有直链硅氧烷基的化合物可包括甲基硅氧烷、乙基硅氧烷、丙基硅氧烷、丁基硅氧烷、戊基硅氧烷、二甲基硅氧烷、二乙基硅氧烷、二丙基硅氧烷、二丁基硅氧烷、二戊基硅氧烷、三甲基硅氧烷、三乙基硅氧烷、三丙基硅氧烷、三丁基硅氧烷、六甲基二硅氧烷、六乙基二硅氧烷、八甲基三硅氧烷、八乙基三硅氧烷、十甲基四硅氧烷、四甲氧基硅烷(TMOS)、四乙氧基硅烷(TEOS)、甲基三甲氧基硅烷(MTMS)、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基甲基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、2-(3,4-乙氧基环己基)乙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和3-巯基丙基三甲氧基硅烷。可以使用选自其中的一种类型,或使用两种以上类型的混合物,但本发明不限于此。例如,可以单独使用具有直链硅氧烷基的含烷氧基单体,例如TMOS、TEOS、MTMS、乙烯基三(2-甲氧基乙氧基)硅烷和N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷,或者可以使用两种以上这些单体的混合物。
环硅氧烷可包括选自以下物质中的一种或两种以上的混合物:环三硅氧烷,例如甲基氢-环硅氧烷、六甲基-环三硅氧烷和六乙基-环三硅氧烷;环四硅氧烷,例如四辛基-环四硅氧烷、六甲基-环四硅氧烷和八甲基-环四硅氧烷;四-和五-甲基环四硅氧烷;四-、五-、六-和七-甲基环五硅氧烷;四-、五-和六甲基-环六硅氧烷、四乙基-环四硅氧烷和四苯基环四硅氧烷;和十甲基-环五硅氧烷、十二甲基环硅氧烷、1,3,5,7-四甲基-环四硅氧烷、1,3,5,7,9-五甲基-环五硅氧烷和1,3,5,7,9,11-六甲基环六硅氧烷,但本发明不限于此。
此外,四(二甲基甲硅烷氧基)硅烷、四(二苯基甲硅烷氧基)硅烷或四(二乙基甲硅烷氧基)硅烷或它们的混合物可作为具有四面体硅氧烷基的单体使用,但本发明不限于此。
除了直链、环状和四面体硅氧烷外,举例而言,倍半硅氧烷(SSQ)可用作交联键合化合物,倍半硅氧烷可通过甲基三氯硅氧烷和二甲基氯硅氧烷的反应合成。倍半硅氧烷可被合成为通过交联键而具有梯状结构或笼状结构的聚倍半硅氧烷。例如,通过水解有机三氯硅烷获得具有部分笼状结构的七聚体形式的硅氧烷,或具有笼状结构的七聚体形式和八聚体形式的硅氧烷。可利用溶解度差异来分离七聚体形式的硅氧烷,倍半硅氧烷单体可通过有机三烷氧基硅烷或有机三氯硅烷的缩合反应而获得。倍半硅氧烷具有高的热稳定性和低介电常数。倍半硅氧烷通过利用酸催化剂的水解缩合反应而产生。如果在倍半硅氧烷中以使其具有纳米多孔的方式引入孔,则可以获得降低折射率和介电常数的优点。此外,当形成遮光材料制剂时,倍半硅氧烷因粘合剂的纳米多孔立体结构而具有高磨料分散性。因此,可以获得以下优点:遮光层的储存稳定性因均一的分散而得到提高。
基于100重量份的遮光材料,上述粘合剂的含量可以为1至30重量份。在此情况下,如果粘合剂的含量为1重量份以上,则可能获得以下优点:可减少或阻止与基板的粘合力的下降。如果粘合剂含量为30重量份以下,则可存在以下优点:遮光层的遮光特性得到改进。
形成本发明实施方式的遮光材料的溶剂用于分散固体,例如,纳米颗粒和粘合剂,并控制遮光材料的粘度。亲水性溶剂或疏水性溶剂可用作能够分散纳米颗粒和粘合剂的溶剂。例如,亲水性溶剂可包括选自以下的有机溶剂:水;醇类型的萜品醇,例如,乙醇、甲醇、异丙醇、丁醇、2-乙基己醇、甲氧基戊醇、丁氧基乙醇、乙氧基乙氧基乙醇、丁氧基乙氧基乙醇、甲氧基丙氧基丙醇、Texanol、α-萜品醇;四氢呋喃(THF);甘油、亚烷基二醇,例如,乙二醇、三乙二醇、聚乙二醇、丙二醇、二丙二醇、二己二醇,或它们的烷基醚(例如,丙二醇甲基醚(PGME)、二乙二醇丁基醚、二乙二醇乙基醚、二丙二醇甲基醚、二己二醇乙基醚);和甘油、N-甲基吡咯烷酮(NMP)、2-吡咯烷酮、乙酰丙酮、1,3-二甲基咪唑啉酮、硫二甘醇、二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、环丁砜、二乙醇胺和三乙醇胺,或者包含其中两种以上的混合物的有机溶剂。
疏水性溶剂可包括例如:酮类,例如甲基乙基酮或环戊酮;芳香化合物,例如二甲苯、甲苯或苯;醚,例如二丙烯甲基醚;或脂肪烃,例如二氯甲烷或氯仿,可以是其中单独一种或两种以上的混合物。
基于100重量份的遮光材料,溶剂的含量可以为40至90重量份。在此情况下,如果溶剂的含量为40重量份以上,则可获得以下优点:容易形成1μm以下的薄膜厚度。如果溶剂的含量为90重量份以下,则可获得以下优点:容易形成200nm以上的薄膜厚度。
除了上述成分之外,本发明实施方式的遮光材料还可包含功能性添加剂,例如,用于诱导遮光材料分散的表面活性剂、用于加速硬化的硬化加速剂、和用于防止氧化的抗氧化剂。
表面活性剂涂覆在纳米颗粒的表面上,并且可用于引起空间斥力。表面活性剂可吸附在纳米颗粒的表而上,并可用于形成稳定的胶体分散液,且还可充当偶联剂。能够诱导本发明实施方式的遮光材料所含的纳米颗粒分散的表面活性剂可包括阴离子表面活性剂、阳离子表面活性剂、两性(amphiprotic)表面活性剂和非离子表面活性剂。
烷基磺酸(磺酸盐)、烷基硫酸(硫酸盐)、芳烷基和烷芳基负离子表面活性剂、烷基琥珀酸(琥珀酸盐)或烷基磺基琥珀酸盐可以用作阴离子性表面活性剂。特别是,烷芳基磺酸、烷基硫酸、烷芳基硫酸的钠、镁、铵、单乙醇胺、二乙醇胺和三乙醇胺盐可以用作阴离子性表面活性剂。铵盐或胺衍生物可用作阳离子表面活性剂。胺盐类阳离子表面活性剂可包括聚氧乙烯烷基胺,并且烷基季铵类阳离子表面活性剂可包括四烷基铵和吡啶鎓盐。例如,季铵类阳离子表面活性剂可包括烷基三甲基铵盐,例如,鲸蜡基三甲基溴化铵(CTAB)、十六烷基三甲基溴化铵和鲸蜡基三甲基氯化铵(CTAC)、鲸蜡基氯化吡啶鎓(CPC)、氯化苯甲烷铵(BAC)、苄索氯铵(BZT)、5-溴-5-硝基-1,3-二噁烷、二甲基二(十八烷基)氯化铵和二(十八烷基)甲基溴化铵(DODAB)。
两性表面活性剂包括椰油基两性羧基甘氨酸盐、椰油基两性羧基丙酸盐、椰油基甜菜碱、N-椰油酰氨基丙基二甲基甘氨酸和N-月桂基-N-羧基甲基-N-(2-羟基乙基)乙二胺。其他合适的两性表面活性剂包括环季亚胺酯和甜菜碱,例如,α-(十四烷基二甲基氨)乙酸酯、β-(十六烷基二乙基氨)丙酸酯和γ-(癸基二甲基氨)丁酸酯和磺内酯,例如,3-(十二烷基二甲基氨)-丙烷-1-磺酸酯和3-(十四烷基二甲基氨)乙烷-i-磺酸酯。
此外,非离子表面活性剂可选自包括以下物质的组:脂肪酸链烷醇酰胺表面活性剂和胺氧化物表面活性剂。脂肪酸链烷醇酰胺表面活性剂是通过利用链烷醇胺与脂肪酸或脂肪酸酯之间的反应形成酰胺而获得的非离子表面活性剂,所述链烷醇胺例如为单乙醇胺、二乙醇胺、单异丙醇胺或二异丙醇胺。脂肪酸链烷醇酰胺表面活性剂可包括例如:脂肪酸二乙醇酰胺,例如,异硬脂酸二乙醇酰胺,月桂酸二乙醇酰胺,癸酸二乙醇酰胺,椰子脂肪酸二乙醇酰胺,亚油酸二乙醇酰胺,肉豆蔻酸二乙醇酰胺,油酸二乙醇酰胺和硬脂酸二乙醇酰胺;脂肪酸单乙醇酰胺,例如,椰子脂肪酸单乙醇酰胺;和脂肪酸单异丙醇酰胺,例如,油酸单异丙醇酰胺和月桂酸单异丙醇酰胺。
除了上述表面活性剂以外,还可以使用由聚硅氧烷制成的硅系表面活性剂。例如,可以由聚醚改性的有机硅氧烷制造硅类表面活性剂。聚醚改性的二甲基聚硅氧烷的共聚物可用作硅类表面活性剂。上述表面活性剂可以单独使用,也可以使用其两种以上的混合物。表面活性剂的含量可以根据所用的纳米颗粒和溶剂的类型以及它们的含量而变化,但基于100重量份的遮光材料,表而活性剂的含量可以为0.01至0.5重量份。
硬化加速剂包括:胺,特别是二甲基苯胺,特别是叔胺(例如,单乙基胺、三甲基胺和辛基二甲基胺),和三氟化硼或三氯化硼的复合化合物(例如,二甲基苯胺和三氟化硼的复合化合物)。另外,硬化加速剂可包括选自以下物质中的一种或两种以上的混合物:例如,叔胺类,例如,1,1′-亚甲基二(3-甲基哌啶)(MBMP)、二甲基苯甲基胺(DMBA)、三(二甲基氨基甲基)苯酚(TDMAMP)、六亚甲基四胺和1,6-二(二甲基氨基)己烷;脲衍生物,例如,N-4-氯苯基-N′,N′-二甲基脲(灭草隆),N-3-氯-4-甲基苯基-N′,N′-二甲基脲(氯麦隆),N-(2-羟基苯基)-N′,N′-二甲基脲,和N-(2-羟基-4-硝基苯基)-N′,N′-二甲基脲;取代或未取代的咪唑类,例如,咪唑,苯并咪唑,1-甲基咪唑,3-甲基咪唑,1,2-二甲基咪唑,2-乙基-4-甲基咪唑,1-乙烯基咪唑,2-乙烯基咪唑,2-苯基咪唑,2-苯基-4-甲基咪唑,1-(2,6-二氯苯甲酰基)-2-苯基咪唑,和1-(2,4,6-三甲基苯甲酰基)-2-苯基咪唑;和有机膦类,例如,三苯基膦。硬化加速剂含量可以根据遮光材料中所包含的纳米颗粒和溶剂的类型及含量而变化,但基于100重量份的遮光材料,可以为0.01至0.1重量份。
此外,抗氧化剂可包括具有支链的酚类或羟基肉桂酸酯/盐类物质,抗氧化剂可用于降低或阻止由热导致的组合物的氧化反应,并赋予热稳定性,但本发明不限于此。例如,抗氧化剂可包括选自以下物质中的一种或多种:四(亚甲基-(3,5-二叔丁基-4-羟基肉桂酸酯))甲烷、3,5-二(1,1-二甲基乙基)-4-羟基苯丙酸硫醇二-2,1-亚乙基酯、十八烷基3,5-二叔丁基-4-羟基肉桂酸酯、2,6-二叔丁基对甲基苯酚、2,2-硫基二(4-甲基-6-叔丁基苯酚)和2,6-叔丁基苯酚,但本发明不限于这些抗氧化剂。抗氧化剂的含量可以根据遮光材料中所包含的纳米颗粒和溶剂的类型及含量而变化,但相对于遮光材料可以为0.01至0.3重量份。
本发明实施方式的遮光材料还可以包括金属醇盐(M(OR)x)。金属醇盐可用于为遮光层的低反射特性产生光学散射效应。金属醇盐中可使用的金属可包括具有优异反射性的铝(Al)、铜(Cu)、钼(Mo)、钛(Ti)、银(Ag)或金(Au)。
如上所述,形成本发明实施方式遮光层的遮光材料包括芯-壳结构的纳米颗粒、粘合剂和用于分散纳米颗粒和粘合剂的溶剂,并且可包括其他添加剂。
下面描述本发明实施方式的遮光材料。以下实施例仅用于说明本发明的一些实施方式,本发明不限于以下实施例。
制造纳米颗粒
〈实施例1〉
将1g聚(N-乙烯基吡咯烷酮(PVP))于室温下溶于100g乙醇。在将1gCrO2颗粒放入溶液中并搅拌1小时后,通过过滤和干燥工序形成经PVP表面处理的芯颗粒。然后,将1.0g经表面处理的芯颗粒投入100g乙醇(甲醇)中,并在该溶液中加入氨水溶液从而使溶液变为pH11。接下来,在室温下在氮气氛围中将0.8g正硅酸四乙酯(TEOS)投入溶液,并搅拌12小时。通过过滤和干燥工序制得芯-壳结构的纳米颗粒。图4A和4B是所制造的纳米颗粒的图像。
遮光材料的各芯材料的耐热性测试
〈实施例2〉
在与实施例1相同的工艺条件下用炭黑颗粒替代CrO2颗粒制造了芯-壳纳米颗粒。将所制造的芯-壳纳米颗粒混合在硅氧烷粘合剂和溶剂中,以制得遮光材料。
为了检查实施例1和2制造的遮光材料的耐热性,进行热重分析TGA,其结果如图5A(实施例2)和图5B(实施例1)所示。此外,为了检查实施例1和2制造的遮光材料的烟雾(fume)产生,测量了吹扫捕集质谱(P&TMS),其结果如图6A(实施例2)和图6B(实施例1)所示。
图5A和5B显示出,利用炭黑颗粒的实施例2的遮光材料的重量在150℃至350℃的加温阶段中的总减少为9.62%,而利用CrO2颗粒的实施例1的遮光材料的重量在150℃至350℃的加温阶段中的总减少为0.38%以下,并且具有优异的耐热性。
此外,图6A和6B显示出,利用炭黑颗粒的实施例2的遮光材料中产生的烟雾量为1.2E+10以上,而在利用CrO2颗粒的实施例1的遮光材料中没有检测到烟雾,因此利用CrO2颗粒的实施例1的遮光材料具有优异的可靠性。(注:“参照”是指利用以下物质制造的有机绝缘膜:其中,将总共15重量份的丙烯酸树脂、粘合剂苯甲基丙烯酸(BAA)、甲基丙烯酸甲酯(MM)和缩水甘油基甲基丙烯酸酯(GM)、5重量份的光引发剂(1-羟基环己基)苯基甲酮和80重量份的溶剂PGMEA混合,并且该物质中不包含炭黑颗粒或纳米颗粒)。
粘合剂的耐热性比较
对两种硅氧烷物质和两种倍半硅氧烷物质进行热重分析TGA,其结果如表1所示。测定P&TMS,其结果如图7所示。
表1
参考表1,两种硅氧烷物质的重量减少为2.79%和2.32%,两种倍半硅氧烷物质的重量减少为0.07%和0.25%。
此外,参考图7,与“参照”相比,两种硅氧烷物质中所产生的烟雾量分别为2.50E+09和2.00E+09以上,而两种倍半硅氧烷物质中所产生的烟雾量为1.50E+09和1.00E+09以下。
根据以上结果可以看出倍半硅氧烷比硅氧烷具有更好的耐热性和烟雾产生特性。
制造遮光层
〈实施例3〉
将在与实施例1相同的工艺条件下制造的1g纳米颗粒、25.5gTEOS、20gPGMEA和53.5gDI水混合,从而制得遮光材料。将遮光材料以2μm的厚度旋涂在玻璃基板上并固化,从而完成了遮光层。
〈实施例4〉
在与实施例3相同的工艺条件下用PVP替代TEOS形成壳,从而制造遮光层。
〈实施例5〉
在与实施例3相同的工艺条件下用丙烯酸系树脂(Acryl)替代TEOS形成壳,从而制造遮光层。
〈实施例6〉
在与实施例3相同的工艺条件下用倍半硅氧烷替代TEOS形成壳,从而制造遮光层。
对按照实施例3至6制造的遮光层的表面电阻、反射率和透光率进行测量,测量结果如表2所示。在以下描述中,“基板表面”表示基板底部的反射率,“涂层表面”是指遮光层表面的反射率。
表2
根据表2可以看出,实施例3和6的包含由SiO2无机物质制成的壳的纳米颗粒与实施例4和5的包含由例如丙烯酸系树脂或PVP等有机物质制成的壳的纳米颗粒相比,具有更高的表面电阻和比电阻,但具有更低的反射率。此外可以看出,实施例3和6的透光率接近包含炭黑颗粒的实施例4和5的透光率,并具有优异的遮光特性。特别是,可以看出包含倍半硅氧烷的实施例6因为反射率和透过率低而比包含硅氧烷的实施例3具有更好的遮光特性。
遮光材料的耐热性比较
对按照实施例3和实施例6制造的遮光材料进行热重分析TGA,分析结果如表3和图8所示。测量P&TMS,测量结果如图9所示。
表3
参考表3和图8,实施例3的重量减少为0.38%,实施例6的重量减少为0.25%。此外,参考图9,与“参照”相比,实施例3中烟雾产生量为1.20E+09,实施例6中烟雾产生量为4.00E+08以下。
根据这些结果可以看出,利用倍半硅氧烷作为粘合剂的遮光材料比利用硅氧烷作为粘合剂的遮光材料具有更好的耐热性和烟雾产生特性。
遮光层图案的测量
在根据实施例6制造的遮光层为600nm后,利用临界尺寸(CD)为10μm的掩模形成遮光层图案。利用4倍放大和10倍放大的光学显微镜测量掩模和遮光层图案,测量结果如图10所示。遮光层图案的SEM图像如图11所示。此外,测量遮光层图案对波长为400至700nm的光的反射率,测量结果如图12所示。
根据图10和11,与掩模的10μm的CD相符,遮光层图案的CD准确地为10μm,并且遮光层图案的边缘部分的形状清晰。此外,根据图12,可以看出遮光层图案对波长为400至700nm的光的反射率为4.95。
根据以上结果可以看出,用本发明实施方式的遮光材料制成的遮光层具有准确的图案和非常低的反射率。
如上所述,本发明实施方式的遮光材料的优点在于:其耐热性优异,原因是其具有多个纳米颗粒,该纳米颗粒包含由黑色金属氧化物制成的芯和绝缘壳;其可靠性优异,原因是不会产生烟雾。
另外,用本发明实施方式的遮光材料制成的遮光层的优点在于:其遮光性优异,原因是表面电阻和比电阻高并且其反射率和透光率低。此外,包含本发明实施方式的遮光层的显示装置优点在于:显示装置可具有改进的显示品质,并且可省略用于阻止反射的偏光板。
对于本领域技术人员显而易见的是,可以根据本发明进行各种修改和变化而不背离本发明的实质或范围。因此,本发明意在涵盖处于所附权利要求及其等同方式的范围内的本发明的各种修改和变化。
Claims (20)
1.一种遮光材料,其包含:
多个纳米颗粒,每个纳米颗粒均具有芯和在所述芯外的壳;和
粘合剂和溶剂,
其中,所述芯包含金属氧化物,并且所述壳包含绝缘材料。
2.如权利要求1所述的遮光材料,其中,所述金属氧化物是铜锰氧化物(CuMnOx)、铜(铬,锰)氧化物(Cu(Cr,Mn)xOy)、铜(铬,铁)氧化物(Cu(Cr,Fe)xOy)和(铁,锰)(铁,锰)氧化物((Fe,Mn)(Fe,Mn)xOy)中的一种。
3.如权利要求1所述的遮光材料,其中,所述绝缘材料是硅氧烷、硅氧化物(SiOx)、硅氮化物(SiNx)、氧化钛(TiO2)和硅烷中的一种。
4.如权利要求1所述的遮光材料,其中,所述粘合剂包含能够经受350℃以下的过程的高耐热溶液型物质。
5.如权利要求4所述的遮光材料,其中,所述粘合剂包含倍半硅氧烷(SSQ)。
6.一种显示装置,其包含:
基板上的多个像素;和
在所述基板上的限定或划分所述多个像素的遮光层,
其中,所述遮光层包含多个纳米颗粒,每个纳米颗粒均具有芯和在所述芯外的壳,
其中,所述芯包含金属氧化物,并且所述壳包含绝缘材料。
7.如权利要求6所述的显示装置,其中,所述金属氧化物是铜锰氧化物(CuMnOx)、铜(铬,锰)氧化物(Cu(Cr,Mn)xOy)、铜(铬,铁)氧化物(Cu(Cr,Fe)xOy)和(铁,锰)(铁,锰)氧化物((Fe,Mn)(Fe,Mn)xOy)中的一种。
8.如权利要求6所述的显示装置,其中,所述绝缘材料是硅氧烷、硅氧化物(SiOx)、硅氮化物(SiNx)、氧化钛(TiO2)和硅烷中的一种。
9.如权利要求6所述的显示装置,其中,所述遮光层还包含粘合剂,所述粘合剂包含能够经受350℃以下的过程的高耐热溶液型物质。
10.如权利要求9所述的显示装置,其中,所述粘合剂包含倍半硅氧烷(SSQ)。
11.如权利要求6所述的显示装置,其中,每个像素都具有:薄膜晶体管,和所述薄膜晶体管的包含氧化物半导体的有源层。
12.如权利要求6所述的显示装置,其中,所述遮光层具有3.2×1012以上的表面电阻。
13.如权利要求6所述的显示装置,其中,所述遮光层对于350nm至500nm的光具有1.59%以下的透光率,并且对于550nm的光具有2.03%以下的透光率。
14.如权利要求6所述的显示装置,其中,所述遮光层对于400nm至700nm的光具有7.56%以下的反射率。
15.如权利要求6所述的显示装置,其中,所述显示装置是有机电致发光显示器,并且所述遮光层用作所述多个像素之间的堤层。
16.如权利要求6所述的显示装置,其中,所述显示装置是液晶显示器,并且所述遮光层用作所述多个像素之间的黑底。
17.如权利要求6所述的显示装置,其中,所述芯的尺寸为10nm至100nm。
18.如权利要求6所述的显示装置,其中,所述壳以1nm至50nm的厚度包围所述芯。
19.如权利要求6所述的显示装置,其中,所述遮光层还包含金属醇盐(M(OR)x)。
20.如权利要求19所述的显示装置,其中,所述金属醇盐中的金属是铝(Al)、铜(Cu)、钼(Mo)、钛(Ti)、银(Ag)和金(Au)中的一种。
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