CN107257941A - 电控干涉滤色片及其用途 - Google Patents

电控干涉滤色片及其用途 Download PDF

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CN107257941A
CN107257941A CN201580073372.XA CN201580073372A CN107257941A CN 107257941 A CN107257941 A CN 107257941A CN 201580073372 A CN201580073372 A CN 201580073372A CN 107257941 A CN107257941 A CN 107257941A
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阿诺·西博特
德特勒夫·勒奇
克里斯汀·拉贝
彼得·弗拉奇
马蒂亚斯·吉特内尔
哈根·巴尔奇
勒内·德拉·巴雷
罗兰·巴特曼
迈克尔·韦格赫尔
斯蒂芬·布伦斯
托马斯·诺伊贝特
约翰娜·费舍尔
格哈德·朔特纳
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Abstract

本发明涉及一种电控干涉滤色片，其具有至少两个透明电极、至少一个向列型液晶层以及用于所述液晶取向的取向层。通过施加电场，可以实现所述液晶的再取向和伴随再取向的所述干涉滤色片的透射波长范围的位移。

Description

电控干涉滤色片及其用途
技术领域
本发明涉及一种电控干涉滤色片，其具有至少两个透明电极、至少一个向列型液晶层以及用于所述液晶取向的取向层。通过施加电场，可以实现所述液晶的再取向和伴随再取向的所述干涉滤色片的透射波长范围的位移。
背景技术
通常有两种类型的滤色片：干涉滤色片和吸收滤色片。电控滤色片只基于干涉原理。但是已知类型的干涉滤色片的操作模式和光学特性部分地有很大不同。基于Lyot原理的电控滤色片可由LOT公司以商品名“VariSpec filter”商购获得。Lyot滤色片由双折射材料的层结构和随后的偏振滤色片组成。如果入射的光未被线性偏振，则前接附加的偏振滤色片。单级Lyot滤色片既不实用也不是商购可得。串联的Lyot滤色片越多，自由光谱范围越大。在“VariSpec滤色片”的情况下，液晶单元被用作电控双折射材料，并且通常串联12个或更多个Lyot滤色片以形成滤色片叠层。作为构造条件，由此产生几厘米(通常1.5英寸＝3.8厘米)的滤色片厚度。复杂的构造方法和长切换时间(>50ms)是“VariSpec滤色片”的另一个缺点。在DE3727655A1中描述了一种电控调制滤色片，其包括具有手性近晶C相的铁电液晶材料。通过所述铁电液晶在电场中的再取向，事实上所述调制滤色片的透射率在可见光谱范围内变化，对波长敏感而不会获得特定波长下的有效阻挡。例如在US2003/0075721A1或US2008/0030635A1中描述的基于螺旋胆甾醇型LC排布的滤色片以及如US3，693，115中描述的所有可机械控制的滤色片对于运动图像是不可行的。
发明内容
由此开始，本发明的目的是提供一种电控干涉滤色片，其中可以省去偏振滤色片的使用，并且可以通过电气控制来影响非偏振光的透射。
通过具有权利要求1的特征的电控干涉滤色片实现该目的。在权利要求13和14中，描述了根据本发明的用途。
根据本发明，提供了具有至少两个透明电极、至少一个取向层以及向列型液晶层的电控干涉滤色片。所述向列型液晶层和所述至少一个取向层直接接触，使所述液晶能够取向。通过施加电场，所述干涉滤色片的透射波长范围可以通过所述向列型液晶层中的液晶的再取向发生位移。
所述向列型液晶层优选具有100nm至1000nm，特别是500至900nm范围内的层厚。因此所述干涉滤色片的两条相邻谐振线之间的间隔与所述向列型液晶层的层厚以及所述至少一个取向层的层厚成反比。为了在可见光范围内获得两条谐振线之间足够宽的自由光谱范围，该层厚必须小于2λ/n。
原则上，所有向列型液晶结构或其混合物都适合作为液晶：优选的结构是联苯类、三联苯类、四联苯类和二苯乙炔类，例如，亚联苯基、亚三联苯基(terphenylene)、亚四联苯基(quaterphenylene)、二苯乙炔或其混合物的氰基氰酸酯、氟代氰酸酯、异硫氰酸酯。由于所述滤色片的波长偏移随着Δn＝ne-n0的增加而增加，所以ne和n0之间的差应当尽可能大。应当期望达到至少5％的数值，优选10％和更大。
对于本领域技术人员来说，具有正或负介电常数的向列相的选择显然与闭合模式(off-mode)下的所述液晶的均匀的平面取向或垂直取向直接相关(尤其参见M.Schadt等人，Nature，381，212，1996；或A.Seeboth，Displays，20，131，1999)。所述取向层优选是单分子的。根据光学定律(C.K.Madsen和J.H.Zhao，光学滤色片设计和分析(Optical FilterDesign and Analysis)，John Wiley&Sons，Inc.1999)，由所述液晶层(106)和所述取向层(105)的厚度构成的介电反射层(103)之间的间隔对于滤色片必须等于/小于2λ/n。随着所述取向层的层厚增加，滤色片效果相应地受到不利影响。此外，所述取向层优选地化学共价键合到相邻的固体表面，如在US 4,842,375中已经对于非单分子的取向层所描述的。对于单分子取向层，化学表面固定代表了额外的要求。为了将所述取向层固定到金属氧化物表面(例如SiO2、Ta2O5、Nb2O5或TiO2)，一方面，绝对必须有化学活性官能团F如O-、COO-、NH2-、SiX4-、Si(OX)4-或SiXn(OX)4-n基团(X＝H、CH3、C2H5、卤素如F、Cl、Br、I)，这些基团可以与反射层中的如Si-O-Si或Ti-O-Ti基团反应形成共价键，如H.H.Dunken等人，PhysikalischeChemie der (玻璃表面的物理化学)(Physical Chemistry of the GlassSurface)，VEB German Press for Basic Material Industry 1981内的详细描述。另一方面，这些具有所述官能团的结构单元必须既不负面影响所述取向层的形貌也不负面影响其界面张力γOS。否则将不再能确保所述液晶的均匀取向和足够的有序程度。所述向列型液晶通过毛细力的填充过程同样是不可能的。根据本发明，可以以已知方式测定的所述取向层的界面张力γOS和所述液晶的界面张力γLC(A.Seeboth等人，胶体和表面A(Colloidsand Surfaces A)，78，177，1993)优选最大范围地相同：Δγ＝γOS-γLC≈0。
用于所述取向层的合适的基本结构是具有光活性乙烯基团的化合物，例如香豆基-、苯基丙烯酰基-、3-(2-呋喃基)丙烯酰基-、3-(2-噻吩基)丙烯酰基-和反式-芪衍生物，如图2a所示，其中Ar表示苯基、萘基、蒽基、呋喃基、噻吩基或任何其它芳族基团。然而，为了将所述取向层固定到所述金属氧化物表面，该基本结构还需要另外的附加官能团F，其通过间隔基S或偶联到如图2b的芳族核上，或偶联到如图2c的主分子的脂肪族部分的任何点上。显然，图2c中的间隔基也可以键合在其它地方，例如如图2d所示。此外，对于分子设计可以使用所有可能的其它组合，例如既偶联到脂族分子部分也偶联到芳族分子部分，如图2e所示。图2a-2e中记作R1、R2、R3、R4的取代基代表例如氢、卤素(F、Cl、Br、I)、烷基、烷氧基、环烷基、苯基、萘基、蒽基、呋喃基、噻吩基或任何其它芳族基团。所述间隔基S优选是具有2-8个碳原子的烃链，其可以例如通过酰胺、醚或酯桥中断。所述官能团F优选为O-、COO-、NH2-、SiX4-、Si(OX)4或SiXn(OX)4-n基团(X＝H、CH3、C2H5、卤素如F、Cl、Br、I)。
每个取代基R1、R2、R3、R4可以仅是本身或以R1、R2、R3、R4之间的任何组合出现。
优选地，所述向列型液晶层在两个表面分别与一个取向层直接接触。
此外，优选所述干涉滤色片包括具有至少一个接纳所述向列型液晶层的凹部的定距层。因此，可以通过所述定距层调节所述向列型液晶层的层厚。因此优选以喷镀法生成所述定距层，由此使得可以在个位数nm范围内精确地调节所述定距层的层厚。
更优选的实施方案提供了所述干涉滤色片具有至少一个介电反射层。
所述介电反射层优选地由低折射材料和高折射材料的交替成对的层组成，n是正整数。作为低折射材料，可以使用例如在589nm处折射率为1.46的SiO2，和作为高折射材料可以使用在589nm处折射率在2.15和2.45之间的Ta2O5、Nb2O5或TiO2。所述介电材料的选择对于可见光谱范围是经优化的。
对于所述介电反射层的排布，存在三种变型。在第一种变型的情况下，所述介电反射层可以设置在朝向所述向列型液晶层的透明电极侧。第二种变型提供了所述介电反射层设置在远离所述向列型液晶层的透明电极侧和第三种变型涉及在所述介电反射层中透明电极的集成。
优选所述透明电极包括透明导电材料或由其组成。
其例子是氧化铟锡(ITO)、铝掺杂氧化锌(AZO)、氧化氟锡(FTO)、氧化锑锡(ATO)、石墨烯、银纳米线和碳纳米管。
根据本发明的主题旨在参考随后的附图和实施例更详细地说明，而不希望将所述主题限于本文示出的特定实施方案。
附图说明
图1示出了根据本发明的干涉滤色片的示意结构。
图2示出了对于所述取向层根据本发明使用的组分的多种结构。
图3示出了在不用于光透射的光谱范围内根据本发明的干涉滤色片的透射范围的位移，参见示意图。
在图1中示出了根据本发明的干涉滤色片，该滤色片有两个取向层(105)和(105')，在其之间设置了向列型液晶层(106)。所述向列型液晶层(106)的厚度由周围的定距层(104)规定。在所述取向层(105)和(105')的远离所述向列型液晶层(106)的一侧，分别设置介电反射层(103)和(103')。在其上依次沉积透明电极(102)和(102')。此外，根据本发明的干涉滤色片还有外部载体层(101)和(101')。
实施例1
实施例1涉及为波长575nm的绿光设计的电控干涉滤色片。
为了本实施例，使用 Glas&Optik GmbH公司的商业ITO玻璃(CEC050P)，其表面电阻为40Ω/□。所述ITO玻璃的透射率在450nm时为80％，在700nm时为87％。分别用为575nm的波长设计的介电反射层(103)涂覆两个这样的ITO玻璃。所述介电反射层由四个SiO2层和四个Ta2O5层组成，它们以SiO2开始以交替层序列进行喷镀(S[HL]^4H-575nm)。
随后，在具有反射层的两个生成的ITO玻璃的第一个上，将反式-3-(3-(5-氯戊氧基)苯基)丙烯酸苯酯以浸渍法共价键合到所述反射层表面，结果形成具有光活性乙烯基团的单分子有机层。通过用线性偏振光进行光化学交联，由此生成所述取向层(105)的结构化表面。椭圆偏光测量表明：正如对于单分子层所预期的，取向层的厚度低于2nm的受工艺影响的检测极限。
在带有反射层的第二个ITO玻璃上，将定距层(104)以两个腹板(Steg)的形式施加在基体的相对两端。因此在所述基体的中心形成凹部，在两个半电池(half-cells)(ITO玻璃+反射层+取向层/ITO玻璃+反射层+定距层)组装之后，形成了填充有所述液晶层(106)的空腔。为了能够精确地调节所述超薄定距层(104)，并因此调节得到的超薄液晶层(106)，以喷镀法生成所述定距层，其中所述空腔表面被掩模覆盖。对于本实施方案，喷镀SiO2形成753nm的层厚。生成近似753nm的LC层。
根据传统的LCD组装技术，平面平行地连接两个半电池(ITO玻璃+反射层+取向层/ITO玻璃+反射层+定距层)形成干涉滤色片。
在最后一步中，用向列型液晶填充所述干涉滤色片的空腔。在本实施方案中，为此目的使用共晶液晶混合物，该混合物在室温下具有Δn＝6％的向列相，其适应于所述取向层的界面张力为Δγ＝γOS-γLC＝0.8mN/m。
可以通过施加11V的电压将因此生成的滤色片连接到其ITO电极上。所述滤色片的切换时间在μs/ms范围内，其中t开＝580μs和t关＝1.33ms。如果使用中心波长为575nm的单色光或窄带光(LED或激光二极管)作为背光，则电池的切换效果与肉眼清晰可见的绿色至黑色的切换效果相关。在“关”状态下，所述滤色片对于波长为575nm的光是透明的，而在“开”状态下，实际上完全阻挡了背光。“开”状态下的透射波长处于未使用的光谱范围内。对于520nm至600nm的波长范围，所述滤色片在“关”和“开”状态下的透射光谱示于图3。这些光谱用非偏振光测量。
在“关”状态下，所述滤色片在观察到的波长范围内具有最大值为545nm和575nm的两个透射峰。它们之间的范围被定义为自由光谱范围。作为施加电压的函数，所述峰从575nm连续位移到545nm。
实施例2
实施例2是为波长450nm的蓝光设计的电控干涉滤色片。类似于实施方案1制备实施方案2。为了适应改变的透射波长，首先将反射层(103)的SiO2和Ta2O5层的厚度改变为76.36nm(SiO2)/51.07nm(Ta2O5)，其次间隔层(spacer layer)的厚度为558nm。这样生成的滤色片在其ITO电极处于9.2V电压处切换。使用单色背光，所述滤色片从蓝色切换到黑色。同样如实施方案1，切换效果肉眼清晰可见。
实施例3
实施例3是为波长632nm的红光设计的电控干涉滤色片。类似于实施方案1，同样制备实施方案3，其中SiO2和Ta2O5层的厚度适应为反射层95.53nm(SiO2)/64.12(Ta2O5)和间隔层的厚度适应为798nm。这样生成的滤色片在其ITO电极处于11.9V电压处切换。使用单色背光，所述滤色片从红色切换到黑色。同样如实施方案1和2，切换效果肉眼清晰可见。
对于本领域技术人员很显然，通过改变选择向列型液晶(Δn、Δε、粘度的改变)、反射层构型和层材料(反射层的组成对数、层厚和层的介电性质)、所述液晶层的厚度、单分子取向层的化学结构(界面性质的改变)，电控滤色片的切换时间和阈值电压既可以位移到较高的值也可以位移到较低的值。同样明显的是：波长的最大位移范围取决于Δn，并且可以通过电压可变地控制使用的位移范围。这些实施方案可以以单个滤色片或以RGB滤色片使用，也可以以矩阵形式使用。

Claims (14)

1.电控干涉滤色片，包括至少两个透明电极(102，102')、至少一个取向层(105，105')以及向列型液晶层(106)，其中所述向列型液晶层(106))和至少一个取向层(105,105')直接接触用于所述液晶的取向，其中通过施加电场，所述干涉滤色片的透射波长范围通过所述液晶的再取向可位移。
2.根据权利要求1的干涉滤色片，其中所述向列型液晶层(106)具有100nm至1，000nm范围内，特别是500nm至900nm范围内的层厚。
3.根据权利要求1或2之一的干涉滤色片，其中所述向列型液晶层(106)包括液晶，优选自联苯类、三联苯类、四联苯类和二苯乙炔类，例如亚联苯基、亚三联苯基、亚四联苯基或二苯乙炔的氰基氰酸酯、氟代氰酸酯或异硫氰酸酯。
4.根据权利要求1至3之一的干涉滤色片，其中所述向列型液晶层(106)在两个表面上分别与一个取向层(105，105')直接接触。
5.根据权利要求1至4之一的干涉滤色片，其中所述至少一个取向层(105，105')优选自光活性乙烯基团，特别是香豆基-、苯基丙烯酰基-、2-(2-呋喃基)丙烯酰基-3-(2-噻吩基)丙烯酰基-和反式-芪衍生物。
6.根据权利要求1至5之一的干涉滤色片，其中所述至少一个取向层(105，105')是单分子的并且化学共价键合到所述至少一个介电反射层(103，103')。
7.根据权利要求1至6之一的干涉滤色片，其中所述至少一个取向层(105，105')的界面张力基本上与所述向列型液晶层(106)的界面张力相当，其界面张力差最大为1mN/m。
8.根据权利要求1至7之一的干涉滤色片，其中所述干涉滤色片具有定距层(104)，所述定距层具有接纳所述向列型液晶层(106)的至少一个凹部。
9.根据权利要求1至8之一的干涉滤色片，其中所述干涉滤色片具有至少一个介电反射层(103，103')。
10.根据权利要求9的干涉滤色片，其中所述至少一个介电反射层(103，103')由若干对层组成，所述层由折射率<1.5的材料特别是SiO2和折射率>2.0的材料特别是Ta2O5、Nb2O5或TiO2制成。
11.根据权利要求9或10之一的干涉滤色片，其中所述介电反射层(103，103')集成在所述透明电极(102，102')朝向所述向列型液晶层(106)的一侧、集成在所述透明电极远离所述向列型液晶层(106)的一侧或所述透明电极(102，102')集成在介电反射层(103，103')内。
12.根据权利要求1至11之一的干涉滤色片，其中所述透明电极(102，102')包括透明导电材料或由其组成，特别是氧化铟锡(ITO)、铝掺杂氧化锌(AZO)、氧化氟锡(FTO)、氧化锑锡(ATO)、石墨烯、银纳米线和碳纳米管。
13.根据权利要求1至12之一的干涉滤色片作为用于规定波长范围的可切换阻隔滤色片的用途。
14.根据权利要求13的用途，其中所述干涉滤色片用于背景光，特别是来自光二极管或激光二极管的可切换阻隔和透射。
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