WO2021175034A1 - 复合粒子及包含复合粒子的调光器件 - Google Patents

复合粒子及包含复合粒子的调光器件 Download PDF

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WO2021175034A1
WO2021175034A1 PCT/CN2021/073061 CN2021073061W WO2021175034A1 WO 2021175034 A1 WO2021175034 A1 WO 2021175034A1 CN 2021073061 W CN2021073061 W CN 2021073061W WO 2021175034 A1 WO2021175034 A1 WO 2021175034A1
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inner core
composite particle
composite
particle
particles
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PCT/CN2021/073061
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English (en)
French (fr)
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王耀
谷小虎
邱运昌
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江苏集萃智能液晶科技有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • 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 
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13731—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a field-induced phase transition
    • G02F1/13737—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a field-induced phase transition in liquid crystals doped with a pleochroic dye
    • G—PHYSICS
    • G02—OPTICS
    • 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 
    • G02F1/17—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 variable-absorption elements not provided for in groups G02F1/015 - G02F1/169

Definitions

  • the present invention relates to composite particles having a core-shell structure, and in particular to composite particles having dichroism and a dimming device containing the composite particles.
  • PDLC smart glass and electrochromic smart glass are more mature. Among them, PDLC smart glass can only switch between transparency and haze, and cannot achieve the effects of shading and heat insulation, while electrochromic smart glass Glass has problems such as complex film process and slow response time (8-20s).
  • SPD light valve technology Another more mature technology is the SPD light valve technology.
  • the suspended particles By suspending suspended particles in the dimming layer, the suspended particles perform Brownian motion without applying an electric field, thereby absorbing, scattering or reflecting incident light to make SPD light
  • the valve presents a dark state; when an electric field is applied, the suspended particles are polarized and arranged in a straight line according to the direction of the electric field, so that most of the incident light can use the dimming layer, and the SPD light valve presents a bright state, such as US patent application US5650872A Revealed.
  • the shape and size of the suspended particles are very important for the later effect.
  • both the shape and size of suspended particles cannot be precisely controlled.
  • the US patent application US5368780A mentions a method for preparing iodine nanorods, but the size of the nanorods is large and does not Evenly. At the same time, the conventionally prepared suspended particles have a single size and shape, resulting in a single color, which cannot meet various needs.
  • one aspect of the present invention provides a composite particle comprising an inner core and an outer shell, wherein the inner core has an aspherically symmetrical shape, and the outer shell is composed of a material different from that of the inner core.
  • the shape of the inner core is regularly distributed, so that the composite particles have optical dichroism and dielectric anisotropy.
  • the shape of the inner core is rod-like, ribbon-like, sheet-like, needle-like, thread-like or disc-like.
  • the size of the shortest axis of the inner core is 0.1-100 nanometers. In another preferred embodiment, the size ratio of the longest axis to the shortest axis of the inner core is 2:1-50:1.
  • the material of the inner core is metal and its compound, non-metallic inorganic substance or organic substance.
  • the material of the outer shell is anisotropic metal particles, semiconductor crystals, metal transition chalcogenides, carbon nanotubes, dichroic dyes or alkaloid polyhalide particles.
  • the alkaloid polyhalides are pyrroles, thiazoles, imidazoles, pyrazoles, pyridines, pyrimidines, quinines, pyrazines, phenanthrolines or purine compounds. halide.
  • the alkaloid polyhalide is an alkaloid polyiodide.
  • the dichroic dyes include azo, oligothiophene, and anthraquinone dyes.
  • the present invention also provides a dimming device comprising the above-mentioned composite particles.
  • the dimming device includes a first transparent base layer, a first transparent conductive layer, a dimming layer, a second transparent conductive layer, and a second transparent base layer, wherein the dimming device
  • the layer includes composite particles, a particle stabilizer and a dispersion medium, and the composite particles are suspended in the dispersion medium.
  • the size of the longest axis of the composite particle is 10-1000 nanometers.
  • the size and aspect ratio of the final composite particles can be effectively controlled to make them have structural anisotropy; by using the optical dichroism of the shell material
  • the final composite particles have both optical dichroism and dielectric anisotropy, and can provide rich colors, making them more widely used in dimming devices.
  • Figure 1 is a schematic diagram of the structure of a composite particle provided by the present invention.
  • FIG. 2 is a schematic diagram of the structure and working principle of the dimming device provided by the present invention when no power is applied;
  • FIG. 3 is a schematic diagram of the structure and a working principle diagram of the dimming device provided by the present invention when it is powered on;
  • Figure 4 is a TEM image of (a) core and (b) composite particles according to an embodiment of the present invention.
  • Fig. 5 is a T-V curve of a dimming device according to an embodiment of the present invention.
  • Figure 6 is a microscope view of composite particles according to an embodiment of the present invention.
  • Fig. 7 is a microscope image of composite particles according to an embodiment of the present invention.
  • the composite particle 1 disclosed in the present invention has a core-shell structure, and includes an inner core 10 having an aspherically symmetrical shape and an outer shell 20 composed of a material different from that of the inner core.
  • the outer shell 20 may completely surround the inner core 10 (as shown in FIG. 1 ), or may only partially surround the inner core 10.
  • the core 10 has an aspherically symmetrical shape (that is, at least two optical axes in its structure are not equal in length), such as a rod shape, a ribbon shape, a sheet shape, a needle shape, a wire shape, or a disk shape.
  • the present invention is not limited to this, and other non-spherically symmetrical shapes that meet the requirements can also be used.
  • the shortest axis is generally nanometer-sized, and the size ratio of the longest axis to the shortest axis is greater than one.
  • the size of the shortest axis of the core 10 is 0.1-100 nanometers, preferably, 0.1-60 nanometers.
  • the size ratio of the longest axis to the shortest axis of the inner core 10 is 2:1-50:1, preferably, 2:1-40:1.
  • the material of the core 10 may be metal and its compound, non-metallic inorganic substance or organic substance.
  • the core 10 may be gold nanowires, silver nanosheets, ferroferric oxide nanorods, molybdenum disulfide nanosheets, hydroxyapatite nanorods, cellulose nanocrystal rods, and the like.
  • the outer shell 20 is made of a material different from that of the inner core. These materials can exhibit optical dichroism under certain circumstances, such as anisotropic metal particles (such as gold nanorods), semiconductor crystals (such as GeAs crystals), and metal transitions. Group chalcogen compounds (such as BaTiS 3 ), carbon nanotubes, dichroic dyes or alkaloid polyhalide particles.
  • the alkaloid polyhalides are polyhalides of pyrroles, thiazoles, imidazoles, pyrazoles, pyridines, pyrimidines, quinines, pyrazines, phenanthrolines, and purine compounds.
  • alkaloid polyhalides of nitrogen-containing heterocycles and their derivatives can also be used.
  • the alkaloid polyhalide may also be an alkaloid polyiodide, such as iodoquinine sulfate, iodophenanthroline dicarboxylic acid, iodopyrazine dicarboxylic acid, iodopyridine dicarboxylic acid, and the like.
  • Dichroic dyes include azo, oligothiophene or anthraquinone dyes, such as 1,5-dicarboxy-4,8-diamino-2-p-alkoxyphenylanthraquinone, 1-amino- 4-hydroxy-2-phenylmercaptoanthraquinone or 5,5"-dialdehyde-2,3':4'2"-trithiophene.
  • the material of the shell 20 is regularly distributed along the shape of the core, so that the composite particles have optical dichroism and dielectric anisotropy.
  • the shell material is an anisotropic material
  • the long axis of the anisotropic shell material is basically distributed along a certain fixed axis of the core; if the shell material is crystal, these crystals make it
  • the growth direction is basically distributed along a certain fixed axis of the inner core, but the present invention is not limited to this, and other regular distribution methods may also be included.
  • the composite particle 1 can retain the asymmetric characteristics of the structure of the core 10, and the size and aspect ratio of the final composite particle 1 can be controlled by controlling the size and aspect ratio of the core 10.
  • the thickness and growth trend of the shell 20 a different aspect ratio from the inner core 10 can be formed.
  • the thickness and production trend of the shell can be controlled in various ways (such as controlling the growth time, reaction method or reaction rate of the shell, etc. ). Therefore, the composite particle 1 has optical dichroism, structural anisotropy, and dielectric anisotropy at the same time as a whole, so that it exhibits different optical and electrical properties.
  • the present invention also provides a dimming device, which includes a first transparent base layer 100, a first transparent conductive layer 200, a dimming layer 300, a second transparent conductive layer 400, and a second transparent The base layer 500.
  • the light-adjusting layer 300 includes composite particles 1, a particle stabilizer (not shown), and a dispersion medium 2, wherein the composite particles 1 are suspended in the dispersion medium 2.
  • the particle stabilizer is used to prevent the agglomeration of the composite particles 1 so that they can be dispersed and suspended in the dispersion medium 2.
  • the particle stabilizer can be dispersed in the dispersion medium 2 or attached to the surface of the composite particle 1.
  • the particle stabilizer and dispersion medium can use the polymerization stabilizer and liquid suspension medium disclosed by SPD, which will not be listed here.
  • the composite particles perform Brownian motion in the dispersion medium and are randomly arranged in any direction in the dimming layer 300.
  • the scattering and reflection of the incident light are the largest.
  • the dichroic material absorbs incident light in different directions, and its absorption varies with the angle between the optical axis of the dichroic material and the electric vector of the incident light, the composite particles at this time The optical axis is in any direction, so the absorption of incident light is also the largest.
  • the transmittance of incident light is the smallest, and the dimming device presents a dark state.
  • the entire dimming device can present a certain color.
  • the size of the composite particles needs to be controlled at the nanometer level.
  • the size of the longest axis of the composite particle is 10-1000 nanometers, more preferably, 10-500 nanometers.
  • the material of the first transparent base layer 100 and the second transparent base layer 500 may be transparent glass or polymer materials, such as PET, PEN, PC, PP, PMMA, PBT, PVC, PI, cellulose, etc.
  • the first transparent conductive layer 200 and the second transparent conductive layer 400 can be carbon-based conductive films, metal nanowire conductive films, metal oxide conductive films, etc.
  • the carbon-based conductive films mainly include graphene oxide and carbon nanotubes.
  • Commonly used metal nanowire conductive films include silver nanowires, copper nanowires, etc.
  • metal oxide films include indium tin oxide, indium oxide, tin oxide, zinc oxide, and other metal oxide mixtures.
  • both the first transparent base layer 100 and the second transparent base layer 500 are made of transparent glass, and the first transparent conductive layer 200 and the second transparent conductive layer 400 are both ITO layers.
  • the concentrations are all mass concentrations.
  • the sizes of the inner core and composite particles are all obtained by TEM image or microscope image statistics.
  • the nanorods, the particle stabilizer and the dispersion medium prepared above are mixed in a certain ratio, and the ratio is: 5% of the nanorods, 2% of the particle stabilizer nitrocellulose, and 93% of the dispersion medium dioctyl adipate.
  • Ultrasound to obtain a suspension with composite particles Pour the uniformly mixed suspension into a 5 ⁇ 5 cm dimming device, where the thickness of the dimming layer is 12 microns. Under 100Hz alternating current of 0V-30V, the light transmittance change of the dimming device can be observed, and the light transmittance curve with the voltage change is shown in Fig. 5.
  • the dimming device is light gray; when the light transmittance is the minimum, the dimming device is dark blue.
  • the size and aspect ratio of the final composite particle can be effectively controlled.
  • the formed composite particles can provide rich colors and optical anisotropy, and can be used in dimming devices to achieve changes in light transmittance and color.
  • the composite particles and the dimming device containing the composite particles can be applied to the optical field.

Abstract

一种复合粒子包括内核(10)和外壳(20)，其中内核(10)具有非球对称的形状，外壳(20)由与内核(10)的材料不同的材料构成，外壳(20)的材料顺着内核(10)的形状规则地分布，使得复合粒子具有光学二向色性和介电各向异性。还提供一种包含复合粒子的调光器件。通过控制复合粒子的内核(10)的尺寸和形状，可以有效地控制最终形成的复合粒子的尺寸和长径比，使其具有结构各向异性；通过利用外壳(20)材料的光学二向色性，最终形成的复合粒子同时具有光学二向色性和介电各向异性，能够提供丰富的颜色，使其在调光器件中的应用更为广泛。

Description

复合粒子及包含复合粒子的调光器件 技术领域
本发明涉及具有核壳结构的复合粒子，具体涉及具有二向色性的复合粒子及包含该复合粒子的调光器件。
背景技术
随着科技的发展，调光玻璃在建筑、交通和办公领域的应用越来越广泛，尤其是在汽车、高铁、飞机等领域的应用得到更多的注意。现有调光玻璃市场中比较成熟的是PDLC智能玻璃及电致变色智能玻璃，其中，PDLC智能玻璃只能实现透明与雾度的切换，不能实现遮光和隔热的效果，而电致变色智能玻璃存在膜层工艺复杂、响应时间慢(8～20s)等问题。
另一种比较成熟的技术为SPD光阀技术，通过将悬浮颗粒悬浮在调光层中，在不施加电场的状态下，悬浮颗粒进行布朗运动，从而吸收、散射或反射入射光，使SPD光阀呈现暗态；当施加电场时，悬浮颗粒被极化，从而按照电场的方向排成直线，使大部分入射光可以用过调光层，使SPD光阀呈现亮态，如美国专利申请US5650872A所揭示的。在这个技术中，悬浮颗粒的形状和尺寸对后期的效果非常重要。但由于受材料和制备工艺的影响，无论是悬浮颗粒的形状和尺寸都无法做到精确控制，如美国专利申请US5368780A提到了一种碘纳米棒的制备方法，但纳米棒尺寸较大，且不均匀。同时，常规制备的悬浮颗粒尺寸和形状单一，从而产生的颜色也较单一，无法满足各种各样的需求。
因此，需要提供一种颗粒，该颗粒不仅能有效地控制尺寸和长径比，还能在保证其结构和光电的各向异性的同时提供丰富的颜色。
发明内容
为了解决上述问题，本发明的一个方面提供了一种复合粒子，该复合粒子包括内核和外壳，其中内核具有非球对称的形状，外壳由与内核的材料不同的材料构成，外壳的材料顺着内核的形状规则分布，使得复合粒子具有光学二向色性和介电各向异性。
在优选实施方案中，内核的形状为棒状、带状、片状、针状、线状或盘状。在优选实施方案中，内核的最短轴的尺寸为0.1～100纳米。在另一个优选实施方案中，内核的最长轴与最短轴的尺寸比为2:1～50:1。
在优选实施方案中，内核的材料为金属及其化合物、非金属无机物或有机物。
在优选实施方案中，外壳的材料为各向异性的金属粒子、半导体晶体、金属过渡族硫属化合物、碳纳米管、二向色性染料或生物碱类多卤化物的颗粒。
在优选实施方案中，生物碱类多卤化物为吡咯类、噻唑类、咪唑类、吡唑类、吡啶类、嘧啶类、奎宁类、吡嗪类、菲咯啉类或嘌呤类化合物的多卤化物。在另一个优选实施方案中，生物碱类多卤化物为生物碱类多碘化物。
在另一个优选实施方案中，二向色性染料包括偶氮类、低聚噻吩类和蒽醌类染料。
本发明还提供了一种包含上述复合粒子的调光器件，该调光器件包括第一透明基层、第一透明导电层、调光层、第二透明导电层和第二透明基层，其中调光层包括复合粒子、颗粒稳定剂和分散介质，复合粒子悬浮在分散介质中。
在优选实施方案中，复合粒子的最长轴的尺寸为10～1000纳米。
对于本发明提供的复合粒子，通过控制其内核的尺寸和形状，可以有效地控制最终形成的复合粒子的尺寸和长径比，使其具有结构各向异性；通过利用外壳材料的光学二向色性，最终形成的复合粒子同时具有光学二向色性和介电各向异性，能够提供丰富的颜色，使其在调光器件中的应用更为广泛。
附图说明
通过参照对本发明的实施方案的图示说明可以更好地理解本发明，在附图中：
图1是本发明所提供的复合粒子的结构示意图；
图2是本发明所提供的调光器件在不加电时的结构示意图及工作原理图；
图3是本发明所提供的调光器件在加电时的结构示意图及工作原理图；
图4是根据本发明实施方案的(a)内核和(b)复合粒子的TEM图；
图5是根据本发明实施方案的调光器件的T-V曲线；
图6是根据本发明实施方案的复合粒子的显微镜图；
图7是根据本发明实施方案的复合粒子的显微镜图。
具体实施方式
在以下的描述中，为了达到解释说明的目的以对本发明有一个全面的认识，阐述了大量的具体细节，然而，很明显的，对本领域技术人员而言，无需这些具体细节也可以实现本发明。所举的说明性的示例实施方案仅为了说明，并不对本发明造成限制。因此，本发明的保护范围并不受上述具体实施方案所限，仅以所附的权利要求书的范围为准。
如图1所示，本发明公开的复合粒子1为核壳结构，包括具有非球对称的形状的内核10和由与内核的材料不同的材料构成的外壳20。外壳20可以完全地包围内核10(如图1所示)，也可以仅部分地包围内核10。内核10具有非球对称的形状(即，其结构中至少有两个光学轴长度不相等)，如棒状、带状、片状、针状、线状或盘状。但本发明不限于此，也可采用其他符合要求的非球对称的形状。对于具有非球对称的形状的内核10，其最短轴一般为纳米级尺寸，而其最长轴和最短轴的尺寸比大于1。内核10的最短轴的尺寸为0.1～100纳米，优选地，0.1～60纳米。内核10的最长轴与最短轴的尺寸比为2:1～50:1，优选地，2:1～40:1。内核10的材料可为金属及其化合物、非金属无机物或有机物。例如，内核10可以是金纳米线、银纳米片、四氧化三铁纳米棒、二硫化钼纳米片、羟基磷灰石纳米棒、纤维素纳米晶棒等。
外壳20由与内核的材料不同的材料构成，这些材料在特定情况下可呈现光学二向色性，如各向异性的金属粒子(如金纳米棒)、半导体晶体(如GeAs晶体)、金属过渡族硫属化合物(如BaTiS 3)、碳纳米管、二向色性染料或生物碱类多卤化物的颗粒。优选地，生物碱类多卤化物为吡咯类、噻唑类、咪唑类、吡唑类、吡啶类、嘧啶类、奎宁类、吡嗪类、菲咯啉类和嘌呤类化合物的多卤化物。但本发明不限于此，也可采用其他含氮杂环及其衍生物的生物碱类多卤化物。生物碱类多卤化物也可为生物碱类多碘化物，如碘硫酸奎宁、碘菲咯啉二甲酸、碘吡嗪二羧酸、碘吡啶二羧酸等。二向色性染料包括偶氮类、低聚噻吩类或蒽醌类染料，如1,5-二羧基-4,8-二氨基-2-对烷氧基苯基蒽醌、1-氨基-4-羟基-2-苯巯基蒽醌或5,5”-二醛基-2,3’:4’2”-三噻吩。外壳20的材料顺着内核的形状规则地分布，使得复合粒子具有光学二向色性和介电各向异性。具体地，如果外壳材料是各向异性的材料，则该各向异性的外壳材料使其长轴方向基本上都顺着内核的某一固定轴分布；如果外壳材料是晶体，则这些晶体使其生长方向基本上顺着内核的某一固定轴分布，但本发明不限于此，也可以包括其他规则的分布方式。
由于特殊的核壳结构，复合粒子1可保留其内核10结构上的不对称特性，可通过控制内核10的尺寸和长径比控制最终复合粒子1的尺寸和长径比。同时，通过控制外壳20的厚度和生长趋势，可形成与内核10不同的长径比，其中外壳的厚度和生产趋势可通过多种方式控制(如控制外壳的生长时间、反应方法或反应速率等)。由此，复合粒子1在整体上同时具有光学二向色性、结构各向异性和介电各向异性，使其呈现不同的光学性能和电学性能。
如图2所示，本发明还提供了一种调光器件，该调光器件包括第一透明基层100、第一透明导电层200、调光层300、第二透明导电层400和第二透明基层500。调光层300包括复合粒子1、颗粒稳定剂(图未示)和分散介质2，其中复合粒子1悬浮在分散介质2中。颗粒稳定剂用以阻止复合粒子1的团聚，使其可以分散并悬浮在分散介质2中。颗粒稳定剂可分散在分散介质2中，也可连接在复合粒子1表面。颗粒稳定剂和分散介质可使用SPD所公开的聚合稳定剂和液体悬浮介质，这里就不一一列举。
在不施加电场的状态下，复合粒子在分散介质中进行布朗运动，并且在调光层300中以任意方向随机排列，此时其对入射光的散射和反射是最大的。同时，由于二向色性材料对入射光在不同方向有不同的吸收，且其吸收随着二向色性材料的光学轴与入射光的电矢量的夹角而变化，而此时的复合粒子的光学轴是任意方向的，所以对入射光的吸收也是最大的。此时，入射光的透过率最小，调光器件呈现暗态。此外，由于复合粒子的光学二向色性，整个调光器件可以呈现一定颜色。如图3所示，当施加电场时，由于复合粒子的结构各向异性和介电各向异性，复合粒子使其长轴趋向沿着平行于电场的方向排列，复合粒子的光学轴与入射光的电矢量的夹角变小，对入射光的吸收相应地变少，对入射光的散射或反射也进一步降低，从而导致入射光的透过率增加，使得调光器件呈现亮态。通过调节施加电场的大小，调光器件可实现透过率的连续调控。为了使复合粒子在调光器件中可自由转动，复合粒子的尺寸需要控制在纳米级。优选地，复合粒子的最长轴的尺寸为10～1000纳米，更优选地，10～500纳米。
第一透明基层100和第二透明基层500的材质可以是透明的玻璃或高分子材料，如PET、PEN、PC、PP、PMMA、PBT、PVC、PI、纤维素等。第一透明导电层200和第二透明导电层400可以采用碳系导电薄膜、金属纳米线导电薄膜、金属氧化导电薄膜等，其中碳系导电薄膜主要包括氧化石墨烯和碳纳米管两大类，常用的金属纳米线导电薄膜包括银纳米线、铜纳米线等，金属氧化薄膜包括氧化铟锡、氧化铟、氧化锡、氧化锌、以及其他金属氧化物的混合物。在下列实施例中，第一透明基层100和第二透明基层500均采用透明玻璃，第一透明导电层200和第二透明导电层400均为ITO层。
在以下实施例中，如无特殊标明，浓度均为质量浓度。内核以及复合粒子的尺寸均通过TEM图或显微镜图统计得到。
实施例1
将2.80克硝化纤维、37.20克癸二酸二辛酯、0.10克油溶性羟基磷灰石纳米棒(平均长度：32纳米，平均宽度：10纳米，如图4(a)所示)、1.13克碘、0.5克甲醇、0.84克CaI 2·4H 2O、0.75克2,5-吡嗪二羧酸置于100毫升容器中。用摇床在42℃搅拌反应16小时后，离心分离，清洗，再次离心分离后得到蓝色纳米棒(平均长度：约400纳米，平均宽度：约40纳米，如图4(b)所示)。
以一定比例混合上述制备的纳米棒、颗粒稳定剂和分散介质，所述比例为：纳米棒5％、颗粒稳定剂硝化纤维2％、分散介质己二酸二辛酯93％。超声，得到具有复合粒子的悬浮液。将混合均匀的悬浮液灌入5×5厘米大小的调光器件，其中调光层的厚度为12微米。在0V-30V的100Hz交流电下，可观察到调光器件的透光率变化，其透光率随电压变化的曲线如图5所示。在透光率最大时，调光器件呈浅灰色；在透光率最小时，调光器件呈深蓝色。
实施例2
将2.80克硝化纤维、37.20克癸二酸二辛酯、0.10克油溶性羟基磷灰石纳米棒(平均尺寸：长32纳米，宽10纳米)、1.13克碘、0.5克甲醇、0.84克CaI 2·4H 2O、0.75克2,5-吡嗪二羧酸置于100mL容器中。用摇床在42℃搅拌反应3小时后，离心分离，清洗，再次离心分离后得到棕黄色纳米棒(平均长度：约50-100纳米，平均宽度：约10-20纳米，如图6所示)。将其按照实施例1的方式制备成调光器件，随着施加电压的变化，同样能观察到透光率及颜色的变化。
实施例3
将8.40克硝化纤维、111.60克癸二酸二辛酯、0.30克油溶性羟基磷灰石纳米棒(平均尺寸：长200纳米，宽50纳米)、3.40克碘、1.50克甲醇、2.52克CaI 2·4H 2O，2.25克2,5-吡嗪二羧酸置于500毫升不锈钢罐中。用分散盘在42℃搅拌反应1小时后，离心分离，清洗，再次离心分离后得到深紫色纳米棒(平均长度：约1000纳米，平均宽度：约250纳米，如图7所示)。由于其尺寸较大，无法按照实施例1的方式制备成调光器件。
实施例4
混合10.5克水、0.56克3,8-(双-2-噻吩基)-1,10-菲咯啉、0.07克浓硫酸、0.5克水溶性二硫化钼纳米片(平均直径：约30纳米，平均厚度：约1-2纳米)，搅拌12小时，得到溶液A。混合0.37克碘、0.23克碘化钾、8.1毫克ZnSO 4、7.50克水和1.75克乙醇，超声混合15分钟，得到溶液B。将溶液B加入溶液A，搅拌1.5小时，生成绿色固体沉淀。取绿色固体0.1克，将其溶于10克乙醇和10克丙酮的混合溶液中。加入0.1克硝化纤维和10克对苯二甲酸二异壬酯，超声混合均匀。在60℃烘箱中烘至容器壁出现黑色固体，取出容器，并将其自然冷却至溶液中析出固体，超声30分钟，得到黑色纳米颗粒的分散液。将其按照实施例1的方式制备成调光器件，随着施加电压的变化，同样能观察到透光率和颜色的变化。
实施例5
将0.12克油溶性四氧化三铁纳米棒(平均长度：48纳米，平均宽度：12纳米)加入20毫升邻二氯苯，超声分散，并同时滴加20毫升溶有240毫克丁烷四羧酸的DMF溶液，密封。以一定转速磁力搅拌，在100℃油浴保温48小时，反应完成后将溶液冷却至室温，加入适量五氧化二磷，搅拌6小时后，用DMF洗涤数次。加入20mL吡啶和0.12克1,5-二羧基-4,8-二氨基-2-对烷氧基苯基蒽醌，搅拌24小时后离心，清洗，得到深棕色纳米颗粒的分散液。将其按照实施例1的方式制备成调光器件，随着施加电压的变化，同样能观察到透光率和颜色的变化。
从上述实施例可以看出，通过控制复合粒子的内核的尺寸和形状，可以有效地控制最终形成的复合粒子的尺寸和长径比。同时，形成的复合粒子能够提供丰富的颜色和光学各向异性，应用在调光器件中可实现透光率和颜色的变化。
尽管已经在上面以细节描述了数个示例性实施方案，但是所公开的实施方案仅是示例性而非限制性的，并且本领域技术人员将容易意识到，在示例性实施方案中很多其他修改、改动和/或替换是可能的，而不实质偏离本公开的新颖性教导和优点。因此，所有这些修改、改动和/或替换意图被包括在如所附权利要求书所限定的本公开的范围内。
工业实用性
本发明所涉及的复合粒子及包含复合粒子的调光器件可以应用于光学领域。

Claims (11)

  1. 一种复合粒子，所述复合粒子包括内核和外壳，其中所述内核具有非球对称的形状，所述外壳由与所述内核的材料不同的材料构成，所述外壳的材料顺着所述内核的形状规则地分布，使得所述复合粒子具有光学二向色性和介电各向异性。
  2. 如权利要求1所述的复合粒子，其中所述内核的形状为棒状、带状、片状、针状、线状或盘状。
  3. 如权利要求2所述的复合粒子，其中所述内核的最短轴的尺寸为0.1～100纳米。
  4. 如权利要求2所述的复合粒子，其中所述内核的最长轴与最短轴的尺寸比为2:1～50:1。
  5. 如权利要求1所述的复合粒子，其中所述内核的材料为金属及其化合物、非金属无机物或有机物。
  6. 如权利要求1所述的复合粒子，其中所述外壳的材料为各向异性的金属粒子、半导体晶体、金属过渡族硫属化合物、碳纳米管、二向色性染料或生物碱类多卤化物的颗粒。
  7. 如权利要求6所述的复合粒子，其中所述生物碱类多卤化物为吡咯类、噻唑类、咪唑类、吡唑类、吡啶类、嘧啶类、奎宁类、吡嗪类、菲咯啉类或嘌呤类化合物的多卤化物。
  8. 如权利要求6所述的复合粒子，其中所述生物碱类多卤化物为生物碱类多碘化物。
  9. 如权利要求6所述的复合粒子，其中所述二向色性染料包括偶氮类、低聚噻吩类和蒽醌类染料。
  10. 一种包含如权利要求1-9中任一项所述的复合粒子的调光器件，所述调光器件包括第一透明基层、第一透明导电层、调光层、第二透明导电层和第二透明基层，其中所述调光层包括所述复合粒子、颗粒稳定剂和分散介质，所述复合粒子悬浮在所述分散介质中。
  11. 如权利要求10所述的调光器件，其中所述复合粒子的最长轴的尺寸为10～1000纳米。
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CN109491174A (zh) * 2018-11-19 2019-03-19 浙江精新材料科技有限公司 一种无机-有机杂化核壳型纳米棒及带有该纳米棒的光阀

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CN116360169A (zh) * 2023-06-02 2023-06-30 合肥精卓光电有限责任公司 一种近黑色调光器件及其制备方法
CN116400539A (zh) * 2023-06-02 2023-07-07 合肥精卓光电有限责任公司 一种近黑色调光器件及其制备方法
CN116400539B (zh) * 2023-06-02 2023-10-24 合肥精卓光电有限责任公司 一种近黑色调光器件及其制备方法
CN116360169B (zh) * 2023-06-02 2023-10-24 合肥精卓光电有限责任公司 一种近黑色调光器件及其制备方法

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