电润湿电子纸显示应用物理研究概述与进展

刘飞龙; 程彦锟; 张境恒; 唐彪; 周国富

doi:10.7498/aps.72.20230837

摘要

电润湿是指通过改变作用于液体-固体电极间的电势, 来影响固体和液体间的界面张力, 从而改变固液界面的润湿性, 即接触角, 使液滴产生形变、位移的现象. 电润湿电子纸显示是基于快速响应微流体操控技术的新型反射式“类纸”显示技术. 该技术拥有已商业化的电泳电子纸显示产品低能耗、视觉健康、可柔性等优点, 同时突破了“彩色”和“视频播放”两项当前束缚电子纸显示技术应用领域的瓶颈. 未来, 电润湿电子纸显示将为我国军用、民用市场提供全天候“绿色”显示产品, 具有千亿规模的直接市场和巨大产业辐射力. 本文对电润湿显示器件中涉及的多个物理方向, 特别是润湿与电润湿、两相流体力学、微观与界面物理、光物理、电介质物理、热物理、瞬态物理等, 进行了系统综述; 并且对基本器件工作原理、微观与介观物理图像、器件运行内在机制、器件可靠性等进行了全面介绍.

关键词:

Abstract

Electrowetting refers to the phenomenon of modifying the surface tension between a liquid and a solid by adjusting the externally applied electric potential between the liquid and solid electrodes, thereby changing the contact angle between the two and causing a deformation and displacement of the droplets. Electrowetting electronic paper display is a new reflective “paper-like” display technology based on a rapid response microfluidic control technology. It has the advantages of low energy consumption, visual health, and flexibility of commercial electrophoretic electronic paper display products, while breaking through the bottlenecks of “full-color” and “video-speed response” that currently restrict the application of electronic paper display technology. In this paper, several physical directions involved in electrowetting display devices, especially wetting and electrowetting, binary phase fluid mechanics, microscopic and interfacial physics, photophysics, dielectric physics, thermophysics, and transient physics, are systematically reviewed; the basic principles of device operation, microscopic and mesoscopic physical pictures, internal mechanisms of device operation, and device reliability are also discussed in detail.

Keywords:

作者及机构信息

华南师范大学华南先进光电子研究院, 彩色动态电子纸显示技术研究所, 广东省光信息材料与技术重点实验室, 广州　510006

通信作者: 唐彪, tangbiao@scnu.edu.cn ; 周国富, guofu.zhou@m.scnu.edu.cn

基金项目: 国家重点研发计划(批准号: 2021YFB3600602)、国家自然科学基金(批准号: 62005083, 52175403)、科技部外国专家重点支撑计划(重大科研)(批准号: zcgx2022002L)、广东省海外高层次人才引进计划(青年拔尖)(批准号: 2021QN02X369)、“广东特支计划”本土创新创业团队(批准号: 2019BT02C241)、教育部长江学者和创新团队发展计划(批准号: IRT 17R40)、广东省光信息材料与技术重点实验室(批准号: 2017B030301007)、广州市类纸显示材料与器件重点实验室(批准号: 201705030007)、教育部光信息国际合作联合实验室和高等学校学科创新引智计划资助的课题.

Authors and contacts

Guangdong Provincial Key Laboratory of Optical Information Materials and Technology, Institute of Electronic Paper Displays, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006, China

Corresponding author: Tang Biao, tangbiao@scnu.edu.cn ; Zhou Guo-Fu, guofu.zhou@m.scnu.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2021YFB3600602), the National Natural Science Foundation of China (Grant Nos. 62005083, 52175403), the Key Support Program for Foreign Experts of the Ministry of Science and Technology of China (Grant No. zcgx2022002L), the Overseas High Level Talent Introduction Program (Top Youth) of Guangdong Province, China (Grant No. 2021QN02X369), the “Guangdong Special Supprot Program” Local Innovative and Entrepreneurship Teams, China (Grant No. 2019BT02C241), the Program for Chang Jiang Scholars and Innovative Research Teams in Universities of Ministry of Education of China (Grant No. IRT 17R40), the Guangdong Key Laboratory of Optical Information Materials and Technology, China (Grant No. 2017B030301007), the Guangzhou Key Laboratory of Electronic Paper Displays Materials and Devices, China (Grant No. 201705030007), the Joint Laboratory of Optical Information International Cooperation of Ministry of Education, China, and the 111 Project, China.

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施引文献

图 1 主流显示器件类型及其工作原理　(a) LCD液晶显示, 对背光源透射光进行调制; (b) OLED有机发光显示, 利用电光转换实现自发光; (c) E-Paper电子纸显示, 对环境光的反射进行调制

Fig. 1. Working principles of mainstream display devices: (a) LCD (liquid crystal) display, based on modulation of backlight transmisssion; (b) OLED (organic light-emitting) display, based on self-emission by conversion from electricity to light; (c) E-Paper (electronic paper) display, based on modulation of reflective light from environment.

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图 2 电泳电子纸显示原理. 微胶囊包裹的两色电异性颗粒体系, 通过施加电场的极性及强度控制颗粒运动, 实现白色(左)、灰色(中)、黑色(右)等灰阶显示

Fig. 2. Working principles of electrophoretic e-paper display. Microcapsules are composed of positively charged white pigment chips and negatively charged black pigment chips. Particle motion is controlled by polarity and strength of external electric fields, resulting in display of white (left), grey (middle), and black (right) colors.

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图 3 电润湿电子纸显示原理. 像素单元内两相流体体系通过施加电场强度控制油水界面运动, 实现灰阶调控　(a) 未加电状态; (b) 加电状态

Fig. 3. Working principles of electrowetting e-paper display. Binary phase fluids composed of colored oil and transparent water are controlled by strength of external electric fields, resulting in color modulation: (a) Without electric bias; (b) with electric bias.

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图 4 电润湿原理示意图

Fig. 4. Schematics of electrowetting.

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图 5 三相接触线及固液表面附近的电场力分布

Fig. 5. Electric force distribution at the solid-liquid interface and near the three-phase contact line.

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图 6 实验中典型的电润湿曲线

Fig. 6. Typical electrowetting characteristics in experiments

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图 7 流体体系基础理论研究方法　(a) 微观尺度: 分子动力学; (b) 介观尺度: 格子玻尔兹曼方法; (c) 宏观尺度: 纳维斯托克斯方程

Fig. 7. Fundamental theoretical methods for fluid systems: (a) Microscopic scale: molecular dynamics; (b) mesoscopic scale: lattice Boltzmann method; (c) macroscopic scale: Navier-Stokes equation.

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图 8 格子玻尔兹曼方法流体力学计算流程

Fig. 8. Process of lattice Boltzmann method for computational fluid mechanics.

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图 9 固液界面加电条件下的离子分布　(a) Helmholtz模型; (b) Gouy-Chapman模型; (c) Gouy-Chapman-Stern模型

Fig. 9. Ion distribution near solid-liquid interfaces under electric stress: (a) Helmholtz model; (b) Gouy-Chapman model; (c) Gouy-Chapman-Stern model.

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图 10 液滴在粗糙固体表面形成的不同润湿状态　(a) Wenzel状态^[67]; (b) Cassie-Baxter状态^[67]

Fig. 10. Different wetting states of a liquid droplet at a rough solid surface: (a) Wenzel state^[67]; (b) Cassie-Baxter state^[67].

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图 11 几何结构导致的钉扎/去钉扎效应示意图　(a) 接触角等于$ \theta $; (b) 接触角等于$ \theta + \alpha $; (c) 接触角大于$ \theta + \alpha $

Fig. 11. Pinning/depinning effect due to geometric structures: (a) Contact angle = $ \theta $; (b) contact angle = $ \theta + \alpha $; (c) contact angle >$ \theta + \alpha $.

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图 12 润湿梯度导致的钉扎/去钉扎效应示意图　(a) 通过表面改性方法制备的不同几何图案的润湿梯度^[70]; (b) 测量得到的润湿角与填充液体体积关系^[70]

Fig. 12. Pinning/depinning effect due to wetting gradients: (a) Wetting gradient patterns fabricated by surface treatment processes^[70]; (b) measured contact angle as a function of droplet volume^[70].

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图 13 电润湿显示器件中电荷转移导致的电化学反应与器件老化机制^[71]

Fig. 13. Charge transfer induced electrochemical reactions and degradation mechanisms in electrowetting display devices^[71].

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图 14 蒽醌型电润湿显示染料结构式^[73]

Fig. 14. Chemical structure of anthraquinone-type dye molecules for electrowetting display^[73].

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图 15 偶氮苯环型电润湿显示染料结构式

Fig. 15. Chemical structure of azobenzene-type dye molecules for electrowetting display.

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图 16 吡唑啉酮型电润湿显示染料结构式^[74]

Fig. 16. Chemical structure of pyrazolone-type dye molecules for electrowetting display^[74].

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图 17 金属络合类电润湿显示染料结构式

Fig. 17. Chemical structure of metal-complex-type dye molecules for electrowetting display.

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图 18 有机苝型电润湿显示染料结构式

Fig. 18. Chemical structure of organic-perylene-type dye molecules for electrowetting display.

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图 19 实际的各色电润湿显示油墨及其吸收光谱

Fig. 19. Practical various-color oils for electrowetting display and their absorption spectra.

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图 20 基于彩色滤光片的全彩电润湿显示结构^[80]

Fig. 20. Full-color electrowetting display device structure based on color filters^[80].

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图 21 基于彩色滤光片的透射式全彩电润湿显示屏　(a) θ~0º^[81]; (b) θ~50º^[81]

Fig. 21. Transmissive full-color electrowetting display screens based on color filters: (a) θ~0º^[81]; (b) θ~50º^[81].

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图 22 基于彩色滤光片的透射式全彩电润湿显示屏色域^[81]

Fig. 22. Color gamut of transmissive full-color electrowetting display screesn based on color filters^[81].

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图 23 相减混色原理

Fig. 23. Principle of subtractive color mixing.

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图 24 (a) 三层叠加彩色电润湿显示器结构; (b)三层叠加彩色电润湿显示器原理图及(c)混色方法^[83]

Fig. 24. (a) Structures of three-layer superposed color electrowetting display; (b) principles of three-layer superposed color electrowetting display and (c) methods of color mixing^[83].

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图 25 基于三层叠加的全彩电润湿显示样机(a)及其色域(b)

Fig. 25. Prototype of full color electrowetting display devices (a) based on three-layer superposition and its color gamut (b).

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图 26 基于电润湿原理的可变焦距液体微透镜　(a) 施加电压后, 润湿性增加导致θ<θ₀; (b)可调焦距液体透镜的电润湿液滴^[84]

Fig. 26. Microlens with tunable focal lengths based on electrowetting: (a)After applying voltage, the increase in wettability causesθ<θ₀; (b) an electrowetting-actuated liquid droplet as a tunable-focus liquid lens^[84].

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图 27 电润湿显示器件开关过程中导致的电容变化^[90]

Fig. 27. Capcaitance change during the switching of electrowetting display devices^[90].

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图 28 介电材料漏电微观物理机制^[92]

Fig. 28. Microscopic physical mechanism of leakage current through dielectric materials^[92].

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图 29 电润湿显示器件在热加速老化实验下的失效过程^[94]

Fig. 29. Failure process of electrowetting display devices under thermal accelerated aging experiments^[94].

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图 30 多晶介电薄膜老化失效的物理模型及计算流程图^[96]

Fig. 30. Flow diagram and physical modeling of dielectric breakdown for polycrystalline thin films^[96].

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图 31 液体介电泳现象　(a) 介电液体朝向更强电场的方向运动^[97]; (b) 介电液体中的气泡远离强电场方向运动^[97]; (c) 液体的自由界面趋向与电场线平行^[97]

Fig. 31. Liquid DEP phenomenology: (a) Dielectric liquid drawn into a strong electric field^[97]; (b) bubble repelled from a strong electric field^[97]; (c) controlled liquid profile with surface parallel to the applied electric field^[97].

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图 32 液体介电泳实验操控微流体向上运动, 直至介电泳力与重力相平衡. 图中介电性的油性液体在两个平行共面电极之间的缝隙中上升, 并且截面为与电场线相平行的半圆形状^[97]

Fig. 32. Liquid DEP experiments with micro liquid moving upwards until DEP is balanced by gravity. Dielectric oil moves upwards within the slit between two parallel co-planar electrodes, with the cross section of the liquid in a semi-circle shape parallel to electric fields^[97].

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图 33 流体内部在自然对流情形下不同瑞利数Ra对应的等温线分布　(a) $ Ra = {10^3} $^[99]; (b) $ Ra = {10^4} $^[99]; (c) $ Ra = $$ {10^5} $^[99]; (d) $ Ra = {10^6} $^[99]

Fig. 33. Isotherms for a fluid under natural convection, with different Rayleigh numbers: (a) $ Ra = {10^3} $^[99]; (b) $ Ra = $$ {10^4} $^[99]; (c) $ Ra = {10^5} $^[99]; (d) $ Ra = {10^6} $^[99].

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图 34 流体内部在自然对流情形下不同瑞利数对应的流线分布, 分别对应图33中的四种情况　(a) $ Ra = {10^3} $^[99]; (b) $ Ra = {10^4} $^[99]; (c) $ Ra = {10^5} $^[99]; (d) $ Ra = {10^6} $^[99]

Fig. 34. Streamlines for a fluid under natural convection, for the four cases in Fig. 33: (a) $ Ra = {10^3} $^[99]; (b) $ Ra = $$ {10^4} $^[99]; (c) $ Ra = {10^5} $^[99]; (d) $ Ra = {10^6} $^[99].

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图 35 电润湿效应对临界沸腾液体中气泡生长速度的增强实验结果　(a) 未加电情况^[20]; (b) 施加交流电润湿情况^[20]

Fig. 35. Effects of electrowetting on bubble ebullition at onset of nucleate boiling: (a) Without electrowetting^[20]; (b) with AC electrowetting^[20].

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图 36 温度梯度导致的液滴输运在亲疏水情形下表现出相反的运动方向　(a) 液滴中心位置与时间的关系^[57]; (b) 亲疏水情况下的流场、温度场的分布^[57]

Fig. 36. Droplet transport driven by temperature gradient, with opposite directions for hydrophilic and hydrophobic surfaces: (a) Droplet centroid position as a function of time^[57]; (b) streamlines and isotherms for hydrophilic and hydrophobic cases^[57].

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图 37 电润湿显示器件中油墨破裂的瞬态过程^[101]

Fig. 37. Transient behavior of oil rupture in electrowetting display devices^[101].

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图 38 电润湿显示像素参数对光电响应曲线影响

Fig. 38. Effects of pixel parameters in an electrowetting display on electro-optical response curves.

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图 39 电润湿油墨驱动迟滞曲线开口率变化

Fig. 39. Change of aperture ratio in the driving delay curve of electrowetting oil.

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图 40 电润湿显示油墨驱动电压波形及其对应油墨状态, (a)—(d)分别对应状态①—④

Fig. 40. Driving voltage waveform design for electrowetting display and the corresponding states of oil rupture. (a)–(d) corresponding to ①–④.

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表 1 流体中离子动力学物理模型概况

Table 1. Overview of modeling of ion dynamics in fluids.

理论	重要特征	前提假设
Helmholtz	表面电荷被单分子层的反离子中和; 表面电势在两层离子间线性变化	离子热运动、离子扩散、离子表面吸附、溶剂-固体表面相互作用均忽略
Gouy-Chapman	考虑了离子热运动; 离子被假设为点电荷	离子实际尺寸被忽略; 固体表面电荷均匀分布; 非库仑相互作用被忽略
Stern	考虑了离子的有限尺寸及水合离子作用; 考虑了离子在固体表面的吸附作用(即Stern层)	Stern层厚度小于实际尺寸; Stern层流速假设为0

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表 2 电润湿显示器件常用介电绝缘材料及其性能概况^[87–89]

Table 2. Overview of common dielectric materials and their properties used in electrowetting display devices^[87–89].

聚合物绝缘材料
介电材料	Parylene -C/N	Teflon ®AF 1600	Teflon PTFE	Cytop^TM	PDMS	聚氨酯
介电强度/(kV·mm^–1)	268/276	21	60	110	21.2	22
介电常数	2.65/3.15	1.93	2.1	2.1	2.3—2.8	3.4
击穿电压/V	±240(DC) <1 k(AC 50—20 kHz)	—	<300(DC) <600 k(AC 1 kHz)	<120(DC) <800(AC 2 kHz)	±500(DC)	<400 (DC)
厚度/μm	3.5—30.0	0.01—0.10	25—50	0.1—1.0	38	6—35
接触角/(°)	126	120	114	110	120	50—80
加工工艺	气相沉积	旋涂/浸涂	成泡膜材料	旋涂	旋涂	旋涂
无机绝缘材料
介电材料	二氧化硅		氮化硅		BST
介电强度 /(kV·mm^–1)	400—600		500		18—54
介电常数	3.9		7.5		225—265
击穿电压/V	V_DC≥25		>40		V_DC≥15
厚度/μm	0.1—1.0		0.15		0.07
接触角/(°)	46.7		30		40.8
加工工艺	PECVD		气相沉积		MOCVD

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