基于钌配合物自组装微晶的薄膜及发光成像器件制备

doi:10.12422/j.issn.1672-6952.2025.05.005

摘要/Abstract

摘要：

钌配合物因其较高的发光量子效率和可调的发光波长特性，在发光器件领域具有重要的应用价值。然而，传统溶液加工方法易引发分子无序聚集，使发光效率和稳定性下降；常规真空沉积方法则存在工艺复杂、成本高等弊端，不利于材料和器件的利用和推广。为了解决上述问题，开发了一种制备三联吡啶钌(Ⅱ)配合物微晶薄膜的方法，该方法通过混合溶剂诱导钌配合物在导电玻璃表面自组装形成微晶结构；在此基础上，采用镓铟合金作为对电极，制备了肉眼可见的高强度发光简易器件；通过模具和液态金属制备图案化电极，结合该电极和钌配合物微晶薄膜，实现了发光图案器件的有效制备。该研究成果为制备基于钌配合物的低成本、大面积发光的器件提供了一种新方法。

关键词: 钌配合物, 发光器件, 自组装, 微晶, 混合溶剂

Abstract:

Ruthenium complexes exhibit considerable potential for application in devices owing to their high photoluminescence quantum yields and tunable emission wavelengths.Nevertheless,traditional solution?processing methods often lead to disordered molecular aggregation,which detrimentally affects both luminescence efficiency and material stability.Conventional vacuum deposition methods involve complicated procedures and high production costs,which hinder the practical utilization and broader adoption of these materials and devices.To address these challenges,this work presents a novel approach for fabricating tris(bipyridine)ruthenium(Ⅱ) complex microcrystalline films.By employing a mixed?solvent approach,the ruthenium complex is guided to self?assemble on the surface of conductive glass,leading to the formation of microcrystalline architectures.Utilizing gallium?indium (Ga?In) alloy as the counter electrode,a simple device capable of high?intensity visible emission was successfully fabricated. Furthermore, patterned electrodes were prepared using molds and liquid metal.Combining these electrodes with the ruthenium complex microcrystalline films enabled the fabrication of devices capable of emitting patterned light.This study offers a promising pathway for the low?cost and large?area manufacturing of ruthenium?based light?emitting devices.

Key words: Ruthenium complexes, Luminescent devices, Self?assembly, Microcrystals, Mixed solvents

中图分类号:

TN383

范子期, 黄旭豪, 温储赫, 王江干, 张琼. 基于钌配合物自组装微晶的薄膜及发光成像器件制备[J]. 辽宁石油化工大学学报, 2025, 45(5): 37-45.

Ziqi FAN, Xuhao HUANG, Chuhe WEN, Jianggan WANG, Qiong ZHANG. Fabrication of Thin Films and Luminescent Imaging Devices Based on Self⁃Assembled Microcrystals of Ruthenium Complex[J]. Journal of Liaoning Petrochemical University, 2025, 45(5): 37-45.

图/表 10

图1 发光器件的发光原理

Fig.1 Luminescence mechanism of light?emitting devices

图2 不同乙醇体积分数溶液在导电玻璃表面的接触角

Fig.2 The contact angle of ethanol solutions with different volume fractions on the surface of conductive glass

图3 双溶剂薄膜和水溶液薄膜的SEM图像（a）双溶剂薄膜（b）水溶液薄膜

Fig.3 SEM images of the dual?solvent film and the aqueous solution film

图4 双溶剂薄膜和水溶液薄膜部分区域的C、F元素分布

Fig.4 Distribution of C and F elements in partial areas of the dual?solvent film and the aqueous solution film

图5 利用双溶剂薄膜的XRD图

Fig.5 The XRD picture of using the dual?solvent film

图6 含[Ru(bpy)3](BF4)2的乙腈溶液、双溶剂薄膜及水溶液薄膜的归一化吸收光谱图

Fig.6 Normalized absorption spectra of [Ru(bpy)3](BF4)2?containing acetonitrile solution, binary?solvent film, and aqueous film

图7 双溶剂薄膜和水溶液薄膜微区发光亮度（a）双溶剂薄膜（六边形规整结构）（b）双溶剂薄膜（片状结构）（c）水溶液薄膜

Fig.7 The micro?area luminescence intensity of the dual?solvent film and the aqueous solution film

图8 基于模具和液态金属注射的创新器件制作流程图

Fig.8 Flowchart of the innovative device fabrication process using molds and liquid metal injection

图 9 基于双溶剂薄膜的发光器件的发射光谱及CIE坐标图

Fig.9 Emission spectra and CIE coordinate diagrams of light?emitting devices based on dual?solvent films

图 10 发光器件的发光强度衰减和循环稳定性曲线

Fig.10 Luminous intensity decay plot and cycling stability curve of the light?emitting device

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