导电聚合物薄膜的喷墨打印制备及其光电器件

聚(3,4-乙撑二氧基噻吩):聚(苯乙烯磺酸)(PEDOT:PSS)由于兼备优良的导电性和透光率,被广泛用于透明功能性薄膜的制备,可作为空穴传输层或直接用作电极,运用到有机光伏器件(OPV)、有机场效应晶体管(OFET)、有机发光二极管(OLED)等薄膜器件的结构中,部分实现了氧化铟锡(ITO)薄膜的替代。常见的溶液成膜工艺是旋涂法,这种工艺操作较为简便,但原料利用率低,并且难以大面积均匀制备及图案化制膜, 不利于规模化生产和推广。近年来,喷墨打印制膜技术得到人们越来越多的关注。由于喷墨打印制膜技术可在多种基底上快速、高效地制备均匀大面积薄膜,并可轻易地实现各种精细图案化的制作,可溶液加工,更与卷对卷加工技术兼容,因此能够很好地节约原料,降低能耗和制作成本。目前已被广泛应用于有机电子学各个领域,特别是在制备柔性器件方面,展现出独特优势。本文对基于导电聚合物PEDOT:PSS的喷墨打印工艺进行了系统的阐述,对其制膜、图案化及其电子器件应用等相关研究作了较为全面的总结,并展望了其应用前景,对于更为全面、深刻地理解和推动喷墨打印制膜技术在有机电子学领域的应用具有重要的指导和借鉴意义。     

Warm white light from Y4MgSi3O13:Bi, Eu nanophosphor for white light-emitting diodes

Y₄MgSi₃O₁₃:Bi³⁺, Eu³⁺ nanophosphors have been prepared by a facile sol–gel method. The products have been characterized by X-ray diffraction, field-emission scanning electron microscopy and fluorescence measurements. The results show that the nanophosphors are of single phase hexagonal Y₄MgSi₃O₁₃ with size-distribution of 50–90 nm in diameter. White-light emission has been obtained from Bi³⁺ and Eu³⁺ co-doped Y₄MgSi₃O₁₃ nanophosphors upon excitation of 350 nm ultraviolet light. It is noted that Bi³⁺ ions can occupy two different Y³⁺ sites and generate different emissions from the ³p₁ → ¹s₀ transition. Warm white light has been obtained from Y₄MgSi₃O₁₃:Bi³⁺, Eu³⁺ nanophosphors according to Commission International de I’Eclairage (CIE) chromaticity coordinates and color temperature (T_c) with appropriately adjusted contents of Bi³⁺ and Eu³⁺. The results indicate that Y₄MgSi₃O₁₃:0.08Bi³⁺, 0.04Eu³⁺ (x = 0.31, y = 0.31, T_c = 6907 K) are potential nanophosphors for white light-emitting diodes (LEDs) applications.     

Rational design of donor–π–acceptor n-butyl-1,8-naphthalimide-cored branched molecules as charge transport and luminescent materials for organic light-emitting diodes

Four D–π–A bipolar molecules with n-butyl-1,8-naphthalimide (BNI) fragments as acceptors, acetylenes as π-spacers, and different aromatic groups as donors have been designed to explore their optical, electronic, and charge transport properties as charge transport and luminescent materials for organic light-emitting diodes (OLEDs). The frontier molecular orbitals (FMOs) and local density of states analysis have turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer (ICT). The calculated results show that their optical and electronic properties are affected by the different donors of the bipolar molecules. Our results suggest that D–π–A 1,8-naphthalimide derivatives with donors triphenylamine (1), 1-nitrobenzene (2), anisole (3), and 4-phenylbenzo[c][1,2,5]thiadiazole (4) fragments are expected to be promising luminescent materials. Furthermore, 2–4 are expected to be promising candidates for both electron and hole transport materials as well as potential ambipolar charge transport material, whereas BNI and 1 can serve as hole transfer materials only. We have also predicted the mobility of 4 with better performance in three different space groups. On the basis of investigated results, we proposed a rational way for the design of charge transport and/or luminescent materials simultaneously.     

Effect of oxygen plasma treatment on the surface properties of tin-doped indium oxide substrates for polymer LEDs

The effect of oxygen plasma treatment on the surface properties of tin-doped indium oxide (ITO) substrates and the changes in surface properties of treated ITO substrates with ageing time were investigated by X-ray photoelectron spectroscopy (XPS), contact angle and surface free energy measurements. Experimental results show that oxygen plasma treatment increases the oxygen concentration, decreases the carbon concentration, and enhances the surface free energy and polarity, and thereby improves the surface properties of ITO substrates. However, the improved ITO surface properties tended to decay and the surface free energy decreased, with ageing time. In addition, the ageing effect of treated ITO substrates on the performance of polymer light-emitting diodes (LEDs) was studied with respect to the driving voltage, electroluminescent luminance and efficiency. We observe that the ITO substrates aged for various times result in significant differences in optical and electrical characteristics which become worse as the ageing time increases. The optical and electrical performance of polymer LEDs is closely related to the surface properties of ITO substrate and the interface characteristics of ITO/polymer.     

An efficient synthesis of novel spiro[[8H]indeno[2,1-b]-thiophene-8,9′-fluorene] building block for blue light-emitting materials

We have developed efficient synthetic routes to obtain a novel building block spiro[[8H]indeno[2,1-b]thiophene-8,9′-fluorene] (SITF), a monothiophene-containing spirobifluorene analogue, and constructed blue light-emitting materials, including 2′,7′-bis([1,1′-biphenyl]-4-yl)-spiro[indeno[2,1-b]thiophene-8,9′-fluorene] (BBP-SITF) and 2′,7′-bis(9,9′-spirobifluoren-2-yl)spiro[[8H]indeno[2,1-b]-thiophene-8,9′-fluorene] (BSBF-SITF). BSBF-SITF has shown to be a stable blue light-emitting material with high PL quantum efficiency (89%) and unique regioselective feature at the C2 of thiophene, which indicate that BSBF-SITF will be useful for constructing complicated optoelectronic systems.     

Four-coordinate boron compounds derived from 2-(2-pyridyl)phenol ligand as novel hole-blocking materials for phosphorescent OLEDs

Four-coordinate boron compounds of Ph₂B · 1 (2) and (C₆F₅)₃B(1 · H) (3) were prepared from the reaction of 2-(2-pyridyl)phenol (1 · H) ligand with triarylborane starting materials, BPh₃ and B(C₆F₅)₃, respectively, and tested as hole-blocking layer (HBL) materials in phosphorescent OLEDs. While the crystal structure of 2 reveals the pseudo-tetrahedral geometry around the boron center with bidentate [N,O] chelation by 1, 3 is characterized as the zwitterionic four-coordinate system where the ligand 1 · H acts as monodentate [O] chelator with N-protonation. UV-Vis absorption and PL spectra of 2 and 3 are consistent with the ligand-centered, HOMO-LUMO electronic transitions with charge transfer from a phenoxide ring to a pyridine, which was further supported by time dependent DFT calculation for 2. Both compounds are found to possess the HOMO-LUMO energy gap of 3.1 eV appropriate for hole-blocking materials for phosphorescent OLEDs. The devices incorporating 2 and 3 as HBL materials displayed stable green phosphorescence of Ir(ppy)₃ (ppy = 2-phenylpyridine) with low turn-on voltage of 3.2 and 3.4 V, respectively, indicating that 2 and 3 function as HBL materials. Although both devices show the short lifetime (<1 h) probably owing to the low thermal stability, the device based on 2 displays better performances in terms of luminance, power and luminance efficiency, and external quantum efficiency in a wide range of current densities (0.1-100 mA/cm²) than the reference device incorporating BAlq as HBL materials.     

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

A series of cyclometalating platinum(II) complexes with substituted 9-arylcarbazolyl chromophores have been synthesized and characterized. These complexes are thermally stable and most of them have been characterized by X-ray crystallography. The phosphorescence emissions of the complexes are dominated by ³MLCT excited states. The excited state properties of these complexes can be modulated by varying the electronic characteristics of the cyclometalating ligands via substituent effects, thus allowing the emission to be tuned from bright green to yellow, orange and red light. The correlation between the functional properties of these metallophosphors and the results of density functional theory calculations was made. Because of the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such moiety can increase the highest occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent platinum(II) phosphor with 2-phenylpyridine ligand. The solution-processed electrophosphorescent organic light-emitting diodes doped with these platinum-based phosphors have been fabricated which showed a maximum external quantum efficiency of 2.77% for the best device, corresponding to a power efficiency of 3.48 lm/W and a luminance efficiency of 8.49 cd/A. The present work enables the rational design of platinum-carbazolyl electrophosphors by synthetically tailoring the structure of carbazolylpyridine ring that can permit good color-tuning versatility suitable for multi-color display technology.     

Constructing Charge‐Transfer Excited States Based on Frontier Molecular Orbital Engineering: Narrowband Green Electroluminescence with High Color Purity and Efficiency

The design and synthesis of organic materials with a narrow emission band in the longer wavelength region beyond 510 nm remain a great challenge. For constructing narrowband green emitters, we propose a unique molecular design strategy based on frontier molecular orbital engineering (FMOE), which can integrate the advantages of a twisted donor–acceptor (D‐A) structure and a multiple resonance (MR) delayed fluorescence skeleton. Attaching an auxiliary donor to a MR skeleton leads to a novel molecule with twisted D‐A and MR structure characteristics. Importantly, a remarkable red‐shift of the emission maximum and a narrowband spectrum are achieved simultaneously. The target molecule has been employed as an emitter to fabricate green organic light‐emitting diodes (OLEDs) with Commission Internationale de L'Eclairage (CIE) coordinates of (0.23, 0.69) and a maximum external quantum efficiency (EQE) of 27.0 %.     

Perdeuterated Conjugated Polymers for Ultralow‐Frequency Magnetic Resonance of OLEDs

The formation of excitons in OLEDs is spin dependent and can be controlled by electron‐paramagnetic resonance, affecting device resistance and electroluminescence yield. We explore electrically detected magnetic resonance in the regime of very low magnetic fields (<1 mT). A pronounced feature emerges at zero field in addition to the conventional spin‐ Zeeman resonance for which the Larmor frequency matches that of the incident radiation. By comparing a conventional π‐conjugated polymer as the active material to a perdeuterated analogue, we demonstrate the interplay between the zero‐field feature and local hyperfine fields. The zero‐field peak results from a quasistatic magnetic‐field effect of the RF radiation for periods comparable to the carrier‐pair lifetime. Zeeman resonances are resolved down to 3.2 MHz, approximately twice the Larmor frequency of an electron in Earth's field. However, since reducing hyperfine fields sharpens the Zeeman peak at the cost of an increased zero‐field peak, we suggest that this result may constitute a fundamental low‐field limit of magnetic resonance in carrier‐pair‐based systems. OLEDs offer an alternative solid‐state platform to investigate the radical‐pair mechanism of magnetic‐field effects in photochemical reactions, allowing models of biological magnetoreception to be tested by measuring spin decoherence directly in the time domain by pulsed experiments.     

Mechanochromic Delayed Fluorescence Switching in Propeller‐Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli‐Responsive Intramolecular Charge‐Transfer Excited States

Herein, the universal design of high‐efficiency stimuli‐responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli‐triggered TADF switching for a series of carbazole–isophthalonitrile‐based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X‐ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited‐state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light‐emitting diodes using a single TADF emitter.