Organic LED device based on PtOEP phosphor without doping in host material

Electroluminescence (EL) and photoluminescence (PL) have been studied on multi-layer organic light-emitting diode (OLED) devices based on phosphorescent platinum octaethyl porphine (PtOEP) molecule. A multi-layer OLED (called Pt5) which has 100% PtOEP without doping in host as the emitting layer is investigated and compared its EL and PL characteristics with those of the other OLEDs (Pt2 and Pt3) with emitting layer of PtOEP doped in 4,4′-N,N′-dicarbazole-biphenyl (CBP) host material. It is observed that Pt5 shows a lower EL efficiency than Pt2 and Pt3. Three broad EL bands are observed at 500, 527 and 570 nm in the multi-layer device in addition to red sharp EL band due to PtOEP in Pt5, while only the red PtOEP EL is observed in Pt2 and Pt3. The 500, 527 and 570 nm EL peaks arise from absorption of the broad 525 nm Alq₃ emission band by PtOEP layer. The emission from the Alq₃ electron-transport layer is caused by the carrier leakage from the hole-blocking BAlq layer. The intensity of red EL due to PtOEP is much weaker in Pt5 than in Pt2. Taking into account the result of PL, it is suggested that highly efficient energy transfer from CBP host to PtOEP guest occurs in Pt2 and Pt3, giving rise to higher PtOEP luminance, while concentration quenching occurs in PtOEP layer in Pt5.     

Red top-emitting organic light-emitting device using 6, 13-di-(3, 5-diphenyl)phenylpentacene doped emitting system

Fluorescent red organic light-emitting devices (OLEDs) with narrow emission and negligible current-induced quenching by using a pentacene derivative of 6,13-di-(3,5-diphenyl)phenylpentacene (PDT) doped emitting system were demonstrated. With the incorporation of C₆₀ outcoupling layer, the PDT-based top-emitting OLED showed superior electroluminescence performances with Commission Internationale d’Eclairage color coordinates of (0.64, 0.36) and luminous efficiency of ～3 cd/A. To clarify the actual energy transfer process in PDT-doped emitting system, the Förster’s radius was calculated. The results indicated that the energy transfer process is predominantly from the host of tris(8-hydroquinoline) aluminum to guest of PDT via the assistant dopant of 5,6,11,12-tetraphenylnaphthacene.     

Enhanced Device Performances of Blue‐Emitting PLEDs Coupled with Silver‐Nanoicosahedrons

Silver‐nanoicosahedron particles (AgNIPs) are produced by chemical reduction and photochemical methods and doped into the hole transport layer (HTL) or emissive layer (EML) of blue‐emitting polymer light‐emitting diodes (PLEDs) to improve their luminous efficiency. The optimal distributed‐densities of the AgNIPs are determined from current density–voltage–luminance measurements at different doping concentrations. The AgNIP dopant doses that maximize the average luminous efficiency of the proposed PLED are 6.71 µg cm^?2 in EML (achieving 3.48 cd A^?1) and 6.88 µg cm^?2 in HTL (achieving 3.35 cd A^?1). Although the luminous efficiencies of the blue‐emitting PLEDs fabricated by both doping methods are not significantly different, the maximum plasmonic enhancement (around 30‐fold) of the blue‐emitting PLED with AgNIPs in EML is red‐shifted to the green region (≈530 nm in the electroluminescence spectrum), seriously degrading the luminescent monochromaticity of the blue‐emitting PLED. The maximum plasmonic enhancement (around 33‐fold) of blue‐emitting PLED with AgNIPs in HTL occurred at 430 nm, overlapping the localized surface‐plasmon resonance extinctions of the AgNIPs in HTL (425 nm), thus favoring the enhancement of fluorescence emission. Therefore, to enhance the large‐area emission of blue‐emitting PLEDs, the AgNIPs should be doped in the HTL rather than the EML.     

Abrupt change of luminescence spectrum in single-layer phosphorescent polymer light emitting diode

PVK-based single-layer phosphorescent polymer OLEDs (organic light emitting diodes) with different rubrene concentrations were fabricated and examined for the Förster energy transfer from phosphorescent FIrpic dye to rubrene. We found out that at a certain rubrene concentration the energy transfer occurs abruptly and the transfer shows an abnormal evolution of electroluminescence (EL) spectrum due to the coincidence of peak wavelengths of bis[(4,6-difluorophenyl)-pyridinato-N,C^2′](picolinate) iridium(III) (FIrpic) emission and 5,6,11,12-tetraphenylnaphthacene (rubrene) absorption. With the calculation of Förster radius and average distance between FIrpic molecules, we have related the calculated ratio between the number of FIrpic molecules within to that out of Förster radius with the degree of Förster energy transfer from EL spectra measured in the experiment. Experimental results were found to fit well with the predicted results especially at low rubrene concentrations.     

DCM掺杂PVK体系的超快光谱

利用稳态荧光光谱和时间分辨超快光谱研究了DCM掺杂PVK(聚乙烯咔唑)体系的发光特性和能量转移。根据DCM的吸收光谱与PVK的荧光光谱,用Frster理论估算出DCM:PVK掺杂体系能量转移的临界半径及其效率。在DCM:PVK掺杂薄膜中,随着掺杂浓度的升高,DCM的发射强度增强,PVK的发射强度减弱,两者相对强度之比与估算结果一致。还利用时间分辨超快光谱研究了DCM:PVK掺杂薄膜体系的能量转移动力学过程,观察到DCM:PVK掺杂薄膜的荧光寿命随着掺杂浓度的升高逐渐变短。结果表明,在DCM:PVK掺杂薄膜中,存在从PVK到DCM较为有效的Frster能量转移。     

利用级联式能量传递的有机电致发光器件

为了提高掺杂型有机电致发光器件(OLED)中主体发光材料与客体荧光染料间能量传递的效率,2-对联苯-8-羟基喹啉锌(Zn ₂)作为NPB : DCJTB掺杂体系的能量助传递剂,制备了结构如:ITO/NPB/NPB : DCJTB/Zn ₂/BCP/Al的有机电致发光器件。助传递剂Zn ₂的加入,能够两次利用Frster能量转移,实现NPB向DCJTB级联式的能量传递过程,提高低浓度时掺杂染料DCJTB红光发射的纯度;此外,还探讨了三者间能量传递的有效距离,即当助传递剂与掺杂体系的距离在小于10 nm的范围内,其参与能量传递的效率随着距离的增加而逐渐下降。     

Pure red emission of dye-doped organic molecules from microcavity organic light emitting diode

Organic red emitting diode was fabricated by using 4-dicyanomethylene-2-methyl-6-[2-(2,3,6,7-tetrahydro-1 H,5H-benzo[ij]quinolizin-8-yl)vinyl]-4H-pyran (DCM)-doped tri-(8-quinolitolato) aluminum (Alq₃) as emitter with the structure of G/ITO/NPB(25 nm)/DCM:Alq₃(55 nm)/Alq₃(20 nm)/LiF (1.2 nm)/Al(84 nm), (glass/indium–tin-oxide/4,4-bis-[N-(1-naphthyl)-N-phenyl-amino]biphenyl, G/ITO/NPB), the wavelength of the maximal emission of which is 615 nm. By introducing cavity to Organic light emitting diode (OLED), we got pure red emitting diode with wavelength of the maximal emission of 621 nm and full-width at half-maximum (FWHM) of 27 nm. As far as we know, it is the best result in the dye-doped organic red emitting diode. We also made a device of G/ITO/NPB(25 nm)/DCM:Alq₃(29 nm)/DCM:PBD(26 nm)/Alq₃(20 nm)/LiF(1.2 nm)/Al(84 nm), in order to compare the performance of Alq₃ with that of 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) as host material. It was found that the performance of device A is better than that of C both in brightness and color purity,as well as in EL efficiency.     

掺杂型红色有机电致发光显示器件

全色显示是有机电致发光显示(OLED)器件发展的目标,而高性能红色发光器件一直是制约全彩色OLED器件实用化的瓶颈,也是目前有机电致发光显示研究的热点。制作了掺杂DCJTB和不同浓度的rubrene两种荧光染料的红色有机电致发光显示器件,以NPB和Alq₃分别作为空穴传输层和电子传输层,发现器件性能与只掺杂DCJTB的器件相比有明显提高,发光效率提高到2～3倍。通过Frster理论和能带理论分析了器件的能量转移机理,研究发现Frster能量转移不是掺杂器件能量转移的主要形式,载流子俘获机制才是器件效率提高的主要原因;rubrene的引入使得能量能够更有效地从Alq₃转移到DCJTB,从而显著地提高了器件的发光效率和性能。     

Enhanced amplified spontaneous emission by assistant Förster energy transfer in DCJTB-C545T-Alq3 coguest-host system

Amplified spontaneous emission (ASE) characteristics of a red fluorescent dye 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) were significantly improved by assistant Förster energy transfer. The coguest-host system was composed of an electron transport organic molecule tris(8-hydroxyquinoline) aluminum (Alq₃) as host and a green fluorescent dye (10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one) (C545T) as assistant dopant codoped with the guest red dye DCJTB as emitter in a matrix of polystyrene (PS). It was found that the threshold and loss were greatly reduced to 0.007 mJ?pulse^-1 and 7 cm^-1, and the gain was significantly enhanced to 52 cm^-1 by doping of C545T. The improvement of ASE performance in Alq₃:C545T:DCJTB film was attributed to the energy assistant effect of C545T, leading more exciton energy to transfer to DCJTB.     

Excitation energy transfer in dye-doped ternary polymer blends for light-emitting diodes and lasers

We present the organic electroluminescent devices and lasers of which the colors are tuned by utilizing the Förster excitation energy transfer. Fluorene-based light emitting polymers, poly(2,7-bis(p-stiryl)-9,9^′-di-n-hexylfluorene sebacate) (PBSDHFS), poly(9,9^′-di-n-hexyl fluorenediylvinylene-alt-1,4-phenylenevinylene) (PDHFPPV), and a laser dye, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) were used as the components of the energy transfer systems. Color-tunable photoluminescence, electroluminescence, and laser emission in the PBSDHFS/PDHFPPV binary and PBSDHFS/PDHFPPV/DCM ternary blends are demonstrated.     

基于器件结构提高TADF-OLED器件的发光性能

为了提高以TADF材料作为主体、天蓝色荧光材料作为客体的混合薄膜的OLED器件光电性能,我们调整了器件结构,使主体材料发挥其优势。制备了基本结构为ITO/NPB(40 nm)/DMAC-DPS∶x%BUBD-1(40 nm)/Bphen(30 nm)/LiF(0.5 nm)/Al的OLED器件。研究了主-客体材料在不同掺杂浓度下的OLED器件的光电特性。为了提高主体材料的利用率,在空穴传输层和发光层之间加入10 nm的DMAC-DPS作为间隔层;然后,在阳极和空穴传输层之间加入HAT-CN作为空穴注入层,形成HAT-CN/NPB结构的PN结,有效降低了器件的启亮电压(2.7 V)。测量了有无HAT-CN的单空穴器件的阻抗谱。结果表明,在最佳掺杂比例(2%)下,器件的外量子效率(EQE)达到4.92%,接近荧光OLED的EQE理论极限值;加入10 nm的DMAC-DPS作为间隔层,使得器件的EQE达到5.37%;HAT-CN/NPB结构的PN结有效地降低了器件的启亮电压(2.7 V),将OLED器件的EQE提高到5.76%;HAT-CN的加入提高了器件的空穴迁移率,降低了单空穴器件的阻抗。TADF材料作为主体材料在提高OLED器件的光电性能方面具有很大的潜力。     

发光层掺杂对红光OLED性能影响研究

制备高效率、高亮度的红光有机发光二极管是显示器实现全彩色的关键,对高性能的红光有机发光二极管器件研究具有十分重要的意义.本文主要研究了掺杂剂(DCJTB)浓度对红光有机发光二极管性能影响.实验采用真空热蒸镀的方法,选取结构为ITO／2-TNATA(20 nm)/NPB(30 nm)/AlQ(50 nm):(X%)DCJTB／AlQ(30 nm)／LiF(0.8 nm)／Al(100 nm)的红光器件,在高准确度膜厚控制仪的监控下,实现了有机薄膜功能材料的精确蒸镀.研究表明:红光掺杂剂掺杂浓度为(2.5~3.0)%时,在12 V电压下,可以得到发光亮度最高达到8 900 cd/m²,发光效率大于2.8 cd/A,且发光光谱波长为610~618 nm较为理想的红光有机发光二极管器件.     

Red organic light emitting device based on TPP and a new host material

A novel coating method for fabrication of red OLEDs by using a new host material has been developed with the aid of a single furnace. The host material, zinc complex, was prepared from the reaction of zinc acetate and 2-methyl-8-hydroxyquinoline and after characterization by UV-vis, FT-IR, and ¹H NMR spectroscopes was used as an emitting material in the fabrication of OLEDs. Since meso-tetraphenylporphyrin (TPP) and zinc complex have a close molecular weight, both materials were evaporated from a single furnace. Devices with TPP and structures of ITO/PEDOT:PSS (55 nm)/PVK (90 nm)/zinc complex:TPP (65 nm)/Al (180 nm) were fabricated; Without TPP green and with TPP red emission was achieved. The device with 2 % TPP that doped into the zinc complex showed the purest red emission among all devices. The device showed the CIE coordinates of 0.70 and 0.28 at 14 V and a maximum luminance of about 94.2 cd/m². This new method is a promising candidate for fabrication of low cost red OLEDs with a more homogeneous layer.     

Efficiency Improvement in Polymer Light‐Emitting Diodes by “Far‐Field” Effect of Gold Nanoparticles

The “far‐field” effect of metal nanoparticles (NPs), when chromophores localized nearby metal NPs (typically the distance >λ/10), is an important optical effect to enhance emission in photoluminescence. The far‐field effect originates mainly from the interaction between origin emission and mirror‐reflected emission, resulting in the increased irradiative rate of chromophores on the mirror‐type substrate. Here, the far‐field effect is used to improve emission efficiency of polymer light‐emitting diodes (PLEDs). A universal performance improvement is achieved for the full visible light (red, green, blue) PLEDs, utilizing gold (Au) NPs to modify the indium tin oxide (ITO) substrates; this is shown by experimental and theoretical simulation to mainly come from the far‐field effect. The optimized distance, between the NPs and chromophores with visible light emission ranging from 400 to 700 nm, is 80–120 nm. Thus the scope of the far‐field may overlap the light‐emitting profile very well to enhance the efficiency of optoelectronic devices. The 30–40% enhancement is obtained for different color‐emitting materials through distance optimization. The far‐field effect is demonstrated to enhance device performance for materials in the full‐visible spectral range, which extends the optoelectric applications of Au NPs.     

Bandgap engineering of GaxZn1–xO nanowire arrays for wavelength‐tunable light‐emitting diodes

Wavelength‐tunable light‐emitting diodes (LEDs) of Ga_xZn_1–xO nanowire arrays are demonstrated by a simple modified chemical vapor deposition heteroepitaxial growth on p‐GaN substrate. As a gallium atom has similar electronegativity and ion radius to a zinc atom, high‐level Ga‐doped Ga_xZn_1–xO nanowire arrays have been fabricated. As the x value gradually increases from 0 to 0.66, the near‐band‐edge emission peak of Ga_xZn_1–xO nanowires shows a significant shift from 378 nm (3.28 eV) to 418 nm (2.96 eV) in room‐temperature photoluminescence (PL) measurement. Importantly, the electroluminescence (EL) emission of Ga_xZn_1–xO nanowire arrays LED continuously shifts with a wider range (∼100 nm), from the ultraviolet (382 nm) to the visible (480 nm) spectral region. The presented work demonstrates the possibility of bandgap engineering of low‐dimensional ZnO nanowires by gallium doping and the potential application for wavelength‐tunable LEDs.     

The DFT study on non‐conjugated polymer host materials based on styrene derivatives for phosphorescent polymer light‐emitting diodes

A series of poly(4,4‐vinyltriphenylamine) based non‐conjugated polymer as host molecules are designed and studied by density functional theory. The results show that the substituent has a great influence on the properties of polymer. The parent molecule directly linked para‐carbazole, β‐pyrrole and triphenylamine are favorable to hole injection, and para‐carbazole could significantly increase E_T of the host molecules. The large changes of structural parameters between the lowest triplet state and ground state can cause the decrease of E_T. Moreover, parent molecule directly linked carbazole and triphenylamine units possess strong intramolecular charge transfer and low singlet and triplet energy difference (?E_ST). The calculated results also show that all designed host molecules are suitable for green emitter by comparing with the E_T. S₁ → S₁ and T₁ → T₁ energy transfer mechanism between host and guest is thermodynamically feasible. In addition, host–guest model is built to study the charge transfer nature, and the results indicate that a good intermolecular charge transfer can be achieved between host and guest materials. In the designed host molecules, the N atom of parent molecule linked para‐carbazole substituent shows a great potential for the green phosphorescent polymer light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

基于新型有机红色材料的薄膜电致发光

对一种名为N,N双[4[2(4二氰甲烯基6甲基)4H吡喃2基]乙烯基]苯基苯胺的新型有机红色材料(BDCM)进行了薄膜发光行为的研究.此材料的一个三苯胺(给电子基)和两个二氰甲烯吡喃(受电子基)所形成的较好空间位阻和强荧光发射能力,使得其固体薄膜具有很高的红色荧光量子产率.所构成的ITO/CuPc/DPPP/BDCM/Mg:Ag红色薄膜电致发光器件在外加电压为19V时亮度达到582cd/m².且此器件的发光颜色不随外加电流密度的改变而变化,表明此材料有很好的电子传输和红色发射性能     

Enhancement of electroluminescent properties of organic optoelectronic integrated device by doping phosphorescent dye

Organic optoelectronic integrated devices(OIDs) with ultraviolet(UV) photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence(TADF) material 4, 5-bis(carbazol-9-yl)-1, 2-dicyanobenzene(2 CzPN) as host. The OIDs doping with typical red phosphorescent dye [tris(1-phenylisoquinoline)iridium(Ⅲ), Ir(piq)_3], orange phosphorescent dye {bis[2-(4-tertbutylphenyl)benzothiazolato-N,C~(2')]iridium(acetylacetonate),(tbt)_2 Ir(acac)}, and blue phosphorescent dye [bis(2, 4-di-fluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(Ⅲ), FIr6] were investigated and compared. The(tbt)_2 Ir(acac)-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the(tbt)_2 Ir(acac)-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m~2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10~(11) Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.     

新型蓝绿色磷光配合物二(1-苯基吡唑)铱(吡啶三唑)的发光性能

利用1-苯基吡唑、吡啶三唑与水合三氯化铱反应合成了一种新型铱配合物Ir(2N)₂(PZ),研究了配合物的吸收光谱、光致发光光谱以及光致发光效率。利用该材料作为磷光客体,掺杂到高分子主体材料中制作了电致发光器件,研究了其电致发光光谱。结果表明,该配合物在228,250,328nm处存在自旋允许的¹π-π^*跃迁;荧光光谱结果显示在470nm处有较强的磷光发射;电致发光光谱与光致发光光谱相比却发生较大程度的红移。     

有机混合薄膜中的F(o)rster能量转移

通过掺杂不同的染料有机电致发光器件可以得到不同颜色的光发射。掺杂小分子有机材料?p酸四甲酯perylene-3,4,9,10-tetracarboxylicacid(TMEP)到蓝色发光聚合物poly(N-vinyl-carbazole)聚乙烯基咔唑(PVK),得到了很好的绿光发射。TEMP掺杂质量分数为0.01时,295. 5nm激发波长的荧光光谱可以明显观察到在420 nm处PVK和530 nm处TEMP的发射峰值;当TMEP掺杂质量分数达到0.05～0.10之间,器件的电致发光光谱和荧光光谱发射峰几乎完全被TEMP的绿光所占据。光谱的转移归因于从聚合物PVK到小分子有机材料TMEP的Forster能量转移。荧光光谱中随着TMEP掺杂浓度的的增大发射峰值有明显的红移,这种现象被归因于在TMEP高浓度掺杂情况下激基缔合物的形成。激基缔合物的形成从TMEP在薄膜状态下与溶液状态下的荧光光谱的比较中得到证实。