Synthesis and electroluminescent properties of highly efficient anthracene derivatives with bulky side groups

Three new asymmetric light emitting organic compounds were synthesized with diphenylamine or triphenylamine side groups; 10-(3,5-diphenylphenyl)-N,N-diphenylanthracen-9-amine (MADa), 4-(10-(3,5-diphenylphenyl)anthracen-9-yl)-N,N-diphenylaniline (MATa), and 4-(10-(3′,5′-diphenylbiphenyl-4-yl)anthracen-9-yl)-N,N-diphenylaniline (TATa). MATa and TATa had a PL_max at 463 nm in the blue region, and MADa had a PL_max at 498 nm. MADa and MATa had T_g values greater than 120 °C, and TATa had a T_g of 139 °C. EL devices containing the synthesized compounds were fabricated in the configuration: ITO/4,4′,4′′-tris(N-(2-naphthyl)-N-phenyl-amino)-triphenylamine (2-TNATA) (60 nm)/N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB) (15 nm)/MADa or MATa or TATa or 9,10-di(2′-naphthyl)anthracene (MADN) (30 nm)/8-hydroxyquinoline aluminum (Alq₃) (30 nm)/LiF (1 nm)/Al (200 nm). The efficiency and color coordinate values (respectively) were 10.3 cd/A and (0.199, 0.152; bluish-green) for the MADa device, 4.67 cd/A and (0.151, 0.177) for the MATa device, and 6.07 cd/A and (0.149, 0.177) for the TATa device. The TATa device had a high external quantum efficiency (EQE) of 6.19%, and its luminance and power efficiencies and life-time were more than twice those of the MADN device.     

White emission polymer light-emitting devices with efficient electron injection from alcohol/water-soluble polymer/Al bilayer cathode

We demonstrate highly efficient white emission polymer light-emitting diodes (WPLEDs) from multilayer structure formed by solution processed technique, in which alcohol/water-soluble polymer, poly [(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) was incorporated as electron-injection layer and Al as cathode. It was found that the device performance was very sensitive to the solvents from solution of which the PFN electron-injection layer was cast. Devices with electron-injection layer cast from methanol solution show degraded performance while the best device performance was obtained when mixed solvent of water and methanol with ratio of 1:3 was used. We attribute the variation in device performance to washing out the electron transport material in the emissive layer due to rinse effect. As a result of alleviative loss of electron transport material in the emissive layer, the optimized device with a peak luminous efficiency of 18.5 cd A^?1 for forward-viewing was achieved, which is comparable to that of the device with same emissive layer but with low work-function metal Ba cathode (16.6 cd A^?1). White emission color with Commission International de I’Eclairage coordinates of (0.321, 0.345) at current 10 mA cm^?2 was observed.     

Design and synthesis of indole-substituted fullerene derivatives with different side groups for organic photovoltaic devices

A series of indole-substituted fulleropyrrolidine derivatives with different side groups on a pyrrolidine rings, including methyl (OIMC60P), benzyl (OIBC60P), 2,5-difluoroinebenzyl (OIB2FC60P), and 2,3,4,5,6-pentafluoroinebenzyl (OIB5FC60P), have been synthesized and used as electron acceptor in the active layer of polymer-fullerene solar cells to investigate the effect of various substitute groups on the electronic structures, morphologies, and device performances. Optical absorption, electrochemical properties and solubility of the fullerene derivatives have been explored and compared. The inverted photovoltaic devices with the configuration ITO/ZnO/Poly(3-hexylthiophene)(P3HT):[60]fullerene derivatives/MoO₃/Ag have been prepared including the reference cell based on the P3HT: methyl [6,6]-phenyl-C61-butylate (PCBM) blend films. All the devices properties were measured in air without encapsulation. We also investigated the effect of the thermal annealing on the crystallinity and morphology of the active layer and the device performance. The device based on the blend film of P3HT and OIBC60P showed a power conversion efficiency of 2.46% under illumination by AM1.5G (100 mW/cm²) after the annealing treatment at 120 °C for 10 min in air.     

具有高效空穴注入的高电子传输层的白光电致发光器件

以M003或m-MTDATA作为空穴注入层,Alqa或Bphen作为电子传输层组合了4组白色有机电致发光器件.发光层为9,10-bis(2-naphthyl)-2-t-butylanthracene(TBADN)掺杂3%的P-bis(P-N,N-diphenyl-aminos-tyryl)benzene(DSA-ph)作为蓝色掺杂剂和0.05%的4-(dicyanomethylene)-2-t-bul:yl-6-(1,1,7,7,-tetramethyl-julolidy-9-enyl)-4H-pyran(DCJTB)作为红色掺杂剂.研究表明基于M003//Bphen结构的器件大大降低了驱动电压,改善了功率效率,在电流密度为20 mA/cm2时,其值分别为5.43 V和4.54 lm/W.与基于m-MTDA-TA//Alq3结构的器件相比,驱动电压降低了40%,功率效率提高57%.     

Atomic layer deposited zirconium oxide electron injection layer for efficient organic light emitting diodes

In this work, we demonstrate efficient polyfluorene-based light emitting diodes on which conformal, thin ZrO₂ layers, formed by atomic layer deposition at a relatively low temperature (175 °C), in order to avoid introducing any damage in the organic under layer, efficiently inject electrons from their high lying conduction band to the polymer’s LUMO. An optimal thickness of 2 nm for ZrO₂ results in a threefold improvement in luminous current efficiency compared to the reference device. The relationship between the thickness of the ZrO₂ layer and the device operational characteristics is further investigated and the possible reasons for the improved device performance are discussed based on the experimental results obtained by a combination of photoemission spectroscopy and electrical/optical measurements.     

Polymer with conjugated alkylthiophenylthienyl side chains for efficient photovoltaic cells

A donor-acceptor (D-A) conjugated copolymer PSBT-FTT, incorporating alkylthiophenylthienyl (SBT) side chains on benzo[1,2-b:4,5-b']dithiophene units (BDT), was designed and synthesized. Compared to the analogical polymer PSB-FTT with alkylthiophenyl (SB) side chains, PSBT-FTT exhibits stronger interchain π-π interaction, more redshifted absorption spectrum, stronger absorption coefficient, better compatibility with (7,7)-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), more effective exciton dissociation and higher hole mobility. Therefore, the PSBT-FTT-based bulk heterojunction polymer solar cells (PSCs) achieved a PCE value of 7.06% that is almost 50% higher than 4.83% of the PSB-FTT based PSCs. The result indicates that the introducing SBT side chains is an excellent strategy for designing high performance photovoltaic polymers.     

Ethoxylated polyethylenimine as an efficient electron injection layer for conventional and inverted polymer light emitting diodes

We report inverted light emitting devices using ethoxylated polyethylenimine (PEIE) as a single electron injection layer for indium tin oxide cathode, which possess comparable efficiency to those using ZnO/PEIE double electron injection layers. Implementation of a PEIE layer between light emitting polymer layer and aluminum has been shown to significantly enhance device efficiency as well. Improvement of device efficiency can be attributed to increased electron injection due to the reduced work function of PEIE modified cathode as well as the hole blocking effect of PEIE layer. Furthermore, PEIE serves as an efficient electron injector for a range of light emitting polymers with wide distribution of energy levels.     

Low sublimation temperature cesium pivalate complex as an efficient electron injection material for organic light-emitting diode devices

Cesium pivalate ((CH₃)₃CCOOCs) has been synthesized and applied as an electron injection material for organic light-emitting diodes, which showed low sublimation temperature of 180 °C. Typical bilayer structure of ITO/NPB (60 nm)/Alq₃ (50 nm)/EIL/Al was used to evaluate the electron injection efficacy of (CH₃)₃CCOOCs, the results showed (CH₃)₃CCOOCs/Al exhibits better electron injection than LiF/Al cathode and the power efficiency was improved by about 19% at current density of 50 mA/cm². More interestingly, in the typical three layer OLED structure ITO/2-TNATA (60 nm)/NPB (10 nm)/Alq₃:2% C545T (40 nm)/MADN (15 nm)/(CH₃)₃CCOOCs (2 nm)/Al, the maximum current efficiency is up to 20 cd/A with Commission Internationale d’Eclairage (CIE_x,_y) color coordinates of (x = 0.30, y = 0.65) at current density of 140 mA/cm², which indicates that the non-aromatic alkali metal complex can also have good match with the chemically stable compound and exhibit good electron injection properties.     

An oligothiophene dye with triphenylamine as side chains for efficient dye-sensitized solar cells

A novel oligothiophene-cyanoacrylic acid photosensitizer with two triphenylamine side chains (7T-2TPA) is designed and synthesized for dye-sensitized solar cells. 7T-2TPA exhibits broad (250-600 nm) and strong absorption (ε = 5.0 × 10⁴ L mol⁻¹ cm⁻¹ at 496 nm). The optical band gap (E_g) is estimated from the onset absorption edge to be 2.07 eV. The oxidation potential E_ox and reduction potential E_red vs NHE of the dye is 0.93 and −1.14 V, respectively. Dye-sensitized solar cell (DSSC) based on 7T-2TPA exhibits an open-circuit voltage (V_oc) of 724 mV, a short-circuit current density (J_sc) of 16.28 mA cm⁻², a fill factor (FF) of 0.684 and a power conversion efficiency of 8.06%. The efficiency of 8.06% is similar to that for widely used N719-based cell fabricated and measured under the same conditions.     

Novel 4-(2,2-diphenyl-vinyl)-phenyl substituted pyrene derivatives as efficient emitters for organic light-emitting diodes

Two pyrene derivatives (PVPP and TPVPP) bearing 4-(2,2-diphenyl-vinyl)-phenyl side unit were developed for organic light-emitting diodes. Their photophysical, thermal, electrochemical, and electroluminescent properties as well as the film morphologies have been investigated in detail. Both of them exhibit high solid-state quantum yields, good thermal stability, and high glass-transition temperatures in the range of 127–150 °C. In particular, it is found that multiple side units can significantly affect the electrochemical properties to improve the electron injection. The LUMO energy level of TPVPP is −2.76 eV, which is very close to that of commonly used electron transport materials. The maximum luminance of OLED devices using TPVPP as an emitter layer is 103835 cd/m² with a maximum current efficiency of 5.19 cd/A and a maximum power efficiency of 3.38 lm/W.     

Tuning electron injection/transporting properties of 9,10-diphenylanthracene based electron transporters via optimizing the number of peripheral pyridine for highly efficient fluorescent OLEDs

By incorporating different number of pyridine rings to the periphery of the 9,10-diphenylanthracene (DPA) core, four new pyridine-containing DPA derivatives, 3-(4-(10-phenylanthracen-9-yl)phenyl)pyridine (AnPy), 9,10-bis(4-(pyridin-3-yl)phenyl)anthracene (AnDPy), 3,3'-((2-(pyridin-3-yl)anthracene-9,10-diyl)bis(4,1-phenylene))dipyridine (AnTPy), 3,3'-(9,10-bis(4-(pyridin-3-yl)phenyl)anthracene-2,6-diyl)dipyridine (AnFPy) were designed and synthesized as electron transporters. Their photophysical properties, energy levels and electron mobilities can be readily regulated through tuning the quantity of the pyridine ring. Through optimizing electron injection/transporting properties, AnTPy exhibits not only a suitable lowest unoccupied molecular orbital (LUMO) energy level for electron injection into light-emitting layer (EML), but also a relatively high electron mobility of around 10⁻³ cm² V⁻¹ s⁻¹, which is about two orders of magnitude higher than that of the widely used material Alq₃. As expected, the blue fluorescent OLEDs with AnPy, AnTPy and AnFPy as an electron-transporting layer (ETL) exhibited superior performance compared to that using Alq₃, remarkably lowering the driving voltages and improving efficiencies. In particular, the device with AnTPy as an ETL showed a maximum current efficiency of 14.4 cd A⁻¹, a maximum power efficiency of 12.1 lm W⁻¹, a maximum external quantum efficiency (EQE) of 8.15% and low efficiency roll-off even at an illumination-relevant luminance of 10,000 cd m⁻². These results clearly demonstrated that tuning electron injection/transporting properties by optimizing the number of peripheral electron-withdrawing groups was an efficient strategy to achieve high-performance ETMs.     

Increased photooxidation stability of pentacene derivatives linked with aromatic groups for OTFTs

Pentacene derivatives linked with aromatic groups at the 6,13-positions have been synthesized and characterized for their photooxidation properties. They exhibit high solubility which provides low-cost solution deposition methods. However, most of them are highly susceptible to photooxidation in solution determined with a few minutes of their half-life time under ambient conditions, practically precluding them from solution fabrication applications. Interestingly, their photooxidation stability can be significantly increased by blocking out light. The thin film transistor device for 3,4,5-trifluorophenyl-substituted pentacene (2c) showed the highest mobility of 1.1 × 10⁻² cm² V⁻¹ s⁻¹ with the threshold voltage of 20 V when it was prepared in the dark condition.     

Buffer-enhanced electron injection in organic light-emitting devices with copper cathode

We explore in this work the use of Cu as a cathode material in organic light-emitting devices (OLEDs) and find a dual electron–injection enhancement mechanism derived from the LiF layer. Different from what observed previously in Ag- and Au-cathode devices, the LiF buffer layer in the Cu-cathode OLEDs starts to play its role in performance improvement when it is much thinner than 3 nm, the optimal value of buffer thickness, and in the case of optimal thickness, the device exhibits excellent performance comparable to conventional Al-cathode device. The phenomenon observed is ascribed to enhanced electron injection as a result of combined effect of interfacial reaction and tunneling barrier reduction mechanism: while chemical reaction plays a key role at the very beginning of interface formation, tunneling dominates in the subsequent stage leading to the tremendous improvement of the characteristics.     

石墨烯掺杂Cs2CO3作为高效电子注入层的OLEDs性能研究

研制了石墨烯掺杂Cs₂CO₃(Cs₂CO₃:Graphe ne )作为高效电子注入层、结构为ITO/N,N′-bis-(1-naphthyl) -N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB)(50 nm)/tris-(8-hydroxy quinoline)-aluminum Alq₃(80 nm)/Cs₂CO₃:Gra phene (mss 20% 1nm)/Al(120 nm)的OLEDs。将其与标准器件ITO/NPB(50 nm)/Alq₃(80 n m)/LiF(0.5 nm)/Al(120 nm)作性能比较,研究石墨烯掺杂在Cs₂CO₃中作为电子注入层 对 OLEDs性能的影响。结果表明,基于Cs₂CO₃:Graphene结构作为电子注入层的器 件效率要高于LiF作为电子注入层的器件,其最大电流效率达到2.02 cd/A, 是标准器件的2.59倍;亮度也高于LiF作为电子注入层的器件,在10 V时达 到最大值7690cd/m²,是标准器件最大亮度 的2.07倍。性能得到提高的主要机理是由于Cs₂CO₃:Graphene的引入提高了电子注入效率。     

Electron injection in inverted organic light-emitting diodes with poly(ethyleneimine) electron injection layers

Electron-injection mechanisms from the air-stable metal-oxide cathode to light-emitting polymer layer are studied. The device configuration is aluminum (Al) doped zinc oxide (AZO)/poly(ethyleneimine) (PEI)/poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT)/molybdenum trioxide/Al, known as an inverted organic light-emitting diode (iOLED). PEI reduces the electron injection barrier between AZO and F8BT by 0.4 eV, and blocks holes at AZO(PEI)/F8BT interface in iOLEDs. The accumulation of holes at the interface greatly enhances the electron injection because of the Fowler-Nordheim type tunneling injection, leading to high current efficiency of iOLEDs.     

Highly efficient near-infrared emission from binuclear cyclo-metalated platinum complexes bridged with 5-(4-octyloxyphenyl)-1,3,4-oxadiazole-2-thiol in PLEDs

A novel near-infrared-emitting binuclear platinum complex of (piq)₂Pt₂(μ-C₈OXT)₂ was synthesized and characterized, in which piq is 1-phenylisoquinolinato and C₈OXT is a bridging ancillary ligand of 5-(4-octyloxyphenyl)-1,3,4-oxadiazole)-2-thiol. Its optophysical, electrochemical and electroluminescent characteristics were primary studied. This binuclear platinum complex exhibited an intense UV absorption at about 493 nm from the metal–metal-to-ligand charge transfer transition and a bright near-infrared emission at 721 nm in chloromethane. Using (piq)₂Pt₂(μ-C₈OXT)₂ as a single dopant, its single-emissive-layer polymer light-emitting devices presented a high-efficiency near-infrared emission peaked at 702 nm with the maximum external quantum efficiency of 6.3% at 7.6 mA cm^?2. This work provides an efficient approach to realize high-efficiency near-infrared emission by binuclear platinum complexes.     

Lithium phenolate complexes for an electron injection layer in organic light-emitting diodes

We synthesized π-conjugated lithium phenolate complexes, lithium 2-(2-pyridyl)phenolate (LiPP), lithium 2-(2′, 2′′-bipyridine-6′-yl)phenolate (LiBPP), and lithium 2-(isoquinoline-1′-yl)phenolate (LiIQP). These complexes showed lower sublimation temperatures of 305–332 °C compared to 717 °C of LiF. The organic light-emitting devices (OLEDs) using these complexes as an electron injection layer exhibited high efficiencies which are comparable to that of the device using LiF. Especially, a 40-nm thick film of LiBPP or LiPP was effective as an electron injection material, providing low driving voltages, while such a thick film of LiF serves as a complete insulator, resulting in high driving voltages.     

A high performance inverted organic light emitting diode using an electron transporting material with low energy barrier for electron injection

A high performance inverted green emission organic light emitting diode with a maximum external quantum efficiency of 20% and a maximum power efficiency of 80 lm/W was realized by properly selecting an electron transporting material to have no energy barrier for electron injection between the n-doped electron transporting layer (n-ETL) and the ETL. Based on the energy levels and the current density–voltage characteristics of electron only devices, we demonstrate that the interface between an n-ETL and an ETL even in homo-junction is as important as the interface between the cathode and the n-ETL for efficient electron injection into an emitting layer.     

Novel viologen derivatives for electrochromic ion gels showing a green-colored state with improved stability

We successfully synthesized a novel viologen derivative (1,1′-bis(3-fluoro-4-(trifluoromethyl)phenyl)-4,4′-bipyridinium bis(trifluoromethylsulfonyl)imide, TFMFPhV(TFSI)₂) exhibiting a green-colored state. We selected cyanophenyl viologen (CNPhV²⁺), a conventional electrochromic (EC) chromophore with a green color indication, to compare EC performance. Ion gels consisting of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) were employed as a solid-state electrolyte for EC devices (ECDs). In comparison to CNPhV²⁺-containing devices, the ECDs with TFMFPhV²⁺ showed higher transmittance contrast, larger coloration efficiency, faster coloration and bleaching responses, and better coloration/bleaching operational stability. Cyclic voltammetry revealed that the more stable redox behavior of TFMFPhV²⁺ is the origin of the outstanding ECD performance.     

Development of a gas injection/specimen heating holder for use with transmission electron microscope

A new gas injection/specimen heating holder is developed for the purpose of in situ observation of gas reaction of materials at high temperatures in a transmission electron microscope at near-atomic resolution. A fine tungsten wire is employed as a heating element of the holder and a battery is used as the power source. Gas was injected onto specimens in the form of particles lying on the heating element via a nozzle. The maximum pressure near specimens was middle of 10(-2) Pa, while the pressure in the electron-gun chamber was kept to 2 x 10(-4) Pa. This gas injection/specimen heating holder was applied to observe solid-gas reactions. The reactions observed include oxidation of pure In into In2O3, reduction of SiO2 into Si and re-oxidation of Si into SiO2.