Li掺杂8-羟基喹啉铝的密度泛函理论研究

采用密度泛函理论研究了Li原子掺杂8-羟基喹啉铝(Alq₃)分子的几何构型、 前线分子轨道及电子转移特性. 研究结果表明, Li原子掺杂Alq₃后, Li原子与Alq₃的O, N原子键合, 形成电子转移复合物. Li原子将部分电子转移到Alq₃的吡啶环上, 在Alq₃的带隙内形成施主能级, 这种n型掺杂结构有效地提高了电子的传输效率; 但过多的Li原子的掺杂会使Alq₃分解, 从而减弱其电子传输能力. 为使Alq₃的电子传输能力达到最高, Li原子的掺杂应保持在2:1左右的比例.     

Highly Luminescent Material Based on Alq3:Ag Nanoparticles

Tris (8-hydroxyquinoline) aluminum (Alq₃) is an organic semiconductor molecule, widely used as an electron transport layer, light emitting layer in organic light-emitting diodes and a host for fluorescent and phosphorescent dyes. In this work thin films of pure and silver (Ag), cupper (Cu), terbium (Tb) doped Alq₃ nanoparticles were synthesized using the physical vapor condensation method. They were fabricated on glass substrates and characterized by X-ray diffraction, scanning electron microscope (SEM), energy dispersive spectroscopy, atomic force microscope (AFM), UV-visible absorption spectra and studied for their photoluminescence (PL) properties. SEM and AFM results show spherical nanoparticles with size around 70–80 nm. These nanoparticles have almost equal sizes and a homogeneous size distribution. The maximum absorption of Alq₃ nanoparticles is observed at 300 nm, while the surface plasmon resonant band of Ag doped sample appears at 450 nm. The PL emission spectra of Tb, Cu and Ag doped Alq₃ nanoparticles show a single broad band at around 515 nm, which is similar to that of the pure one, but with enhanced PL intensity. The sample doped with Ag at a concentration ratio of Alq₃:Ag?=?1:0.8 is found to have the highest PL intensity, which is around 2 times stronger than that of the pure one. This enhancement could be attributed to the surface plasmon resonance of Ag ions that might have increased the absorption and then the quantum yield. These remarkable result suggest that Alq₃ nanoparticles incorporated with Ag ions might be quite useful for future nano-optoelectronic devices.     

On the origin of exciton formation in dye doped Alq3 OLEDs

Electrically Detected Magnetic Resonance (EDMR) was used to investigate the influence of dye doping on spin-dependent exciton formation in aluminum (III) 8-hydroxyquinoline (Alq₃) based Organic Light Emitting Diodes (OLEDs) with different device structures. 4-(dicyanomethylene)-2-methyl-6-{2-[(4-diphenylamino)-phenyl]ethyl}-4H-pyran (DCM-TPA) and 5,6,11,12-tetraphenylnaphthacene (Rubrene) were used as dopants. Results at room temperature show significant differences on the EDMR spectra (g-factor and linewidth) of doped and undoped devices. Signals from DCM-TPA and Rubrene dye doped OLEDs showed strong temperature dependence, with signal intensity increasing by 2 orders of magnitude below 200 K for DCM-TPA dye doped OLEDs and increasing by ～1 order of magnitude below 225 K for the Rubrene dye doped device, while undoped devices shows almost no temperature dependence. By adding a “spacer” layer of undoped Alq₃ at the recombination zone, changes in bias voltage were used to shift the recombination from doped to undoped region and correlate that with changes in the EDMR spectrum. Our results are indicating that charge trapping on the dopant followed by recombination is the main mechanism of light emission in the investigated devices.     

Effect of distance between acceptor and donor on optical properties of composite semiconducting polymer films

The excitation energy transfer from poly(N-vinylcarbazole) (PVK) to tris(8-hydroxyquinoline) aluminum (Alq₃) in composite films was investigated by adding an inert polymer, poly(methyl methacrylate) (PMMA). The energy transfer efficiency calculated from the photoluminescence (PL) excitation spectra is consistent with that from the time-resolved PL decay data of the composite films. We have found a linear relationship between the two kinds of the distances, which are calculated according to volume density and the Förster theory. Experimental results and analyses provide a facile method to infer the energy transfer efficiency and the distance between the donor and the acceptor molecules in the composite films.     

Optical functions of tris (8-hydroxyquinoline) aluminum (Alq3) by spectroscopic ellipsometry

Optical functions of tris (8-hydroxyquinoline) aluminum (Alq₃) have been studied in the spectral range from 1.55 eV to 5 eV using spectroscopic ellipsometry. The samples have been deposited by thermal evaporation on glass substrates. Optical functions of Alq₃ deposited on unheated substrates and on substrates kept at 100 °C have been determined. The optical functions have been modeled using point-to-point fitting, with the conventional oscillator model and modified oscillator model. It has been found that point-to-point fitting gives the best agreement with the experimental data, and that the modified oscillator model yields better agreement with the experimental data than the conventional oscillator model. Received: 3 September 2001 / Accepted: 22 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +852-2559/8738, E-mail: dalek@eee.hku.hk     

Growth, morphology and optical properties of tris(8-hydroxyquinoline)aluminum/zinc oxide hybrid nanowires

Hybrid tris(8-hydroxyquinoline)aluminum/zinc oxide (Alq₃/ZnO) nanowires were successfully grown from a one-step solution method at very low temperature. The transformation of amorphous Alq₃ into α-phase crystalline nanowires was achieved by incorporating a certain weight fraction of crystalline ZnO nanomaterials. A growth mechanism was proposed to validate the formation of crystalline Alq₃-ZnO hybrid nanowires with the help of nucleation initiated by the ZnO nanomaterials, followed by Alq₃ molecular aggregation. Effects of temperature on the evolution of morphologies of hybrid nanowires were examined by the field-emission scanning electron microscopy (FESEM). The photoluminescence (PL) spectra of hybrid nanowires showed a significant threefold enhancement in PL intensity, along with a slight blue-shift emission, when compared to the pure Alq₃ molecules, which were attributed due to the incorporation of crystalline ZnO nanomaterials and also the shielding effect of ZnO nanomaterials to avoid the excimer formation between the Alq₃ molecules in the excited state.     

Porphyrin doping of Alq3 for electroluminescence

Organic light emitting devices based on tris(8-hydroxyquinoline)aluminium (Alq₃) doped with two fluorescent porphyrin derivatives, 5,15-diphenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin and the corresponding zinc metalated one, were fabricated. As a consequence, the light emission changed, from standard green light from Alq₃, to reddish and yellowish white respectively. The different spectral content in the two cases indicates a possible route to a white light emitter, based on several dopants from the same family of molecules with different central atoms. The turn-on voltage of the devices was not increased by the doping.     

The influence of exciton behavior on luminescent characteristics of organic light-emitting diodes

We used N,N′-bis-(1-naphthyl)-N,N′-1-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB), 4,4′-N,N′-dicarbazole-biphenyl (CBP) and tris(8-hydroxyquinoline) aluminum (Alq₃) to fabricate tri-layer electroluminescent (EL) device (device structure: ITO/NPB/CBP/Alq₃/Al). In photoluminescence (PL) spectra of this device, the emission from NPB shifted to shorter wavelength accompanying with the decrease of its emission intensity and moreover the emission intensity of Alq₃ increased relatively with the increase of reverse bias voltage. The blue-shifted emission and the decrease in emission intensity of NPB were attributed to the polarization and dissociation of NPB excitons under reverse bias voltage. The increase of emission intensity of Alq₃ benefited from the recombination of electrons (produced by the dissociation of NPB exciton) and holes (injected from the Al cathode).     

1.53 μm electroluminescence from ErF3-doped organic light-emitting diodes

Near-infrared (NIR) organic light-emitting devices (OLEDs) are demonstrated by employing erbium fluoride (ErF₃)-doped tris-(8-hydroxyquinoline) aluminum (Alq₃) as the emitting layer. The device structure is ITO/N,N′-di-1-naphthyl-N,N′-diphenylbenzidine (NPB)/Alq₃: ErF₃/2,2′,2″-(1,3,5-phenylene)tris(1-phenyl-1H-benzimidazole) (TPBI)/Alq₃/Al. Room-temperature electroluminescence around 1530 nm is observed due to the ⁴I_13/2–⁴I_15/2 transition of Er³⁺. Full width at half maximum (FWHM) of the electroluminescent (EL) spectrum is ～50 nm. NIR EL intensity from the ErF₃-based device is ～4 times higher than that of Er(DBM)₃Phen-based device at the same current. Alq₃–ErF₃ composite films are investigated by the measurements of X-ray diffraction (XRD), absorption, photoluminescence (PL) and PL decay time. Electron-only devices are also fabricated. The results indicate that energy transfer mechanism and charge trapping mechanism coexist in the NIR EL process.     

Influence of small-molecule material on performance of polymer solar cells based on MEH-PPV:PCBM blend

In this work,the influence of a small-molecule material,tris(8-hydroxyquinoline) aluminum (Alq 3),on bulk het-erojunction (BHJ) polymer solar cells (PSCs) is investigated in devices based on the blend of poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM).By dop-ing Alq 3 into MEH-PPV:PCBM solution,the number of MEH-PPV excitons can be effectively increased due to the energy transfer from Alq 3 to MEH-PPV,which probably induces the increase of photocurrent generated by excitons dissociation.However,the low carrier mobility of Alq 3 is detrimental to the efficient charge transport,thereby blocking the charge collection by the respective electrodes.The balance between photon absorption and charge transport in the active layer plays a key role in the performance of PSCs.For the case of 5 wt.% Alq 3 doping,the device performance is deteriorated rather than improved as compared with that of the undoped device.On the other hand,we adopt Alq 3 as a buffer layer instead of commonly used LiF.All the photovoltaic parameters are improved,yielding an 80% increase in power conversion efficiency (PCE) at the optimum thickness (1 nm) as compared with that of the device without any buffer layer.Even for the 5 wt.% Alq 3 doped device,the PCE has a slight enhancement compared with that of the standard device after modification with 1 nm (or 2 nm) thermally evaporated Alq 3.The performance deterioration of Alq 3-doped devices can be explained by the low solubility of Alq 3,which probably deteriorates the bicontinuous D-A network morphology;while the performance improvement of the devices with Alq 3 as a buffer layer is attributed to the increased light harvesting,as well as blocking the hole leakage from MEH-PPV to the aluminum (Al) electrode due to the lower highest occupied molecular orbital (HOMO) level of Alq 3 compared with that of MEH-PPV.     

Deep‐level characterization of emissive interface states in Alq3‐based OLEDs

We have succesfully investigated emissive interface states in fabricated indium‐tin‐oxide (ITO)/N,N′‐di‐1‐naphthyl‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4′diamine (α‐NPD)/tris(8‐hydroxyquinoline) aluminum (Alq₃)/LiF/Al organic light‐emitting diodes (OLEDs) by a modified deep‐level optical spectroscopy (DLOS) technique. In the vicinity of the α‐NPD/Alq₃ emissive interface, a discrete trap level was found to be located at ～1.77 eV below the conduction band of Alq₃, in addition to band‐to‐band transitions of carriers from α‐NPD to Alq₃. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of alkaline metal chlorides on the properties of organic light-emitting diodes

The multilayer organic light-emitting diodes (OLEDs) have been fabricated with a thin alkaline metal chloride layer inserted inside an electron transport layer (ETL), tris (8-hydroxyquinoline) aluminum (Alq₃). The alkaline metal chloride layer was inserted inside 60 nm Alq₃ at d=0, 10, 20 and 30 nm positions (d is the distance of the interlayer away from the Al cathode). The devices, with alkaline metal chlorides inserted at the Alq₃/Al interface, showed electron injection and electroluminescence (EL) intensity improvements. When the alkaline metal chlorides were inserted inside the Alq₃ layer at 10, 20 or 30 nm position apart from the Al cathode, both EL intensity and efficiency were enhanced for the devices with a thin potassium chloride (KCl) or rubidium chloride (RbCl) layer. On the contrary, the improvements were not observed for the OLEDs with a thin sodium chloride (NaCl) layer. A proposed insulator buffer layer model is employed to explain these characteristics of the devices.     

Photoluminescence spectroscopy study on tris(8-hydroxyquinoline) aluminum film

In situ photoluminescence spectroscopy (PL) measurements of tris(8-hydroxyquinoline) aluminum (Alq₃) film were carried out. Upon deposition of Alq₃ on the glass substrate, the PL intensity changes dramatically, while the peak position of Alq₃ emission shows a sharp red-shift from 524 nm at the initial deposition of Alq₃, and tends to a saturation value of 536 nm for the film thickness range from 2 to 500 nm. This red-shift is associated with the change from the 2D to 3D exciton state with increasing Alq₃ film thickness. Temperature dependent PL spectra of Alq₃ films showed, besides the changes in the PL intensity, clearly a blue-shift of Alq₃ emission about 9 nm for the film annealing up to 150 °C, while no any shift of Alq₃ emission was observed for the film annealing below 130 °C. Both changes in PL intensity, and especially in the peak position of Alq₃ emission were attributed to crystallization (thermal) effect of Alq₃ film upon annealing.     

Swift heavy ion irradiation-induced modifications of tris-(8-hydroxyquinoline)aluminum thin films

Tris-(8-hydroxyquinoline)aluminum (Alq₃), one of the most widely used light emitting and electron transport materials in organic luminescent devices, has been synthesized. Alq₃ thin films have been deposited by a thermal evaporation process on glass substrates. The effect of swift heavy ion (SHI) irradiation using 40 MeV Li³⁺ on the Alq₃ thin films has been studied by UV-visible, infrared, photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectroscopy. From TRPL studies, it is found that the PL of Alq₃ thin films arises from two species corresponding to its two geometrical isomers, namely facial and meridional having two different life times. It is also confirmed that the PL and lifetimes of excitons decrease with the increase of ion fluences of SHI of 40 MeV Li³⁺, indicating a transfer of exciton energy to unstable cationic Alq₃ species generated by SHI irradiation.     

Influence of atmospheric exposure of tris (8-hydroxyquinoline) aluminum (Alq<Subscript>3</Subscript>): a photoluminescence and absorption study

We have investigated the effects of atmospheric exposure on the properties of tris (8-hydroxyquinoline) aluminum (Alq₃) thin films by photoluminescence (PL) and UV-Vis absorption measurements. Alq₃ films were evaporated on glass substrates at different temperatures. The influence of annealing on the environmental stability of the films has also been investigated. It has been found that deposition at higher substrate temperature and annealing of the samples deposited at room temperature yield an improvement in the environmental stability of the films, i.e. less decrease in the PL intensity over time with exposure to atmosphere, as well as increased PL intensity. To investigate further the effects of the air exposure, films deposited at room temperature were stored for four days in air, nitrogen, and oxygen. No decrease in PL intensity has been found for storage in nitrogen, while the decrease for the film stored in oxygen was smaller than that for the film stored in air, indicating that both humidity and oxygen play a role in the PL intensity decrease in Alq₃ thin films. PACS 78.55.Kz; 78.40.Me     

Electrical bistability of CdS nanoparticles sandwiched between aluminum tris (8-hydroxyquinoline) layers

We report the electrical bistability of cadmium sulfide (CdS) nanoparticles (NPs) capped by dodecanethiol, which are sandwiched between aluminum tris (8-hydroxyquinoline) (Alq₃) layers. The current density–voltage (J–V) characteristics of the device with Al/Alq₃/CdS NPs/Alq₃/Al structures show the high- and low-conducting state at the same voltage, and the two states are reproducible by applying different negative sweeping voltages. The Ohmic model and the space–charge limited model are proposed and supported by the current density–voltage results, which give a possible transport mechanism for the electrical bistability of our devices.     

Effect of polar dopant on energetic and positional disorders in tris(8-hydroxyquinolinato) aluminum (Alq3)

The influence of polar dopant on the charge carrier transport in amorphous tris (8-hydroxyquinolinato) aluminum (Alq₃) was studied by time-of-flight measurement. The 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) was doped into Alq₃ with various concentration from 0.5 to 24 wt. %. The electron mobility was reduced by about one order by DCM doping in Alq₃. The electric-field dependence electron mobility in Alq₃:DCM films separated into two discrete regions of critical fields E_c ^1/2. The value of E_c ^1/2ranged from 360 to 405 (V/cm)^1/2 depending on the DCM concentration in Alq₃ films. The energetic disorder in Alq₃:DCM films increased from 0.01 eV to 0.09 eV with DCM doping concentration. The positional disorder in Alq₃:DCM films also increased from 0.3 to 6.5 with DCM doping concentration up to 24 wt. %. These results indicated the strong Coulombic and dipole–dipole interactions between DCM and Alq₃ molecules. The interactions between randomly located DCM molecules, Alq₃ dipoles and oriented dipoles are the major caused of positional disorder. PACS 73.50.-h; 73.61.Ph; 71.20.Rv     

Investigation of an efficient YbF3/Al cathode for tris-(8-hydroxyquinoline)aluminum-based small molecular organic light-emitting diodes

Efficient tris-(8-hydroxyquinoline)aluminum (Alq₃)-based organic light-emitting diodes (OLEDs) using YbF₃ as the electron injection layer have been investigated. With an YbF₃ (3.0 nm)/Al cathode, the device with Alq₃ as the emitting layer achieved a better performance than the control device with a LiF (0.5 nm)/Al cathode. The release of the low-work-function metal Yb is responsible for the performance enhancement. From the analysis by atomic force spectroscopy and X-ray photoemission spectroscopy, it is observed that the Alq₃-cathode interface could be well covered by YbF₃ at an optimum thickness of 3.0 nm, which helps to prevent the contact between Alq₃ and Al, and to reduce the destruction of Alq₃ by Al.     

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.     

Electronic structure of Alq3 and Liq using soft X-ray spectroscopy and density functional theory calculation

The electronic structure of aluminum tris-8-hydroxyquinoline (Alq₃) and 8-hydroquinolatolithium (Liq) was investigated using a combination of X-ray emission spectroscopy (XES), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and spectral simulation with density functional theory. The chemical bonding states of Alq₃ and Liq were analyzed using XPS core-level spectra. The band gaps of Alq₃ and Liq were measured by combining the XAS and XES results. Additionally, resonant and non-resonant XES were used to measure the density of states for O sites in the molecules.