Hole transport materials with high glass transition temperatures for highly stable organic light-emitting diodes

Two hole transport materials with high glass transition temperatures (T_g ~ 200 °C) have been synthesized by replacing the phenyl groups of 4,4′-bis[N-(1-naphthyl-1)-N′-phenyl-amino]-biphenyl (α-NPD) with the bulkier phenanthrene (N,N′-di(naphthalene-1-yl)-N,N′-di(phenanthrene-9-yl)biphenyl-4,4′-diamine, NPhenD) or anthracene (N,N′-di(anthracene-9-yl)-N,N′-di(naphthalene-1-yl)biphenyl-4,4′-diamine, NAD). The organic light-emitting diodes (OLEDs) using these hole transport materials exhibited stable operation at high temperatures up to 420 K, improved device lifetimes, and reduced operating voltage changes compared to the conventional hole transport materials owing to their high T_g. Although NAD has quite small bandgap as a hole transport material, superior thermal properties of NPhenD and NAD suggest that they can be promising materials for highly stable and high temperature-durable OLEDs and other organic optoelectronic devices.     

Highly efficient red phosphorescent Ir(III) complexes for organic light- emitting diodes based on aryl(6-arylpyridin-3-yl)methanone ligands

A series of phosphorescent Ir(III) complexes 1-4 were synthesized based on aryl(6-arylpyridin-3-yl)methanone ligands, and their photophysical and electroluminescent properties were characterized. Multilayer devices with the configuration, Indium tin oxide/4,4′,4″-tris(N-(naphthalene-2-yl)-N-phenyl-amino)triphenylamine (60 nm)/4,4′-bis(N-(1-naphthyl)-N-phenylamino)biphenyl (20 nm)/Ir(III) complexes doped in N,N′-dicarbazolyl-4,4′-biphenyl (30 nm, 8%)/2,9-dimethyl-4,7-diphenyl-phenathroline (10 nm)/tris(8-hydroxyquinoline)-aluminum (20 nm)/lithium quinolate (2 nm)/ Al (100 nm), were fabricated. Among these, the device employing complex 2 as a dopant exhibited efficient red emission with a maximum luminance, luminous efficiency, power efficiency and quantum efficiency of 16200 cd/m² at 14.0 V, 12.20 cd/A at 20 mA/cm², 4.26 lm/W and 9.26% at 20 mA/cm², respectively, with Commission Internationale de l'Énclairage coordinates of (0.63, 0.37) at 12.0 V.     

Oxygen-sensing properties of ormosil hybrid materials doped with ruthenium(II) complexes via a sol-gel process

Organically modified silicate (ormosil) materials doped with [4,4′-dimethyl-2,2′-bipyridine-bis(2,2′-bipyridine)] ruthenium(II) dichloride ([Ru-mbpy]²⁺) and [4,4′-dimethylformate-2,2′-bipyridine-bis(2,2′-bipyridine)] ruthenium(II) dichloride ([Ru-dmfbpy]²⁺) were prepared by a sol-gel procedure for oxygen-sensing applications. The results indicated that the concentrations of the Ru(II) diimine complexes obviously influenced the linearity of Stern-Volmer plots (I₀ /I vs. O₂%). The best suitable concentrations of [Ru-mbpy]²⁺ and [Ru-dmfbpy]²⁺ in the sol for oxygen sensors were found to be 1.0 × 10^− 3 M and 2.5 × 10^− 3 M, respectively. The fluorescence quenching time and recovery time of oxygen sensor doped with [Ru-mbpy]²⁺ (1.0 × 10^− 3 M) were 18 s and 38 s and those doped with [Ru-dmfbpy]²⁺ (1.0 × 10^− 3 M) were 13 s and 32 s, respectively. The oxygen sensor based on Ru(II) complex modified by esterification demonstrated excellent linear calibration relationship and improved long-term stability.     

Spray-pyrolysis Cd2SnO4 films for electrochemical applications

Conductive cadmium stannate (Cd₂SnO₄,) films were grown by a simple spray-pyrolysis technique using aerosols ultrasonically generated from solutions containing Cd(thd)₂(TMEDA) and ⁿBu₂Sn(AcAc)₂, and monoglyme as solvent (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate, TMEDA = N,N,N′,N′-tetramethylethylenediamine, AcAc = acethylacetonate). The overall film growing procedure was carried out at or below 400 °C thus allowing low-melting temperature materials like glass to be used as film substrates. Typical resistivity values of Cd₂SnO₄ films were found to be ∼ 2 · 10 ⁻³ Ωcm. The films exhibit excellent electrochemical activity with comparable or higher electron transfer rates than cadmium stannate films obtained via sol-gel methods at high annealing temperature.     

Photo/electroluminescence properties of an europium (III) complex doped in 4,4′-N,N′-dicarbazole-biphenyl matrix

The photoluminescence properties of one europium complex Eu(TFNB)₃Phen (TFNB = 4,4,4-trifluoro-1-(naphthyl)-1,3-butanedione, Phen = 1,10-phenanthroline) doped in a hole-transporting material CBP (4,4′-N,N′-dicarbazole-biphenyl) films were studied. A series of organic light-emitting devices (OLEDs) using Eu(TFNB)₃Phen as the emitter were fabricated with a multilayer structure of indium tin oxide, 250 Ω/square)/TPD (N,N′-diphenyl-N,N′-bis(3-methyllphenyl)-(1,1′-biphenyl)-4,4′-diamine, 50 nm)/Eu(TFNB)₃phen (x): CBP (4,4′-N,N′-dicarbazole-biphenyl, 45 nm)/BCP (2,9-dimethyl-4,7-diphenyl-l,10 phenanthroline, 20 nm)/AlQ (tris(8-hydroxy-quinoline) aluminium, 30 nm)/LiF (1 nm)/Al (100 nm), where x is the weight percentage of Eu(TFNB)₃phen doped in the CBP matrix (1-6%). A red emission at 612 nm with a half bandwidth of 3 nm, characteristic of Eu(III) ion, was observed with all devices. The device with a 3% dopant concentration shows the maximum luminance up to 1169 cd/m² (18 V) and the device with a 5% dopant concentration exhibits a current efficiency of 4.46 cd/A and power efficiency of 2.03 lm/W. The mechanism of the electroluminescence was also discussed.     

Organic and inorganic hybrid film with second-order nonlinear optical and pyroelectric properties

An organic and inorganic hybrid material was prepared from a nonlinear optically active imidazole derivative 4-(nitrophenyl)-2,4-Bis-(4,4′-[N,N-bis-(2-hydroxyethyl)aminophenyl]) imidazole and metal alkoxide of Nb(V) via sol-gel process. The second-order nonlinear optical and pyroelectric properties of the hybrid film were investigated in terms of the second harmonic generation (SHG) and pyroelectric coefficient measurement. The SHG coefficient d₃₃ was found to be 29.3 pm/V at the fundamental wavelength of 1064 nm and the pyroelectric coefficient P was found to be 1.47 × 10^− 6 C/cm² K.     

Blue electroluminescent materials based on 2,7-distyrylfluorene for organic light-emitting diodes

A series of blue fluorescent 9,9-diethyl-2,7-distyryl-9H-fluorene derivatives with various capping moieties such as diphenylamino; diphenylphosphino; triphenylsilyl; phenoxy; phenylmercapto; phenylselenoxy; and triphenymethyl groups were synthesized using the Honor-Emmons reaction. The highest occupied molecular orbital-lowest unoccupied molecular orbital energy levels were characterized with a photoelectron spectrometer and rationalized with quantum mechanical density functional theory calculations. The electroluminescent properties were explored through the fabrication of multilayer devices with a structure of Indium-tin-oxide/N,N′-diphenyl-N,N′-(1-napthyl)-(1,1′-phenyl)-4,4′-diamine/2-methyl-9,10-di(2-naphthyl)anthracene:blue dopants (5-15 wt.%)/4,7-diphenyl-1,10-phenanthroline/lithium quinolate/Al. All devices, except that using NPh₂, exhibited a Commission Internationale de I'Eclairage (CIE) y value less than 0.19. The best luminous efficiency of 3.87 cd/A and external quantum efficiency of 2.65% at 20 mA/cm² were obtained in a device comprising the 4-phenylsulfanyl capped 9,9-diethyl-2,7-distyrylfluorene derivative with CIE coordinates (0.16, 0.18).     

Red-phosphorescent OLEDs employing iridium (III) complexes based on 5-benzoyl-2-phenylpyridine derivatives

A series of red-phosphorescent iridium (III) complexes 1-4 based on 5-benzoyl-2-phenylpyridine derivatives was synthesized. Their photophysical and electrophosphorescent properties were investigated. Multilayered OLEDs were fabricated with a device structure ITO/4,4′,4″-tris(N-(naphtalen-2-yl)-N-phenyl-amino)triphenylamine (60 nm)/4,4′-bis(N-naphtylphenylamino)biphenyl (20 nm)/Ir(III) complexes (8%) doped in 4,4′-N,N′-dicarbazolebiphenyl (30 nm)/2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (10 nm)/tris(8-hydroxyquinolinyl)aluminum(III) (20 nm)/Liq (2 nm)/Al (100 nm). All devices exhibited efficient red emissions. Among those, in a device containing iridium complex 1 dopant, the maximum luminance was 14200 cd/m² at 14.0 V. Also, its luminous, power, and quantum efficiency were 10.40 cd/A, 3.44 lm/W and 9.21% at 20 mA/cm², respectively. The peak wavelength of the electroluminescence was 607 nm, with CIE coordinates of (0.615, 0.383) at 12.0 V, and the device also showed a stable color chromaticity with various voltages.     

Electroluminescence of a device based on europium β-diketonate with phosphine oxide complex

Rare earth (RE) ions have spectroscopic characteristics to emit light in narrow lines, which makes RE complexes with organic ligands candidates for full color OLED (Organic Light Emitting Diode) applications. In particular, β-diketone rare earth (RE³⁺) complexes show high fluorescence emission efficiency due to the high absorption coefficient of the β-diketone and energy transfer to the central ion. In this work, the fabrication and the electroluminescent properties of devices containing a double and triple-layer OLED using a new β-diketone complex, [Eu(bmdm)₃(tppo)₂], as transporting and emitting layers are compared and discussed. The double and triple-layer devices based on this complex present the following configurations respectively: device 1: ITO/TPD (40 nm)/[Eu(bmdm)₃(tppo)₂] (40 nm)/Al (150 nm); device 2: ITO/TPD (40 nm)/[Eu(bmdm)₃(tppo)₂] (40 nm)/Alq₃ (20 nm)/Al (150 nm) and device 3: ITO/TPD (40 nm)/bmdm-ligand (40 nm)/Al (150 nm), were TPD is (N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1-biphenil-4,4-diamine) and bmdm is butyl methoxy-dibenzoyl-methane. All the films were deposited by thermal evaporation carried out in a high vacuum system. These devices exhibit high intensity photo- (PL) and electro-luminescent (EL) emission. Electroluminescence spectra show emission from Eu³⁺ ions attributed to the ⁵D₀ to ⁷F_J (J = 0, 1, 2, 3 and 4) transitions with the hypersensitive ⁵D₀ → ⁷F₂ transition (around 612 nm) as the most prominent one. Moreover, a transition from ⁵D₁ to ⁷F₁ is also observed around 538 nm. The OLED light emission was almost linear with the current density. The EL CIE chromaticity coordinates (X = 0.66 and Y = 0.33) show the dominant wavelength, λ_d = 609 nm, and the color gamut achieved by this device is 0.99 in the CIE color space.     

Preparation and properties of transparent conductive indium-tin-oxide/polyimide substrates via a sol-gel process

High temperature, flexible and colorless indium-tin-oxide (ITO) coated plastic substrates have been prepared from a series of thermally stable, high glass transition temperature (T_g) and colorless copolyimide films. The copolyimides were synthesized from 3,3′-diaminodiphenylsulfone, 9,9′-bis(4-aminophenyl) fluorene and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride monomers. Their T_gs were around 285-365 °C. The conductive ITO was synthesized by a sol-gel method, and then deposited onto the copolyimide films by a spin coating process. After thermal treatment at 300 °C under a nitrogen/hydrogen mixture gas for 24 h, the resistivity of the ITO film was 10⁻³ Ω cm, and its transmittance was 75% at the visible light region. Scanning electron microscopy and X-ray diffraction were used to observe the surface and morphology of the ITO films. UV-visible spectroscopy and the four-probe method were used to study their optical and electrical properties. The high performance ITO/plastic substrates can be used in the next generation flexible flat panel displays and solar cell.     

Dependence of efficiency of thin-film CdS/CdTe solar cell on parameters of absorber layer and barrier structure

Dependences of the open-circuit voltage, short-circuit current, fill factor, and efficiency of a CdS/CdTe solar cell on the resistivity and thickness of the p-CdTe absorber layer, the noncompensated acceptor concentration N_a-N_d, and carrier lifetime τ in CdTe, are investigated, and optimization of these parameters in order to improve the solar cell efficiency is performed. It has been shown that the observed low efficiency of CdS/CdTe solar cells is caused by the too short electron lifetime in the range of 10^− 10-10^− 9 s and too thin (3-5 µm) CdTe layer currently used for fabrication of CdTe/CdS solar cells. To achieve an efficiency of 28-30%, the resistivity and thickness of the CdTe absorber layer, the noncompensated acceptor concentration, and carrier lifetime should be ∼ 0.1 Ω·cm, ≥ 20-30 µm, ≥ 10¹⁶ cm^− 3, and ≥ 10^− 6 s, respectively.     

Structural, electrical and optical properties of Ga-doped ZnO films on cyclo-olefin polymer substrates

Ga-doped ZnO (GZO) films with a thickness of 100 nm were prepared on cyclo-olefin polymer (COP) and glass substrates at various temperatures below 100 °C by ion plating with direct-current arc discharge. The dependences of the characteristics of GZO films on the substrate temperature Ts were investigated. All the polycrystalline GZO films, which exhibited a high average visible transmittance of greater than 86%, were crystallized with a wurtzite structure oriented along the c-axis. The lowest resistivities of the GZO films were 5.3 × 10^− 4 Ωcm on the glass substrate and 5.9 × 10^− 4 Ωcm on the COP substrate.     

Influence of thermal annealing on photoluminescence and structural properties of N,N′-diphenyl-N,N′-bis(1-naphthylphenyl)-1,1′-biphenyl-4,4′-diamine (α-NPD) organic thin films

Photoluminescence (PL) spectra and intensities of thin N,N′-diphenyl-N,N′-bis(1-naphthylphenyl)-1,1′-biphenyl-4,4′-diamine (α-NPD) films have been measured at room temperature, during sample heating with various rates and annealing times at constant temperatures, and after annealing. It was found that the temperature of T = 80 °C being considerably lower than the glass transition temperature of α-NPD is sufficient to cause substantial irreversible changes in PL and PL excitation characteristics. A PL efficiency increase up to 10 times, an emission spectrum short-wavelength shift up to 130 meV and a spectral narrowing from 69 to 39 nm are reached using annealing. The surface roughness of the films annealed at the moderate temperature of 80 °C does not undergo observable changes contrary to films annealed at higher temperatures.     

Electrical and optical properties of indium tin oxide films prepared on plastic substrates by radio frequency magnetron sputtering

The influence of deposition power, thickness and oxygen gas flow rate on electrical and optical properties of indium tin oxide (ITO) films deposited on flexible, transparent substrates, such as polycarbonate (PC) and metallocene cyclo-olefin copolymers (mCOC), at room temperature was studied. The ITO films were prepared by radio frequency magnetron sputtering with the target made by sintering a mixture of 90 wt.% of indium oxide (In₂O₃) and 10 wt.% of tin oxide (SnO₂). The results show that (1) average transmission in the visible range (400-700 nm) was about 85%-90%, and (2) ITO films deposited on glass, PC and mCOC at 100 W without supplying additional oxygen gas had optimum resistivity of 6.35 × 10⁻⁴ Ω-cm, 5.86 × 10⁻⁴ Ω-cm and 6.72 × 10⁻⁴ Ω-cm, respectively. In terms of both electrical and optical properties of indium tin oxide films, the optimum thickness was observed to be 150-300 nm.     

RF diode reactive sputtering of n- and p-type zinc oxide thin films

We present the relationship between parameters of reactive RF diode sputtering from a zinc oxide (ZnO) target and the crystalline, electrical and optical properties of n-/p-type ZnO thin films. The properties of the ZnO thin films depended on RF power, substrate temperature and, particularly, on working gas mixtures of Ar/O₂ and of Ar/N₂. Sputtering in Ar+O₂ working gas (up to 75% of O₂) improved the structure of an n-type ZnO thin film, from fibrous ZnO grains to columnar crystallites, both preferentially oriented along the c-axis normally to the substrate (〈0 0 2〉 direction). These films had good piezoelectric properties but also high resistivity (ρ≈10³ Ω cm). ZnO:N p-type films exhibited nanograin structure with preferential 〈0 0 2〉 orientation at 25% N₂ and 〈1 0 0〉 orientation for higher N₂ content. The presence of nitrogen N_O at O-sites forming N_O-O acceptor complexes in ZnO was proven by SIMS and Raman spectroscopy. A minimum value of resistivity of 790 Ω cm, a p-type carrier concentration of 3.6×10¹⁴ cm⁻³ and a Hall mobility of 22 cm² V⁻¹ s⁻¹ were obtained at 75% N₂.     

Very-low temperature specific heat of Torlon

The specific heat of Torlon has been measured in the 0.15-4.2 K temperature range. Data below 1 K can be represented by c(T) = P₁T^1+δ + P₂T³, with P₁ = (5.41 ± 0.08)·10⁻⁶J K^−(2+δ) g⁻¹, P₂ = (2.82 ± 0.03) ·10⁻⁵JK⁻⁴g⁻¹ and δ = 0.28 ± 0.01, as predicted by the tunnelling theory. Above 1 K, the behaviour of c(T) is similar to that of other amorphous materials and can be expressed as: c(T) = P · T^Ω with P = (2.68 ± 0.07)·10⁻⁵JK^Ω+1g⁻¹ and Ω = 3.32 ± 0.02.     

Self-assembly of perylenediimide based semiconductor on polymer substrate

The continuous bi-layer composites consisting of top, ordered crystalline layer of perylenediimide derivative (2,9-di(pent-3-yl)-anthra[,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetrone) - PTCDI-C5(3) and bottom poly(3-hexylthiophene-2,5-diyl) (P3HT) support were obtained from one solution, with a use of so called “two-step reticulate doping” method. Optical, atomic force and scanning electron microscopy images show that the top crystalline layer is made of relatively large, anisotropic domains composed of long, parallel crystals. The crystalline character of the surface layer of PTCDI-C5(3) grown on the P3HT film was confirmed by wide angle X-ray scattering measurements. Furthermore, the grazing-incidence angle X-ray diffraction experiments revealed that the self-assembly of PTCDI-C5(3) molecules on P3HT is dominated by π−π interaction between the conjugated perylene cores, and the stacks are parallel to the long axis of the crystals and to the polymer surface. The surface conductivity, measured along the long axis of the crystals was estimated to be ca. 2.4 10^− 8 Ω^− 1 square^− 1 at 285 K. Temperature dependence of the conductivity in the range 140-285 K reveal semiconductor-like behaviour with activation energy ca. 150 meV.     

Deposition of zirconium oxynitride films by reactive cathodic arc evaporation and investigation of physical properties

The area of metal oxynitrides is poorly explored, and understanding of the fundamental mechanism that explains structural, mechanical, electrical, and optical properties is still insufficient. Therefore, the purpose of the present investigation is to analyze structural, electrical, and optical properties of ZrN_xO_y films deposited by reactive cathodic arc evaporation.Depending on the oxygen flow, cubic ZrN:O, monoclinic ZrO₂:N, and tetragonal ZrO₂:N phases films were prepared. The sheet resistance and the optical transmittance very much depend on the oxygen flow. Optical transparent ZrN_xO_y films with transmittance of 86% at 650 nm, the sheet resistance 1.1 · 10³ Ω/sq, and the figure of merit 2 · 10^− 4 Ω^− 1 are deposited with the 60 sccm oxygen flow.     

Relaxor ferroelectric like giant permittivity in PrCrO3 semiconductor ceramics

The electrical behavior of PrCrO₃ ceramics prepared by citric acid route and sintered at 1200 °C has been characterized by a combination of permittivity measurements, and impedance spectroscopy (IS). The effective permittivity obtained in frequency range 100 Hz to 1 MHz and temperature range 80–300 K, exhibits giant permittivity value of 3 × 10⁴ near room temperature. The response is similar to that observed for relaxor ferroelectrics. IS data analysis revealed the ceramics to be electrically heterogeneous semiconductor with room temperature resistivity <10² Ω m consisting of semiconducting grains with permittivity ?′ ∼ 100 and more resistive grain boundaries with effective permittivity ?′ ∼ 10⁴. We conclude, therefore that grain boundary effect is the primary source for the high effective permittivity in PrCrO₃ ceramics.     

Conduction mechanism and magnetic behavior of dysprosium strontium iron garnet (DySrIG) nanocrystals

Garnet nanoparticles Dy_2.8Sr_0.2Fe₅O₁₂ (DySrIG) were prepared by citrate auto-combustion method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and differential thermal analysis (DTA). The suitable formation of this garnet in single phase was at 1100 °C with crystallite of size 95 nm. The Curie temperature of DySrIG is obtained at 610 K. The effective magnetic moment μ_eff was calculated experimentally and theoretically and they are compatible with each other. The dielectric constant ?′ increases from order 10² at room temperature to 10⁴ at 850 K passing by four transition temperatures. The temperature dependence of the resistivity of DySrIG at different frequencies (f) 100 kHz ≤ f ≤ 5 MHz indicates the presence of 5 transition temperatures which are slightly different from those of ?′ data. The resistivity data are frequency independent at f < 1 MHz. The transition height is decreased by increasing the temperature from ≈5 MΩ cm at 320 K and 200 kHz to ≈20 Ω cm at 700 K. Accordingly, Dy_2.8Sr_0.2Fe₅O₁₂ (DySrIG) is recommended for the use in phase shifter, circulators and microwave applications.