Change of the dominant luminescent mechanism with increasing current density in molecularly doped organic light-emitting devices

We have fabricated and measured a series of electroluminescent devices with the structure of ITO/TPD/Eu(TTA)(3)phen (x):CBP/BCP/ ALQ/LiF/Al, where x is the weight percentage of Eu(TTA)3phen (from 0% to 6%). At very low current density, carrier trapping is the dominant luminescent mechanism and the 4% doped device shows the highest electroluminescence (EL) efficiency among all these devices. With increasing current density, Forster energy transfer participates in EL process. At the current density of 10.0 and 80.0mA/ cm(2), 2% and 3% doped devices show the highest EL efficiency, respectively. From analysis of the EL spectra and the EL efficiency-current density characteristics, we found that the EL efficiency is manipulated by Forster energy transfer efficiency at high current density. So we suggest that the dominant luminescent mechanism changes gradually from carrier trapping to Forster energy transfer with increasing current density. Moreover, the conversion of dominant EL mechanism was suspected to be partly responsible for the EL efficiency roll-off because of the lower EL quantum efficiency of Forster energy transfer compared with carrier trapping.

Improved color purity and efficiency by a coguest emitter system in doped red light-emitting devices

We demonstrate red organic light-emitting diodes (OLEDs) with improved color purity and electroluminescence (EL) efficiency by codoping a green fluorescent sensitizer 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1, 1, 7,7-tetramethyl-1H, 5H, 11H-(1)-benzopyropyrano(6,7-8-ij)quinolizin-11-one (C545T) as the second dopant and a red fluorescent dye 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as the lumophore into tris(8-hydroquinoline) aluminum (Alq(3)) host. It was found that the C545 T dopant did not by itself emit but assisted the carrier trapping from the host Alq(3) to the red emitting dopant. The red OLEDs realized by this approach not only kept the purity of the emission color, but also significantly improved the EL efficiency. The current efficiency and power efficiency, respectively, reached 12 cd/A at a current density of 0.3 mA/cm(2) and 10lm/W at a current density of 0.02 mA/cm(2), which are enhanced by 1.4 and 2.6 times compared with devices where the emissive layer is composed of the DCJTB doped Alq(3), and a stable red emission (chromaticity coordinates: x = 0.64, y = 0.36) was obtained in a wide range of voltage. Our results indicate that the coguest system is a promising method for obtaining high-efficiency red OLEDs.

Effect of doped dye on the charge-carrier transport and electroluminescent performance in molecularly doped polymer light-emitting diodes

The effects of the concentration of 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzopyropyrano(6, 78-i,j)quinolizin-11-one (C545T) as dopant in polyfluorene (PFO) on the charge-carrier transport and electroluminescence (EL) performance were investigated by steady-state and transient EL measurements. A fully green emission from C545T was observed and the EL performance depends strongly on the C545T concentration. The mobility in the C545T-doped PFO film was determined by transient EL. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the C545T molecules. The mobility in C545T:PFO changed significantly with the C545T concentration, and showed a nontrivial dependence on the doping level. The behavior may be understood in terms of the formation of an additional energy disorder due to potential fluctuation caused by the Coulomb interaction of the randomly distributed doping molecules.

Effects of doped dye on the charge carrier injection, transport, and electroluminescent performance in polymeric light-emitting diodes

The effects of doped fluorescent dye 4-(dicyanomethylene)-2-i-propyl-6-(1, 1, 7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTI) on the charge carrier injection, transport and electroluminescence (EL) performance in polyfluorene (PFO)-based polymer light-emitting diodes (PLEDs) were investigated by steady-state current-voltage (I-V) characteristics and transient EL measurements. A red EL from DCJTI was observed and the EL performance depended strongly on the DCJTI concentration. The analysis of the steady-state I-V characteristics at different DCJTI concentrations found that three regions was shown in the I-V characteristics, and each region was controlled by different processes depending on the applied electric field. The effect of the dopant concentration on the potential-barrier height of the interface is estimated using the Fowler-Nordheim model. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the DCJTI molecules. The mobility in DCJTI: PFO changed significantly with the DCJTI concentration, and showed a nontrivial dependence on the doping level. The behavior may be understood in terms of the formation of an additional energy disorder due to potential fluctuation caused by the Coulomb interaction of the randomly distributed doping molecules.

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

Effect of dye concentration on the charge carrier transport in molecularly doped organic light-emitting diodes

The effect of the concentration of 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant in tris(8-quinolinolato) aluminum (Alq(3)) on the charge carrier transport in Alq(3):DCJTB was investigated by measuring the steady current-voltage characteristics and the transient electroluminescence. The dopant concentration dependence of the current-voltage relationship clearly indicates the carrier trapping by the DCJTB molecule. The DCJTB concentration significantly affects the electron mobility in Alq(3):DCJTB. The mobility has a nontrivial dependence on the doping level. For relatively low doping levels, less than 1%, the electron mobility of Alq(3):DCJTB decreases with the doping level. An increasing mobility is then observed if the dopant concentration is further increased, followed by a decrease for doping levels larger than similar to2%. The change of the electron mobility with the DCJTB concentration in Alq(3) is attributed to the additional energetic disorder due to potential fluctuations caused by the dipole-dipole interaction of random distribution dopant at the relatively low doping concentration, and to the phase separation at the high doping concentration.

Study on the instability of organic field-effect transistors based on fluorinated copper phthalocyanine

The effects of positive and negative gate-bias stress on organic field-effect transistors (OFET) based on tantalum (Ta)/tantalum pentoxide (Ta2O5)/fluorinated copper phthalocyanine (F16CuPc) structure are investigated as a function of stress time and stress temperature. It is shown that gate-bias stress induces a parallel threshold voltage shift (DeltaV(T)) of OFETs without changes of field-effect mobility mu(EF) and sub-threshold slope (DeltaS). The DeltaV(T) is observed to be logarithmically dependent on time at high gate-bias appropriate to OFET operation. More importantly, the shift is directional, namely, be large shift under positive stress and almost do not move under negative stress. The threshold voltage shift is temperature dependent with activation energy of 0.51 eV We concluded that threshold voltage shift of the OFET with F16CuPc as active layer is due to charge trapping in the insulator in which trapped carriers have redistribution.

The complex kinetics of protein folding in wide temperature ranges

The complex protein folding kinetics in wide temperature ranges is studied through diffusive dynamics on the underlying energy landscape. The well-known kinetic chevron rollover behavior is recovered from the mean first passage time, with the U-shape dependence on temperature. The fastest folding temperature T-0 is found to be smaller than the folding transition temperature T-f. We found that the fluctuations of the kinetics through the distribution of first passage time show rather universal behavior, from high-temperature exponential Poissonian kinetics to the relatively low-temperature highly nonexponential kinetics. The transition temperature is at T-k and T-0, T-k, T-f. In certain low-temperature regimes, a power law behavior at long time emerges. At very low temperatures ( lower than trapping transition temperature T< T-0/(4&SIM;6)), the kinetics is an exponential Poissonian process again.

Blue light-emitting polymer with polyfluorene as the host and highly fluorescent 4-dimethylamino-1,8-naphthalimide as the dopant in the sidechain

The dopant/host concept, which is an efficient approach to enhance the electroluminescence (EL) efficiency and stability for organic light-emitting diodes (OLEDs) devices, has been applied to design efficient and stable blue light-emitting polymers. By covalently attaching 0.2 mol % highly fluorescent 4-dimethylamino-1,8-naphthalimide (DMAN) unit (photoluminescence quantum efficiency: Phi(PL)=0.84) to the pendant chain of polyfluorene, an efficient and colorfast blue light-emitting polymer with a dopant/host system and a molecular dispersion feature was developed. The single-layer device (indium tin oxide/PEDOT/polymer/Ca/Al) exhibited the maximum luminance efficiency of 6.85 cd/A and maximum power efficiency of 5.38 lm/W with the CIE coordinates of (0.15, 0.19). Moreover, no undesired long-wavelength green emission was observed in the EL spectra when the device was thermal annealed in air at 180 degrees C for 1 h before cathode deposition. These significant improvements in both efficiency and color stability are due to the charge trapping and energy transfer from polyfluorene host to highly fluorescent DMAN dopant in the molecular level.

Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1,8-naphthalimide as green dopant

The dopant/host methodology, which enables efficient tuning of emission color and enhancement of the electroluminescence (EL) efficiency of organic light emitting diodes (OLEDs) based on small molecules, is applied to the design and synthesis of highly efficient green light emitting polymers. Highly efficient green light emitting polymers were obtained by covalently attaching just 0.3-1.0 mol% of a green dopant, 4-(N,N-diphenyl) amino-1,8-naphthaliniide (DPAN), to the pendant chain of polyfluorene (the host). The polymers emit green light and exhibit a high photoluminescence (PL) quantum yield of Lip to 0.96 in solid films, which is attributed to the energy transfer from the polyfluorene host to the DPAN dopant unit. Single layer devices (device configuration: ITO/PEDOT/Polymer/Ca/Al) of the polymers exhibit a turn on voltage of 4.8 V, luminance efficiency of 7.43 cd A(-1), power efficiency of 2.96 lm W-1 and CIE coordinates at (0.26, 0.58). The good device performance can be attributed to the energy transfer and charge trapping from the polyfluorene host to the DPAN dopant unit as well as the molecular dispersion of the dopant in the host.

Green electroluminescent polyfluorenes containing 1,8-naphthalimide moieties as color tuner

A series of copolymers (CNPFs) containing low-band-gap 1,8-naphthalimide moieties as color tuner was prepared by a Yamamoto coupling reaction of 2,7-dibromo-9,9-dioctylfluorene (DBF) and different amount of 4-(3,6-dibromocarbazol-9-yl)-N-(4'-tert-butyl-phenyl)-1,8-naphthalimide (Br-CN) (0.05-1 mol% feed ratio). The light emitting properties of the resulting copolymers showed a heavy dependence on the feed ratio. In photoluminescence (PL) studies, an efficient color tuning through the Forster energy transfer mechanism was revealed from blue to green as the increase of Br-CN content, while in electroluminescence (EL) studies, the color tuning was found to go through a charge trapping mechanism. It was found that by introduction of a very small amount of Br-CN (0.1-0.5 mol%) into polyfluorene, the emission color can be tuned from blue to pure green with Commission International de l'Echairage (CIE) coordinates being (0.21, 0.42) and (0.21, 0.48). A green emitting EL single-layer device based on CNPF containing 0.1 mol% of Br-CN showed good performances with a low turn-on voltage of 4.2 V, a brightness of 9104 cd/m(2), the maximum luminous efficiency of 2.74 cd/A and the maximum power efficiency of 1.51 lm/W.

Negative differential resistance and multilevel memory effects in organic devices

Negative differential resistance ( NDR) and multilevel memory effects were obtained in organic devices consisting of an anthracene derivative, 9,10-bis-{ 9,9-di-[ 4-(phenyl-p-tolyl-amino)-phenyl]-9H-fluoren-2-yl}-anthracene ( DAFA), sandwiched between Ag and ITO electrodes. The application of a negative bias voltage leads to negative differential resistance in current-voltage characteristics and different negative voltages produce different conductance currents, resulting in the multilevel memory capability of the devices. The NDR property has been attributed to charge trapping at the DAFA/Ag interface. This opens up a wide range of application possibilities of such organic-based NDR devices in memory and logic circuits.

Energy landscape theory, funnels, specificity, and optimal criterion of biomolecular binding

We study the nature of biomolecular binding. We found that in general there exists several thermodynamic phases: a native binding phase, a non-native phase, and a glass or local trapping phase. The quantitative optimal criterion for the binding specificity is found to be the maximization of the ratio of the binding transition temperature versus the trapping transition temperature, or equivalently the ratio of the energy gap of binding between the native state and the average non-native states versus the dispersion or variance of the non-native states. This leads to a funneled binding energy landscape.

AFM studies of DNA structures on mica in the presence of alkaline earth metal ions

As counterions of DNA on mica, Mg2+, Ca2+, Sr2+ and Ba2+ were used for,clarifying whether DNA molecules equilibrate or are trapped on mica surface. End to end distance and contour lengths were determined from statistical analysis of AFM data. It was revealed that DNA molecules can equilibrate on mica when Mg2+, Ca2+ and Sr2+ are counterions. When Ba2+ is present, significantly crossovered DNA molecules indicate that it is most difficult for DNA to equilibrate on mica and the trapping degree is different under different preparation conditions. In the presence of ethanol, using AFM we have also observed the dependence of B A conformational transition on counterion identities. The four alkaline earth metal ions cause the B-A transition in different degrees, in which Sr2+ induces the greatest structural transition.

Long lasting phosphorescence, thermoluminescence and electron spin resonance property of Mn2+ activated ZnO-Al2O3SiO2 ceramic

The long lasting phosphorescence (LLP) phenomenon in Mn2+-doped ceramic based on ZnO-Al2O3-SiO2 (ZASM) is observed. After irradiation by a UVP standard mercury lamp peaking at 254 nm with a power of 0.6 mW/cm(2) for 15 min, the ceramic sample emits a bright green light peaking at 519 nm, which can be seen in the dark even 15 h after the removal of UVP standard mercury lamp by the naked eyes whose limit of light perception is 0.32 mcd/m(2). The initial afterglow intensity reaches about 1900 mcd/m(2), and the color coordinate (X, Y) is (0.2280, 0.5767) at about 10 s after stopping irradiation. The thermoluminescence (TL) spectra show that there are at least three kinds of trap centers with different trap levels while electron spin resonance (ESR) spectra indicate that there are electron- and hole-trapping centers induced after irradiation by a UVP standard mercury lamp. Based on these measurements, the LLP is considered to be due to the recombination of electrons and holes at trapping centers with different levels, which are firstly thermally released back to Mn2+ and then give rise to the bright green LLP at room temperature.