In vitro comparison of the charge-injection limits of activated iridium oxide (AIROF) and platinum-iridium microelectrodes

The charge-injection limits of activated iridium oxide electrodes (AIROF) and PtIr microelectrodes with similar geometric area and shape have been compared in vitro using a stimulation waveform that delivers cathodal current pulses with current-limited control of the electrode bias potential in the interpulse period. Charge-injection limits were compared over a bias range of 0.1-0.7 V (versus Ag/AgCl) and pulse frequencies of 20, 50, and 100 Hz. The AIROF was capable of injecting between 4 and 10 times the charge of the PtIr electrode, with a maximum value of 3.9 mC/cm2 obtained at a 0.7 V bias and 20 Hz frequency.     

Chronic neural stimulation with thin-film, iridium oxide electrodes

Experiments were conducted to assess the effect of chronic stimulation on the electrical properties of the electrode-tissue system, as measured using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Silicon, micromachined probes with multiple iridium oxide stimulating electrodes (400-1600 micron 2) were implanted in guinea pig cortex. A 10-17 day post-operative recovery period was followed by five days of monopolar stimulation, two hours/electrode each day using biphasic, constant current stimulation (5-100 microA, 100 microseconds/phase). EIS and CV data were taken before and after stimulation. The post-stimulation impedance [at mid-range frequencies (100 Hz-100 kHz)] consistently and significantly decreased relative to prestimulation levels. Impedance magnitude increased permanently at low frequencies (< 100 Hz), correlating to a change in the charge storage capacity (the area under a cyclic voltammagram). Impedance magnitude significantly increased during the recovery period, though this increase could be mostly reversed by applying small currents. A mathematical model of the electrode-tissue system impedance was used to analyze in vivo behavior. The data and modeling results shows that applying charge to the electrode can consistently reduce the impedance of the electrode-tissue system. Analysis of explanted probes suggests that the interaction between the tissue and electrode is dependent on whether chronic pulses were applied. It is hypothesized that the interface between the tissue and metal is altered by current pulsing, resulting in a temporary impedance shift.     

Charge injection limits of activated iridium oxide electrodes with 0.2 ms pulses in bicarbonate buffered saline (neurological stimulation application)

The maximum charge injection without electrode solution decomposition for activated iridium wire electrodes in bicarbonate buffered saline was 2.1 and 1.0 mC/cm/sup 2/ geometric for anodic-first and cathodic-first, respectively, 0.2-ms balanced-charge biphasic current pulses. Electrodes biased at +0.8 V vs. SCE (saturated calomel electrode) accepted charge up to 3.5 mC/cm/sup 2/ geometric with monophasic cathodal pulses.<>     

CMOS LSI-based multichip flexible neural stimulation device with embedded bulk Pt electrodes

A CMOS LSI-based flexible neural stimulation device application with new fabrication technologies has been developed. The device was designed for application in retinal prosthesis. The device is based on multichip architecture, which enables the LSI-based stimulation device to be flexible. A fabrication process of arrayed bulk Pt electrodes, and a packaging structure of LSI chips with flip-chip bonding technology have been developed. These features provide the fabricated device with a lifetime of ten days in saline solution     

Cationic iridium(III) complexes with different-sized negative counter-ions for solution-processed deep-blue-emitting diodes

A series of blue-emitting cationic iridium(III) complexes featuring the same coordinated iridium(III) cation while different-sized negative counter-ions are reported and investigated. Anionic influence on the physicochemical properties and device performance is studied and explained. Introduction of counter-ions with large steric hindrance, (i) effectively reduces the ionic interaction and molecular aggregation in solid states, improving the photoluminescence efficiency and avoiding the common bathochromic shift; (ii) also restricts anionic drift under the working bias in the optoelectronic devices, achieving solution-processed deep-blue-emitting diodes with a major peak at only 452 nm, among the shortest emission wavelengths of devices based on ionic transition metal complexes.     

Transverse versus longitudinal tripolar configuration for selective stimulation with multipolar cuff electrodes

The ability to stimulate subareas of a nerve selectively is highly desirable, since it has the potential of simplifying surgery to implanting one cuff on a large nerve instead of many cuffs on smaller nerves or muscles, or alternatively can improve function where surgical access to the smaller nerves is limited. In this paper, stimulation was performed with a four-channel multipolar cuff electrode implanted on the sciatic nerve of nine rabbits to compare the extensively researched longitudinal tripolar configuration with the transverse tripolar configuration, which has received less interest. The performance of these configurations was evaluated in terms of selectivity in recruitment of the three branches of the sciatic nerve. The results showed that the transverse configuration was able to selectively activate the sciatic nerve branches to a functionally relevant level in more cases than the longitudinal configuration (20/27 versus 11/27 branches) and overall achieved a higher mean selectivity [0.79 ± 0.13 versus 0.61 ± 0.09 (mean ± standard deviation)]. The transverse configuration was most successful at recruiting the small cutaneous and medium-sized peroneal branches, and less successful at recruiting the large tibial nerve.     

Progress on benzimidazole-based iridium(III) complexes for application in phosphorescent OLEDs

Benzimidazole-based iridium (III) [Ir(III)] complexes as emissive phosphors in organic light-emitting diodes (OLEDs) have received extensive investigation due to their good electron mobility, excellent thermal stability and flexible modification ability. In this overview, recent advance of benzimidazole-based Ir(III) complexes have been reviewed with focus on the design strategies, photophysical properties and EL performances of phosphorescent OLEDs with various benzimidazole derivatives including substituents, functionalized ancillary ligand and dendrimers.     

Two novel orange cationic iridium(III) complexes with multifunctional ancillary ligands used for polymer light-emitting diodes

Two novel orange cationic iridium complexes [(npy)₂Ir(o-phen)]PF₆ and [(npy)₂Ir(c-phen)]PF₆ were synthesized. Hnpy: 2-(naphthalen-1-yl)pyridine; o-phen: a 1,10-phenanthroline derivative containing an electron-transporting functional group of 2,5-diphenyl-1,3,4-oxadiazole and a crystallization-resistant tert-butyl functional group; c-phen: a 1,10-phenanthroline derivative containing a hole-transporting functional group of carbazole and a crystallization-resistant 2-ethylhexyl functional group. Both of them are amorphous and possess high thermal stability with 5% weight-reduction temperatures (ΔT_5%) of 386 °C and 383 °C, and glass-transition temperatures (T_g) of 267 °C and 195 °C respectively. They were used as phosphorescent dopants in polymer light-emitting diodes (PLEDs) fabricated by solution-processed technology with configuration of ITO/PEDOT:PSS/PVK:PBD:iridium complex/TPBI/CsF/Al. At the optimal doping concentration of 2.0 wt%, the corresponding PLEDs exhibited the maximum current efficiencies of 9.1 cd A⁻¹ and 10.0 cd A⁻¹, the maximum external quantum efficiencies of 6.5% and 7.1%, and the maximum luminance of 2314 cd m⁻² and 3157 cd m⁻² respectively, with the same CIE coordinates of (0.57, 0.40). The results indicate that cationic iridium complexes are promising candidates for PLED applications when they are designed reasonably.     

Heteroleptic iridium (III) complexes with three different ligands: Unusual triplet emitters for light-emitting electrochemical cells

Two cationic iridium (III) complexes [Ir(dfppy)(tpy)(bpy)](PF₆) and [Ir(dfppy)(tpy)(phen)](PF₆) bearing three different ligands were tested as triplet emitters for Light-Emitting Electrochemical Cells (LECs). These two phosphorescent materials only constitute the third and fourth examples of triple heteroleptic cationic iridium complexes to be tested in electroluminescent devices. LECs fabricated with this almost unknown class of iridium complex furnished green-emitting devices. Parallel to investigations devoted to electroluminescent properties, photophysical and electrochemical properties of the two new complexes were examined. Density functional theory calculations were also performed to provide insight into the electronic structure of the two emitters.     

A neural network approach-decision neural network (DNN) for preference assessment

A new neural-network-based approach to assess the preference of a decision-maker (DM) for the multiple objective decision making (MODM) problem is presented in this paper. A new neural network structure with a "twin-topology" is introduced in this approach. We call this neural network a decision neural network (DNN). The characteristics of the DNN are discussed, and the training algorithm for DNN is presented as well. The DNN enables the decision-maker to make pairwise comparisons between different alternatives, and these comparison results are used as learning samples to train the DNN. The DNN is applicable for both accurate and inaccurate comparisons (results are given in approximate values or interval scales). The performance of the DNN is evaluated with several typical forms of utility functions. Results show that DNN is an effective and efficient way for modeling the preference of a decision-maker.     

Multifunctional homoleptic iridium(III) dendrimers towards solution-processed nondoped electrophosphorescence with low efficiency roll-off

A series of new iridium dendrimers comprised of bifunctional charge transport peripheral groups have been designed and facilely synthesized. The relationship between the structures and their photophysical, electrochemical and electrophosphorescent performances is investigated. Through the incorporation of rigid electron-transporting phosphine oxide groups and/or hole-transporting arylamine units, the new complexes all have good thermal stabilities with high glass-transition temperature up to 284 °C. Besides, the peripheries sufficiently shield the emissive core from the intermolecular interactions and prevent luminance quenching in neat films. Solution-processed phosphorescent organic light-emitting device (PhOLED) based on bipolar phosphor 2 as neat emitter achieves a maximum current efficiency of 12.4 cd A⁻¹ with Commission Internationale de l’Eclairage coordinates of (0.57, 0.42), and the value remains at 11.5 cd A⁻¹ at a practical luminance of 1000 cd m⁻². This low roll-off can be attributed to the bipolar nature of the emitter. This indicates that rational incorporation of charge-transporting moieties into the sphere of iridium(III) core is a simple and effective approach to develop efficient host-free phosphors for solution-processable nondoped PhOLEDs.     

Synthesis,characterization of the phenylquinoline-based on iridium(III) complexes for solution processable phosphorescent organic light-emitting diodes

A new series of highly efficient Ir(III) complexes, (DPQ)₂Ir(pic-N-O), (F₄PPQ)₂Ir(pic-N-O), (FPQ)₂Ir(pic-N-O), and (CPQ)₂Ir(pic-N-O) were synthesized for phosphorescent organic light-emitting diodes (PhOLEDs), and their photophysical, electrochemical, and electroluminescent (EL) properties were investigated. The Ir(III) complexes, including picolinic acid N-oxide (pic-N-O) ancillary ligand, are comprised with the various main ligands such as 2,4-diphenylquinoline (DPQ), 4-phenyl-2-(2,3,4,5-tetrafluorophenyl)quinoline (F₄PPQ), 2-(9,9-diethyl-9H-fluoren-2-yl)-4-phenylquinoline (FPQ) and 9-ethyl-3-(4-phenylquinolin-2-yl)-9H-carbazole. Remarkably, high performance PhOLEDs using a solution-processable (DPQ)₂Ir(pic-N-O) doped CBP host emission layer were fabricated to give a high luminance efficiency (LE) of 26.9 cd/A, equivalent to an external quantum efficiency (EQE) of 14.2%.The calculated HOMO–LUMO energy gaps for (DPQ)₂Ir(pic-N-O), (F₄PPQ)₂Ir(pic-N-O), (FPQ)₂Ir(pic-N-O) and (CPQ)₂Ir(pic-N-O) were in good agreement with the experimental results.     

Highly branched green phosphorescent tris-cyclometalated iridium(III) complexes for solution-processed organic light-emitting diodes

A series benzoimidazole-based dendritric complexes of iridium dendrimers containing Fréchet-type dendrons with peripheral fluorenyl surface groups have been synthesized. These iridium dendrimers are green-emitting with high phosphorescence quantum yield, and can be spin-coated as films of good quality. From cyclic voltammograms (CV), high onset potentials at 1.42–1.58 V due to the peripheral fluorene group were observed. Device from a second generation dendrimer 17 with structure of ITO/PEDOT:PSS/CBP: 20 wt% 17/TPBI/LiF/Al (PEDOT:PSS = poly(ethylene dioxythiophene): polystyrenesulfonate and CBP = bis(N-carbazolyl)biphenyl) has the best performance: maximum external quantum efficiency of 13.58% and maximum current efficiency of 45.7 cd/A. Space-charge-limited current (SCLC) flow technique was used to measure the mobility of charge carriers in the blend films of the compounds in CBP. Blend films of higher generation dendrimers have lower hole mobility, albeit with higher device efficiencies.     

Phenylimidazole-based homoleptic iridium(III) compounds for blue phosphorescent organic light-emitting diodes with high efficiency and long lifetime

In order to obtain triplet emitters with high stability and efficiency, three homoleptic iridium(III) compounds — specifically, Ir(tpim)₃ (1), Ir(mtpim)₃ (2), and Ir(itpim)₃ (3), where tpim = 1-([1,1′:3′,1″-terphenyl]-2′-yl)-2-(4-fluorophenyl)-1H-imidazole, mtpim = 2-(4-fluorophenyl)-1-(5′-methyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1H-imidazole, and itpim = 2-(4-fluorophenyl)-1-(5′-isopropyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1H-imidazole — were prepared by one-pot reaction of the corresponding phenylimidazole ligand with an Ir(I) complex as a starting material. Compounds 1–3 emit bright sky-blue phosphorescence with λ_max = 459–463 nm and phosphorescent quantum efficiencies of 0.38–0.50. Multi-layer phosphorescent organic light-emitting diodes using compounds 1–3 as the triplet emitters and mCBP (3,3-di(9H-carbazol-9-yl)biphenyl) as the host have been fabricated. Compound 3 doped in the emissive layer demonstrate external quantum efficiency as high as 20.1% at 1000 cd/m². In addition, the device based on compound 1 as an emitter shows a stable lifetime greater than 300 h at 1000 cd/m², which is one of the best results concerning the device lifetime.     

Electronically asymmetric poly(1,4-phenylenevinylene)s for photovoltaic cells

We report a study on the feasibility of using an intramolecular dipole to enhance charge separation for organic photovoltaic applications. We have developed a poly(1,4-phenylenevinylene) derivative, poly{2-[(9,9-di-n-propyl-9H-7-nitrofluoren-2-yl)]-5-(2-ethylhexyloxy)-1,4-phenylenevinylene} 12, which has electronically asymmetric chromophores as a result of the para attachment of alkoxy and nitrofluorenyl groups on the phenyl units of the polymer backbone. The luminescence of the polymer with the electronically asymmetric chromophores was found to be smaller by a factor of eight when compared to the equivalent polymer but without the nitro group attached to the fluorenyl unit. Light-induced electron spin resonance experiments showed that the polymer with the electronically asymmetric chromophores had more photo-induced spins, showing that the quenching of the luminescence was due to intramolecular charge separation. Single layer photovoltaic devices containing neat films of 12 showed efficiencies similar to other single layer devices and this was ascribed to poor transport of the separated charges. This was confirmed by a strong improvement in device power efficiency to 0.52% at AM1.5 by blending the polymer with an electron transporting material.     

An advanced technique for fabricating hemispherical-grained (HSG)silicon storage electrodes

In this new fabrication technology for high-density DRAM's, an electrode with even-surface amorphous-silicon is changed to one with uneven-surface hemispherical-grained Si (HSG-Si). This fabrication method consists of easily controllable processes: formation of smooth amorphous Si electrodes by low-pressure chemical vapor deposition followed by removal of native oxide and high-vacuum annealing. This annealing process can form HSG-Si covering the entire surface of all types of storage electrodes, including side-wall surfaces which had previously been dry-etched. The resulting storage electrode with HSG-Si can store 1.8 times as much charge as can be stored on an electrode without HSG-Si. Such an increase makes it possible to reduce the height of storage electrodes. This technique is applicable to the fabrication of high-density DRAM's     

Highly efficient thienylquinoline-based phosphorescent iridium(III) complexes for red and white organic light-emitting diodes

Highly efficient 2-(thiophen-2-yl)quinoline-based phosphorescent iridium(III) complexes bearing 2-(3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine or picolinic acid as ancillary ligands are designed and synthetised. The variation of ancillary ligands is attempted to finely tune the photophysical properties of these complexes, especially the solution phosphorescent quantum yields (ΦPL), full width at half maximum (FWHM), etc. The picolinic acid-based complex displays the slightly red-shifted dual-peak emission compared to triazolpyridine-based one. The complexes show bright emission with broad FWHM up to 83 nm, and the emissions are in red region with the very high absolute ΦPL up to 0.76 in solution. Moreover, high-performance red and three-color-based white organic light-emitting diodes (OLEDs) with excellent color stability have been fabricated. The maximum external quantum efficiencies of red and white OLEDs can reach 16.2% and 15.1%, respectively. The maximum current efficiency and power efficiency of white OLED are as high as 35.5 cd A⁻¹ and 34.0 lm W⁻¹, respectively. Especially, the designed white OLED exhibits excellent spectral stability under wide operating voltage range, and the 1931 Commission Internationale de L'Eclairage of white OLED only changes from (0.43, 0.42) to (0.44, 0.44), the color rendering index is in a narrow range of 75–77.     

高浓度掺杂Ir(ppy)3和Rubrene的高效率有机发光器件

通过采用CBP主体材料中高浓度掺杂Ir(ppy)a和Rubrene,利用Ir(ppy)3敏化黄光发射的方法,制备了高性能的有机电致发光器件(OLED).器件采用的结构为:ITO/2T-NATA(20 nm)/NPBX(40 nm)/x%CBP:y%(ppy)3:z%rubrene(20 nm)/NPBX(10 nm)/DPVBi(60 nm)/Alq(60 nm)/LiF(1 nm)/Al,在该器件中限定.各功能层的厚度保持不变,当CBP、Ir(ppy)3、Rubrene各组分的比例x、y、z分别为:65%、20%、15%时,器件的性能较好,在电压为12 V时,其电流效率最大为21.1 ed/A.在电压为24 V时,其亮度为最大,达到22 670 ca/m2.该器件的色度随电压的增加逐步趋近于白光等能点(0.33,0.33).     

An efficient bis(2-phenylquinoline) (acetylacetonate) iridium(III)-based red organic light-emitting diode with alternating guest:host emitting layers

We report a highly efficient electrophosphorescent bis(2-phenylquinoline) (acetylacetonate) iridium(III) [Ir(2-phq)₂(acac)]-based red organic light-emitting diode. The emission layer consists of a periodic thin layer of guest material of Ir(2-phq)₂(acac) separated by host material of 4,4′-Bis(carbazol-9-yl)biphenyl. The guest and host thicknesses were optimized independently to obtain the best performance. The current efficiency reaches to a maximum of 16.2 cd/A then drops to 15 and 11 cd/A at brightness of 10 and 100 cd/m², respectively. By reducing the thickness of the host layer, the power efficiency was further improved. Device with a maximum power efficiency of 8.3 lm/W was obtained. We also found that the concentration quenching in Ir(2-phq)₂(acac) is dominated by molecular aggregation. Excitonic quenching by radiationless Förster process is miniscule.