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.     

Green and blue–green light-emitting electrochemical cells based on cationic iridium complexes with 2-(4-ethyl-2-pyridyl)-1H-imidazole ancillary ligand

The ionic iridium complexes, [Ir(ppy)₂(EP-Imid)]PF₆ (Complex 1) and [Ir(dfppy)₂(EP-Imid)]PF₆ (Complex 2) are used as the light-emitting material for the fabrication of light-emitting electrochemical cells (LECs). These complexes have been synthesized, employing 2-(4-ethyl-2-pyridyl)-1H-imidazole (EP-Imid) as the ancillary ligand, 2-phenylpyridine (ppy) and 2-(2,4-difluorophenyl)pyridine (dfppy) as the cyclometalated ligands, which were characterized by various spectroscopic, photophysical and electrochemical methods. The photoluminescence (PL) emission spectra in acetonitrile solution show blue–green and blue light emission for Complexes 1 and 2 respectively. However, LECs incorporating these complexes resulted in green (522 nm) light emission for Complex 1 with the Commission Internationale de L’Eclairage (CIE) coordinates of (0.33, 0.56) and blue–green (500 nm) light emission for Complex 2 with the CIE coordinates of (0.24, 0.44). Using Complex 1, a maximum luminance of 1191 cd m⁻² and current efficiency of 1.0 cd A⁻¹ are obtained while that of Complex 2 are 741 cd m⁻² and 0.88 cd A⁻¹ respectively.     

Highly efficient two component phosphorescent organic light-emitting diodes based on direct hole injection into dopant and gradient doping

A series of two component phosphorescent organic light-emitting diodes (PHOLEDs) combing the direct hole injection into dopant strategy with a gradient doping profile were demonstrated. The dopant, host, as well as molybdenum oxide (MoO₃)-modified indium tin oxide (ITO) anode were investigated. It is found that the devices ITO/MoO₃ (0 or 1 nm)/fac-tris(2-phenylpyridine)iridium [Ir(ppy)₃]:1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi) (30 → 0 wt%, 105 nm)/LiF (1 nm)/Al (100 nm) show maximum external quantum efficiency (EQE) over 20%, which are comparable to multi-layered PHOLEDs. Moreover, the systematic variation of the host from TPBi to 4,7-diphenyl-1,10-phenanthroline (Bphen), dopant from Ir(ppy)₃ to bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)], and anodes between ITO and ITO/MoO₃ indicates that balancing the charge as well as controlling the charge recombination zone play critical roles in the design of highly efficient two component PHOLEDs.     

Optoelectronic characteristics of MEH-PPV polymer LEDs with thin,doped composition-graded a-SiC:H carrier injection layers

The optoelectronic characteristics of poly(2-methoxy-5-(2′ethyl-hexoxy)-1,4-phenylene-vinylene) (MEH-PPV) polymer LEDs (PLEDs) have been improved by employing thin doped composition-graded (CG) hydrogenated amorphous silicon–carbide (a-SiC:H) films as carrier injection layers and O₂-plasma treatment on indium–tin-oxide (ITO) transparent electrode, as compared with previously reported ones having doped constant-optical-gap a-SiC:H carrier injection layers. For PLEDs with an n-type a-SiC:H electron injection layer (EIL) only, the electroluminescence (EL) threshold voltage and brightness were improved from 7.3 V, 3162 cd/m² to 6.3 V, 5829 cd/m² (at a current density J = 0.6 A/cm²), respectively, by using the CG technique. The enhancement of EL performance of the CG technique was due to the increased electron injection efficiency resulting from a smoother barrier and reduced recombination of charge carriers at the EIL and MEH-PPV interface. Also, surface modification of the ITO transparent electrode by O₂-plasma treatment was used to further improve the EL threshold voltage and brightness of this PLED to 5.1 V, 6250 cd/m² (at J = 0.6 A/cm²). Furthermore, by employing the CG n[p]-a-SiC:H film as EIL [hole injection layer (HIL)] and O₂-plasma treatment on the ITO electrode, the brightness of PLEDs could be enhanced to 9350 cd/m² (at a J = 0.3 A/cm²), as compared with the 6450 cd/m² obtained from a previously reported PLED with a constant-optical-gap n-a-SiCGe:H EIL and p-a-Si:H HIL.     

Alcohol-soluble polyfluorenes containing dibenzothiophene-S,S-dioxide segments for cathode interfacial layer in PLEDs and PSCs

A series of alcohol-soluble amino-functionalized polyfluorene derivatives (PF-N-S, PF-N-SC8 and PF-N-SOC8) comprising various ratios of dibenzothiophene-S,S-dioxide segments (S/SC8/SOC8) in the main chains, respectively, were synthesized and utilized as cathode interfacial layer (CIL) in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs) with high-work-function Al (or Au) electrode. The polymers possess LUMO/HOMO levels at −2.78 to −3.53 eV/−5.69 to −6.32 eV. Multilayer PLEDs and PSCs with device configurations of ITO/PEDOT:PSS (40 nm)/P-PPV or PFO-DBT35:PCBM = 1:2 (80 nm)/CIL (3–15 nm)/Al (or Au) (100 nm) were fabricated. The PF-N-S-10/Al (or Au) cathode PLEDs displayed maximum luminous efficiency of 24.4 cd A⁻¹ (or 11.9 cd A⁻¹), significantly higher than bare Al (or Au) cathode device, exceeding well-known Ba/Al and poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN)/Al (or PFN/Au) cathode devices. The enhanced open-circuit voltages (V_ocs), electron reflux and reduced work functions clarify that the electron injection barrier from the Al (or Au) electrode can be lowered by inserting the polymers as CIL. The resulted PSCs also show device performances exceeding Al and PFN/Al cathode devices. The results indicate that PF-N-S, PF-N-SC8 and PF-N-SOC8 are excellent CIL materials for PLEDs and PSCs with high-work-function Al or Au electrode.     

Highly efficient bluish green phosphorescent organic light-emitting diodes based on heteroleptic iridium(III) complexes with phenylpyridine main skeleton

A new series of heteroleptic iridium(III) complexes, bis(2-phenylpyridinato-N,C2′)iridium (2-(2′,4′-difluorophenyl)-4-methylpyridine), (ppy)₂Ir(dfpmpy) and bis(2-(2′,4′-difluorophenyl)-4-methylpyridinato-N,C2′)iridium (2-phenylpyridine) (dfpmpy)₂Ir(ppy), have been synthesized by using phenylpyridine as a main skeleton for bluish green phosphorescent organic light-emitting diodes (PhOLEDs). The Ir(III) complexes showed high thermal stability and high photoluminescent (PL) quantum yields of 95% ± 4% simultaneously. As a result, the PhOLEDs with the heteroleptic Ir(III) complexes showed excellent performances approaching 100% internal quantum efficiency with a very high external quantum efficiency (EQE) of ∼27%, a low turn-on voltage of 2.4 V, high power efficiency of ∼85 lm/W, and very low efficiency roll-off up to 20,000 cd/m².     

Fluorene-based cathode interlayer polymers for high performance solution processed organic optoelectronic devices

A hydrophilic polyfluorene-based conjugated polyelectrolyte (CPE) Poly[9,9-bis(4′-(6″-(diethanolamino)hexyloxy) phenyl)fluorene], PPFN-OH (Scheme 1) has been synthesized and utilized as cathode interlayer for both polymer light emitting diodes (PLEDs) and solar cells (PSCs). For comparison, another CPE namely Poly[9,9-bis(6′-(diethanolamino)hexyl)fluorene] (PFN-OH) has also been investigated. They comprise the same polyfluorene backbone structures with, respectively, diethanolaminohexyl (PFN-OH) and diethanolaminohexoxyphenyl (PPFN-OH) substituents attached to the C9 carbon of the fluorene repeat unit. In comparison to reference devices with more reactive Ca/Al cathodes, utilizing these CPEs as interlayers allowed an Al cathode to be used for blue light emission PLEDs, yielding 51% and 92% enhancement of maximum luminous efficiency (LE) for PFN-OH and PPFN-OH, respectively. The PLEDs with PPFN-OH showed both higher maximum LE and maximum luminance (L) (LE = 2.53 cd/A at 6.2 V, L = 9917 cd/m² at 8.3 V) than devices with PFN-OH (2.00 cd/A at 4.1 V, 3237 cd/m² at 7.2 V). The PPFN-OH PLEDs also showed no significant roll-off in efficiency with increasing current density up to 400 mA/cm², indicating excellent electron injection ability and stability for this interlayer. The insertion of alkoxy-phenyl groups at the C9-position in PPFN-OH is clearly advantageous. This simple modification significantly improves the CPE cathode interlayer performance. Parallel investigations of the electron extraction properties of PPFN-OH in inverted architecture PSCs with PCDTBT:PC₇₀BM bulk heterojunction active layers demonstrated a power conversion efficiency enhancement of ∼19% (from 4.99% to 5.95%) for indium tin oxide cathode devices compared with reference devices using Ca/Al cathodes. These results confirm PPFN-OH to be a promising interlayer material for high performance solution processed organic optoelectronic devices.     

Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

Multiple exciton generation regions in phosphorescent white organic light emitting devices

We demonstrate a white electrophosphorescent organic light emitting device (WOLED) with a three-section emission layer (EML) where excitons are formed in the multiple emission regions. The EML consists of a stepped progression of highest occupied and lowest unoccupied molecular orbital energies of the ambipolar hosts. Analysis shows that (36 ± 6)% of the excitons form in the blue emitting region, while (64 ± 6)% form in the green emitting region at 100 mA/cm². The doping of the red, green and blue phosphors, each in its own host, allows for efficient utilization of excitons formed in these multiple regions. Based on this architecture, the WOLED has an internal quantum efficiency close to unity. The WOLED has total external quantum and power efficiencies of η_ext,t = (26 ± 1)% and η_p,t = (63 ± 3) lm/W at 12 cd/m², decreasing to η_ext,t = (23 ± 1)% and η_p,t = (37 ± 2) lm/W at 500 cd/m². When an undoped electron transport layer is used, the peak efficiency is η_ext,t = (28 ± 1)%. Due to the distributed exciton formation in the EML, the WOLED exhibits higher total efficiency than monochromatic devices employing the same red, green and blue dopant–host combinations.     

Efficient and stable red organic light emitting devices from a tetradentate cyclometalated platinum complex

An efficient and stable red phosphorescent organic light emitting diode was developed using a tetradentate cyclometalated platinum complex. Devices employing the phosphorescent molecule, platinum(II)-9-(4-methylpyridin-2-yl)-2-(3-(quinolin-2-yl)phenoxy)-9H-carbazole (PtON11Me), yielded high external quantum efficiencies and high operational lifetimes. A maximum EQE of 12.5% and color coordinates CIE (x = 0.61, y = 0.36) was achieved in devices employing efficient hole blocking and transporting materials and a high operational lifetime of T_0.97 ∼ 3200 h was achieved in devices utilizing electrochemically stable hole blocking and transporting materials.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th₄(1,4) with high hole mobility (μ_h) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μ_h of 1.06 cm² (V s)⁻¹ were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications.     

A highly efficient OLED based on terbium complexes

A neutral ligand 9-(4-tert-butylphenyl)-3,6-bis(diphenylphosphineoxide)-carbazole (DPPOC) and its complex Tb(PMIP)₃DPPOC (A, where PMIP stands for 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) were synthesized. DPPOC has a suitable lowest triplet energy level (24,691 cm^?1) for the sensitization of Tb(III) (⁵D₄: 20,400 cm^?1) and a significantly higher thermal stability (glass transition temperature 137 °C) compared with the familiar ligand triphenylphosphine oxide (TPPO). Experiments revealed that the emission layer of the Tb(PMIP)₃DPPOC film could be prepared by vacuum co-deposition of the complex Tb(PMIP)₃(H₂O)₂ (B) and DPPOC (molar ratio = 1:1). The electroluminescent (EL) device ITO/N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-diphenyl-4,4′-diamine (NPB; 10 nm)/Tb(PMIP)₃ (20 nm)/co-deposited Tb(PMIP)₃DPPOC (30 nm)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP; 10 nm)/tris(8-hydroxyquinoline) (AlQ; 20 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) exhibited pure emission from terbium ions, even at the highest current density. The highest efficiency obtained was 16.1 lm W^?1, 36.0 cd A^?1 at 6 V. At a practical brightness of 119 cd m^?2 (11 V) the efficiency remained above 4.5 lm W^?1, 15.7 cd A^?1. These values are a significant improvement over the previously reported Tb(PMIP)₃(TPPO)₂ (C).     

Enhanced pure red electroluminescence intensity of Eu(o-BBA)3(phen) by red dye co-doping and inorganic semiconductor as charge carrier function layer

There is an emission peak at 494 nm in the electroluminescence (EL) of PVK [poly(n-vinylcarbazole)]: Eu(o-BBA)₃(phen) besides PVK exciton emission and Eu³⁺ characteristic emissions. Both the peaking at 494 nm emission and PVK emission influenced the color purity of red emission from Eu(o-BBA)₃(phen). In order to restrain these emissions and obtain high intensity red emission, 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7,-tetramethyljulolidy-9-enyl)-4Hpyran (DCJTB) and Eu(o-BBA)₃(phen) were co-doped in PVK solution and used as the active emission layer. The EL intensity of co-doped devices reached to 420 cd/m² at 20 V driving voltage. The chromaticity coordinates of EL was invariable (x = 0.55, y = 0.36) with the increase of driving voltage. For further improvement of EL intensity, organic–inorganic hybrid devices (ITO/active emission layer/ZnS/Al) were fabricated. The EL intensity was increased by a factor of 2.5 [(420 cd/m²)/(168 cd/m²)] when the Eu complex was doped with an efficient dye DCJTB, and by a factor of ≈4 [(650 cd/m²)/(168 cd/m²)] when in addition ZnS layer was deposited on such an emitting layer prior to evaporation of the Al cathode.     

Efficient red electrophosphorescence from a fluorene-based bipolar host material

We have prepared efficient red organic light-emitting diodes (OLEDs) incorporating 2,7-bis(diphenylphosphoryl)-9-[4-(N,N-diphenylamino)phenyl]-9-phenylfluorene (POAPF) as the host material doped with the osmium phosphor Os(fptz)₂(PPh₂Me)₂ (fptz = 3-trifluoromethyl-5-pyridyl-1,2,4-triazole). POAPF, which possesses bipolar functionalities, can facilitate both hole- and electron-injection from the charge transport layers to provide a balanced charge flux within the emission layer. The peak electroluminescence performance of the device reached as high as 19.9% and 34.5 lm/W – the highest values reported to date for a red phosphorescent OLED. In addition, we fabricated a POAPF-based white light OLED – containing red-[doped with Os(fptz)₂(PPh₂Me)₂] and blue-emitting {doped with iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C^2′] picolinate, FIrpic} layers – that also exhibited satisfactory efficiencies (18.4% and 43.9 lm/W).     

High-efficiency red electroluminescence from europium complex containing a neutral dipyrido(3,2-a:2′,3′-c)phenazine ligand in PLEDs

In order to obtain high-efficiency monochromatic red emission in polymer light-emitting devices, a tris(dibenzoylmethanato)(dipyrido(3,2-a:2′,3′-c)phenazine) europium [Eu(DBM)₃(DPPZ)] doped single-emissive-layer devices were fabricated using a blend of poly(9,9-dioctyl-fluorence) and 2-tert-butyl-phenyl-5-biphenyl-1,3,4-oxadiazole as a host matrix by solution process. Significantly improved electro-luminescent properties with sharp red emission at 611.5 nm were displayed in the Eu(DBM)₃(DPPZ)-doped devices at dopant concentrations from 1 to 8 wt.%. The highest luminance up to 1783 cd/m² at 2 wt.% dopant concentration, as well as the maximum external quantum efficiency of 2.5% and current efficiency of 3.8 cd/A were obtained at 1 wt.% dopant concentration.     

Development of a new diindenopyrazine–benzotriazole copolymer for multifunctional application in organic field-effect transistors,polymer solar cells and light-emitting diodes

A new donor–acceptor (D?A) copolymer (PIPY–DTBTA) containing 6,12-dihydro-diindeno[1,2-b;1′,2′-e]pyrazine donor and benzotriazole acceptor was synthesized and characterized for multifunctional applications in organic field-effect transistors (OFETs), polymer solar cells (PSCs) and polymer light-emitting diodes (PLEDs). The polymer exhibits high molecular weights, excellent film-forming ability, a deep HOMO energy level, and good solution processability. Solution-processed thin film OFETs based on this polymer revealed good p-type characteristic with a high hole mobility up to 0.0521 cm² V^?1 s^?1. Bulk-heterojunction PSCs comprising this polymer and PC₆₁BM gave a power conversion efficiency (PCE) of 0.77%. The single-layer PLEDs based on PIPY–DTBTA emitted a yellow–red light with a maximum brightness of 385 cd m^?2 at the turn-on voltage of 6 V.     

Structure,charge-transfer and luminescent properties of bis(2-(2-hydroxyphenyl)benzothiazolate)beryllium

A luminescent Be(II) complex of aromatic N, O-chelate ligand, namely Be(BTZ)₂ (BTZ = 2-(2-hydroxyphenyl)benzothiazolate), has been synthesized and characterized by X-ray crystallography. Its charge-transfer and luminescent properties were studied. The results indicated that the single crystal of Be(BTZ)₂ is monoclinic, space group C2/c. With larger the electron-transfer rate than hole-transfer rate, Be(BTZ)₂ may serve as candidate for electron-transport material. The highest occupied molecular orbital energy level (E_HOMO) and the lowest unoccupied molecular orbital energy level (E_LUMO) are −5.79 eV and −2.98 eV, respectively. Be(BTZ)₂displays strong photoluminescence (PL) in the blue region at 456 nm, and the electroluminescent (EL) peak wavelength is located at 460 nm, CIE coordinates are X = 0.1525, Y = 0.1803.     

Design,development and reliability testing of a low power bridge-type micromachined hotplate

In this paper, the development and reliability of a platinum-based microheater with low power consumption are demonstrated. The microheater is fabricated on a thin SiO₂ bridge-type suspended membrane supported by four arms. The structure consists of a 0.6 μm-thick SiO₂ membrane of size 50 μm × 50 μm over which a platinum resistor is laid out. The simulation of the structure was carried out using MEMS-CAD Tool COVENTORWARE. The platinum resistor of 31.0 Ω is fabricated on SiO₂ membrane using lift-off technique. The bulk micromachining technique is used to create the suspended SiO₂ membrane. The temperature coefficient of resistance (TCR) of platinum used for temperature estimation of the hotplate is measured and found to be 2.2 × 10⁻³/°C. The test results indicate that the microhotplate consumes only 11.8 mW when heated up to 400 °C. For reliability testing, the hotplate is continuously operated at higher temperatures. It was found that at 404 °C, 508 °C and 595 °C, the microhotplate continuously operated up to 16.5 h, 4.3 h and 4 min respectively without degrading its performance. It can sustain at least 53 cycles pulse-mode of operation at 540 °C with ultra-low resistance and temperature drifts. The structure has maximum current capability of 19.06 mA and it can also sustain the ultrasonic vibration at least for 30 min without any damage.     

Dry growth of n-octylphosphonic acid monolayer for low-voltage organic thin-film transistors

Dry method for monolayer deposition of n-octylphosphonic acid (C₈PA) on the surface of aluminium oxide (AlO_x) is presented. Vacuum thermal evaporation is employed to deposit initial thickness corresponding to several C₈PA monolayers, followed by a thermal desorption of the physisorbed C₈PA molecules. AlO_x functionalized with such C₈PA monolayer exhibits leakage current density of ～10^?7 A/cm² at 3 V, electric breakdown field of ～6 MV/cm, and a root-mean-square surface roughness of 0.36 nm. The performance of low-voltage pentacene thin-film transistors that implement this dry AlO_x/C₈PA gate dielectric depends on C₈PA desorption time. When the desorption time rises from 25 to 210 min, the field-effect mobility increases from ～0.02 to ～0.04 cm²/V s, threshold voltage rises from ～?1.2 to ～?1.4 V, sub-threshold slope decreases from ～120 to ～80 mV/decade, off-current decreases from ～5 × 10^?12 to ～1 × 10^?12 A, on/off current ratio rises from ～3.8 × 10⁴ to ～2.5 × 10⁵, and the transistor hysteresis decreases from 61 to 26 mV. These results collectively support a two stage model of the desorption process where the removal of the physisorbed C₈PA molecules is followed by the annealing of the defect sites in the remaining C₈PA monolayer.