D. D. Gebler

Alternating‐current light‐emitting devices based on conjugated polymers

Most polymer electroluminescent devices to date are represented as tunnel diodes and operate under direct‐current (dc) driving field. Here we report the fabrication of symmetrically configured alternating‐current (ac) light‐emitting (SCALE) devices based on conjugated polymers. The new devices consist of an emissive polymer layer sandwiched between two redox polymer layers. This configuration enables the SCALE devices to work under both forward and reverse dc bias as well as in ac modes. The nearly ohmic electrode/redox polymer contacts improve the charge injection efficiency significantly and make the SCALE device operation insensitive to electrode work functions. Symmetric operation supports the key role of redox polymer/emissive polymer interface states.

EXCIPLEX EMISSION IN BILAYER POLYMER LIGHT-EMITTING DEVICES

Photoluminescent and electroluminescent studies of bilayer heterojunctions formed from a poly(pyridyl vinylene phenylene vinylene) (PPyVPV) derivative and poly(vinyl carbazole) (PVK) show an emission peak which cannot be ascribed to either the PPyVPV derivative or PVK layer. Through studies of absorption and photoluminescence excitation (PLE) spectra we demonstrate that the additional feature results from an exciplex at the bilayer interface. The photoluminescence efficiency of the exciplex is greater than 20%. The electroluminescence spectrum from the bilayer devices is entirely due to exciplex emission, with internal efficiencies initially achieved exceeding 0.1%.

Blue electroluminescent devices based on soluble poly(p‐pyridine)

We have fabricated unilayer electroluminescent devices from soluble poly(p‐pyridine) (PPy). The solubility of PPy in weak acids allows direct spin casting of the polymer films. The electroluminescence spectrum peaks at 2.5 eV (497 nm) corresponding to white light weighted towards the blue end of the spectrum. The photoluminescence spectrum peaks at 2.35 eV (530 nm). The operating voltages of the devices ranged from 4 to 12 V with current densities of 6 to 8 mA/mm2. We compare our devices with similar blue emitting devices based on poly(p‐phenylene).

Light-emitting devices based on pyridine-containing conjugated polymers

We report the fabrication of light-emitting devices based on several pyridine-containing conjugated polymers and copolymers in various device configurations. The high electron affinity of pyridine based polymers enables the use of relatively stable metals such as Al or even ITO as electron injecting contacts. Taking advantages of the better electron transport properties of the pyridine-containing polymers, we fabricate bilayer devices utilizing poly(9-vinyl carbazole) (PVK) as hole transporting/electron blocking polymer, which improves the device efficiency and brightness significantly due to the charge confinement and exciplex emission at the PVK/emitting polymer interface. The incorporation of conducting polyaniline network electrode to PVK reduces the device turn on voltage significantly while maintaining the high efficiency. The control of the aggregate formation in the polymer films by blending with insulating host polymers opens up the possibility of making voltage-controlled multi-color light-emitting devices.

Poly (p-pyridine) - and poly (p-pyridyl vinylene) -based polymers: their photophysics and application to SCALE devices

Abstract Photophysics and light-emitting device applications of poly ( p -pyridine) - and poly( p -pyridyl vinylene)-based polymers are presented. Extensive time-resolved (ps to ms) photoluminescence, stimulated emission and photoinduced absorption studies of solutions, powders and films demonstrate that the primary photoexcitation of these polymers is an intrachain singlet exciton. The presence of (n,π * ) states leads to enhanced intersystem crossing to triplet excitons for the powder form, while aggregate formation plays a key role in the films. Polarons are important at longer times. These polymers were used to fabricate ‘conventional’ polymer light-emitting diodes. In addition, these polymers were used to demonstrate a novel light-emitting structure, the symmetrically configured a.c. light-emitting (SCALE) device. These new devices have potential advantages in their use with high workfunction electrodes, such as gold, and also in their a.c. operation.

Exciplex emission from bilayers of poly(vinyl carbazole) and pyridine based conjugated copolymers

We present photoluminescence and electroluminescence studies of bilayers and blends formed from poly(vinyl carbazole) (PVK) and poly(pyridyl vinylene phenylene vinylene) (PPyVPV) copolymer derivatives. Bilayers of PVK and the PPyVPV copolymers have a photoluminescence emission which cannot be assigned to either the photoluminescence of PVK or the PPyVPV layer. The blends of the two polymers show a similar new photoluminescence emission for a large range of concentrations. Absorption and photoluminescence excitation spectra confirm that the additional feature is an excited state species which results from an exciplex at the polymer/polymer interface. Bilayer light-emitting devices utilizing the PPyVPV copolymers show an electroluminescence spectrum consistent with emission from the exciplex. The efficiency of the bilayer devices as compared to single layer devices increases by over three orders of magnitude due to the exciplex formation and the elimination of exciton formation near the luminescence quenchi...

Novel light-emitting diodes involving heterocyclic aromatic conjugated polymers

We report the fabrication and properties of three-, four-, and five-layer electroluminescent devices fabricated from light emissive N-based heterocyclic novel polymeric derivatives of PPP and PPV with which they are isoelectronic. They include poly(pyridine vinylene), (PPyV), and poly(2,5-dihexadecanoxy phenylene vinylene pyridyl vinylene), (PPV.PPyV). Some of the devices operate in both forward and reverse bias modes thus enabling operation in an ac mode. One type of device has the general construction: M/I/polymer/I/ITO where M equals Cu or Al, I equals polyaniline (emeraldine base, EB) or poly(3-hexylthiophene), (P3HT), and polymer equals PPV.PPyV. Under low frequency ac (sinusoidal) driving, light pulses with twice the driving frequency were observed in a device where M equals Al or Cu, I equals EB and polymer equals PPV.PPyV; and in a device where M equals Al, I equals P3HT and polymer equals PPV.PPyV. In the latter device the electroluminescence spectrum in the reverse bias mode differed from that in the forward bias mode. It was also shown that blends of PPyV in Nylon 6,6 exhibit a lower operating voltage than the pure polymer.

Color variable bipolar/ac light-emitting devices based on conjugated polymers

There is increased interest in developing color variable light emitting devices. We report here the fabrication of color variable bipolar/ac light-emitting devices based on conjugated polymers. The devices consist of blends of pyridine-phenylene and thiophene-phenylene based copolymers sandwiched between the emeraldine base form and the sulfonated form of polyaniline. ITO and Al are used as electrodes. The devices operate under either polarity of driving voltage with different colors of light being emitted, red under forward bias, and green under reverse bias. The relative fast time response allows the rapid switching of colors and ac operation.

Novel light-emitting devices based on pyridine-containing conjugated polymers

We present novel light-emitting devices based on several pyridine-containing conjugated polymers and copolymers in various device configurations. The high electron affinity of pyridine-based polymers improves stability and electron transport properties of the polymers and enables the use of relatively stable metals such as Al as electron injecting contacts. Bilayer devices utilizing poly(9-vinyl carbazole) (PVK) as a hole-transporting/electron-blocking polymer show dramatically improved efficiency and brightness as compared to single layer devices. This is attributed to charge confinement and exciplex emission at the PVK/emitting polymer interface. The incorporation of conducting polyaniline network electrode into PVK reduces the device turn-on voltage significantly while maintaining the high efficiency. Two novel device configurations that enable the use of high work function metals as electrodes are pointed out.

Experimental and theoretical study of ring substituent induced effects on the structural and optical properties of poly(p-pyridylvinylene- phenylenevinelyne)s

Optical absorption and photoluminescence spectroscopy have been carried out on a new class of (phenylene) ring substituted p-pyridylvinylenephenylenevinelyne polymers used as active materials in light emitting diodes. The effects of the ring substitutions on the optical absorption and photoluminescence energies are qualitatively explained through the use of semiempirical quantum chemical modeling of the ring torsion angles. Reduced aggregation through the use of “strap” substituents on the phenylene rings also is discussed.