We present work on the modification, processing, and analysis of ultrathin films for display devices primarily using the supramolecular assembly strategy. This involves the use of various molecular assembly techniques (organic, polymer, metal) in which layer order and functionality is achieved at defined length scales approaching that of ultrathin films (a few to several hundred nm thicknesses). The use of alternate polyelectrolyte deposition (APD) is primarily investigated in ultrathin films that have significance in the fabrication of display devices. The first application involves modifying a polymer light emitting diode (PLED) device fabricated using the ITO/MEH-PPV/Ca protocol with polyaniline derivatives. The second is the use of the “command layer” amplification concept and photo-induced alignment using polarized light with ultrathin films of azo dye/polyelectrolytes in a hybrid liquid crystal (LC) cell configuration. Both strategies rely on the use of surface sensitive spectroscopic and microscopic techniques to correlate device performance with layer ordering at the molecular level. The concept of functional ultrathin layers for device fabrication and modification is emphasized.

The temperature dependence of the photoluminescence as a function of excitation energy has been investigated for aluminium tris(8-hydroxyquinoline) (AlQ). It was observed that the peak position of the photoluminescence is a function of both temperature and excitation energy. The observed photoluminescence spectra can be deconvolved into three peaks, with varying weighting factors, the positions of which do not change with temperature. Using these three peaks the measured photoluminescence data was then modeled using a rate-equation approach.

We studied the surface properties of indium-tin oxide (ITO) modified by wet (aquaregia, ultrasonication, RCA) and dry (oxygen- and argon-plasma) treatments. The surface modification was investigated by surface energy, surface morphology, sheet resistance, carrier concentration, carrier mobility, and workfunction measurements. We report that the studied oxygen-plasma treatment induces: the highest surface energy with the highest polarity, the smoothest surface, the highest carrier density but the lowest mobility, the lowest sheet resistance, and the highest workfunction (stable in air). Polymer light-emitting diodes fabricated with the oxygen plasma treated substrates give the best performance in terms of electroluminescence efficiency and device lifetime. This is attributed to a favorable surface modification of ITO anodes by oxygen-plasma.

Doped organic light-emitting diodes (OLEDs), such as PVK containing the electron transport molecule PBD and molecular dyes, have demonstrated three-color capabilities and efficiencies over 1%, but there are concerns about reliability due to recrystallization of the small molecule PBD. In this work we describe the incorporation of both hole and electron transport groups into a single copolymer to avoid recrystallization and phase segregation (which could occur if two separate polymers were used) as well as the application of such copolymers in dye-doped OLEDs. The polymers were synthesized through free radical copolymerization of the electron- donating monomer N-vinylcarbazole (NVK) with the electron-withdrawing monomer 2-(4-tert-butylphenyl)-5-{4-[(4'-vinyl)phenylmethoxy] phenyl}-1,3,4- oxadiazole (BVO). The radical reactivity ratios of the two monomers were estimated to be rNVK=0.052 and rBvo=12. The copolymers are transparent in the visible region, homogeneous as characterized by both GPC and DSC, and have good thermal stability. External quantum efficiencies of 0.07%, 0.3% and 0.4% were achieved in LEDs with device structures of ITO/COP:C47/Mg:Ag, ITO/COP:C6/Mg:Ag and ITO/COP:NR/Mg:Ag, respectively, where COP stands for copolymer, C47 for Coumarin 47, C6 for Coumarin 6 and NR for Nile Red. The introduction of the oxadiazole group balances the injection of holes and electrons by decreasing the hole injection and transport ability and enhancing the electron injection and transport ability of the copolymers relative to PVK.

We studied the influence of various surface treatments of indium-tin oxide anodes on the operational stability of high-efficiency green-emitting polymer light-emitting diodes, fabilicated with a doped poly(3,4-ethylene dioxythiophene) PEDOT hole transport layer, a polyfluorene-based emissive layer, and Ca-Al cathodes. The anodes were modified by physical (oxygen-plasma), chemical (aquaregia), or combined treatments. Oxygen-plasma improves the stability under constant current over all the other anodes, with half-brightness lifetimes (initial brightness, 200 cd/m2) two to five times longer than for untreated samples, and 1000 times longer than for aquaregia ones. We derive two major indications for optimisation of PLEDs. First, thermal management of the diode is of the uppermost importance. Second, the ITO anode and in general the electrical properties of the hole-injecting contact are crucial to device operation, even in the presence of a hole transport layer.

The vacuum level shift A was determined by Kelvin probe method for TPD/metal systems prepared in ultrahigh vacuum (TPD: N, N'-bis(3-methylphenyl)-N, N'-diphenyl-[1, 1'-biphenyl]-4,4'-diamine). The energy of the vacuum level sharply changed at the initial stage of depositing TPD on the metal substrates, and further bending was not observed up to 100 nm thickness of TPD. This result is consistent with our previous studies of ultraviolet photoelectron spectroscopy. These results indicate the invalidity of traditional model with a common vacuum level at organic/metal interface. We discussed the dependence of the vacuum level shift on the work function Φm of the metal substrate (Au, Cu, Ag, Mg, and Ca). A liner correlation between Δ and Φm was observed only in the region of 3.8 eV < Φm < 4.5 eV, indicating that Fermi level alignment is not achieved at least for some interfaces. We found that Δ for TPD film on the air-exposed metal substrate is smaller than that of TPD on clean metals and was observed a liner relation between Φm and Δ except for the Cu substrate.

We investigate the electrical properties of Polymer Light Emitting Diodes (LED's). The experimental data consists of steady state current-voltage characteristics and radiance as a function of temperature.

The basic LED structure is Anode/MEH-PPV (2-methoxy,5-(2'-ethyl-hexyloxy)-l,4-phenylene vinylene)/Cathode, with a polymer film 120-140 nm thick. We use different anode/cathode pairs to study transport and light emission properties. Measurements of external quantum efficiency of bipolar and monopolar devices are presented from 200 K to 300 K. The electron and hole mobilities are derived in the trap-free limit and at high voltages.

This contribution describes the use of self-limiting siloxane chemisoroption processes to self-assemble building blocks for the modification of vacuum-deposited organic LED (OLED) devices. One approach consists of the use of self-assembling OLED hole transport materials for application in hybrid self-assembled + vapor deposited two-layer devices. Another approach involves the application of self-limiting, chemisorptive self-assembly techniques to introduce thin dielectric films between the anode and hole transport layer of a vapor deposited two-layer OLED device.

A versatile, and generally applicable modular approach for making second-order nonlinear optical (NLO) side-chain aromatic polyquinolines has been developed. This approach emphasizes the ease of incorporating NLO chromophores onto the pendent phenyl moieties of parent polyquinolines at the final stage via mild Mitsunobu reaction. This method provides the synthesis of polyquinolines with a broad variation of the polymer backbones and great flexibility in the selection of NLO chromophores. These side-chain NLO polyquinolines demonstrate high electro-optic (E-O) activity (up to 35 pm/V at 830 nm and 22 pm/V at 1300 nm, respectively) and a good combination of thermal, optical, electrical and mechanical properties.

Comparatively, two new electroluminescent (EL) polyquinolines have been prepared via the Friedlander condensation and nucleophilic reaction. The resulting polymers contain a bipolar property with both an efficient hole-transporting moiety, tetraphenyldiaminobiphenyl (TPD), and an electron affinitive light-emitting moiety, bis-quinoline. In addition, they possess high thermal stability, excellent electrochemical reversibility, good thin film-forming ability, and bright light-emitting property. Electrical characterization of two-layer diode devices based on the configurations of ITO/CuPc/TPD-PQ or TPD-PQE/Al showed excellent electroluminescence performance (a rectification ratio greater than 105 and a low turn-on voltage of less than 4 V).

Organic light emitting diodes have been fabricated using erbium tris(8-hydroxy-quinoline) as the emitting layer and N, N'-diphenyl-N, N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD) as the hole transporting layer. Room temperature electroluminescence was observed at 1.5 μm due to intra-atomic transitions between the 4I13/2 and 4I15/2 levels in the Er3+, ion. These results make the possibility of producing silicon compatible 1.5 μm technology based on such devices a reality.

A survey of the literature shows that reverse bias current IL of an illuminated conducting polymer Schottky diode increases with voltage. We suggest that this increase in IL with applied reverse bias is due to a combination of two factors: (1) increase of mobility, and (2) dissociation of excitons. The experimental results agree with the values of IL calculated using either of the two mechanisms. Therefore it is difficult to determine the relative importance of the two mechanisms. The relative importance can be determined only if reliable values of material parameters are available. We have fabricated Schottky diodes and FETs using 5-ring n-octyloxy-substituted oligo[p-phenylene vinylene](Ooct-OPV5) and C60. The mobility of the oligomer derived from the measured characteristics of the diode is 3.29×10−7cm2/Vs and from the FET data, 3.24 × 10−4 cm2/Vs. These results show that the mobility (and other material parameters) depend strongly on the structure of the device. Therefore for interpreting the IL data it is important to measure the material parameters on the same structure on which IL measurements are made.

The delayed fluorescence of poly(p-phenylene vinylene) (PPV) and poly(p-phenylene ethynylene) (PPE) derivative solids and frozen solutions at 20 K is described. It provides strong evidence for triplet-triplet annihilation to singlets excitons accounting for up to ∼3% of the total emission in PPV films and ∼1.5% in PPE powder. It also yields triplet lifetimes of 70 and 110 μs in PPV films and frozen solutions, and ∼200 and ∼500 μs in PPE powder and frozen solutions, respectively.

Qualitatively, the basic principles behind the operation of OLEDs are well established. In order to optimize device parameters such as power efficiency and operating voltage, to explore the limits of performance and to understand changes in the electrical properties as diodes age, it is necessary to develop a quantitative understanding of each of the relevant processes: injection of electrons and holes at the cathode and anode, charge transport, recombination and exciton formation, and emission. In this paper, we summarize our experimental, theoretical and numerical studies to address these issues.

The intrinsic degradation of tris(8-hydroxyquinoline) aluminum (AlQ3)-based organic light emitting devices, that leads to the long-term decrease in the electroluminescence efficiency of the devices operated under constant current conditions, is studied. The injection of holes in A1Q3 is found to be the main factor responsible for device degradation. OLEDs with dual HTLs in different arrangements are also presented to demonstrate the proposed degradation mechanism. The role of various approaches to increase OLED lifetime, such as, doping the hole transport layer, introducing a buffer layer at the hole-injecting contact, or using a mixed emitting layer of hole and electron transporting molecules, is explained.

A method to locally pattern the distribution of dye by diffusion into the polymer film of organic light-emitting diodes is introduced. Using a large-area diffusion source, the diffusion of dye into the polymer film can be controlled with a shadow mask. The materials used are the polymer poly(9-vinylcarbazole) (PVK) combined with electron transport molecules (PBD), and the dyes bimane, coumarin 6 and Nile red. The temperature dependence of the diffusion is investigated along with the effect of annealing of the polymer film. A model of the dye distribution is introduced and estimations of the dye profile based on this model and PL measurement are discussed. A 3-color integrated device was demonstrated.

This paper focuses on some experiments done using field emitter arrays (FEAs) produced at CEA-LETI, experiments which are outside of the display or microwave amplifier contexts. Among various studies done at CEA-LETI with FEAs we have selected:

- the search towards a spin polarized electron source,

- a study on the spatial coherence of the electron beam emitted by a single emitter,

- the incorporation of an optical command in a FEA and finally,

- the application of a FEA to electron injection into rare gas liquids.

Thin films of Si/Cs/O nanoclusters have been synthesized by the technique of supersaturated thermal vaporization of Si and Cs in an oxygen background gas. These films, which were deposited onto conducting or semiconducting substrates, exhibit negative electron affinity (NEA) as evidenced by ultraviolet photoemission spectroscopy (UPS). Photo and field electron emission properties of these nanocluster films were investigated with photo-electron emission microscopy (PEEM), field electron emission microscopy (FEEM), and current-voltage measurements. Flat cathodes covered with thin films of Si/Cs/O nanoclusters exhibited high current outputs and low turn-on fields. The films' NEA is unaffected by air exposure and is stable to high temperature annealing (550 TC). A field emission display unit with a simple diode structure containing a flat cathode coated with a patterned thin film of Si/Cs/O nanoclusters has also been built to demonstrate the potential application of this material in cold cathode electron emitting devices, particularly field emission flat panel displays.

In the past, we have proposed a new cold cathode emitter which consists of a thin region of CdS (Cadmium Sulfide) sandwiched between a heavily doped InP (Indium Phosphide) substrate and a low work function LaS (Lanthanum Sulfide) semimetallic thin film. In this paper, we briefly review the principle of operation of the cathode and discuss the preliminary experimental steps undertaken to realize prototypes of the device. More specifically, we describe the growth of bulk samples of LaS which is used to achieve Negative Electron Affinity of the CdS/LaS surface. X-ray diffraction and micro-Raman experiments show the successful growth of the fcc cubic phase of LaS samples.

Secondary electron emission spectroscopy is used to examine the transport and emission of low-energy electrons in several wide bandgap materials. In particular, the secondary emission properties of C(100), C(111), and CVD diamond samples are compared in order to examine the effect of crystallographic orientation on the emission characteristics. Very high yields are obtained from hydrogenated and cesiated negative-electron-affinity surfaces of all three samples, indicating that low-energy electrons are transported and emitted very efficiently in the diamond materials. While the energy distribution of the emitted electrons is found to be sharply peaked at low energy for all three samples, the energy distributions measured from the C(111) surfaces are broader and reveal structure in the energy gap. The different emission processes at the C(100) and C(111) surfaces may account for the energy distributions observed from the polycrystalline CVD diamond. Finally, initial secondary emission measurements are taken from GaN and AlGaN films grown by molecular beam epitaxy. The secondary emission is not as strong as from the diamond samples, and the measurements reveal the impact of interface and surface barriers on the emission process.