TW200301668A - Method of forming electroluminescent devices - Google Patents

Abstract

An electroluminescent device comprising an electroluminescent layer which is deposited by melt deposition. An electroluminescent device comprising in sequence, (i) an anode, (ii) a layer of an electroluminescent compound of general formula (Lα)nM where M is one or more of a rare earth, lanthanide or an actinide, or a non rare earth metal or a mixture of rare earth and/or non rare earth metals, Lα is one or more organic complexes and the organic complexes can be the same or different, and n is the valence state of M and (iii) a cathode, in which the electroluminescent compound is deposited on the preceding layer by melt deposition.

Description

200301668 发明 、 Explanation of the invention:.-:-: &Quot; [Technical Field to which the Invention belongs] The present invention relates to an electroluminescent device and a display. [Prior Art] Materials that emit light when an electric current is passed are well known and used in a wide range of display applications. Liquid crystal devices and devices based on inorganic semiconductor systems are widely used, but these have disadvantages such as high energy consumption, high manufacturing cost, low quantum efficiency, and inability to manufacture flat panel displays. Organic light-emitting polymers cannot obtain pure colors, and their manufacturing systems are expensive and relatively inefficient. Patent application WO98 / 58037 describes a range of lanthanide complexes which can be used in electroluminescent devices, and which have improved characteristics and give better results. Patent applications PCT / GB98 / 01773, PCT / GB99 / 03619, PCT / GB99 / 04030, PCT / GB99 / 04024, PCT / GB99 / 04028, PCT / GBOO / 0〇268 describe electrochemistry using rare earth chelates Luminescent complex, structure and device. The disclosed method for depositing an electroluminescent layer on a previous layer to constitute an electroluminescent device can be achieved by directly evaporating a solution of a material in an organic solvent. The solvent used will depend on the material, but chlorinated hydrocarbons such as dichloromethane and n-methylpyrrolidone, dimethylboron, tetrahydrofuran, dimethylformamide and the like are suitable for many situations. Alternatively, the material can be deposited from a solution by spin coating or from a solid state by vacuum deposition, such as sputtering. Fused deposition usually cannot use organic polymer electroluminescent compounds. 200301668 Because organic polymers are unstable under the required temperature conditions and cannot be used with aluminum quinone, however, we have found that when the electroluminescent material is an organic metal For compounds, fused deposition techniques can be used. [Summary of the Invention] The present invention provides an electroluminescence device, which sequentially includes a rhenium anode, (ii) an electroluminescent compound layer of the general formula (La) nM, wherein μ is one or more rare earth elements, lanthanide elements, or europium Elements, or non-rare-earth metals or a mixture of rare-earth elements and / or non-rare-earth metals, La is one or more organic complexes, and the organic complexes may be the same or different. Valence, and (iii) the cathode, wherein the electroluminescent compound is deposited on the previous layer by fused deposition. [Embodiment] The previous layer means a layer formed on a substrate on which an electroluminescent layer is deposited. As described below, there may be other layers between the anode and the electroluminescent layer, such as a hole transport material layer and a buffer layer, and there may be other layers between the cathode and the electroluminescent layer, such as an electron transport material layer and Coating to adjust the work function of the cathode. The electroluminescent compound usable in the present invention is a general formula (La) nM, in which M is a rare earth element, a lanthanide or an actinide, a La-based organic complex, and η is a valence state of M. Other electroluminescent compounds that can be used in the present invention are of the following formula. A preferred electroluminescent compound that can be used in the present invention is the following formula 200301668 (Loon > M-Lp where La and Lp are organic ligands and M is Rare earth element, transition metal, lanthanide or copper element, and valence state of η metal M. Ligand

La may be the same or different, and may have many identical or different ligands Lp. For example, (LiXLJO ^ KL.OMap), where M is a rare earth element, a transition metal, a lanthanide or an actinide, (Loa ^ a ^ KL ...) are the same or different organic complexes, and (Lp) is a neutral ligand. The total charge of the ligand (LDO ^ KLsXL ..) is equal to the valence state of the metal M. If there are three radicals La corresponding to the III valence state of M, the complex has the formula (LDaja ^ Map) and the different radicals αοα ^ κι ^) may be the same or different.

Lp can be monodentate, bidentate, or multidentate, and can have one or more ligands

Lp 〇 Preferably, M is a metal ion with an unfilled inner shell, and the preferred metal system is selected from Sm (III), Eu (II), Eu (III), Tb (III), Dy (III), Yb (III), Lu (III), Gd (III), Gd (III) U (III), Tm (III), Ce (III), Pr (III), Nd (III), Pm ( III), Dy (III), Ho (III), Er (III), and more preferably Eu (III), Tb (III), Dy (III), Gd (III). Other electroluminescent compounds that can be used in the present invention are those of the general formula (Ethylene Glycol). Among them,% is the same as the above M, M2 is a non-rare earth metal, La is as above, and η is% and M2. The combined valence state. The complex may also include one or more neutral ligands Lp. The europium complex has the general formula (LoOnMiMJLp), where Lp is as above. The metal M2 may be any non-rare earth element, transition metal , Lanthanide or copper-based metals, examples of useful 200301668 metals include lithium, sodium, potassium, thallium, planer, beryllium, magnesium, calcium, thallium, barium, copper (I), copper (II), silver, Gold, zinc, ytterbium, boron, aluminum, gallium, indium, germanium, tin (II), tin (IV), chain (II), antimony (iv), give (II), give (iv), at different prices State transition metals of the first, second, and third group metals, such as manganese, iron, nail, starvation, cobalt, nickel, palladium (II), palladium (IV), uranium (11), platinum (IV), cadmium , Chromium, titanium, vanadium, pin, giant, molybdenum, rhodium, iridium, titanium, niobium, scandium, yttrium. For example (LiKLJO ^ KL.OMap), where M is a rare earth element, a transition metal, a lanthanide or a copper element , And (Ll) ( L2) (L3) (L · ·.) And (Lp) are the same or different organic complexes. Other organometallic complexes that can be used in the present invention are dinuclear, trinuclear and multinuclear organometallic complexes, For example, the following formula is (LirOxM)-M2 (Ln) y, such as (Lm) xMi ^ j) M "Ln) y, where L is a bridging ligand, Mi is a rare earth metal, and ^ is rhenium or a non-rare metal , Lm and Ln are the same or different organic ligands La as defined above, and the valence state of X is 虬 and the valence state of y. In these complexes, there may be metal-to-metal bonding, or There may be one or more bridged ligands between M! And M2, and the groups Lm and Ln may be the same or different. Trinuclear means that three rare earth metals are connected via a metal-to-metal bond, that is, the following formula ( Lm) xM 1 — M3 (Ln) y —m2 (lp) 2 200301668

(Lm) xM!-M3 (Ln

(LP) Z different rare earth metals, while X is the valence state of Mm, y is the same! M !, M 2 and M 3 are the same, and Lm, Ln and Lp are the organic ligands La, M: the valence state, 2 Is the valence state of A, "may be the same or different from 1 ^ 1 and Ln 〇 rare earth metals and non-rare earth metals may be connected via metal-to-metal bonds and / or via intermediate bridge atoms, ligands or molecular groups For example, metals can be linked by bridging ligands, such as (Lm) xM! M3 (Ln) y M2 (Lp) z

Among them, L is a bridging ligand. Multicore means that more than two metals are metal-to-metal bonded and 200301668 / or connected via an intermediate ligand Μ! —Μ2 — Μ3—Μ 4 or

Mj—Μ2—M4—M3 or m2

Ml " M3 --- NM4 or ^ Ln M1 M2 M4 M3 NX 乂 where Mi, M2, M3 and M4 are rare earth metals' and L is a bridging ligand. [Metal] \ 42 may be any metal that is not a rare earth element, transition metal, lanthanide or actinide. Examples of useful metals include lithium, sodium, potassium, thallium, planed beryllium, magnesium, calcium, thallium, barium, Copper, silver, gold, zinc, cadmium, boron, aluminum, gallium, indium, germanium, tin, antimony, lead, and first, second and third group metals of transition metals, such as manganese, iron, ruthenium, hungry, Cobalt, nickel, palladium, platinum, cadmium, chromium, titanium, vanadium, zirconium, giant, molybdenum, rhodium, iridium, titanium, niobium, hafnium, yttrium, etc. Preferably, La is selected from β-diketone, which is

(I) (II) (III) 200301668 I, R1, I and R3 may be the same or different and are selected from hydrogen, substituted and unsubstituted hydrocarbon groups, such as substituted and unsubstituted aliphatic groups , Substituted and unsubstituted aromatic, heterocyclic and polycyclic structures, fluorocarbons, such as trifluoromethyl, halogen, such as fluorine, or thiophenyl; R !, R2 and R3 can also form substituted or Unsubstituted fused aromatic, heterocyclic and polycyclic structures and copolymerizable with monomers such as styrene. χ series Se'S or O 'γ can be hydrogen, substituted or unsubstituted hydrocarbon groups, such as substituted and unsubstituted aromatic, heterocyclic and polycyclic structures, fluorine, fluorocarbons, such as trifluoromethyl Radical, halogen, such as fluorine or thiophenyl or nitrile. Examples of oxo and / or R2 and / or R3 include aliphatic, aromatic and heterocycloalkoxy, aryloxy and carboxyl, substituted and unsubstituted phenyl, fluorophenyl, biphenyl, phenanthrene, Rhen, naphthyl and fluorenylalkyl such as tertiary butyl, and heterocyclyl such as carbazole. Some different groups La can also be the same or different charged groups, such as carboxylate groups, fluorenyl groups L! Can be defined as above and the groups L2, L3 ... can be charged groups such as R-ci: ° (IV) Wherein R is I as defined above, or the groups Li and L2 may be defined as above, and L3 ... etc. are other charged groups.

Ri, 1 ^ 2 and R3 can also be 11 200301668

Wherein X is 0, S, Se or NH.

The preferred component h is trifluoromethyl CF3, and examples of the diketone are benzamidine trifluoroacetone, p-chlorobenzidine trifluoroacetone, p-bromotrifluoroacetone, p-phenyltrifluoroacetone, 1- Naphthyridine trifluoroacetone, 2-naphthyridine trifluoroacetone, 2-phenanthrenetrifluoroacetone, 3-phenanthrenetrifluoroacetone, 9-cyclyltrifluoroacetone trifluoroacetone, cinnamon tincture Trifluoroacetone and 2-thienylmethyltrifluoroacetone. Different radicals La can be the same or different ligands of the formula

(VI) wherein X is 0, S or Se, and Ri, R2 and R3 are as described above. Different radicals La can be the same or different quinone ester derivatives, such as

(VII)

(VIII) or 12 200301668 in which R is a hydrocarbon group, an aliphatic, an aromatic or a heterocyclic carboxyl group, an aryloxy group, a hydroxy group or an alkoxy group, such as an 8-hydroxyquinone ester derivative or

Ri

(IX) r2

οο (X) where Ri, Xin and R3 are as above or Η or F, such as Ri and 1

(XI) (XII)

As mentioned above, different groups La can also be the same or different carboxylic acid ester groups, such as 13 200301668 R5-c

(Χΐιΐ) where R5 is substituted or unsubstituted aromatic, polycyclic or heterocyclic polypyridyl, R5 may also be 2-ethylhexyl, fluorene, 2-ethylhexanoate, or R5 may be It is a chair-type structure, and the stilbene is 2-ethylsulfonyl cyclohexanoate, or La may be

Ο

R (XIV) wherein R is as above, for example an alkyl, alkenyl, amine or fused ring, such as a cyclic or polycyclic ring. Different base La can also be

(XV) (XVI)

14 200301668

(XVII) (XVIIa) wherein R, 1 and 112 are as described above. The group Lp may be selected from

Ph Ph

n I I 〇 = P —N = P — Ph

I I

Ph ph (XVIII) wherein each Ph may be the same or different and may be phenyl⑴pNp) or substituted phenyl, other substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic or polycyclic Base, substituted or unsubstituted fused aryl, such as naphthyl, aryl, phenanthrene or fluorenyl. The substituent may be, for example, an alkyl group, an alkyl group, an alkyl group, a square group, a heterocyclic ring, a polycyclic group, a halogen such as fluorine, a cyano group, an amino group, a substituted amino group, or the like. Examples are given in Figures 1 and 2, where R, Ri, R2, Rs and r4 may be the same or different and are selected from hydrogen, hydrocarbyl, substituted or unsubstituted aromatic, heterocyclic or polycyclic structures, Fluorocarbons such as trifluoromethyl, halogens such as fluorine or thiophenyl; R, R !, R2, R3, and R4 may also form substituted or unsubstituted fused aromatic, heterocyclic, and polycyclic structures, and It can be copolymerized with a monomer such as styrene 200301668. R, l, R2, R3 and R4 can also be unsaturated alkenyl, such as vinyl or the following-c- CH2 = CH plant R where R is as above.

Lq can also be a compound of the formula

Where R !, R2, and R3 are as defined above, such as the red phenanthrene (bathophen) shown in Figure 3, where R is as above or

(XXII) (XXIII) wherein Ri, 1 and R3 are as defined above.

Lp can also be 16 200301668

Ph Ph I-I — 3 ——— p -n-P S I I Ph Ph or (XXIV) ph_ N -p- pII o

X (X rrph ο wherein Ph is as above. Other examples of Lp chelate compounds are shown in Figure 4, examples of fluorene and hydrazone derivatives are shown in Figure 5, and compounds of the formula shown in Figures 6 to 8 are shown.

Specific examples of La and Lp are tripyridyl and TMHD, and butyl] ^ 110 complex, 〇 ^, (^, 〇 ^ tripyridyl, crown ether, naphthene, cold alkane, phthalocyanine, hydrazone, Ethylenediamine tetramine (EDTA), DCTA, DTPA and TTHA. Among them, TMHD is 2,2,6,6-tetramethyl-3,5-heptanedioic acid group, while OPNP is diphenylphosphine amine, Phenyl orthophosphoric acid. The formula for polyamines is shown in Figure 9. Other useful electroluminescent materials include gold quinone salts such as lithium quinate, and non-rare earth metal complexes such as aluminum, magnesium, zinc, and europium. Materials, such as β-diketone complexes, such as ginseng- (1,3-diphenyl-1,3-propanedione) (DBM), and suitable metal complexes are A1 (DBM) 3, Zn (DBM) 2 and Mg (DBM) 2, Sc (DBM) 3, etc. Other useful electroluminescent materials include metal complexes of the formula 17 200301668

Where M is a metal other than a rare earth element, a transition metal, a lanthanide or an actinide; η is the valence of M; Ri, R2 and R3 may be the same or different and are selected from the group consisting of hydrogen, hydrocarbon, substituted and unsubstituted Substituted aliphatic groups, substituted and unsubstituted aromatic, heterocyclic and polycyclic structures, fluorocarbons such as trifluoromethyl, halogens such as fluorine, or thiophenyl or nitrile; h and R3 may also form Ring structure, and h, R2 and R3 can be copolymerized with a monomer such as styrene. Preferably, M is aluminum and R3 is phenyl or substituted phenyl. These complexes are described in patent application PCT / GB02 / 003 163, the contents of which are incorporated herein by reference. Electroluminescent materials and devices are described in patent applications PCT / GB98 / 01773, PCT / GB99 / 03619, PCT / GB99 / 04030, PCT / GB99 / 04024, PCT / GB99 / 04028, PCT / GB00 / 00268, PCT / GB01 / 05113, PCT / GB01 / 05111, PCT / GB01 / 05135, PCT / GB021264, PCT / GB02 / 01837, PCT / GB02 / 018884, PCT / GB02 / 01839, PCT / GB02 / 01844, PCT / GB02 / 02094, 18 200301668 PCT / GB02 / 02092 and PCT / GB02 / 02093, the contents of which are incorporated herein by reference. The first electrode is preferably a transparent substrate, such as conductive glass or plastic material, which acts as an anode. The preferred substrate is a conductive glass, such as indium tin oxide-coated glass, but any conductivity or metal material such as Or the glass of the conductive layer of a conductive polymer. It is also possible to use conductive polymers and glass or plastic materials coated with conductive polymers as the substrate. There may be a hole-transporting material layer between the electroluminescent material and the anode. The hole-transporting material may be an amine complex, such as poly (vinylcarbazide), N, N'-diphenyl-N, N'-bis (3-methylphenylbiphenyl-4,4, diamine (TPD), unsubstituted or substituted polymers of aromatic compounds substituted with aromatic compounds, polyaniline, substituted poly Aniline, polythiophene, substituted polyquinone, polysilane, etc. Examples of polyaniline are the following polymers

Where R is in ortho or meta position and is hydrogen, CM8 alkyl, oxo, amine, chlorine, bromine, hydroxyl or lower

Wherein R is alkyl or aryl, and R 'is hydrogen, C1-6 alkyl or aryl, 19 200301668 and at least one other monomer of formula i. Or the hole transport material may be a kind of polyaniline, and the polyaniline used in the present invention has a general formula

R

XX Η / ρ _ (XXVII) where P is 1 to 10, and η is 1 to 20, R is as defined above, and X is an anion, preferably selected from Cl, Br, S04, BF4, PF6, and H2P. 3.H2P04, arylsulfonate, aromatic hydrocarbon dicarboxylate, polystyrene sulfonate, polyacrylate, alkylsulfonate, vinylbenzenesulfonate, cellulose sulfonate, camphor sulfonate, cellulose sulfonate or perfluoro Chemical polyanion. Examples of aryl sulfonates are p-toluenesulfonate, benzenesulfonate, 9,10-quinone sulfonate and benzosulfonate, examples of aromatic dicarboxylates are peptidate, and examples of aromatic carboxylates are benzoate . We have found that protonated polymers of unsubstituted or substituted polymers of amine-substituted aromatic compounds, such as polyaniline, are difficult to evaporate or cannot be evaporated, but we have surprisingly found that An unsubstituted or substituted polymer of a substituted aromatic compound is deprotonated so that it can be easily evaporated, that is, the polymer is vaporizable. Deprotonated polymers using unsubstituted or substituted polymers which are vaporizable amine-substituted aromatic compounds are preferred. Amino-substituted aromatic 20 200301668 Deprotonated unsubstituted or substituted polymers of compounds can be polymerized by treatment with a base such as ammonium hydroxide or an alkali metal hydroxide such as sodium or potassium hydroxide Matter is formed by deprotonation. The degree of protonation can be controlled by forming protonated polyaniline and deprotonation. A. G. MacDiarmid and A. F. Epstein, Faraday Discussions, Chem Soc. 88 P319 1989 describe methods for preparing polyaniline. The conductivity of polyaniline depends on the degree of protonation, and the maximum conductivity is when the degree of protonation is between 40 and 60%, such as about 50%. Preferably, the polymer system is substantially completely deprotonated. Polyaniline can be formed from octamer units, ie P is 4, for example

The conductivity of polyaniline can be lxl0j Siemens cnr1 series or higher. The aromatic ring may be substituted or unsubstituted, for example, by a C1-20 alkyl group such as ethyl. Polyaniline may be a copolymer of aniline, and a preferred copolymer is a copolymer of aniline and o-anisidine, m-aminobenzenesulfonic acid or o-aminophenol, or o-toluidine and o-aminophenol, o-ethylaniline, Copolymer of o-phenylenediamine or amino group. Useful polymers of other amine-substituted aromatic compounds include substituted or unsubstituted polynaphthalenes, polyaminos, polyphenanthrenes, and the like, and polymers of any other condensed polyaromatics. Polyamines and their manufacturing methods 21 200301668 The legal system is disclosed in US Patent No. 6,153,726. The aromatic ring may be unsubstituted or substituted, for example, by a group R as defined above. Other hole-transporting materials are conjugated polymers, and useful conjugated polymers can be any of the disclosed conjugated polymers or reference us 5807627, PCT / WO90 / 13148 and PCT / WO92 / 03490. Preferred conjugated polymers are poly (copolymers of p-phenylene vinylene> PPV and 3 PPV. Other preferred polymer systems are poly (2 > diaminooxy vinyl phenylene vinyl), such as poly ( 2-methoxy-5- (2-methoxypentyloxy 丄 'phenylene vinylene), poly (2-methoxypentyloxy) -i, 4-phenylene vinylene) , Poly (2-methoxy-5- (2-decyloxy-1,4-phenylene vinylene) and other poly (2,5-dialkoxyphenylene vinylene), of which at least one alkane Oxygen is a long-chain solubilizing alkoxy group, polyfluorene and oligomeric fluorene, polyphenylene and oligophenylene, polyallium and oligomeric, polythiophene and oligothiophene. In PPV, benzene ring is required It may carry one or more substituents, for example each independently selected from alkyl, preferably methyl, alkoxy, preferably methoxy or ethoxy. Φ Any polymer containing substituted derivatives may be used (Phenylene vinylene), and the polyphenylene vinylene ring can be replaced by a condensed ring system such as a ring or a naphthalene ring, and the polyphenylene vinylene moiety can be increased. Vinyl number , Such as up to 7 or higher. Conjugated polymers can be made by the methods disclosed in US 5807627, PCT7WO90 / 13148 and PCT / WO92 / 03490. The thickness of the hole transport layer is preferably 20 nm to 200 nm. Amine Polymers of substituted aromatic compounds such as polyaniline 22 200301668 mentioned above can be used as a buffer layer, have other hole transport materials or cooperate with other hole transport materials. Articles 11, 12, 13, 14, 15 and Figure 16 shows the structural formulas of certain other hole transport materials, where Ri, R2, and R3 can be the same or different and are selected from hydrogen, and substituted and unsubstituted hydrocarbon groups, such as substituted and unsubstituted Aliphatic groups, substituted and unsubstituted aromatic, heterocyclic, and polycyclic structures, fluorocarbons such as trifluoromethyl, halogens such as fluorine, or thiophenyl; & and & can also form Substituted or unsubstituted fused aromatic, heterocyclic, and polycyclic structures, and copolymerizable with monomers such as styrene. Χ series Se, s or 0, γ may be hydrogen, substituted or unsubstituted Hydrocarbyl, such as substituted and unsubstituted square, hetero, and polycyclic structures, fluorine, fluorine Compounds such as trifluoromethyl, halogens such as fluoro or thiophenyl or nitrile. Examples of R! And / or A and / or r3 include aliphatic, aromatic and heterocycloalkoxy, squaroxy and residues , Substituted and unsubstituted phenyl, fluorophenyl, biphenyl, phenanthrene, chiral, zeki and fluorenyl alkyl such as tertiary butyl, heterocyclic group such as carbazole. There may be an electron transport material interposed Between the electroluminescent material and the cathode, the electron injection material is a material that will transport electrons when passed by an electric current, 'comprising metal complexes, such as metal quinate salts, such as aluminum quinate, lithium quinate, and cyano , Such as 9,10-dicyano group, cyano-substituted aromatic compound, tetracyano-dimethyl dimethyl sulfonate, or a compound having the structural formula shown in FIG. 10, Wherein the benzene ring may be substituted by a substituent R as defined above. 23 200301668 Optionally, hole-transporting materials can be mixed with and co-deposited with electroluminescent materials; optionally, hole-transporting materials can be mixed with and co-deposited with electroluminescent materials; optionally, holes The transmission material, the electroluminescent material, and the electron injection material can be mixed together to form a layer, which simplifies the structure. The first electrode is preferably at least partially transparent to light of all or a portion of the wavelength that can be emitted from the device. Of the best, it is substantially transparent. The first electrode may be formed of, for example, ιτο (indium tin oxide), το (tin oxide), or gold |. The first electrode is preferably arranged in the visual direction of the light-emitting area, which is between the light-emitting area and the expected position of the viewer. The first electrode may be layered. The device contains more than one pixel, and a first electrode may be provided to allow (in cooperation with the second electrode) each pixel to be addressed independently. The second electrode functions as a cathode and can be any metal with a low work function, such as aluminum, calcium, lithium, silver / magnesium alloy, rare earth metal alloy, etc., among which aluminum is a preferred metal. A metal fluoride such as an alkali metal, a rare earth metal or an alloy thereof can be used as the second electrode, for example, by forming a metal fluoride layer on a metal. The display of the present invention may be monochrome or multicolor. Electroluminescent rare earth chelate compounds are known and will emit a range of light, such as red, green and blue and white light, and examples are disclosed in patent applications WO98 / 58037, PCT / GB98 / 01773 ^ PCT / GB99 / 03619, PCT / GB99 / 04030, PCT / GB99 / 04024, PCT // GB99 / 4028, PCT / GB00 / 00268, and can be used to form 0LEDs emitting these colors. Therefore, a full-color display can be formed by arranging three independent backplanes, each emitting a different main monochrome on a different side of the optical system. 24 200301668 The combined color image can be seen from the other side. In addition, a rare-earth chelate electroluminescent compound emitting different colors can be produced, and adjacent diode pixels in three adjacent pixel groups generate red, green, and blue light. In another variation, the field-sequential color filter can be mounted on a white-emitting display. One or both of the two electrodes may be formed of silicon, and an interlayer of an electroluminescent material and a hole transporting and electron transporting material may be formed on a sand substrate as a pixel. Preferably, each pixel includes at least one layer of a rare earth chelated electroluminescent material, and a (at least semi-transparent) transparent electrode is in contact with the organic layer on a side remote from the substrate. Preferably, the substrate is a crystalline silicon, and the surface of the substrate may be polished or smoothed to produce a flat surface before the electrode or the electroluminescent compound is deposited. Alternatively, a non-planar silicon substrate can be coated with a layer of conductive polymer to produce a smooth, flat surface before depositing other materials. In a specific aspect, each pixel includes a metal electrode in contact with the substrate. Depending on the relative work functions of the metal and the transparent electrode, either one can be used as the anode 'and the other as the cathode. When the silicon substrate is a cathode, a glass coated with indium tin oxide can act as an anode, and light is emitted through the anode. When a silicon substrate is used as the anode, the cathode may be formed of a transparent electrode having an appropriate work function, such as a glass coated with indium zinc oxide, where the indium zinc oxide has a low work function. The anode may have a metallic clear coating formed thereon, which gives an appropriate work function. These devices are sometimes referred to as top launchers or back launchers. 25 200301668 A metal electrode may be composed of several metal layers. For example, a metal with a higher work function such as aluminum is deposited on a substrate, and a metal with a lower work function such as calcium is deposited on the metal with a higher work function. In another example, a further layer of conductive polymer is on top of a stable metal such as aluminum. Preferably, the electrode also acts as a mirror behind each pixel, and is deposited on or sunk into the planarized surface of the substrate. Alternatively, however, there may be a light absorbing black layer adjacent to the substrate. In still another embodiment, a selected region of the bottom conductive polymer layer is made non-conductive by being exposed to a suitable aqueous solution to form an array of conductive pixel pads (which serve as the bottom contacts of the pixel electrodes). of. As described in WO00 / 60669, the brightness of the light emitted by each pixel is preferably controllable by analogy, that is, by adjusting the voltage or current applied by the matrix circuit or by inputting one into each pixel circuit. A digital signal that is converted into an analog signal. The substrate preferably also provides data drivers, data converters, and scan drivers to process information, address pixel arrays, and generate images. When using electroluminescent materials that emit light of different colors depending on the applied voltage, the color of each pixel can be controlled by adjusting the matrix conversion circuit. In a specific aspect, by a switch including a voltage control element and a variable resistance element (which can be conveniently formed by a metal-oxide-semiconductor field effect transistor (MOSFET)) or an active matrix transistor To control each pixel. In the electroluminescent device, the device may include a cathode, an electroluminescent layer, an electron transporting layer, and a cathode in order on the hole transporting layer, and may have other layers as necessary. When the electroluminescent material is deposited by fused deposition 26 200301668, the layer to which it is deposited should be able to withstand the fused deposition temperature and, if necessary, may have a buffer layer. Hole-transport and electron-transport layers can be deposited by fused deposition, provided they have suitable characteristics and can tolerate the temperatures involved, or they can be deposited by vacuum deposition or other suitable means. When deposited by fused deposition, any material can be mixed with a polymer such as a thermoplastic polymer. Any conventional method of fused deposition that can be used. In one method of fused deposition, the material to be deposited is melted, and then a layer of molten material is deposited on a substrate. This is usually carried out by the relative movement between the substrate and the groove. The hot melt liquid system is extruded through the groove, so that a layer thickness corresponding to the width of the groove is deposited on the substrate. This method is used to deposit a glue layer and a surface treatment layer. One particular application is liquid phase epitaxial fused deposition, which is used to form certain types of semiconductor devices. This method is described in U.S. Patent No. 4,235,191. Another method is inkjet or bubble printing using a molten material. [Schematic description] Figures 1 and 2 show examples of basis Lp. Figure 3 shows an example of Hong Fei. Figure 4 shows an example of an Lp chelate. ‘Figure 5 shows examples of rash and hydrazone derivatives. Figures 6 to 8 show compounds of the formula shown. Figure 9 shows the formula for polyamines. Figures 11 to 16 show the structural formulas of hole transport materials. 27

Claims (1)

200301668 Patent application scope 1. An electroluminescence device, which sequentially includes a rhenium anode, (ii) an electroluminescent compound layer of the general formula (La) nM, wherein M is one or more rare earth elements, lanthanides or Actinides, or non-rare earth metals or a mixture of rare earth elements and / or non-rare earth metals, La is one or more organic complexes, and the organic complexes may be the same or different, and η is M Valence state, and (iii) the cathode, wherein the electroluminescent compound is deposited on the previous layer by fused deposition. 2. The electroluminescent device according to item 1 of the patent application, wherein the electroluminescent material is the following general formula (Loc) n > M- Lp where La and Lp are organic ligands, M is a rare earth element, a transition Metal, lanthanide or actinide, and the valence state of η-based metal M, the ligands La may be the same or different, and there may be many identical or different ligands Lp 'where La and Lp are as shown here As defined. 3. The electroluminescent device according to item 1 of the scope of patent application, wherein in the general formula (LoOnM !! ^ electroluminescent material, it is the same as the above M, M2 is a non-rare earth metal, La is as above, and η is% The combined valence state with M2, and η, and M2 are as defined herein. 4. As for the electroluminescence device of the scope of application for patent 1 or 2, the complex compound also includes one or more neutral ligands Lp, and the complex has the general formula (LoOnMiMJLp). 5. The electroluminescent device according to item 1 of the patent application, wherein the electroluminescent 200301668 optical material is a two-core, three-core and multi-core organic metal of the following formula Complex (Ln ^ Mi —M2 (Ln) y or (Lm) xMiC ^ M "Ln) y where L is a bridging ligand and is a rare earth metal, and M2 is Mm or a non-rare earth metal, Lm and Ln are The same or different organic ligands as defined above, La, X are the valence states of Mm, and y is the valence state of M2 or (Lm) xM i — M3 (Ln) y—M2 (ίρ) z or (Lm) xM ! — M3 (Ln) y (LP) z where Mi, M2 and M3 are the same or different rare earth metals, and Lm, Ln and Lp are the organic ligands La, X is the valence state of M !, and y is M: Valence state, z is the price of m3 State, Lp can be the same or different from Lm and Ln or eight, human (Lm) xM 1 M3 (Ln) y M2 (Lp) 2 or 29 200301668 wherein L is a bridged ligand, and rare earth metals and non-rare earth metals can be linked together by metal-to-metal bonding and / or via intermediate bridged atoms, ligands or molecular groups, or among them Three metals are connected by metal-to-metal bonds and / or via intermediate ligands. 6. The electroluminescent device according to any one of claims 3 to 5, wherein the metal M2 is any metal which is not a rare earth element, a transition metal, a lanthanide or an actinide. 7. The electroluminescent device according to any one of claims 3 to 6, wherein the metal M2 is selected from the group consisting of lithium, sodium, potassium, thallium, planer, beryllium, magnesium, calcium, thallium, barium, copper ( I), copper (II), silver, gold, zinc, cadmium, boron, aluminum, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (II) Lead (IV), the first, second, and third group metals of transition metals in different valence states, such as manganese, iron, ruthenium, starvation, cobalt, nickel, palladium (II), palladium (IV), uranium ( II), platinum (IV), cadmium, chromium, titanium, vanadium, zirconium, giant, molybdenum, rhodium, iridium, titanium, niobium, hafnium, yttrium. 8. The electroluminescent device according to item 1 of the patent application scope, wherein the electroluminescent material is the general formula (XXVa) herein. 9. The electroluminescent device according to any one of the preceding claims, wherein an organic hole transport layer is in contact with the luminescent material layer. 10. The electroluminescent device according to item 9 of the application, wherein the hole transporting material is a poly (vinylcarbazole), N, N, diphenyl_N, N, -bis (3-methyl Phenylbiphenyl-4,4'-diamine (TPD), polyaniline, substituted polyaniline, polythiophene, substituted polythiophene, 30 200301668 polysilane and substituted polysilane selected polymer 11. The electroluminescent device according to item 9 or 10 of the patent application scope, wherein the hole-transporting material is one of the formula (II) or (III) in the present invention, or as in 11, 12, 13, 14, 15, or 16 The thin film of the compound in the figure. 12. The electroluminescent device according to any one of claims 1 to 11, wherein an electron transporting material layer is interposed between the cathode and the electroluminescent material layer. The electroluminescence device of any one of the scope of patents 1 to 12, wherein the electron transporting material is mixed with the light-emitting metal compound to form a layer. 14. For the electroluminescence device of the scope of claims 12 or 13, wherein The electron-transporting material is a metal quinone salt. Electroluminescence device, in which the metal quinolate is aluminum quinate or lithium quinate. 16. For the electroluminescence device in the application scope of item 12 or 13, wherein the electron transport material is cyano group such as 9, 10-II A cyano compound, a polystyrene sulfonate, or a compound having the structural formula shown in Fig. 10. Lu Π. The electroluminescent device according to any one of claims 9 to 16, wherein the hole transport material and The electron transport material and the luminescent metal compound are mixed to form a layer. 18. The electroluminescent device according to any one of the preceding claims, wherein the second electrode is selected from the group consisting of aluminum, calcium, lithium, and silver / magnesium alloy. Schematic is shown on the next page.