EP2286474A2 - Procede de fabrication d'une diode electroluminescente organique - Google Patents

Procede de fabrication d'une diode electroluminescente organique

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Publication number
EP2286474A2
EP2286474A2 EP09761423A EP09761423A EP2286474A2 EP 2286474 A2 EP2286474 A2 EP 2286474A2 EP 09761423 A EP09761423 A EP 09761423A EP 09761423 A EP09761423 A EP 09761423A EP 2286474 A2 EP2286474 A2 EP 2286474A2
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EP
European Patent Office
Prior art keywords
quinolate
layer
carrier gas
lithium
host
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP09761423A
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German (de)
English (en)
Inventor
Poopathy Kathirgamanathan
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Merck Patent GmbH
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Merck Patent GmbH
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Publication date
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Publication of EP2286474A2 publication Critical patent/EP2286474A2/fr
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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/18—Light sources with substantially two-dimensional radiating surfaces characterised by the nature or concentration of the activator
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

Definitions

  • This invention relates to the manufacture of OLEDs.
  • OVPD organic vapor phase deposition
  • US-A-6337102 (Forrest, The Trustees of Princeton University, the disclosure of which is incorporated herein by reference) discloses that organic vapor phase deposition (OVPD) has made progress towards the low cost, large scale deposition of small molecular weight organic layers with numerous potential photonic device applications such as displays.
  • the OVPD process uses carrier gases to transport source materials to a substrate, where the gases condense to form a desired thin film. Because of its capability for controlled co-deposition of materials with radically different vapor pressures, OVPD is considered by the inventors to be the only method for the precise stoichiometric growth of multi-component thin films.
  • the disclosed method comprises the steps of providing a plurality of organic precursors, the organic precursors being in the vapor phase and in a stream of inert carrier gas, and reacting the plurality of organic precursors at a sub-atmospheric pressure in the presence of the substrate to form a thin film on the substrate.
  • LPOVPD low pressure organic vapor deposition
  • Disclosed carrier gases include nitrogen, helium, argon, krypton, xenon, neon and the like. Gases with a reducing character, such as hydrogen, ammonia and methane, are also inert for many organic materials.
  • Deposition pressures are stated to be about 0.001-100 Torr, e.g. about 0.1 Torr to about 10 Torr.
  • optimal pressures for the deposition of single component layers such as tris-(8-hydroxyquinoline) aluminum (AIq 3 ) or N-N'-diphenyl-N,N-bis(3-methylphenyl) 1 ,1'-biphenyl-4,4' diamine(TPD) are stated to be about 0.1-10 Torr.
  • a glass substrate has successively deposited on it a layer of hole transport material (TPD) from a source at 200 ⁇ 0.5 0 C in nitrogen at 0.65 Torr, followed by an electron transport layer of aluminium quinolate a source at 247 ⁇ 0.8 0 C in nitrogen at 0.65 Torr.
  • TPD hole transport material
  • Forrest et al. locate the substrates within a suitably large reactor vessel, and the vapors carried thereto mix and react or condense on the substrate.
  • Another embodiment of the Forrest invention is directed towards coating of large area substrates and putting several such deposition processes in serial fashion with one another.
  • Forrest et al disclosed the use of a gas curtain fed by a gas manifold (defined as "hollow tubes having a line of holes") in order to form a continuous line of depositing material perpendicular to the direction of substrate travel.
  • This method of film deposition is said to be most similar to hydride vapor phase epitaxy used in the growth of Hl-V semiconductors.
  • the organic compound is thermally evaporated and then transported through a hot-walled gas carrier tube into a deposition chamber by an inert carrier gas toward a cooled substrate where condensation occurs.
  • Flow patterns may be engineered to achieve a substrate-selective, uniform distribution of organic vapors, resulting in a very uniform coating thickness and minimized materials waste.
  • Virtually all of the organic materials used in thin film devices have sufficiently high vapor pressures to be evaporated at temperatures below 400°C and then transported in the vapor phase by a carrier gas such as argon or nitrogen. This allows for positioning of evaporation sources outside of the reactor tube, spatially separating the functions of evaporation and transport, thus leading to precise control over the deposition process.
  • an electron injection layer is a practical necessity and that the materials hitherto accepted as being suitable are inorganic compounds e.g. lithium fluoride.
  • inorganic compounds e.g. lithium fluoride.
  • these inorganic compounds have high volatilization temperatures so that their deposition needs different apparatus from organic layer deposition which requires the substrate to be moved between deposition chambers, but also the deposition of e.g. lithium fluoride requires relatively high vacuum conditions, is slow compared to the deposition rate of the organic layers, and can be used only to treat areas of relatively restricted size. Accordingly the electron injection layer deposition step contributes disproportionately to the work, processing time and cost of the manufacturing process, and restricts the size of e.g. display products which it is practical to produce.
  • organometallic complexes can be used as electron injection layers or components thereof and can be deposited under generally similar conditions to other organic layers and in a single apparatus.
  • the invention provides a method of making an OLED by LPOVPD, which includes the step of forming an electron injection layer from an organic complex of a low work function metal, the electron injection layer being deposited in a stream of inert carrier gas in the same reactor as other organic layers of the OLED.
  • organic layer as used herein includes layers of small molecule organic compounds e.g. ⁇ -NPB and compounds which comprise a metal or metalloid (e.g. boron) with an organic ligand, the said layers being vacuum depositable at temperatures of not more than about 400 0 C. It also includes a layer of polymeric material formed e.g. by in situ polymerization of one or more monomers on a substrate.
  • LPOVPD refers to deposition of organic layers at sub- atmospheric temperature and at elevated temperatures up to about 400 0 C, e.g. at pressures less than 760 Torr, in some embodiments from about
  • LOPVD is in embodiments used for deposition of a single electron injection material, a mixture of electron materials and electron injection material(s) and one or more dopants.
  • low work function in relation to a metal component of a complex in an electron injection layer means a metal having a work function less than magnesium, as discussed below.
  • the invention is applicable to known methods and apparatus for depositing OLED layers by LPOVPD, e.g. apparatus available or under development by Aixtron AG.
  • the invention is applicable to deposition of electron injection layers in which e.g. a slit-like orifice forms a curtain of material to be deposited as disclosed in US-A-6337102 (Forrest). It is also applicable to apparatus in which layers, including an electron injection layer, are deposited curtain-wise or area-wise by shower head deposition.
  • US 6962624 (Jurgensen et a/., the disclosure of which is incorporated herein by reference) discloses an OVPD method for depositing organic layers e.g.
  • a heated reactor contains a non-gaseous starting material in a vessel which is sublimed and transported as a vapor from the vessel to a substrate by means of a carrier gas at e.g. about 1.5 torr (2 mbar), and is then deposited on the substrate.
  • a carrier gas at e.g. about 1.5 torr (2 mbar)
  • Irregularities in the rate of sublimation are reduced or avoided by passing a stream of preheated carrier gas from the bottom upwards through a bed of the starting material which is maintained substantially isothermal with respect to the carrier gas on account of heated vessel walls. Rate of growth of the deposited layer is more reproducible, and layers can be deposited on relatively large surface area substrates.
  • the invention is applicable to deposition apparatus in which material in which material to be deposited is directed onto the substrate by means of a deposition head having a linear opening or one or more openings formed in a line or in an area as in a "shower head” type deposition head having a plurality of openings, see e.g. US 5595606, the disclosure of which is incorporated herein by reference.
  • a deposition head having a linear opening or one or more openings formed in a line or in an area as in a "shower head” type deposition head having a plurality of openings
  • a slit-like deposition head or a multi-opening deposition head in which the individual openings are spaced apart along a line or spaced apart over an area not only overcomes the problems of having to use separate deposition apparatus for the electron injection layer and the slowness of formation of the electron injection layer but also avoids limitations on the size of the substrates on which the electron layer can be deposited.
  • a typical device comprises a transparent substrate on which are successively formed an anode layer, a hole injector (buffer) layer, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and an anode layer which may in turn be laminated to a second transparent substrate.
  • Top emitting OLEDs are also possible in which an aluminum or other metallic substrate carries an ITO layer, a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and an ITO or other transparent cathode, light being emitted through the cathode.
  • a further possibility is an inverted OLED in which a cathode of aluminum or aluminum alloyed with a low work function metal carries successively an electron injection layer, an electron transport layer, an electroluminescent layer, a hole transport layer, a hole injection layer and an ITO or other transparent conductive anode, emission of light being through the anode.
  • a hole blocking layer may be inserted e.g. between the electroluminescent layer and the electron transport layer.
  • the electron injection layer is a metal quinolate or substituted quinolate.
  • An electroluminescent device that may be produced by the method of thee invention is formed of:
  • the layer of the metal quinolate is less than 1nm in thickness, typically 1- 0.1 nm in thickness, e.g. about 0.3 nm in thickness. It preferably has a work function of less than 3.5eV, more preferably less than 3eV and most preferably less than 2eV.
  • the work function of a material is the minimum amount of energy required to remove an electron from the surface of a metal.
  • the first electrode is preferably a transparent substrate such as a conductive glass or plastic material which acts as the anode.
  • Preferred substrates are glass coated with tin oxide, indium tin oxide, indium zinc oxide or antimony tin oxide coated glass.
  • any glass which is conductive or has a conductive layer such as a metal or conductive polymer can be used.
  • a single layer may be provided between the anode and the electroluminescent material, but in many embodiments there are at least two layers one of which is a hole injection layer (buffer layer) and the other of which is a hole transport layer, the two layer structure offering in some embodiments improved stability and device life (see US-A-4720432 (VanSlyke et al., Kodak).
  • the hole injection layer may serve to improve the film formation properties of subsequent organic layers and to facilitate the injection of holes into the hole transport layer.
  • Suitable materials for the hole injection layer which may be of thickness e.g. 0.1-200 nm depending on material and cell type e.g.
  • hole-injecting porphyrinic compounds see US-A-4356429 (Tang, Eastman Kodak) e.g. zinc phthalocyanine copper phthalocyanine and ZnTpTP, whose formula is set out below:
  • hole injection layer is ZnTpTP and the electron transport layer is zirconium or hafnium quinolate.
  • Hole transport layers which may be used are preferably of thickness 20 to 200 nm.
  • Suitable hole transport materials comprises sublimable small molecules.
  • aromatic tertiary amines provide a class of preferred hole- transport materials, e.g. aromatic tertiary amines including at least two aromatic tertiary amine moieties (e.g. those based on biphenyl diamine or of a "starburst" configuration).
  • aromatic amines may be used of the general formulae (a)-(g) below
  • any of the formulae in (a) to (g) can be the same or different and are selected from hydrogen; substituted and unsubstituted aliphatic groups; substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures; halogens; and thiophenyl groups; and wherein in formula (a) the methyl groups may be replaced by C 1 -C 4 alkyl or monocyclic or polyclic aryl or heteroraryl which may be further substituted e.g. with alkyl, aryl or arylamino.
  • R 1 -R 4 when appearing in either of the above formulae can be the same or different and are selected from hydrogen; substituted and unsubstituted aliphatic groups; substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures; halogens; and thiophenyl groups.
  • aromatic tertiary amines including at least two aromatic tertiary amine moieties (e.g. those based on biphenyl diamine or of a "starburst" configuration), of which the following are representative:
  • a further possible material is 4,4 l ,4"-tris(carbazolyl)-triphenylamine (TCTA) which is a hole transport material with a wider band gap than ⁇ -NBP and which can in some embodiments assist in confining excitation to the emissive layer.
  • TCTA 4,4 l ,4"-tris(carbazolyl)-triphenylamine
  • spiro-linked molecules which are aromatic amines e.g. spiro-TAD (2,2 l ,7,7'-tetrakis-(diphenylamino)-spiro-9,9'-bifluorene).
  • WO 2006/061594 Kerathirgamanathan er a/
  • Typical compounds include:
  • any sublimable electroluminescent material may be used, including molecular solids which may be fluorescent dyes e.g. perylene dyes, metal complexes e.g. Alq 3 , Ir(III)L 3 , rare earth chelates e.g. Tb(III) complexes, dendrimers and oligomers e.g. sexithiophene.
  • the electroluminescent layer may comprise as luminescent material a metal quinolate, iridium, ruthenium, osmium, rhodium, iridium, palladium or platinum complex, a boron complex or a rare earth complex.
  • It may also include a so-called "blue" aluminium quinolate of the type AIq 2 L where q represents a quinolate and L represents a mono-anionic aryloxy ligand e.g. bis(2-methyl-8-quinolinolato)(4-phenyl-phenolato)AI(lll).
  • q represents a quinolate
  • L represents a mono-anionic aryloxy ligand e.g. bis(2-methyl-8-quinolinolato)(4-phenyl-phenolato)AI(lll).
  • One preferred class of electroluminescent materials comprises host materials doped with one or more dyes which may be fluorescent, phosphorescent or ion-phosphorescent (rare earth).
  • host material doped with one or more dyes which may be fluorescent, phosphorescent or ion-phosphorescent (rare earth).
  • novel compounds described herein as host material also forms part of the invention and they may provide red, green and blue emitters when doped with appropriate dopants, in embodiments one or more than one dopant.
  • electrophosphorescent device includes electrophosphorescent devices.
  • a compound as described above may be doped with dyes such as fluorescent laser dyes, luminescent laser dyes to modify the color spectrum of the emitted light and/ or to and also enhance the photoluminescent and electroluminescent efficiencies.
  • dyes such as fluorescent laser dyes, luminescent laser dyes to modify the color spectrum of the emitted light and/ or to and also enhance the photoluminescent and electroluminescent efficiencies.
  • the compound is doped with a minor amount of a fluorescent or phosphorescent material as a dopant, preferably in an amount of 0.01 to 25% by weight of the doped mixture.
  • the dopant is more preferably present in the compound in an amount of 0.01 % to 10 % by weight e.g. in an amount of 0.01% to 2%.
  • the presence of the fluorescent material permits a choice from amongst a wide latitude of wavelengths of light emission.
  • a minor amount of a fluorescent material capable of emitting light in response to hole-electron recombination the hue of the light emitted from the luminescent zone, can be modified.
  • each material should emit light upon injection of holes and electrons in the luminescent zone.
  • the perceived hue of light emission would be the visual integration of both emissions.
  • the fluorescent material since imposing such a balance of host material and fluorescent materials is limiting, it is preferred to choose the fluorescent material so that it provides the favoured sites for light emission.
  • peak intensity wavelength emissions typical of the host material can be entirely eliminated in favour of a new peak intensity wavelength emission attributable to the fluorescent material.
  • typical amounts are 0.01 to 5 wt%, for example 2-3 wt%. In the case of phosphorescent dyes typical amounts are 0.1 to 15 wt%. In the case of ion phosphorescent materials typical amounts are 0.01-25 wt% or up to
  • Choosing fluorescent materials capable of providing favored sites for light emission necessarily involves relating the properties of the fluorescent material to those of the host material.
  • the host can be viewed as a collector for injected holes and electrons with the fluorescent material providing the molecular sites for light emission.
  • One important relationship for choosing a fluorescent material capable of modifying the hue of light emission when present in the host is a comparison of the reduction potentials of the two materials.
  • the fluorescent materials demonstrated to shift the wavelength of light emission have exhibited a less negative reduction potential than that of the host. Reduction potentials, measured in electron volts, have been widely reported in the literature along with varied techniques for their measurement.
  • a second important relationship for choosing a fluorescent material capable of modifying the hue of light emission when present in the host is a comparison of the band-gap potentials of the two materials.
  • the fluorescent materials demonstrated to shift the wavelength of light emission have exhibited a lower band gap potential than that of the host.
  • the band gap potential of a molecule is taken as the potential difference in electron volts (eV) separating its ground state and first singlet state.
  • eV electron volts
  • spectral coupling it is meant that an overlap exists between the wavelengths of emission characteristic of the host alone and the wavelengths of light absorption of the fluorescent material in the absence of the host.
  • Optimal spectral coupling occurs when the emission wavelength of the host is within +25nm of the maximum absorption of the fluorescent material alone.
  • spectral coupling can occur with peak emission and absorption wavelengths differing by up to 100 nm or more, depending on the width of the peaks and their hypsochromic and bathochromic slopes.
  • a bathochromic as compared to a hypsochromic displacement of the fluorescent material produces more efficient results.
  • Useful fluorescent materials are those capable of being blended with the host and fabricated into thin films satisfying the thickness ranges described above forming the luminescent zones of the EL devices of this invention. While crystalline organometallic complexes do not lend themselves to thin film formation, the limited amounts of fluorescent materials present in the host permit the use of fluorescent materials which are alone incapable of thin film formation.
  • Preferred fluorescent materials are those which form a common phase with the host.
  • Fluorescent dyes constitute a preferred class of fluorescent materials, since dyes lend themselves to molecular level distribution in the host.
  • preferred fluorescent dyes are those which can be vacuum vapour deposited along with the host materials.
  • host materials comprises metal complexes e.g. metal quinolates such as lithium quinolate, aluminium quinolate, titanium quinolate, zirconium quinolate or hafnium quinolate which may be doped with fluorescent materials or dyes as disclosed in patent application WO 2004/058913.
  • metal complexes e.g. metal quinolates such as lithium quinolate, aluminium quinolate, titanium quinolate, zirconium quinolate or hafnium quinolate which may be doped with fluorescent materials or dyes as disclosed in patent application WO 2004/058913.
  • Another class of host materials comprises sublimable polyaromatic small molecules.
  • Fluorescent laser dyes are recognized to be particularly useful fluorescent materials for use in the organic EL devices of this invention.
  • Dopants which can be used include diphenylacridine, coumarins, perylene and their derivatives. Useful fluorescent dopants are disclosed in US 4769292.
  • One class of preferred dopants is coumarins e.g. those of the formula:
  • Ri-R 5 represent hydrogen or alkyl e.g. methyl or ethyl.
  • Compounds of this type include 7-hydroxy-2H-chromen-2-one, 7-hydroxy- 2-oxo-2H-chromene-3-carbonitrile, 7-hydroxy-4-methyl-2-oxo-2H- chromene-3-carbonitrile, 7-(ethylamino)-4,6-dimethyl-2H-chromen-2-one, 7-amino-4-methyl-2H-chromen-2-one, 7-(diethylamino)-4-methyl-2H- chromen-2-one, 7-hydroxy-4-methyl-2H-chromen-2-one, 7- (dimethylamino)-4-(trifluoromethyl)-2H-chromen-2-one, and 7- (dimethylamino)-2,3-dihydrocyclopenta[c]chromen-4(1 H)-one.
  • dyes may be used:
  • dopants that may be used include 3-(benzo[d]thiazol-2-yl)-8- (diethylamino)-2H-benzo[g]chromen-2-one, 3-(1 H-benzo[d]imidazol-2-yl)-8- (diethylamino)-2H-benzo[g]chromen-2-one, 9-(pentan-3-yl)-1 H- benzo[a]phenoxazin-5(4H,7aH,12aH)-one and 10-(2-benzothiazolyl)- 1 ,1 ,7,7-tetramethyl-2,3,6,7-tetrahydro-1 H,5H,11 H-[l]benzo-pyrano[6,7,8- ij]quinolizin-11-one (C-545-T) of formula below and analogs such as C- 545TB and C545MT:
  • dopants that can be used include pyrene and perylene compounds e.g. compounds of one of the formulae below.
  • R 1 to R4 which may be the same or different are selected from hydrogen, hydrocarbyl groups, substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorocarbons e.g. trifluoromethyl, halogen e.g. fluorine or thiophenyl or can be substituted or unsubstituted fused aromatic, heterocyclic and polycyclic ring structures.
  • R 1 to R4 which may be the same or different are selected from hydrogen, hydrocarbyl groups, substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorocarbons e.g. trifluoromethyl, halogen e.g. fluorine or thiophenyl or can be substituted or unsubstituted fused aromatic, heterocyclic and polycyclic ring structures.
  • R 1 to R4 which may be the same or different are selected from hydrogen, hydrocarbyl groups, substituted and unsubstituted aromatic, heterocyclic and
  • R is hydrocarbyl, aryl, heterocyclic, carboxy, aryloxy, hydroxy, alkoxy, amino or substituted amino e.g. styryl.
  • Compounds of this type include polycyclic aromatic hydrocarbons containing at least four fused aromatic rings and optionally one or more alkyl substituents e.g. perylene, tefra/os-(f-butyl)-perylene and 7-(9-anthryl)-dibenzo[a,o]perylene (pAAA) of structure:
  • Bis-perylene and dianthryl dopants may also be employed.
  • Other dopants include perylene and perylene derivatives.
  • the dopant may be a complex of a general formula selected from:
  • Ri 1 R 2 , and R 3 which may be the same or different are selected from the group consisting of hydrogen, alkyl, trifluoromethyl or fluoro;
  • R 4 , R 5 and R 6 which can be the same or different are seleced from the group consisting of hydrogen, alkyl or phenyl which may be unsubstituted or may have one or more alkyl, alkoxy, trifluormethyl or fluoro substituents;
  • M is ruthenium, rhodium, palladium, osmium, indium or platinum;
  • n 1 or 2.
  • the dopant may also be a complex of a general formula selected from:
  • M is ruthenium, rhodium, palladium, osmium, iridium or platinum;
  • n 1 or 2;
  • Ri, R 2 , R3, R4 and R5 which may be the same or different are selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyloxy, halogen, nitrile, amino, dialkylamino, arylamino, diarylamino and thiophenyl;
  • p, s and t are independently are 0, 1 , 2 or 3, subject to the proviso that where any of p, s and t is 2 or 3 only one of them can be other than saturated hydrocarbyl or halogen;
  • q and r are independently are 0, 1 or 2, subject to the proviso that when q or r is 2, only one of them can be other than saturated hydrocarbyl or halogen.
  • R 1 represents alkyl e.g. methyl, ethyl or f-butyl
  • R 2 represents hydrogen or alkyl e.g. methyl, ethyl or f-butyl
  • R 3 and R 4 represent hydrogen, alkyl e.g. methyl or ethyl or C 6 ring structures fused to one another and to the phenyl ring at the 3- and 5-positions and optionally further substituted with one or two alkyl e.g. methyl groups.
  • Examples of such compounds include
  • phosphorescent materials that can be used as red dopants (see WO 2005/080526, the disclosure of which is incorporated herein by reference) include the following:
  • the compounds perylene and 9-(10-(N-(naphthalen-8-yl)-N- phenylamino)anthracen-9-yl)-N-(naphthalen-8-yl)-N-phenylanthracen-10- amine can serve as a blue dopants.
  • Yet further possible dopants comprise aromatic tertiary amines including at least two aromatic tertiary amine moieties (e.g. those based on biphenyl diamine or of a "starburst" configuration) as described above as hole transport materials.
  • dyes such as the fluorescent 4-dicyanomethylene-4H- pyrans and 4-dicyanomethylene-4H-thiopyrans, e.g. the fluorescent dicyanomethylenepyran and thiopyran dyes.
  • Useful fluorescent dyes can also be selected from among known polymethine dyes, which include the cyanines, complex cyanines and merocyanines (i.e. tri-, tetra- and poly- nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines.
  • the cyanine dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as azolium or azinium nuclei, for example, those derived from pyridinium, quinolinium, isoquinolinium, oxazolium, thiazolium, selenazolium, indazolium, pyrazolium, pyrrolium, indolium, 3H-indolium, imidazolium, oxadiazolium, thiadioxazolium, benzoxazolium, benzothiazolium, benzoselenazolium, benzotellurazolium, benzimidazolium, 3H- or 1 H-benzoindolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, naphthotellurazolium, carbazolium, pyrrolopyridinium, phenanthrothiazolium, and
  • phosphorescent dopants include the following compounds:
  • Rare earth chelates are yet further possible dopants, e.g. of the formula (La) n M or (La)n>M ⁇ — Lp where La and Lp are organic ligands, M is a rare earth metal and n is the valence of the metal M. Examples of such compounds are disclosed in patent application WO98/58037 which describes a range of lanthanide complexes and also those disclosed in
  • Di-(2-naphthyl)perylene (DNP) serves as a LEL additive said to extend the operating lifetime of OLEDs by over two orders of magnitude.
  • Deaton et al disclose an ⁇ -NBP host with a "blue" aluminium quinolate as co-host and an iridium dopant. Very good yields were obtained with low concentrations of dopant for phosphorescent devices and it was found that the mixed host device provided increased power efficiency. It was hypothesized that the explanation was a reduction in the energy barrier to inject holes into the emissive layer by mixing the hole- transporting NPB having an ionization potential of 5.40 eV into the dominantly electron-transporting "blue" aluminium quinolate, having a higher ionization potential of 6.02 eV.
  • N.N'-di-i-naphthyl-N.N'-diphenyM .I'-biphenyl-i .i 1 - biphenyl-4,4'-diamine (NPB), and tris (8-hydroxyquinoline) aluminium (AIq 3 ) may be used as the hole transport material and the electron transport material, respectively and N.N'-dimethylquinacridone (DMQ), 5,6,11 ,12- tetraphenylnapthacene (Rubrene), and Nile-red dye (available from Aldrich Chemicals of Milwaukee, Wis.) may be used as dopants.
  • DMQ dimethylquinacridone
  • Rubrene 5,6,11 ,12- tetraphenylnapthacene
  • Nile-red dye available from Aldrich Chemicals of Milwaukee, Wis.
  • US 2002/0074935 also discloses devices with an emissive layer containing PtOEP or bis(benzothienyl-pyridinato-N ⁇ C)lridium(IH) (acetylacetonate) as a dopant and equal proportions of NPB and AIq as host materials. It is explained that the mixed host electroluminescent mixed layer serves to substantially reduce the accumulation of charge that is normally present at the heterojunction interface of heterostructure devices, thereby reducing organic material decomposition and enhancing device stability and efficiency.
  • a light emitting layer of the OLED device contains a wide band gap inert host matrix in combination with a charge carrying material and a phosphorescent emitter.
  • the charge carrying compound can transport holes or electrons, and it is selected so that charge carrying material and phosphorescent emitter transport charges of opposite polarity.
  • M. Furugori et al. in US 2003/0141809 disclose phosphorescent devices where a host material is mixed with another hole- or electron transporting material in the light emitting layer. The document discloses that devices utilizing plural host compounds show higher current and higher efficiencies at a given voltage.
  • T. lgarashi et al. in WO 2004/062324 disclose phosphorescent devices with the light emitting layer containing at least one electron transporting compound, at least one hole transporting compound and a phosphorescent dopant.
  • WO 2006/076092 discloses OLED device comprising a cathode, an anode, and located therebetween a light emitting layer (LEL) comprising at least one hole transporting co-host e.g.
  • LEL light emitting layer
  • an aromatic tertiary amine such as 4,4'-bis[N-(l-naphthyl)-N-phenylamino]biphenyl (NPB) 1 4,4'- bis[N-(l -naphthyl)-N-(2-naphthyl)amino]biphenyl (TNB), 4,4'-bis[N-(3- methylphenyl)-N-phenylamino-]biphenyl (TPD), 4,4'-bis-diphenylamino- terphenyl or 2,6,2',6 l -tetramethyl-N,N,N l ,N I -tetraphenyl-benzidine.and at least one electron transporting co-host e.g.
  • a substituted 1 ,2,4-triazole such as 3- phenyl-4-(l-naphtyl)-5-phenyl-l,2,4-triazole or a substituted 1 ,3,5-triazine such as 2,4,6-tris(diphenylamino)-1 ,3,5-triazine, 2,4,6- tricarbazolo-1 ,3 ,5-triazine, 2,4,6-tris(N-phenyl-2-naphthylamino)-1 ,3,5- triazine, 2,4,6-tris(N-phenyl-1-naphthylamino)-1 ,3,5-triazine and 4,4 1 ,6,6'- tetraphenyl-2,2'-bi-1 ,3,5-triazine together with a phosphorescent emitter, wherein the triplet energy of each of the co-host materials is greater than the triplet energy of the phosphorescent emitter
  • US-A-7045952 discloses an organic light emissive device comprising an emissive region disposed between and electrically connected to an anode and a cathode, wherein the emissive region comprises (i) a first single-host emissive layer, comprising a first host material, and (ii) a mixed-host emissive layer in direct contact with the first single-host emissive layer, wherein the mixed-host emissive layer comprises the first host material, and a second host material, and wherein the first single-host emissive layer and the mixed-host emissive layer each further comprise a phosphorescent emissive material.
  • ETMs electron transport materials
  • metal chelates including aluminium quinolate, which they explain remains the most widely studied metal chelate owing to its superior properties such as high EA ( ⁇ -3.0 eV; measured by the present applicants as - 2.9 eV) and IP ( ⁇ -5.95 eV; measured by the present applicants as about - 5.7 eV), good thermal stability (Tg -172 °C) and ready deposition of pinhole-free thin films by vacuum evaporation.
  • EA ⁇ -3.0 eV
  • IP ⁇ -5.95 eV
  • Tg -172 °C good thermal stability
  • ready deposition of pinhole-free thin films by vacuum evaporation Aluminum quinolate remains a preferred material and a layer of aluminum quinolate may be incorporated as electron transfer layer if desired.
  • Further preferred electron transport materials consist of or comprise zirconium, hafnium or lithium quinolate.
  • Zirconium quinolate has a particularly advantageous combination of properties for use as an electron transport material and which identify it as being a significant improvement on aluminium quinolate for use as an electron transport material. It has high electron mobility. Its melting point (388 0 C) is lower than that of aluminium quinolate (414 0 C). U can be purified by sublimation and unlike aluminium quinolate it resublimes without residue, so that it is even easier to use than aluminium quinolate. Its lowest unoccupied molecular orbital (LUMO) is at - 2.9 eV and its highest occupied molecular orbital (HOMO) is at - 5.6 eV, similar to the values of aluminium quinolate.
  • LUMO lowest unoccupied molecular orbital
  • HOMO highest occupied molecular orbital
  • Embodiments of cells in which the electron transport material is zirconium quinolate can exhibit reduced turn-on voltage and up to four times the lifetime of similar cells in which the electron transport material is zirconium quinolate.
  • aluminium quinolate when aluminium quinolate is used as host in the electroluminescent layer of an OLED, and can therefore be employed by many OLED manufacturers with only small changes to their technology and equipment. It also forms a good electrical and mechanical interface with inorganic electron injection layers e.g. a LiF layer where there is a low likelihood of failure by delamination.
  • inorganic electron injection layers e.g. a LiF layer where there is a low likelihood of failure by delamination.
  • zirconium quinolate can be used both as host in the electroluminescent layer and as electron transfer layer. The properties of hafnium quinolate are generally similar to those of zirconium quinolate.
  • Zirconium or hafnium quinolate may be the totality, or substantially the totality of the electron transport layer. It may be a mixture of co-deposited materials which is predominantly zirconium quinolate.
  • the zirconium or hafnium may be doped as described in GB 06 14847.2 filed 26 July 2006, the contents of which are incorporated herein by reference. Suitable dopants include fluorescent or phosphorescent dyes or ion fluorescent materials e.g. as described above in relation to the electroluminescent layer, e.g. in amounts of 0.01-25 wt% based on the weight of the doped mixture.
  • Other dopants include metals which can provide high brightness at low voltage.
  • the zirconium or hafnium quinolate may be used in admixture with another electron transport material. Such materials may include complexes of metals in the trivalent or pentavalent state which should further increase electron mobility and hence conductivity.
  • the zirconium and hafnium quinolate may be mixed with a quinolate of a metal of group 1 , 2, 3, 13 or 14 of the periodic table, e.g. lithium quinolate or zinc quinolate.
  • the zirconium or hafnium quinolate comprises at least 30 wt% of the electron transport layer, more preferably at least 50 wt%.
  • n is an integer from 1 to 4.
  • [Ar] is a polycyclic aromatic or heteroaromatic scaffold e.g a phenanthroline scaffold optionally substuted with one or more alkyl or alkoxy groups;
  • Ri is a 5-membered heteroaryl group optionally substituted with methyl, methoxy, aryl or heteroaryl, or is phenyl or naphthyl optionally substituted with methyl, methoxy, trifluoromethyl or cyano or is biphenyl or is substituted biphenyl.
  • Representative compounds include 2,9-bis(4,4'-trifluoromethyl styrenyl)phenenthroline, 2,9-bis((E)-2-(5-(thiophen-2-yl)thiophen-2-yl)vinyl)- 1 ,10-phenanthroline, 2,9-bis(4,4'-cyanostyrenyl) phenanthroline and 2,9- bis(2,2'-vinyl-5,5'-phenyl thiophenyl) phenanthroline.
  • n 0 or 1 ;
  • Ar represents aryl or heteroaryl having 1-5 aromatic rings which may be chain or fused or a combination of chain and fused, which may be substituted with alkoxy, fluoro, fluoroalkyl or cyano and which in the case of a 5-memnered ring nitrogen heteroatom may be N-substituted with aryl or substituted aryl optionally further substituted with alkoxy, fluoro, fluoroalkyl or cyano;
  • R 1 and R 2 independently represent aryl or nitrogen, oxygen or sulphur- containing heteroaryl having two to four fused aromatic rings one of which may be 5-membered and optionally substituted by aryl or heteroaryl having 1-5 chain or fused aromatic rings which may be further substituted with alkoxy, fluoro, fluoroalkyl or cyano;
  • R 3 and R 4 independently represent hydrogen, methyl, ethyl or benzyl.
  • Representative compounds include 2,2'-bis (vinylquinolinyl)-1 ,4- benzene; 6,6-bis(phenyl-2,2-vinylquinolinyl) benzene; 6,6-Bis(biphenyl-2,2- vinylquinolinyl) benzene; 6,6-bis(2,4-fluorophenyl-2,2- vinylquinolinyl)benzene; 6,6-bis(napthyl-2,2-vinylquinolinyl) benzene; 6,6'- bis(1 , 1 '-pyrenyl-2,2'-vinylquinolinyl) benzene; 1 ,4-[Bis(2,2-quinoxalin-2- yl)vinyl)] benzene; and 4-[bis(6,6'-(2-thienyl)-2,2'quinolin-2-yl)vinyl)] benzene.
  • the electron injection layer is a distinct layer of different composition from that of the electron transport layer.
  • Embodiments of a layer of small molecule electron injection material are about 0.3-2 nm in thickness, in some particular embodiments about 0.3 nm in thickness and in other embodiments about 0.5-1 nm in thickness and preferably has a work function of less than magnesium 3.7 eV, this being regarded for present purposes as a low work function.
  • the electron injection material may be doped with a low work function metal e.g. lithium, potassium or caesium. In the case of a lithium-based small molecule electron injection material, doping may be with metallic lithium.
  • the electron transport layer is of a quinolate e.g.
  • the electron injection layer is of a different quinolate.
  • the metal quinolate acts to lower the work function of the cathode and enables the electroluminescent device to operate at a lower voltage and improves the lifetime and performance of the device.
  • Suitable metal quinolates include the alkali metal quinolates and the alkaline earth quinolates and substituted derivatives thereof e.g. mono- di- and tri-substituted derivatives and rare earth quinolates.
  • Preferred metal quinolates have the formula
  • M is a metal
  • n is the valence state of M when complexed with quinolate
  • R 1 and R 2 which may be the same or different and may be on the same or different rings are selected from Ci-C 4 alkyl (e.g. methyl, ethyl and tert. butyl) and substituted or unsubstituted monocyclic or polycyclic aryl or heteroaryl.
  • lithium quinolate and substituted lithium quinoate are particularly preferred.
  • Such quinolates may be made by reacting a lithium alkyl or alkoxide with 8-hydroxyquinoline or a substituted 8-hydroxyquinoline in a solvent comprising acetonitrile (see US-A-2006/0003089 Kathirgamanathan, the disclosure of which is incorporated herein by reference). It has been found that the use of acetonitrile as solvent gives a product in surprisingly high yield, that is easy to purify by sublimation and which has a surprisingly good combination of properties compared to when the synthesis reaction is carried out in other solvents. It is believed that lithium quinolates and substituted quinolates form oligomers e.g.
  • Ri is monocyclic or bicyclic aryl, aralkyl or heteroaryl group which may be substituted with one or more CrC 4 alkyl or alkoxy; R 2 and R 3 together form monocyclic aryl or heteroaryl group which may be substituted with Ci-C 4 alkyl or alkoxy;
  • R 4 is hydrogen, Ci-C 4 alkyl or aryl
  • Ar is monocyclic aryl or heteroaryl which may be substituted with one or more d-C 4 -alkyl or alkoxy groups, or an oligomer thereof.
  • a sub-genus of the above compounds is of formula:
  • Ri is monocyclic or bicyclic ring aryl, aralkyl or heteroaryl group which may be substituted with one or more CrC 4 alkyl or alkoxy substituents;
  • R 2 and R 3 together form a monocyclic ring aryl or heteroaryl group which may be substituted with one or more CrC 4 alkyl or alkoxy substituents.
  • Ri is preferably phenyl or substituted phenyl.
  • R 2 and R 3 together may form the same groups as Ri and are preferably also phenyl or substituted phenyl. Where substituents are present they may be methyl, ethyl, propyl or butyl, including t-butyl, or may be methoxy, ethoxy, propoxy or butoxy including t-butoxy substituted.
  • Particular compounds include:
  • Embodiments of the lithium compounds whose formulae are set out above are believed from MS measurements to be capable of forming cluster compounds or oligomers in which 2-8 molecules of formula as set out above are associated e.g. in the form of trimeric, tetrameric, hexameric or octomeric oligomers. It is believed that such lithium compounds may in some embodiments associate in trimeric units having a core structure which has alternating Li and O atoms in a 6-membered ring, and that these trimeric units may further associate in pairs.
  • the electron injection layer is deposited direct onto the cathode and comprises a Schiff base of one of the above mentioned formulae which may be used alone or in combination with another electron injection material e.g. a quinolate such as lithium or zirconium quinolate.
  • the Schiff base comprises at least 30 wt% of the electron injection layer, in further embodiments at least 50 wt%.
  • the cathode on which there is the layer of the metal quinolate is preferably a low work function metal, e.g. aluminium, barium, calcium, lithium, rare earth metals, transition metals, magnesium and alloys thereof such as silver/magnesium alloys, rare earth metal alloys etc; aluminium is a preferred metal.
  • the metal electrode may consist of a plurality of metal layers; for example a higher work function metal such as aluminium deposited on the substrate and a lower work function metal such as calcium deposited on the higher work function metal.
  • the work function of some metals are listed below in Table 1
  • the layer of the metal quinolate is preferably about 0.3 nm in thickness and preferably has a work function of less than 3.5eV.
  • a device is formed using lithium quinolate as a cathode layer deposited in stream of carrier gas.
  • the device consists of ITO(100)/ ⁇ -NPB(65)/Compound-H:Compound-A (25:0.5)/Zrq 4 (20)/Liq(0.3)/AI where ⁇ -NPB is as shown above; compound A is 2,6-di-tert-butyl-9-naphthalen-2-ylmethyl-10-naphthalen-1- ylmethyl-anthracene shown below; compound H is 4,4'-bis-(2,2-diphenyl-vinyl)-biphenyl shown below;
  • Zrq 4 is zirconium quinolate
  • Liq is lithium quinolate made in acetonitrile as solvent as described above
  • Each layer formation step employs a source (or in the case of a doped material more than one source) in a reactor tube at 200-300 0 C depending on the material and subject to a stream of carrier gas (e.g. nitrogen or argon) at e.g. 50-100 seem, a pressure of 0.5 Torr and a growth time of 5-30 minutes depending upon the particular material (or in the case of a doped layer mixture of materials) being deposited.
  • carrier gas e.g. nitrogen or argon
  • Devices with green emitters are formed by the method described above consisting of an anode layer, buffer layer, hole transport layer, electroluminescent layer (doped metal complex), electron transport layer, electron injection layer and cathode layer, film thicknesses being in nm: ITO/ZnTp TP (20)/ ⁇ -NBP(50)/Alq 3 :DPQA (40:0.1)/Zrq 4 (20)/EIL(0.5)/AI wherein DPQA is diphenyl quinacridone and EIL is the electron injection layer and is lithium 2-phenyliminomethyl phenolate (Compound B)
  • the successive organic layers of the device are formed in a single chamber using LPOVPD and without removal of the substrate from the chamber between layer formation steps.
  • Compound B shows greater luminance, greater current and power efficiencies for a given luminance and greater current density for a given applied voltage.
  • compound B also gives better results than lithium quinolate when used as an electron injection layer and evaporates below 300 0 C.

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  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Indole Compounds (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une diode électroluminescente organique par LPOVPD, comprenant l'étape de formation d'une couche d'éjection d'électrons à partir d'un complexe organique d'un métal à travail d'extraction réduit, par exemple de quinolate de lithium ou un complexe de base de Schiff de lithium, la couche d'injection d'électrons étant déposée dans un flux de gaz porteur inerte dans le même agent réactif que les autres couches organiques de la diode électroluminescente organique, par exemple une couche d'injection de trous, une couche de transport de trous, une couche électroluminescente et une couche de transport d'électrons.
EP09761423A 2008-06-10 2009-06-04 Procede de fabrication d'une diode electroluminescente organique Withdrawn EP2286474A2 (fr)

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GBGB0810532.2A GB0810532D0 (en) 2008-06-10 2008-06-10 Method of making an oled
PCT/EP2009/003988 WO2009149860A2 (fr) 2008-06-10 2009-06-04 Procédé de fabrication d'une diode électroluminescente organique

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GB201306365D0 (en) * 2013-04-09 2013-05-22 Kathirgamanathan Poopathy Heterocyclic compounds and their use in electro-optical or opto-electronic devices
EP2999019B1 (fr) * 2014-09-19 2019-06-12 Novaled GmbH Diode électroluminescente organique (OLED) comprenant un empilement de couches de transport d'électrons incluant différents composés de lithium et du métal élémentaire
CN109503610B (zh) * 2018-12-21 2021-01-26 中节能万润股份有限公司 一种含有异香豆素并吡咯并香豆素结构的oled材料、制备方法及其应用
WO2020251696A1 (fr) 2019-06-10 2020-12-17 Applied Materials, Inc. Système de traitement pour former des couches
CN111423450B (zh) * 2020-04-29 2021-10-26 上海天马有机发光显示技术有限公司 化合物、显示面板以及显示装置
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