WO1994015368A1 - Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres - Google Patents

Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres Download PDF

Info

Publication number
WO1994015368A1
WO1994015368A1 PCT/NL1993/000280 NL9300280W WO9415368A1 WO 1994015368 A1 WO1994015368 A1 WO 1994015368A1 NL 9300280 W NL9300280 W NL 9300280W WO 9415368 A1 WO9415368 A1 WO 9415368A1
Authority
WO
WIPO (PCT)
Prior art keywords
blocks
thiophene
block
conjugated
led
Prior art date
Application number
PCT/NL1993/000280
Other languages
English (en)
Inventor
Georges Hadziioannou
Jan Herrema
Jurgen Wildeman
Richard Gill
Reini Wieringa
George Malliaris
Original Assignee
Rijksuniversiteit Te Groningen
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rijksuniversiteit Te Groningen filed Critical Rijksuniversiteit Te Groningen
Priority to EP94904345A priority Critical patent/EP0677208A1/fr
Priority to AU58438/94A priority patent/AU5843894A/en
Priority to JP6515043A priority patent/JPH08505167A/ja
Publication of WO1994015368A1 publication Critical patent/WO1994015368A1/fr
Priority to FI953212A priority patent/FI953212A0/fi
Priority to KR1019950702692A priority patent/KR960700531A/ko

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene

Definitions

  • Multi-block copolymer based tunable light emitting diode polymers suitable therefor and oligomers.
  • the present invention is directed to a tunable light emitting diode (LED) based upon multi-block copolymers, to novel thiophene multi-block copolymers, to thiophene oligomers suitable for preparing said polymers, to processes for preparing said oligomers and said polymers and to the use of said polymers in opto-electronics.
  • LED light emitting diode
  • LED devices are made of inorganic semiconductors e.g. GaAs, GaP etc. which cover almost the whole spectral region. It would be advantageous to have an organic material with electroluminescence in the blue region, as the organic materials are usually more easy to process.
  • LED has certain advantages, especially from the viewpoint of processability.
  • the active polymer or prepolymer can be cast from solution on a substrate which makes it possible to fabricate large-area devices.
  • Conjugated polymers can cover the whole spectral region by chemical tuning of the wavelength of the emission by choice of the polymer and control of the conjugation length of the polymer.
  • Another promising feature is the additional use of a conducting polymer as the hole-injecting electrode resulting in a fully flexible LED.
  • Suitable candidates for applications in stable optoelectronic devices are conjugated polymers.
  • Polymers can be processed relatively easily and especially large area structures are feasible.
  • the first encouraging results were reported by Burroughes et al (Nature, Z, 477 (1992)), Braun et al. (Appl. Phys. Lett. 5fl, 1982(1992)) and Grem et al. (Adv. Mater.4., 36 (1992)), using poly(p-phenylene vinylene)s and poly(p-phenylene) as the electroluminescent layer.
  • the basic element giving rise to injection luminescence is that of a p-n junction diode operated under forward bias as is illustrated in fig. l.
  • the electrons recombine with holes and give rise to bounded excitons, which radiatively decay to photons.
  • each injected electron takes part in the radiative recombination but in practice this is not the case.
  • the quantum efficiency of a device made of an inorganic semiconductor emitting in the visible region lies in the range 0.05 to 4%.
  • the wavelength of the emitted photon is determined by the energy band gap (ideal case) .
  • GaAs has a band gap of 1.43 eV.
  • the energy gap has to be larger than 2 eV.
  • For a blue LED a band gap of 3.4 eV is required.
  • Inorganic semiconductors like SiC with these large band gaps tend to have high resistivities next to fabrication problems because of high melting temperatures and structural stability.
  • LED' s can be made of organic thin films by using a multilayer structure. An emitting layer is combined with or sandwiched between a hole and an electron injecting layer.
  • a LED emitting bright blue light was achieved, thus with a luminance of 700 cd/m2 at a DC drive voltage of 10 v. Unfortunately the stability of the cell is not good yet.
  • LEDs can be made with conjugated polymers. Their main advantage over non-polymeric (in)organic semiconductors is the possibility of processing to form large area structures. The structure of such a LED is shown in figures 2 and 3.
  • a substrate, usually glass is covered with the transparent electrode, e.g. indium/tin oxide (ITO) functioning as the hole injecting cathode.
  • ITO indium/tin oxide
  • the emitting layer or a prepolymer is spincoated on top of this layer and covered with a top electrode e.g. Al or Ca, the electron injecting anode.
  • the choice of the electrodes is important. Metals with a low work function give higher efficiencies. Disadvantage of these electrodes is the oxidative instability.
  • PET polymeric substrate polyethyleneterephthalate
  • transparent processable polyaniline as the hole injecting electrode, G. Gustafsson et al., Nature, 357 477 (1992) even fabricated a fully flexible LED.
  • the electroluminescent polymer used by the above mentioned scientists is poly(p- phenylene vinylene) or a soluble alkoxy derivative thereof.
  • the electroluminescence spectra of these materials are very similar to their photoluminescence spectra.
  • the photoluminescence of PPVs is assigned to radiative combination of the singlet polaron exciton (also called neutral bipolaron) formed by intrachain excitation.
  • the electroluminescence is assigned to the same excited state and is generated by recombinations of holes and electrons injected from opposite sides of the structure.
  • the charge carriers are probably polarons.
  • the quantum yield of photoluminescence of PPV is about 4%, the non- radiative processes limit the efficiency of LEDs. This is caused by migration of the excited states to defect sites which act as non-radiative recombination centres.
  • the quantum yields for electroluminescence of the conjugated/nonconjugated polymers were strongly enhanced.
  • the non-conjugate part acting as a trap for the excitons, preventing the migration to quenching sites.
  • LED being tunable, stable and easy to manufacture at low cost.
  • said electroluminescing material comprises an electroluminescing material, electrodes and optionally carrier material and/or reflecting material, said electroluminescing material comprising at least one block copolymer consisting of at least two types of blocks, active blocks, sandwiched between non-active blocks, said active blocks being a ⁇ -conjugated block of at least 2 and at most 16 monomeric units, said ⁇ -conjugated block having a substantially uniform blocklength throughout the copolymer, and said non-active block having no ⁇ -conjugation.
  • the invention is based thereon that it has been found to be possible to tune the wavelength of the emitted light by sandwiching ⁇ -conjugated blocks having substantially uniform block length between blocks having no ⁇ -conjugation, whereby the length of the ⁇ -conjugated blocks mainly determines the wavelength of the emitted light.
  • this definition of sandwiching ⁇ -conjugated blocks between blocks having no ⁇ -conjugation is intended to include the situation that both blocks have ⁇ -conjugation, whereby there is a large difference in band gaps between the blocks, resulting therein that there is no ⁇ -conjugation between the blocks.
  • these materials have the advantage that they can be processed with deep UV- photolithography, since the polysilanes are deep-UV photoresists.
  • the stability of the above materials under environmental conditions and under the influence of optical and electric fields used, is comparable to that of PPV, the first polymer material used for electroluminescence device applications.
  • the mechanical properties of the oligomer blocks are poor, the mechanical properties of the multi-blocks made out of these oligomers generally are excellent and easy to control by adjusting the number of blocks. Further, the solubility as well as some of the electrical and optical properties are controllable by the substituents on the non-active blocks and the ⁇ -conjugated blocks.
  • the above approach gives ample flexibility to tune not only the mechanical, but also the optical and electrical properties by tuning the length of the oligomers and the number of blocks in the multi-block copolymers and the chemical nature of the side-groups.
  • Suitable ⁇ -conjugated blocks can be based upon all types of components that result in ⁇ -conjugation after polymerization to short blocks. Examples thereof are i.a. thiophenes, suitably substituted thiophenes, vinylene, arylene, vinylene-arylene, thiophene-vinylene and thiophene- arylene.
  • a preferred group of oligomers to be used for the present invention are the, optionally substituted, oligo ⁇ thiophenes.
  • Suitable oligomers are based upon the various components given in the formula sheet (Fig. 4) .
  • a block copolymer based upon a mixture two or three different blocks. In that case each of the components will have substantially the same block length.
  • the ⁇ -conjugated blocks can be prepared from the components that give said ⁇ -conjugated blocks upon polymerization.
  • Essential is the factor that the block length is substantially uniform.
  • various methods in which to obtain said substantially uniform block length are all based thereon that first an oligomer is obtained having a substantially uniform block length. This can for example be accomplished by oligomerising the monomers in a controlled manner to give rise to a product that is already relatively uniform, optionally followed by purification to obtain the required uniform block length.
  • Another approach is to control the reaction in such way, that the components can only react to give a well-defined product.
  • An example of this latter approach is to provide a starting material R having two reactive groups, which reactive groups each react with one other reactant, ⁇ , to give a product S-R-S that possesses the required block length and ⁇ - conjugation (optionally after further treatment, for example removing or adding substituents) .
  • the non-active blocks that can be sandwiched between the ⁇ -conjugated blocks can have any composition, provided that they do not provide ⁇ -conjugation and that they can be sandwiched between the ⁇ -conjugated blocks.
  • examples thereof are oligo-organo-silanes, substituted silicium blocks and oligo styrene and derivatives thereof.
  • the choice of the intermediate group has influence on the properties of the multiblock copolymer.
  • Preferred groups are i.a. ⁇ , ⁇ -unsaturated organic compounds like vinyl and alkylene compounds, oligovinylenes and derivatives thereof, germanium compounds, silicium compounds and carbon compounds.
  • Suitable materials for said blocks are based on silicium, germanium or on carbon-carbon oligomers. Of the latter group, especially the styrenic materials, like oligostyrene, and oligomers of styrene derivatives, as well as vinyl compounds such as vinylcarbazole are Suitable.
  • the silicium, carbon or germanium based materials are preferably of the type.
  • X denotes Si, Ge, C, SiO, or CO
  • R 7 and R 8 being identical or different, each denoting a lineair or branched alkyl substituent having 1-6 carbon atoms or a phenyl, optionally substituted with one or more alkyl and/or alkoxy groups.
  • the non-active, or ⁇ -conjugated blocks do not have such a strong influence on the wavelength of the LED, although the choice of the blocks and the length thereof certainly influences the behaviour of the LED.
  • Suitable block lengths vary between 2 and 8, said block length being based upon the number of atoms in the ⁇ -conjugated block that become part of the polymer chain.
  • the silicon-based blocks have the advantage that they can be processed with deep UV-photolithography, since the polysilanes are deep-UV photoresists.
  • the blocks based upon silicium and germaniumn act also as intrinsic hole transport material, improving thus the quantum efficiency. It is thus possible to prepare a three block copolymer, wherein two types of non- ⁇ -conjugated blocks are present, namely one type having hole and another having electron transport properties.
  • non- ⁇ -conjugated blocks are either directly available chemicals, like vinyl or vinylene oligomers, or can be prepared separately or in situ, i.e. during the assembly of the block copolymer.
  • new semi ⁇ conducting organic and/or organic-inorganic block copolymers can be used, (some of which are shown in figure 4) said polymers being obtainable by making various combinations for the optionally alkylated or alkoxylated active blocks of
  • Oligothiophenes, oligovinylenes, oligophenylenes and oligo(p-phenylenevinylene)s ( ⁇ -conjugated blocks) with oligosilanes ( ⁇ -conjugated blocks) , oligosiloxanes, oligovinypyridine, oligostyrene non-active blocks in order to obtain a heterostructure based on the principal of the selfassembly of the block copolymers.
  • the active block will be sandwiched between the non- active blocks [(-A x -B y -)] z , wherein A x and B y respectively denote the ⁇ -conjugated and the non ⁇ -conjugated blocks, x and y being the respective block-lengths and z being the number of -A x -B y - blocks in the polymer.
  • the values of x, y and z are preferably such that the molecular weight of the polymer will be between 2500 and 500,000. Lower values may lead to problems in the processing to films, whereas higher values do not provide additional advantages in terms of polymer properties and may lead to processing difficulties, due to the high molecular weight.
  • the proposed block copolymers provide various chemical and physicochemical tuning capabilities and improve the properties that have been described previously, concerning the tunable LEDs.
  • the wave length of the emitted light is tuned to a value between 400 and 850.
  • the block length preferably varies between 2 and 16 units, each unit comprising two double and two single C-C bonds. ith shorter block lengths the emitted light is more in the blue/green area, whereas larger block lengths lead to a more reddish colour.
  • the ⁇ -conjugated blocks are either directly available chemicals, like vinyl or vinylene oligomers, or can be prepared separately or in situ, i.e. during the assembly of the block copolymer.
  • the blocks can be assembled into one polymer by known techniques, for example by reaction between the blocks, either directly into one copolymer or in two or more steps.
  • One of the further objects of the present invention is to provide a novel class of multiblock copolymers containing short blocks of thiophene and derivatives thereof, which multiblock copolymers are suitable for use in opto- electronics and more in particular in LED's, as described herein.
  • a further object is to provide a novel class of multiblock copolymers containing short blocks of thiophene and derivatives thereof, which multiblock copolymers are easy to process, for example by spin coating, into a thin layer on a substrate.
  • This block copolymer consists of at least two groups of blocks, thiophene blocks A, sandwiched between no -thiophene blocks B, said thiophene blocks A having the formula l,
  • Ri-R ⁇ may each be selected from H, optionally branched, lower alkyl, i.e. C 1 -C 15 and optionally branched, lower alkoxy.
  • substituents Ri-R ⁇ in the blocks may vary within each block.
  • the block A the thiophene block
  • the block A will be sandwiched between the non-thiophene blocks in the manner [ (-A x -By-) ] z
  • the values of x, y and z are preferably such that the molecular weight of the polymer will be between 2500 and 500,000. Lower value may lead to problems in the processing to films, whereas higher values do not provide additional advantages in terms of polymer properties and may lead to processing difficulties, due to the high molecular weight.
  • the number of thiophene units can be selected, as well as the type and number of substituents. It is preferred that at least one of the thiophene rings has to be substituted as otherwise the processability, especially in spin-coating, is insufficient. Preferably at least two of the rings in each block are substituted with alkyl, aryl, alkaryl, aralkyl, alkoxy, aralkoxy and the like, each substituent containing one to 15 carbon atoms. In practising the invention the substituents Ri and R 2 will generally be identical to R 5 and Re, whereas R 3 and R 4 may be different.
  • the number of substituents on each ring will not exceed one, that means that in each ring at least one of the R-groups will denote H.
  • the selection of the substituents influences the electroluminescent properties of the material to some degree.
  • substituents like butyl, octyl and dodecyl, is very important.
  • Suitable multiblock copolymers preferably contain 2 to 16 or more thiophene units in each thiophene block. It is to be noted that when using these multiblock copolymers of the present invention in opto-electronics and more in particular in electro-luminescent devices, the length of the blocks has a profound influence on the wave length of the light. Also important is the choice of the various substituents.
  • Suitable multiblock copolymers preferably contain 5 or more thiophene units.
  • group B has also influence on the properties of the multiblock copolymer.
  • preferred groups are i.a. ⁇ , ⁇ -unsaturated organic compounds like styrene and derivatives thereof, germanium compounds and silicium compounds. Suitable materials for said blocks are those described hereinbefore in relation to the LED.
  • the blocks can be assembled into one polymer by known techniques, for example by reaction between the blocks, either directly into one copolymer or in two or more steps.
  • new LED's are provided based upon novel semi-conducting organic and/or organic- inorganic block copolymers, said polymers being obtainable by making ' various combinations of ⁇ -conjugated and non- ⁇ - conjugated blocks in order to obtain a heterostructure based on the principal of the selfassembling of the block copolymers.
  • the materials for the electrodes needed for the LEDs and quantum-well devices are chosen appropriately following the work function of the active multi-block copolymers. These materials are well-known in the art of LED's. Suitable materials are described in the literature and can be selected by a person skilled in the art based upon the actual configuration to be used.
  • the LED comprises two layers of electrodes, such as indium-tinoxide and a conducting metal, between which layers the electroluminescent material has been sandwiched.
  • the electroluminescent material is preferably spun-coated on the surface of an electrode.
  • a thin layer of polymer forming a hole injecting electrode, transparent in the region of emission may be applied to a flexible substrate, for example a polyester.
  • This two layer material forms the cathode of the LED, which is placed in contact with the electroluminescent material.
  • the anode can advantageously be evaporated at low pressure onto the surface of the electroluminescent material.
  • Suitable metals are calcium, indium, aluminium, tin, magnesium and alloys of those materials.
  • FIG l the basic element giving rise to injection luminescence, a p-n junction diode operated under forward bias, is illustrated.
  • figures 2 and 3 the schematic set-up of an LED is shown and in figure 4 the general structure of some the multi- block copolymers is given.
  • Figure 5 gives the spectroscopic characterization of thin films of multiblock copolymers with varying block length.
  • Figures 6-9 give some of the reactions that may be used to prepare the block copolymers used in the invention.
  • FIG. 10 shows the wave length pattern of the electroluminescence of two different multiblock copolymers.
  • Route A Polycondensation of dilithiumsalt of oligothienylene and oligosilanylene.
  • Route B Cross coupling of digrignard- bisthienylsilanylene and dibromooligothienylene.
  • Ri, R 2 , R 3 , R 4 , R 5 , Re H, C1-C 2 0 linear or branched alkyl or alkoxyalkyl;
  • Thin films of the polymers were prepared by spincoating 5-15% solutions of the various polymers in an organic solvent on a glass slide covered with Indium Tin Oxide (ITO) .
  • ITO Indium Tin Oxide
  • Various metal electrodes (Ca,Al,In,Sn,Mg and alloys of these metals) were evaporated at low pressure (10-6 torr) .
  • the films were assembled into an LED.
  • the wave length pattern of the electroluminescence of two different multiblock copolymers has been given in Fig. 10.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Diode électroluminescente (DEL) émettant une lumière dont la longueur d'onde est comprise entre 400 et 850, comportant une matière électroluminescente, des électrodes et éventuellement une matière porteuse et/ou une matière réfléchissante. Ladite matière électroluminescente comporte au moins un copolymère en blocs constitué d'au moins deux type de blocs, à savoir des blocs actifs intercalés entre des blocs non actifs, lesdits blocs actifs étant un bloc π-conjugué possédant de 2 à 16 motifs monomères et présentant une longueur sensiblement homogène dans l'ensemble du copolymère, et ledit bloc non actif ne présentant aucune conjugaison π, et éventuellement doté de propriétés supplémentaires de transport d'électrons et/ou de trous. On a également prévu des polymères utilisables dans la préparation d'une telle diode électroluminescente des oligomères pour la préparation desdits copolymères en blocs multiples, et divers procédés.
PCT/NL1993/000280 1992-12-29 1993-12-29 Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres WO1994015368A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP94904345A EP0677208A1 (fr) 1992-12-29 1993-12-29 Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres
AU58438/94A AU5843894A (en) 1992-12-29 1993-12-29 Multi-bloc copolymer based tunable light emitting diode, polymers suitable therefor and oligomers
JP6515043A JPH08505167A (ja) 1992-12-29 1993-12-29 多重ブロック共重合体を基材とする波長可変性発光ダイオード、それに適した重合体およびオリゴマー
FI953212A FI953212A0 (fi) 1992-12-29 1995-06-29 Monilohko-kopolymeereihin perustuva viritettävä valoa emittoiva diodi, sitä varten sopivia polymeereja ja oligomeereja
KR1019950702692A KR960700531A (ko) 1992-12-29 1995-06-29 호조성 광 방출 다이오드에 기초한 멀티-블록 코폴리머, 그에 적합한 폴리머 및 올리고머(multi-bloc copolymer based tunable light emitting diode, polymers suitable therefor and oligomers)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP92204100.9 1992-12-29
EP92204100 1992-12-29
EP93201637.1 1993-06-08
EP93201637 1993-06-08

Publications (1)

Publication Number Publication Date
WO1994015368A1 true WO1994015368A1 (fr) 1994-07-07

Family

ID=26131900

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1993/000280 WO1994015368A1 (fr) 1992-12-29 1993-12-29 Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres

Country Status (6)

Country Link
JP (1) JPH08505167A (fr)
KR (1) KR960700531A (fr)
AU (1) AU5843894A (fr)
CA (1) CA2152922A1 (fr)
FI (1) FI953212A0 (fr)
WO (1) WO1994015368A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996003015A1 (fr) * 1994-07-19 1996-02-01 Forskarpatent I Linköping Ab Dispositif electroluminescent et son procede de fabrication
EP0713999A1 (fr) * 1994-11-24 1996-05-29 Siemens Integra Verkehrstechnik Ag Dispositif de signaux lumineux à diodes électroluminescentes
WO1997007654A1 (fr) * 1995-08-21 1997-02-27 Philips Electronics N.V. Dispositif electroluminescent
WO2000031208A1 (fr) * 1998-11-19 2000-06-02 Organic Display Technology Materiaux organiques electroluminescents et dispositifs associes
US6165383A (en) * 1998-04-10 2000-12-26 Organic Display Technology Useful precursors for organic electroluminescent materials and devices made from such materials
US6344284B1 (en) * 1998-04-10 2002-02-05 Organic Display Technology Organic electroluminescent materials and devices made from such materials
EP1329476A1 (fr) * 2002-01-11 2003-07-23 Xerox Corporation Polythiophènes et dispositifs les contenant
WO2003079400A2 (fr) * 2002-03-15 2003-09-25 Koninklijke Philips Electronics N.V. Dispositif electronique, procede, monomere et polymere
EP1439173A2 (fr) * 2002-10-18 2004-07-21 H.C. Starck GmbH Procédé pour la préparation des oligomères organiques linéaires
WO2005015982A3 (fr) * 2003-08-11 2005-04-28 Univ Cambridge Tech Procede de fabrication de dispositif a base de polymere
WO2006067497A2 (fr) * 2004-12-24 2006-06-29 Cambridge Display Technology Limited Dispositifs optiques et fabrication de ceux-ci
WO2007074920A1 (fr) * 2005-12-28 2007-07-05 Sumitomo Chemical Company, Limited Copolymere sequence
EP1864300A2 (fr) * 2005-03-16 2007-12-12 Plextronics, Inc. Copolymeres de poly(thiophenes) solubles dotes d'un meilleur rendement electronique
WO2006086480A3 (fr) * 2005-02-10 2009-04-30 Plextronics Inc Compositions de couches d'injection et de transport de trous et dispositifs associes

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101278894B1 (ko) 2001-04-27 2013-06-26 스미또모 가가꾸 가부시키가이샤 블록 공중합체 및 고분자 발광소자
US6949762B2 (en) * 2002-01-11 2005-09-27 Xerox Corporation Polythiophenes and devices thereof
US6872801B2 (en) * 2002-01-11 2005-03-29 Xerox Corporation Polythiophenes and devices thereof
US6770904B2 (en) * 2002-01-11 2004-08-03 Xerox Corporation Polythiophenes and electronic devices generated therefrom
KR100518419B1 (ko) * 2002-11-06 2005-09-29 엘지.필립스 엘시디 주식회사 유기전계발광소자
JP2004273981A (ja) * 2003-03-12 2004-09-30 Konica Minolta Holdings Inc 有機半導体および有機薄膜トランジスタ
KR101275449B1 (ko) * 2005-04-01 2013-06-14 카네기 멜론 유니버시티 위치규칙성 중합체, 폴리티오펜 및 블록 공중합체를포함하는 전도성 중합체의 리빙 합성
KR20160021181A (ko) * 2013-06-18 2016-02-24 닛산 가가쿠 고교 가부시키 가이샤 싸이오펜 유도체와 그 이용 및 싸이오펜 유도체의 제조 방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2655655A1 (fr) * 1989-12-07 1991-06-14 Rhone Poulenc Chimie Procede de preparation de polysilthiophenediyle et polymeres obtenus a l'issue de ce procede.
WO1992016023A1 (fr) * 1991-02-27 1992-09-17 The Regents Of The University Of California Diodes electroluminescentes a rayonnement visible elaborees a partir de polymeres semiconducteurs solubles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2655655A1 (fr) * 1989-12-07 1991-06-14 Rhone Poulenc Chimie Procede de preparation de polysilthiophenediyle et polymeres obtenus a l'issue de ce procede.
WO1992016023A1 (fr) * 1991-02-27 1992-09-17 The Regents Of The University Of California Diodes electroluminescentes a rayonnement visible elaborees a partir de polymeres semiconducteurs solubles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G. GUSTAFSSON: "Flexible Light-Emitting Diodes made from soluble conducting polymers", NATURE, vol. 357, 11 June 1992 (1992-06-11), LONDON GB *
JOJI OHSHITA ET AL: "Polymeric Organosilicon Systems. 10. Synthesis and Conducting Properties of Poly[2,5-(disilanylene)thienylenes]", MACROMOLECULES, vol. 24, no. 8, 15 April 1991 (1991-04-15), WASHINGTON, DC, US, pages 2106 - 2108, XP000218353 *
P.L.BURN ET AL.: "Chemical Tuning of Electroluminescent Copolymers to improve Emission Efficiencies and allow Patterning", NATURE, vol. 356, 5 March 1992 (1992-03-05), LONDON GB, pages 47 - 49 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996003015A1 (fr) * 1994-07-19 1996-02-01 Forskarpatent I Linköping Ab Dispositif electroluminescent et son procede de fabrication
US5932965A (en) * 1994-07-19 1999-08-03 Forskarpatent I Linkoping Ab Electroluminescent device and a method for fabricating an electroluminescent device
EP0713999A1 (fr) * 1994-11-24 1996-05-29 Siemens Integra Verkehrstechnik Ag Dispositif de signaux lumineux à diodes électroluminescentes
WO1997007654A1 (fr) * 1995-08-21 1997-02-27 Philips Electronics N.V. Dispositif electroluminescent
US6165383A (en) * 1998-04-10 2000-12-26 Organic Display Technology Useful precursors for organic electroluminescent materials and devices made from such materials
US6344284B1 (en) * 1998-04-10 2002-02-05 Organic Display Technology Organic electroluminescent materials and devices made from such materials
US6361885B1 (en) 1998-04-10 2002-03-26 Organic Display Technology Organic electroluminescent materials and device made from such materials
WO2000031208A1 (fr) * 1998-11-19 2000-06-02 Organic Display Technology Materiaux organiques electroluminescents et dispositifs associes
EP1329476A1 (fr) * 2002-01-11 2003-07-23 Xerox Corporation Polythiophènes et dispositifs les contenant
US7141644B2 (en) 2002-01-11 2006-11-28 Xerox Corporation Polthiophenes and devices thereof
US7517945B2 (en) 2002-01-11 2009-04-14 Xerox Corporation Polythiophenes and devices thereof
WO2003079400A2 (fr) * 2002-03-15 2003-09-25 Koninklijke Philips Electronics N.V. Dispositif electronique, procede, monomere et polymere
WO2003079400A3 (fr) * 2002-03-15 2003-11-27 Koninkl Philips Electronics Nv Dispositif electronique, procede, monomere et polymere
US7279702B2 (en) 2002-03-15 2007-10-09 Koninklijke Philips Electronics N.V. Electronic device, method, monomer and polymer
EP1439173A2 (fr) * 2002-10-18 2004-07-21 H.C. Starck GmbH Procédé pour la préparation des oligomères organiques linéaires
EP1439173A3 (fr) * 2002-10-18 2005-09-14 H.C. Starck GmbH Procédé pour la préparation des oligomères organiques linéaires
EP2336118A1 (fr) * 2002-10-18 2011-06-22 Heraeus Clevios GmbH Oligomères organiques linéaires et des couches les contenant
WO2005015982A3 (fr) * 2003-08-11 2005-04-28 Univ Cambridge Tech Procede de fabrication de dispositif a base de polymere
US7718549B2 (en) 2003-08-11 2010-05-18 Cambridge University Technical Services Limited Method of making a polymer device
WO2006067497A2 (fr) * 2004-12-24 2006-06-29 Cambridge Display Technology Limited Dispositifs optiques et fabrication de ceux-ci
GB2435181A (en) * 2004-12-24 2007-08-15 Cambridge Display Tech Ltd Optical devices and their manufacture
GB2435181B (en) * 2004-12-24 2009-08-19 Cambridge Display Tech Ltd Optical devices and their manufacture
WO2006067497A3 (fr) * 2004-12-24 2006-11-30 Cambridge Display Tech Ltd Dispositifs optiques et fabrication de ceux-ci
US8410241B2 (en) 2004-12-24 2013-04-02 Cambridge Display Technology Limited Optical devices and their manufacture
WO2006086480A3 (fr) * 2005-02-10 2009-04-30 Plextronics Inc Compositions de couches d'injection et de transport de trous et dispositifs associes
EP1864300A2 (fr) * 2005-03-16 2007-12-12 Plextronics, Inc. Copolymeres de poly(thiophenes) solubles dotes d'un meilleur rendement electronique
EP1864300A4 (fr) * 2005-03-16 2009-12-02 Plextronics Inc Copolymeres de poly(thiophenes) solubles dotes d'un meilleur rendement electronique
GB2448098A (en) * 2005-12-28 2008-10-01 Sumitomo Chemical Co Block copolymer
WO2007074920A1 (fr) * 2005-12-28 2007-07-05 Sumitomo Chemical Company, Limited Copolymere sequence
GB2448098B (en) * 2005-12-28 2011-07-06 Sumitomo Chemical Co Block copolymer
US8895675B2 (en) 2005-12-28 2014-11-25 Sumitomo Chemical Company, Limited Block copolymer

Also Published As

Publication number Publication date
JPH08505167A (ja) 1996-06-04
CA2152922A1 (fr) 1994-07-07
FI953212A (fi) 1995-06-29
KR960700531A (ko) 1996-01-20
FI953212A0 (fi) 1995-06-29
AU5843894A (en) 1994-07-19

Similar Documents

Publication Publication Date Title
WO1994015368A1 (fr) Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres
US8361636B2 (en) Luminescent polymer
KR100480769B1 (ko) 백색 전계발광 고분자 및 이를 이용한 유기 전계발광 소자
US20060094859A1 (en) Class of bridged biphenylene polymers
KR101031992B1 (ko) 고분자 형광체 및 이를 사용한 고분자 발광 소자
CA2554940A1 (fr) Polymere organique electroluminescent contenant une unite 9,9-di(fluorenyl)-2,7-fluorenyle, et dispositif organique electroluminescent fabrique avec ce polymere
JP4940495B2 (ja) 高分子蛍光体および高分子発光素子
WO2006062323A1 (fr) Polymere electroluminescent possedant un motif 9-fluoren-2-yl-9-aryl-2,7-fluorenyle et dispositif electroluminescent fabrique au moyen de celui-ci
US7230070B2 (en) Electroactive fluorene copolymers and devices made with such polymers
KR100552683B1 (ko) 청색 전계발광 고분자 및 이를 이용한 유기 전계발광 소자
US6994921B2 (en) Polymeric fluorescent substance and polymer light emitting device
JP2001076880A (ja) 有機エレクトロルミネッセンス素子
C Grimsdale In search of stable blue emission from phenylene-based conjugated polymers
KR100528323B1 (ko) 청색 전계발광 고분자 및 이를 이용한 유기 전계발광 소자
JP5196747B2 (ja) ルミネッセンス用高分子
EP0633614A1 (fr) Diode émettrice de lumière accordable à base d'un polymère
EP0677208A1 (fr) Diode electroluminescente accordable a base de copolymeres en blocs multiples, polymeres associes et oligomeres
KR100537502B1 (ko) 청색 전계발광 고분자 및 이를 이용한 유기 전계발광 소자
Li et al. Semiconducting polymers as light-emitting materials

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AT AU BB BG BR BY CA CH CZ DE DK ES FI GB HU JP KP KR KZ LK LU MG MN MW NL NO NZ PL PT RO RU SD SE SK UA US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994904345

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2152922

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 953212

Country of ref document: FI

ENP Entry into the national phase

Ref document number: 1995 464725

Country of ref document: US

Date of ref document: 19950901

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 1994904345

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1994904345

Country of ref document: EP