WO2015099461A1 - Dispositif électroluminescent organique - Google Patents

Dispositif électroluminescent organique Download PDF

Info

Publication number
WO2015099461A1
WO2015099461A1 PCT/KR2014/012844 KR2014012844W WO2015099461A1 WO 2015099461 A1 WO2015099461 A1 WO 2015099461A1 KR 2014012844 W KR2014012844 W KR 2014012844W WO 2015099461 A1 WO2015099461 A1 WO 2015099461A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
barrier layer
polyimide film
polyimide
layer
Prior art date
Application number
PCT/KR2014/012844
Other languages
English (en)
Korean (ko)
Inventor
문지묵
우학용
홍기일
정학기
Original Assignee
네오뷰코오롱 주식회사
코오롱인더스트리 주식회사
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 네오뷰코오롱 주식회사, 코오롱인더스트리 주식회사 filed Critical 네오뷰코오롱 주식회사
Priority claimed from KR1020140188558A external-priority patent/KR20150075054A/ko
Publication of WO2015099461A1 publication Critical patent/WO2015099461A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED

Definitions

  • the present invention relates to an organic light emitting display device, and more particularly, to an organic light emitting display device having improved transmittance and flexibility.
  • an organic light emitting diode includes a substrate, a lower electrode stacked on the substrate, an organic material layer stacked on the lower electrode, and an upper electrode stacked on the organic material layer.
  • the organic light emitting diode emits light by energization between the lower electrode and the upper electrode. That is, light emission of the organic light emitting diode is generated in the organic material layer interposed between the upper electrode and the lower electrode by the electrons of the upper electrode and the holes of the lower electrode.
  • the organic light emitting diode is a double-sided organic light emitting diode (transparent OLED) to emit light through the upper electrode and the lower electrode according to the light emission method, the top OLED and a lower electrode to emit light through the upper electrode It is divided into a bottom emitting organic light emitting device (bottom OLED) emitting light through.
  • transparent OLED transparent organic light emitting diode
  • bottom OLED bottom emitting organic light emitting device
  • the organic light emitting device emits light through an electrode having permeability among the upper electrode and the lower electrode.
  • both the upper electrode and the lower electrode should have transparency.
  • the upper electrode uses a transparent metal thin film, and when the thickness of the metal thin film is reduced, the transmittance is increased.
  • the thickness reduction of the upper electrode for increasing the transmittance of the upper electrode has a problem of increasing the sheet resistance of the upper electrode.
  • a polyimide (PI) film is a film of a polyimide resin
  • a polyimide resin is a solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by ring closure dehydration at a high temperature.
  • the high heat resistant resin manufactured by imidation is called. Since such polyimide films have excellent mechanical, heat resistance, and electrical insulation properties, they are used in a wide range of fields for electronic materials such as semiconductor insulating films, TFT-LCD electrode protective films, and flexible printed circuit boards.
  • polyimide resins are colored in brown and yellow due to their high aromatic ring density, so they have low transmittance in the visible region and yellow-based color, which results in low light transmittance and high birefringence, making them difficult to use as optical members. have.
  • a method of purifying and polymerizing the monomer and the solvent has been attempted, but the improvement of the transmittance is not large.
  • U.S. Patent No. 553480 describes a method of using an aliphatic ring-based dianhydride component instead of an aromatic dianhydride, and compared to the purification method, there was an improvement in transparency and color when solution or film was formed, but also an improvement in permeability. There was a limit to the high permeability was not satisfactory, and also resulted in degradation of thermal and mechanical properties.
  • No. 5986036, 6262328 and Korean Patent Publication No. 2003-0009437 are monomers having a curved structure connected to a linking group, such as -O-, -SO 2- , CH 2 -and the m-position rather than the p-position
  • a report has been made of a novel polyimide structure having improved transmittance and color transparency using aromatic dianhydride dianhydrides having substituents such as -CF 3 and aromatic diamine monomers, without increasing the thermal properties significantly. In terms of mechanical properties, heat resistance, and birefringence, the results were insufficient to be used for display device materials such as OLED, TFT-LCD, and flexible displays.
  • An object of the present invention is to provide an organic light emitting display device having improved transmittance and flexibility.
  • the present invention provides a polyimide substrate comprising a polyimide film and a silicon oxide-containing barrier layer formed on at least one surface of the polyimide film; A first electrode formed on the polyimide substrate; An organic material layer formed on the first electrode; A second electrode formed on the organic material layer; And a light transmitting layer formed on at least one of upper and lower surfaces of the second electrode.
  • the present invention also provides a second preferred embodiment, comprising: a polyimide substrate comprising a polyimide film and a silicon oxide containing barrier layer formed on at least one surface of the polyimide film; A first electrode formed on the polyimide substrate; An organic material layer formed on the first electrode; A second electrode formed on the organic material layer; A third electrode formed on the second electrode; And a light transmitting layer formed on at least one surface of a lower surface of the second electrode and an upper surface of the third electrode.
  • the polyimide film has an average transmittance of 85% or more, a yellowness of 15 or less, and a time to delamination (TMA) at 350 to 700 nm measured with a UV spectrophotometer based on a film thickness of 10 to 100 ⁇ m.
  • TMA time to delamination
  • the average linear expansion coefficient measured at 50 to 250 ° C. may be 50.0 ppm / ° C. or less.
  • the silicon oxide according to the embodiment may include a unit structure represented by the following formula (1).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen atom, or an aryl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen atom. It is one selected.
  • the barrier layer according to the embodiment may have a thickness of 0.3 ⁇ 3.0 ⁇ m.
  • the polyimide substrate according to the embodiment may further include a wet organic gas barrier layer positioned between the polyimide film and the silicon oxide containing barrier layer.
  • the wet organic gas barrier layer according to the embodiment may include a polyisocyanate compound represented by Formula 2 below.
  • R 3 is an alkyl group having 1 to 10 carbon atoms
  • X 1 and X 2 are represented by the following formula (3) and (4), respectively.
  • n is an integer of 0 to 5
  • m is an integer of 1 to 5
  • R 4 is an alkyl group or hydrogen atom of 1 to 10 carbon atoms
  • R 5 is an alkylene of 1 to 10 carbon atoms.
  • the wet organic gas barrier layer according to the embodiment may have a thickness of 1.0 to 20.0 ⁇ m.
  • the organic light emitting display device uses a polyimide substrate including a polyimide film having colorless transparency and low birefringence and excellent mechanical properties and heat resistance as a substrate, thereby preventing an increase in resistance due to an increase in transmittance of the upper electrode. It can represent a structure that can be done.
  • FIG. 1 shows a longitudinal section of an organic light emitting display device according to the present invention.
  • FIG. 2 shows an example of a structure in which the organic light emitting diode according to the present invention is bonded to an encapsulant.
  • organic light emitting display device 10 substrate
  • first electrode 50 second electrode
  • first light transmitting layer 92 second light transmitting layer
  • encapsulant layer 110 curing type sealing agent
  • the present invention provides a polyimide substrate including a polyimide film and a silicon oxide-containing barrier layer formed on at least one surface of the polyimide film; A first electrode 30 formed on the polyimide substrate; An organic layer 70 formed on the first electrode 30; A second electrode 50 formed on the organic layer 70; And a light transmitting layer 90 formed on at least one of an upper surface and a lower surface of the second electrode 50.
  • the present invention also provides a polyimide substrate comprising a polyimide film and a silicon oxide-containing barrier layer formed on at least one surface of the polyimide film; A first electrode formed on the polyimide substrate; An organic material layer formed on the first electrode; A second electrode formed on the organic material layer; A third electrode 51 formed on the second electrode; And a light transmitting layer formed on at least one surface of a lower surface of the second electrode and an upper surface of the third electrode.
  • the polyimide substrate may include a transparent polymer film having a permeability to transmit light emitted from the organic material layer, and may preferably include a transparent polyimide film.
  • the polyimide substrate may include a polyimide film and a silicon oxide-containing barrier layer formed on at least one surface of the polyimide film.
  • the polyimide film has an average transmittance of 85% or more, a yellowness of 15 or less, and 50 or less according to TMA (Time to Delamination) -Method at 350 to 700 nm measured with a UV spectrophotometer based on a film thickness of 10 to 100. It may be a transparent polyimide film having an average linear expansion coefficient measured at from 250 ° C. to 50.0 ppm / ° C. or less. Such a transparent polyimide film may be made of a polyimide resin described below.
  • the polyimide resin may be prepared by polymerization of a dianhydride monomer and a diamine monomer, and as the dianhydride monomer, 4,4 '-(4,4'-isopropylidenediphenoxy) bis (Phthalic anhydride) (HBDA), biphenyltetracarboxylic acid dianhydride (BPDA) and 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), Bis trifluoromethylbenzidine (TFDB) may be used as the diamine monomer.
  • HBDA 4,4 '-(4,4'-isopropylidenediphenoxy) bis
  • BPDA biphenyltetracarboxylic acid dianhydride
  • 6FDA 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
  • TFDB Bis trifluoromethylbenzidine
  • HBDA phthalic anhydride
  • BPDA biphenyltetracarboxylic acid dianhydride
  • 6FDA 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
  • HBDA phthalic anhydride
  • BPDA biphenyltetracarboxylic acid dianhydride
  • 6FDA 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
  • the 4,4 '-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) (HBDA) may be included in 10 to 45 mol% based on the total moles of dianhydride. In terms of heat resistance, preferably 15 to 30 mol%. If the content of 4,4 '-(4,4'isopropylidenediphenoxy) bis (phthalic anhydride) (HBDA) is less than 10 mol% based on the total moles of dianhydride, mechanical properties If the improvement of is insignificant and exceeds 45 mol%, the mechanical properties are improved, but the heat resistance may be lowered.
  • the biphenyltetracarboxylic acid dianhydride (BPDA) has a lower heat resistance when the content is less than 30 mol% with respect to the total moles of the total dianhydride, and when the content exceeds 50 mol%, the mechanical properties are improved.
  • the biphenyltetracarboxylic dianhydride (BPDA) may include 30 to 50 mol% based on the total moles of the total dianhydride.
  • the content of 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) is less than 20 mol% based on the total moles of dianhydride, the birefringence is lowered and 50 mol% When the birefringence is higher than the birefringence is improved, the mechanical properties can be reduced, the 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) is added to the total dianhydride total weight About 20 to 50 mol% may be included.
  • the diamine used in the present invention may include bis trifluoromethylbenzidine (TFDB), or may further include a diamine having a soft group in bis trifluoromethylbenzidine (TFDB) in terms of birefringence improvement.
  • TFDB bis trifluoromethylbenzidine
  • TFDB bis trifluoromethylbenzidine
  • the diamine having a flexible group means a diamine containing a flexible group such as an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, a carbonyl group, a sulfone group, a sulfide group and the like in the main chain thereof, and Examples include bis (4- (4-aminophenoxy) phenyl) sulfone (BAPS), bis (4- (3-aminophenoxy) phenyl) sulfone (BAPSM), 4,4'-diaminodiphenylsulfone ( 4DDS), 3,3'-diaminodiphenylsulfone (3DDS), 2,2-bis (4- (4-aminophenoxy) phenylpropane (6HDA), 4,4'-diaminodiphenylpropane, 4 , 4'-diaminodiphenylmethane, 4,4'-diamin
  • the bis trifluoromethylbenzidine may include 80 mol% or more with respect to the total moles of diamine in terms of improving mechanical properties, and 20 mol% or less with respect to 1 mole of diamine having a flexible group. Inclusion is desirable to improve birefringence and mechanical properties.
  • the polyamic acid may be prepared by polymerization in a nitrogen or argon atmosphere for a reaction temperature of ⁇ 10 to 80 ° C. and a reaction time of 2 to 48 hours.
  • the solvent (polymerization solvent) for the polymerization reaction of the dianhydride and diamine is not particularly limited as long as it is a solvent in which a polyamic acid is dissolved.
  • Known reaction solvents selected from m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • acetone diethyl acetate
  • polar solvents are used.
  • low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as -butyrolactone may be used.
  • low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such
  • the content of the solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the solvent for polymerization (the first solvent) is preferably 50 to 95% by weight of the total polyamic acid solution, and more preferably. It is more preferable that it is 70 to 90 weight%.
  • the polyimide resin prepared by imidating the polyamic acid solution prepared as described above preferably has a glass transition temperature (Tg) of 200 to 350 ° C. in consideration of thermal stability.
  • the imidation method applied in the step of imidizing a polymerized polyamic acid on a support, may be a thermal imidization method, a chemical imidization method, or a thermal imidization method. And chemical imidization can be used in combination.
  • the thermal imidization method is a method of casting a polyamic acid solution on a support and heating it for 1 to 8 hours while gradually raising the temperature in a temperature range of 40 to 400 ° C. to obtain a polyimide film.
  • the chemical imidization method is a method of injecting an imidization catalyst represented by a dehydrating agent represented by an acid anhydride such as acetic anhydride and tertiary amines such as isoquinoline, -picolin, pyridine and the like into a polyamic acid solution.
  • an imidization catalyst represented by a dehydrating agent represented by an acid anhydride such as acetic anhydride and tertiary amines such as isoquinoline, -picolin, pyridine and the like into a polyamic acid solution.
  • the heating conditions of the polyamic acid solution may vary depending on the kind of the polyamic acid solution, the thickness of the polyimide film to be produced, and the like.
  • the polyimide film can be obtained by heating at 100 to 180 ° C., partially curing and drying by activating the dehydrating agent and imidization catalyst, and then heating at 200 to 400 ° C. for 5 to 400 seconds.
  • a polyimide film may be prepared and used from the obtained polyamic acid solution as follows. That is, after imidating the obtained polyamic acid solution, the imidized solution is added to a second solvent, precipitated, filtered and dried to obtain a solid content of the polyimide resin, and the obtained polyimide resin solid content is added to the first solvent. It can obtain through the film forming process using the dissolved polyimide solution.
  • the first solvent may use the same solvent as the solvent used in the polymerization of the polyamic acid solution, and the second solvent may have a lower polarity than the first solvent in order to obtain a solid content of the polyimide resin. It may be one or more selected from alcohols, ethers and ketones. At this time, the content of the second solvent is not particularly limited, but is preferably 5 to 20% by weight based on the weight of the polyamic acid solution.
  • the conditions for drying after filtering the polyimide resin solid content obtained as described above are preferably 50 to 120 ° C. and 3 to 24 hours in consideration of the boiling point of the second solvent. Thereafter, in the film forming process, the polyimide solution in which the polyimide resin solid content is dissolved is cast on a support, and heated at a temperature range of 40 to 400 ° C. for 1 minute to 8 hours, thereby obtaining a polyimide film.
  • the thickness of the polyimide film obtained by the method as demonstrated above is not specifically limited, It is preferable that it is the range of 10-100 micrometers, More preferably, it is 10-50 micrometers.
  • the polyimide film according to the present invention has a film thickness of 10 ⁇ m, Ro (surface retardation) is 1 nm or less, Rth (thickness retardation) is 70 nm (thickness 10), and a birefringence is 0.01 or less,
  • the polyimide film according to the present invention has a transmittance measured at 550 nm based on a film thickness of 10 to 50 ⁇ m or more, and a transmittance of 100% cut off wavelength of 360 nm or less. It can be used as a display protective layer.
  • the polyimide film according to the present invention has an elongation measured based on ASTM D882 (film thickness of 10 ⁇ 50 ⁇ m) of 6% or more, it is preferable in terms of yield of the manufacturer because it does not bend or tear even after various display processes. Do.
  • the silicon oxide-containing barrier layer may be formed on at least one surface of the polyimide film, and may improve low hygroscopicity of the substrate.
  • the silicon oxide may include a unit structure represented by Formula 1 below.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen atom, or an aryl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen atom. It is one selected.
  • the present invention is not particularly limited thereto, but in the present invention, it is more preferable that the silicon oxide is a polydimethylsiloxane (PDMS) having a structure in which R 1 and R 2 in the formula (1) are methyl. Can be.
  • PDMS polydimethylsiloxane
  • the viscosity range of the silicone compound is preferably in the range of 1 to 10,000 cSt almost no change in viscosity for the shear rate (shear rate) in order to prevent a sudden change in viscosity for the shear rate (shear rate), more Preferably it may be 15 ⁇ 900 cSt.
  • the viscosity is defined as measured according to ISO 9002 as a standard G series oil according to S90 (ZahnCup Visco Tester, Gardner) NIST.
  • the silicon oxide-containing barrier layer may have a thickness of 0.3 to 3.0 ⁇ m, and when the thickness of the silicon oxide-containing barrier layer is less than 0.3 ⁇ m, the barrier property against oxygen and moisture may not be secured. The transmittance is lowered and may not be suitable as a substrate for transparent displays.
  • the polyimide substrate may further include a wet organic gas barrier layer including a polyisocyanate compound represented by Formula 2 between the polyimide film and the silicon oxide-containing barrier layer.
  • R 3 is an alkyl group having 1 to 10 carbon atoms
  • X 1 and X 2 are represented by the following formula (3) and (4), respectively.
  • n is an integer of 0 to 5
  • m is an integer of 1 to 5
  • R 4 is an alkyl group or hydrogen atom of 1 to 10 carbon atoms
  • R 5 is an alkylene of 1 to 10 carbon atoms.
  • the polyisocyanate compound is an organic compound having a plurality of isocyanate groups in one molecule, and the number of isocyanate groups contained in one molecule of the polyisocyanate compound is preferably 5 or less.
  • the polyisocyanate compound may react with an acrylic resin having a hydroxyl group to form a polyisocyanate compound containing an acrylate group.
  • the polyisocyanate compound containing the acrylate group may form a crosslinked structure that may improve the physical properties of the coating film during curing.
  • a crosslinking degree is high and a film
  • membrane can be rigid and a warpage characteristic can be reduced.
  • polyisocyanate compound having two isocyanate groups in one molecule examples include diisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, norbornene diisocyanate and the like, diisocyanates such as xylylene diisocyanate and norbornene diisocyanate.
  • diisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, norbornene diisocyanate and the like
  • diisocyanates such as xylylene diisocyanate and norbornene diisocyanate.
  • Isocyanate monomers may be mentioned, and such diisocyanate monomers may be reacted with an acrylic resin having a hydroxyl group to form a diisocyanate compound containing an acrylate group.
  • the thickness of the wet organic gas barrier layer of the acrylate group-containing polyisocyanate group may be 1.0 to 20.0 ⁇ m, and the thickness of the wet organic gas barrier layer may be 1.0 ⁇ m or more in order to secure desired barrier characteristics of the organic light emitting device. In order to exclude the fall of the softness
  • the wet organic gas barrier layer may be obtained through a series of processes of coating, drying, and curing a solution containing a polyisocyanate containing an acrylate group on a polyimide film.
  • the method for coating the solution containing the polyisocyanate containing the acrylate group on one or both sides of the polyimide film is spray coating, bar coating, spin coating, dip coating Various methods, such as these, can be selected and implemented.
  • Curing of the wet organic gas barrier layer is an ultraviolet curing method, in consideration of this may include a photoinitiator in a solution containing an acrylate group.
  • a photoinitiator may be benzoin ether photoinitiator, benzophenone photoinitiator or a combination thereof.
  • UV curing conditions may be UV cured by irradiating the ultraviolet rays of 312 to 365 nm wavelength to 500 sowl 10,000 J / m2.
  • the organic electroluminescent device includes the barrier layer and the wet organic gas barrier layer together on the polyimide film, thereby further improving the optical and barrier properties of the substrate.
  • the first electrode is formed on a polyimide substrate, commonly referred to as a lower electrode, and is an anode which is a positive electrode.
  • the first electrode may be selected from a permeable indium tin-oxide electrode, an indium zinoxide electrode, and an indium gallium zinc oxide (IGZO) electrode. have.
  • the first electrode may be formed on the polyimide substrate by thermal deposition using a sputtering method, an ion plating method, an electron gun, or the like.
  • the organic material layer 70 is interposed between the first electrode 30 and the second electrode 50 to emit light by energization between the first electrode 30 and the second electrode 50.
  • the organic layer 70 includes a hole injection layer (HIL) 72 and a hole transporting layer (HTL) to emit light by energization between the first electrode 30 and the second electrode 50.
  • HIL hole injection layer
  • HTL hole transporting layer
  • 74 including an emissive layer (EML) 76, an electron transporting layer (ETL) 78, and an electron injection layer (EIL) 79, sequentially stacked from the bottom up. Included in the form.
  • the organic layer 70 may be spin coated, thermal evaporation, spin casting, sputtering, e-beam evaporation and chemical vapor deposition. It may be interposed between the first electrode 30 and the second electrode 50 by a chemical vapor deposition (CVD) method or the like.
  • CVD chemical vapor deposition
  • the hole injection layer 72 serves to inject holes from the first electrode 30, and the hole transfer layer 74 is a hole injected from the hole injection layer 72 is electrons of the second electrode 50 It serves as a movement of holes to meet with.
  • the electron injection layer 79 serves to inject electrons from the second electrode 50, and the electron transfer layer 78 moves electrons injected from the electron injection layer 79 from the hole transport layer 74. It serves as a movement path of electrons to meet in the hole and the light emitting layer (76).
  • the electron transport layer 78 may be formed by doping any one of a metal having a low work function and a composite thereof to facilitate electron injection from the second electrode 50, which may be formed of the electron injection layer 79. It can be applied with or without it.
  • the metals having a low work function may include Cs, Li, Na, K, Ca, and the like, and the complex thereof may include Li-Al, LiF, CsF, Cs 2 CO 3 , and the like.
  • the light emitting layer 76 is interposed between the hole transport layer 74 and the electron transport layer 78 to emit light by holes from the hole transport layer 74 and electrons from the electron transport layer 78. That is, the light emitting layer 76 emits light by holes and electrons which meet at the interface with the hole transport layer 74 and the electron transport layer 78, respectively.
  • the second electrode is formed on the organic material layer, commonly referred to as an upper positive electrode, is a cathode (-) cathode.
  • the second electrode may be formed of a metal selected from among silver (Ag), aluminum (Al), and magnesium-silver (Mg: Ag) alloy, which is a metal having transparency.
  • the second electrode may be formed in the same manner as the first electrode.
  • the third electrode is formed on the second electrode, and the third electrode 51 is selected from silver (Ag), aluminum (Al), and magnesium-silver (Mg: Ag) alloys, which are transparent metals. It may be formed of a metal.
  • the third electrode may be formed in the same manner as the first electrode.
  • the organic light emitting device is a polyimide substrate; A first electrode; Organic layer; Second electrode; And a light transmitting layer
  • the light transmitting layer may be formed on at least one of the upper and lower surfaces of the second electrode. That is, the light transmitting layer may be formed on the upper surface of the second electrode, the lower surface of the second electrode, or the upper and lower surfaces of the second electrode, and the upper surface of the second electrode when the transparent layer is formed on the upper surface and the lower surface of the second electrode.
  • the light transmitting layers respectively formed on the lower surface and the lower surface may be formed of the same material or different materials.
  • the light transmitting layer formed on the top surface of the second electrode 50 is referred to as a second light transmitting layer 92.
  • the light transmitting layer formed on the lower surface of the second electrode 50 may be referred to as a first light transmitting layer 91.
  • the first light transmitting layer may be formed between the lower surface of the second electrode, that is, between the organic material layer and the second electrode, and specifically, may be formed between the electron injection layer and the second electrode of the organic material layer, and electron injection. It can be formed in the layer itself.
  • the second light transmitting layer may be stacked on an upper surface of the second electrode opposite to the first light transmitting layer.
  • the light transmitting layer functions to allow the second electrode to have a high transmittance while having a transmittance.
  • the light-transmitting layer is formed of a thin film to reduce the sheet resistance of the second electrode, it is possible to prevent the performance of the organic electroluminescent device is lowered.
  • the organic electroluminescent device is a polyimide substrate; A first electrode; Organic layer; Second electrode; Third electrode; And a light transmitting layer, the light transmitting layer may be formed on at least one surface of the lower surface of the second electrode and the upper surface of the third electrode. That is, the light transmitting layer may be formed on the bottom surface of the second electrode, the top surface of the third electrode, or the bottom surface of the second electrode and the top surface of the third electrode, and the light transmission layer is formed on the bottom surface of the second electrode and the top surface of the third electrode. If so, the light transmitting layers formed on the bottom surface of the second electrode and the top surface of the third electrode may be formed of the same material or different materials.
  • the light transmitting layer functions to allow the third electrode 51 to have a high transmittance while having a transmittance.
  • the light-transmitting layer is formed of a thin film to reduce the sheet resistance of the third electrode, it is possible to prevent the performance of the organic electroluminescent device is lowered.
  • the light transmitting layer 90 may be formed by one or more selected from the group consisting of oxides, nitrides and salts.
  • the oxide may be at least one selected from the group consisting of MoO 3 , ITO, IZO, IO, ZnO, TO, TiO 2 , SiO 2 , WO 3 , Al 2 O 3 , Cr 2 O 3 , TeO 2 and SrO 2 .
  • the nitride may be one or more selected from the group consisting of SiN and AIN
  • the salt is one selected from the group consisting of Cs 2 CO 3 , LiCO 3 , KCO 3 , NaCO 3 , LiF, CsF and ZnSe It may be abnormal.
  • the light transmitting layer 90 may have a thickness of 0.1 nm or more and less than 100 nm, respectively. If the thickness is less than 0.1 nm, the transmittance is increased, but the resistance is also increased in proportion to this, so that the performance of the organic light emitting device 1 may be degraded. If the thickness is 100 nm or more, the resistance is decreased and the performance is not degraded. The transmittance may decrease with increasing thickness of the light transmitting layer.
  • the light transmitting layer may be formed by thermal evaporation.
  • amorphous silica particles having OH groups bonded to the surface were added to N, N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1%, sonicated until the solvent became transparent, and then prepared.
  • DMAc N, N-dimethylacetamide
  • 100 g of the polyimide of the solid powder of Example 1-1 was dissolved in 670 g of N, N-dimethylacetaamide (DMAc) to obtain a 13 wt% solution.
  • the thus obtained solution was applied to a stainless plate, and cast at 340 ⁇ m. After drying for 30 minutes with hot air at 0 ° C., the film was peeled off the stainless plate and fixed to the frame with a pin.
  • the film on which the film was fixed was placed in a vacuum oven and slowly heated for 2 hours from 100 ° C to 300 ° C, and then slowly cooled to separate from the frame to obtain a polyimide film. After the final heat treatment was performed for 30 minutes at 300 °C again.
  • the prepared polyimide film had a thickness of 50 ⁇ m, an average light transmittance of 89.5%, a yellowness of 2.4, and an average linear expansion coefficient (CTE) measured at 50 to 250 according to TMA-Method.
  • a polyimide film and a barrier were formed by depositing a silicon oxide (silicon manufactured by Kobelco), wherein both R 1 and R 2 are hydrogen atoms in the polyimide film prepared in Preparation Example 1, to form a barrier layer having a thickness of 0.3 ⁇ m.
  • a substrate was prepared in which layers were sequentially stacked.
  • the barrier layer was deposited using Kobelco's roll-to-roll PECVD at a line speed of 1.0 m / min, Power 1.2KHz, and a vacuum of 0.7 pascal.
  • a substrate in which a barrier layer, a polyimide film, and a barrier layer were sequentially stacked was manufactured by fabricating the same method as the thin film transistor substrate of Preparation Example 2-1, but by forming barrier layers on both sides through roll-to-roll PECVD.
  • a barrier layer having a thickness of 1 ⁇ m was formed under the condition of a line speed of 0.45 m / min to form a polyimide film and A substrate in which barrier layers were sequentially stacked was prepared.
  • a substrate in which a barrier layer, a polyimide film, and a barrier layer were sequentially stacked was manufactured by fabricating the same method as the thin film transistor substrate of Preparation Example 2-3, but forming barrier layers on both sides through roll-to-roll PECVD.
  • barrier layer having a thickness of 3 ⁇ m was formed under the condition of Line Speed 0.15 m / min., Power 1.5KHz.
  • the substrate in which the barrier layer, the polyimide film, and the barrier layer were sequentially laminated was produced.
  • Preparation Example 2-6 Substrate fabrication comprising a wet organic gas barrier layer (both sides) and a barrier layer (cross section, 3 ⁇ m thick )
  • the thickness was 3 on condition of Line Speed 0.15 m / min., Power 1.5KHz.
  • the barrier layer was formed to prepare a substrate in which the wet organic gas barrier layer, the polyimide film, the wet organic gas barrier layer, and the barrier layer were sequentially stacked.
  • Preparation Example 2-7 Substrate fabrication comprising a wet organic gas barrier layer (both sides) and a barrier layer (both sides, 3 ⁇ m thick )
  • the polyimide film prepared in Preparation Example 1 was coated with a silicon oxide (PDMS, dowcorning) in which R 1 and R 2 were both methyl in Formula 1 to form a barrier layer having a thickness of 0.3 ⁇ m.
  • a silicon oxide PDMS, dowcorning
  • a substrate in which the barrier layer, the polyimide film, and the barrier layer were sequentially stacked was manufactured by fabricating the same method as the thin film transistor substrate of Preparation Example 2-8, but forming barrier layers on both surfaces.
  • a barrier layer having a thickness of 1 was formed in the same manner as in the thin film transistor substrate of Preparation Example 2-8.
  • a substrate in which the barrier layer, the polyimide film, and the barrier layer were sequentially stacked was manufactured by fabricating the same method as the thin film transistor substrate of Preparation Example 2-10, but forming barrier layers on both surfaces.
  • a substrate in which the barrier layer, the polyimide film, and the barrier layer were sequentially stacked was manufactured by the same method as the thin film transistor substrate of Preparation Example 2-9, but by forming a barrier layer having a thickness of 3.
  • the polyimide film prepared in Preparation Example 1 was prepared, and it was set as Comparative Preparation Example 1-1.
  • the wet organic gas barrier layer, the polyimide film, and the wet organic gas barrier layer are sequentially formed by forming a wet organic gas barrier layer on both sides of the polyimide film in the same manner as in Preparation Example 2-6.
  • the laminated substrate was prepared.
  • a substrate was manufactured in the same manner as in Preparation Example 2-6, but when the barrier layer was formed through roll-to-roll PECVD, a barrier layer having a thickness of 0.2 ⁇ m under the conditions of Line Speed 1.2 m / min., Power 1.5KHz, and vacuum degree of 0.7 pascal
  • the wet organic coating layer, the polyimide film, the wet organic gas barrier layer, and the barrier layer were manufactured by sequentially forming a substrate.
  • a substrate was manufactured in the same manner as in Preparation Example 2-7, but using an optical PET film (188 ⁇ m in thickness, manufactured by KOLON Corporation) instead of a polyimide film, a barrier layer, a wet organic gas barrier layer, a PET film, and a wet organic gas.
  • an optical PET film 188 ⁇ m in thickness, manufactured by KOLON Corporation
  • a substrate in which the barrier layer and the barrier layer were sequentially stacked was manufactured.
  • a substrate was manufactured in the same manner as in Preparation Example 2-6, but a wet organic gas barrier layer was formed by forming a barrier layer having a thickness of 5 ⁇ m under the condition of line speed of 0.15 m / min. When forming a barrier layer through roll-to-roll PECVD.
  • a substrate was prepared in which a polyimide film, a wet organic gas barrier layer, and a barrier layer were sequentially stacked.
  • Preparation Example 3-8 Substrate fabrication comprising a wet organic gas barrier layer (both sides) and a barrier layer (both sides, 5 ⁇ m thick )
  • a moisture absorbent Korean Industries, KFS-1
  • a silicone crosslinker compound (Samho CNE, trade name: 0.50 MMOLE / GM Crosslinker)
  • a catalyst platinum divinyl complex, cSt, 0.05% Platinum Complex in Vinyl Polymer 500
  • the composition for sealing materials was manufactured by mix
  • the transmission layer including the first electrode 30, the organic layer 70 and the second electrode layer on the substrate drawn through the production examples 2-1 to 2-12 and production examples 3-1 to 3-7 (90) were sequentially stacked to form the organic light emitting device portion 1, and then the composition for encapsulation material was directly coated on the device by spin coating to form a sheet. Subsequently, the mixture was heated and cured at 90 ° C. for 30 minutes to obtain an organic light emitting device including the encapsulant 100 layer having a thickness of 20 ⁇ m.
  • the organic light emitting diodes using the substrates of Preparation Examples 2-1 to 2-7 were used as Examples 1 to 7, and the organic light emitting diodes using the substrates of Preparation Examples 3-1 to 3-7 were compared to the present example. Reflected 1-7.
  • Yellowness measurement Yellowness was measured using a spectrophotometer (CU-3700D, KONICA MINOLTA).
  • CTE Thermal expansion coefficient
  • the initial luminous intensity of the OLED devices of Examples and Comparative Examples was measured by IVL TEST (current-voltage supply (model Keithley 2400, manufactured by Keithley), luminance meter (CS-200, manufactured by Minolta), jig part (Youngpoong). CMC) and measured the time that the luminescence intensity decreased to 50% over time while storing it in a 70 ° C RH 80% constant temperature and humidity chamber, and determined it as the device life, and the results are shown in Table 1 below. Shown in
  • Example 1 Board Barrier Layer Thickness ( ⁇ m) Permeability (%) Yellow road Moisture Permeability (g / m 2 / day) Flexural Characteristics (Bending Radius mm) Thermal expansion coefficient (ppm / °C) division Element life (hours) Preparation Example 2-1 0.3 87.8 2.8 0.100 4 20
  • Example 1 720 Preparation Example 2-2 0.3 89.9 3.1 0.040 4 20
  • Example 2 920 Preparation Example 2-3 One 86.8 7.6 0.030 6 20
  • Example 3 960 Preparation Example 2-4 One 89.6 8.6 0.010 7 20
  • Example 4 1040 Preparation Example 2-5 3 85.5 14.8 0.008 10 20
  • Example 5 1080
  • Example 6 1000
  • Example 7 1120 Preparation Example 2-8 0.3 89.8 2.5 0.100 4 20
  • the moisture permeability cannot protect the device from moisture by using the polyimide film alone, and in the case of Preparation Example 3-2, the wet organic gas barrier layer Although formed on both sides, it has been found that its moisture permeability is also not suitable for protecting the device from moisture.
  • the barrier layer although the barrier layer was formed, it was found that the thickness thereof was thin, so that the moisture permeability was high, which was not suitable for protecting the device from moisture.
  • the moisture permeability was also high, or the coefficient of thermal expansion was so large that it was found that it is not suitable for the high temperature process of forming an element in a subsequent process.
  • Preparation Examples 2-1 to 2-12 are all suitable for use as a substrate for thin film transistors of flexible electronic devices as they satisfy all of optical transmittance, yellowness, moisture transmittance, warpage characteristics, and thermal expansion coefficient. It was confirmed that the device lifespans of Preparation Examples 2-8 to 2-12 with different kinds of silicon oxide forming the barrier layer were slightly increased compared to Preparation Examples 2-1 to 2-5. Accordingly, Comparative Examples in which the devices of Examples 1 to 12 using Manufacturing Examples 2-1 to 2-12 having low water permeability and coefficient of thermal expansion as substrates were used for Manufacturing Examples 3-1 to 3-5. It was confirmed that the device life is significantly superior to the device of 1 to 5.

Landscapes

  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un dispositif électroluminescent organique, et propose un dispositif électroluminescent organique comprenant : un substrat de polyimide comprenant un film de polyimide et une couche barrière contenant un oxyde de silicium formée sur au moins une surface du film de polyimide ; une première électrode formée sur le substrat de polyimide ; une couche de matériau organique formée sur la première électrode ; une seconde électrode formée sur la couche de matériau organique ; et une couche transmettant la lumière formée sur au moins l'une des surfaces supérieure et inférieure de la seconde électrode.
PCT/KR2014/012844 2013-12-24 2014-12-24 Dispositif électroluminescent organique WO2015099461A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0162464 2013-12-24
KR20130162464 2013-12-24
KR1020140188558A KR20150075054A (ko) 2013-12-24 2014-12-24 유기전계발광소자
KR10-2014-0188558 2014-12-24

Publications (1)

Publication Number Publication Date
WO2015099461A1 true WO2015099461A1 (fr) 2015-07-02

Family

ID=53479225

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/012844 WO2015099461A1 (fr) 2013-12-24 2014-12-24 Dispositif électroluminescent organique

Country Status (1)

Country Link
WO (1) WO2015099461A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017188630A1 (fr) * 2016-04-26 2017-11-02 주식회사 엘지화학 Polyamide-imide transparent de haute résistance et son procédé de fabrication

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020125822A1 (en) * 1998-12-16 2002-09-12 Graff Gordon L. Environmental barrier material for organic light emitting device and method of making
US20090130463A1 (en) * 2005-10-05 2009-05-21 John Dean Albaugh Coated Substrates and Methods for their Preparation
US20100159792A1 (en) * 2008-12-22 2010-06-24 Vitex Systems, Inc. Encapsulated white oleds having enhanced optical output
US20120027984A1 (en) * 2006-11-01 2012-02-02 Sigurd Wagner Hybrid layers for use in coatings on electronic devices or other articles
US20120135251A1 (en) * 2010-11-26 2012-05-31 Samsung Electronics Co., Ltd. Photosensitive polyimide having silicon modified group, adhesive composition and semiconductor package including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020125822A1 (en) * 1998-12-16 2002-09-12 Graff Gordon L. Environmental barrier material for organic light emitting device and method of making
US20090130463A1 (en) * 2005-10-05 2009-05-21 John Dean Albaugh Coated Substrates and Methods for their Preparation
US20120027984A1 (en) * 2006-11-01 2012-02-02 Sigurd Wagner Hybrid layers for use in coatings on electronic devices or other articles
US20100159792A1 (en) * 2008-12-22 2010-06-24 Vitex Systems, Inc. Encapsulated white oleds having enhanced optical output
US20120135251A1 (en) * 2010-11-26 2012-05-31 Samsung Electronics Co., Ltd. Photosensitive polyimide having silicon modified group, adhesive composition and semiconductor package including the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017188630A1 (fr) * 2016-04-26 2017-11-02 주식회사 엘지화학 Polyamide-imide transparent de haute résistance et son procédé de fabrication
CN108431090A (zh) * 2016-04-26 2018-08-21 株式会社Lg化学 高强度透明聚酰胺-酰亚胺及其制造方法
CN108431090B (zh) * 2016-04-26 2020-08-28 株式会社Lg化学 高强度透明聚酰胺-酰亚胺及其制造方法

Similar Documents

Publication Publication Date Title
WO2014163352A1 (fr) Substrat de capot en polyimide
WO2017179877A1 (fr) Film de polyamide-imide incolore et transparent et son procédé de fabrication
WO2018056573A1 (fr) Solution de précurseur de polyamide et procédé pour sa production
EP2931795A1 (fr) Substrat polyimide transparent et son procédé de fabrication
WO2017209413A1 (fr) Polyamide-imide transparent haute résistance et son procédé de préparation
WO2017111289A1 (fr) Composition de poly(acide amique) à laquelle sont appliqués des monomères alicycliques et film de polyimide transparent l'utilisant
WO2016175344A1 (fr) Résine de polyimide et film utilisant celle-ci
WO2017188630A1 (fr) Polyamide-imide transparent de haute résistance et son procédé de fabrication
WO2017116171A1 (fr) Composition de résine de polysilsesquioxane pour substrat souple
WO2018117551A1 (fr) Film de polyimide transparent
WO2018147618A1 (fr) Procédé de préparation d'un film de polyamide-imide
WO2020091432A1 (fr) Composition de précurseur de polyimide pour améliorer l'adhésivité d'un film de polyimide et film de polyimide fabriqué à partir de celle-ci
TWI791056B (zh) 聚醯亞胺前體及聚醯亞胺、積層體、可撓性裝置
WO2020101383A1 (fr) Film à base de polyimide, composition à base de polyimide et procédé de fabrication de film faisant appel à celle-ci
WO2016108631A1 (fr) Précurseur de polyamide-imide, film de polyamide-imide et dispositif d'affichage le comprenant
WO2018143588A1 (fr) Stratifié pour la fabrication d'un substrat souple et procédé de fabrication d'un substrat souple à l'aide de celui-ci
WO2015099461A1 (fr) Dispositif électroluminescent organique
WO2016003146A1 (fr) Solution de poly(acide amique) résistant à la chaleur élevée et film de polyimide
WO2020159183A1 (fr) Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, l'utilisant chacun
WO2022145891A1 (fr) Film optique comprenant de la résine de polymère ayant un excellent degré de polymérisation et dispositif d'affichage comprenant celui-ci
WO2020071588A1 (fr) Procédé de production d'un film de polyamide-imide et film de polyamide-imide produit à partir de celui-ci
WO2014133297A1 (fr) Procédé de production de pellicule polyimide incolore et transparente imprégnée de tissu de verre et surface de planarisation de celle-ci
WO2019088441A1 (fr) Film de polyimide pour substrat de dispositif d'affichage
WO2016108675A1 (fr) Précurseur de polyamide-imide, film de polyamide-imide, et dispositif d'affichage le comprenant
WO2020055182A1 (fr) Stratifié destiné à la fabrication d'un écran flexible, et procédé de fabrication d'écran flexible mettant en œuvre un tel stratifié

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14875071

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14875071

Country of ref document: EP

Kind code of ref document: A1