CN102185121B - Manufacturing method of organic light-emitting device with inverted structure - Google Patents
Manufacturing method of organic light-emitting device with inverted structure Download PDFInfo
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Abstract
The invention provides a manufacturing method of an organic light-emitting device with an inverted structure. The manufacturing method comprises the following steps of: deposition, namely placing a boride into a specific container, heating the boride to ensure that the boride is evaporated and deposited to a base plate to form a boride film; treatment, namely performing surface treatment on the boride film; and forming, namely forming an electron transport and light-emitting layer, a hole transport layer, a hole injection layer and an anode layer on the boride film in turn.
Description
The application is that application number is " 200910109361.9 ", and name is called the dividing an application of patent application of " a kind of reverse-structured organic light-emitting device and preparation method thereof ".
Technical field
The present invention relates to a kind of organic light emitting apparatus and preparation method thereof, relate in particular to a kind of reverse-structured organic light-emitting device and preparation method thereof.
Background technology
Organic luminescent device (OLED) because have that luminosity is high, driving voltage is low, fast response time, without high, the ultralight advantage such as ultra-thin of visual angle restriction, efficiency, have huge application prospect in fields such as flat-panel monitor, planar light sources.
Present OLED device is made of folder single or multiple lift organic film between two electrodes, and typical operating voltage is 2-10V.Electronics is injected into the conduction band of organic layer from negative electrode, the opaque low workfunction metal of negative electrode normal operation is such as Mg, Ca, Li etc.Because these metals are very active, thereby alloys in common use replaces, and such as Mg-Ag alloy or Al-Li alloy etc., also can adopt stable metal such as Al to add that resilient coating such as LiF finish electronic injection.The hole is injected into the valence band of organic layer from anode, anode is normally transparent, adopts Au or the ITO of high work function, and light is from the anode-side outgoing.
As shown in Figure 1, organic light emitting apparatus comprises and being arranged in order: substrate 1, anode 2, and organic cavity transmission layer 3, electric transmission and luminescent layer 4, and, cathode layer 5.
The active Driving technique of present OLED mainly is amorphous silicon membrane transistor (a-Si TFT) technology and low temperature polycrystalline silicon (LTPS TFT) technology.Compare with a-Si TFT technology, a series of advantages such as LTPS TFT technology has that speed is fast, product is frivolous, cost is low, resolution is high, power saving and reliability height, and can overcome the a-Si TFT technology unvanquishable shortcoming of institute and restriction.Although the LTPSTFT technology has many superiority, because the starting of a-Si TFT technology is early, and has been widely used on the liquid crystal display, therefore to compare with LTPS TFT, it has comparatively ripe technology.
In active-matrix organic light emitting diode (AMOLED) panel (AMOLED), generally adopt the p channel transistor to form constant-current source and drive organic luminescent device.And the transistor of normal operation, the characteristic of n raceway groove (such as carrier mobility) obviously is better than the p channel transistor; Because carrier mobility is very low among the a-Si, and its hole mobility is more much lower than electron mobility, so a-Si TFT can only use the n slot field-effect transistor to make drive circuit.Therefore adopt n channel transistor driving OLED can improve the AMOLED performance.
When making drive circuit with the n slot field-effect transistor, in order to guarantee that it is operated in the saturation region, organic luminescent device must be received the drain electrode of n slot field-effect transistor, the drain electrode that is about to organic light-emitting device negative electrode and n slot field-effect transistor is joined, and this just requires organic luminescent device to have the inverted structure that hearth electrode is negative electrode.
When making employing inverted structure AMOLED, at first make pixel-driving circuit at substrate, then make organic luminescent device, at this moment, organic luminescent device can be made into the top ballistic device (transparent anode) of top bright dipping and the end ballistic device (transparent cathode) of bottom bright dipping.
The core of its manufacture craft is charge injection and the transport properties at electrode and organic material interface and organic material/organic material interface.Because the electron affinity of most of commonly used organic photoelectrical material less (approximate or less than 3eV) is so the organic light-emitting device negative electrode usually uses the metal of low work function.
Utilize the magnesium alloy silver electrode as the organic light-emitting device negative electrode such as the people such as V. Bulovi in 1997, produce the organic luminescent assembly of inversion type structure, but the Electron Injection Characteristics of its negative electrode is not good enough; And for example 2002, X. the people such as the people such as Zhou and S. R. Forrest utilize doping low work function active metal such as lithium (Li) between organic material, caesium (Cs) is as the N-shaped conductiving doping, promote electronics from the negative electrode injection organic material, thereby realize adopting the inversion type structure organic luminescent device of active metal.But these low workfunction metal have high activity, PROCESS FOR TREATMENT difficulty in a large amount of manufacture processes of organic light emitting display, and also the sequencing of metal and organic deposit is different, also can affect the electronic injection ability of metal/organic interface.And according to report lithium (Li), the metallic atoms such as caesium (Cs) are easy to diffusion in organic material, can affect device stability.
In a word, up to the present, all contain the active metal of low work function in inverted structure organic light-emitting device cathode construction and the manufacture craft, easily react and affect device property; On the other hand at present organic light emitting display is made for the PROCESS FOR TREATMENT of active metal and ultrathin membrane still difficult.
Summary of the invention
In view of this, technical problem to be solved by this invention provides organic light emitting apparatus of a kind of inverted structure and preparation method thereof, improves inversion type organic light-emitting device electronic injection ability; Improve the ability that device bears water in air steam and oxygen bad effect; Improve useful life and luminosity and the luminous efficiency of device; So that the stable negative electrode of low work function is compatible mutually with semiconducter process; Under the prerequisite with good performance, to process easyly, cost is comparatively cheap.
The objective of the invention is to be achieved through the following technical solutions:
A kind of manufacture method of reverse-structured organic light-emitting device is characterized in that, comprises the steps:
Deposition step: boride is placed in the specific container, and the heating boride makes its hydatogenesis to substrate, to form a boride film;
Treatment step: described boride film is carried out surface treatment;
Forming step: form electric transmission and luminescent layer, hole transmission layer, hole injection layer and anode layer at described boride film successively.
Wherein, boride film is as the boride cathode layer.The conductivity of boride material is high, and the conductivity with metallic lead (Pb) under the normal temperature is suitable, only a little less than the conductivity of metallic aluminium (A1).Therefore, this negative electrode has good conductivity, can directly inject the data electrode of negative electrode and AMOLED as the reflection type electronic of OLED, has simplified the manufacture craft of AMOLED, and the collocation transparent anode can be realized top-illuminating OLED.
Wherein, the method for heating boride can select to adopt electron beam evaporation, radio frequency sputtering or laser evaporation etc. in the deposition step.Can select to adopt the modes such as beam bombardment or plasma treatment in the treatment step.
Simultaneously, the excellent optical performance of boride film, when film thickness during less than 200 nm, its light transmittance is higher than 60 %.
With respect to cathode material commonly used, good conductivity, the chemical stability of boride material is high, work function is low, is fabulous cathode material.The electron work functon of cathode material commonly used is as shown in the table:
Metal material | Au | Al | Mg | In | Ag | Ca | Nd | Cr | Cu |
Electron work functon (eV) | 5.1 | 4.28 | 3.66 | 4.1-4.2 | 4.6 | 2.9 | 3.2 | 4.3-4.5 | 4.7 |
Adopt technique scheme, can well so that it is compatible mutually with semiconducter process, reduce difficulty of processing and production cost.Simultaneously, in OLED, electronics is injected into the organic semiconductor from the cathode layer that boride film forms under electric field action, this and boride material are widely used as electronic emission material in other electronic device, by the mode that heats (hot cathode) or high electric field (cold cathode) electronics is transmitted into the vacuum from boride cathode and compares, its structure and injection mechanism are fully different.
Be produced on above the organic material with the cathode layer of traditional OLED and compare, technique scheme also has advantages of following uniqueness:
1) can avoid high temperature in the boride film manufacturing process or plasma on the impact of organic layer
2) after boride film completes, be convenient to this film is processed, such as annealing in process etc., can optimize film, obtain low work function to be more convenient for.
3) after boride film completes, can adopt the method for dry method or wet method to carry out the etching moulding.
4) be convenient to easily regulate the thickness of boride film, and adopt reflection or transparent cathode/anode conductive layer, easily realize the multiple OLED structures such as transparent, that the top is luminous, the end is luminous.
Wherein, described boride adopts and selects to adopt the borides such as lanthanum hexaboride (LaB6), cerium boride (CeB6).
Preferably, described boride adopts lanthanum hexaboride.
Certainly, described boride can also be selected to adopt such as cerium boride (CeB6) etc.But, to find through applicant's years of researches and production practices, it is 2.6eV that the lanthanum hexaboride film cathode is convenient to optimize its work function, mates very much with organic material on energy level, is conducive to the injection of electronics.
Preferably, in the described deposition step, adopt evaporation electron beam heating evaporation boride, the vacuum degree of heating environment is
Pa; Described substrate rotates with 10 rev/mins the speed of rotation; The temperature range of described substrate is 150 to 400 degrees centigrade; The deposition rate of described boride film is 1.5 to 10 nm/minute.
The X-ray diffraction spectrum of lanthanum hexaboride (LaB6) film that electron beam evaporation is made as shown in Figure 6.
Certainly, boride film can also adopt such as radio frequency sputtering, or the method such as laser evaporation deposition forms.Above-mentioned preference of the present invention provides a kind of method of electron beam evaporation of optimization, is convenient to obtain the homogeneous film of 2.6eV work function.
Preferably, described treatment step adopts the specific described boride film of electron beam irradiation of processing, and continues 5 minutes, and the temperature that heats described boride film is 150 to 400 degrees centigrade; The beam current density of described processing electron beam is 20 milliamperes/square centimeter, and its voltage is 400 volts.
Preferably, described forming step comprises the steps: successively
On described boride film, the Alq3 film of thermal evaporation 60 nanometer thickness forms electric transmission and luminescent layer;
On described electric transmission and luminescent layer, the NPB of thermal evaporation 60 nanometer thickness forms hole transmission layer;
On described hole transmission layer, the thermal evaporation tungstic acid forms hole injection layer;
On described hole injection layer, splash-proofing sputtering metal or ito thin film form anode layer.
Preferably, described substrate is selected to adopt: glass substrate, metal substrate, silicon chip or ceramic substrate etc.
Wherein, glass substrate can be selected adopting quartz glass or alkali-free glass.
Preferably, described substrate also comprises: be attached to insulating barrier or transparency electrode on described glass substrate, metal substrate, silicon chip or the ceramic substrate.
Preferably, described deposition step also comprises:
The etching electrode step: the substrate that will be attached with described boride film is immersed in the crystal vessel that is loaded with electrochemical corrosive liquid, and described crystal vessel connects the negative pole of power supply, and described boride film connects the positive pole of power supply.
Preferably, also cover has a cask flask in described crystal vessel, is used for the electric field of shielding surrounding environment to the interference of described etching electrode step.
The reverse-structured organic light-emitting device that the present invention also further provides the manufacture method of described reverse-structured organic light-emitting device to make.
Compared with prior art the invention has the advantages that, at first, boride material is typical cathode material.Because work function is low, in electronic device, be widely used as electronic emission material, by the mode that heats (hot cathode) or high electric field (cold cathode) electronics is transmitted into the vacuum from boride cathode.And in OLED, electronics is injected into the organic semiconductor from the boride cathode layer under electric field action, is different with electron emission on structure and injection mechanism.Secondly, the inversion type organic luminescent device is at first made the boride cathode layer, and the cathode layer of traditional OLED is produced on above the organic material.The change of this production order has brought the characteristics of cathode layer uniqueness:
1) can avoid high temperature in the boride film manufacturing process or plasma on the impact of organic layer
2) after boride film completes, film is carried out annealing in process, can optimize film, obtain low work function.
3) after boride film completes, can adopt the method for dry method or wet method to carry out the etching moulding.
4) can easily regulate boride film thickness, and adopt reflection or transparent cathode/anode conductive layer, easily realize the multiple OLED structures such as transparent, that the top is luminous, the end is luminous.
Description of drawings
Fig. 1 is the structural representation of organic light emitting apparatus in the prior art
Fig. 2 is the structural representation of a kind of embodiment of reverse-structured organic light-emitting device of the present invention;
Fig. 3 is the structural representation of the another kind of embodiment of reverse-structured organic light-emitting device of the present invention;
Fig. 4 is the structural representation of the another kind of embodiment of reverse-structured organic light-emitting device of the present invention;
Fig. 5 is the structural representation of the another kind of embodiment of reverse-structured organic light-emitting device of the present invention;
Fig. 6 is lanthanum hexaboride film X-ray diffraction spectrum;
Fig. 7 is the environment schematic diagram of etching electrode among a kind of embodiment of the manufacture method of reverse-structured organic light-emitting device of the present invention.
Embodiment
The invention will be further described below in conjunction with accompanying drawing and preferred embodiment.
As shown in Figure 3, a kind of embodiment of reverse-structured organic light-emitting device comprises and being arranged in order: glass substrate 12, boride cathode layer 13, electric transmission and luminescent layer 14, hole transmission layer 15, adopt the hole injection layer 16 of inorganic material layer, and, transparent anode 17.
Wherein, boride adopts lanthanum hexaboride, and the lanthanum hexaboride of monocrystalline or polycrystalline is placed in the graphite crucible, makes the lanthanum hexaboride hydatogenesis to glass substrate with the electron beam heating.Typical manufacturing conditions is:
10 rev/mins of the rotary speeies of glass substrate 18;
150 to 400 ℃ of the temperature of glass substrate 18;
Deposition rate 1.5 is to 10(nm/min).
The lanthanum hexaboride film has higher optical transmittance, and magnesium silver alloy cathode thin film visible light under this thickness of same thickness almost can not see through.Wavelength be the visible light of 400nm to 750nm to the transmitance of 180nm lanthanum hexaboride film greater than 65%, be 70% 5%, peak transmission 74% is positioned at the 496nm place.
As shown in Figure 6, crystal face 100 diffraction maximums are very strong in the X-ray diffraction spectrum of lanthanum hexaboride film, and are more much higher than the diffraction maximum of other crystal face, illustrate that prepared lanthanum hexaboride film is preferred orientation.The work function of this orientation lanthanum hexaboride film is minimum, and the effusion function of this lanthanum hexaboride film reaches 2.6eV after tested.
Then, before further depositing organic material is made electric transmission and luminescent layer, hole transmission layer, hole injection layer and anode layer, with specific processing electron beam treatment lanthanum hexaboride film surface, typical processing parameter is: beam current density is that 20 milliamperes/square centimeter, high pressure are that 400V, lanthanum hexaboride film temperature are that 150-400 ℃, time are 5 minutes.
Then successively the Alq3 film of thermal evaporation 60 nanometer thickness as electron transfer layer and luminescent layer; The NPB of 60 nanometer thickness is as hole transmission layer, and to the damage of organic layer, the thermal evaporation tungstic acid is as hole injection layer when preventing sputter, and last splash-proofing sputtering metal or ito thin film are as anode.
As shown in Figure 2, reverse-structured organic light-emitting device another kind of embodiment comprises and being arranged in order: glass substrate 6, transparency electrode 7, boride cathode layer 8, electric transmission and luminescent layer 9, and hole transmission layer 10, and, as the reflection anode 11 of anode layer.
As shown in Figure 4, reverse-structured organic light-emitting device another kind of embodiment comprises and being arranged in order: glass substrate 18, transparency electrode 19, boride cathode layer 20, electron transfer layer and luminescent layer 21, hole transmission layer 22, hole injection layer 23, and, as the transparent anode 24 of anode layer.
The difference of Fig. 2, Fig. 4 and embodiment maximum shown in Figure 3 is, has adhered to first transparency electrode on glass substrate, and then adopts said method paying the boride cathode layer in transparency electrode.Like this, be attached with the glass substrate integral body of transparency electrode as substrate.
As shown in Figure 5, the another kind of embodiment of reverse-structured organic light-emitting device, the top illuminating device structure chart that the N-type thin-film transistor drives.
Comprising: glass substrate 25, insulating barrier 26, gate insulator 27, interlayer insulating film 28, source electrode 29, OLED assembly 30, N+ doped region 31, polysilicon raceway groove 32, grid 33, and, drain electrode 34.
Wherein, source electrode 29 also is the negative electrode of OLED.
The manufacture method of above-described embodiment is as follows:
(1) on the glass substrate that quartz glass or alkali-free glass etc. consists of, the using plasma chemical vapour deposition technique forms insulating barrier 26 and a-Si film successively.
(2) a-Si film dehydrogenation
(3) the surface irradiation laser beam of a-Si film carried out annealing in process, and a-Si dissolved recrystallize and form the semiconductor film 32 that is consisted of by poly-Si.
(4) Poly-Si island definition: on semiconductor film, form the island polysilicon by photoetching process, and again form N-type impurity range 31 by photoetching.Behind Impurity injection, utilize RTA (rapid thermal annealing) method to anneal.Form source region 31a and drain region 31b.
(5) deposition of gate insulation layer: adopt the PECVD method at semiconductor film, form dielectric film 27.
(6) on gate insulating film 27, form the aluminum metal film by sputtering method, with as grid electric conductor film 33.
(7) adopt self-registered technology to form N+ doped region 31.
(8) deposition interlayer insulating film 28 and adopt photoetching process forms contact hole.
(9) on the substrate that above-mentioned steps forms, adopt the lanthanum hexaboride with monocrystalline or polycrystalline to be placed in the graphite crucible, make the lanthanum hexaboride hydatogenesis to this substrate with the electron beam heating, to form the lanthanum hexaboride film as lanthanum hexaboride source-drain electrode layer.
(10) as shown in Figure 5, adopt the method for electrochemical corrosion to etch source- drain electrode 34 and 29 at lanthanum hexaboride source-drain electrode layer.Electrochemical corrosive liquid is selected:
Electrochemical corrosive liquid is placed in the graphite tube 400.In graphite tube 400 bottoms one metallic conductor 600 and graphite tube 400 good contacts arranged, it is as the negative electrode in the electrochemical corrosion course.In addition, be mounted with polyvinyl fluoride shielding cylinder 200 in graphite tube 400, be used for shielding graphite tube 400 peripheral electric fields, graphite tube 400 connects the negative electrode of external power 500.Adjust at last substrate 300 with lanthanum hexaboride source-drain electrode layer and the distance between the metallic conductor 600, then plugged 500 carries out electrochemical corrosion.
(10) with the specific electron beam treatment lanthanum hexaboride film surface of processing, typical processing parameter is: beam current density is that 20mA/ square centimeter, high pressure are that 400V, lanthanum hexaboride film temperature are that 150-400 ℃, time are 5 minutes.
(11) organic illuminating element 30 is formed on the conductive layer 29.Luminous on the direction relative with substrate.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (2)
1. the manufacture method of a reverse-structured organic light-emitting device is characterized in that, comprises the steps:
Deposition step: the lanthanum hexaboride of monocrystalline or polycrystalline is placed in the graphite crucible, makes the lanthanum hexaboride hydatogenesis to the substrate that forms through following step (1)~(8) with the electron beam heating, to form the lanthanum hexaboride film as lanthanum hexaboride source, drain electrode layer; The formation of described substrate comprises the steps: (1) on glass substrate, and the using plasma chemical vapour deposition technique forms insulating barrier and a-Si film successively; (2) a-Si film dehydrogenation; (3) the surface irradiation laser beam of a-Si film carried out annealing in process, and a-Si dissolved recrystallize and form the semiconductor film that is consisted of by poly-Si; (4) Poly-Si island definition: on semiconductor film, form the island polysilicon by photoetching process, and again form the N-type impurity range by photoetching, behind Impurity injection, utilize the rapid thermal annealing method to anneal, form source region and drain region; (5) deposition of gate insulation layer: adopt the PECVD method at semiconductor film, form gate insulating film; (6) on gate insulating film, form the aluminum metal film by sputtering method, with as grid electric conductor film; (7) adopt self-registered technology to form the N+ doped region; (8) deposition interlayer insulating film, and adopt photoetching process, form contact hole;
Described deposition step also comprises: the etching electrode step: adopt the method for electrochemical corrosion to etch source, drain electrode in lanthanum hexaboride source, drain electrode layer, electrochemical corrosive liquid is selected: phosphoric acid: absolute ethyl alcohol: the solution of water=5:20:20;
Treatment step: described boride film is carried out surface treatment;
Forming step: form electric transmission and luminescent layer, hole transmission layer, hole injection layer and anode layer at described boride film successively;
Described forming step comprises the steps: successively
On described boride film, the Alq3 film of thermal evaporation 60 nanometer thickness forms electric transmission and luminescent layer;
On described electric transmission and luminescent layer, the NPB of thermal evaporation 60 nanometer thickness forms hole transmission layer;
On described hole transmission layer, the thermal evaporation tungstic acid forms hole injection layer;
On described hole injection layer, splash-proofing sputtering metal or ito thin film form anode layer.
2. the manufacture method of reverse-structured organic light-emitting device as claimed in claim 1 is characterized in that, also cover has a cask flask in described crystal vessel, is used for the electric field of shielding surrounding environment to the interference of described etching electrode step.
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CN1407836A (en) * | 2001-08-24 | 2003-04-02 | 株式会社半导体能源研究所 | Luminous device |
CN101179115A (en) * | 2007-12-17 | 2008-05-14 | 中国科学院长春应用化学研究所 | White light organic electroluminescent device based on fluorescent dye and its preparation method |
CN101249580A (en) * | 2008-03-14 | 2008-08-27 | 江苏大学 | Electrochemical-laser mask focusing micro-etching processing method and device |
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CN1407836A (en) * | 2001-08-24 | 2003-04-02 | 株式会社半导体能源研究所 | Luminous device |
CN101179115A (en) * | 2007-12-17 | 2008-05-14 | 中国科学院长春应用化学研究所 | White light organic electroluminescent device based on fluorescent dye and its preparation method |
CN101249580A (en) * | 2008-03-14 | 2008-08-27 | 江苏大学 | Electrochemical-laser mask focusing micro-etching processing method and device |
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