CN102201546A - Organic electroluminescent device with boss interface structure and preparation method thereof - Google Patents
Organic electroluminescent device with boss interface structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic electroluminescent device with a boss interface structure. The device consists of a glass substrate, an anode layer, an organic functional layer with one or a plurality of layers of interface structures, an inorganic functional layer and a cathode layer in turn from bottom to top, wherein the organic functional layer and the cathode layer are provided with boss interface structures, namely each interface consists of a plane layer and at least one boss which is integrally arranged on the plane layer, and the boss which is positioned on the next plane layer of the interface is embedded into the last plane layer of the interface. By utilizing the boss interface structure, on one hand, the area of a current carrier composite interface is enlarged, and the functions of dispersing excitons and reducing exciton quenching are exerted; and on the other hand, coupled output of waveguide light of the device is improved, and the aim of improving the luminous efficiency of the device is fulfilled. Experiments prove that: the luminous efficiency of an organic electrophosphorescent device with the boss interface structure is improved by about 10 to 80 percent, and the luminous efficiency of an organic electrofluorescent device is improved by about 10 to 110 percent.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, relate to a kind of organic electroluminescence device, particularly a kind of organic electroluminescence device with boss interfacial structure.The invention still further relates to the preparation method of this organic electroluminescence device.
Background technology
Organic electroluminescence device because have from main light emission, low-voltage DC driven, solidify entirely, advantages such as the visual angle is wide, color is abundant, easy and integrated circuit coupling, in flat panel display and the lighting field prospect that is widely used.Product based on organic electroluminescent comes out at present, but also has distance from its extensive use, device lifetime is short, efficient is low is its principal element of applying of restriction, address this problem, on the one hand being the material (comprising carrier transmission material, luminescent material, electrode material etc.) that exploitation is used for the function admirable of organic electroluminescence device, is that the structure to luminescent device is optimized on the other hand.
1989, the people such as C.W.Tang of U.S. Kodak company (J.Appl.Phys., 1989,65,913) doped with fluorescent dyes in the luminescent layer of device improved the efficient of OLEDs.1999, people such as the Forrest of Princeton University Doping Phosphorus photoinitiator dye in the luminescent layer of device improve device efficient (Nature 1998,395,151; Appl. Phys. Lett. 1999,75, and 4).The introducing of phosphorescent coloring makes device can effectively utilize singlet and triplet excitons simultaneously, and the luminous efficiency of device has obtained significantly promoting.Because the triplet excitons diffusion length is big, compare with the organic electroluminescence fluorescent device, organic electro phosphorescent device generally will insert electronic barrier layer between hole transmission layer and luminescent layer, insert hole blocking layer between luminescent layer and electron transfer layer, to improve the luminous efficiency of device.The greatest problem that organic electro phosphorescent device exists is the cancellation of triplet excitons under the high current density, therefore, compares the less stable of phosphorescence device with fluorescent device.
The structure optimization of organic electroluminescence device also is the important channel of improving the device luminous efficiency.In the individual layer OLED device in early days,, cause the luminous efficiency of device not good because of injected electrons or hole differ greatly at the transfer ability of this layer.Bilayer afterwards, three layers structure, since improved charge carrier injection, transport and compound, device efficiency is effectively improved, in device, insert carrier injection layer, exciton barrier-layer etc. afterwards and developed sandwich construction, improve the injection of charge carrier, and charge carrier is limited in the luminous zone effectively, improve the recombination probability of charge carrier, thereby improved the luminous efficiency of device.In recent years, developed optical microcavity structure (Appl. Phys. Lett. 1996,69,1997 again; J. Appl. Phys. 1999,86,2407), series-mode frame (Appl. Phys. Lett. 2004,84,167; Adv. Funct. Mater. 2010,20, and 1) and pin structure (Appl. Phys. Lett. 2006,89,061111).Utilize the microcavity resonance effects that device efficiency is promoted, but this structure complicated process of preparation, and luminous intensity and glow color change with the visual angle; Series-mode frame can make the efficient of device and life-span all get a promotion, but this technology intermediate connecting layer is made complexity, cost is high, the driving voltage height; The pin structure can reduce the operating voltage of device greatly, improves the luminous efficiency of device, but the life-span of device remain to be improved, and manufacture craft is complicated equally, the cost height.
Summary of the invention
The purpose of this invention is to provide a kind of organic electroluminescence device with boss interfacial structure, utilize this boss interfacial structure, can reduce device current, increase charge carrier compound interface area, reduce the exciton cancellation, and the coupling output that can improve device waveguide light, thereby reach the purpose that improves the device luminous efficiency.
Organic electroluminescence device and existing organic electroluminescence device structural similarity with boss interfacial structure provided by the invention bottom-uply is made up of substrate of glass, anode layer, the organic function layer with one or more layers interfacial structure, inorganic functional layer and cathode layer successively.Wherein, organic function layer can be made up of hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer; Also can form by hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer; Also can form by hole transmission layer, electronic barrier layer, luminescent layer, electron transfer layer; Also can form by hole transmission layer, luminescent layer, electron transfer layer; Can also single form by luminescent layer.Described inorganic functional layer is as electron injecting layer.
Different with existing organic electroluminescence device structure is, described organic function layer of organic electroluminescence device of the present invention and cathode layer have the boss interfacial structure, be that each interface is to be made of one the boss of being no less than that a plane layer and one are located on this plane layer, and the boss that is arranged on next plane layer of interface embed a plane layer on the interface.That is to say, the organic functions bed boundary that promptly is connected with anode layer except that basecoat has the complete plane layer, plane layer of the present invention is not the plane layer on the absolute sense, the bottom of a plane layer on the interface is owing to the embedding of next plane layer convex platform of interface forms and embed the corresponding groove of boss.
On the organic electroluminescence device of the present invention, the boss quantity that is provided with on the plane layer of each interface of organic function layer and cathode layer equates that the position is relative.
Further, in the above-mentioned organic electroluminescence device with boss interfacial structure, boss thickness on its next plane layer of organic functions bed boundary is not more than the thickness that is positioned at an organic function layer plane layer on its interface, can embed fully on the interface in the plane layer to guarantee boss on next plane layer of interface.
Need to prove, inorganic functional layer of the present invention is as electron injecting layer, its thickness is much smaller than each interface of organic function layer, so can not form the boss of thickness as organic function layer and cathode layer, just on the organic functions laminar surface that is adjacent, form the thin layer of a uniform thickness consistent with its surface configuration.
In the organic electroluminescence device that the present invention proposes with boss interfacial structure, the shape of its described boss can be a rectangle, also can be trapezoidal, but the shape of boss is not limited thereto, all shapes with boss characteristic all should belong to the boss of indication of the present invention.
Preparing above-mentioned a kind of method with organic electroluminescence device of boss interfacial structure is:
1) handles the electro-conductive glass that has anode layer with conventional method;
2) electro-conductive glass of handling well is placed the vacuum evaporation stove, anode layer faces down, and distillation needs the organic functions layer material powder attached to the anode layer surface, grows into a plane rete at the anode layer surface deposition;
3) it is parallel and be close to the below of above-mentioned plane rete to have a mould of one or more slit with one, and the above-mentioned organic functions layer material powder that distils once more is in step 2) deposition growing forms one or more boss on the plane rete of preparation;
4) remove mould, continue other organic function layers of evaporation, inorganic functional layer and cathode layer, the gaseous molecular after the distillation continues deposition growing on the rete with boss that step 3) forms, the organic electroluminescence device that obtains having the boss interfacial structure.
The present invention also provides a kind of particular manufacturing craft that is applicable to that above-mentioned preparation method uses, this mould can be used to prepare the organic electroluminescence device with 0～3 boss, and can prepare 4 organic electroluminescence devices with same structure on same electro-conductive glass at every turn.
Above-mentioned particular manufacturing craft of the present invention is a circular die, is divided into A, B, four zones of C, D, and each zone subdivision becomes three parts, wherein:
The A1 place of zone A has a square hole, and the A2 place has the single seam that is symmetrically distributed up and down, and the A3 place has 4 slots;
The B1 place of area B has the square hole with A1, and the B2 place has the double slit that is symmetrically distributed up and down, and the B3 place has 4 slots with A3;
The C1 place of zone C has the square hole with A1, and the C2 place has three seams that are symmetrically distributed up and down, and the C3 place has 4 slots with A3;
The D1 place of region D has the square hole with A1, and the D2 place is seamless, and the D3 place has 4 slots with A3;
The uniform circumference that is looped around circular die in described zone.
The present invention is by constructing the boss interfacial structure on the organic functions bed boundary of organic electroluminescence device and cathode layer, increased the area of charge carrier compound interface on the one hand, played the effect that disperses exciton, reduces the exciton cancellation, improve the coupling output of device waveguide light on the other hand, thereby reached the purpose that improves the device luminous efficiency.It is about 10～80% that the luminous efficiency that experiment showed, the organic electro phosphorescent device that adopts boss interfacial structure of the present invention improves, and adopts the luminous efficiency of the organic electroluminescence fluorescent device of boss interfacial structure of the present invention to improve about 10～110%.
Description of drawings
Fig. 1 is the sectional view that the interface has the organic electroluminescence device of a rectangular boss.
Fig. 2 is the sectional view that the interface has the organic electroluminescence device of two rectangular boss.
Fig. 3 is the sectional view that the interface has the organic electroluminescence device of three rectangular boss.
Fig. 4 is the sectional view that the interface has the organic electroluminescence device of a trapezoid boss.
Fig. 5 is the sectional view that the interface has the organic electroluminescence device of two trapezoid boss.
Fig. 6 is the sectional view that the interface has the organic electroluminescence device of three trapezoid boss.
Fig. 7 is used to prepare the structural representation with boss interfacial structure organic electroluminescence device particular manufacturing craft;
Fig. 8 is the regional A structural representation of mould shown in Figure 7.
Fig. 9 is the area B structural representation of mould shown in Figure 7.
Figure 10 is the zone C structural representation of mould shown in Figure 7.
Figure 11 is the region D structural representation of mould shown in Figure 7.
Figure 12 is the shape through the indium tin oxide anode layer of carving decorations.
Figure 13 is the device B of embodiment 1 preparation and brightness-current density curve of Comparative Examples device A.
Figure 14 is the device B of embodiment 1 preparation and current efficiency-current density curve of Comparative Examples device A.
Figure 15 is the device C of embodiment 2 preparations and brightness-current density curve of Comparative Examples device A.
Figure 16 is the device C of embodiment 2 preparations and current efficiency-current density curve of Comparative Examples device A.
Figure 17 is the device D of embodiment 3 preparations and brightness-current density curve of Comparative Examples device A.
Figure 18 is the device D of embodiment 3 preparations and current efficiency-current density curve of Comparative Examples device A.
Figure 19 is the device F of embodiment 4 preparations and brightness-voltage curve of Comparative Examples device E1, E2.
Figure 20 is the device F of embodiment 4 preparations and current efficiency-current density curve of Comparative Examples device E1, E2.
Figure 21 is the device G of embodiment 5 preparations and brightness-voltage curve of Comparative Examples device E1, E2.
Figure 22 is the device G of embodiment 5 preparations and current efficiency-current density curve of Comparative Examples device E1, E2.
Figure 23 is the device H of embodiment 6 preparations and brightness-voltage curve of Comparative Examples device E1, E3.
Figure 24 is the device H of embodiment 6 preparations and current efficiency-current density curve of Comparative Examples device E1, E3.
Figure 25 is the device I of embodiment 7 preparations and brightness-voltage curve of Comparative Examples device E1, E4.
Figure 26 is the device I of embodiment 7 preparations and current efficiency-current density curve of Comparative Examples device E1, E4.
Figure 27 is the device L of embodiment 8 preparations and brightness-current density curve of Comparative Examples device K1, K2.
Figure 28 is the device L of embodiment 8 preparations and current efficiency-current density curve of Comparative Examples device K1, K2.
Figure 29 is the device M of embodiment 9 preparations and brightness-current density curve of Comparative Examples device K1, K3.
Figure 30 is the device M of embodiment 9 preparations and current efficiency-current density curve of Comparative Examples device K1, K3.
Figure 31 is the device N of embodiment 10 preparations and brightness-current density curve of Comparative Examples device K4, K5.
Figure 32 is the device N of embodiment 10 preparations and current efficiency-current density curve of Comparative Examples device K4, K5.
Among Fig. 1～Fig. 6: 1 is transparent glass substrate, 2 is anode layer, adopts indium tin oxide (ITO), and 3 is hole transmission layer, 4 is electronic barrier layer, 5 is luminescent layer, can be the main body luminescent layer, also can be the luminescent layer that doped with fluorescent dyes or phosphorescent coloring form in material of main part, 6 is hole blocking layer, 7 is electron transfer layer, and 8 is electrodeless functional layer (electron injecting layer), and 9 is cathode layer.3～7 layers are referred to as organic function layer.Wherein, 3,4,6,7 organic function layer can be selected going or staying according to concrete device.
Embodiment
All embodiment of the present invention all adopt following particular manufacturing craft, prepare the organic electroluminescence device with boss interfacial structure with following preparation method.
The structure of particular manufacturing craft such as Fig. 7 are a circular die, are divided into A, B, four zones of C, D, and each zone subdivision becomes three parts, the uniform circumference that is looped around circular die in described zone.Wherein:
Structure such as Fig. 8 of zone A have the square hole of one 10mm * 10mm at A1 place, A2 place has singly stitching of being symmetrically distributed up and down, and the dimension of each seam is 20mm * 0.5mm, and the A3 place has the slot of 4 3mm * 9mm;
The structure of area B such as Fig. 9 have the square hole of 10mm * 10mm at the B1 place, the B2 place has the double slit that is symmetrically distributed up and down, and the dimension of each seam is 20mm * 0.5mm, and the B3 place has the slot of 4 3mm * 9mm;
The structure of zone C such as Figure 10 have the square hole of 10mm * 10mm at the C1 place, the C2 place has three seams that are symmetrically distributed up and down, and the dimension of each seam is 20mm * 0.5mm, and the C3 place has the slot of 4 3mm * 9mm;
The structure of region D such as Figure 11 have the square hole with 10mm * 10mm of A1 at the D1 place, the seamless atresia in D2 place, and the D3 place has the slot of 4 3mm * 9mm.
A1, B1, C1, D1 is identical, is the rectangular hole of 10mm * 10mm, uses during for the evaporation except that following particular case; A3, B3, C3, D3 is identical, is the slot of four 3mm * 9mm, for the evaporation cathode layer is used; A2, B2, C2 has single seam, double slit and three seams that are symmetrically distributed up and down respectively, each stitches the wide 0.5mm that is, for evaporation ground floor organic functions bed boundary to form boss usefulness, A2 is that 1 boss in evaporation interface is used, B2 is that 2 boss in evaporation interface are used, C2 is 3 the boss usefulness in evaporation interface, and the seamless atresia of D2 is for using at the straight interface of evaporation.
The above-mentioned die size that is of a size of the use of the preparation embodiment of the invention, but above-mentioned yardstick is not the qualification to mould, can adjust the size of mould in the practical application according to the size of preparation organic electroluminescence device.
The A district is 1 the boss usefulness in evaporation interface, in 3 parts, A1 evaporation organic layer and inorganic layer, A2 evaporation organic layer projection section, A3 evaporation cathode layer, can be in each organic functions bed boundary and cathode layer form a boss.
The B district is 2 boss usefulness of evaporation, in 3 parts, and B1 evaporation organic layer and inorganic layer, B2 evaporation organic layer projection section, B3 evaporation cathode layer can form two boss in each organic functions bed boundary and cathode layer.
The C district is 3 boss usefulness of evaporation, in 3 parts, and C1 evaporation organic layer and inorganic layer, C2 evaporation organic layer projection section, C3 evaporation cathode layer can form three boss in each organic functions bed boundary and cathode layer.
The organic electroluminescence device of preparation does not have boss in the D district, in 2 live parts, and each organic function layer of D1 evaporation, D3 evaporation cathode layer can prepare the straight reference organic electroluminescence device in interface, and each functional layer interface is the plane.
The organic electroluminescence device that each embodiment has the boss interfacial structure adopts following preparation method's preparation.
1, cleaning, etching, oven dry, treatment with ultraviolet light electro-conductive glass
1) cleaning specification with deionized water dipping is electro-conductive glass 10～15min of 20mm * 20mm, dries;
2) clean electro-conductive glass 10～15min with the acetone dipping, dry;
3) the tin indium oxide face of determining electro-conductive glass is for positive, with wide be the front of the adhesive tape stickup electro-conductive glass of 8mm;
4) hydrochloric acid 50ml is placed beaker, add zinc granule 5g, stir 10～15min, be mixed with etching liquid;
5) electro-conductive glass that will post adhesive tape places beaker, and the position that the submergence etching is not covered by adhesive tape is taken out after the etching and dried, and throws off adhesive tape, forms the conducting film of shape shown in Figure 12;
6) electro-conductive glass after the etching is cleaned with cotton balls after, place ultrasonic cleaner, add deionized water, ultrasonic cleaning 10～15min dries;
7) electro-conductive glass after will drying places ultrasonic cleaner, adds acetone, and ultrasonic cleaning 10～15min dries;
8) electro-conductive glass after the ultrasonic cleaning is placed quartz boat, in vacuum drying chamber, 40 ℃ ± 5 ℃ drying 10～15min;
9) dried electro-conductive glass is placed the UV-irradiation case, tin indium oxide faces up, and opens ultraviolet source, uv power 8W, wavelength 254nm, irradiation time 8～10min.
2, the vacuum evaporation preparation has the organic electroluminescence device of interface boss structure
1) opens the vacuum evaporation stove, four electro-conductive glass of handling well are placed on the rotating disk at furnace chamber top, the electro-conductive glass tin indium oxide faces down, and fix with above-mentioned special-purpose film tool, the film tool is parallel with electro-conductive glass, and at first with the centre of four electro-conductive glass sheets respectively with the center aligned of the A1, the B1 that have 10mm * 10mm square aperture, C1, D1;
2), comprise that hole transport layer material, electronic barrier layer material, luminescent layer material of main part, luminescent layer dopant material, hole barrier layer material, electric transmission layer material, electron injecting layer material, cathode layer materials place each evaporation crucible of furnace chamber bottom respectively with deposition material;
3) the quartzy Thicknesser probe on the adjustment furnace wall, the electro-conductive glass on the high alignment probe rotating disk, low alignment probe holds the crucible of dopant;
4) close vacuum evaporation stove bell, and sealing;
5) open oil-sealed rotary pump, taking out in the furnace chamber is vacuum, and making the interior vacuum degree of stove is 3Pa; Open molecular pump, taking out in the furnace chamber is vacuum, and making the interior vacuum degree of stove is 0.0005Pa, and keeps constant;
6) open the bombarding current controller, bombardment furnace chamber electro-conductive glass, electric current 50mA, time 8～10min improves the electro-conductive glass work function, and purifies furnace chamber;
7) open rotating disk, electro-conductive glass is rotated with rotating disk;
8) open quartzy Thicknesser probe;
9) each functional layer of evaporation;
I, evaporation hole transmission layer
Unlatching fills the crucible power supply of hole mobile material, and electric current remains on 28～30mA, the distillation of hole mobile material powder, and the deposition growing on electro-conductive glass of the gaseous molecular after the distillation becomes the plane rete, and thickness is 10～25nm; Close this crucible power supply then, stop evaporation;
II, evaporation hole transmission layer boss
Utilize manipulator to rotate the rotating disk of placing the electro-conductive glass sheet, with A2, B2, C2, the D2 on four electro-conductive glass sheets difference aligning film tools, open the crucible power supply that fills hole mobile material once more, electric current remains on 28～30mA, the distillation of hole mobile material powder, and the gaseous molecular after the distillation continues deposition growing on the plane rete of step I preparation, forming width respectively is 0.5mm, highly be one, two, three of the boss of 5～20nm, close this crucible power supply then, stop evaporation; Because the seamless atresia in D2 place, so hole mobile material can not continue deposition growing again on the plane rete that deposits hole mobile material that is positioned under the D2, i.e. the device of D2 place electro-conductive glass sheet preparation does not form the interface boss, and the interface is a plane;
III, evaporation electronic barrier layer
Rotate the rotating disk of placing the electro-conductive glass sheet once more, with four electro-conductive glass sheets A1, B1, C1 on the aligning film tool respectively once more, D1, unlatching fill the electronic barrier layer material the crucible power supply, electric current remains on 28～30mA, electronic barrier layer material powder distillation, gaseous molecular after the distillation continues to form deposition growing on the rete with boss in the step II, evaporation thickness is 10～20nm, closes this crucible power supply then, stops evaporation;
IV, evaporation luminescent layer
For luminescent layer doping device, unlatching fills the crucible power supply of material of main part and dopant, electric current remains on 26～28mA and 24～26mA respectively, material of main part and dopant become gaseous state by solid-state distillation, the material of main part after the distillation and the gaseous molecular of dopant continue while deposition growing on the rete with boss that the step III forms, by the doping ratio of controlled doping agent in main body of just popping one's head in, evaporation thickness is 20～30nm, form luminescent layer, close this crucible power supply then, stop evaporation; For the non-doping device of luminescent layer, unlatching fills the crucible power supply of luminescent material, electric current remains on 24～26mA, luminescent material becomes gaseous state by solid-state distillation, the gaseous molecular of the luminescent material after the distillation continues deposition growing on the rete with boss that the step III forms, and evaporation thickness is 20～30nm, forms luminescent layer, close this crucible power supply then, stop evaporation;
V, evaporation hole blocking layer
Unlatching fills the crucible power supply of hole barrier layer material, electric current remains on 26～28mA, the hole barrier layer material is by the solid-state gaseous state that sublimes up into, distillation back gaseous molecular is continuing deposition growing on the rete with boss that the step IV forms, evaporation thickness is 10～20nm, close this crucible power supply then, stop evaporation;
VI, evaporation electron transfer layer
Unlatching fills the crucible power supply of electric transmission layer material, electric current remains on 30～32mA respectively, electric transmission layer material powder is by the solid-state gaseous state that sublimes up into, distillation back gaseous molecular is continuing deposition growing on the rete with boss that the step V forms, thickness is 30～40nm, close this crucible power supply then, stop evaporation;
VII, evaporation electron injecting layer
Unlatching fills the crucible power supply of electron injecting layer material, electric current remains on 35～40mA, electron injecting layer material powder is by the solid-state gaseous state that sublimes up into, distillation back gaseous molecular continues deposition growing on the rete with boss that the step VI forms, thickness is 1～1.5nm, close this crucible power supply then, stop evaporation;
VIII, evaporation cathode layer
Utilize manipulator to rotate the rotating disk of placing the electro-conductive glass sheet for the third time, with A3, B3, the C3 on four electro-conductive glass sheets difference aligning film tools, D3, unlatching fills the crucible power supply of cathode material, electric current remains on 35～40mA, cathode material is by the solid-state gaseous state that sublimes up into, and distillation back gaseous molecular continues deposition growing on the rete with boss that the step VII forms, and thickness is 150nm～200nm;
In preparation process, quartzy Thicknesser probe is measured evaporation thickness, and shows its one-tenth-value thickness 1/10 by display screen;
Wherein, the evaporation step of above organic function layer can be selected going or staying according to concrete device;
10) close evaporation stove crucible heater, the interior temperature of stove is cooled to room temperature under the vacuum state;
11) closure molecule vacuum pump, oil-sealed rotary pump are opened vent valve, open the evaporation bell, take out electro-conductive glass, and it is the organic electroluminescence device of 3mm * 3mm that four identical light-emitting areas are all arranged on the every electro-conductive glass;
12) device to preparation encapsulates with epoxide resin material, and airtight lucifuge is stored in cool place, drying, clean environment, waterproof, protection against the tide, anti-oxidation, acid-proof alkali salt erosion, 20 ℃ ± 2 ℃ of temperature, relative humidity≤10%.
3, detect, analyze, characterize, contrast
Photoelectric properties to the organic electroluminescence device prepared detect, analyze, characterize, contrast: carry out luminosity-voltage characteristic with ST-900M type photometer and measure; Carry out voltammetric characteristic measuring with 2400 digital source tables.
Adopt above-mentioned particular manufacturing craft and preparation method, can prepare simultaneously at every turn have 1 boss respectively, 2 boss, 3 boss and do not have 4 kinds of organic electroluminescence devices of boss, and every kind of device all is to prepare 4 organic electroluminescence devices with identical structure on same electro-conductive glass.
Anode layer adopts indium tin oxide (ITO), hole transport layer material adopts N, N'-two (1-naphthyl)-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamines (NPB, purity 99.99%), the luminescent layer material of main part adopts 4,4'-two (9-carbazole)-biphenyl (CBP, purity 99.99%), the luminescent layer dopant adopts phosphorescent dopants three (2-phenylpyridine) iridium (Ir (ppy)
3, purity 99.99%), the hole barrier layer material adopts two (2-methyl-oxine)-4-xenol aluminium (BAlq, purity 99.99%), and electron transfer layer adopts oxine aluminium (Alq
3, purity 99.99%), electron injecting layer adopts lithium fluoride (LiF, purity 99.99%), and cathode layer adopts aluminium electrode (Al, purity 99.99%).The face resistance of indium tin oxide-coated glass is 10 Ω/.
The Comparative Examples device is to be obtained by D district shown in Figure 7, and its structure is: ITO/NPB (30nm)/CBP:Ir (ppy)
3(30nm, 6wt%)/BAlq (10nm)/Alq
3(30nm)/LiF(1nm)/and Al (150nm), each functional layer interface is straight interface, device number is A.
ITO/NPB (20nm)/NPB projection (10nm)/CBP:Ir (ppy)
3(30nm, 6wt%)/BAlq (10nm)/Alq
3(30nm)/and LiF/Al (150nm), boss thickness 10nm, device number is B.
Figure 13,14 is respectively brightness-current density, the current efficiency-current density curve chart of embodiment 1 device B and Comparative Examples device A.At 200mA/cm
2, the brightness of embodiment 1 device B is 24701cd/m
2, the brightness of Comparative Examples device A is 21286cd/m
2The maximum current efficient of embodiment 1 device B is 20.8cd/A, and the maximum current efficient of Comparative Examples device A is 17.3cd/A, and efficient has improved 20.2%.
ITO/NPB (20nm)/NPB projection (10nm)/CBP:Ir (ppy)
3(30nm, 6wt%)/BAlq (10nm)/Alq
3(30nm)/and LiF (1nm)/Al (150nm), boss thickness 10nm, device number is C.
Figure 15,16 is respectively brightness-current density, the current efficiency-current density curve chart of embodiment 2 device C and Comparative Examples device A.At 200mA/cm
2, the brightness of embodiment 2 device C is 25138cd/m
2, the brightness of Comparative Examples device A is 21286cd/m
2The maximum current efficient of embodiment 2 device C is 24.3cd/A, and the maximum current efficient of Comparative Examples device A is 17.3cd/A, and efficient has improved 40.5%.
ITO/NPB (20nm)/NPB projection (10nm)/CBP:Ir (ppy)
3(30nm, 6wt%)/BAlq (10nm)/Alq
3(30nm)/LiF(1nm)/Al(150nm), boss thickness 10nm, device number is D.
Figure 17,18 is respectively brightness-current density, the current efficiency-current density curve chart of embodiment 1 device D and Comparative Examples device A.At 200mA/cm
2, the brightness of embodiment 3 device D is 34553cd/m
2, the brightness of Comparative Examples device A is 21286cd/m
2The maximum current efficient of embodiment 2 device D is 30.8cd/A, and the maximum current efficient of Comparative Examples device A is 17.3cd/A, and efficient has improved 78%.
Anode layer adopts indium tin oxide (ITO), and hole transport layer material adopts N, N'-two (1-naphthyl)-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamines (NPB, purity 99.99%), the luminescent layer material adopts 2-(2-hydroxy phenyl) benzothiazole zinc (Zn (BTZ)
2, purity 99.99%), the double electron transfer layer of doing, LiF does electron injecting layer, and cathode layer adopts the Al electrode.The face resistance of indium tin oxide-coated glass is 10 Ω/.
The Comparative Examples device is to be obtained by D district shown in Figure 7, and each functional layer interface is straight interface, is respectively:
ITO/NPB (40nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), device number is E1;
ITO/NPB (30nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), device number is E2;
ITO/NPB (20nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), device number is E3;
ITO/NPB (15nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), device number is E4.
ITO/NPB (30nm)/NPB projection (10nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), boss thickness 10nm, device number is F.
Figure 19,20 has provided device E1, E2, voltage-brightness of F, current density-current efficiency curve, under the 6V, and the brightness 1044cd/m of device F
2, the brightness of comparative device E1 is 480cd/m
2, the brightness of comparative device E3 is 612 cd/m
2The maximum current efficient of device F is 1.36cd/A, and the maximum current efficient of comparative device E1 is 1.10cd/A, and the maximum current efficient of comparative device E2 is 1.16 cd/A, with device E1 mutually specific efficiency improved 23.6%, with device E2 mutually specific efficiency improved 14.7%.
ITO/NPB (30nm)/NPB projection (10nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), boss thickness 10nm, device number is G.
Figure 21,22 has provided device E1, E2, voltage-brightness of G, current density-current efficiency curve, under the 6V, and the brightness 963cd/m of device G
2, the brightness of comparative device E1 is 480cd/m
2, the brightness of comparative device E2 is 612 cd/m
2The maximum current efficient of device G is 1.59cd/A, and the maximum current efficient of comparative device E1 is 1.10cd/A, and the maximum current efficient of comparative device E2 is 1.16 cd/A, with device E1 mutually specific efficiency improved 44.5%, with device E2 mutually specific efficiency improved 37.1%.
ITO/NPB (20nm)/NPB projection (20nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), boss thickness 20nm, device number is H.
Figure 23,24 has provided device E1, E3, voltage-brightness of H, current density-current efficiency curve, under the 6V, and the brightness 1203cd/m of device H
2, the brightness of comparative device E1 is 480cd/m
2, the brightness of comparative device E3 is 949 cd/m
2The maximum current efficient of device H is 1.52cd/A, and the maximum current efficient of comparative device E1 is 1.10cd/A, and the maximum current efficient of comparative device E3 is 1.27 cd/A, with device E1 mutually specific efficiency improved 38.2%, with device E3 mutually specific efficiency improved 19.7%.
ITO/NPB (15nm)/NPB projection (25nm)/Zn (BTZ)
2(60nm)/and LiF (1nm)/Al (150nm), boss thickness 25nm, device number is I.
Figure 25,26 has provided device E1, E4, voltage-brightness of I, current density-current efficiency curve, under the 6V, and the brightness 988cd/m of device I
2, the brightness of comparative device E1 is 480cd/m
2, the brightness of comparative device E4 is 1283 cd/m
2, but device E4 instability is after this with regard to cancellation.The maximum current efficient of device I is 1.38cd/A, and the maximum current efficient of comparative device E1 is 1.10cd/A, and the maximum current efficient of comparative device E4 is 1.17 cd/A, with device E1 mutually specific efficiency improved 25.5%, with device E4 mutually specific efficiency improved 17.9%.
Anode layer adopts indium tin oxide (ITO), and hole transport layer material adopts N, N'-two (1-naphthyl)-N, and N'-diphenyl-1,1'-biphenyl-4,4'-diamines (NPB, purity 99.99%), luminescent layer material adopt oxine aluminium (Alq
3, purity 99.99%), the double electron transfer layer of doing, electron injecting layer adopts LiF, and cathode layer adopts the Al electrode.The face resistance of indium tin oxide-coated glass is 10 Ω/.
The Comparative Examples device is to be obtained by D district shown in Figure 7, and each functional layer interface is straight interface, is respectively:
ITO/NPB (50nm)/Alq
3(70nm)/and liF (1nm)/Al (150nm), device number is K1;
ITO/NPB (40nm)/Alq
3(70nm)/and liF (1nm)/Al (150nm), device number is K2;
ITO/NPB (35nm)/Alq
3(70nm)/and liF (1nm)/Al (150nm), device number is K3;
ITO/NPB (50nm)/Alq
3(40nm)/and liF (1nm)/Al (150nm), device number is K4;
ITO/NPB (40nm)/Alq
3(40nm)/and liF (1nm)/Al (150nm), device number is K5.
ITO/NPB (40nm)/protruding NPB (10nm)/Alq
3(70nm)/and LiF (1nm)/Al (150nm), boss thickness 10nm, device number is L.
Figure 27,28 has provided device K1, K2, current density-brightness of L, current density-current efficiency curve, 200mA/cm
2Down, the brightness 4067cd/m of device L
2, the brightness of comparative device K1 is 3389cd/m
2, the brightness of comparative device K2 is 2633cd/m
2The maximum current efficient of device L is 2.28cd/A, and the maximum current efficient of comparative device K1 is 2.09cd/A, and the maximum current efficient of comparative device K2 is 1.45cd/A, with device K1 mutually specific efficiency improved 9.1%, with device K2 mutually specific efficiency improved 57.2%.
ITO/NPB (35nm)/protruding NPB (15nm)/Alq
3(70nm)/and LiF (1nm)/Al (150nm), boss thickness 15nm, device number is M.
Figure 29,30 has provided device K1, K3, current density-brightness of M, current density-current efficiency curve, 200mA/cm
2Down, the brightness 4026cd/m of device M
2, the brightness of comparative device K1 is 3389cd/m
2, the brightness of comparative device K3 is 2468cd/m
2The maximum current efficient of device M is 2.72cd/A, and the maximum current efficient of comparative device K1 is 2.09cd/A, and the maximum current efficient of comparative device K3 is 1.27cd/A, with device K1 mutually specific efficiency improved 30%, with device K3 mutually specific efficiency improved 114%.
ITO/NPB (40nm)/protruding NPB (10nm)/Alq
3(40nm)/and LiF (1nm)/Al (150nm), boss thickness 10nm, device number is N.
Figure 31,32 has provided device K4, K5, current density-brightness of N, current density-current efficiency curve, 200mA/cm
2Down, the brightness 5251cd/m of device N
2, the brightness of comparative device K4 is 2539cd/m
2, the brightness of comparative device K5 is 3078cd/m
2The maximum current efficient of device N is 2.9cd/A, and the maximum current efficient of comparative device K4 is 1.50cd/A, and the maximum current efficient of comparative device K5 is 1.78cd/A, with device K4 mutually specific efficiency improved 93%, with device K5 mutually specific efficiency improved 62.6%.
Claims (8)
1. organic electroluminescence device with boss interfacial structure, bottom-uply form by substrate of glass, anode layer, organic function layer, inorganic functional layer and cathode layer successively with one or more layers interfacial structure, it is characterized in that, described organic function layer and cathode layer have the boss interfacial structure, be that each interface is to be made of one the boss of being no less than that a plane layer and one are located on this plane layer, and the boss that is arranged on next plane layer of interface embed a plane layer on the interface.
2. the organic electroluminescence device with boss interfacial structure according to claim 1 is characterized in that, the boss quantity that is provided with on the plane layer of each interface of organic function layer and cathode layer equates that the position is relative.
3. the organic electroluminescence device with boss interfacial structure according to claim 1 is characterized in that, the boss thickness on next plane layer of organic functions bed boundary is not more than the thickness that is positioned at an organic function layer plane layer on its interface.
4. the organic electroluminescence device with boss interfacial structure according to claim 1 is characterized in that, the shape of described boss is a rectangle or trapezoidal.
5. the organic electroluminescence device with boss interfacial structure according to claim 1, it is characterized in that, described organic function layer is made up of hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, perhaps form by hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, perhaps form by hole transmission layer, electronic barrier layer, luminescent layer, electron transfer layer, perhaps be made up of hole transmission layer, luminescent layer, electron transfer layer, perhaps list is made up of luminescent layer.
6. prepare the described method of claim 1, may further comprise the steps with organic electroluminescence device of boss interfacial structure:
1) handles the electro-conductive glass that has anode layer with conventional method;
2) electro-conductive glass of handling well is placed the vacuum evaporation stove, anode layer faces down, and distillation needs the organic functions layer material powder attached to the anode layer surface, grows into a plane rete at the anode layer surface deposition;
3) it is parallel and be close to the below of above-mentioned plane rete to have a mould of one or more slit with one, and the above-mentioned organic functions layer material powder that distils once more is in step 2) deposition growing forms one or more boss on the plane rete of preparation;
4) remove mould, continue other organic function layers of evaporation, inorganic functional layer and cathode layer, the gaseous molecular after the distillation continues deposition growing on the rete with boss that step 3) forms, the organic electroluminescence device that obtains having the boss interfacial structure.
7. be used to prepare the described particular manufacturing craft with organic electroluminescence device of boss interfacial structure of claim 1, it is characterized in that, described particular manufacturing craft is divided into A, B, four zones of C, D, and each zone subdivision becomes three parts, wherein:
The A1 place of zone A has a square hole, and the A2 place has the single seam that is symmetrically distributed up and down, and the A3 place has 4 slots;
The B1 place of area B has the square hole with A1, and the B2 place has the double slit that is symmetrically distributed up and down, and the B3 place has 4 slots with A3;
The C1 place of zone C has the square hole with A1, and the C2 place has three seams that are symmetrically distributed up and down, and the C3 place has 4 slots with A3;
The D1 place of region D has the square hole with A1, and the D2 place is seamless, and the D3 place has 4 slots with A3.
8. particular manufacturing craft according to claim 7 is characterized in that, described particular manufacturing craft is a circular die, and described A, B, four zones of C, D are uniform to be looped around on the circumference of circular die.
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