CN104979489A - Organic light-emitting diode and preparation method therefor - Google Patents
Organic light-emitting diode and preparation method therefor Download PDFInfo
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Abstract
The invention provides an organic light-emitting diode, comprising a substrate, an anode, a hold transfer layer, a light emitting layer, an electron transfer layer, a cathode layer and a packaging layer which are laminated in sequence. A block functional layer is laminated between the substrate and the anode. The block functional layer comprises m first inorganic barrier layers and m-1 first organic getter layers, wherein m is an integer from 3 to 8. A first organic getter layer is arranged between adjacent two first inorganic barrier layers. The packaging layer comprises n second inorganic barrier layers and n-1 second organic getter layers, wherein n is an integer from 3 to 8. A second organic getter layer is arranged between adjacent two second inorganic barrier layers. Materials of the first inorganic barrier layers and the second inorganic barrier layers are silica or alumina. Material of the first organic getter layers and the second organic getter layers are bi(3-methylbutyl)beryllium. The organic light-emitting diode is good in flexural property and has a long service life.
Description
Technical field
The present invention relates to electronic device association area, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) have active illuminating, luminous efficiency high, low in energy consumption, light, thin, without advantages such as angle limitations, thought by insider to be most likely at the device of new generation following illumination and display device market occupying dominance.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, achieves huge achievement.More and more throw light on due to the whole world and show producer and drop into research and development one after another, promoted the industrialization process of OLED greatly, make the growth rate of OLED industry surprising, reached the eve of scale of mass production at present.
Flexible product is the development trend of organic electroluminescence device, but also there are some problems in flexible OLED light-emitting device, typical problem is that its useful life is shorter, its reason is, use the OLED light-emitting device of flexible base, board, the water oxygen permeability of substrate is too high, causes water oxygen easily to infiltrate in device, and impact uses.And because packaging film adopts inorganic material to prepare, its toughness is poor, under repeatedly bending, easily crackle and pin hole occurs, thus forms the passage of water oxygen infiltration, thus affect useful life.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.Barrier functionality layer in this organic electroluminescence device can reduce steam, oxygen effectively to the erosion of organic electroluminescence device; organic functional material and the electrode of protection organic electroluminescence device exempt from destruction; encapsulated layer comprises the second inorganic barrier layer and second organic getter layer simultaneously; the generation of crackle and pin hole can be reduced; improve the flexural property of organic electroluminescence device, the life-span of OLED is increased significantly.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise the substrate, anode, hole transmission layer, luminescent layer, electron transfer layer, cathode layer and the encapsulated layer that stack gradually, barrier functionality layer is laminated with between described substrate and anode, described barrier functionality layer comprises m layer first inorganic barrier layer and the organic getter layer of m-1 layer first, described m is the integer of 3 ~ 8, a first organic getter layer is set between adjacent two the first inorganic barrier layers, and described first inorganic barrier layer is on the substrate stacked; Described encapsulated layer comprises n layer second inorganic barrier layer and the organic getter layer of n-1 layer second, described n is the integer of 3 ~ 8, arrange a second organic getter layer between adjacent two the second inorganic barrier layers, the material of described first inorganic barrier layer and the second inorganic barrier layer is silicon dioxide (SiO
2) or aluminium oxide (Al
2o
3), the material of described first organic getter layer and second organic getter layer is two (3-methyl butyl) beryllium.
The chemical formula of described two (3-methyl butyl) beryllium is
Preferably, described m is 3 or 4.
Preferably, the thickness of described first inorganic barrier layer is 100 ~ 300nm, and the thickness of described first organic getter layer is 50 ~ 100nm.
Preferably, the thickness of described barrier functionality layer is 0.4 ~ 1.5 μm.
Preferably, described n is 3 or 4.
Preferably, the thickness of described second inorganic barrier layer is 100 ~ 300nm, and the thickness of described second organic getter layer is 100 ~ 200nm.
Preferably, the thickness of described encapsulated layer is 0.5 ~ 1.5 μm.
At described substrate surface, barrier functionality layer is set, described barrier functionality layer comprises m layer first inorganic barrier layer and the organic getter layer of m-1 layer first, first inorganic barrier layer absorbent is stronger, the material of first organic getter layer is two (3-methyl butyl) beryllium, two (3-methyl butyl) beryllium is more active, can with infiltrate device inside gas particularly oxygen carry out chemical reaction, thus avoid the destruction of oxygen to the organic material in OLED especially luminescent material, described barrier functionality layer can avoid water oxygen to penetrate into the luminescent layer of organic electroluminescence device by substrate, raising can life-span of organic electroluminescence device.Simultaneously, described barrier functionality layer arranges a first organic getter layer between adjacent two the first inorganic barrier layers, first organic getter layer effectively can alleviate the internal stress of the first inorganic barrier layer generation when carrying out flexible operation, decrease the generation of crackle and hole, thus can improve the flexural property of organic electroluminescence device.
Described encapsulated layer comprises n layer second inorganic barrier layer and the organic getter layer of n-1 layer second, a second organic getter layer is set between adjacent two the second inorganic barrier layers, the internal stress effectively can alleviated the second inorganic barrier layer on the one hand and produce is set like this, prevent the second inorganic barrier layer from occurring the phenomenons such as be full of cracks, reduce the impact on packaging effect, on the other hand, extend water, Oxygen permeation path, excellent packaging effect can be reached, the outside water of effective minimizing, oxygen isoreactivity material, to the erosion of organic electroluminescence device, extend device lifetime.
Preferably, described substrate is polymeric transparent film.
More preferably, described substrate is PET film (polyethylene terephthalate), PES(polyether sulfone) film, PC(Merlon) film or PI(polyimides) film, described substrate thickness is 0.1 ~ 0.5mm.
Preferably, described anode is tin indium oxide (ITO).
Preferably, described hole transmission layer material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) or 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), thickness is 20 ~ 60nm.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq3) or 4,7-diphenyl-o-phenanthroline (Bphen), and thickness is 20 ~ 40nm.
Preferably, the material of described luminescent layer is 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene) or 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), and light emitting layer thickness is 5 ~ 30nm.
In organic electroluminescence device of the present invention, hole injection layer, electron injecting layer, hole blocking layer or electronic barrier layer etc. can also be set.
Preferably, described cathode layer material is silver or aluminium, and thickness is 70 ~ 200nm.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
(1) prepare barrier functionality layer at the substrate surface of cleaning, comprising:
Adopt the method for electron beam evaporation to prepare the first inorganic barrier layer at described substrate surface, evaporation rate is 0.2 ~ 1nm/s; Then adopt the method for vacuum evaporation to prepare first organic getter layer on described first inorganic barrier layer surface, evaporation rate is 0.1 ~ 0.5nm/s; Adopt the method for electron beam evaporation to prepare the first inorganic barrier layer on described first organic getter layer surface subsequently, evaporation rate is 0.2 ~ 1nm/s; Repeat the organic getter layer of preparation first and the first inorganic barrier layer as stated above, barrier functionality layer is obtained at the substrate surface of cleaning, described barrier functionality layer comprises m layer first inorganic barrier layer and the organic getter layer of m-1 layer first, described m is the integer of 3 ~ 8, arranges a first organic getter layer between adjacent two the first inorganic barrier layers;
(2) anode, hole transmission layer, luminescent layer, electron transfer layer and cathode layer is prepared successively on described barrier functionality layer surface;
(3) prepare encapsulated layer on described cathode layer surface, comprising:
Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on described cathode layer surface, evaporation rate is 0.2 ~ 1nm/s; Then adopt the method for vacuum evaporation to prepare second organic getter layer on described second inorganic barrier layer surface, evaporation rate is 0.1 ~ 0.5nm/s; Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on described second organic getter layer surface subsequently, evaporation rate is 0.2 ~ 1nm/s; Repeat the organic getter layer of preparation second and the second inorganic barrier layer as stated above, encapsulated layer is prepared on described cathode layer surface, described barrier functionality layer comprises n layer second inorganic barrier layer and the organic getter layer of n-1 layer second, described n is the integer of 3 ~ 8, arranges a second organic getter layer between adjacent two the second inorganic barrier layers;
The material of described first inorganic barrier layer and the second inorganic barrier layer is silica or aluminium oxide, and the material of described first organic getter layer and second organic getter layer is two (3-methyl butyl) beryllium.
Preferably, described m is 3 or 4.
Preferably, the thickness of described first inorganic barrier layer is 100 ~ 300nm, and the thickness of described first organic getter layer is 50 ~ 100nm.
Preferably, the thickness of described barrier functionality layer is 0.4 ~ 1.5 μm.
Preferably, described n is 3 or 4.
Preferably, the thickness of described second inorganic barrier layer is 100 ~ 300nm, and the thickness of described second organic getter layer is 100 ~ 200nm.
Preferably, the thickness of described encapsulated layer is 0.5 ~ 1.5 μm.
Preferably, adopt the method for magnetron sputtering evaporation to prepare anode layer on described barrier functionality layer surface, evaporation rate is 0.2 ~ 1nm/s.
Preferably, the method for vacuum evaporation is adopted to prepare hole transmission layer on anode layer surface; Evaporation rate is 0.1 ~ 1nm/s.
Preferably, the method for vacuum evaporation is adopted to prepare luminescent layer on described hole transmission layer surface; Evaporation rate is 0.01 ~ 1nm/s.
Preferably, the method for vacuum evaporation is adopted to prepare electron transfer layer on described luminescent layer surface; Evaporation rate is 0.1 ~ 1nm/s.
Preferably, vacuum evaporation is adopted to prepare negative electrode on described electron transfer layer surface; Evaporation rate is 0.1 ~ 1nm/s.
Preferably, described vacuum evaporation, magnetron sputtering and electron beam evaporation time vacuum degree be 1 × 10
-5~ 1 × 10
-3pa.
At described substrate surface, barrier functionality layer is set, described barrier functionality layer comprises m layer first inorganic barrier layer and the organic getter layer of m-1 layer first, first inorganic barrier layer absorbent is stronger, the material of first organic getter layer is two (3-methyl butyl) beryllium, two (3-methyl butyl) beryllium is more active, can with infiltrate device inside gas particularly oxygen carry out chemical reaction, thus avoid the destruction of oxygen to the organic material in OLED especially luminescent material, described barrier functionality layer can avoid water oxygen to penetrate into the luminescent layer of organic electroluminescence device by substrate, raising can life-span of organic electroluminescence device.Simultaneously, described barrier functionality layer arranges a first organic getter layer between adjacent two the first inorganic barrier layers, first organic getter layer effectively can alleviate the internal stress of the first inorganic barrier layer generation when carrying out flexible operation, decrease the generation of crackle and hole, thus can improve the flexural property of flexible device.
Described encapsulated layer comprises n layer second inorganic barrier layer and the organic getter layer of n-1 layer second, between described adjacent two the second inorganic barrier layers, a second organic getter layer is set, the internal stress effectively can alleviated the second inorganic barrier layer on the one hand and produce is set like this, prevent inorganic barrier layer from occurring the phenomenons such as be full of cracks, reduce the impact on packaging effect, on the other hand, extend water, Oxygen permeation path, excellent packaging effect can be reached, the outside water of effective minimizing, oxygen isoreactivity material, to the erosion of organic electroluminescence device, extend device lifetime.
Preferably, described substrate is polymeric transparent film.
More preferably, described substrate is PET film (polyethylene terephthalate), PES(polyether sulfone) film, PC(Merlon) film or PI(polyimides) film, thickness is 0.1 ~ 0.5mm.
Preferably, described anode is tin indium oxide (ITO).
Preferably, described hole transmission layer material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) or 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), thickness is 20 ~ 60nm.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq3) or 4,7-diphenyl-o-phenanthroline (Bphen), and thickness is 20 ~ 40nm.
Preferably, the material of described luminescent layer is 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene) or 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), and light emitting layer thickness is 5 ~ 30nm.
Organic electroluminescence device of the present invention can also arrange hole injection layer, electron injecting layer, hole blocking layer or electronic barrier layer etc.
Preferably, described cathode layer material is silver or aluminium, and thickness is 70 ~ 200nm.
The present invention prepares the cheaper starting materials that organic electroluminescence device adopts, and preparation method is simple, and easy large area preparation, is suitable for industrialization and uses on a large scale.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) the barrier functionality layer in organic electroluminescence device of the present invention can reduce outside water, oxygen isoreactivity material effectively to the erosion of organic electroluminescence device, thus effective protection is formed to device organic functional material and electrode, improve the life-span of organic electroluminescence device significantly;
(2) described encapsulated layer arranges a second organic getter layer between adjacent two the second inorganic barrier layers, second organic getter layer effectively can alleviate the internal stress of the second inorganic barrier layer generation when carrying out flexible operation, decrease the generation of crackle and hole, thus can improve the flexural property of organic electroluminescence device;
(3) cheaper starting materials of organic electroluminescence device employing of the present invention, preparation method is simple, and easy large area preparation, is suitable for industrialization and uses on a large scale.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention 1 organic electroluminescence device.
Embodiment
The following stated is the preferred embodiment of the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvement and adjustment, these improve and adjustment is also considered as in protection scope of the present invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) provide clean pet substrate 1, thickness is 0.1mm, prepares barrier functionality layer 2, comprising on pet substrate 1 surface:
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, the material adopting the method for electron beam evaporation to prepare the first inorganic barrier layer 21, first inorganic barrier layer 21 on substrate 1 surface is Al
2o
3, thickness is 100nm, and evaporation rate is 0.2nm/s; Then adopting the method for vacuum evaporation to prepare organic getter layer 22 material of first organic getter layer 22, first on the first inorganic barrier layer 21 surface is two (3-methyl butyl) beryllium, and thickness is 50nm, and evaporation rate is 0.1nm/s; The material adopting the method for electron beam evaporation to prepare the first inorganic barrier layer 21, first inorganic barrier layer 21 on first organic getter layer 22 surface is subsequently Al
2o
3, thickness is 100nm, and evaporation rate is 0.2nm/s; Repeat the organic getter layer of preparation first and the first inorganic barrier layer as stated above, barrier functionality layer is obtained at substrate surface, barrier functionality layer comprises three layer of first inorganic barrier layer 21 and two-layer first organic getter layer 22, arrange a first organic getter layer 22 between adjacent two the first inorganic barrier layers 21, the gross thickness of barrier functionality layer is 0.4 μm;
(2) anode 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6 and cathode layer 7 is prepared successively on barrier functionality layer 2 surface; Concrete grammar is:
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt the method for magnetron sputtering evaporation to prepare anode on barrier functionality layer surface, the material of anode is ITO, and thickness is 70nm, and sputter vaporization speed is 0.2nm/s;
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare hole transmission layer at anode surface, hole transmission layer material is NPB, and thickness is 20nm, and evaporation rate is 0.1nm/s;
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare luminescent layer on hole transmission layer surface, material is Rubrene, and the thickness of luminescent layer is 5nm, and evaporation rate is 0.1nm/s;
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare electron transfer layer on luminescent layer surface, material is Alq3, and electric transmission layer thickness is 20nm, and evaporation rate is 0.1nm/s;
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare cathode layer on electron transfer layer surface, material is metal A l, and thickness is 70nm, and evaporation rate is 0.1nm/s;
(3) prepare encapsulated layer 8 on cathode layer 7 surface, comprising:
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare the second inorganic barrier layer 81 on cathode layer 7 surface, material is Al
2o
3, thickness is 100nm, and evaporation rate is 0.2nm/s; Then adopting the method for vacuum evaporation to prepare organic getter layer 82 material of second organic getter layer 82, second on the second inorganic barrier layer 81 surface is two (3-methyl butyl) beryllium, and thickness is 100nm, and evaporation rate is 0.1nm/s; Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer 81 on second organic getter layer 82 surface subsequently, material is Al
2o
3, thickness is 100nm, and evaporation rate is 0.2nm/s; Repeat the organic getter layer of preparation second and the second inorganic barrier layer as stated above, at the obtained encapsulated layer 8 in cathode layer 7 surface, encapsulated layer 8 comprises three layer of second inorganic barrier layer 81 and two-layer second organic getter layer 82, arrange a second organic getter layer 82 between two adjacent the second inorganic barrier layers 81, the gross thickness of encapsulated layer is 0.5 μm.
Fig. 1 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 1 obtains.As shown in Figure 1, the present embodiment organic electroluminescence device, comprise substrate 1 successively, barrier functionality layer 2, anode 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, cathode layer 7 and encapsulated layer 8, barrier functionality layer 2 comprises the first inorganic barrier layer 21 stacked gradually, first organic getter layer 22, first inorganic barrier layer 21, first organic getter layer 22 and the first inorganic barrier layer 21, encapsulated layer 8 comprises the second inorganic barrier layer 81 stacked gradually, second organic getter layer 82, second inorganic barrier layer 81, second organic getter layer 82 and the second inorganic barrier layer 81.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) provide clean PES substrate, thickness is 0.5mm, prepares barrier functionality layer, comprising at PES substrate surface:
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare the first inorganic barrier layer at substrate surface, the material of the first inorganic barrier layer is SiO
2, thickness is 300nm, and evaporation rate is 1nm/s; Then adopt the method for vacuum evaporation to prepare first organic getter layer on the first inorganic barrier layer surface, first organic getter layer material is two (3-methyl butyl) beryllium, and thickness is 100nm, and evaporation rate is 0.5nm/s; Adopt the method for electron beam evaporation to prepare the first inorganic barrier layer on first organic getter layer surface subsequently, the material of the first inorganic barrier layer is SiO
2, thickness is 300nm, and evaporation rate is 1nm/s; Repeat the organic getter layer of preparation first and the first inorganic barrier layer as stated above, barrier functionality layer is obtained at substrate surface, barrier functionality layer comprises four layer of first inorganic barrier layer and three layer of first organic getter layer, arrange a first organic getter layer between adjacent two the first inorganic barrier layers, the gross thickness of barrier functionality layer is 1.5 μm;
(2) anode, hole transmission layer, luminescent layer, electron transfer layer and cathode layer is prepared successively on barrier functionality layer surface; Concrete grammar is:
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for magnetron sputtering evaporation to prepare anode on barrier functionality layer surface, the material of anode is ITO, and thickness is 200nm, and sputter vaporization speed is 0.5nm/s;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare hole transmission layer at anode surface, hole transmission layer material is m-MTDATA, and thickness is 60nm, and evaporation rate is 1nm/s;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare luminescent layer on hole transmission layer surface, material is DPVBi, and the thickness of luminescent layer is 30nm, and evaporation rate is 1nm/s;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare electron transfer layer on luminescent layer surface, material is Bphen, and thickness is 60nm, and evaporation rate is 1nm/s;
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare cathode layer on electron transfer layer surface, material is metal A g, and thickness is 200nm, and evaporation rate is 1nm/s;
(3) prepare encapsulated layer on cathode layer surface, comprising:
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on cathode layer surface, material is SiO
2, thickness is 300nm, and evaporation rate is 1nm/s; Then adopt the method for vacuum evaporation to prepare second organic getter layer on the second inorganic barrier layer surface, second organic getter layer material is two (3-methyl butyl) beryllium, and thickness is 100nm, and evaporation rate is 0.5nm/s; Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on second organic getter layer surface subsequently, material is SiO
2, thickness is 300nm, and evaporation rate is 1nm/s; Repeat the organic getter layer of preparation second and the second inorganic barrier layer as stated above, at the obtained encapsulated layer in cathode layer surface, encapsulated layer comprises four layer of second inorganic barrier layer and three layer of second organic getter layer, arrange a second organic getter layer between the second adjacent inorganic barrier layer, the gross thickness of encapsulated layer is 1.5 μm.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) provide clean PI substrate, thickness is 0.2mm, prepares barrier functionality layer, comprising at PI substrate surface:
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare the first inorganic barrier layer at substrate surface, the material of the first inorganic barrier layer is Al
2o
3, thickness is 200nm, and evaporation rate is 0.5nm/s; Then adopt the method for vacuum evaporation to prepare first organic getter layer on the first inorganic barrier layer surface, first organic getter layer material is two (3-methyl butyl) beryllium, and thickness is 80nm, and evaporation rate is 0.2nm/s; Adopt the method for electron beam evaporation to prepare the first inorganic barrier layer on first organic getter layer surface subsequently, the material of the first inorganic barrier layer is Al
2o
3, thickness is 200nm, and evaporation rate is 0.5nm/s; Repeat the organic getter layer of preparation first and the first inorganic barrier layer as stated above, barrier functionality layer is obtained at substrate surface, barrier functionality layer comprises three layer of first inorganic barrier layer and two-layer first organic getter layer, arranges a first organic getter layer between adjacent two the first inorganic barrier layers; The gross thickness of barrier functionality layer is 0.76 μm;
(2) anode, hole transmission layer, luminescent layer, electron transfer layer and cathode layer is prepared successively on barrier functionality layer surface; Concrete grammar is:
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for magnetron sputtering evaporation to prepare anode in the surface evaporation of barrier functionality layer, the material of anode is ITO, and thickness is 100nm, and sputter vaporization speed is 1nm/s;
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare hole transmission layer at anode surface, hole transmission layer material is NPB, and thickness is 40nm, and evaporation rate is 0.5nm/s;
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare luminescent layer on hole transmission layer surface, material is DPVBi, and the thickness of luminescent layer is 20nm, and evaporation rate is 0.5nm/s;
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare electron transfer layer on luminescent layer surface, material is BCP, and thickness is 15nm, and evaporation rate is 0.5nm/s;
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for vacuum evaporation to prepare cathode layer on electron transfer layer surface, material is metal A g, and thickness is 100nm, and evaporation rate is 0.5nm/s;
(3) prepare encapsulated layer on cathode layer surface, comprising:
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare the second inorganic barrier layer at cathode surface, material is Al
2o
3, thickness is 200nm, and evaporation rate is 0.5nm/s; Then adopt the method for vacuum evaporation to prepare second organic getter layer on the second inorganic barrier layer surface, second organic getter layer material is two (3-methyl butyl) beryllium, and thickness is 200nm, and evaporation rate is 0.5nm/s; Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on second organic getter layer surface subsequently, material is Al
2o
3, thickness is 200nm, and evaporation rate is 0.5nm/s; Repeat the organic getter layer of preparation second and the second inorganic barrier layer as stated above, at the obtained encapsulated layer in cathode layer surface, encapsulated layer comprises three layer of second inorganic barrier layer and two-layer second organic getter layer, arrange a second organic getter layer between two adjacent the second inorganic barrier layers, the gross thickness of encapsulated layer is 1 μm.
Comparative example 1
Comparative example 1 is to only have one deck first inorganic barrier layer in the barrier functionality layer in comparative example 1 with the difference of embodiment, and only have one deck second inorganic barrier layer in the encapsulated layer in comparative example 1, the material of the first inorganic barrier layer and the second inorganic barrier layer is Al
2o
3, thickness is 800nm, and adopt the method preparation of electron beam evaporation, evaporation rate is 1nm/s.
Effect example
For the beneficial effect of valid certificates organic electroluminescence device of the present invention and preparation method thereof, provide relevant experimental data as follows.Test and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), U.S. marine optics Ocean Optics USB4000 fiber spectrometer testing electroluminescent spectrum, Keithley company of U.S. Keithley2400 tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company.
The organic electroluminescence device of embodiment 1 and comparative example 1 is carried out test and comparison under differently curved number of times, the luminosity changing value of organic electroluminescence device.The initial value of luminosity is 1000cd/m
2, in testing, remain driving voltage value now.Flexure method of testing is:
The two ends of organic electroluminescence device are fixed in two pieces of opposing parallel rigid plate, the position of fixing wherein one piece of rigid plate, then move in parallel the position of another block rigid plate, the distance between two pieces of rigid plate is changed, and then organic electroluminescence device is bent.The initial length of organic electroluminescence device is designated as L
a, move in parallel wherein one piece of rigid plate, the distance at this moment between two pieces of rigid plate be designated as L
b, work as L
a: L
bwhen reaching 1:0.5, stop mobile rigid plate, and then the mobile rigid plate length recovered between two pieces of rigid plate is L
a, this process is designated as 1 time and bends.According to test request, repeatedly repeat the process that this moves and recovers.
Table 1 is the luminosity changing value of embodiment 1 ~ 3 and comparative example 1 under differently curved number of times, as seen from Table 1, after 2000 times bending, the luminosity of organic electroluminescence device prepared by embodiment 1 ~ 3 can reach 70.4% of original intensity respectively, 71.2%, 71.7%, comparative example 1 then only has 49.1% of original intensity.Show under repeatedly flexible operation, the encapsulated layer of flexible OLED devices provided by the invention still can keep good water oxygen blocking effect and packaging effect, luminosity change is little, the long service life of device, and the organic electroluminescence device of comparative example 1 destroys under repeatedly bending, crack and hole, luminosity alters a great deal, and useful life is short.
The luminosity changing value of table 1 embodiment 1 ~ 3 and comparative example 1 under differently curved number of times
The organic electroluminescence device of embodiment 1 and comparative example 1 is tested, the luminous efficiency of comparator device and T70 life-span, luminous efficiency is carried out under the driving voltage of 6V, and the T70 life-span is organic electroluminescence device brightness decay to original intensity 70% time used.
Table 2 is the test results obtained, as can be seen from Table 2, the luminous efficiency of embodiment 1 is suitable with comparative example 1, illustrate in organic electroluminescence device of the present invention and barrier functionality layer is set and the light efficiency of encapsulated layer on organic electroluminescence device does not affect, but from useful life, the T70 life-span of the organic electroluminescence device of embodiment 1 improves 52% than the T70 life-span of comparative example 1.This is because the material of the organic getter layer of the present invention first and second organic getter layer is two (3-methyl butyl) beryllium, two (3-methyl butyl) beryllium can eliminate the gas particularly oxygen entered in OLED structure further, thus ensure that the stability of emitting device structure, final useful life of improving device.
The T70 life-span of table 2 embodiment 1 and comparative example 1 and luminous efficiency
| T70 life-span (h) | Luminous efficiency (lm/W) | |
| Embodiment 1 | 9857 | 16.2 |
| Comparative example 1 | 6478 | 15.8 |
To sum up; organic electroluminescence device provided by the invention can reduce outside water, oxygen isoreactivity material effectively to the erosion of organic electroluminescence device; thus effective protection is formed to device organic functional material and electrode; meet the sealing requirements of encapsulation, the life-span of OLED can be improved significantly.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic electroluminescence device, comprise the substrate, anode, hole transmission layer, luminescent layer, electron transfer layer, cathode layer and the encapsulated layer that stack gradually, it is characterized in that, barrier functionality layer is laminated with between described substrate and anode, described barrier functionality layer comprises m layer first inorganic barrier layer and the organic getter layer of m-1 layer first, described m is the integer of 3 ~ 8, a first organic getter layer is set between adjacent two the first inorganic barrier layers, and described first inorganic barrier layer is on the substrate stacked; Described encapsulated layer comprises n layer second inorganic barrier layer and the organic getter layer of n-1 layer second, and described n is the integer of 3 ~ 8, arranges a second organic getter layer between adjacent two the second inorganic barrier layers; The material of described first inorganic barrier layer and the second inorganic barrier layer is silicon dioxide or aluminium oxide, and the material of described first organic getter layer and second organic getter layer is two (3-methyl butyl) beryllium.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, described m is 3 or 4.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described first inorganic barrier layer is 100 ~ 300nm, and the thickness of described first organic getter layer is 50 ~ 100nm.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, described n is 3 or 4.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described second inorganic barrier layer is 100 ~ 300nm, and the thickness of described second organic getter layer is 100 ~ 200nm.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
(1) prepare barrier functionality layer at the substrate surface of cleaning, comprising:
Adopt the method for electron beam evaporation to prepare the first inorganic barrier layer at described substrate surface, evaporation rate is 0.2 ~ 1nm/s; Then adopt the method for vacuum evaporation to prepare first organic getter layer on described first inorganic barrier layer surface, evaporation rate is 0.1 ~ 0.5nm/s; Adopt the method for electron beam evaporation to prepare the first inorganic barrier layer on described first organic getter layer surface subsequently, evaporation rate is 0.2 ~ 1nm/s; Repeat the organic getter layer of preparation first and the first inorganic barrier layer as stated above, barrier functionality layer is obtained at the substrate surface of cleaning, described barrier functionality layer comprises m layer first inorganic barrier layer and the organic getter layer of m-1 layer first, described m is the integer of 3 ~ 8, arranges a first organic getter layer between adjacent two the first inorganic barrier layers;
(2) anode, hole transmission layer, luminescent layer, electron transfer layer and cathode layer is prepared successively on described barrier functionality layer surface;
(3) prepare encapsulated layer on described cathode layer surface, comprising:
Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on described cathode layer surface, evaporation rate is 0.2 ~ 1nm/s; Then adopt the method for vacuum evaporation to prepare second organic getter layer on described second inorganic barrier layer surface, evaporation rate is 0.1 ~ 0.5nm/s; Adopt the method for electron beam evaporation to prepare the second inorganic barrier layer on described second organic getter layer surface subsequently, evaporation rate is 0.2 ~ 1nm/s; Repeat the organic getter layer of preparation second and the second inorganic barrier layer as stated above, at the obtained encapsulated layer in described cathode layer surface, described encapsulated layer comprises n layer second inorganic barrier layer and the organic getter layer of n-1 layer second, described n is the integer of 3 ~ 8, arranges a second organic getter layer between adjacent two the second inorganic barrier layers;
The material of described first inorganic barrier layer and the second inorganic barrier layer is silica or aluminium oxide, and the material of described first organic getter layer and second organic getter layer is two (3-methyl butyl) beryllium.
7. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described m is 3 or 4.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the thickness of described first inorganic barrier layer is 100 ~ 300nm, and the thickness of described first organic getter layer is 50 ~ 100nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, described n is 3 or 4.
10. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the thickness of described second inorganic barrier layer is 100 ~ 300nm, and the thickness of described second organic getter layer is 100 ~ 200nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106531904A (en) * | 2016-11-22 | 2017-03-22 | 武汉船舶通信研究所 | OLED display device package and packaging method |
| WO2018154888A1 (en) * | 2017-02-22 | 2018-08-30 | 株式会社半導体エネルギー研究所 | Display device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106531904A (en) * | 2016-11-22 | 2017-03-22 | 武汉船舶通信研究所 | OLED display device package and packaging method |
| WO2018154888A1 (en) * | 2017-02-22 | 2018-08-30 | 株式会社半導体エネルギー研究所 | Display device |
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