CN104638126A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
- Publication number
- CN104638126A CN104638126A CN201310561744.6A CN201310561744A CN104638126A CN 104638126 A CN104638126 A CN 104638126A CN 201310561744 A CN201310561744 A CN 201310561744A CN 104638126 A CN104638126 A CN 104638126A
- Authority
- CN
- China
- Prior art keywords
- barrier layer
- layer
- inorganic material
- electroluminescence device
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides an organic light-emitting device. The organic light-emitting device comprises an anode conductive substrate, an organic light-emitting functional layer, a cathode layer and a packaging layer in sequentially overlapped arrangement, and the packaging layer is formed by sequentially overlapping mixed barrier layers and organic barrier layers. Each mixed barrier layer is made of an organic material, a first inorganic material, a second inorganic material and a third inorganic material, wherein the first inorganic material, the second inorganic material and the third inorganic material are doped in the organic material. The organic barrier layers are made of hydrogenated carbon nitrides. The packaging layer of the organic light-emitting device is high in resistance to oxygen and moisture, minimum vapor permeability of the organic light-emitting device is only 6.21*10-6g/m<2> per day after packaging is finished, and service life of the organic light-emitting device is longer than 17,200 hours (T70@1000cd/m<2>). The invention further provides a preparation method of the organic light-emitting device. The method is particularly applicable to packaging of flexible organic light-emitting devices.
Description
Technical field
The invention belongs to organic electroluminescence device field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is that the luminous organic material preparing one deck tens nanometer thickness on ito glass makes luminescent layer, and be metal electrode above luminescent layer, when electrode being added with voltage, luminescent layer just produces light radiation.
Electroluminescent organic material invades responsive especially to oxygen and steam, on the one hand because oxygen is quencher, luminous quantum efficiency can be made significantly to decline, and oxygen also can make its transmittability decline to the oxidation of hole transmission layer; On the other hand, the main failure mode of steam is the hydrolysis of organic compound, its stability is declined, thus causes component failure.Thus; the degeneration of effective suppression OLED in long-term work process and inefficacy; make the life-span that its steady operation reaches enough, this proposes high requirement to the barrier of encapsulating material, and the encapsulation technology playing seal protection effect becomes the break-through point solving OLED life problems.
Encapsulation technology is the interlayer by forming compact structure, realizes physical protection to the core component in encapsulation region.Flexible product is the development trend of organic electroluminescence device, and the barrier property of flexible device plastic-substrates usually used all cannot reach the requirement of OLED encapsulation, the problem that therefore the flexible organic electroluminescent device ubiquity life-span is short.At present, introduction is had been reported by SiN
xor SiO
xbe arranged on cathode layer surface etc. inorganic material by methods such as magnetron sputterings, as the encapsulated layer of organic electroluminescence device, but under the high-temperature operation condition of magnetron sputtering, cathode layer surface is subject to destruction; On the other hand, single inorganic layer hardness is high, cannot realize flexible package, and in use residual stress can cause encapsulated layer fracture failure, causes greatly shorten device lifetime.Given this, solving problems faced in flexible organic electroluminescent device encapsulation process, is the key promoting flexible OLED production development.
Summary of the invention
The invention provides a kind of organic electroluminescence device, the encapsulated layer of this organic electroluminescence device adopts organic-inorganic to replace the pattern of compound, effectively can reduce oxygen and steam to the erosion of organic electroluminescence device, improve the life-span of organic electroluminescence device significantly.Present invention also offers a kind of preparation method of organic electroluminescence device, the method technique is simple, easy large area preparation and mass production; The even film layer of preparation is fine and close, and barrier property is excellent; The inventive method is applicable to encapsulate the organic electroluminescence device prepared with conducting glass substrate, is also applicable to encapsulate the flexible organic electroluminescent device prepared for substrate with plastics or metal, is particularly useful for encapsulating flexible organic electroluminescent device.
First aspect, the invention provides a kind of organic electroluminescence device, the organic luminescence function layer, cathode layer and the encapsulated layer that comprise anode conducting substrate and be cascading at anode conducting substrate surface, described encapsulated layer comprises the mixing barrier layer and inorganic barrier layer that are cascading;
The material on described mixing barrier layer comprises organic material and is entrained in the first inorganic material, the second inorganic material and the 3rd inorganic material in described organic material; Described organic material is 1,1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 1,3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), described first inorganic material is magnesium fluoride (MgF
2), aluminum fluoride (AlF
3) and hexafluoro conjunction sodium aluminate (Na
3alF
6) at least one, described second inorganic material is lanthanum fluoride (LaF
3), neodymium fluoride (NdF
3) and gadolinium fluoride (GdF
3) at least one, described 3rd inorganic material is molybdenum trioxide (MoO
3), vanadic oxide (V
2o
5), tungstic acid (WO
3), cesium oxide (Cs
2o), nickel oxide (NiO) and manganese dioxide (MnO
2) at least one;
The material of described inorganic barrier layer is hydrogenated carbon nitrogen compound.
Preferably, the mass fraction of described first inorganic material shared by described mixing barrier layer is 10% ~ 20%, the mass fraction of described second inorganic material shared by described mixing barrier layer is 10% ~ 20%, and the mass fraction of described 3rd inorganic material shared by described mixing barrier layer is 10% ~ 20%.
Preferably, the thickness on described mixing barrier layer is 100nm ~ 200nm.
Organic material in described mixing barrier layer, as base material, can make even film layer continuous, smooth densification, and have good adhesive force between cathode layer; Doping three kinds of inorganic material simultaneously, two kinds of fluorides can the chemical stability of enhanced film and anticorrosive property, it is to make the mixture stress of formation reduce that two kinds of fluorides add respectively, oxide assume responsibility for main water oxygen iris action, fine and close and evenness is high, has low mechanical strength simultaneously, so both can make up the deficiency of simple organic material barrier property difference, can have complementary advantages again, synergy, all has excellent barrier property to oxygen and steam.
Preferably, the thickness of described inorganic barrier layer is 400nm ~ 600nm.
The material of described inorganic barrier layer adopts hydrogenated carbon nitrogen compound (to be expressed as CN
x: H, wherein 0 < x≤0.7), described hydrogenated carbon nitrogen compound is highly cross-linked solid film, the doping of nitrogen-atoms, decline than undoped agraphitic carbon film hardness, but still maintain good chemical stability, and to steam and oxygen, there is excellent barrier property; On the other hand, hydrogenated carbon nitrogen compound layer all has good slow releasing function to bending stress and thermal stress, can ensure that flexible device can not crack after bending, thus significantly improve the life-span of device.
Preferably, described mixing barrier layer and inorganic barrier layer form a construction unit, and described encapsulated layer is that the multilayer that 3 ~ 5 construction units are laminated replaces structure of composite membrane.Adopt described multilayer alternating structure can increase the length of steam and oxygen infiltration " passage " on the one hand, make up the harmful effect of single rete defect for whole packaging effect, effectively strengthen the effect on barrier layer; On the other hand, mixing barrier layer and inorganic barrier layer synergy, have complementary advantages, make device still have excellent barrier property under high-stress state, be specially adapted to the encapsulation of flexible device.
Preferably, anode conducting substrate is conducting glass substrate or conduction organic film substrate, and more preferably, the material of described conducting glass substrate is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO); The material of described conduction organic film substrate is the one in PETG (PET), polysulfones ether (PES), polyethylene naphthalate (PEN), polyimides (PI).
Preferably, described organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
(1) prepare the anode pattern of organic electroluminescence device on the electrically-conductive backing plate surface of cleaning, form anode conducting substrate;
(2) prepare organic luminescence function layer and cathode layer by the mode of vacuum evaporation successively at anode conducting substrate surface, evaporation rate is
vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa;
(3) prepare encapsulated layer on cathode layer surface, described encapsulated layer comprises the inorganic barrier layer and inorganic barrier layer that are cascading, and the preparation method of described encapsulated layer is as follows:
A () adopts the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
the material on described mixing barrier layer comprises organic material and is entrained in the first inorganic material, the second inorganic material and the 3rd inorganic material in described organic material; Described organic material is 1,1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 1,3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), described first inorganic material is magnesium fluoride (MgF
2), aluminum fluoride (AlF
3) and hexafluoro conjunction sodium aluminate (Na
3alF
6) at least one, described second inorganic material is lanthanum fluoride (LaF
3), neodymium fluoride (NdF
3) and gadolinium fluoride (GdF
3) at least one, described 3rd inorganic material is molybdenum trioxide (MoO
3), vanadic oxide (V
2o
5), tungstic acid (WO
3), cesium oxide (Cs
2o), nickel oxide (NiO) and manganese dioxide (MnO
2) at least one;
B () adopts the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 5sccm ~ 15sccm, N
2flow is 5sccm ~ 15sccm, and operating pressure is 10Pa ~ 80Pa, and radio-frequency power is 0.1W/cm
2~ 0.5W/cm
2.
Preferably, the mass fraction of first inorganic material described in step (a) shared by described mixing barrier layer is 10% ~ 20%, the mass fraction of described second inorganic material shared by described mixing barrier layer is 10% ~ 20%, and the mass fraction of described 3rd inorganic material shared by described mixing barrier layer is 10% ~ 20%.
Preferably, the thickness mixing barrier layer described in step (a) is 100nm ~ 200nm.
Preferably, the deposit thickness of inorganic barrier layer described in step (b) is 400nm ~ 600nm.
Using plasma strengthens chemical vapour deposition technique and prepares inorganic barrier layer in described step (b), and major advantage is that depositing temperature is low, to the structure of matrix and impact on physical properties little; The thickness of film and homogeneity of ingredients good, membrane tissue is fine and close, pin hole is few, strong to the obstructing capacity of steam and oxygen; The strong adhesion of rete, effectively can avoid the device failure that steam and oxygen infiltrate from interface and brings.
Preferably, described mixing barrier layer and inorganic barrier layer form a construction unit, repeat step (3) 3 ~ 5 times successively after step (b) by step (a) and (b) sequence alternate, prepare the encapsulated layer that 3 ~ 5 described construction units repeat to be formed.
Preferably, described electrically-conductive backing plate is conducting glass substrate or conduction organic film substrate, and more preferably, the material of described conducting glass substrate is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO); The material of described conduction organic film substrate is the one in PETG (PET), polysulfones ether (PES), polyethylene naphthalate (PEN), polyimides (PI).
Preferably, described in step (2), organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
Compared with prior art, its beneficial effect is embodied in the following aspects in the present invention:
(1) barrier layer and inorganic barrier layer alternately synergy is mixed in the encapsulated layer that the present invention adopts, both the length of steam and oxygen infiltration " passage " can have been increased, strengthen the effect on barrier layer, thus minimizing oxygen and steam are to the erosion of organic electroluminescence device effectively, after encapsulation, the vapor permeability of organic electroluminescence device is minimum is only 6.21 × 10
-6g/m
2day, the life-span reaches 17, more than 200 hours (T70@1000cd/m
2), the weight of device can be alleviated again, make device portability more;
(2) in the present invention, inorganic barrier layer adopts hydrogenated carbon nitrogen compound, described hydrogenated carbon nitrogen compound has excellent barrier property and stress slow releasing function concurrently, device is made still to have excellent barrier property under high-stress state, the useful life of significant prolongation device.
(3) the inventive method is applicable to encapsulate the organic electroluminescence device prepared with conducting glass substrate, also be applicable to encapsulate the flexible organic electroluminescent device prepared for substrate with plastics or metal, the inventive method is particularly useful for encapsulating flexible organic electroluminescent device.
(4) preparation method's technique provided by the invention is simple, and automaticity is high, easy large area preparation and mass production.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic electroluminescence device in embodiment 1;
Fig. 2 is the structural representation of encapsulated layer in Fig. 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Fig. 1 is the structural representation of a kind of organic electroluminescence device that the present embodiment provides.As shown in Figure 1, this organic electroluminescence device, comprises the conducting glass substrate 10, organic luminescence function layer 20, cathode layer 30 and the encapsulated layer 40 that are cascading from lower to upper.Wherein, described organic luminescence function layer 20 comprises the hole injection layer 21, hole transmission layer 22, luminescent layer 23, electron transfer layer 24 and the electron injecting layer 25 that are cascading from bottom to top.Fig. 2 is the structural representation of encapsulated layer in Fig. 1, as shown in Figure 2, described encapsulated layer 40 comprises the mixing barrier layer 41 and inorganic barrier layer 42 that are cascading, described mixing barrier layer 41 and inorganic barrier layer 42 form a construction unit, and described encapsulated layer 40 is the composite construction be laminated by 5 construction units.The preparation method of this organic electroluminescence device, comprises the following steps:
(1) ito glass substrate 10 pre-treatment: ito glass substrate, successively through acetone, ethanol, deionized water, ethanol purge, all cleans with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface; ITO thickness is 100nm;
(2) organic luminescence function layer 20 and cathode layer 30 is prepared by the mode of vacuum evaporation successively on conducting glass substrate 10 surface:
The preparation of hole injection layer 21: material is MoO
3be entrained in N, the composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), MoO
3mass fraction shared in described composite material is 30%, and thickness is 10nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of hole transmission layer 22: material is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), evaporation thickness 30nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of luminescent layer 23: material of main part adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), guest materials accounts for 5% of emitting layer material gross mass, evaporation thickness 20nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of electron transfer layer 24: material is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 10nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of electron injecting layer 25: material is CsN
3be entrained in the composite material formed in Bphen, CsN
3mass fraction shared in described composite material is 30%, and thickness is 20nm, vacuum degree 3 × 10
-5pa, evaporation rate
The preparation of cathode layer 30: it is 10nm that cathode layer adopts ZnS/Ag/ZnS, ZnS layer thickness to be 30nm, Ag layer thickness, and vacuum degree is 1 × 10
-5pa, evaporation rate
(3) preparation of encapsulated layer 40:
The preparation on (a) mixing barrier layer 41: adopt the mode of vacuum evaporation on preparation mixing barrier layer 41, cathode layer 30 surface, the material on described mixing barrier layer comprises 1,1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane (TAPC) and the Na be entrained in described TAPC
3alF
6, LaF
3and MoO
3(be expressed as TAPC:Na
3alF
6: LaF
3: MoO
3), wherein Na
3alF
6, LaF
3and MoO
3doping mass fraction respectively be 15%, 15%, 13%; The vacuum degree adopted is 1 × 10
-5pa, evaporation rate is
thickness is 200nm;
The preparation of (b) inorganic barrier layer 42: adopt the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer 42 on mixing surface, barrier layer 41; Adopt CH
4and N
2as reacting gas, control CH
4flow is 10sccm, N
2flow is 8sccm, and operating pressure is 50Pa, and radio-frequency power is 0.2W/cm
2, deposit thickness is 600nm.
(4) step (3) 5 times are repeated by described (a) and (b) sequence alternate successively.
The encapsulated layer 40 of organic electroluminescence device prepared by the present embodiment is that 5 construction units are laminated, and it is the TAPC:Na of 200nm that described construction unit comprises the thickness be cascading
3alF
6: LaF
3: MoO
3layer 41 and thickness are the hydrogenated carbon nitrogen compound layer 42 of 600nm, and described encapsulated layer 40 is TAPC:Na
3alF
6: LaF
3: MoO
3the alternately repeated composite construction of layer/hydrogenated carbon nitrogen compound layer, general thickness is 4 μm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the organic electroluminescence device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 6.21 × 10
-6g/m
2day, the life-span is 17,349 hours.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, the material on described mixing barrier layer comprises N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1,1'-biphenyl-4,4'-diamines (NPB) and the AlF be entrained in described NPB
3, NdF
3and V
2o
5(be expressed as NPB:AlF
3: NdF
3: V
2o
5), wherein AlF
3, NdF
3and V
2o
5doping mass fraction respectively be 20%, 10%, 20%; The vacuum degree adopted is 1 × 10
-5pa, evaporation rate is
thickness is 200nm;
The preparation of (b) inorganic barrier layer: adopt the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 12sccm, N
2flow is 10sccm, and operating pressure is 20Pa, and radio-frequency power is 0.3W/cm
2, deposit thickness is 550nm.
(4) step (3) 4 times are repeated by described (a) and (b) sequence alternate successively.
The encapsulated layer of organic electroluminescence device prepared by the present embodiment is that 4 construction units are laminated, and it is the NPB:AlF of 200nm that described construction unit comprises the thickness be cascading
3: NdF
3: V
2o
5layer and thickness are the hydrogenated carbon nitrogen compound layer of 550nm, and described encapsulated layer is NPB:AlF
3: NdF
3: V
2o
5the alternately repeated composite construction of layer/hydrogenated carbon nitrogen compound layer, general thickness is 3 μm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the organic electroluminescence device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 6.23 × 10
-6g/m
2day, the life-span is 17,306 hours.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, the MgF that the material on described mixing barrier layer comprises oxine aluminium (Alq3) and is entrained in described Alq3
2, GdF
3and WO
3(be expressed as Alq3:MgF
2: GdF
3: WO
3), wherein MgF
2, GdF
3and WO
3doping mass fraction respectively be 10%, 20%, 10%; The vacuum degree adopted is 1 × 10
-5pa, evaporation rate is
thickness is 100nm;
The preparation of (b) inorganic barrier layer: adopt the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 8sccm, N
2flow is 10sccm, and operating pressure is 60Pa, and radio-frequency power is 0.4W/cm
2, deposit thickness is 450nm.
(4) step (3) 3 times are repeated by described (a) and (b) sequence alternate successively.
The encapsulated layer of organic electroluminescence device prepared by the present embodiment is that 3 construction units are laminated, and it is the Alq3:MgF of 100nm that described construction unit comprises the thickness be cascading
2: GdF
3: WO
3layer and thickness are the hydrogenated carbon nitrogen compound layer of 450nm, and described encapsulated layer is Alq3:MgF
2: GdF
3: WO
3the alternately repeated composite construction of layer/hydrogenated carbon nitrogen compound layer, general thickness is 1.65 μm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the organic electroluminescence device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 6.24 × 10
-6g/m
2day, the life-span is 17,264 hours.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, the material on described mixing barrier layer comprises 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA) and the Na be entrained in described m-MTDATA
3alF
6, LaF
3and Cs
2o(is expressed as m-MTDATA:Na
3alF
6: LaF
3: Cs
2o), wherein Na
3alF
6, LaF
3and Cs
2the doping mass fraction of O respectively is 16%, 13%, 15%; The vacuum degree adopted is 5 × 10
-5pa, evaporation rate is
thickness is 130nm;
The preparation of (b) inorganic barrier layer: adopt the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 15sccm, N
2flow is 15sccm, and operating pressure is 80Pa, and radio-frequency power is 0.5W/cm
2, deposit thickness is 500nm.
(4) step (3) 3 times are repeated by described (a) and (b) sequence alternate successively.
The encapsulated layer of organic electroluminescence device prepared by the present embodiment is that 3 construction units are laminated, and it is the m-MTDATA:Na of 130nm that described construction unit comprises the thickness be cascading
3alF
6: LaF
3: Cs
2o layer and thickness are the hydrogenated carbon nitrogen compound layer of 500nm, and described encapsulated layer is m-MTDATA:Na
3alF
6: LaF
3: Cs
2o layer/alternately repeated composite construction of hydrogenated carbon nitrogen compound layer, general thickness is 1.89 μm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the organic electroluminescence device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 6.25 × 10
-6g/m
2day, the life-span is 17,243 hours.
Embodiment 5
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, the AlF that the material on described mixing barrier layer comprises 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and is entrained in described BCP
3, NdF
3bCP:AlF is expressed as with NiO(
3: NdF
3: Ni
2o), wherein AlF
3, NdF
3and Ni
2the doping mass fraction of O respectively is 16%, 11%, 14%; The vacuum degree adopted is 5 × 10
-5pa, evaporation rate is
thickness is 140nm;
The preparation of (b) inorganic barrier layer: adopt the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 5sccm, N
2flow is 5sccm, and operating pressure is 10Pa, and radio-frequency power is 0.1W/cm
2, deposit thickness is 450nm.
(4) step (3) 3 times are repeated by described (a) and (b) sequence alternate successively.
The encapsulated layer of organic electroluminescence device prepared by the present embodiment is that 3 construction units are laminated, and it is the BCP:AlF of 140nm that described construction unit comprises the thickness be cascading
3: NdF
3: NiO layer and thickness are the hydrogenated carbon nitrogen compound layer of 450nm, and described encapsulated layer is BCP:AlF
3: NdF
3: Ni
2o layer/alternately repeated composite construction of hydrogenated carbon nitrogen compound layer, general thickness is 1.77 μm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the organic electroluminescence device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 6.26 × 10
-6g/m
2day, the life-span is 17,226 hours.
Embodiment 6
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, the material on described mixing barrier layer comprises 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and the MgF be entrained in described TPBi
2, GdF
3and MnO
2(be expressed as TPBi:MgF
2: GdF
3: MnO
2), wherein MgF
2, GdF
3and MnO
2doping mass fraction respectively be 12%, 12%, 13%; The vacuum degree adopted is 1 × 10
-3pa, evaporation rate is
thickness is 120nm;
The preparation of (b) inorganic barrier layer: adopt the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 5sccm, N
2flow is 10sccm, and operating pressure is 25Pa, and radio-frequency power is 0.2W/cm
2, deposit thickness is 400nm.
(4) step (3) 3 times are repeated by described (a) and (b) sequence alternate successively.
The encapsulated layer of organic electroluminescence device prepared by the present embodiment is that 3 construction units are laminated, and it is the TPBi:MgF of 120nm that described construction unit comprises the thickness be cascading
2: GdF
3: MnO
2layer and thickness are the hydrogenated carbon nitrogen compound layer of 400nm, and described encapsulated layer is TPBi:MgF
2: GdF
3: MnO
2the alternately repeated composite construction of layer/hydrogenated carbon nitrogen compound layer, general thickness is 1.56 μm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the organic electroluminescence device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 6.29 × 10
-6g/m
2day, the life-span is 17,205 hours.
Effect example
For the beneficial effect of valid certificates organic electroluminescence device of the present invention and preparation method thereof, the vapor permeability (WVTR) of test organic electroluminescence device, and test (the T70@1000cd/m in useful life of organic electroluminescence device
2), from original intensity 1000cd/m
2decay to the time needed for 70%.Vapor permeability and the useful life of the organic electroluminescence device of the embodiment of the present invention 1 ~ 6 preparation are as shown in table 1.
The vapor permeability of organic electroluminescence device prepared by table 1 embodiment 1 ~ 6 and useful life
As can be seen from Table 1, the vapor permeability (WVTR) of the organic electroluminescence device after encapsulation technology encapsulation of the present invention is all 10
-6g/m
2the day order of magnitude, is minimumly only 6.21 × 10
-6g/m
2day, useful life reaches 17, more than 200 hours (T70@1000cd/m
2).This is owing to the selection of encapsulated layer material and multilayer alternating structure, and extraneous oxygen and steam, through heavy stop, are difficult to enter device inside and cause erosion to organic electroluminescence device, so substantially prolongs the life-span of organic electroluminescence device.
To sum up, the encapsulated layer of organic electroluminescence device provided by the invention can reduce oxygen and steam effectively to the erosion of organic electroluminescence device, improves the life-span of organic electroluminescence device significantly, and cathode layer can be protected to exempt from destruction.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, the organic luminescence function layer, cathode layer and the encapsulated layer that comprise anode conducting substrate and be cascading at anode conducting substrate surface, it is characterized in that, described encapsulated layer comprises the mixing barrier layer and inorganic barrier layer that are cascading;
The material on described mixing barrier layer comprises organic material and is entrained in the first inorganic material, the second inorganic material and the 3rd inorganic material in described organic material, described organic material is 1, 1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, oxine aluminium, 4, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline and 1, 3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, described first inorganic material is magnesium fluoride, aluminum fluoride and hexafluoro close at least one in sodium aluminate, described second inorganic material is lanthanum fluoride, at least one in neodymium fluoride and gadolinium fluoride, described 3rd inorganic material is molybdenum trioxide, vanadic oxide, tungstic acid, cesium oxide, at least one in nickel oxide and manganese dioxide,
The material of described inorganic barrier layer is hydrogenated carbon nitrogen compound.
2. organic electroluminescence device according to claim 1, it is characterized in that, the mass fraction of described first inorganic material shared by described mixing barrier layer is 10% ~ 20%, the mass fraction of described second inorganic material shared by described mixing barrier layer is 10% ~ 20%, and the mass fraction of described 3rd inorganic material shared by described mixing barrier layer is 10% ~ 20%.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness on described mixing barrier layer is 100nm ~ 200nm.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described inorganic barrier layer is 400nm ~ 600nm.
5. organic electroluminescence device according to claim 1, is characterized in that, described mixing barrier layer and inorganic barrier layer form a construction unit, and described encapsulated layer is that 3 ~ 5 construction units are laminated.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
(1) prepare the anode pattern of organic electroluminescence device on the electrically-conductive backing plate surface of cleaning, form anode conducting substrate;
(2) prepare organic luminescence function layer and cathode layer by the mode of vacuum evaporation successively at anode conducting substrate surface, evaporation rate is
vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa;
(3) prepare encapsulated layer on cathode layer surface, described encapsulated layer comprises the mixing barrier layer and inorganic barrier layer that are cascading, and the preparation method of described encapsulated layer is as follows:
A () adopts the mode of vacuum evaporation on preparation mixing barrier layer, cathode layer surface, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
the material on described mixing barrier layer comprises organic material and is entrained in the first inorganic material, the second inorganic material and the 3rd inorganic material in described organic material, described organic material is 1, 1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, oxine aluminium, 4, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline and 1, 3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, described first inorganic material is magnesium fluoride, aluminum fluoride and hexafluoro close at least one in sodium aluminate, described second inorganic material is lanthanum fluoride, at least one in neodymium fluoride and gadolinium fluoride, described 3rd inorganic material is molybdenum trioxide, vanadic oxide, tungstic acid, cesium oxide, at least one in nickel oxide and manganese dioxide,
B () adopts the method for plasma reinforced chemical vapour deposition to prepare inorganic barrier layer at mixing barrier layer surface; Adopt CH
4and N
2as reacting gas, control CH
4flow is 5sccm ~ 15sccm, N
2flow is 5sccm ~ 15sccm, and operating pressure is 10Pa ~ 80Pa, and radio-frequency power is 0.1W/cm
2~ 0.5W/cm
2.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the mass fraction of first inorganic material described in step (a) shared by described mixing barrier layer is 10% ~ 20%, the mass fraction of described second inorganic material shared by described mixing barrier layer is 10% ~ 20%, and the mass fraction of described 3rd inorganic material shared by described mixing barrier layer is 10% ~ 20%.
8. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness mixing barrier layer described in step (a) is 100nm ~ 200nm.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the deposit thickness of inorganic barrier layer described in step (b) is 400nm ~ 600nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, described mixing barrier layer and inorganic barrier layer form a construction unit, repeat step (3) 3 ~ 5 times by step (a) and (b) sequence alternate successively after step (b), prepare the encapsulated layer that 3 ~ 5 described construction units repeat to be formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310561744.6A CN104638126A (en) | 2013-11-12 | 2013-11-12 | Organic light-emitting device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310561744.6A CN104638126A (en) | 2013-11-12 | 2013-11-12 | Organic light-emitting device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104638126A true CN104638126A (en) | 2015-05-20 |
Family
ID=53216629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310561744.6A Pending CN104638126A (en) | 2013-11-12 | 2013-11-12 | Organic light-emitting device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104638126A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047895A (en) * | 2017-12-14 | 2018-05-18 | 溧阳东翼通用航空科技有限公司 | Helicopter anticorrosion water-proof paint and preparation method thereof |
| WO2019019263A1 (en) * | 2017-07-25 | 2019-01-31 | 武汉华星光电半导体显示技术有限公司 | Oled flexible display panel and manufacturing method therefor |
-
2013
- 2013-11-12 CN CN201310561744.6A patent/CN104638126A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019019263A1 (en) * | 2017-07-25 | 2019-01-31 | 武汉华星光电半导体显示技术有限公司 | Oled flexible display panel and manufacturing method therefor |
| CN108047895A (en) * | 2017-12-14 | 2018-05-18 | 溧阳东翼通用航空科技有限公司 | Helicopter anticorrosion water-proof paint and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104638183A (en) | Transparent organic light-emitting device and method for manufacturing same | |
| CN104638126A (en) | Organic light-emitting device and preparation method thereof | |
| CN103904246A (en) | Organic electroluminescent device and preparing method thereof | |
| CN104638165A (en) | Organic light-emitting device and preparation method thereof | |
| CN104882560A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104638113A (en) | Organic electroluminescent device and production method thereof | |
| CN104638166A (en) | Organic light-emitting device and preparation method thereof | |
| CN103904244B (en) | A kind of organic electroluminescence device and preparation method thereof | |
| CN103427024A (en) | Organic light-emitting device and preparation method thereof | |
| CN104078601B (en) | Organic electroluminescence device and preparation method thereof | |
| CN104103764A (en) | Organic light-emitting display and manufacturing method thereof | |
| CN103904251B (en) | A kind of organic electroluminescence device and preparation method | |
| CN104638169A (en) | Organic light-emitting device and preparation method thereof | |
| CN103904241B (en) | Organic electroluminescence device and preparation method | |
| CN104638112A (en) | Organic electroluminescent device and production method thereof | |
| CN104638156A (en) | Organic electroluminescent device and production method thereof | |
| CN104518101A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103904242A (en) | Organic electroluminescent device and preparing method thereof | |
| CN104518095A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104638119A (en) | Transparent organic light-emitting device and method for manufacturing same | |
| CN103904235B (en) | Organic electroluminescence device and preparation method thereof | |
| CN104518131A (en) | Organic electroluminescent device and preparation method | |
| CN103904232A (en) | Organic light-emitting device and preparation method | |
| CN104167503A (en) | Organic light-emitting diode and preparation method thereof | |
| CN103904231B (en) | A kind of organic electroluminescence device and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150520 |
|
| WD01 | Invention patent application deemed withdrawn after publication |