CN104638159A - Organic electroluminescence device and production method thereof - Google Patents
Organic electroluminescence device and production method thereof Download PDFInfo
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- CN104638159A CN104638159A CN201310560627.8A CN201310560627A CN104638159A CN 104638159 A CN104638159 A CN 104638159A CN 201310560627 A CN201310560627 A CN 201310560627A CN 104638159 A CN104638159 A CN 104638159A
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Abstract
The invention aims to provide an organic electroluminescence device with an encapsulation layer. The encapsulation layer includes organic barrier layers and mixed barrier layers which are stacked alternately. Each organic barrier layer is made of one of BeO, MgO, CaO, SrO and BaO. Each barrier layer is a mixture formed by mixing one of AlF3, HfF4, ZrF4, LiF, CeF2 and YF3 and boron straight-chain alkane with a structural formula showed in the description and the claims. In the structural formula, k is 1, 2, 3 or 4, and the molar ratio of fluoride is 20-40%. The encapsulation layer can effectively prevent external active substances such as water and oxygen from eroding the organic electroluminescence device and prolong the service life of the organic electroluminescence device. The invention further provides a production method of the organic electroluminescence device. The production method is simple in process, cheap in raw materials, and easy in large-area production.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of is luminescent material with organic material, can be the energy conversion device of luminous energy the electric energy conversion applied.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, has application prospect very widely in fields such as display, illuminations.
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, steam can produce hydrolysis to organic compound, its stability is declined greatly, thus causes component failure, shortens the life-span of OLED.Therefore, usually need to carry out packaging protection process to OLED, luminescent device and external environment isolated, divides to prevent water, the intrusion of pernicious gas etc., and then improve stability and the useful life of OLED.
For OLED product, if use traditional OLED encapsulation technology, add encapsulation cover plate in device back, the problems such as weight is large, cost is high, bad mechanical strength can be produced, limit the performance of OLED product.At present, the water oxygen resistant ability of most OLED is not strong, and useful life is shorter, and complicated process of preparation, cost are high.
Summary of the invention
In order to solve the problem; the present invention aims to provide a kind of organic electroluminescence device with encapsulation layer structure; this encapsulated layer 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, extend the useful life of organic electroluminescence device.Present invention also offers a kind of preparation method of organic electroluminescence device, this preparation method's technique is simple, cheaper starting materials, is easy to large area preparation.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the anode conducting substrate, light emitting functional layer, negative electrode and the encapsulated layer that stack gradually, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually, and described encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The material of described inorganic barrier layer is the one in BeO, MgO, CaO, SrO and BaO;
The material on described mixing barrier layer is AlF
3, HfF
4, ZrF
4, LiF, CeF
2and YF
3in the mixture that is mixed to form of a kind of straight chain alkane of the boron as follows with structural formula, wherein molar ratio shared by fluoride is 20% ~ 40%;
In formula, k is 1,2,3 or 4.
Arrange encapsulated layer at cathode outer side, encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer.Preferably, adjacent with negative electrode is inorganic barrier layer.
Inorganic barrier layer and mixing barrier layer obtain better water oxygen barriering effect through repeatedly alternately laminated.Preferably, encapsulated layer is inorganic barrier layer and the mixing barrier layer of alternately laminated 4 ~ 6 times.
The material of inorganic barrier layer is the one in BeO, MgO, CaO, SrO and BaO.
Preferably, the thickness of inorganic barrier layer is 15 ~ 20nm.
Preferably, the thickness mixing barrier layer is 200 ~ 300nm.
The straight chain alkane of the boron that the present invention uses directly can be bought from market and obtain.
The straight chain alkane evenness of boron is good, and stress is little, has certain absorption to oxygen simultaneously; Fluoride stability is good, and anticorrosive property is strong, by AlF
3, HfF
4, ZrF
4, LiF, CeF
2and YF
3in a kind ofly to adulterate with the straight chain alkane of beryllium, the compactness of rete can be strengthened, have stronger effect to stop steam, effectively can extend water Oxygen permeation path, reach good packaging effect.
Preferably, the material of anode conducting substrate is conducting glass substrate or conduction organic film substrate.More preferably, anode conducting substrate is indium tin oxide (ITO).
Preferably, the thickness of anode conducting substrate is 100nm.
Light emitting functional layer is arranged on anode conducting substrate.
Light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, the material of hole injection layer is MoO
3the mixture be mixed to form according to mass ratio 3:7 with NPB.
Preferably, the thickness of hole injection layer is 10nm.
Preferably, the material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA).
Preferably, the thickness of hole transmission layer is 30nm.
Preferably, the material of luminescent layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) mixture that is mixed to form according to mass ratio 5:95 with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi).
Preferably, the thickness of luminescent layer is 20nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen)
Preferably, the thickness of electron transfer layer is 10nm.
Preferably, the material of electron injecting layer is cesium azide (CsN
3) mixture that is mixed to form according to mass ratio 3:7 with Bphen.
Preferably, the thickness of electron injecting layer is 20nm.
Negative electrode is arranged in light emitting functional layer.
Preferably, the material of negative electrode is aluminium (Al).
Preferably, the thickness of negative electrode is 100nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
S1, provide clean anode conducting substrate, and activation processing is carried out to described anode conducting substrate;
S2, prepare light emitting functional layer and negative electrode in the vacuum evaporation of described anode conducting substrate surface, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually;
S3, atomic layer deposition method is adopted to make inorganic barrier layer at described cathode surface, the organic electroluminescence device sample of negative electrode is had to be placed in the settling chamber of atomic layer deposition system preparation, then in described settling chamber, inject source metal and oxygen source respectively, described source metal is two (ethyl cyclopentadiene) beryllium (Be (CpEt)
2), two (ethyl cyclopentadiene) magnesium (Mg (CpEt)
2), two (ethyl cyclopentadiene) calcium (Ca (CpEt)
2), two (ethyl cyclopentadiene) strontium (Sr (CpEt)
2) or two (ethyl cyclopentadiene) barium (Ba (CpEt)
2), described oxygen source is steam, obtains described inorganic barrier layer after reaction, and the material of described inorganic barrier layer is the one in BeO, MgO, CaO, SrO and BaO;
S4, adopt magnetically controlled sputter method to make mixing barrier layer on described inorganic barrier layer surface, the material on mixing barrier layer is AlF
3, HfF
4, ZrF
4, LiF, CeF
2and YF
3in the mixture that is mixed to form of a kind of straight chain alkane of the boron as follows with structural formula, wherein molar ratio shared by fluoride is 20% ~ 40%;
In formula, k is 1,2,3 or 4;
Repeat step S3 ~ S4 and obtain alternately laminated inorganic barrier layer and mixing barrier layer, finally obtain described organic electroluminescence device.
In step S1, by the cleaning of antianode electrically-conductive backing plate, the organic pollution of removing anode conducting substrate surface.
Particularly, the clean operation of anode conducting substrate is: cleaned in supersonic wave cleaning machine with acetone, ethanol, deionized water, ethanol successively by anode conducting substrate, then dry up with nitrogen, stove-drying, obtains the anode conducting substrate cleaned.
Surface activation process is carried out to the anode conducting substrate after cleaning, to increase the oxygen content of conductive surface layer, improves the work function of conductive layer surface.
Preferably, the material of anode conducting substrate is conducting glass substrate or conduction organic film substrate.More preferably, anode conducting substrate is indium tin oxide (ITO).
Preferably, the thickness of anode conducting substrate is 100nm.
In step S2, light emitting functional layer is arranged on anode conducting substrate by vacuum evaporation.
Preferably, during vacuum evaporation light emitting functional layer, condition is vacuum degree 3 × 10
-5pa, evaporation rate
Light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, the material of hole injection layer is MoO
3the mixture be mixed to form according to mass ratio 3:7 with NPB.
Preferably, the thickness of hole injection layer is 10nm.
Preferably, the material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA).
Preferably, the thickness of hole transmission layer is 30nm.
Preferably, the material of luminescent layer is that three (2-phenylpyridines) close iridium (Ir (ppy)
3) mixture that is mixed to form according to mass ratio 5:95 with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi).
Preferably, the thickness of luminescent layer is 20nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen)
Preferably, the thickness of electron transfer layer is 10nm.
Preferably, the material of electron injecting layer is cesium azide (CsN
3) mixture that is mixed to form according to mass ratio 1:3 with Bphen.
Preferably, the thickness of electron injecting layer is 20nm.
Negative electrode is arranged in light emitting functional layer by vacuum evaporation.
Preferably, during vacuum evaporation negative electrode, condition is vacuum degree 3 × 10
-5pa, evaporation rate
Preferably, the material of negative electrode is aluminium (Al).
Preferably, the thickness of negative electrode is 100nm.
In step S3, two (ethyl cyclopentadiene) beryllium (Be (CpEt)
2), two (ethyl cyclopentadiene) magnesium (Mg (CpEt)
2), two (ethyl cyclopentadiene) calcium (Ca (CpEt)
2), two (ethyl cyclopentadiene) strontium (Sr (CpEt)
2) and two (ethyl cyclopentadiene) barium (Ba (CpEt)
2) chemical structural formula be respectively:
Inorganic barrier layer is with Be (CpEt)
2, Mg (CpEt)
2, Ca (CpEt)
2, Sr (CpEt)
2or Ba (CpEt)
2for source metal, take steam as oxygen source, cathode surface is arranged on by atomic layer deposition method, by single ald, the material obtaining inorganic barrier layer is BeO, MgO, CaO, SrO or BaO, thin-film material, with stable form close-packed arrays, obtain the film that compactness is good, and smooth surface is smooth.
Particularly, there is the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then in settling chamber, inject source metal and oxygen source respectively, be alternately exposed to sample surfaces and react, after multiple ald growth cycle, obtain inorganic barrier layer.
Ald growth cycle is divided into four steps:
The first step: source metal is injected described settling chamber with carrier gas, and absorption is on the cathode, injection length is 10 ~ 20ms, and carrier gas flux is 10 ~ 20sccm;
Second step: inject carrier gas purification settling chamber, remove unnecessary presoma, injection length is 5 ~ 10s, and flow is 10 ~ 20sccm;
3rd step: steam is injected settling chamber with carrier gas, and reacts with described source metal, until the source metal on surface consumes completely, injection length is 10 ~ 20ms, and carrier gas flux is 10 ~ 20sccm;
4th step: inject carrier gas purification settling chamber, avoid the gas-phase reaction of accessory substance, injection length is 5 ~ 10s, and flow is 10 ~ 20sccm.
Preferably, carrier gas is inert gas.
Preferably, the thickness of inorganic barrier layer is 15 ~ 20nm.
In step S4, mixing barrier layer adopts magnetically controlled sputter method to be arranged on described inorganic barrier layer surface.
After completing steps S3 ~ S4, obtained alternately laminated inorganic barrier layer and mixing barrier layer, finally obtain described organic electroluminescence device.
Preferably, step S3 ~ S4 is implemented 4 ~ 6 times, obtain inorganic barrier layer and the mixing barrier layer of alternately laminated 4 ~ 6 times.
The present invention has following beneficial effect:
(1) a kind of organic electroluminescence device with encapsulation layer structure provided by the invention, effectively can prevent outside water, oxygen isoreactivity material to the erosion of organic electroluminescence device, have good sealing and longer useful life.
(2) the straight chain alkane evenness of boron is good, and stress is little, has certain absorption to oxygen simultaneously; Fluoride stability is good, and anticorrosive property is strong, by AlF
3, HfF
4, ZrF
4, LiF, CeF
2and YF
3in a kind ofly to adulterate with the straight chain alkane of beryllium, the compactness of rete can be strengthened, have stronger effect to stop steam, effectively can extend water Oxygen permeation path, reach good packaging effect.
(3) preparation method of a kind of organic electroluminescence device provided by the invention, this preparation method's technique is simple, cheaper starting materials, is easy to large area preparation.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structure chart of the organic electroluminescence device that the embodiment of the present invention 6 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1) clean anode conducting substrate is provided:
Cleaned in supersonic wave cleaning machine with acetone, ethanol, deionized water, ethanol successively by ito glass substrate, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by; Surface activation process is carried out to the ito glass after cleaning; ITO thickness is 100nm;
(2) vacuum evaporation light emitting functional layer on ito glass substrate:
Particularly, light emitting functional layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
The preparation of hole injection layer: by MoO
3the mixture be mixed to get according to mass ratio 3:7 with NPB as the material of hole injection layer, thickness 10nm, vacuum degree 3 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) as hole mobile material, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 30nm;
The preparation of luminescent layer: adopt Ir (ppy)
3the mixture be mixed to form according to mass ratio 5:95 with TPBi as the material of luminescent layer, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 20nm;
The preparation of electron transfer layer: evaporation one deck 4,7-diphenyl-1,10-phenanthroline (Bphen) as electron transport material, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 10nm;
The preparation of electron injecting layer: by CsN
3the mixture be mixed to form according to mass ratio 3:7 with Bphen as the material of electron injecting layer, vacuum degree 3 × 10
-5pa, evaporation rate
evaporation thickness 20nm;
(3) negative electrode is prepared on light emitting functional layer surface:
Metallic cathode adopts aluminium (Al), and thickness is 100nm, vacuum degree 3 × 10
-5pa, evaporation rate
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The making of inorganic barrier layer: have the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then,
A () is by source metal Be (CpEt)
2inject settling chamber with nitrogen and deposit on negative electrode, injection length is 15ms, and nitrogen flow is 15sccm;
B () nitrogen injection rinses settling chamber, injection length is 7s, and flow is 15sccm;
C then steam is injected settling chamber with nitrogen by (), react with source metal, injection length is 15ms, and nitrogen flow is 15sccm;
D () nitrogen injection rinses settling chamber, injection length is 7s, and flow is 15sccm;
Repetition period (a) ~ (d) step, obtains the inorganic barrier layer that thickness is 20nm, and material is BeO;
Mixing barrier layer making: in sputter coating room, on inorganic barrier layer sputter three (3-methyl butyl) boron (structural formula is:
and AlF
3preparation mixing barrier layer, wherein AlF
3shared molar ratio is 40%, and sputtering condition is background vacuum 1 × 10
-5pa, accelerating voltage 500V, magnetic field 100G, power density 20W/cm
2; The thickness on mixing barrier layer is 300nm;
Alternately preparation 6 inorganic barrier layers and mixing barrier layer, finally obtain organic electroluminescence device.
Embodiment 2:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The making of inorganic barrier layer: have the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then,
A () is by source metal Mg (CpEt)
2inject settling chamber with nitrogen and deposit on negative electrode, injection length is 20ms, and nitrogen flow is 20sccm;
B () nitrogen injection rinses settling chamber, injection length is 10s, and flow is 20sccm;
C then steam is injected settling chamber with nitrogen by (), react with source metal, injection length is 20ms, and nitrogen flow is 20sccm;
D () nitrogen injection rinses settling chamber, injection length is 10s, and flow is 20sccm;
Repetition period (a) ~ (d) step, obtains the inorganic barrier layer that thickness is 19nm, and material is MgO;
Mixing barrier layer making: in sputter coating room, on inorganic barrier layer sputter three (3,7-dimethyl octyl group) boron (structural formula is:
and HfF
4preparation mixing barrier layer, wherein HfF
4shared molar ratio is 25%, and sputtering condition is background vacuum 1 × 10
-5pa, accelerating voltage 800V, magnetic field 50G, power density 40W/cm
2; The thickness on mixing barrier layer is 250nm;
Alternately preparation 6 inorganic barrier layers and mixing barrier layer, finally obtain organic electroluminescence device.
Embodiment 3:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The making of inorganic barrier layer: have the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then,
A () is by source metal Ca (CpEt)
2inject settling chamber with nitrogen and deposit on negative electrode, injection length is 10ms, and nitrogen flow is 10sccm;
B () nitrogen injection rinses settling chamber, injection length is 5s, and flow is 10sccm;
C then steam is injected settling chamber with nitrogen by (), react with source metal, injection length is 10ms, and nitrogen flow is 10sccm;
D () nitrogen injection rinses settling chamber, injection length is 5s, and flow is 10sccm;
Repetition period (a) ~ (d) step, obtains the inorganic barrier layer that thickness is 18nm, and material is CaO;
Mixing barrier layer making: in sputter coating room, on inorganic barrier layer sputter three (3,7,11-trimethyldodecane base) boron (structural formula is:
and ZrF
4preparation mixing barrier layer, wherein ZrF
4shared molar ratio is 20%, and sputtering condition is background vacuum 1 × 10
-4pa, accelerating voltage 300V, magnetic field 200G, power density 10W/cm
2; The thickness on mixing barrier layer is 200nm;
Alternately preparation 6 inorganic barrier layers and mixing barrier layer, finally obtain organic electroluminescence device.
Embodiment 4:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The making of inorganic barrier layer: have the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then,
A () is by source metal Sr (CpEt)
2inject settling chamber with nitrogen and deposit on negative electrode, injection length is 15ms, and nitrogen flow is 17sccm;
B () nitrogen injection rinses settling chamber, injection length is 7s, and flow is 17sccm;
C then steam is injected settling chamber with nitrogen by (), react with source metal, injection length is 15ms, and nitrogen flow is 17sccm;
D () nitrogen injection rinses settling chamber, injection length is 7s, and flow is 17sccm;
Repetition period (a) ~ (d) step, obtains the inorganic barrier layer that thickness is 16nm, and material is SrO;
Mixing barrier layer making: in sputter coating room, on inorganic barrier layer sputter three (3,7,11,15-tetramethyl cetyl) boron (structural formula is:
with LiF preparation mixing barrier layer, wherein molar ratio shared by LiF is 25%, and sputtering condition is background vacuum 1 × 10
-4pa, accelerating voltage 400V, magnetic field 150G, power density 25W/cm
2; The thickness on mixing barrier layer is 250nm;
Alternately preparation 5 inorganic barrier layers and mixing barrier layer, finally obtain organic electroluminescence device.
Embodiment 5:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The making of inorganic barrier layer: have the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then,
A () is by source metal Ba (CpEt)
2inject settling chamber with nitrogen and deposit on negative electrode, injection length is 15ms, and nitrogen flow is 11sccm;
B () nitrogen injection rinses settling chamber, injection length is 7s, and flow is 11sccm;
C then steam is injected settling chamber with nitrogen by (), react with source metal, injection length is 15ms, and nitrogen flow is 11sccm;
D () nitrogen injection rinses settling chamber, injection length is 7s, and flow is 11sccm;
Repetition period (a) ~ (d) step, obtains the inorganic barrier layer that thickness is 15nm, and material is BaO;
Mixing barrier layer making: in sputter coating room, on inorganic barrier layer sputter three (3-methyl butyl) boron (structural formula is:
and CeF
2preparation mixing barrier layer, wherein CeF
2shared molar ratio is 20%, and sputtering condition is background vacuum 1 × 10
-4pa, accelerating voltage 500V, magnetic field 100G, power density 20W/cm
2; The thickness on mixing barrier layer is 220nm;
Alternately preparation 5 inorganic barrier layers and mixing barrier layer, finally obtain organic electroluminescence device.
Embodiment 6:
A kind of organic electroluminescence device, is obtained by following operating procedure:
(1), (2), (3) are with embodiment 1;
(4) encapsulated layer is prepared at cathode outer side:
Encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The making of inorganic barrier layer: have the organic electroluminescence device sample of negative electrode to be placed in the settling chamber of atomic layer deposition system preparation, then,
A () is by source metal Ba (CpEt)
2inject settling chamber with nitrogen and deposit on negative electrode, injection length is 10ms, and nitrogen flow is 15sccm;
B () nitrogen injection rinses settling chamber, injection length is 10s, and flow is 15sccm;
C then steam is injected settling chamber with nitrogen by (), react with source metal, injection length is 10ms, and nitrogen flow is 15sccm;
D () nitrogen injection rinses settling chamber, injection length is 10s, and flow is 15sccm;
Repetition period (a) ~ (d) step, obtains the inorganic barrier layer that thickness is 15nm, and material is BaO;
Mixing barrier layer making: in sputter coating room, on inorganic barrier layer sputter three (3,7-dimethyl octyl group) boron (structural formula is:
and YF
3preparation mixing barrier layer, wherein YF
3shared molar ratio is 25%, and sputtering condition is background vacuum 1 × 10
-3pa, accelerating voltage 500V, magnetic field 100G, power density 20W/cm
2; The thickness on mixing barrier layer is 210nm;
Alternately preparation 4 inorganic barrier layers and mixing barrier layer, finally obtain organic electroluminescence device.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment 6.As shown in Figure 1, the structure of this organic electroluminescence device comprises the anode conducting substrate 10, light emitting functional layer 20, negative electrode 30, the encapsulated layer 40(that stack gradually and comprises inorganic barrier layer 401, mixing barrier layer 402, inorganic barrier layer 403, mixing barrier layer 404, inorganic barrier layer 405, mixing barrier layer 406, inorganic barrier layer 407, mixing barrier layer 408).
Effect example
Life-span (the T70@1000cd/m of test organic electroluminescence device
2), from original intensity 1000cd/m
2decay to the time needed for 70%.The life-span of organic electroluminescence device prepared by the embodiment of the present invention 1 ~ 6 is as shown in table 1.As can be seen from the table, the life time of organic electroluminescence device remains on more than 10000, the longlyest reaches 10085 hours.This illustrates, the organic electroluminescence device of encapsulation layer structure that prepared by the present invention have can prevent outside water, oxygen isoreactivity material to the erosion of organic electroluminescence device effectively, has good sealing and longer useful life.
Table 1
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 (8)
1. an organic electroluminescence device, comprise the anode conducting substrate, light emitting functional layer, negative electrode and the encapsulated layer that stack gradually, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually, it is characterized in that, described encapsulated layer is alternately laminated inorganic barrier layer and mixing barrier layer;
The material of described inorganic barrier layer is the one in BeO, MgO, CaO, SrO and BaO;
The material on described mixing barrier layer is AlF
3, HfF
4, ZrF
4, LiF, CeF
2and YF
3in the mixture that is mixed to form of a kind of straight chain alkane of the boron as follows with structural formula, wherein molar ratio shared by fluoride is 20% ~ 40%;
In formula, k is 1,2,3 or 4.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described encapsulated layer is inorganic barrier layer and the mixing barrier layer of alternately laminated 4 ~ 6 times.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described inorganic barrier layer is 15 ~ 20nm, and the thickness on described mixer barrier layer is 200 ~ 300nm.
4. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
S1, provide clean anode conducting substrate, and activation processing is carried out to described anode conducting substrate;
S2, prepare light emitting functional layer and negative electrode in the vacuum evaporation of described anode conducting substrate surface, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually;
S3, atomic layer deposition method is adopted to make inorganic barrier layer at described cathode surface, the organic electroluminescence device sample of negative electrode is had to be placed in the settling chamber of atomic layer deposition system preparation, then in described settling chamber, source metal and oxygen source is injected respectively, described source metal is two (ethyl cyclopentadiene) berylliums, two (ethyl cyclopentadiene) magnesium, two (ethyl cyclopentadiene) calcium, two (ethyl cyclopentadiene) strontium or two (ethyl cyclopentadiene) barium, described oxygen source is steam, described inorganic barrier layer is obtained after reaction, the material of described inorganic barrier layer is BeO, MgO, CaO, one in SrO and BaO,
S4, adopt magnetically controlled sputter method to make mixing barrier layer on described inorganic barrier layer surface, the material on mixing barrier layer is AlF
3, HfF
4, ZrF
4, LiF, CeF
2and YF
3in the mixture that is mixed to form of a kind of straight chain alkane of the boron as follows with structural formula, wherein molar ratio shared by fluoride is 20% ~ 40%;
In formula, k is 1,2,3 or 4;
Repeat step S3 ~ S4 and obtain alternately laminated inorganic barrier layer and mixing barrier layer, finally obtain described organic electroluminescence device.
5. the preparation method of organic electroluminescence device as claimed in claim 4, it is characterized in that, a manufacturing cycle of the atomic layer deposition method of step S3 is:
A source metal is injected described settling chamber with carrier gas and is deposited on the cathode by (), injection length is 10 ~ 20ms, and carrier gas flux is 10 ~ 20sccm;
B () is injected carrier gas and is rinsed settling chamber, injection length is 5 ~ 10s, and flow is 10 ~ 20sccm;
C then steam is injected settling chamber with carrier gas by (), react with described source metal, injection length is 10 ~ 20ms, and carrier gas flux is 10 ~ 20sccm;
D () is injected carrier gas and is rinsed settling chamber, injection length is 5 ~ 10s, and flow is 10 ~ 20sccm.
6. the preparation method of organic electroluminescence device as claimed in claim 4, it is characterized in that, in step S4, magnetron sputtering condition is background vacuum 1 × 10
-5~ 1 × 10
-3pa, accelerating voltage 300 ~ 800V, magnetic field 50 ~ 200G, power density 1 ~ 40W/cm
2.
7. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, described encapsulated layer is inorganic barrier layer and the mixing barrier layer of alternately laminated 4 ~ 6 times.
8. the preparation method of organic electroluminescence device as claimed in claim 4, it is characterized in that, the thickness of described inorganic barrier layer is 15 ~ 20nm, and the thickness on described mixing barrier layer is 200 ~ 300nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017016327A1 (en) * | 2015-07-30 | 2017-02-02 | 西安宝莱特光电科技有限公司 | Dynamic two-dimensional code device for oled and manufacturing method therefor |
| WO2017016328A1 (en) * | 2015-07-30 | 2017-02-02 | 西安宝莱特光电科技有限公司 | Dynamic one-dimensional code device for oled and manufacturing method therefor |
-
2013
- 2013-11-12 CN CN201310560627.8A patent/CN104638159A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017016327A1 (en) * | 2015-07-30 | 2017-02-02 | 西安宝莱特光电科技有限公司 | Dynamic two-dimensional code device for oled and manufacturing method therefor |
| WO2017016328A1 (en) * | 2015-07-30 | 2017-02-02 | 西安宝莱特光电科技有限公司 | Dynamic one-dimensional code device for oled and manufacturing method therefor |
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