CN102496682A - Blue-green organic light-emitting device and manufacture method thereof - Google Patents
Blue-green organic light-emitting device and manufacture method thereof Download PDFInfo
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- CN102496682A CN102496682A CN2011103819478A CN201110381947A CN102496682A CN 102496682 A CN102496682 A CN 102496682A CN 2011103819478 A CN2011103819478 A CN 2011103819478A CN 201110381947 A CN201110381947 A CN 201110381947A CN 102496682 A CN102496682 A CN 102496682A
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Abstract
The present invention provides a kind of blue-green organic electroluminescent device and preparation method thereof, which includes: substrate; Stack gradually the anode in substrate surface, hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, buffer layer and cathode; Wherein, it is (9~12): the complex of iridium and first or second organic host material of 100 formula (I) structure that the first luminescent layer and the second luminescent layer, which include weight ratio,. Above-mentioned complex of iridium material has both high-luminous-efficiency and superior electron transport ability, thus improves the luminous efficiency and current density of device. Double emitting layers, the first luminescent layer material based on cavity type material, the second luminescent layer material based on electron type material is arranged in above-mentioned device. First luminescent layer can reduce hole in the accumulation in section that shines, and the second luminescent layer can reduce electronics in the accumulation in section that shines, and the two collective effect widens the luminous section of device, so that the efficiency of device delayed to decay.
Formula (I).
Description
Technical field
The present invention relates to the organic electroluminescence device field, particularly a kind of blue-green organic electroluminescence device and preparation method thereof.
Background technology
(organic light emitting diode OLED) is the self-luminous flat-panel display device that receives much concern in recent years to organic electroluminescence device.Organic electroluminescence device is high bright higher, and its visual angle is wider, can reach more than 170 degree; Reaction time is fast, is about 1 μ s magnitude; The material range of choice is wide, can realize the demonstration of ruddiness to any color of blue light.With respect to flat-panel monitors such as FED, PDP and LCD, organic electroluminescence device has lower driving voltage, and operating temperature range is wide, and is lower to production technology and equipment requirements, and production cost is lower.In view of the above-mentioned advantage of organic electroluminescence device, organic electroluminescence device has boundless application prospect, is expected to realize quick response, slimming, lightweight, the low-voltageization of display device.In addition, organic electroluminescence device can also use as new type light source.
Organic electroluminescence device generally includes electron injection electrode (negative electrode), hole injecting electrode (anode); And be arranged at the organic membrane between electron injection electrode and the hole injecting electrode; Be connected with additional power source between electron injection electrode and the hole injecting electrode; When electric charge was injected into the organic luminous layer between electron injection electrode and the hole injecting electrode, meeting and take place compoundly subsequently in electronics and hole, produces photon thus.
The blue-green organic electroluminescence device is one type of important organic electroluminescence device.All the time; The trivalent complex of iridium is regarded as desirable electroluminescent organic material because having advantages such as the high and glow color of luminous efficiency is adjustable by academia and industrial circle; Many research teams both domestic and external set about with the device optimization aspect from material is synthetic, and the combination property of making great efforts to improve the blue-green organic electroluminescence device is in the hope of satisfying the needs of industrialization.For example: the people such as S.R.Forrest of Princeton university in 2003 adopt the complex of iridium FIrpic with blue-green emission as luminescent material, make organic electroluminescence device through the method for mixing.Though this device shows that comparatively desirable blue-green is luminous, however unbalanced charge carrier inject and cause the efficient of device and brightness lower, the operating voltage of device is also higher in addition.
In order to address the above problem, the people such as Franky So of U.S. good fortune Flo-Rida-Low university in 2008 are through mixing high efficiency complex of iridium the blue-green organic electroluminescence device that has made sandwich construction in the preferred material of main part.This device has higher maximum luminous efficiency and high-high brightness, yet the luminous efficiency of device promptly decays along with the raising of current density.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of blue-green organic electroluminescence device with higher photoluminescence efficiency, current density and brightness and preparation method thereof.
In view of this, the present invention provides a kind of blue-green organic electroluminescence device, comprising:
Substrate;
Stack gradually anode, hole transmission layer, first luminescent layer, second luminescent layer, hole blocking layer, resilient coating and negative electrode in said substrate surface;
Said first luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the first organic main body material;
The said first organic main body material is 4,4 '-N, N '-two carbazole diphenyl, 1; 3-two carbazoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole, 1; 3,5-three (9-carbazyl) benzene or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine;
Said second luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the second organic main body material;
The said second organic main body material is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl);
Preferably, hole transmission layer be 4,4 '-cyclohexyl two [N, N-two (4-aminomethyl phenyl) aniline].
Preferably, said hole blocking layer is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl).
Preferably, the thickness of said first luminescent layer is 10～30nm.
Preferably, the thickness of said second luminescent layer is 5～15nm.
Accordingly, the present invention also provides a kind of preparation method of above-mentioned blue-green organic electroluminescence device, comprising:
The substrate of the surface being had anode carries out the Low Pressure Oxygen plasma treatment;
At said anode surface vacuum evaporation hole transmission layer successively, first luminescent layer, second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Said first luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the first organic main body material;
The said first organic main body material is 4,4 '-N, N '-two carbazole diphenyl, 1; 3-two carbazoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole, 1; 3,5-three (9-carbazyl) benzene or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine;
Said second luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the second organic main body material;
The said second organic main body material is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl);
Preferably, the vacuum degree of said plasma treatment is 8～15Pa, and voltage is 350～500V.
Preferably, said vacuum evaporation is specially:
In (1～2) * 10
-5Condition under, carry out the step of vapor deposition hole transmission layer, the step of vapor deposition first luminescent layer, the step of vapor deposition second luminescent layer, the step of vapor deposition hole blocking layer successively at said anode surface;
In (4～6) * 10
-5Condition under condition under, carry out the step of vapor deposition resilient coating, the step of vapor deposition negative electrode successively at said hole barrier laminar surface.
Preferably, the step of said vapor deposition first luminescent layer is specially:
In (1～2) * 10
-5Under the condition of Pa, the evaporation rate that the said complex of iridium and the first organic main body material are set is than being (9～12): 100, carry out vapor deposition.
Preferably, the step of said vapor deposition second luminescent layer is specially:
In (1～2) * 10
-5Under the condition of Pa, the evaporation rate that the said complex of iridium and the second organic main body material are set is than being (9～12): 100, carry out vapor deposition.
The present invention provides a kind of blue-green organic electroluminescence device, comprises substrate, anode, hole transmission layer, first luminescent layer, second luminescent layer, hole blocking layer, resilient coating and negative electrode.With respect to prior art, at first, the present invention adopts the complex of iridium of formula (I) structure as luminescent material, and this material has high-luminous-efficiency and superior electron transport ability concurrently, improves luminous efficiency, current density and the brightness of device thus.Simultaneously, the present invention is provided with two luminescent layers, and first luminescent layer is the main light emission layer, and it is a material of main part with the cavity type material, makes thus and wins luminescent layer except producing photon, also plays the effect of transporting holes; Second luminescent layer is the auxiliary light emission layer, and it is a material of main part with the electron type material, makes second luminescent layer thus except producing photon, also plays the effect of transmission electronic.First luminescent layer can reduce the accumulation of hole between the luminous zone; Second luminescent layer can reduce the accumulation of electronics between the luminous zone; The two acting in conjunction helps being limited between the recombination region with electronics and hole the center of luminescent layer; Make full use of the exciton that electronics and hole-recombination produce, and then widen between the luminous zone of device, thereby the efficient that has delayed device decays.Therefore, blue-green organic electroluminescence device provided by the invention has higher luminous efficiency, current density and brightness.
Description of drawings
Fig. 1 is the structural representation of blue-green organic electroluminescence device provided by the invention;
Fig. 2 is the voltage-to-current density-luminosity response of the blue-green organic electroluminescence device of embodiment 1 preparation;
Fig. 3 is the current density-power efficiency-current efficiency characteristic curve of the blue-green organic electroluminescence device of embodiment 1 preparation;
Fig. 4 is 20000cd/m for the blue-green organic electroluminescence device of embodiment 1 preparation in brightness
2The time spectrogram;
Fig. 5 is the voltage-to-current density-luminosity response of the blue-green organic electroluminescence device of embodiment 2 preparations;
Fig. 6 is the current density-power efficiency-current efficiency characteristic curve of the blue-green organic electroluminescence device of embodiment 2 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The invention discloses a kind of blue-green organic electroluminescence device, its structure is as shown in Figure 1, and this blue-green organic electroluminescence device comprises:
Stack gradually anode 2 in said substrate 1 surface, hole transmission layer 3, first luminescent layer 4, second luminescent layer 5, hole blocking layer 6, resilient coating 7 and negative electrode 8;
Wherein, first luminescent layer 4 comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the first organic main body material;
The said first organic main body material is 4,4 '-N, N '-two carbazole diphenyl (CBP), 1; 3-two carbazoles-9-base benzene (MCP), 9; 9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole (Simcp), 1,3; 5-three (9-carbazyl) benzene or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine (26DczPPy);
Said second luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the second organic main body material;
The said second organic main body material is 1,3,5-three (benzene (TPBi) or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine (3TPYMB) of 1-phenyl-1H-benzimidazolyl-2 radicals-yl);
Above-mentioned blue-green organic electroluminescence device provided by the invention, the complex of iridium of employing formula (I) structure are as luminescent material, and it is that two (2-(4, the 6-difluorophenyl) pyridine)-(two (diphenyl phosphinylidyne) amine) close iridium, hereinafter to be referred as Ir (dfppy)
2(tpip), this complex of iridium has higher luminous efficiency, and its electron transport ability is stronger, improves luminous efficiency, current density and the brightness of organic electroluminescence device thus.
In addition, above-mentioned blue-green organic electroluminescence device is provided with two luminescent layers, and wherein, first luminescent layer is main luminescent layer, and second luminescent layer plays the effect of auxiliary light emission.First luminescent layer is with 4,4 '-N, N '-two carbazole diphenyl, 1; 3-two carbazoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole, 1; 3,5-three (9-carbazyl) benzene (TCP) or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine is as material of main part.Above-claimed cpd is the cavity type material, makes thus to win luminescent layer except producing photon, also plays the effect of transporting holes.
Second luminescent layer is with 1,3, and (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl) is as material of main part for 5-three.Above-mentioned material is the electron type material, makes second luminescent layer thus except producing photon, also plays the effect of transmission electronic.
Thus; First luminescent layer can reduce the accumulation of hole between the luminous zone; Second luminescent layer can reduce the accumulation of electronics between the luminous zone, helps being limited between the recombination region with electronics and hole the center of luminescent layer, makes full use of the exciton that electronics and hole-recombination produce; Help widening between the luminous zone of device, thereby the efficient that has delayed device decays.
In above-mentioned first luminescent layer 4 and second luminescent layer 5 complex of iridium and material of main part weight ratio influential to the luminous efficiency of device; Complex of iridium of the present invention and material of main part Weight control be (9～12): 100; Ratio is excessive or too smallly be prone to cause the luminous efficiency of device to decline to a great extent; Also can make simultaneously operating voltage improve, and the illuminant colour purity of device also can reduce.The weight ratio that the present invention preferably controls complex of iridium described in first luminescent layer 4 and second luminescent layer 5 and material of main part is (9～11): 100.In the above-mentioned blue-green organic electroluminescence device, the thickness of first luminescent layer is preferably 10～30nm, and the thickness of second luminescent layer is preferably 5～15nm.
Substrate, anode, hole transmission layer, hole blocking layer, resilient coating and negative electrode in the blue-green organic electroluminescence device provided by the invention can adopt the respective material of existing blue-green organic electroluminescence device.As preferred version, among the present invention, hole transmission layer preferably adopts 4; 4 '-cyclohexyl two [N; N-two (4-aminomethyl phenyl) aniline] (TAPC), this layer has the function that hole injection, hole transport and electronics stop concurrently, simplified structure when reducing the device operating voltage.The thickness of hole transmission layer is preferably 40～60nm.
Substrate is preferably glass substrate, and anode layer preferably adopts indium tin oxide (ITO), and its face resistance is preferably 10～15 Ω.Negative electrode preferably adopts metallic aluminium (Al), and its thickness is preferably 90～150nm.The effect of resilient coating 7 is to improve the electronics injectability of device, preferably adopts lithium fluoride (LiF), and the thickness of resilient coating 7 is preferably 0.8～1.2nm.
The course of work of above-mentioned blue-green organic electroluminescence device provided by the invention is following:
Under the effect of extra electric field, the hole gets into first luminescent layer from the anode injection device through hole transmission layer, has a small amount of hole can get into second luminescent layer; Simultaneously, electronics gets into second luminescent layer from the negative electrode injection device through hole blocking layer, gets into first luminescent layer then.So electronics and hole are fettered by complex of iridium at first luminescent layer and second luminescent layer, so take place compound cause luminous.
Can be known that by such scheme the present invention at first adopts the complex of iridium of formula (I) structure as luminescent material, this material has high-luminous-efficiency and superior electron transport ability concurrently, improves luminous efficiency, current density and the brightness of device thus.Simultaneously, the present invention is provided with two luminescent layers, and first luminescent layer is the main light emission layer, and it is a material of main part with the cavity type material, makes thus and wins luminescent layer except producing photon, also plays the effect of transporting holes; Second luminescent layer is the auxiliary light emission layer, and it is a material of main part with the electron type material, makes second luminescent layer thus except producing photon, also plays the effect of transmission electronic.First luminescent layer can reduce the accumulation of hole between the luminous zone; Second luminescent layer can reduce the accumulation of electronics between the luminous zone; The two acting in conjunction helps being limited between the recombination region with electronics and hole the center of luminescent layer; Make full use of the exciton that electronics and hole-recombination produce, and then widen between the luminous zone of device, thereby the efficient that has delayed device decays.
The present invention also provides a kind of preparation method of above-mentioned blue-green organic electroluminescence device, comprising:
The substrate that the surface is covered with anode carries out the Low Pressure Oxygen plasma treatment;
At said anode surface vacuum evaporation hole transmission layer successively, first luminescent layer, second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Wherein, said first luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the first organic main body material;
The said first organic main body material is 4,4 '-N, N '-two carbazole diphenyl, 1; 3-two carbazoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole, 1; 3,5-three (9-carbazyl) benzene or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine;
Said second luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the second organic main body material;
The said second organic main body material is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl);
Among the above-mentioned preparation method, at first the Low Pressure Oxygen plasma treatment is carried out on the antianode surface, and its purpose is further to clean anode surface and improve hole injection rate.In the Low Pressure Oxygen plasma treatment process, vacuum degree is preferably 8～15Pa, and voltage is preferably 350～500V, and the time is preferably 5～15min.
Before carrying out vacuum evaporation, also preferably carry out the step that substrate cleans, preferably adopt ultrasonic cleaning, carry out drying after the cleaning.
The operation of vacuum evaporation is preferably carried out according to following mode among the present invention:
In (1～2) * 10
-5Under the condition of Pa, carry out the step of vapor deposition hole transmission layer, the step of vapor deposition first luminescent layer, the step of vapor deposition second luminescent layer, the step of vapor deposition hole blocking layer successively at said anode surface;
In (4～6) * 10
-5Under the condition under the condition of Pa, carry out the step of vapor deposition resilient coating, vapor deposition negative electrode successively at said hole barrier laminar surface.
Wherein, the step of vapor deposition first luminescent layer preferably is specially:
In (1～2) * 10
-5Under the condition of Pa, the evaporation rate that the above-mentioned complex of iridium and the first organic main body material are set is than being (9～12): 100, carry out vapor deposition.
The step of vapor deposition second luminescent layer preferably is specially:
In (1～2) * 10
-5Under the condition of Pa, the evaporation rate that the above-mentioned complex of iridium and the second organic main body material are set is than being (9～12): 100, carry out vapor deposition.
Among the present invention; The material of main part of first luminescent layer is CBP, Simcp, TCP or 26DczPPy; The material of main part TPBi or the 3TPYMB of second luminescent layer, hole transmission layer preferably adopts TAPC, and hole blocking layer is preferably TPBi or 3TPMB; In the vacuum evaporation process, the evaporation rate of above-mentioned material preferably is controlled to be 0.05～0.1nm/s.The evaporation rate of complex of iridium is preferably 0.0045～0.012nm/s.Resilient coating preferably adopts LiF, and evaporation rate is preferably 0.005～0.015nm/s.Negative electrode preferably adopts metallic aluminium, and evaporation rate is preferably 0.5～1.5nm/s.
The blue-green organic electroluminescence device of preparing according to the method described above has higher luminous efficiency, current density and brightness, and operating voltage is lower.
In order further to understand the present invention, below in conjunction with embodiment blue-green organic electroluminescence device provided by the invention and preparation method thereof to be described, protection scope of the present invention is not limited by the following examples.
Ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long; Then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.
Dried substrate is put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 400 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.
In vacuum degree is (1～2) * 10
-5In the organic vapor deposition chamber of handkerchief, the TAPC hole transmission layer of vapor deposition 50 nanometer thickness, 20 nanometer thickness Ir (dfppy) successively on the ITO layer
2(tpip) first luminescent layer of doping MCP, 10 nanometer thickness Ir (dfppy)
2(tpip) the TPBi hole blocking layer of second luminescent layer of doping TPBi and 30 nanometer thickness.
Device is transferred to the metal evaporation chamber, in (4～6) * 10
-5The LiF resilient coating of vapor deposition 1.0 nanometer thickness under the vacuum of handkerchief, through the metal A l electrode of mask vapor deposition 100 nanometer thickness on the LiF layer, being prepared into structure is ITO/TAPC/Ir (dfppy)
2(tpip) (10%): MCP/Ir (dfppy)
2(tpip) organic electroluminescence device of (10%): TPBi/TPBi/LiF/Al.The light-emitting area of this device is 10 square millimeters.
In the evaporate process:
The evaporation rate of TAPC is controlled at 0.05 nm/sec in the hole transmission layer;
Ir in first luminescent layer (dfppy)
2(tpip) and the evaporation rate of MCP be controlled to be 0.01 nm/sec and 0.1 nm/sec respectively;
Ir in second luminescent layer (dfppy)
2(tpip) and the evaporation rate of TPBi be controlled to be 0.01 nm/sec and 0.1 nm/sec respectively;
The evaporation rate of TPBi is controlled at 0.05 nm/sec in the hole blocking layer;
The evaporation rate of resilient coating LiF is controlled at 0.005 nm/sec;
The evaporation rate of negative electrode Al is controlled at 0.5 nm/sec.
Fig. 2 is the voltage-to-current density-luminosity response of the blue-green organic electroluminescence device of present embodiment preparation.Can be known by Fig. 2: the brightness of device raises along with the rising of current density and driving voltage, and the bright voltage that rises of device is 3.3 volts, is that 11.5 volts, current density are 589.9 milliamperes of every square centimeter of (mA/cm at voltage
2) time device obtain every square metre of (cd/m of high-high brightness 56678.8 candelas
2).
Fig. 3 is the current density-power efficiency-current efficiency characteristic curve of the blue-green organic electroluminescence device of present embodiment preparation.Can be known by Fig. 3: the maximum current efficient of this device is every ampere of 35.22 candela (cd/A), and maximum power efficiency is every watt of 26.36 lumen (lm/W).
Fig. 4 be present embodiment preparation the blue-green organic electroluminescence device be 20000cd/m in brightness
2The time spectrogram, the spectrum main peak is positioned at 488 nanometers, acromion is positioned at 516 nanometers.The device chromaticity coordinates is (0.145,0.426).
Ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long; Then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.
Dried substrate is put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 400 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.
In vacuum degree is (1～2) * 10
-5In the organic vapor deposition chamber of handkerchief, the TAPC hole transmission layer of vapor deposition 40 nanometer thickness, 20 nanometer thickness Ir (dfppy) successively on the ITO layer
2(tpip) first luminescent layer of doping MCP, 10 nanometer thickness Ir (dfppy)
2(tpip) the TPBi hole blocking layer of second luminescent layer of doping TPBi and 30 nanometer thickness.
Device is transferred to the metal evaporation chamber, in (4～6) * 10
-5The LiF resilient coating of vapor deposition 1.0 nanometer thickness under the vacuum of handkerchief, through the metal A l electrode of mask vapor deposition 100 nanometer thickness on the LiF layer, being prepared into structure is ITO/TAPC/Ir (dfppy)
2(tpip) organic electroluminescence device of (10%): MCP/Ir (dfppy) 2 (tpip) (10%): TPBi/TPBi/LiF/Al.The light-emitting area of this device is 10 square millimeters.
In the evaporate process:
The evaporation rate of TAPC is controlled at 0.05 nm/sec in the hole transmission layer;
Ir in first luminescent layer (dfppy)
2(tpip) and the evaporation rate of MCP be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
Ir in second luminescent layer (dfppy)
2(tpip) and the evaporation rate of TPBi be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
The evaporation rate of TPBi is controlled at 0.05 nm/sec in the hole blocking layer;
The evaporation rate of resilient coating LiF is controlled at 0.005 nm/sec;
The evaporation rate of negative electrode Al is controlled at 0.5 nm/sec.
The present embodiment obtained device shows that main peak is positioned at the bluish-green coloured light that 488 nanometer acromions are positioned at 516 nanometers under direct voltage drive.When brightness is 20000cd/m
2The time, the chromaticity coordinates of device is (0.148,0.418); Along with the variation of operating voltage, the chromaticity coordinates of device is almost constant.
Fig. 5 is the voltage-to-current density-luminosity response of the blue-green organic electroluminescence device of present embodiment preparation.Can be known by Fig. 5: the brightness of this device raises along with the rising of current density and driving voltage, and the bright voltage that rises of device is 3.2 volts, is 11.5 volts at voltage, device acquisition high-high brightness 53749.9cd/m when current density is 648.88mA/cm2
2
Fig. 6 is the current density-power efficiency-current efficiency characteristic curve of the blue-green organic electroluminescence device of present embodiment preparation.Can be known by Fig. 6: the maximum current efficient of this device is 29.77cd/A, and maximum power efficiency is 22.40lm/W.
Embodiment 3
Ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.
Dried substrate is put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 400 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.
In vacuum degree is (1～2) * 10
-5In the organic vapor deposition chamber of handkerchief, the TAPC hole transmission layer of vapor deposition 30 nanometer thickness, 30 nanometer thickness Ir (dfppy) successively on the ITO layer
2(tpip) first luminescent layer of doping MCP, 10 nanometer thickness Ir (dfppy)
2(tpip) the TPBi hole blocking layer of second luminescent layer of doping TPBi and 30 nanometer thickness.
Device is transferred to the metal evaporation chamber, in (4～6) * 10
-5The LiF resilient coating of vapor deposition 1.0 nanometer thickness under the vacuum of handkerchief, through the metal A l electrode of mask vapor deposition 100 nanometer thickness on the LiF layer, being prepared into structure is ITO/TAPC/Ir (dfppy)
2(tpip) (10%): MCP/Ir (dfppy)
2(tpip) organic electroluminescence device of (10%): TPBi/TPBi/LiF/Al.The light-emitting area of this device is 10 square millimeters.
In the evaporate process:
The evaporation rate of TAPC is controlled at 0.05 nm/sec in the hole transmission layer;
Ir in first luminescent layer (dfppy)
2(tpip) and the evaporation rate of MCP be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
Ir in second luminescent layer (dfppy)
2(tpip) and the evaporation rate of TPBi be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
The evaporation rate of TPBi is controlled at 0.05 nm/sec in the hole blocking layer;
The evaporation rate of resilient coating LiF is controlled at 0.005 nm/sec;
The evaporation rate of negative electrode Al is controlled at 0.5 nm/sec.
The present embodiment obtained device shows that main peak is positioned at the bluish-green coloured light that 488 nanometer acromions are positioned at 516 nanometers under direct voltage drive.When brightness is 20000cd/m
2The time, the chromaticity coordinates of device is (0.143,0.427); Along with the variation of operating voltage, the chromaticity coordinates of device is almost constant.A bright voltage of device is 3.5 volts, and the high-high brightness of device is 55128.7cd/m2.The maximum current efficient of device is 27.39cd/A, and maximum power efficiency is 24.38lm/W.
Ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.
Dried substrate is put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 400 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.
In vacuum degree is (1～2) * 10
-5In the organic vapor deposition chamber of handkerchief, the TAPC hole transmission layer of vapor deposition 40 nanometer thickness, 20 nanometer thickness Ir (dfppy) successively on the ITO layer
2(tpip) first luminescent layer of doping MCP, 10 nanometer thickness Ir (dfppy)
2(tpip) the TPBi hole blocking layer of second luminescent layer of doping TPBi and 20 nanometer thickness.
Device is transferred to the metal evaporation chamber, in (4～6) * 10
-5The LiF resilient coating of vapor deposition 1.0 nanometer thickness under the vacuum of handkerchief, through the metal A l electrode of mask vapor deposition 100 nanometer thickness on the LiF layer, being prepared into structure is ITO/TAPC/Ir (dfppy)
2(tpip) (10%): MCP/Ir (dfppy)
2(tpip) organic electroluminescence device of (10%): TPBi/TPBi/LiF/Al.The light-emitting area of this device is 10 square millimeters.
In the evaporate process:
The evaporation rate of TAPC is controlled at 0.05 nm/sec in the hole transmission layer;
Ir in first luminescent layer (dfppy)
2(tpip) and the evaporation rate of MCP be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
Ir in second luminescent layer (dfppy)
2(tpip) and the evaporation rate of TPBi be controlled at 0.01 nm/sec and 0.1 nm/sec;
The evaporation rate of TPBi is controlled at 0.05 nm/sec in the hole blocking layer;
The evaporation rate of resilient coating LiF is controlled at 0.005 nm/sec;
The evaporation rate of negative electrode Al is controlled at 0.5 nm/sec.
The present embodiment obtained device shows that main peak is positioned at the bluish-green coloured light that 488 nanometer acromions are positioned at 516 nanometers under direct voltage drive.When brightness is 20000cd/m
2The time, the chromaticity coordinates of device is (0.144,0.428); Along with the variation of operating voltage, the chromaticity coordinates of device is almost constant.A bright voltage of device is 3.2 volts, and the high-high brightness of device is 41195.9cd/m
2The maximum current efficient of device is 20.82cd/A, and maximum power efficiency is 14.03lm/W.
Embodiment 5
Ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.
Dried substrate is put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 400 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.
In vacuum degree is (1～2) * 10
-5In the organic vapor deposition chamber of handkerchief, the TAPC hole transmission layer of vapor deposition 40 nanometer thickness, 20 nanometer thickness Ir (dfppy) successively on the ITO layer
2(tpip) first luminescent layer of doping MCP, 10 nanometer thickness Ir (dfppy)
2(tpip) the TPBi hole blocking layer of second luminescent layer of doping TPBi and 30 nanometer thickness.
Device is transferred to the metal evaporation chamber, in (4～6) * 10
-5The LiF resilient coating of vapor deposition 1.0 nanometer thickness under the vacuum of handkerchief, through the metal A l electrode of mask vapor deposition 100 nanometer thickness on the LiF layer, being prepared into structure is ITO/TAPC/Ir (dfppy)
2(tpip) (12%): MCP/Ir (dfppy)
2(tpip) organic electroluminescence device of (12%): TPBi/TPBi/LiF/Al.The light-emitting area of this device is 10 square millimeters.
In the evaporate process:
The evaporation rate of TAPC is controlled at 0.05 nm/sec in the hole transmission layer;
Ir in first luminescent layer (dfppy)
2(tpip) and the evaporation rate of MCP be controlled at 0.012 nm/sec and 0.1 nm/sec respectively;
Ir in second luminescent layer (dfppy)
2(tpip) and the evaporation rate of TPBi be controlled at 0.012 nm/sec and 0.1 nm/sec respectively;
The evaporation rate of TPBi is controlled at 0.05 nm/sec in the hole blocking layer;
The evaporation rate of resilient coating LiF is controlled at 0.005 nm/sec;
The evaporation rate of negative electrode Al is controlled at 0.5 nm/sec.
The present embodiment obtained device shows that main peak is positioned at the bluish-green coloured light that 488 nanometer acromions are positioned at 516 nanometers under direct voltage drive.When brightness is 20000cd/m
2The time, the chromaticity coordinates of device is (0.146,0.429); Along with the variation of operating voltage, the chromaticity coordinates of device is almost constant.A bright voltage of device is 3.3 volts, and the high-high brightness of device is 54877.4cd/m
2The maximum current efficient of device is 27.58cd/A, and maximum power efficiency is 19.33lm/W.
Ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.
Dried substrate is put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 400 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.
In vacuum degree is (1～2) * 10
-5In the organic vapor deposition chamber of handkerchief, the TAPC hole transmission layer of vapor deposition 40 nanometer thickness, 10 nanometer thickness Ir (dfppy) successively on the ITO layer
2(tpip) first luminescent layer of doping MCP, 10 nanometer thickness Ir (dfppy)
2(tpip) the TPBi hole blocking layer of second luminescent layer of doping TPBi and 30 nanometer thickness.
Device is transferred to the metal evaporation chamber, in (4～6) * 10
-5The LiF resilient coating of vapor deposition 1.0 nanometer thickness under the vacuum of handkerchief, through the metal A l electrode of mask vapor deposition 100 nanometer thickness on the LiF layer, being prepared into structure is ITO/TAPC/Ir (dfppy)
2(tpip) (10%): MCP/Ir (dfppy)
2(tpip) organic electroluminescence device of (10%): TPBi/TPBi/LiF/Al.The light-emitting area of this device is 10 square millimeters.
In the evaporate process:
The evaporation rate of TAPC is controlled at 0.05 nm/sec in the hole transmission layer;
Ir in first luminescent layer (dfppy)
2(tpip) and the evaporation rate of MCP be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
Ir in second luminescent layer (dfppy)
2(tpip) and the evaporation rate of TPBi be controlled at 0.01 nm/sec and 0.1 nm/sec respectively;
The evaporation rate of TPBi is controlled at 0.05 nm/sec in the hole blocking layer;
The evaporation rate of resilient coating LiF is controlled at 0.005 nm/sec;
The evaporation rate of negative electrode Al is controlled at 0.5 nm/sec.
The present embodiment obtained device shows that main peak is positioned at the bluish-green coloured light that 488 nanometer acromions are positioned at 516 nanometers under direct voltage drive.When brightness is 20000cd/m
2The time, the chromaticity coordinates of device is (0.144,0.427); Along with the variation of operating voltage, the chromaticity coordinates of device is almost constant.A bright voltage of device is 3.1 volts, and the high-high brightness of device is 35936.9cd/m
2The maximum current efficient of device is 26.70cd/A, and maximum power efficiency is 24.68lm/W.
Can know by The above results; Blue-green organic electroluminescence device provided by the invention has higher luminous efficiency, current density and brightness; Maximum power efficiency can reach 26.36lm/W, and maximum current efficient can reach 35.22cd/A, and high-high brightness can reach 566788.8cd/m
2, operating voltage is lower.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. a blue-green organic electroluminescence device is characterized in that, comprising:
Substrate;
Stack gradually anode, hole transmission layer, first luminescent layer, second luminescent layer, hole blocking layer, resilient coating and negative electrode in said substrate surface;
Said first luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the first organic main body material;
The said first organic main body material is 4,4 '-N, N '-two carbazole diphenyl, 1; 3-two carbazoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole, 1; 3,5-three (9-carbazyl) benzene or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine;
Said second luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the second organic main body material;
The said second organic main body material is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl);
2. blue-green organic electroluminescence device according to claim 1 is characterized in that, said hole transmission layer is 4,4 '-cyclohexyl two [N, N-two (4-aminomethyl phenyl) aniline].
3. blue-green organic electroluminescence device according to claim 1 is characterized in that, said hole blocking layer is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl).
4. blue-green organic electroluminescence device according to claim 1 is characterized in that, the thickness of said first luminescent layer is 10～30nm.
5. blue-green organic electroluminescence device according to claim 1 is characterized in that, the thickness of said second luminescent layer is 5～15nm.
6. the preparation method of the described blue-green organic electroluminescence device of claim 1 comprises:
The substrate that the surface is covered with anode carries out the Low Pressure Oxygen plasma treatment;
At said anode surface vacuum evaporation hole transmission layer successively, first luminescent layer, second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Said first luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the first organic main body material;
The said first organic main body material is 4,4 '-N, N '-two carbazole diphenyl, 1; 3-two carbazoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazole, 1; 3,5-three (9-carbazyl) benzene or 2,6-two [3-(9H-9-carbazyl) phenyl] pyridine;
Said second luminescent layer comprises that weight ratio is (9～12): the complex of iridium of 100 formula (I) structure and the second organic main body material;
The said second organic main body material is 1,3,5-three (benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of 1-phenyl-1H-benzimidazolyl-2 radicals-yl);
7. preparation method according to claim 6 is characterized in that, the vacuum degree of said Low Pressure Oxygen plasma treatment is 8～15Pa, and voltage is 350～500V.
8. preparation method according to claim 6 is characterized in that, said vacuum evaporation is specially:
In (1～2) * 10
-5Under the condition of Pa, carry out the step of vapor deposition hole transmission layer, the step of vapor deposition first luminescent layer, the step of vapor deposition second luminescent layer, the step of vapor deposition hole blocking layer successively at said anode surface;
In (4～6) * 10
-5Under the condition under the condition of Pa, carry out the step of vapor deposition resilient coating, the step of vapor deposition negative electrode successively at said hole barrier laminar surface.
9. preparation method according to claim 8 is characterized in that, the step of said vapor deposition first luminescent layer is specially:
In (1～2) * 10
-5Under the condition of Pa, the evaporation rate that the said complex of iridium and the first organic main body material are set is than being (9～12): 100, carry out vapor deposition.
10. preparation method according to claim 8 is characterized in that, the step of said vapor deposition second luminescent layer is specially:
In (1～2) * 10
-5Under the condition of Pa, the evaporation rate that the said complex of iridium and the second organic main body material are set is than being (9～12): 100, carry out vapor deposition.
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