CN102496682B - blue-green organic electroluminescent device and preparation method thereof - Google Patents
blue-green organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN102496682B CN102496682B CN201110381947.8A CN201110381947A CN102496682B CN 102496682 B CN102496682 B CN 102496682B CN 201110381947 A CN201110381947 A CN 201110381947A CN 102496682 B CN102496682 B CN 102496682B
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Abstract
The invention provides a kind of blue-green organic electroluminescent device and preparation method thereof, this device comprises: substrate; Stack gradually in the anode of substrate surface, hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode; Wherein, the first luminescent layer and the second luminescent layer include weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first or second organic host material.Above-mentioned complex of iridium material has high-luminous-efficiency and superior electron transport ability concurrently, improves luminous efficiency and the current density of device thus.Above-mentioned device arranges double emitting layers, the first luminescent layer with cavity type material for material of main part, the second luminescent layer with electron type material for material of main part.First luminescent layer can reduce the accumulation of hole between luminous zone, and the second luminescent layer can reduce the accumulation of electronics between luminous zone, and the two acting in conjunction is widened between the luminous zone of device, thus has delayed the efficiency decay of device.
formula (I).
Description
Technical field
The present invention relates to organic electroluminescence device field, particularly a kind of blue-green organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device (organiclightemittingdiode, OLED) is the self-luminous flat-panel display device received much concern in recent years.Organic electroluminescence device is highlighted higher, and its visual angle is comparatively wide, can reach more than 170 degree; Reaction time is fast, is about 1 μ s magnitude; Material selection range is wide, can realize the display of ruddiness to any color of blue light.Relative to flat-panel monitors such as FED, PDP and LCD, organic electroluminescence device has lower driving voltage, and operating temperature range is wide, to production technology and equipment requirement lower, 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 the quick response of display device, slimming, lightweight, lower voltage.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 the organic film be arranged between electron injection electrode and hole injecting electrode, additional power source is connected with between electron injection electrode and hole injecting electrode, when electric charge is injected into the organic luminous layer between electron injection electrode and hole injecting electrode, meeting and subsequently compound occur in electronics and hole, produces photon thus.
Blue-green organic electroluminescent device is the important organic electroluminescence device of a class.All the time, trivalent complex of iridium is considered as desirable electroluminescent organic material because having the 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 from materials synthesis and device optimization aspect, make great efforts the combination property of raising blue-green organic electroluminescent device to meeting the needs of industrialization.Such as: the people such as the S.R.Forrest of Princeton university in 2003 adopt the complex of iridium FIrpic with blue-green transmitting as luminescent material, obtain organic electroluminescence device by the method for doping.Although it is luminous that this device shows ideal blue-green, however unbalanced carrier injection cause the efficiency of device and brightness lower, the operating voltage of device is also higher in addition.
In order to solve the problem, the people such as the FrankySo of good fortune Flo-Rida-Low university of the U.S. in 2008 have obtained the blue-green organic electroluminescent device of sandwich construction by being mixed in preferred material of main part by high efficiency complex of iridium.This device has higher maximum luminous efficiency and high-high brightness, but 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 electroluminescent device and preparation method thereof with higher photoluminescence efficiency, current density and brightness.
In view of this, the invention provides a kind of blue-green organic electroluminescent device, comprising:
Substrate;
Stack gradually in the anode of described substrate surface, hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Described first luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first organic host material;
Described first organic host material is 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-carbazole-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine;
Described second luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the second organic host material;
Described second organic host material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine;
formula (I).
Preferably, hole transmission layer is 4,4 '-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline].
Preferably, described hole blocking layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine.
Preferably, the thickness of described first luminescent layer is 10 ~ 30nm.
Preferably, the thickness of described second luminescent layer is 5 ~ 15nm.
Accordingly, the present invention also provides a kind of preparation method of above-mentioned blue-green organic electroluminescent device, comprising:
Effects on surface carries out Low Pressure Oxygen plasma treatment with the substrate of anode;
At described anode surface successively vacuum evaporation hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Described first luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first organic host material;
Described first organic host material is 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-carbazole-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine;
Described second luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the second organic host material;
Described second organic host material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine;
formula (I).
Preferably, the vacuum degree of described plasma treatment is 8 ~ 15Pa, and voltage is 350 ~ 500V.
Preferably, described vacuum evaporation is specially:
In (1 ~ 2) × 10
-5condition under, carry out step, the step of evaporation first luminescent layer, the step of evaporation second luminescent layer, the step of evaporation hole blocking layer of evaporation hole transmission layer successively at described anode surface;
In (4 ~ 6) × 10
-5condition under condition under, carry out the step of evaporation resilient coating, the step of evaporation negative electrode successively on described hole blocking layer surface.
Preferably, the step of described evaporation first luminescent layer is specially:
In (1 ~ 2) × 10
-5under the condition of Pa, the evaporation rate of described complex of iridium and the first organic host material being set than being (9 ~ 12): 100, carrying out evaporation.
Preferably, the step of described evaporation second luminescent layer is specially:
In (1 ~ 2) × 10
-5under the condition of Pa, the evaporation rate of described complex of iridium and the second organic host material being set than being (9 ~ 12): 100, carrying out evaporation.
The invention provides a kind of blue-green organic electroluminescent device, comprise substrate, anode, hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode.Relative to prior art, 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 the luminous efficiency of device, current density and brightness thus.Meanwhile, the present invention arranges double emitting layers, and the first luminescent layer is main light emission layer, and it for material of main part with cavity type material, makes the first luminescent layer thus except producing photon, also play the effect of transporting holes; Second luminescent layer is auxiliary light emission layer, and it for material of main part with electron type material, makes the second luminescent layer thus except producing photon, also play the effect of transmission electronic.First luminescent layer can reduce the accumulation of hole between luminous zone, second luminescent layer can reduce the accumulation of electronics between luminous zone, the two acting in conjunction is conducive to the center being limited in luminescent layer between the recombination region by electronics and hole, make full use of the exciton of electronics and hole-recombination generation, and then between the luminous zone of widening device, thus delay the efficiency decay of device.Therefore, blue-green organic electroluminescent device provided by the invention has higher luminous efficiency, current density and brightness.
Accompanying drawing explanation
Fig. 1 is the structural representation of blue-green organic electroluminescent device provided by the invention;
Fig. 2 is the voltage-current density-luminosity response of blue-green organic electroluminescent device prepared by embodiment 1;
Fig. 3 is the current density-power efficiency-current efficiency characteristics curve of blue-green organic electroluminescent device prepared by embodiment 1;
Fig. 4 is blue-green organic electroluminescent device prepared by embodiment 1 is 20000cd/m in brightness
2time spectrogram;
Fig. 5 is the voltage-current density-luminosity response of blue-green organic electroluminescent device prepared by embodiment 2;
Fig. 6 is the current density-power efficiency-current efficiency characteristics curve of blue-green organic electroluminescent device prepared by embodiment 2.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention discloses a kind of blue-green organic electroluminescent device, as shown in Figure 1, this blue-green organic electroluminescent device comprises its structure:
Substrate 1;
Stack gradually the anode 2 in described 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, the first luminescent layer 4 comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first organic host material;
Described first organic host material is 4,4 '-N, N '-two carbazole diphenyl (CBP), 1,3-bis-carbazole-9-base benzene (MCP), 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles (Simcp), 1,3,5-tri-(9-carbazyl) benzene or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine (26DczPPy);
Described second luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the second organic host material;
Described second organic host material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine (3TPYMB);
formula (I).
Above-mentioned blue-green organic electroluminescent device provided by the invention, the complex of iridium of employing formula (I) structure is as luminescent material, it is two (2-(4,6-difluorophenyl) pyridine)-(two (diphenyl phosphinylidyne) amine) close iridium, hereinafter referred to as Ir (dfppy)
2(tpip), this complex of iridium has higher luminous efficiency, and its electron transport ability is comparatively strong, improves the luminous efficiency of organic electroluminescence device, current density and brightness thus.
In addition, above-mentioned blue-green organic electroluminescent device is provided with double emitting layers, and wherein, the first luminescent layer is main luminescent layer, and the second luminescent layer plays the effect of auxiliary light emission.First luminescent layer is with 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-carbazole-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene (TCP) or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine are as material of main part.Above-claimed cpd is cavity type material, makes the first luminescent layer thus except producing photon, also plays the effect of transporting holes.
Second luminescent layer with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine as material of main part.Above-mentioned material is electron type material, makes the 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 luminous zone, second luminescent layer can reduce the accumulation of electronics between luminous zone, be conducive to the center being limited in luminescent layer between the recombination region by electronics and hole, make full use of the exciton of electronics and hole-recombination generation, between the luminous zone being conducive to widening device, thus delay the efficiency decay of device.
In above-mentioned first luminescent layer 4 and the second luminescent layer 5 complex of iridium and material of main part the luminous efficiency of weight ratio on device have impact, complex of iridium of the present invention and material of main part Weight control be (9 ~ 12): 100, excessive or the too small luminous efficiency of device that easily causes of ratio declines to a great extent, also operating voltage can be made to improve, and the illuminant colour purity of device also can reduce simultaneously.The present invention preferably controls the weight ratio of complex of iridium and material of main part described in the first luminescent layer 4 and the second luminescent layer 5 for (9 ~ 11): 100.In above-mentioned blue-green organic electroluminescent device, the thickness of the first luminescent layer is preferably 10 ~ 30nm, and the thickness of the second luminescent layer is preferably 5 ~ 15nm.
Substrate in blue-green organic electroluminescent device provided by the invention, anode, hole transmission layer, hole blocking layer, resilient coating and negative electrode can adopt the respective material of existing blue-green organic electroluminescent device.Preferably, in the present invention, hole transmission layer preferably adopts 4,4 '-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline] (TAPC), this layer has that hole is injected, the function of hole transport and electronic blocking concurrently, simplified structure while reducing device operating voltages.The thickness of hole transmission layer is preferably 40 ~ 60nm.
Hole blocking layer 6 is preferably 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, this layer has the function of hole barrier, electric transmission and electron injection concurrently, simplified structure while reducing device operating voltages.Hole blocking layer 6 thickness is preferably 20 ~ 40nm.
Substrate is preferably glass substrate, and anode layer preferably adopts indium tin oxide (ITO), and the resistance of its face 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 the electron injection ability improving device, and preferably adopt lithium fluoride (LiF), the thickness of resilient coating 7 is preferably 0.8 ~ 1.2nm.
The course of work of above-mentioned blue-green organic electroluminescent device provided by the invention is as follows:
Under the effect of extra electric field, hole, from anode injection device, enters the first luminescent layer through hole transmission layer, has a small amount of hole can enter the second luminescent layer; Meanwhile, electronics, from negative electrode injection device, enters the second luminescent layer through hole blocking layer, then enters the first luminescent layer.So electronics and hole are fettered by complex of iridium at the first luminescent layer and the second luminescent layer, and then there is composite guide photoluminescence.
From such scheme, 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 the luminous efficiency of device, current density and brightness thus.Meanwhile, the present invention arranges double emitting layers, and the first luminescent layer is main light emission layer, and it for material of main part with cavity type material, makes the first luminescent layer thus except producing photon, also play the effect of transporting holes; Second luminescent layer is auxiliary light emission layer, and it for material of main part with electron type material, makes the second luminescent layer thus except producing photon, also play the effect of transmission electronic.First luminescent layer can reduce the accumulation of hole between luminous zone, second luminescent layer can reduce the accumulation of electronics between luminous zone, the two acting in conjunction is conducive to the center being limited in luminescent layer between the recombination region by electronics and hole, make full use of the exciton of electronics and hole-recombination generation, and then between the luminous zone of widening device, thus delay the efficiency decay of device.
The present invention also provides a kind of preparation method of above-mentioned blue-green organic electroluminescent device, comprising:
The substrate that effects on surface is covered with anode carries out Low Pressure Oxygen plasma treatment;
At described anode surface successively vacuum evaporation hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Wherein, described first luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first organic host material;
Described first organic host material is 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-carbazole-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine;
Described second luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the second organic host material;
Described second organic host material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine;
formula (I).
In above-mentioned preparation method, first Low Pressure Oxygen plasma treatment is carried out on antianode surface, its object is to clean anode surface further and improve hole injection rate.In 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 of substrate cleaning, preferably adopt ultrasonic cleaning, after cleaning, carry out drying.
In the present invention, the operation of vacuum evaporation is preferably carried out in the following manner:
In (1 ~ 2) × 10
-5under the condition of Pa, carry out step, the step of evaporation first luminescent layer, the step of evaporation second luminescent layer, the step of evaporation hole blocking layer of evaporation hole transmission layer successively at described anode surface;
In (4 ~ 6) × 10
-5under condition under the condition of Pa, carry out the step of evaporation resilient coating, evaporation negative electrode successively on described hole blocking layer surface.
Wherein, the step of evaporation first luminescent layer is preferably specially:
In (1 ~ 2) × 10
-5under the condition of Pa, the evaporation rate of above-mentioned complex of iridium and the first organic host material being set than being (9 ~ 12): 100, carrying out evaporation.
The step of evaporation second luminescent layer is preferably specially:
In (1 ~ 2) × 10
-5under the condition of Pa, the evaporation rate of above-mentioned complex of iridium and the second organic host material being set than being (9 ~ 12): 100, carrying out evaporation.
In the present invention, the material of main part of the first luminescent layer is CBP, Simcp, TCP or 26DczPPy, material of main part TPBi or 3TPYMB of the second luminescent layer, hole transmission layer preferably adopts TAPC, hole blocking layer is preferably TPBi or 3TPMB, in vacuum evaporation process, the evaporation rate of above-mentioned material preferably controls 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 electroluminescent device prepared according to the method described above has higher luminous efficiency, current density and brightness, and operating voltage is lower.
In order to understand the present invention further, be described blue-green organic electroluminescent device provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Ito anode layer chemical corrosion on ito glass is become the strip shaped electric poles of 10 mm wides, 30 millimeters long; Then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying.
Substrate after drying is put into preliminary treatment vacuum chamber, after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is transferred to organic vapor deposition room.
Be (1 ~ 2) × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, TAPC hole transmission layer, the 20 nanometer thickness Ir (dfppy) of evaporation 50 nanometer thickness successively on the ito layer
2(tpip) the first luminescent layer, the 10 nanometer thickness Ir (dfppy) of doping MCP
2(tpip) adulterate second luminescent layer of TPBi and the TPBi hole blocking layer of 30 nanometer thickness.
Device is transferred to metal evaporation room, in (4 ~ 6) × 10
-5the LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of mask evaporation 100 nanometer thickness on 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 evaporate process:
In hole transmission layer, the evaporation rate of TAPC controls in 0.05 nm/sec;
Ir (dfppy) in first luminescent layer
2(tpip) and the evaporation rate of MCP be controlled as 0.01 nm/sec and 0.1 nm/sec;
Ir (dfppy) in second luminescent layer
2(tpip) and the evaporation rate of TPBi be controlled as 0.01 nm/sec and 0.1 nm/sec;
In hole blocking layer, the evaporation rate of TPBi controls in 0.05 nm/sec;
The evaporation rate of resilient coating LiF controls in 0.005 nm/sec;
The evaporation rate of negative electrode Al controls in 0.5 nm/sec.
Fig. 2 is the voltage-current density-luminosity response of blue-green organic electroluminescent device prepared by the present embodiment.As shown in Figure 2: the brightness of device raises along with the rising of current density and driving voltage, device to play bright voltage be 3.3 volts, voltage be 11.5 volts, current density is 589.9 milliamperes of every square centimeter of (mA/cm
2) time device obtain high-high brightness 56678.8 candela every square metre of (cd/m
2).
Fig. 3 is the current density-power efficiency-current efficiency characteristics curve of blue-green organic electroluminescent device prepared by the present embodiment.As shown in Figure 3: the maximum current efficiency of this device is 35.22 candela every ampere (cd/A), and maximum power efficiency is 26.36 lumen per Watt (lm/W).
Fig. 4 be the blue-green organic electroluminescent device prepared of the present embodiment be 20000cd/m in brightness
2time spectrogram, spectrum main peak is positioned at 488 nanometers, and acromion is positioned at 516 nanometers.Device chromaticity coordinates is (0.145,0.426).
Embodiment 2
Ito anode layer chemical corrosion on ito glass is become the strip shaped electric poles of 10 mm wides, 30 millimeters long; Then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying.
Substrate after drying is put into preliminary treatment vacuum chamber, after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is transferred to organic vapor deposition room.
Be (1 ~ 2) × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, TAPC hole transmission layer, the 20 nanometer thickness Ir (dfppy) of evaporation 40 nanometer thickness successively on the ito layer
2(tpip) the first luminescent layer, the 10 nanometer thickness Ir (dfppy) of doping MCP
2(tpip) adulterate second luminescent layer of TPBi and the TPBi hole blocking layer of 30 nanometer thickness.
Device is transferred to metal evaporation room, in (4 ~ 6) × 10
-5the LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of mask evaporation 100 nanometer thickness on 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 evaporate process:
In hole transmission layer, the evaporation rate of TAPC controls in 0.05 nm/sec;
Ir (dfppy) in first luminescent layer
2(tpip) and the evaporation rate of MCP control in 0.01 nm/sec and 0.1 nm/sec respectively;
Ir (dfppy) in second luminescent layer
2(tpip) and the evaporation rate of TPBi control in 0.01 nm/sec and 0.1 nm/sec respectively;
In hole blocking layer, the evaporation rate of TPBi controls in 0.05 nm/sec;
The evaporation rate of resilient coating LiF controls in 0.005 nm/sec;
The evaporation rate of negative electrode Al controls in 0.5 nm/sec.
The present embodiment obtained device is under direct voltage drive, and display main peak is positioned at the blue green light that 488 nanometer acromions are positioned at 516 nanometers.When brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.148,0.418); Along with the change of operating voltage, the chromaticity coordinates of device is almost constant.
Fig. 5 is the voltage-current density-luminosity response of blue-green organic electroluminescent device prepared by the present embodiment.As shown in Figure 5: the brightness of this device raises along with the rising of current density and driving voltage, device to play bright voltage be 3.2 volts, voltage be 11.5 volts, current density be 648.88mA/cm2 time device obtain high-high brightness 53749.9cd/m
2.
Fig. 6 is the current density-power efficiency-current efficiency characteristics curve of blue-green organic electroluminescent device prepared by the present embodiment.As shown in Figure 6: the maximum current efficiency of this device is 29.77cd/A, and maximum power efficiency is 22.40lm/W.
Embodiment 3
Ito anode layer chemical corrosion on ito glass is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying.
Substrate after drying is put into preliminary treatment vacuum chamber, after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is transferred to organic vapor deposition room.
Be (1 ~ 2) × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, TAPC hole transmission layer, the 30 nanometer thickness Ir (dfppy) of evaporation 30 nanometer thickness successively on the ito layer
2(tpip) the first luminescent layer, the 10 nanometer thickness Ir (dfppy) of doping MCP
2(tpip) adulterate second luminescent layer of TPBi and the TPBi hole blocking layer of 30 nanometer thickness.
Device is transferred to metal evaporation room, in (4 ~ 6) × 10
-5the LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of mask evaporation 100 nanometer thickness on 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 evaporate process:
In hole transmission layer, the evaporation rate of TAPC controls in 0.05 nm/sec;
Ir (dfppy) in first luminescent layer
2(tpip) and the evaporation rate of MCP control in 0.01 nm/sec and 0.1 nm/sec respectively;
Ir (dfppy) in second luminescent layer
2(tpip) and the evaporation rate of TPBi control in 0.01 nm/sec and 0.1 nm/sec respectively;
In hole blocking layer, the evaporation rate of TPBi controls in 0.05 nm/sec;
The evaporation rate of resilient coating LiF controls in 0.005 nm/sec;
The evaporation rate of negative electrode Al controls in 0.5 nm/sec.
The present embodiment obtained device is under direct voltage drive, and display main peak is positioned at the blue green light that 488 nanometer acromions are positioned at 516 nanometers.When brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.143,0.427); Along with the change 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 efficiency of device is 27.39cd/A, and maximum power efficiency is 24.38lm/W.
Embodiment 4
Ito anode layer chemical corrosion on ito glass is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying.
Substrate after drying is put into preliminary treatment vacuum chamber, after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is transferred to organic vapor deposition room.
Be (1 ~ 2) × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, TAPC hole transmission layer, the 20 nanometer thickness Ir (dfppy) of evaporation 40 nanometer thickness successively on the ito layer
2(tpip) the first luminescent layer, the 10 nanometer thickness Ir (dfppy) of doping MCP
2(tpip) adulterate second luminescent layer of TPBi and the TPBi hole blocking layer of 20 nanometer thickness.
Device is transferred to metal evaporation room, in (4 ~ 6) × 10
-5the LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of mask evaporation 100 nanometer thickness on 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 evaporate process:
In hole transmission layer, the evaporation rate of TAPC controls in 0.05 nm/sec;
Ir (dfppy) in first luminescent layer
2(tpip) and the evaporation rate of MCP control in 0.01 nm/sec and 0.1 nm/sec respectively;
Ir (dfppy) in second luminescent layer
2(tpip) and the evaporation rate of TPBi control in 0.01 nm/sec and 0.1 nm/sec;
In hole blocking layer, the evaporation rate of TPBi controls in 0.05 nm/sec;
The evaporation rate of resilient coating LiF controls in 0.005 nm/sec;
The evaporation rate of negative electrode Al controls in 0.5 nm/sec.
The present embodiment obtained device is under direct voltage drive, and display main peak is positioned at the blue green light that 488 nanometer acromions are positioned at 516 nanometers.When brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.144,0.428); Along with the change 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
2.The maximum current efficiency of device is 20.82cd/A, and maximum power efficiency is 14.03lm/W.
Embodiment 5
Ito anode layer chemical corrosion on ito glass is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying.
Substrate after drying is put into preliminary treatment vacuum chamber, after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is transferred to organic vapor deposition room.
Be (1 ~ 2) × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, TAPC hole transmission layer, the 20 nanometer thickness Ir (dfppy) of evaporation 40 nanometer thickness successively on the ito layer
2(tpip) the first luminescent layer, the 10 nanometer thickness Ir (dfppy) of doping MCP
2(tpip) adulterate second luminescent layer of TPBi and the TPBi hole blocking layer of 30 nanometer thickness.
Device is transferred to metal evaporation room, in (4 ~ 6) × 10
-5the LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of mask evaporation 100 nanometer thickness on 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 evaporate process:
In hole transmission layer, the evaporation rate of TAPC controls in 0.05 nm/sec;
Ir (dfppy) in first luminescent layer
2(tpip) and the evaporation rate of MCP control in 0.012 nm/sec and 0.1 nm/sec respectively;
Ir (dfppy) in second luminescent layer
2(tpip) and the evaporation rate of TPBi control in 0.012 nm/sec and 0.1 nm/sec respectively;
In hole blocking layer, the evaporation rate of TPBi controls in 0.05 nm/sec;
The evaporation rate of resilient coating LiF controls in 0.005 nm/sec;
The evaporation rate of negative electrode Al controls in 0.5 nm/sec.
The present embodiment obtained device is under direct voltage drive, and display main peak is positioned at the blue green light that 488 nanometer acromions are positioned at 516 nanometers.When brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.146,0.429); Along with the change 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
2.The maximum current efficiency of device is 27.58cd/A, and maximum power efficiency is 19.33lm/W.
Embodiment 6
Ito anode layer chemical corrosion on ito glass is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying.
Substrate after drying is put into preliminary treatment vacuum chamber, after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is transferred to organic vapor deposition room.
Be (1 ~ 2) × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, TAPC hole transmission layer, the 10 nanometer thickness Ir (dfppy) of evaporation 40 nanometer thickness successively on the ito layer
2(tpip) the first luminescent layer, the 10 nanometer thickness Ir (dfppy) of doping MCP
2(tpip) adulterate second luminescent layer of TPBi and the TPBi hole blocking layer of 30 nanometer thickness.
Device is transferred to metal evaporation room, in (4 ~ 6) × 10
-5the LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of mask evaporation 100 nanometer thickness on 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 evaporate process:
In hole transmission layer, the evaporation rate of TAPC controls in 0.05 nm/sec;
Ir (dfppy) in first luminescent layer
2(tpip) and the evaporation rate of MCP control in 0.01 nm/sec and 0.1 nm/sec respectively;
Ir (dfppy) in second luminescent layer
2(tpip) and the evaporation rate of TPBi control in 0.01 nm/sec and 0.1 nm/sec respectively;
In hole blocking layer, the evaporation rate of TPBi controls in 0.05 nm/sec;
The evaporation rate of resilient coating LiF controls in 0.005 nm/sec;
The evaporation rate of negative electrode Al controls in 0.5 nm/sec.
The present embodiment obtained device is under direct voltage drive, and display main peak is positioned at the blue green light that 488 nanometer acromions are positioned at 516 nanometers.When brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.144,0.427); Along with the change 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
2.The maximum current efficiency of device is 26.70cd/A, and maximum power efficiency is 24.68lm/W.
From the above results, blue-green organic electroluminescent device provided by the invention has higher luminous efficiency, current density and brightness, maximum power efficiency can reach 26.36lm/W, and maximum current efficiency 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 understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a blue-green organic electroluminescent device, is characterized in that, is made up of following structure:
Substrate;
Stack gradually in the anode of described substrate surface, hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Described first luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first organic host material;
Described first organic host material is 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-carbazole-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine;
Described second luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the second organic host material;
Described second organic host material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine;
formula (I);
Described hole blocking layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine;
Described resilient coating is LiF; The thickness of described resilient coating is 0.8 ~ 1.2nm.
2. blue-green organic electroluminescent device according to claim 1, is characterized in that, described hole transmission layer is 4,4'-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline].
3. blue-green organic electroluminescent device according to claim 1, is characterized in that, the thickness of described first luminescent layer is 10 ~ 30nm.
4. blue-green organic electroluminescent device according to claim 1, is characterized in that, the thickness of described second luminescent layer is 5 ~ 15nm.
5. the preparation method of blue-green organic electroluminescent device according to claim 1, comprising:
The substrate that effects on surface is covered with anode carries out Low Pressure Oxygen plasma treatment;
At described anode surface successively vacuum evaporation hole transmission layer, the first luminescent layer, the second luminescent layer, hole blocking layer, resilient coating and negative electrode;
Described first luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the first organic host material;
Described first organic host material is 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-carbazole-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene or 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine;
Described second luminescent layer comprises weight ratio for (9 ~ 12): the complex of iridium of formula (I) structure of 100 and the second organic host material;
Described second organic host material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine;
formula (I).
6. preparation method according to claim 5, is characterized in that, the vacuum degree of described Low Pressure Oxygen plasma treatment is 8 ~ 15Pa, and voltage is 350 ~ 500V.
7. preparation method according to claim 5, is characterized in that, described vacuum evaporation is specially:
In (1 ~ 2) × 10
-5under the condition of Pa, carry out step, the step of evaporation first luminescent layer, the step of evaporation second luminescent layer, the step of evaporation hole blocking layer of evaporation hole transmission layer successively at described anode surface;
In (4 ~ 6) × 10
-5under condition under the condition of Pa, carry out the step of evaporation resilient coating, the step of evaporation negative electrode successively on described hole blocking layer surface.
8. preparation method according to claim 7, is characterized in that, the step of described evaporation first luminescent layer is specially:
In (1 ~ 2) × 10
-5under the condition of Pa, the evaporation rate of described complex of iridium and the first organic host material being set than being (9 ~ 12): 100, carrying out evaporation.
9. preparation method according to claim 7, is characterized in that, the step of described evaporation second luminescent layer is specially:
In (1 ~ 2) × 10
-5under the condition of Pa, the evaporation rate of described complex of iridium and the second organic host material being set than being (9 ~ 12): 100, carrying out evaporation.
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| CN103965885A (en) * | 2013-01-30 | 2014-08-06 | 海洋王照明科技股份有限公司 | Blue light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device |
| CN103450283B (en) * | 2013-05-08 | 2015-10-14 | 南京大学 | One class complex of iridium and method for making thereof and the application at organic electroluminescence device |
| KR102047230B1 (en) * | 2013-08-30 | 2019-11-21 | 엘지디스플레이 주식회사 | White organic light emitting diode and display device using the same |
| CN103762317B (en) * | 2013-12-30 | 2016-08-17 | 昆山工研院新型平板显示技术中心有限公司 | A kind of organic electroluminescence device |
| CN104282840B (en) * | 2014-10-29 | 2017-07-07 | 中国科学院长春应用化学研究所 | A kind of yellow organic electroluminescence device and preparation method thereof |
| CN104269500B (en) * | 2014-10-29 | 2017-04-12 | 中国科学院长春应用化学研究所 | Red organic electroluminescent device and preparation method thereof |
| CN104650156B (en) | 2015-03-03 | 2017-12-19 | 合肥京东方光电科技有限公司 | Metal complex and its production and use, display device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101043069A (en) * | 2006-03-21 | 2007-09-26 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic device |
| CN101630721A (en) * | 2009-08-11 | 2010-01-20 | 昆山维信诺显示技术有限公司 | Organic electroluminescent component |
| CN102208552A (en) * | 2011-05-20 | 2011-10-05 | 电子科技大学 | White-light organic electroluminescent device and preparation method thereof |
-
2011
- 2011-11-25 CN CN201110381947.8A patent/CN102496682B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101043069A (en) * | 2006-03-21 | 2007-09-26 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic device |
| CN101630721A (en) * | 2009-08-11 | 2010-01-20 | 昆山维信诺显示技术有限公司 | Organic electroluminescent component |
| CN102208552A (en) * | 2011-05-20 | 2011-10-05 | 电子科技大学 | White-light organic electroluminescent device and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Highly Efficient Green and Blue-Green Phosphorescent OLEDs Based on Iridium Complexes with the Tetraphenylimidodiphosphinate Ligand;Yu-Cheng Zhu et.al;《Advanced Materials》;20110729(第23期);第4041页右栏第14行-第4043页左栏倒数第1行 * |
| New Dopant and Host Materials for Blue-Light-Emitting Phosphorescent Organic Electroluminescent Devices;Shi-Jay Yeh et al.;《Advanced Materials》;20050204;第17卷(第3期);第285-289页 * |
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