CN1409412A - Organic electroluminescence device using organic quantum trap as hole transmission layer - Google Patents
Organic electroluminescence device using organic quantum trap as hole transmission layer Download PDFInfo
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- CN1409412A CN1409412A CN02116537A CN02116537A CN1409412A CN 1409412 A CN1409412 A CN 1409412A CN 02116537 A CN02116537 A CN 02116537A CN 02116537 A CN02116537 A CN 02116537A CN 1409412 A CN1409412 A CN 1409412A
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Abstract
This invention relates to organic electro-luminance apparatus with organic quantum trap structure as the cavity transmission layer. This quantum trap transmission structure is composed of two organic materials, in which energy levels of the two materials match mutually to form a cavity potential well at the quantum trap interface. This invention cavity transmission layer applies the organic quantum trap structure enabling to control the migrating of cavity carrier in the cavity transmission layer for realizing the inserting balance ofluminance layer electrons and cavities, so as to increase the luminance effect and brightness of the apparatus.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device that adopts organic quantum trap as hole transmission layer, belong to technical field of organic electroluminescence.
Background technology
Now, along with the arriving of Development of Multimedia Technology and information-intensive society, more and more higher to the flat-panel monitor performance demands.In recent years emerging three kinds of Display Techniques: plasma display, Field Emission Display and display of organic electroluminescence have all remedied the deficiency of cathode ray tube and LCD to a certain extent.Wherein, a series of advantages such as display of organic electroluminescence has from main light emission, low-voltage DC driven, solidifies entirely, the visual angle is wide, color is abundant, compare with LCD, display of organic electroluminescence does not need backlight, and the visual angle is big, and power is low, its response speed can reach 1000 times of LCD, its manufacturing cost but is lower than the LCD of equal resolution, and therefore, display of organic electroluminescence has broad application prospects.
1987, people such as the C.W.TANG (C.W.Tang of U.S. Kodak company, S.A.Slyke, Appl.Phys.Lett.51,913 (1987)) adopt double-decker first, with the aromatic diamines analog derivative as hole mobile material, with a kind of fluorescence efficiency very high and can make with Vacuum Coating method the high-quality thin film of even compact organic small molecule material---8-hydroxyquinoline aluminum is (hereinafter to be referred as Alq
3) as the luminescent layer material, prepare higher quantum efficiency (1%), high-luminous-efficiency (＞1.51m/W), high brightness (＞1000cd/m
2) and low driving voltage (＜10V) organic electroluminescence device (OrganicElectroluminescent Devices is hereinafter to be referred as OLEDs) makes the research work in this field enter a brand-new era.Nineteen ninety, Britain Cambridge university Cavan enlightening is permitted breadboard Burroughes and his colleague finds that polymeric material also has good electroluminescent properties, and this important discovery is arrived polymer arts with the research promotion of electroluminescent organic material.Over year, people constantly improve the preparation technology of organic electroluminescence device surplus in the of ten, and its correlation technique development rapidly.
The internal quantum efficiency of OLEDs depends primarily on injection, transmission, the combined efficiency of charge carrier, also is subjected to the material impact that charge carrier injects balance simultaneously.Organic quantum trap improves the device luminous efficiency helping to reduce the OLEDs luminescent spectrum width, and aspects such as switching device glow color have obtained some successes.But organic quantum trap generally is used for improving the electronics of luminescent layer and the concentration in hole in the present research, and then improves the combined efficiency of charge carrier.Such as, people such as N.Tada (N.Tada, S.Tatsuhara, A.Fujii, Y.Ohmori and K.Yoshino, Jpn.J.Appl.Phys.36,421 (1997)) use Alq at the luminescent layer of OLEDs
3And N, N '-diphenyl-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines (hereinafter to be referred as TPD) alternate multiple quantum well structure, (luminescent layer only uses Alq to the luminous efficiency of device than traditional structure
3) increase.Similarly experiment further confirms the improvement of this performance, the raising of mainly giving the credit to the luminescent layer carrier concentration.
Summary of the invention
The purpose of this invention is to provide a kind of organic electroluminescence device that adopts organic quantum trap as hole transmission layer, be the migration of control holoe carrier in hole transmission layer, realize the injection balance in luminescent layer electronics and hole, adopt organic multi-quantum pit structure at this device hole transmission layer.
For achieving the above object, technical scheme of the present invention provides a kind of organic electroluminescence device that adopts organic quantum trap as hole transmission layer, it comprises transparent substrate, first and second electrode layers, but and the organic luminous layer that is clipped in resilient coating, hole transmission layer, transition zone and transmission electronic between described two electrode layers, it is characterized in that: hole transmission layer adopts organic quantum trap, this quantum well transmission structure is made up of two kinds of organic materials, wherein the energy level of two kinds of materials matches each other, and forms the potential well in hole at the interface in quantum well.
The organic electroluminescence device structure of the employing organic quantum trap as hole transmission layer that technique scheme proposes is as follows:
Transparent substrate/first electrode layer (anode layer) but/organic luminous layer/the second electrode lay (cathode layer) (1) of resilient coating/hole transmission layer-organic quantum trap/transition zone/transmission electronic
Wherein the transparent substrate in the structural formula (1) can be glass or flexible substrate, as polyester, polyamide; First electrode layer (anode layer) is a conductive film, is generally the higher metals of work function such as metal oxides such as tin indium oxide (hereinafter to be referred as ITO), zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as; Resilient coating is generally phthalocyanine compound, polymethyl methacrylate, polyimides, fluoropolymer, perhaps LiF, AlF
3, CaF
2, MgF
2, SiO
2, MgO, Al
2O
3With inorganic matters such as diamonds, the present invention is preferably copper phthalocyanine (hereinafter to be referred as CuPc); Hole transmission layer is the Multiple Quantum Well transmission structure of being made up of two kinds of organic materials, wherein the energy level of two kinds of materials matches each other, and because a kind of energy level potential barrier effect of material, make the potential well in electronics and hole in commaterial, the present invention is preferably [N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines (hereinafter to be referred as NPB)/CuPc]
nThe multi-layer quantum well structure, wherein quantum well periodicity n is 1～10; The material that the energy level of transition zone employing and luminescent layer is complementary is if the multi layer quantum well structure optimization of hole transmission layer is (NPB/CuPc)
n, transition zone can be preferably NPB; But the organic luminous layer of transmission electronic is generally metal complex, through being preferably Alq
3, (salicylidene adjacent amine phenol)-(oxine) close aluminium (III) (hereinafter to be referred as Al (Saph-q)), 9-hydroxy-acridine zinc (hereinafter to be referred as Zn (Ac)
2) etc.; The second electrode lay (cathode layer) is a metal level, is generally the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver, and the present invention is preferably Mg successively: Ag alloy-layer, Ag layer.
The organic electroluminescence device of the employing organic quantum trap as hole transmission layer that the present invention proposes, have the following advantages: significantly control the migration of holoe carrier in hole transmission layer, thereby realized the injection balance in luminescent layer electronics and hole, thereby improved the luminous efficiency and the luminosity of device.
Below by description of drawings, it is clearer that the present invention can become.
Description of drawings
Fig. 1 is the structural representation of the organic electroluminescence device of the employing organic quantum trap as hole transmission layer that proposes of the present invention, wherein 1 is transparent substrate, 2 is first electrode layer (anode layers), the 3rd, resilient coating, the 4th, hole transmission layer (having organic multi-quantum pit structure), the 5th, transition zone, the 6th, but the organic luminous layer of transmission electronic, the 7th, the second electrode lay (cathode layer), the 8th, power supply.
Fig. 2 is that (structure is Glass/ITO/CuPc/ (NPB/CuPc) for the organic electroluminescence device of the employing organic quantum trap as hole transmission layer that proposes of the present invention
n/ NPB/Alq
3/ Mg: energy level schematic diagram Ag/Ag).
Fig. 3 is that (structure is Glass/ITO/CuPc/ (NPB/CuPc) for the organic electroluminescence device of the employing organic quantum trap as hole transmission layer that proposes of the present invention
n/ NPB/Alq
3/ Mg: the Ag/Ag) brightness-current density curve that changes with quantum well periodicity n.
Fig. 4 is that (structure is Glass/ITO/CuPc/ (NPB/CuPc) for the organic electroluminescence device of the employing organic quantum trap as hole transmission layer that proposes of the present invention
n/ NPB/Alq
3/ Mg: Ag/Ag) with the luminous efficiency-current density curve of the variation of quantum well periodicity n.
Elaborate content of the present invention below in conjunction with the drawings and specific embodiments, should be appreciated that the present invention is not limited to following preferred implementation, preferred implementation is as just illustrative embodiment of the present invention.
Embodiment
The organic electroluminescence device structure of the employing organic quantum trap as hole transmission layer that the present invention proposes as shown in Figure 1, wherein: 1 is transparent substrate, can be glass or flexible substrate, as polyester, polyamide; 2 is first electrode layer (anode layer), is generally the higher metals of work function such as metal oxides such as ITO, zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as; 3 is resilient coating, is generally phthalocyanine compound, polymethyl methacrylate, polyimides, fluoropolymer, perhaps LiF, AlF
3, CaF
2, MgF
2, SiO
2, MgO, Al
2O
3With inorganic matters such as diamonds, the present invention is preferably CuPc; 4 is hole transmission layer, the Multiple Quantum Well transmission structure that employing is made up of two kinds of organic materials, wherein the energy level of two kinds of materials matches each other, and because a kind of energy level potential barrier effect of material, make the potential well in electronics and hole in commaterial, the present invention is preferably (NPB/CuPc)
nThe multi-layer quantum well structure, wherein quantum well periodicity n is 1～10, the highest occupied molecular orbital energy level (hereinafter to be referred as HOMO) of NPB and CuPc is respectively-5.2eV ,-4.8eV, lowest unoccupied molecular orbital energy level (hereinafter to be referred as LUMO) is respectively-1.8eV ,-2.7eV, by this preferred (NPB/CuPc)
nDo hole transmission layer device energy level schematic diagram (see figure 2) as can be seen because NPB to the potential barrier effect of CuPc, has formed the potential well in electronics and hole in CuPc; 5 materials that adopt the energy level with luminescent layer to be complementary for transition zone are if the multi layer quantum well structure optimization of hole transmission layer is (NPB/CuPc)
n, transition zone can be preferably NPB; But 6 is the organic luminous layer of transmission electronic, is generally metal complex, through being preferably Alq
3, Al (Saph-q), Zn (Ac)
2Deng; 7 is that the second electrode lay (cathode layer) is a metal level, is generally the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver, and the present invention is preferably Mg successively: Ag alloy-layer, Ag layer.
The structure of the organic electroluminescence device of the employing organic quantum trap as hole transmission layer that proposes according to the present invention, the following (see figure 1) of structure when each layer adopts concrete material:
Glass/ITO/CuPc/(NPB/CuPc)
n/NPB/Alq
3/Mg∶Ag/Ag (2)
Wherein n is the periodicity of NPB/CuPc quantum well in the structural formula (2), and the n value can be 1～10.According to said structure formula (2), be described below in conjunction with the detailed execution mode of preparation process of device:
1. utilizing washing agent to boil with the ultrasonic method of deionized water carries out clearly the transparent conduction base sheet ito glass
Wash, dry, wherein the ITO film above the conductive substrate is as the anode of device, the square of ITO film
Resistance is 5 Ω～100 Ω, and thickness is 80～220nm;
2. the ito glass behind the above-mentioned cleaning, drying being placed pressure is 1 * 10
-5～5 * 10
-3The vacuum chamber of Pa
In, on above-mentioned ITO film evaporation one deck CuPc as the resilient coating of device, the evaporation speed of film
Be 0.02～0.1nm/s, thickness is 0.5～20nm;
3. continue the evaporation hole transmission layer on above-mentioned CuPc film, hole transmission layer adopts organic multi-quantum pit
Structure promptly adopts NPB/CuPc to replace the quantum well structure of n layer, n is 1～10, wherein CuPc
Evaporation speed is 0.02～0.1nm/s, in the quantum well structure thickness of each layer CuPc be 0.5～
10nm, the evaporation speed of NPB is 0.1～0.6nm/s, the thickness of each layer NPB in the quantum well structure
Be 1.5～30nm;
4. evaporation one deck NPB is as the transition zone of device on above-mentioned hole transmission layer, and the evaporation speed of film is
0.1～0.6nm/s, thickness are 10～45nm;
5. on above-mentioned NPB film, continue evaporating Al q
3As the luminescent layer of device, Alq
3Also has transmission
The ability of son, the evaporation speed of film is 0.1～0.6nm/s, thickness is 40～100nm;
6. at above-mentioned Alq
3Evaporation Mg successively on the film: Ag alloy-layer, Ag layer be as the negative electrode of device, its
Middle alloy-layer Mg, Ag evaporation speed ratio are 10: 1, and the total speed of evaporation is 0.6～2.0nm/s, evaporation
Gross thickness is 50～200nm, and Ag protective layer evaporation speed is 0.3～0.8nm/s, thickness is 40～
200nm。
The performance of the organic electroluminescence device of the employing organic quantum trap as hole transmission layer that proposes for the ease of the present invention and the property comparison of traditional structure (being n=0) device, that uses in the material of each layer of traditional structure (n=0) use and the specific embodiment of the present invention is identical, and its structure is as follows:
Glass/ITO/CuPc/NPB/Alq
3/Mg∶Ag/Ag (3)
And for the ease of the contrast of device performance, all CuPc film (comprising buffer layer part) gross thickness are 12nm in the maintenance device, all NPB films (comprising the transition zone part) gross thickness is 30nm, be that resilient coating CuPc thickness is 6nm in the structural formula (2), transition zone NPB thickness is 15nm, the gross thickness of n layer CuPc film is 6nm in the hole transmission layer, and the gross thickness of n layer NPB film is 15nm, and the thickness of resilient coating CuPc and transition zone NPB is respectively 12nm, 30nm in the structural formula (3).With quantum well periodicity n not simultaneously, the structure of OLEDs is as shown in table 1, and the brightness of device-current density curve, luminous efficiency-current density curve are seen Fig. 3, Fig. 4 respectively.
Table 1
The structure of n OLEDs
0?Glass/ITO/CuPc(12.0nm)/NPB(30.0nm)/Alq
3(60.0nm)/Mg∶Ag/Ag
2?Glass/ITO/CuPc(6.0nm)/[NPB(7.5nm)/CuPc(3.0nm)]
2/NPB(15.0nm)/Alq
3(60.0nm)/Mg∶Ag/Ag
4?Glass/ITO/CuPc(6.0nm)/[NPB(3.8nm)/CuPc(1.5nm)]
4/NPB(15.0nm)/Alq
3(60.0nm)/Mg∶Ag/Ag
Embodiment one:
Utilize washing agent boil with the ultrasonic method of deionized water be that the ito glass of 15 Ω cleans, dries to square resistance, wherein the thickness of ITO is 180nm.It is 1 * 10 that ito glass after the oven dry is placed pressure
-3In the vacuum chamber of Pa, utilize thermal evaporation method evaporation CuPc buffer thin film on the ITO film, evaporation speed is 0.04nm/s, and thickness is 6nm.On the CuPc buffer thin film, continue evaporation alternate multiple hole transmission layer (NPB/CuPc)
4, wherein the evaporation speed of NPB film is 0.2nm/s, and thickness is 3.75nm, and the evaporation speed of CuPc film is 0.04nm/s, and thickness is 1.5nm.The NPB layer that continues evaporation 15nm on this hole transmission layer is as transition zone, and evaporation speed is 0.4nm/s, on continue evaporation organic function layer Alq
3, evaporation speed is 0.2nm/s, thickness is 60nm.At Alq
3Continue evaporated metal layer on the layer, metal level is successively by Mg: Ag alloy and Ag form, Mg: the total evaporation speed of Ag is 1.5nm/s, and the ratio of Mg and Ag evaporation speed is 10: 1, and thickness is 100nm; The evaporation speed of Ag is 0.5nm/s, and evaporation thickness is 100nm.It is 2.5V that device opens bright voltage, and maximum luminousing brightness is 15000cd/m
2, current density is 34mA/cm
2The time, corresponding maximum luminous efficiency is 10.7cd/A.
Embodiment two:
Utilize washing agent boil with the ultrasonic method of deionized water be that the ito glass of 60 Ω cleans, dries to square resistance, wherein the thickness of ITO is 100nm.It is 2 * 10 that ito glass after the oven dry is placed pressure
-3In the vacuum chamber of Pa, utilize thermal evaporation method evaporation CuPc buffer thin film on the ITO film, evaporation speed is 0.06nm/s, and film thickness is 8nm.On the CuPc buffer thin film, continue evaporation alternate multiple hole transmission layer (NPB/CuPc)
2, wherein the evaporation speed of NPB film is 0.2nm/s, and thickness is 7.5nm, and the evaporation speed of CuPc film is 0.06nm/s, and thickness is 3nm.The NPB layer that continues evaporation 20nm on this hole transmission layer is as transition zone, and evaporation speed is 0.2nm/s, on continue evaporation organic function layer Al (Saph-q), evaporation speed is 0.2nm/s, thickness is 60nm.Continue evaporated metal layer on Al (Saph-q) layer, metal level is successively by Mg: Ag alloy and Ag form, Mg: the total evaporation speed of Ag is 1.5nm/s, and the ratio of Mg and Ag evaporation speed is 10: 1, and thickness is 150nm; The evaporation speed of Ag is 0.4nm/s, and evaporation thickness is 50nm.It is 2.8V that device opens bright voltage, and maximum luminousing brightness is 13000cd/m
2
Embodiment three:
Utilize washing agent boil with the ultrasonic method of deionized water be that the ito glass of 30 Ω cleans, dries to square resistance, wherein the thickness of ITO is 140nm.It is 1.5 * 10 that ito glass after the oven dry is placed pressure
-3In the vacuum chamber of Pa, utilize thermal evaporation method evaporation CuPc buffer thin film on the ITO film, evaporation speed is 0.03nm/s, and film thickness is 4nm.On the CuPc buffer thin film, continue evaporation alternate multiple hole transmission layer (NPB/CuPc)
8, wherein the evaporation speed of NPB film is 0.2nm/s, and thickness is 2nm, and the evaporation speed of CuPc film is 0.01nm/s, and thickness is 0.75nm.The NPB layer that continues evaporation 20nm on this transport layer is as transition layer structure, and evaporation speed is 0.2nm/s, on continue evaporation organic function layer Zn (Ac)
2, evaporation speed is 0.2nm/s, thickness is 60nm.At Zn (Ac)
2Continue evaporated metal layer on the layer, metal level is successively by Mg: Ag alloy and Ag form, Mg: the total evaporation speed of Ag is 1.5nm/s, and the ratio of Mg and Ag evaporation speed is 10: 1, and thickness is 180nm; The evaporation speed of Ag is 0.5nm/s, and evaporation thickness is 50nm.It is 2.9V that device opens bright voltage, and maximum luminousing brightness is 12000cd/m
2
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to the foregoing description, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.
Claims (8)
1. organic electroluminescence device that adopts organic quantum trap as hole transmission layer, it comprises transparent substrate (1), first (2) and the second electrode lay (7), and be clipped in resilient coating (3) between described two electrode layers, hole transmission layer (4), transition zone (5) but and the organic luminous layer of transmission electronic (6), it is characterized in that: hole transmission layer (4) adopts organic quantum trap, this quantum well transmission structure is made up of two kinds of organic materials, wherein the energy level of two kinds of materials matches each other, and forms the potential well in hole at the interface in quantum well.
2. according to the organic electroluminescence device of claim 1, it is characterized in that the periodicity of the organic quantum trap that wherein said hole transmission layer (4) adopts is 1～10.
3. according to the organic electroluminescence device of claim 1, the material that it is characterized in that the organic quantum trap that wherein said hole transmission layer (4) adopts is preferably N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines/copper phthalocyanine.
4. according to the organic electroluminescence device of claim 1, it is characterized in that wherein said first electrode layer (2) material is preferably tin indium oxide.
5. according to the organic electroluminescence device of claim 1, it is characterized in that wherein said resilient coating (3) material is preferably copper phthalocyanine.
6. according to the organic electroluminescence device of claim 1, it is characterized in that wherein said transition zone (5) material is preferably N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines.
7. according to the organic electroluminescence device of claim 1, but organic luminous layer (6) material that it is characterized in that wherein said transmission electronic is preferably 8-hydroxyquinoline aluminum or (the adjacent amine phenol of salicylidene)-(oxine) closes aluminium (III) or 9-hydroxy-acridine zinc.
8. according to the organic electroluminescence device of claim 1, it is characterized in that wherein said the second electrode lay (7) material is preferably Mg successively: Ag alloy-layer, Ag layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02116537A CN1409412A (en) | 2002-04-03 | 2002-04-03 | Organic electroluminescence device using organic quantum trap as hole transmission layer |
| US10/351,070 US6806491B2 (en) | 2002-04-03 | 2003-01-24 | Organic light-emitting devices |
| CNB031210635A CN1161002C (en) | 2002-04-03 | 2003-03-21 | Organic electroluminescent device |
| JP2003100660A JP3615536B2 (en) | 2002-04-03 | 2003-04-03 | Organic EL light emitting device |
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| CN02116537A CN1409412A (en) | 2002-04-03 | 2002-04-03 | Organic electroluminescence device using organic quantum trap as hole transmission layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102956833A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN103427031A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN103427027A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN103824939A (en) * | 2012-11-19 | 2014-05-28 | 海洋王照明科技股份有限公司 | Polymer solar cell and preparation method thereof |
| WO2014082307A1 (en) * | 2012-11-30 | 2014-06-05 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparing method thereof |
-
2002
- 2002-04-03 CN CN02116537A patent/CN1409412A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956833A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN102956833B (en) * | 2011-08-29 | 2015-10-28 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and preparation method thereof |
| CN103427031A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN103427027A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN103824939A (en) * | 2012-11-19 | 2014-05-28 | 海洋王照明科技股份有限公司 | Polymer solar cell and preparation method thereof |
| WO2014082307A1 (en) * | 2012-11-30 | 2014-06-05 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparing method thereof |
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