CN101118952A - Low voltage organic light emitting diode device and manufacturing method thereof - Google Patents
Low voltage organic light emitting diode device and manufacturing method thereof Download PDFInfo
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- CN101118952A CN101118952A CNA2006100635537A CN200610063553A CN101118952A CN 101118952 A CN101118952 A CN 101118952A CN A2006100635537 A CNA2006100635537 A CN A2006100635537A CN 200610063553 A CN200610063553 A CN 200610063553A CN 101118952 A CN101118952 A CN 101118952A
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Abstract
The present invention discloses a low-voltage organic LED element which comprises a substrate, an anode on the substrate, an organic electroluminescent layer on the substrate, a hollow transferring layer, an electronic transferring layer close to the organic electroluminescent layer and a cathode formed on the function; a hollow injecting layer can be added between the strong receptor organic molecule material buffer layer and the hollow transferring layer. The improving points of the present invention are that adding the organic molecule material buffer layer between the anode and the organic electroluminescent function layer, and also the producing method of the low-voltage organic LED element is disclosed. The present invention has the advantages of low voltage of element and high efficiency and can balance the electric charge injection.
Description
Technical field
The present invention relates to a kind of electrode structure of organic light emitting diode device, more particularly, relate in particular to improvement anode construction of a kind of low voltage organic light emitting diode device and preparation method thereof.
Background technology
At present, in the display technology field, liquid crystal display device (LCD) is in light weight, low in energy consumption and be widely used as flat-panel monitor with it, yet, because liquid crystal display device is a passive device, but not selfluminous element, and because its technical limitations aspect brightness, contrast, visual angle and screen expansion, thereby research and development novel flat-plate display device just becomes the problem of this area with the above-mentioned shortcoming that overcomes LCD.
Organic light emitting diode device (be called for short OLED) is emerging a kind of flat-panel monitor at present, and because of it has active illuminating, plurality of advantages such as the contrast height can slimming, and response speed is fast is acknowledged as the main force of display of future generation.As shown in Figure 1, in the organic light emitting diode device of prior art, generally include a glass substrate 1, usually an anode 2 that is formed by tin indium oxide is arranged on glass substrate 1, negative electrode 7 and the organic functional material between described anode 2 and negative electrode 7, the principle of luminosity of OLED is the extremely thin multilayer organic functional material of evaporation between former and later two electrodes just, logical dc powered and luminous.The organic function layer of Organic Light Emitting Diode OLED, generally constitute by three layers, be respectively hole transport functional layer 4 (being called for short HTL), organic electroluminescent functional layer 5 (being called for short EML), electric transmission functional layer 6 (being called for short ETL), in order to strengthen the injection in hole, can increase one deck hole injection layer 8 (being called for short HIL) before the htl layer.General anode 2 adopts the electric conducting material of high work function, mainly is the electric charge injection barrier that reduces between anode 2 and the HTL4, increases the injection of electric charge, reduces the voltage of device, and relatively Chang Yong method has ITO ultraviolet light ozone treatment, and oxygen plasma is handled, CF
4Plasma treatment etc., main effect are cleaning ITO surfaces, increase work function, and are still, limited to reducing the device voltage effect; Another kind method is that the strong hole of doped p type is subjected to semiconductor material body in HTL, its principle is the cavity transmission ability that increases HTL4, reduce voltage, but the HTL4 cavity transmission ability of often mixing is too fast, is difficult to the electron transport material that finds electron transport ability fast, it is fast hole transport to occur, electric transmission is slow, charge unbalance, and the ETL6 technology that the n type mixes is big because of the active instability of alkalinous metal, diffusion, technology is immature, and the electric charge of device injects equilibrium problem to be difficult to solve.
Summary of the invention
There is above-mentioned shortcoming in the organic light emitting diode device of the present invention in view of prior art and carries out, an object of the present invention is to provide and a kind ofly can reduce the hole injection barrier, reduce voltage and can fine solution electric charge inject the low voltage organic light emitting diode device of equilibrium problem.
Another object of the present invention provides a kind of manufacture method of low voltage organic light emitting diode device.
The technical scheme that the present invention adopts for achieving the above object is:
The low voltage organic light emitting diode device that the present invention relates to comprises: a substrate, the anode that on substrate, forms, the organic electroluminescent functional layer that on substrate, forms, with the adjoining hole transport functional layer of described organic electroluminescent functional layer and electric transmission functional layer and the negative electrode that on functional layer, forms, wherein, between described anode and described hole transport functional layer, also comprise the strong acceptor organic molecule material of one deck resilient coating, its effect is injection and the transmission that helps the hole, reduce the injection barrier of device, improve the transmission speed in hole, thereby reduce its device voltage, can also reduce the use amount of material by Fig. 2 structure, reduce cost.
In order to strengthen the injection in hole, between described strong acceptor organic molecule material resilient coating and described hole transport functional layer, also increase one deck hole injection layer.
Described strong acceptor organic molecule material comprises 2,3,5,6-tetrafluoro-7,7,8,8, four cyano is to secondary methylbenzoquinone (being called for short F4-TCNQ), 7,7,8,8 ,-four cyano to secondary methylbenzoquinone, four cyano to secondary methylnaphthoquinone, 1,4,5,8 tetrahydroxys 1,4,5,8 tetrathio bases-2,3,6, at least a in the 7-4 cyano group anthraquinone, this strong acceptor organic molecule material buffer layer thickness is this scope of 0.1 nanometer-100 nanometer.
Inject the good device of balance in order to obtain hole and electronics, can select and the thickness adjustment, make its electric charge inject balance and reach best by the material of adjusting the hole transport functional layer.
For the device of bottom-emission or double-side, described anode uses transparent conductive oxide, as tin indium oxide (ITO), and indium-zinc oxide (IZO), aluminium zinc oxide (AZO).
And for the device of top light emitting, described anode is selected the non-transparent metals material for use, as silver (Ag), and gold (Au).
The manufacture method of low voltage organic light emitting diode device of the present invention may further comprise the steps:
A. on substrate, form anode;
B. on electrode, form anode pattern, insulating barrier, electrode isolation layers successively with photoetching process;
C. the substrate that will do good pattern forms strong acceptor organic molecule material resilient coating then with examples such as oxygen cleaning;
D. form hole transport functional layer, organic electroluminescent functional layer, electric transmission functional layer and negative electrode then successively;
E. in high pure nitrogen, be packaged into device.
In order to strengthen the injection in hole, can further include the step that forms hole injection layer between step c and the steps d.
In the manufacture method of low voltage organic light emitting diode device of the present invention, the described strong acceptor organic molecule material resilient coating of step c (3) is to adopt thermal evaporation film-forming, also can be solution spun-dried and forming, and other depositional mode.
The described strong acceptor organic molecule material of step c comprises 2,3,5,6-tetrafluoro-7,7,8,8, four cyano is to secondary methylbenzoquinone, 7,7,8,8 ,-four cyano to secondary methylbenzoquinone, four cyano to secondary methylnaphthoquinone, 1,4,5,8 tetrahydroxys 1,4,5,8 tetrathio bases-2,3,6, at least a in the 7-4 cyano group anthraquinone, the formed strong acceptor organic molecule material buffer layer thickness of step c is 0.1 nanometer-100 nanometer.
In the embodiment that the present invention provides, the described anode of step a selects for use tin indium oxide to make material, certainly, the material selection of anode of the present invention is followed such principle: for the device of bottom-emission or double-side, described anode uses transparent conductive oxide, as tin indium oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO).
And for the device of top light emitting, described anode is selected the non-transparent metals material for use, as silver (Ag), and gold (Au).
Compared with prior art, organic light emitting diode device of the present invention has the advantage that device voltage is low, efficient is high, can keep electric charge injection balance.
Description of drawings:
Fig. 1 is a kind of structural representation of organic light emitting diode device of prior art;
Fig. 2 is the low voltage organic light emitting diode device structural representation of an embodiment providing of the present invention;
Fig. 3 is the low voltage organic light emitting diode device structural representation of another embodiment of providing of the present invention.
Among the figure, 1-substrate, 2-anode, the strong acceptor organic molecule material of 3-resilient coating, 4-hole transport functional layer, 5-organic electroluminescence functional layer, 6-electric transmission functional layer, 7-negative electrode, 8-hole injection layer.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is further set forth:
What Fig. 2 disclosed is the low voltage organic light emitting diode device (OLED) of one embodiment of the invention, this OLED device comprises a glass substrate 1, an anode 2 is positioned on the glass substrate 1, an organic electroluminescent functional layer 5 is positioned on the anode 2, described organic electroluminescent functional layer 5 both sides are respectively the electric transmission functional layers 6 that is in the hole transport functional layer 4 of downside and is in upside, the organic molecule material resilient coating 3 that between described hole transport functional layer 4 and anode 2, also has the strong acceptor of one deck, this layer material includes but not limited to following one group of material or its combination: 2,3,5,6-tetrafluoro-7,7,8,8, four cyano is to secondary methylbenzoquinone (being called for short F4-TCNQ), 7,7,8,8 ,-four cyano is to the secondary methylbenzoquinone, four cyano is to the secondary methylnaphthoquinone, 1,4,5,8 tetrahydroxys 1,4,5,8 tetrathio bases-2,3,6,7-4 cyano group anthraquinone, the effect that increases such one deck resilient coating is injection and the transmission that helps the hole, reduces the injection barrier of device, improves the transmission speed in hole, thereby reduction device voltage, according to the low voltage organic light emitting diode device structure of the present embodiment, can also reduce the use amount of material, reduce cost; Inject the good device of balance in order to obtain hole and electronics, can select and the thickness adjustment, make its electric charge inject balance and reach best by adjusting the HTL material; Anode 2 is selected ITO for use, and perhaps other transparent conductive oxide obtains the organic light emitting diode device of bottom-emission, increases the such resilient coating 3 of one deck, voltage that can very effective reduction device; Perhaps, select for use nontransparent metals such as Ag, make the device of top light emitting, increase the such resilient coating of one deck 3 equally, also can reduce the voltage of device, raise the efficiency as anode material.
What Fig. 3 disclosed is the low voltage organic light emitting diode device (OLED) of another embodiment of the invention, this OLED device comprises a glass substrate 1, an anode 2 is positioned on the glass substrate 1, an organic electroluminescent functional layer 5 is positioned on the anode 2, described organic electroluminescent functional layer 5 both sides are respectively the electric transmission functional layers 6 that is in the hole transport functional layer 4 of downside and is in upside, and, before forming hole transport functional layer 4, also increase one deck hole injection layer 8, to strengthen the injection in hole, between described hole injection layer 8 and anode 2, also have the organic molecule material resilient coating 3 of the strong acceptor of one deck, this layer material includes but not limited to following one group of material or its combination: 2,3,5,6-tetrafluoro-7,7,8,8, four cyano is to the secondary methylbenzoquinone, 7,7,8,8 ,-four cyano is to the secondary methylbenzoquinone, four cyano is to the secondary methylnaphthoquinone, 1,4,5,8 tetrahydroxys 1,4,5,8 tetrathio bases-2,3,6,7-4 cyano group anthraquinone, the effect that increases such one deck resilient coating is injection and the transmission that helps the hole, reduce the injection barrier of device, improve the transmission speed in hole, thereby reduce device voltage; Inject the good device of balance in order to obtain hole and electronics, can select and the thickness adjustment, make its electric charge inject balance and reach best by adjusting the HTL material; Anode 2 is selected ITO for use, and perhaps other transparent conductive oxide obtains the organic light emitting diode device of bottom-emission, increases the such resilient coating 3 of one deck, voltage that can very effective reduction device; Perhaps, select for use nontransparent metals such as Ag, make the device of top light emitting, increase the such resilient coating of one deck 3 equally, also can reduce the voltage of device, raise the efficiency as anode material.
The manufacture method of low voltage organic light emitting diode device of the present invention is described in detail in detail below:
Be applied in the processing procedure of dot matrix resolution 96 * 64 monochromatic blue OLED screens pixel size 0.21mm * 0.21mm in this embodiment of enumerating.Manufacturing process is: select glass substrate 1 for use, with tin indium oxide (ITO) as anode 2, make ITO pattern, insulating barrier, electrode isolation layers successively with photoetching process, after doing examples such as the glass substrate 1 usefulness oxygen cleaning of good pattern, the strong acceptor organic molecule material resilient coating 3 of first evaporation 1nm in the high-vacuum apparatus of 6E (5) holder; Evaporation formation hole injection layer 8, hole transport functional layer 4, blue light-emitting layer are organic electroluminescence functional layer 5, electric transmission functional layer 6, negative electrode 7 successively then, and blue light-emitting layer subject and object double source closes steaming, and negative electrode 7 is 1nm lithium fluoride and 150nm rafifinal; In high pure nitrogen, be packaged into device then.Luminance test equipment PR705, testing power supply are the Keithly2400 constant-current supply.This example has been made six devices (device A, B, C, D, E, F), and material therefor TC56, TC57 are from the brilliant suitable company in Taiwan), ET4 is from Japanese Chisso company, and other are from Kodak.Device architecture is as follows respectively:
Embodiment one
Device A:ITO/2TNATA (60nm)/NPB (20nm)/TC56:TC57 (300,3%)/Alq3 (20nm)/LiF (1nm)/Al (150nm)
Device B:ITO/F4-TCNQ (1nm)/2TNATA (60nm)/NPB (20nm)/TC56:TC57 (300,3%)/Alq3 (20nm)/LiF (1nm)/Al (150nm)
Embodiment two:
Device C:ITO/NPB (80nm)/TC56:TC57 (300,3%)/Alq3 (20nm)/LiF (1nm)/Al (150nm)
Device D:ITO/F4-TCNQ (1nm)/NPB (80nm)/TC56:TC57 (300,3%)/Alq3 (20nm)/LiF (1nm)/Al (150nm)
Embodiment three:
Device E:ITO/2TNATA:F4-TCNQ (60nm, 3%)/NPB (20nm)/TC56:TC57 (300,3%)/ET4 (20nm)/LiF (1nm)/Al (150nm)
Device F:ITO/F4-TCNQ (1nm)/2TNATA:F4-TCNQ (60nm, 3%)/NPB (20nm)/TC56:TC57 (300,3%)/ET4 (20nm)/LiF (1nm)/Al (150nm)
Test data is as follows
| Embodiment | Device number | Voltage * | Current efficiency | Power efficiency | CIE |
| One | A | 8.5 | 9.5 | 3.51 | 0.15，0.24 |
| B | 6.24 | 9.25 | 4.65 | 0.15，0.24 | |
| Two | C | 8.9 | 10.2 | 3.60 | 0.15，0.23 |
| D | 6.41 | 9.65 | 4.73 | 0.15，0.23 | |
| Three | E | 6.15 | 9.5 | 4.85 | 0.15，0.25 |
| F | 5.8 | 9.8 | 5.31 | 0.15，0.25 |
* annotate: voltage, current efficiency, power efficiency, CIE record under current density 50mA/cm2.
Can see that from above data (F) obviously (E) voltage is low for A, C, and the efficient height illustrates the very effective reduction device voltage of resilient coating energy, improves the efficient of device than the device that does not have resilient coating for B, D for the device of increase resilient coating.
It is as follows that English in the specification of the present invention is called for short corresponding Chinese:
OLED=Organic Light Emitting Diode CF
4=tetrafluoromethane
HIL=hole transmission layer HTL=hole transmission layer
EML=luminescent layer ETL=electron transfer layer
ITO=indium tin oxide IZO=indium-zinc oxide
AZO=aluminium zinc oxide Ag=silver
Au=gold LiF=lithium fluoride
Al=aluminium
2TNATA=4,4,4-three-((2-naphthyl)-phenylamino) triphenylamine (English full name: 4,4,4-tris-((2-naphthyl)--phenylamino) triphenylamine) NPB=naphthyl phenylenediamine (English full name: di (naphthalen-1---diphenylbenzidine) Alq3=(three (eight hydroxyls) quinoline aluminum (English full name: tris (8-hydroxyquinolinato) aluminum)
F4-TCNQ=2,3,5,6-tetrafluoro-7,7,8,8, four cyano to the secondary methylbenzoquinone (English full name: 2,3,5,6 ,-tetrafluoro-7,7,8,8 ,-tetracyanoquinodimethane).
Claims (12)
1. low voltage organic light emitting diode device comprises:
Substrate (1);
Go up the anode (2) that forms at substrate (1);
Go up the organic electroluminescent functional layer (5) that forms at substrate (1);
With adjoining hole transport functional layer (4) and the electric transmission functional layer (6) of described organic electroluminescent functional layer (5); With
The negative electrode that on functional layer, forms (7);
It is characterized in that: between described anode (2) and described hole transport functional layer (4), also comprise the strong acceptor organic molecule material of one deck resilient coating (3).
2. low voltage organic light emitting diode device as claimed in claim 1 is characterized in that: also increase one deck between described strong acceptor organic molecule material resilient coating (3) and the described hole transport functional layer (4) and strengthen hole injected holes implanted layer (8).
3. low voltage organic light emitting diode device as claimed in claim 1 or 2 is characterized in that: described strong acceptor organic molecule material comprises 2,3,5,6-tetrafluoro-7,7,8,8, four cyano is to secondary methylbenzoquinone, 7,7,8,8,-four cyano to secondary methylbenzoquinone, four cyano to secondary methylnaphthoquinone, 1,4,5,8 tetrahydroxys 1,4,5,8 tetrathio bases-2,3,6, at least a in the middle of the 7-4 cyano group anthraquinone.
4. low voltage organic light emitting diode device as claimed in claim 1 or 2 is characterized in that: described strong acceptor organic molecule material resilient coating (3) thickness is 0.1 nanometer-100 nanometer.
5. low voltage organic light emitting diode device as claimed in claim 1 or 2 is characterized in that: described anode (2) is selected transparent conductive oxide for use.
6. low voltage organic light emitting diode device as claimed in claim 1 or 2 is characterized in that: described anode (2) is selected the non-transparent metals material for use.
7. the manufacture method of low voltage organic light emitting diode device as claimed in claim 1 may further comprise the steps:
A. go up at substrate (1) and form anode (2);
B. on electrode, form anode pattern, insulating barrier, electrode isolation layers successively with photoetching process;
C. the substrate that will do good pattern forms strong acceptor organic molecule material resilient coating (3) then with examples such as oxygen cleaning;
D. form hole transport functional layer (4), organic electroluminescent functional layer (5), electric transmission functional layer (6) and negative electrode (7) then successively;
E. in high pure nitrogen, be packaged into device.
8. the manufacture method of low voltage organic light emitting diode device as claimed in claim 7 is characterized in that: also further comprise the step that forms hole injection layer (8) between step c and the steps d.
9. the manufacture method of low voltage organic light emitting diode device as claimed in claim 7 is characterized in that: strong acceptor organic molecule material resilient coating (3) is to adopt thermal evaporation film-forming or solution spun-dried and form among the step c.
10. as the manufacture method of claim 7,8 or 9 described low voltage organic light emitting diode devices, it is characterized in that: the described strong acceptor organic molecule material of step c comprises 2,3,5,6-tetrafluoro-7,7,8,8, four cyano is to secondary methylbenzoquinone, 7,7,8,8,-four cyano to secondary methylbenzoquinone, four cyano to secondary methylnaphthoquinone, 1,4,5,8 tetrahydroxys 1,4,5,8 tetrathio bases-2,3,6, at least a in the middle of the 7-4 cyano group anthraquinone.
11. the manufacture method as claim 7,8 or 9 described low voltage organic light emitting diode devices is characterized in that: the formed strong acceptor organic molecule material resilient coating of step c (3) thickness is 0.1 nanometer-100 nanometer.
12. the manufacture method as claim 7,8 or 9 described low voltage organic light emitting diode devices is characterized in that: the described anode of step a (2) selects for use tin indium oxide to make material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349854A (en) * | 2019-12-25 | 2021-02-09 | 广东聚华印刷显示技术有限公司 | Display device, preparation method thereof and display panel |
| CN114203923A (en) * | 2021-12-07 | 2022-03-18 | 深圳市华星光电半导体显示技术有限公司 | Hole buffer material, preparation method thereof and OLED device |
-
2006
- 2006-11-07 CN CNB2006100635537A patent/CN100544061C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349854A (en) * | 2019-12-25 | 2021-02-09 | 广东聚华印刷显示技术有限公司 | Display device, preparation method thereof and display panel |
| CN114203923A (en) * | 2021-12-07 | 2022-03-18 | 深圳市华星光电半导体显示技术有限公司 | Hole buffer material, preparation method thereof and OLED device |
| CN114203923B (en) * | 2021-12-07 | 2023-12-05 | 深圳市华星光电半导体显示技术有限公司 | Hole buffer material, preparation method thereof and OLED device |
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