Organic electroluminescent device, method of preparing same, display substrate, and display apparatus

• US 9,941,482 B2
• Filed: 01/13/2015
• Issued: 04/10/2018
• Est. Priority Date: 09/25/2014
• Status: Active Grant

• Current Assignee: BOE Technology Group Co., Ltd.
• Original Assignee: BOE Technology Group Co., Ltd.
• Inventors: He, Xiaolong, Cao, Zhanfeng, Yao, Qi
• Primary Examiner(s): Clark, Gregory D
• Application Number:
  US14/775,847
• Publication Number:
  US 20160301024A1
• Time in Patent Office: 1,183 Days
• CPC Class Codes: H10K 2102/351 Thickness
• CPC Class Codes: H10K 50/115 comprising active inorganic nanostructures, e.g. luminescent quantum dots
• CPC Class Codes: H10K 50/15 Hole transporting layers
• CPC Class Codes: H10K 50/16 Electron transporting layers
• CPC Class Codes: H10K 50/17 Carrier injection layers
• CPC Class Codes: H10K 50/171 Electron injection layers
• CPC Class Codes: H10K 50/18 Carrier blocking layers
• CPC Class Codes: H10K 71/00 Manufacture or treatment specially adapted for the organic devices covered by this subclass
• CPC Class Codes: H10K 71/15 characterised by the solvent used
• CPC Class Codes: H10K 85/115 Polyfluorene; Derivatives thereof

Abstract

This invention provides an organic electroluminescent device, a method of preparing the same, a display substrate comprising the same, and a display apparatus. According to the invention, the agglomeration and self quenching of quantum dots can be effectively prevented as the quantum dots are uniformly dispersed in electroluminescent polymer fibers. Due to the fluorescence resonance energy transfer effect between the electroluminescent polymer and the quantum dots, a higher quantum yield is achieved, and the luminescence efficiency of the quantum dots can be improved accordingly. Furthermore, since the light emission from the quantum dots is achieved by the fluorescence resonance energy transfer effect, which is an energy transfer process without damage to the quantum dots, the damage to quantum dots is less and thus the lifetime thereof can be beneficially increased, as compared to the direct charge injection mode of the prior art.

Claims

1. A method of preparing an organic electroluminescent device, comprising the following steps:

mixing an organic solvent, a charge control agent, an electroluminescent polymer and quantum dots homogeneously to obtain an electrostatic spinning solution; and

forming the electrostatic spinning solution into a quantum dot-containing organic electroluminescent film by an electrostatic spinning process, wherein the quantum dot-containing organic electroluminescent film is formed from fibers of the electroluminescent polymer dispersed with the quantum dots.

2. The method of preparing an organic electroluminescent device according to claim 1, characterized in that,

(a) the organic solvent includes one or more selected from acyclic alkanes, cycloalkanes, haloalkanes, aromatic hydrocarbons, and derivatives thereof, wherein the organic solvent is liquid at room temperature and has a boiling point lower than 200°

C.;

(b) the charge control agent includes any one or more of dimethylformamide, dimethylacetamide, propionamide, phenylpropanamide, succinimide, and phthalamide;

(c) the electroluminescent polymer includes any one or more of polyphenylenes, polyindenofluorenes, polyfluorenes, and derivatives thereof; and

/or

(d) the quantum dots include any one or more of CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CulnSe, and AlSb.

3. The method of preparing an organic electroluminescent device according to claim 2, characterized in that, the organic solvent includes any one or more of hexane, heptane, octane, cyclohexane, chloroform, toluene, ethylbenzene, and xylene.

4. The method of preparing an organic electroluminescent device according to claim 2, characterized in that, the electroluminescent polymer is selected from ladder-type polyphenylenes, polyphenylenes, polyindenofluorenes, polyfluorenes, copolyfluorenes whose main chains merely consist of fluorene units, and copolyfluorenes whose main chains comprise fluorene units and other units, wherein the other units are derived from aniline, fluorenone, thiophene, or any combinations thereof.

5. The method of preparing an organic electroluminescent device according to claim 2, characterized in that, the quantum dots are quantum dots having a core-shell structure.

6. The method of preparing an organic electroluminescent device according to claim 5, characterized in that, the quantum dots having a core-shell structure respectively comprise a core composed of a material selected from CdS, CdSe, CdTe, PbSe, CuInS and CuInSe, and one or more shells respectively composed of a material selected from CdS, ZnO, ZnS, ZnSe and ZnTe.

7. The method of preparing an organic electroluminescent device according to claim 6, characterized in that, the quantum dots having a core-shell structure are selected from any one or more of CdSe/CdS, CdS/ZnS, CdSe/ZnS, and CdSe/CdS/ZnS.

8. The method of preparing an organic electroluminescent device according to claim 1, characterized in that, the electrostatic spinning solution comprises, by mass %:

the charge control agent, 0.1%-10%;

the electroluminescent polymer, 1%-70%;

the quantum dots, 0.05%-20%; and

the balance being the organic solvent.

9. The method of preparing an organic electroluminescent device according to claim 1, characterized in that, the electrostatic spinning process is performed under the following conditions:

electrospinning voltage, 0.5-50 KV;

syringe diameter, 0.5-5 mm;

injection rate of the electrostatic spinning solution from the syringe, 0.1-10 mL/h; and

the gap between two electrodes forming an electrostatic field, 5-40 cm.

10. An organic electroluminescent device, comprising a quantum dot-containing organic electroluminescent film formed from fibers of electroluminescent polymer dispersed with quantum dots, wherein the fibers further comprise a charge control agent.

11. The organic electroluminescent device according to claim 10, characterized in that, the average distance between adjacent quantum dots in the quantum dot-containing organic electroluminescent film ranges from 0.5 to 30 times the average particle size of the quantum dots.

12. The organic electroluminescent device according to claim 10, further comprising, on one side of the quantum dot-containing organic electroluminescent film:

a hole transport layer, a hole injection layer, and an anode, which are disposed sequentially in a direction away from the film; and

comprising, on the other side of the quantum dot-containing organic electroluminescent film;

a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode, which are disposed sequentially in a direction away from the film.

13. The organic electroluminescent device according to claim 10, characterized in that, the quantum dot-containing organic electroluminescent film has a thickness in the range of 10 nm-500 nm.

14. The organic electroluminescent device according to claim 10, characterized in that,

(a) the quantum dots include any one or more of CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CulnSe, and AlSb;

(b) the electroluminescent polymer includes any one or more of polyphenylenes, polyindenofluorenes, polyfluorenes, and derivatives thereof

(c) the charge control agent is selected from dimethylformamide, dimethylacetamide, propionamide, phenylpropanamide, succinimide, phthalamide, or any combinations thereof; and

/or

(d) the mass ratio of quantum dots;

electroluminescent polymer;

charge control agent is (0.5-200);

(10-700);

(1-100).

15. The organic electroluminescent device according to claim 14, characterized in that, the electroluminescent polymer is selected from ladder-type polyphenylenes, polyphenylenes, polyindenofluorenes, polyfluorenes, copolyfluorenes whose main chains merely consist of fluorene units, and copolyfluorenes whose main chains comprise fluorene units and other units, wherein the other units are derived from aniline, fluorenone, thiophene, or any combinations thereof.

16. The organic electroluminescent device according to claim 14, characterized in that, the quantum dots are quantum dots having a core-shell structure.

17. The organic electroluminescent device according to claim 16, characterized in that, the quantum dots having a core-shell structure respectively comprise a core composed of a material selected from CdS, CdSe, CdTe, PbSe, CuInS and CulnSe, and one or more shells respectively composed of a material selected from CdS, ZnO, ZnS, ZnSe and ZnTe.

18. The organic electroluminescent device according to claim 17, characterized in that, the quantum dots having a core-shell structure are selected from any one or more of CdSe/CdS, CdS/ZnS, CdSe/ZnS, and CdSe/CdS/ZnS.

19. An organic electroluminescent display substrate, comprising an organic electroluminescent device according to claim 10.

20. An organic electroluminescent display apparatus, comprising an organic electroluminescent display substrate according to claim 19.