Device comprising organometallic complex luminescent material

Abstract

The present invention relates to a device containing an organometal-complex luminescent material. The device comprises a luminescent layer. The luminescent layer contains an organometal complex which has a structural formula (I), wherein A, B and C refer to substituted or unsubstituted C, N, O and S atoms independently; a dashed ring for linkage between A and B atoms refers to a substituted or unsubstituted conjugated ring structure; L1, L2, L3 and L4 are single bonds or double bonds independently, wherein L3 and L4 are part of the conjugated ring structure for linkage between A and B atoms; X, X1, Y and Y1 are C, N, O and S atoms independently; Ar1 and Ar2 are substituted or unsubstituted conjugated ring structures independently; M refers to Pt, W and Au atoms. An organometal complex in the luminescent material is high in fluorescence quantum efficiency and heat stability and low in quenching constant and can be used for manufacturing high-efficiency and low-efficiency roll-off red-light OLEDs. ##STR00001##

Claims

1. A light-emitting diode device containing an organometal-complex luminescent material, comprising a luminescent layer that contains an organometal complex as shown in formula I, ##STR00028## wherein A, B and C refer to substituted or unsubstituted C, N, O and S atoms independently; a dashed ring for linkage between A and B atoms refers to a substituted or unsubstituted conjugated ring structure; L1, L2, L3 and L4 are single bonds or double bonds independently, wherein L3 and L4 are part of the conjugated ring structure for linkage between A and B atoms; X, X1, Y and Y1 are C, N, O and S atoms independently; Ar1 and Ar2 are substituted or unsubstituted conjugated ring structures independently; M refers to Pt, W and Au atoms; and the term substituted means being substituted by the following groups: hydrogen, deuterium, sulfur, halogen, hydroxyl, acyl, alkoxyl, acyloxyl, amino, nitro, acylamino, cyano, carboxyl, styryl, aminocarbonyl, carbamoyl, benzylcarbonyl, aryloxyl, a saturated alkyl chain containing 1-30 C atoms, an unsaturated alkyl chain containing 1-30 C atoms, an aromatic ring containing 6-30 C atoms, and a heteroaromatic ring containing 6-30 C atoms.

2. The light-emitting diode device according to claim 1, wherein the X and X1 are N atoms, the Y and Y1 are O atoms, and the M is a Pt atom.

3. The light-emitting diode device according to claim 2, wherein the formula (I) has a structure as shown in Formula (II), ##STR00029## in which, m, n, and p are integers from 0 to 30; R.sup.1, R.sup.2, and R.sup.3 are substituents other than hydrogen on the rings D, E, and F, R.sup.1, R.sup.2, and R.sup.3 are independently selected from deuterium, sulfur, halogen, hydroxyl, acyl, alkoxyl, acyloxyl, amino, nitro, acylamino, cyano, carboxyl, styryl, aminocarbonyl, carbamoyl, benzylcarbonyl, aryloxyl, saturated alkyl containing 1-30 C atoms, unsaturated alkyl containing 1-30 C atoms, an aromatic ring group containing 6-30 C atoms, and a heteroaromatic ring group containing 6-30 C atoms; adjacent R.sup.1, R.sup.2, and R.sup.3 can be independently connected to one another through a covalent bond to form a ring; and D and E are aromatic or heteroaryl rings each containing 6-30 C atoms; F is an aromatic or heteroaryl ring containing 9-30 C atoms.

4. The light-emitting diode device according to claim 3, wherein the D is a five- or six-membered aromatic ring or heterocyclic ring, a benzoaromatic ring or a benzohetercyclic ring; the E is a five- or six-membered heterocyclic ring or a benzohetercyclic ring; the F is a bi- or tri-cyclic aromatic ring, wherein R.sup.1, R.sup.2, R.sup.3 are independently selected from halogen, a saturated alkyl chain containing 1-20 C atoms, an aromatic ring containing 6-20 C atoms, and a heteroaromatic ring containing 6-20 C atoms; adjacent R.sup.1, R.sup.2, and R.sup.3 can be independently connected to one another through a covalent bond to form a ring; and m, n, and p are integers from 0 to 10.

5. The light-emitting diode device according to claim 4, wherein the D is a benzene ring or a naphthalene ring, the E is a pyridine ring or a quinoline ring, and the F is a naphthalene ring or an anthracene ring, wherein R.sup.1, R.sup.2, R.sup.3 are independently selected from halogen, a saturated alkyl chain containing 1-10 C atoms, an aromatic ring containing 6-10 C atoms, and a heteroaromatic ring containing 6-10 C atoms; adjacent R.sup.1, R.sup.2, and R.sup.3 can be independently connected to one another through a covalent bond to form a ring; and m, n, and p are integers from 0 to 6.

6. The light-emitting diode device according to claim 5, wherein the D is a benzene ring, the E is a pyridine ring, and the F is a naphthalene ring, wherein R.sup.1 is hydrogen or halogen, wherein R.sup.2, R.sup.3 are independently selected from halogen, a saturated alkyl chain containing 1-10 C atoms, and an aromatic ring containing 6-10 C atoms; and m, n, and p are integers from 0 to 3.

7. The light-emitting diode device according to claim 1, wherein the organometal complex as shown in formula (I) has one of the following structures: ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049##

8. The light-emitting diode device according to claim 7, wherein the organometal complex as shown in formula (I) has the following structure: ##STR00050##

9. The light-emitting diode device according to claim 1, wherein the luminescent layer comprises a host material and a dopant, and the organometal complex as shown in formula (I) is the dopant.

10. The light-emitting diode device according to claim 1, wherein the host material is TCTA, and the dopant accounts for 1.5% of the total weight of the luminescent layer.

11. Organometal complex as shown in formula (I) has one of the following structures: ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070##

12. The light-emitting diode device according to claim 11, wherein the organometal complex as shown in formula (I) has the following structure: ##STR00071##

13. The light-emitting diode device according to claim 3, wherein the organometal complex as shown in formula (I) has one of the following structures: ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091##

14. The light-emitting diode device according to claim 13, wherein the organometal complex as shown in formula (I) has the following structure: ##STR00092##

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The FIGURE illustrates an embodiment of a device.

DETAILED DESCRIPTION

(2) The present invention will be further described in detail with reference to the following embodiments.

Embodiment 1

(3) ##STR00021##

(4) Preparation of Molecules

(5) ##STR00022##

(6) Compounds 1, 2, 4 and the inorganic salts, catalysts, catalyst ligands, and solvents used in the reaction are all commercially available raw materials.

(7) Synthesis of compound 3: 18.6 g (0.1 mol) of compound 1 and 15.2 g (0.11 mol) of compound 2 are added to a round-bottom flask. 0.575 g (0.001 mol) of Pd (dba).sub.2 and 0.82 g (0.002 mol) of SPhos are added, vacuumized for 30 minutes, and then filled with nitrogen for protection; 400 ml of toluene is bubbled with nitrogen for 30 min, and then added to the flask; 150 ml of potassium carbonate aqueous solution having a concentration of 2M is bubbled with nitrogen for 30 minutes, and then added to the flask. The mixture is reacted for 12 hours under a nitrogen atmosphere, cooled, washed with water, dried over anhydrous magnesium sulfate, and filtered. After a toluene solvent is distilled off from the organic phase, the solid is recrystallized with a n-hexane/dichloromethane system. 18.3 g of pale yellow solid is obtained with a yield of 92%. Mass spectrum (APCI) m/z: 199.

(8) Synthesis of compound 5: 10 g (0.063 mol) of compound 4 is dissolved in 30 ml of ethanol, added with 33.3 ml of saturated sodium bisulfite aqueous solution, and refluxed for 24 hours. 66.7 ml of potassium hydroxide aqueous solution having a concentration of 6M is added and refluxed for 2 hours. The resulting product is acidified with diluted hydrochloric acid and extracted with ethyl acetate. The organic phase is collected, dried over anhydrous magnesium sulfate, and concentrated to obtain 8.14 g of a brown-red solid with a yield of 81.5%. Mass spectrum (APCI) m/z: 159.

(9) Synthesis of compound 6: 5 g (0.025 mol) of compound 3 and 4 g (0.025 mol) of compound 5 are dissolved in toluene, and refluxed for 12 hours under the protection of nitrogen, and the produced water is removed by a water separator. After cooling, the solution is dried with anhydrous magnesium sulfate, and concentrated, and then toluene is recrystallized to obtain 8.1 g of orange-red needle-like crystals with a yield of 95%. Mass spectrum (APCI) m/z: 340.

(10) Synthesis of compound S1: 5 g (0.0147 mol) of compound 6 and 2.4 g of anhydrous sodium acetate (0.0294 mol) are dissolved in 100 ml of DMSO, stirred, and heated to 80° C. 6.10 g (0.0147 mol) of potassium tetrachloroplatinate is added, heated 120° C., and reacted for 5 hours. The reactant is added with 500 ml of water, and filtered to collect solids, and the solids are washed with water for multiple times, and rinsed with a small amount of methanol. After recrystallization of toluene, the resulting product is sublimed at 290° C. to obtain 5.48 g of dark red crystals with a total yield of 70%. Mass spectrum (APCI) m/z: 533.

Embodiment 2

(11) ##STR00023##

(12) Preparation of Molecules

(13) The preparation method is the same as that of the S1 molecule, with the only difference being that compound 7 is used instead of compound 2. The molecular formula of compound 7 is shown in formula (III):

(14) ##STR00024##

(15) The synthetic route of compound 7 is as follows:

(16) ##STR00025##

(17) The structure of Comparative Example E1 is shown in formula (IV):

(18) ##STR00026##

(19) The synthesis of compound E1 refers to the synthesis method in Patent US20050233167.

(20) The followings are application examples of the compound of the present invention.

(21) Device materials TCTA (4,4′, 4″-Tri (9-carbazoyl) triphenylamine), TAPC (1,1-Bis [4-[N, N-di (p-tolyl) amino] phenyl] cyclohexane), and TmPYPB (1,3,5-tri [(3-pyridyl)-phen-3-yl] benzene) are all commercially available materials, and their specific structures are respectively shown in formula (V):

(22) ##STR00027##

(23) Other materials such as ITO, LiF, and Al are also commercially available materials.

(24) The device structure is shown in the FIGURE. The device preparation method is as follows.

(25) First, transparent conductive ITO glass (a glass substrate 10 with an anode 20) is sequentially washed with a detergent solution, deionized water, ultrasonic cleaning with acetone, and isopropanol vapor, and then subjected to plasma treatment with oxygen for 5 minutes.

(26) Then, 40 nm-thick TAPC is deposited on the ITO as a hole transport layer 30.

(27) Then, a 20 nm-thick luminescent layer 40 is deposited, wherein a host material is TCTA, and an organometal-complex (dopant) with a mass concentration of 1.5% is doped.

(28) Then, 30 nm-thick TmPYPB is deposited as an electron transport layer 50.

(29) Finally, 1 nm-thick LiF is deposited as an electron injection layer 60 and 100 nm metal Al is deposited as a cathode 70.

(30) The structures and manufacturing methods of the devices 1, 2, and 3 are completely the same, with the difference being that the organometal-complexes S1, S23, and E1 are sequentially used as the dopants in the luminescent layer.

(31) The device comparison results are shown in Table 1:

(32) TABLE-US-00001 Device 1 Device 2 Device 3 Maximum external quantum efficiency 9.4% 13% 9.8% External quantum efficiency at   6%  9% 4.5% 100 mA/cm.sup.−2 Current efficiency at 100 mA/cm.sup.−2 11.7 cd/A 14.3 cd/A 10.8 cd/A CIE (x, y) 0.62, 0.30 0.65, 0.33 0.65, 0.35

(33) Compared with a reference device, the performances of the organic electroluminescent device prepared by the material of the present invention are improved to different extents.