Organic electroluminescence element and method of manufacturing thereof

• US 9,029,842 B2
• Filed: 01/16/2013
• Issued: 05/12/2015
• Est. Priority Date: 08/06/2010
• Status: Expired due to Fees

• Current Assignee: JOLED Inc.
• Original Assignee: JOLED Inc.
• Inventors: Harada, Kenji, Nishiyama, Seiji, Komatsu, Takahiro, Takeuchi, Takayuki, Fujimura, Shinya, Ohuchi, Satoru, Fujita, Hirofumi, Tsukamoto, Yoshiaki
• Primary Examiner(s): Such, Matthew W
• Assistant Examiner(s): Kilpatrick, Warren H
• Application Number:
  US13/742,600
• Publication Number:
  US 20130126848A1
• Time in Patent Office: 846 Days
• Field of Search: 257/40, 438/22
• US Class Current: 257/40
• CPC Class Codes: H10K 2102/331 Nanoparticles used in non-emissive layers, e.g. in packaging layer
• CPC Class Codes: H10K 50/00 Organic light-emitting devices integrated devices or assemblies of multiple devices H10K59/00, H10K65/00; organic semiconductor lasers H01S5/36
• CPC Class Codes: H10K 50/17 Carrier injection layers
• CPC Class Codes: H10K 59/122 Pixel-defining structures or layers, e.g. banks
• CPC Class Codes: H10K 71/00 Manufacture or treatment specially adapted for the organic devices covered by this subclass

Abstract

An organic light-emitting element comprising: an anode; a cathode; banks; a functional layer between the anode and the cathode; and a hole injection layer between the anode and the functional layer. The functional layer includes at least a light-emitting sublayer defined by the banks and that contains an organic material. The hole injection layer comprises tungsten oxide and includes a crystal of the tungsten oxide, whose particle diameter is on an order of nanometers. Tungsten atoms constituting the tungsten oxide include both tungsten atoms with a valence of six and tungsten atoms with a valence less than six. The hole injection layer has a surface facing the functional layer, and a portion of the surface overlapping with the light-emitting sublayer is located closer to the anode than other portions, thereby forming a recessed structure having a recessed portion whose inner surface is in contact with the functional layer.

Claims

1. An organic EL element comprising:

an anode;

a cathode;

banks;

a functional layer between the anode and the cathode, the functional layer including one or more sublayers, the one or more sublayers including a light-emitting sublayer, the light-emitting sublayer defined by the banks and containing an organic material; and

a hole injection layer between the anode and the functional layer, wherein

the hole injection layer comprises tungsten oxide,

tungsten atoms constituting the tungsten oxide include both tungsten atoms with a valence of six and tungsten atoms with a valence less than six,

the hole injection layer includes a crystal of the tungsten oxide, a particle diameter of the crystal being on an order of nanometers,

the hole injection layer has a surface facing the functional layer and has a recessed structure such that a portion of the surface overlapping with the light-emitting sublayer is located closer to the anode than other portions of the surface overlapping with the banks,

the portion of the surface overlapping with the light-emitting sublayer and the other portions of the surface overlapping with the banks are located closer to the anode than a peripheral bottom surface of each of the banks, and

the recessed structure comprises (i) an inner bottom surface that is in contact with a bottom surface of the functional layer, and (ii) an inner side surface that is continuous with the inner bottom surface and in contact at least with part of a side surface of the functional layer, and

the inner side surface of the recessed structure has a lower edge and an upper edge, the lower edge being continuous with the inner bottom surface, and the upper edge being one of (i) aligned with part of a lower edge of the bank, the part being in contact with the light-emitting layer, and (ii) in contact with a bottom surface of the bank.

2. The organic EL element of claim 1, wherein

the tungsten atoms with a valence less than six are tungsten atoms with a valence of five.

3. The organic EL element of claim 2, wherein

a ratio W⁵⁺/W⁶⁺ of the number of the tungsten atoms with a valence of five to the number of the tungsten atoms with a valence of six is at least 3.2%.

4. The organic EL element of claim 3, wherein

the ratio W⁵⁺/W⁶⁺ is at least 3.2% and at most 7.4%.

5. The organic EL element of claim 1, wherein

a hard X-ray photoelectron spectroscopy spectrum of a surface of the hole injection layer exhibits a first peak and a second peak, the first peak corresponding to a 4f_7/2 energy level of the tungsten atoms with a valence of six, and the second peak being in a region lower than the first peak in terms of binding energy.

6. The organic EL element of claim 5, wherein

the second peak is in a region between 0.3 electron volts and 1.8 electron volts lower, in terms of binding energy, than the first peak.

7. The organic EL element of claim 5, wherein

an area intensity of the second peak is between 3.2% and 7.4% of an area intensity of the first peak.

8. The organic EL element of claim 1, wherein

the tungsten atoms with a valence less than six cause a band structure of the hole injection layer to have an occupied energy level in a range between 1.8 electron volts and 3.6 electron volts lower than a lowest energy level of a valence band in terms of binding energy.

9. The organic EL element of claim 1, wherein

the hole injection layer includes a plurality of crystals of the tungsten oxide, each of the crystals having a particle diameter from 3 nm to 10 nm.

10. The organic EL element of claim 1, wherein

regular linear structures at intervals from 1.85 angstroms to 5.55 angstroms appear in a lattice image by transmission electron microscopy observation of the hole injection layer.

11. The organic EL element of claim 10, wherein

in a 2D Fourier transform image of the lattice image, a pattern of concentric circles centering on a center point of the 2D Fourier transform image appears.

12. The organic EL element of claim 11, wherein

in a plot of distance from the center point versus normalized luminance, the normalized luminance being a normalized value of the luminance of the 2D Fourier transform image at the corresponding distance, at least one peak of the normalized luminance appears.

13. The organic EL element of claim 12, wherein

with a peak width being a difference between the distance corresponding to a position of a peak of the normalized luminance appearing closest to the center point in the plot and the distance corresponding to a position at which the peak of the normalized luminance begins to rise, the peak width is less than 22 when a difference between the distance corresponding to the center point and the distance corresponding to the peak of the normalized luminance appearing closest to the center point is 100.

14. The organic EL element of claim 1, wherein

the functional layer includes amine-containing material.

15. The organic EL element of claim 1, wherein

the functional layer further includes one of a hole transfer sublayer that transfers holes and a buffer sublayer that adjusts optical characteristics of the organic EL element and/or blocks electrons.

16. The organic EL element of claim 1, wherein

the banks are liquid-repellent and the hole injection layer is liquid-philic.

17. An organic EL panel comprising the organic EL element of claim 1.

18. An organic EL light-emitting apparatus comprising the organic EL element of claim 1.

19. An organic EL display apparatus comprising the organic EL element of claim 1.

24. The organic EL element of claim 1, wherein

the recess structure extends under the peripheral bottom surface of at least one of the banks.

27. The organic EL element of claim 1, wherein

the inner bottom surface of the recessed structure is planar and parallel with an upper surface of the anode, and

a film thickness of the light-emitting layer is uniform over the inner bottom surface of the recessed structure.

20. A manufacturing method for an organic EL element, comprising:

preparing an anode;

forming a tungsten oxide layer on the anode by using a sputtering gas including argon gas and oxygen gas and by using tungsten as a sputtering target, under film forming conditions such that a total pressure of the sputtering gas is at least 2.3 Pa and at most 7.0 Pa, a partial pressure of the oxygen gas in the sputtering gas is at least 50% and at most 70%, an input power density per unit area of the sputtering target is at least 1.5 W/cm² and at most 6.0 W/cm², and a value yielded by dividing the total pressure of the sputtering gas by the input power density is larger than 0.7 Pa·

cm²/W;

forming banks above the tungsten oxide layer by forming a resist film including resist material above the tungsten oxide layer and etching the resist film with a developing solution;

forming a hole injection layer, subsequent to forming the banks, by;

cleaning, with a cleaning fluid, a surface of the tungsten oxide layer and thereby removing residuals of the resist film adhering to the surface of the tungsten oxide layer; and

dissolving a part of the tungsten oxide layer with the cleaning fluid, the hole injection layer formed such that a portion of an upper surface of the hole injection layer facing the functional layer is located closer to the anode than other portions of the upper surface overlapping with the banks, the portion forming a recessed structure comprising an inner surface that is in contact with the functional layer, the inner surface including an inner bottom surface and an inner side surface that is continuous with the inner bottom surface;

forming a functional layer by depositing ink into a region of the hole injection layer defined by the banks, applying the ink with respect to the inner bottom surface and the inner side surface such that the ink is in contact with the inner bottom surface and the inner side surface, and drying the ink; and

forming a cathode above the functional layer,

wherein the portion of the surface facing the functional layer and the other portions of the surface overlapping with the banks are located closer to the anode than a peripheral bottom surface of each of the banks, and

in the formation of the hole injection layer, the inner side surface of the recessed structure is formed to have a lower edge and an upper edge, the lower edge continuous with the inner bottom surface, and the upper edge being one of (i) aligned with part of a lower edge of the bank, the part being in contact with the light-emitting layer, and (ii) in contact with a bottom surface of the bank.

22. The manufacturing method of claim 20, wherein

the tungsten oxide layer is formed such that tungsten atoms constituting the tungsten oxide layer include both tungsten atoms with a maximum valence thereof and tungsten atoms with a valence less than the maximum valence, and so as to include a tungsten oxide crystal having a particle diameter on an order of nanometers.

23. The manufacturing method of claim 20, wherein

the value yielded by dividing the total pressure of the sputtering gas by the input power density is less than 3.2 Pa·

cm²/W.

25. The manufacturing method of claim 20, wherein

the recess structure extends under the peripheral bottom surface of at least one of the banks.

28. The manufacturing method of claim 20, wherein

the inner bottom surface of the recessed structure is planar and parallel with an upper surface of the anode, and

a film thickness of the light-emitting layer is uniform over the inner bottom surface of the recessed structure.

21. A manufacturing method for an organic EL element, comprising:

preparing an anode;

forming a tungsten oxide layer on the anode by using a sputtering gas including argon gas and oxygen gas and by using tungsten as a sputtering target, under film forming conditions such that a total pressure of the sputtering gas is at least 2.3 Pa and at most 7.0 Pa, a partial pressure of the oxygen gas in the sputtering gas is at least 50% and at most 70%, an input power density per unit area of the sputtering target is at least 1.5 W/cm² and at most 6.0 W/cm², and a value yielded by dividing the total pressure of the sputtering gas by the input power density is larger than 0.7 Pa·

cm²/W;

forming a hole injection layer, while forming banks above the tungsten oxide layer by forming a resist film including resist material above the tungsten oxide layer and etching the resist film with a developing solution, by;

cleaning, with the developing solution, a surface of the tungsten oxide layer and thereby removing residuals of the resist film adhering to the surface of the tungsten oxide layer; and

dissolving a part of the tungsten oxide layer with the developing solution, the hole injection layer formed such that a portion of an upper surface of the hole injection layer facing the functional layer is located closer to the anode than other portions of the upper surface overlapping with the banks, the portion forming a recessed structure comprising an inner surface that is in contact with the functional layer, the inner surface including an inner bottom surface and an inner side surface that is continuous with the inner bottom surface;

forming a functional layer by depositing ink into a region of the hole injection layer defined by the banks, applying the ink with respect to the inner bottom surface and the inner side surface such that the ink is in contact with the inner bottom surface and the inner side surface, and drying the ink; and

forming a cathode above the functional layer,

wherein the portion of the surface facing the functional layer and the other portions of the surface overlapping with the banks are located closer to the anode than a peripheral bottom surface of each of the banks, and

in the formation of the hole injection layer, the inner side surface of the recessed structure is formed to have a lower edge and an upper edge, the lower edge being continuous with the inner bottom surface, and the upper edge being one of (i) aligned with part of a lower edge of the bank, the part being in contact with the light-emitting layer, and (ii) in contact with a bottom surface of the bank.

26. The manufacturing method of claim 21, wherein

the recess structure extends under the peripheral bottom surface of at least one of the banks.

29. The manufacturing method of claim 21, wherein

the inner bottom surface of the recessed structure is planar and parallel with an upper surface of the anode, and

a film thickness of the light-emitting layer is uniform over the inner bottom surface of the recessed structure.