Cu / AZO composite transparent anode material and preparation method and application thereof

Abstract

This invention discloses a Cu / AZO composite transparent anode material, its preparation method, and its applications, relating to the field of anode material preparation technology. The Cu / AZO composite transparent anode material comprises, from bottom to top: a polymer substrate; an aluminum-doped zinc oxide thin film disposed on the polymer substrate; and a copper metal mesh layer directly attached to the surface of the aluminum-doped zinc oxide thin film. This invention solves the problem of weak adhesion and easy detachment of the copper metal mesh on the polymer substrate. Furthermore, the prepared Cu / AZO composite transparent anode material exhibits high conductivity, high light transmittance, good flexibility, and good interlayer adhesion. It is also non-toxic and low-cost, making it an ideal substitute for indium tin oxide (ITO) and widely applicable to optoelectronic devices such as flexible organic light-emitting diodes (OLEDs).

Description

Technical Field

[0001] This invention relates to the field of anode material preparation technology, and in particular to a Cu / AZO composite transparent anode material, its preparation method, and its application. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are considered a next-generation display technology to replace liquid crystal displays (LCDs), offering advantages such as high color saturation, wide viewing angles, and fast response times. The photoelectric properties of OLEDs are primarily determined by the electrode materials; therefore, the fabrication of anode materials with high transmittance and high conductivity is of great significance.

[0003] Currently, indium tin oxide (ITO) is the most widely used anode material, possessing advantages such as low resistivity and high transparency, and is widely used in flat panel displays, OLEDs, plasma displays, solar cells, and other fields. However, ITO contains the rare and toxic element indium, resulting in high costs and making it unsuitable for the development needs of flexible devices.

[0004] Among transparent conductive oxides (TCOs), ZnO thin films have attracted much attention due to their excellent n-type conductivity. Their conductivity can be further improved by doping with elements such as Al, Ga, and In. Among these, aluminum-doped zinc oxide (AZO) is a strong alternative to ITO due to its non-toxicity, low cost, and environmental friendliness.

[0005] Copper mesh (CuM) possesses excellent mechanical flexibility, optical transparency, and electrical conductivity; however, its adhesion to polymer substrates (such as PET) is weak, making it prone to detachment and leading to conductive film failure. Studies have shown that copper layers exhibit good adhesion to oxygen layers when their thickness exceeds 100 nm. Summary of the Invention

[0006] The purpose of this invention is to provide a Cu / AZO composite transparent anode material, its preparation method and application, and to prepare a flexible transparent anode material with good conductivity, high light transmittance and strong adhesion.

[0007] To achieve the above objectives, the present invention provides a Cu / AZO composite transparent anode material, comprising, from bottom to top: Polymer substrate; Aluminum-doped zinc oxide thin film is disposed on a polymer substrate; A copper metal mesh layer is directly attached to the surface of an aluminum-doped zinc oxide thin film.

[0008] Preferably, the polymer substrate is PET.

[0009] Preferably, the thickness of the aluminum-doped zinc oxide film is 180nm-220nm.

[0010] Preferably, the thickness of the copper metal mesh layer is 150nm-250nm.

[0011] Preferably, the mass ratio of ZnO to Al2O3 in the aluminum-doped zinc oxide film is 98:3.

[0012] This invention provides a method for preparing a Cu / AZO composite transparent anode material, which includes the following steps: S1. Clean the polymer substrate; S2. Deposit an aluminum-doped zinc oxide thin film on the cleaned polymer substrate by magnetron sputtering. S3. A copper metal mesh layer is deposited on an aluminum-doped zinc oxide thin film by magnetron sputtering.

[0013] Preferably, the cleaning process in step S1 includes: cleaning with toluene, acetone, alcohol, and deionized water in sequence, followed by drying with N2.

[0014] Preferably, the sputtering gas used in the magnetron sputtering method in step S2 is at least one of high-purity argon and high-purity oxygen.

[0015] Preferably, the sputtering gas used in the magnetron sputtering method in step S2 is high-purity argon.

[0016] This invention provides an application of Cu / AZO composite transparent anode material, which is used to prepare flexible organic light-emitting diode devices.

[0017] In summary, the Cu / AZO composite transparent anode material, its preparation method, and its application provided by this invention offer the following advantages compared to traditional technologies: (1) In this invention, the copper metal mesh layer of the Cu / AZO composite transparent anode material is directly attached to the surface of the aluminum-doped zinc oxide film, which solves the problem that the copper metal mesh layer is easy to fall off on the polymer substrate; (2) The Cu / AZO composite transparent anode material prepared by the present invention has high conductivity, high light transmittance and good mechanical flexibility; (3) The Cu / AZO composite transparent anode material prepared by the present invention is non-toxic and low-cost, suitable for replacing ITO, and applicable to optoelectronic devices such as flexible OLED.

[0018] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0019] Figure 1 This is a structural diagram of the Cu / AZO composite transparent anode material in this invention; Figure 2 This is a flowchart of the preparation method of Cu / AZO composite transparent anode material in this invention; Figure 3 This is a transmittance test diagram of the Cu / AZO composite transparent anode material prepared in Example 1 of the present invention; Figure 4 This is a structural diagram of the flexible organic light-emitting diode device fabricated based on the Cu / AZO composite transparent anode material in Example 1 of the present invention; Figure 5 The current density-voltage characteristic curve of the flexible organic light-emitting diode device prepared based on the Cu / AZO composite transparent anode material in Example 1 of this invention is shown. Figure 6 The current efficiency-brightness characteristic curve of the flexible organic light-emitting diode device prepared based on the Cu / AZO composite transparent anode material in Example 1 of this invention is shown. Figure 7 The image shows the electroluminescence spectrum of the flexible organic light-emitting diode device prepared based on the Cu / AZO composite transparent anode material in Example 1 under specific driving conditions. Figure 8 This is a characteristic curve showing the brightness of the flexible organic light-emitting diode device prepared based on the Cu / AZO composite transparent anode material in Example 1 of this invention as a function of driving voltage.

[0020] Figure label: 1. Copper metal mesh layer; 2. Aluminum-doped zinc oxide thin film; 3. Polymer substrate; 4. Cu / AZO composite transparent anode material; 5. Organic light-emitting layer; 6. Cathode. Detailed Implementation

[0021] The technical method of the present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that, unless otherwise specifically stated, the relative arrangement of steps, numerical expressions, and values ​​in these embodiments do not limit the scope of this application.

[0022] The following description of at least one exemplary embodiment is merely illustrative and is not intended to limit the scope of this application or its application or use.

[0023] In all the examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values.

[0024] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0025] In recent years, with the rapid development of flexible electronic devices, there has been considerable interest in using aluminum-doped zinc oxide (AZO) films deposited on flexible polymer substrates. Copper mesh (CuM) possesses excellent mechanical properties, optical transparency, and electrical conductivity; however, its adhesion to polymer substrates is very weak, and CuM films prepared on polymer substrates are prone to detachment, leading to the complete failure of CuM-based transparent conductive films. Based on current research, copper layers exhibit excellent adhesion to oxygen layers at deposition thicknesses exceeding 100 nm. Therefore, combining CuM and AZO films to prepare high-performance flexible transparent conductive films is of great significance.

[0026] This invention provides a Cu / AZO composite transparent anode material, such as... Figure 1 As shown, from bottom to top, it includes: a polymer substrate, an aluminum-doped zinc oxide thin film, and a copper metal mesh layer. The aluminum-doped zinc oxide thin film is disposed on the polymer substrate, and the copper metal mesh layer is directly attached to the surface of the aluminum-doped zinc oxide thin film.

[0027] This invention provides a method for preparing a Cu / AZO composite transparent anode material, such as... Figure 2 As shown, it includes the following steps: S1. Clean the polymer substrate.

[0028] S2. Deposit an aluminum-doped zinc oxide thin film on the cleaned polymer substrate by magnetron sputtering.

[0029] S3. A copper metal mesh layer is deposited on an aluminum-doped zinc oxide thin film by magnetron sputtering.

[0030] The specific embodiments provided by this invention are as follows: Example 1 A method for preparing a Cu / AZO composite transparent anode material includes the following steps: S1. Cut the PET substrate to a suitable size as a polymer substrate, i.e., PET polymer substrate. Then, ultrasonically clean it with toluene for 5 minutes to remove surface organic matter. Then, ultrasonically clean it with acetone, alcohol and deionized water for 5 minutes each in sequence. Finally, dry it with N2 for 30 minutes.

[0031] S2. The cleaned PET polymer substrate is placed in a magnetron sputtering apparatus using an AZO ceramic target and high-purity argon and oxygen as sputtering gases to deposit an AZO thin film with a thickness controlled at 200 nm, thus obtaining the AZO / PET material. The mass ratio of ZnO to Al2O3 in the AZO thin film is 98:3.

[0032] S3. On the AZO / PET material, a CuM layer with a thickness of 200 nm is deposited by magnetron sputtering using high-purity argon as the sputtering gas to obtain a Cu / AZO composite transparent anode material, denoted as AS-06.

[0033] The transmittance of the Cu / AZO composite transparent anode material (AS-06) prepared in Example 1 was tested, and the results are as follows: Figure 3 As shown.

[0034] according to Figure 3 It can be seen that the Cu / AZO composite transparent anode material (AS-06) prepared in Example 1 has excellent light transmittance, with a light transmittance as high as 92%.

[0035] The Cu / AZO composite transparent anode material from Example 1 was used to fabricate a flexible organic light-emitting diode device (denoted as OS-G09), with the structure as follows: Figure 4 As shown, it includes: a cathode, an organic light-emitting layer, and a Cu / AZO composite transparent anode material.

[0036] Figure 5 This is a current density-voltage (JV) characteristic curve of the flexible organic light-emitting diode device (OS-G09). Figure 5 As can be seen, this flexible organic light-emitting diode device exhibits a low turn-on voltage and a high current density, indicating that it has good conductivity characteristics. Figure 6 This is a current efficiency-luminosity characteristic curve for the flexible organic light-emitting diode device (OS-G09). Based on... Figure 6 It can be seen that at a brightness of 10000 cd / m² 2 At this point, its current efficiency reaches 98 cd / A, indicating that the anode material can effectively achieve carrier injection and balance, thereby obtaining high luminous efficiency.

[0037] Figure 7 This is the electroluminescence spectrum of a flexible organic light-emitting diode (OS-G09) under specific driving conditions. Based on... Figure 7 It is known that the main peak of this flexible organic light-emitting diode device is located in the standard green light band, and the spectral shape is highly consistent with the theoretical emission spectrum, indicating that the transparent anode material of this invention meets the requirements of high-quality flexible organic light-emitting diode devices in terms of optical transmittance. Furthermore, the Cu / AZO composite anode has high transmittance in the visible light band and does not cause significant absorption or interference modulation to the emission spectrum, thus maintaining the original color purity of the luminescent material.

[0038] Figure 8This is a graph showing the brightness (LV) of a flexible organic light-emitting diode (OS-G09) device as a function of driving voltage. Test results show that the flexible OLED device begins to emit light at relatively low voltages, exhibiting excellent carrier injection capability; and as the driving voltage gradually increases from 2.5V to 6.0V, the device brightness shows a rapid upward trend. At a driving voltage of 6.0V, the device brightness approaches 60,000 cd / m². 2 The brightness is significantly higher than the typical brightness required for general display applications, demonstrating that the Cu / AZO composite transparent anode material structure in Embodiment 1 of this invention can effectively reduce the contact barrier between the anode and the hole injection layer, promoting hole injection and transport, thereby achieving extremely high brightness output at a relatively low voltage. This performance is at an advanced level among similar flexible transparent anode devices, fully verifying the significant synergistic effect of the CuM and AZO composite structure in improving the optoelectronic performance of the device.

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A Cu / AZO composite transparent anode material, characterized in that, From bottom to top, they include: Polymer substrate; Aluminum-doped zinc oxide thin film is disposed on a polymer substrate; A copper metal mesh layer is directly attached to the surface of an aluminum-doped zinc oxide thin film.

2. The Cu / AZO composite transparent anode material according to claim 1, characterized in that, The polymer substrate is PET.

3. The Cu / AZO composite transparent anode material according to claim 1, characterized in that, The thickness of the aluminum-doped zinc oxide thin film is 180nm-220nm.

4. The Cu / AZO composite transparent anode material according to claim 1, characterized in that, The thickness of the copper metal mesh layer is 150nm-250nm.

5. The Cu / AZO composite transparent anode material according to claim 1, characterized in that, The mass ratio of ZnO to Al2O3 in the aluminum-doped zinc oxide thin film is 98:

3.

6. A method for preparing a Cu / AZO composite transparent anode material, characterized in that, The preparation of the Cu / AZO composite transparent anode material according to any one of claims 1-5 includes the following steps: S1. Clean the polymer substrate; S2. Deposit an aluminum-doped zinc oxide thin film on the cleaned polymer substrate by magnetron sputtering. S3. A copper metal mesh layer is deposited on an aluminum-doped zinc oxide thin film by magnetron sputtering.

7. The method for preparing the Cu / AZO composite transparent anode material according to claim 6, characterized in that, The cleaning process described in step S1 includes: cleaning with toluene, acetone, alcohol, and deionized water in sequence, followed by drying with N2.

8. The method for preparing the Cu / AZO composite transparent anode material according to claim 6, characterized in that, The sputtering gas used in the magnetron sputtering method described in step S2 is at least one of high-purity argon and high-purity oxygen.

9. The method for preparing the Cu / AZO composite transparent anode material according to claim 6, characterized in that, The sputtering gas used in the magnetron sputtering method described in step S2 is high-purity argon.

10. An application of a Cu / AZO composite transparent anode material, characterized in that, The Cu / AZO composite transparent anode material according to any one of claims 1-5 is used to prepare flexible organic light-emitting diode devices.

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