Laminated transparent conductive film with excellent conductivity and light transmission and preparation method and application thereof

Abstract

The invention relates to a laminated transparent conductive film with excellent conductivity and light transmission and a preparation method and application thereof. The invention belongs to the field of transparent conductive films. The invention aims to solve the problem that the existing laminated transparent conductive film cannot give consideration to both excellent conductivity and light transmission. The method comprises the following steps: sequentially depositing a MoO3 layer, a Mo layer, a Cu layer, a Mo layer and a ZnO layer on the surface of a substrate layer by layer through magnetron sputtering, and carrying out annealing treatment after deposition is completed. Different Mo and Cu thicknesses are changed, meanwhile, the transition layer Mo is introduced between the Cu layer and the MoO3 layer, the lattice mismatch rate is reduced, interface defects are improved, gradient transition is formed, interface stress is buffered, Cu oxidation and diffusion are avoided, and finally the transparent conductive film with low resistivity and high transmittance is prepared. The compound is applied to the fields of OLED and electrochromic materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of transparent conductive films, and particularly relates to a laminated transparent conductive film with excellent conductivity and light transmittance, and a preparation method and application thereof. BACKGROUND

[0002] Indium tin oxide (ITO) as a representative of transparent conductive films has a resistivity as low as 10 -4 -10 -5 Ω·cm, an average transmittance of visible light > 85%, and is relatively mature in technology and is widely used in the industry, but ITO has some problems, such as high processing temperature, poor chemical and thermal stability, limited mechanical flexibility, and high cost.

[0003] On the one hand, co-doping ZnO with multiple elements can effectively improve the light transmittance and conductivity of metal oxides, but there is a mutual restriction relationship between resistivity and transparency. In recent years, the oxide / metal / oxide (OMO) multilayer structure has attracted widespread attention due to its high conductivity and transparency, and is compatible with flexible substrates, and can be applied to transparent electrodes of OLED, electrochromic materials, photovoltaic cell devices, etc. The oxide layer is mostly AZO, ZnO, ITO, which can prevent the metal layer from being affected by oxygen and water vapor, promote the performance of the film to be more stable, and increase the light transmittance; the metal layer can improve the conductivity, and the metal layer is mostly Au, Ag layer, which has good conductivity but high cost. SUMMARY

[0004] Therefore, the present application aims to provide a laminated transparent conductive film with excellent conductivity and light transmittance, and a preparation method and application thereof.

[0005] The technical solution of the present application is as follows: One of the purposes of the present application is to provide a preparation method of a laminated transparent conductive film with excellent conductivity and light transmittance, which is performed according to the following steps: MoO3 layer, Mo layer, Cu layer, Mo layer and ZnO layer are sequentially deposited on the surface of the substrate layer by layer by magnetron sputtering, and annealing treatment is performed after deposition is completed.

[0006] Further limitation, the substrate is glass or PI.

[0007] Further limitation, the substrate is cleaned before use: sequentially cleaned with soap water (concentration 20%), acetone, methanol, deionized water for 15 min, 10 min, 15 min and 10 min respectively, and dried with nitrogen (purity 99.99%).

[0008] Further limited, MoO3 layer magnetron sputtering parameters: the gas is high-purity Ar gas and oxygen, Ar:O2 flow ratio is 50:20 sccm, working pressure is 0.5~1Pa, sputtering power is 80~100W, sputtering time is 4~6min.

[0009] Further limited, two layers of Mo layer magnetron sputtering parameters are the same, specifically: the gas is high-purity Ar gas, flow is 30~60sccm, working pressure is 0.5~1Pa, sputtering power is 80~100W, sputtering time is 10~25s.

[0010] Further limited, Cu layer magnetron sputtering parameters: the gas is high-purity Ar gas, flow is 30~60sccm, working pressure is 0.4~0.8Pa, sputtering power is 40~60W, sputtering time is 60~90s.

[0011] Further limited, ZnO layer magnetron sputtering parameters: the gas is high-purity Ar gas, flow is 30~60sccm, working pressure is 0.5~1Pa, sputtering power is 120~150W, sputtering time is 4~6min.

[0012] Further limited, annealing temperature is 150~250℃, time is 0.5~1.5h.

[0013] The second object of the application is to provide a laminated transparent conductive film prepared by the above method, the film thickness is 80~110nm, resistivity is ≤3×10 -4 Ω·cm, light transmittance in visible light range is >75%.

[0014] The third object of the application is to provide an application of the laminated transparent conductive film prepared by the above method in OLED, electrochromic material.

[0015] Compared with the prior art, the application has the following advantages: The application uses a preparation method of laminated transparent conductive film, deposits MoO3, Mo, Cu, Mo, ZnO films in argon atmosphere by magnetron sputtering, changes the thickness of different Mo and Cu to realize the preparation of zinc oxide transparent conductive film with low resistivity and high transmittance; at the same time, the application introduces a transition layer Mo between the Cu layer and the MoO3 layer, reduces the lattice mismatch rate of the Cu layer and the MoO3 layer, improves the interface defects between the Cu layer and the MoO3 layer, forms a "gradient transition", buffers the interface stress, avoids Cu oxidation and diffusion, and finally the prepared transparent conductive film has a resistivity of less than 3×10 -4 Ω·cm, light transmittance in visible light range is >75%. It can be applied to OLED, electrochromic material and other transparent conductive films, which is conducive to improving the conductivity and optical transmittance and reducing the production cost. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a schematic diagram of the laminated transparent conductive film structure obtained by the present application; wherein 1 is a substrate, 2 is a MoO3 layer, 3 is a Mo layer, 4 is a Cu layer, and 5 is a ZnO layer. DETAILED DESCRIPTION

[0017] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0018] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained by commercial channels by those skilled in the art.

[0019] The high-purity Ar gas used in the examples has a purity of 99.999%.

[0020] Example 1, a preparation method of a laminated transparent conductive film with excellent conductivity and light transmittance is carried out according to the following steps: (1) Substrate cleaning The glass is sequentially cleaned with soap water (concentration 20%), acetone, methanol and deionized water for 15 min, 10 min, 15 min and 10 min respectively, and then dried with nitrogen (purity 99.99%) to remove surface contaminants.

[0021] (2) Magnetron sputtering The glass substrate cleaned in step (1) is placed on the sample stage of the PVD film coating equipment, the target-substrate distance is 70 mm, the base vacuum is extracted to 3x10 -4Pa, then Ar gas with a flow rate of 40 sccm was introduced, and the glass was cleaned using an ion source. During the coating process, the sample stage rotated at a speed of 10 r / min. When coating the MoO3 layer, high-purity Ar gas and oxygen were used, the Ar:O2 flow rate ratio was 50:20 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 5 min, and the film thickness was 35 nm. When coating the Mo layer, high-purity Ar gas was used, the Ar flow rate was 40 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 10 s, and the film thickness was 2 nm. When coating the Cu layer, high-purity Ar gas was used, the Ar flow rate was 30 sccm, the working pressure was 0.5 Pa, the sputtering power was 60 W, the sputtering time was 75 s, and the film thickness was 15 nm. When coating the Mo layer again, high-purity Ar gas was used, the Ar flow rate was 40 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 10 s, and the film thickness was 2 nm. When coating the ZnO layer, high-purity Ar gas was used, the Ar flow rate was 40 sccm, the working pressure was 0.7 Pa, the sputtering power was 120 W, the sputtering time was 6 min, and the film thickness was 40 nm.

[0022] (3) Annealing treatment The annealing temperature was 200°C, and the annealing time was 1 h under a nitrogen atmosphere.

[0023] Example 2: A method for preparing a laminated transparent conductive film with excellent conductivity and light transmittance was performed according to the following steps: (1) Substrate cleaning The glass was sequentially cleaned with soap water (concentration 20%), acetone, methanol, and deionized water for 15 min, 10 min, 15 min, and 10 min, respectively, and then dried with nitrogen (purity 99.99%) to remove surface contaminants.

[0024] (2) Magnetron sputtering The glass substrate cleaned in step (1) was placed on the sample stage of a PVD coating device, the target-substrate distance was 70 mm, the base vacuum was extracted to 3×10 -4Pa, then Ar gas with a flow rate of 40 sccm was introduced, and the glass was cleaned using an ion source. During the coating process, the sample stage rotated at a speed of 10 r / min. When coating the MoO3 layer, high-purity Ar gas and oxygen were used, the Ar:O2 flow rate ratio was 50:20 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 5 min, and the film thickness was 35 nm. When coating the Mo layer, high-purity Ar gas was used, the Ar flow rate was 40 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 10 s, and the film thickness was 2 nm. When coating the Cu layer, high-purity Ar gas was used, the Ar flow rate was 30 sccm, the working pressure was 0.5 Pa, the sputtering power was 60 W, the sputtering time was 85 s, and the film thickness was 17 nm. When coating the Mo layer again, high-purity Ar gas was used, the Ar flow rate was 40 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 10 s, and the film thickness was 2 nm. When coating the ZnO layer, high-purity Ar gas was used, the Ar flow rate was 40 sccm, the working pressure was 0.7 Pa, the sputtering power was 120 W, the sputtering time was 6 min, and the film thickness was 40 nm.

[0025] (3) Annealing treatment The annealing temperature was 200°C, and the annealing time was 1 h under a nitrogen atmosphere.

[0026] Example 3: A method for preparing a laminated transparent conductive film with excellent conductivity and light transmittance was performed according to the following steps: (1) Substrate cleaning The glass was sequentially cleaned with soap water (concentration 20%), acetone, methanol, and deionized water for 15 min, 10 min, 15 min, and 10 min, respectively, and then dried with nitrogen (purity 99.99%) to remove surface contaminants.

[0027] (2) Magnetron sputtering The glass substrate cleaned in step (1) was placed on the sample stage of a PVD coating device, the target-substrate distance was 70 mm, the base vacuum was extracted to 3×10 -4Pa, then Ar gas with a flow rate of 40 sccm was introduced, and the glass was cleaned using an ion source. During the coating process, the sample stage rotated at a speed of 10 r / min. When coating the MoO3 layer, the gas was high-purity Ar and oxygen, the Ar:O2 flow rate was 50:20 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 5 min, and the film thickness was 35 nm. When coating the Mo layer, the gas was high-purity Ar, the Ar flow rate was 40 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 15 s, and the film thickness was 3 nm. When coating the Cu layer, the gas was high-purity Ar, the Ar flow rate was 30 sccm, the working pressure was 0.5 Pa, the sputtering power was 60 W, the sputtering time was 75 s, and the film thickness was 15 nm. When coating the Mo layer again, the gas was high-purity Ar, the Ar flow rate was 40 sccm, the working pressure was 1 Pa, the sputtering power was 80 W, the sputtering time was 15 s, and the film thickness was 3 nm. When coating the ZnO layer, the gas was high-purity Ar, the Ar flow rate was 40 sccm, the working pressure was 0.7 Pa, the sputtering power was 120 W, the sputtering time was 6 min, and the film thickness was 40 nm.

[0028] (3) Annealing treatment The annealing temperature was 200°C, and the annealing time was 1 h under a nitrogen atmosphere.

[0029] Comparative Example 1: The MoO3 / Cu / ZnO transparent conductive film of the present comparative example was prepared by the following method: (1) Substrate cleaning The glass was sequentially cleaned with soap water (concentration 20%), acetone, methanol, and deionized water for 15 min, 10 min, 15 min, and 10 min, respectively, and then dried with nitrogen (purity 99.99%) to remove surface contaminants.

[0030] (2) Magnetron sputtering The glass substrate cleaned in step (1) was placed on the sample stage of a PVD coating device, the target-substrate distance was 70 mm, the base vacuum was extracted to 3×10 -4The glass was cleaned using an ion source after passing through Ar gas at a flow rate of 40 sccm. During deposition, the stage rotation speed was 10 r / min. For MoO3 layer deposition, the gas mixture was high-purity Ar and oxygen, with an Ar:O2 flow rate ratio of 50:20 sccm, a working pressure of 1 Pa, a sputtering power of 80 W, a sputtering time of 5 min, and a film thickness of 35 nm. For Cu layer deposition, the gas mixture was high-purity Ar, with an Ar flow rate of 30 sccm, a working pressure of 0.5 Pa, a sputtering power of 60 W, a sputtering time of 75 s, and a film thickness of 15 nm. For ZnO layer deposition, the gas mixture was high-purity Ar, with an Ar flow rate of 40 sccm, a working pressure of 0.7 Pa, a sputtering power of 120 W, a sputtering time of 6 min, and a film thickness of 40 nm.

[0031] (3) Annealing treatment Under a nitrogen atmosphere, the annealing temperature was 200℃ and the annealing time was 1 hour.

[0032] Comparative Example 2: The preparation method of the ZnO / Cu / ZnO transparent conductive film in this comparative example includes the following steps: (1) Substrate cleaning The glass was washed sequentially with soapy water (20% concentration), acetone, methanol, and deionized water for 15 min, 10 min, 15 min, and 10 min respectively, and then dried with nitrogen gas (99.99% purity) to remove surface contaminants.

[0033] (2) Magnetron sputtering The cleaned glass substrate from step (1) is placed on the sample stage of the PVD coating equipment with a target-substrate distance of 70 mm. The base vacuum is then reduced to 3 × 10⁻⁶ mm. -4 The glass was cleaned using an ion source after passing through Ar gas at a flow rate of 40 sccm. During deposition, the stage rotation speed was 10 r / min. For ZnO deposition, high-purity Ar gas was used at a flow rate of 40 sccm, the working pressure was 0.7 Pa, the sputtering power was 120 W, the sputtering time was 5 min, and the film thickness was 34 nm. For Cu deposition, high-purity Ar gas was used at a flow rate of 30 sccm, the working pressure was 0.5 Pa, the sputtering power was 60 W, the sputtering time was 75 s, and the film thickness was 15 nm. For ZnO deposition, high-purity Ar gas was used at a flow rate of 40 sccm, the working pressure was 0.7 Pa, the sputtering power was 120 W, the sputtering time was 6 min, and the film thickness was 40 nm.

[0034] (3) Annealing treatment Under a nitrogen atmosphere, the annealing temperature was 200℃ and the annealing time was 1 hour.

[0035] The performance results of the transparent conductive films obtained in Examples 1-3 and the transparent conductive film obtained in Comparative Example 1-2 are shown in Table 1.

[0036] Table 1 Performance of transparent conductive films of Examples 1-3 and Comparative Example 1-2

[0037] The above descriptions are only preferred embodiments of the present application, which are different implementations based on the overall concept of the present application, and the protection scope of the present application is not limited to this. Any changes or replacements that can be easily thought of by those skilled in the art within the technical scope disclosed by the present application should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing a multilayer transparent conductive film with excellent conductivity and light transmittance, characterized in that, The method described: MoO3, Mo, Cu, Mo and ZnO layers were sequentially deposited on the substrate surface by magnetron sputtering, followed by annealing.

2. The method according to claim 1, characterized in that, The substrate is glass or PI.

3. The method according to claim 1, characterized in that, The substrate should be cleaned before use.

4. The method according to claim 1, characterized in that, The parameters for magnetron sputtering of MoO3 layers are as follows: the gas is high-purity Ar and oxygen, the Ar:O2 flow ratio is 50:20 sccm, the working pressure is 0.5~1 Pa, the sputtering power is 80~100 W, and the sputtering time is 4~6 min.

5. The method according to claim 1, characterized in that, The magnetron sputtering parameters for the two Mo layers are the same: the gas is high-purity Ar gas, the flow rate is 30~60 sccm, the working gas pressure is 0.5~1Pa, the sputtering power is 80~100W, and the sputtering time is 10~25s.

6. The method according to claim 1, characterized in that, The parameters for magnetron sputtering of Cu layers are as follows: the gas is high-purity Ar gas, the flow rate is 30~60 sccm, the working pressure is 0.4~0.8Pa, the sputtering power is 40~60W, and the sputtering time is 60~90s.

7. The method according to claim 1, characterized in that, ZnO layer magnetron sputtering parameters: high-purity Ar gas, flow rate 30~60 sccm, working pressure 0.5~1Pa, sputtering power 120~150W, sputtering time 4~6min.

8. The method according to claim 1, characterized in that, The annealing temperature is 150~250℃ and the time is 0.5~1.5h.

9. The multilayer transparent conductive film prepared by the method according to any one of claims 1-8, characterized in that, The film has a thickness of 80~110 nm and a resistivity of ≤3×10⁻⁶. -4 Ω·cm, transmittance in the visible light range >75%.

10. The application of the multilayer transparent conductive film prepared by the method of any one of claims 1-8 in OLEDs and electrochromic materials.

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