A method for preparing ITO transparent conductive film glass

Abstract

The present invention relates to a method for preparing an ITO transparent conductive film glass, and the method for preparing the ITO transparent conductive film glass comprises the following steps: S1: cleaning a glass substrate, drying for standby use; S2: growing a first film layer on a glass substrate based on sputtering condition 1; S3: growing a second film layer on the first film layer based on sputtering condition 2; S4: growing a third film layer on the second film layer based on sputtering condition 1; S5: annealing treatment, that is, wherein the first film layer and the third film layer are 60-80nm ITO high-transmittance film layers; the second film layer is a 60-100nm Zr-Nb co-doped ITO high-conductivity film layer; and after the first film layer and the second film layer are grown, 13-16% phosphoric acid is used to treat the film surface for 10-15min, and then deionized water is rinsed and dried. The preparation method achieves the purpose of simultaneously optimizing the conductivity and permeability of the film through the design and treatment of different ITO film layers.

Description

Technical Field

[0001] The invention relates to the field of conductive glass, and in particular to a method for preparing ITO transparent conductive film glass. Background Art

[0002] ITO conductive film glass is a technical product formed by coating a layer of ITO transparent conductive film on soda lime glass or borosilicate glass as a substrate. This product has a low resistivity (about 10 -4 With its advantages of high resistance (about 85%-89%), high transmittance (about 85%-89%), and corrosion resistance, it is widely used in liquid crystal display screens, touch screens, solar panels, etc. The performance of existing ITO films is mainly adjusted by adjusting their sputtering process parameters. However, since the film resistance and transmittance change inversely, it is difficult to further optimize the photoelectric performance of ITO films by adjusting the process alone.

[0003] The thin film can be enhanced in transmittance and reduced in resistance. The present application further optimizes the photoelectric performance of the ITO thin film through thin film structure design and process parameter adjustment. Summary of the invention

[0004] In order to make up for the deficiencies of the prior art, the present invention provides a method for preparing an ITO transparent conductive film glass, which achieves the purpose of simultaneously optimizing the conductivity and permeability of the film through the design and treatment of different ITO film layers.

[0005] The technical solution adopted by the present invention to solve the above technical problems is:

[0006] A method for preparing ITO transparent conductive film glass comprises the following steps: S1: cleaning a glass substrate and drying it for standby use; S2: growing a first film layer on the glass substrate based on sputtering condition 1; S3: growing a second film layer on the first film layer based on sputtering condition 2; S4: growing a third film layer on the second film layer based on sputtering condition 1; S5: annealing treatment to obtain;

[0007] The first film layer and the third film layer are 60-80nm ITO high-transmittance film layers; the second film layer is 60-100nm Zr-Nb co-doped ITO high-conductivity film layer; and after the growth of the first film layer and the second film layer, the surface of the film layer is treated with 13-16% phosphoric acid for 10-15 minutes, and then rinsed with deionized water and dried;

[0008] Sputtering condition 1: ITO ceramic target, the weight ratio of indium oxide to tin oxide in the target is 9:1, DC sputtering power is 80-110w, vacuum degree is 10 -4 Pa, working pressure is 0.32-0.35Pa, argon flow rate is 40sccm; oxygen flow rate is 4sccm;

[0009] Sputtering condition 2: ITO ceramic target and Zr-Nb2O5 target were used for co-sputtering; the weight ratio of indium oxide to tin oxide in the front target was 9:1, and the DC sputtering power was 45W; the weight ratio of zirconium to niobium pentoxide in the rear target was 3:1, and the RF sputtering power was 10W; the vacuum degree was 10 -4 Pa; working pressure is 0.48-0.52Pa; argon flow rate is 45sccm; oxygen flow rate is 0.3sccm.

[0010] Furthermore, a silicon dioxide barrier coating is provided between the glass substrate and the first film layer, and the thickness of the silicon dioxide barrier coating is 20-25 nm.

[0011] Furthermore, the annealing temperature is 250-300° C., and the time is 2-3 min.

[0012] Furthermore, the temperature of the glass substrate during sputtering is 250-300°C.

[0013] Furthermore, in S1, when cleaning the glass substrate, it is first wiped, then ultrasonically cleaned with deionized water and then ultrasonically cleaned with ethanol, and then dried for standby use.

[0014] Furthermore, the glass substrate is made of soda-lime glass.

[0015] Furthermore, after the third film layer is grown, the surface of the film layer is also treated with 13-16% phosphoric acid for 10-15 minutes, and then rinsed with deionized water and dried.

[0016] The present invention adopts the above structure, which has the advantages that: the preparation method of the ITO transparent conductive film glass optimizes the conductivity and permeability of the overall film structure through the design of different ITO film layers.

[0017] Specifically, by doping the ITO film with Zr and Nb, the concentration of carriers and the number of oxygen vacancies in the corresponding film can be increased, thereby reducing the resistivity of the corresponding film layer, while having little effect on the film transmittance. By adjusting the power and oxygen flow data in the sputtering process, the sufficiency of the oxidation reaction in the sputtering process is improved, and then a layer of ITO high-transmittance film layer can be formed on both sides of the doped ITO film, and since the surface is treated with acid after each film formation, it is conducive to forming a three-layer structure with clear interfaces between the layers, which is similar to the existing D / M / D sandwich film system structure. Under this structure, since the resistance of the middle film layer is significantly lower than that of the upper and lower layers, the resistance of each layer in series mainly depends on the resistance of the middle layer, thereby achieving the purpose of reducing the resistivity of the overall film layer. The upper and lower sides of the middle layer are ITO high-transmittance film layers, thereby achieving the purpose of increasing transmittance. In summary, the present invention achieves the purpose of optimizing the conductivity and permeability of the overall film.

[0018] In addition, since all three layers of the film are based on ITO material, the binding force between the interface molecules of each layer is relatively strong, which helps to improve the stability of the overall film structure. DETAILED DESCRIPTION

[0019] In order to clearly illustrate the technical features of the present solution, the present invention is described in detail below through specific implementation methods and in conjunction with the accompanying drawings.

[0020] 1. Preparation of ITO transparent conductive film glass of the present invention

[0021] Preparation method: S1 wipe the glass substrate, then use deionized water ultrasonic cleaning and ethanol ultrasonic cleaning in sequence, and dry it for use; S2 use a glass substrate coated with a silicon dioxide barrier layer, or first grow a 20nm silicon dioxide barrier coating on a pure glass substrate, and then grow a first film layer on the glass substrate based on sputtering condition 1; S3 grow a second film layer on the first film layer based on sputtering condition 2; S4 grow a third film layer on the second film layer based on sputtering condition 1; S5 anneal at 250°C for 3 minutes to obtain the experimental sample;

[0022] The first film layer and the third film layer are 80nm ITO high-transmittance film layers; the second film layer is 80nm Zr-Nb co-doped ITO high-conductivity film layer; and after the growth of the first film layer and the second film layer, the surface of the film layer is treated with 15% phosphoric acid for 10 minutes, and then rinsed with deionized water and dried;

[0023] Sputtering condition 1: ITO ceramic target, the weight ratio of indium oxide to tin oxide in the target is 9:1, sputtering power is 110w, vacuum degree is 10 -4 Pa, working pressure is 0.35Pa, argon flow rate is 40sccm; oxygen flow rate is 4sccm;

[0024] Sputtering condition 2: ITO ceramic target and Zr-Nb2O5 target were co-sputtered, the weight ratio of indium oxide to tin oxide in the front target was 9:1, the DC sputtering power was 45W; the weight ratio of zirconium to niobium pentoxide in the rear target was 3:1, the RF sputtering power was 10W; the vacuum degree was 10 -4 Pa; working pressure is 0.5Pa; argon flow rate is 45sccm; oxygen flow rate is 0.3sccm.

[0025] 2. Preparation of comparative samples

[0026] (1) Comparative sample 1: The difference from the preparation method of the present invention is that an undoped ITO film layer is continuously grown under condition 2, the thickness of which is consistent with the thickness of the experimental sample, and no acid treatment is performed.

[0027] (2) Comparative sample 2: The difference from the preparation method of the present invention is that no acid treatment is performed.

[0028] (3) Comparative sample 3: The difference from the preparation method of the present invention is that the second film layer is not doped with Zr and Nb.

[0029] (4) Comparative sample 4: The difference from the preparation method of the present invention is that the second film layer is only doped with Zr.

[0030] (5) Comparison with sample 5: The difference from the preparation method of the present invention is that the second film layer is only doped with Nb.

[0031] 3. Performance testing

[0032] The resistivity of the experimental samples and comparative samples 1-5 was tested using a four-point probe device; the transmittance of the experimental samples and comparative samples 1-5 was tested using an ultraviolet-visible spectrophotometer, and the average measurement results at wavelengths of 500nm, 600nm, and 700nm are shown in Table 1.

[0033] Table 1 Resistivity and transmittance test results of samples

[0034] sample Resistivity / Ω·CM Transmittance / % Experimental samples <![CDATA[9.17ⅹ10 -5 ]]> 93.4％ Comparative sample 1 <![CDATA[3.28ⅹ10 -4 ]]> 85.6％ Comparative sample 2 <![CDATA[6.24ⅹ10 -2 ]]> 92.9％ Comparative sample 3 <![CDATA[8.36ⅹ10 -4 ]]> 90.1％ Comparative sample 4 <![CDATA[1.89ⅹ10 -4 ]]> 91.5％ Comparative sample 5 <![CDATA[2.16ⅹ10 -4 ]]> 90.9％

[0035] From the results in Table 1, we can see that the resistivity of the experimental sample can reach 9.17ⅹ10 -5 Ω·CM, the transmittance can reach 93.4%. Compared with the single-layer ITO comparison sample 1 prepared by conventional methods, its resistivity and transmittance have been significantly improved.

[0036] The results of the experimental samples and the comparative sample 2 show that the surface of each film layer is flattened by acid treatment of a certain concentration, which helps to form a clear interface layer. At this time, the resistance of each layer can be calculated in parallel, and the total resistance value depends on the resistance of the middle layer. If the acid treatment is not performed, the interface of each layer is not clear enough, and the resistance tends to be calculated in series. Since the resistance values ​​of the first and second film layers are large, the overall resistivity will be large. Acid treatment has little effect on the membrane transmittance.

[0037] The results of the experimental samples and comparative samples 3-4 show that doping with Zr or Nb helps to improve the transmittance of the film and reduce the resistivity. Among them, doping with Zr has a greater impact on the performance of the film, while doping with Zr and Nb at a certain ratio can significantly improve the resistivity of the film and help improve the transmittance, but the impact on the transmittance is not as great as the impact on the resistivity.

[0038] The above specific implementations cannot be used as limitations on the scope of protection of the present invention. For those skilled in the art, any replacement, improvement or change made to the implementations of the present invention falls within the scope of protection of the present invention. The parts not described in detail in the present invention are all known technologies to those skilled in the art.

Claims

1. A method for preparing ITO transparent conductive film glass, characterized in that: The method comprises the following steps: S1: cleaning a glass substrate and drying it for standby use; S2: growing a first film layer on the glass substrate based on sputtering condition 1; S3: growing a second film layer on the first film layer based on sputtering condition 2; S4: growing a third film layer on the second film layer based on sputtering condition 1; S5: annealing treatment to obtain; The first film layer and the third film layer are 60-80nm ITO high-transmittance film layers; the second film layer is 60-100nm Zr-Nb co-doped ITO high-conductivity film layer; and after the growth of the first film layer and the second film layer, the surface of the film layer is treated with 13-16% phosphoric acid for 10-15 minutes, and then rinsed with deionized water and dried; Sputtering condition 1: ITO ceramic target, the weight ratio of indium oxide to tin oxide in the target is 9:1, DC sputtering power is 80-110w; vacuum degree is 10 -4 Pa, working pressure is 0.32-0.35Pa, argon flow rate is 40sccm; oxygen flow rate is 4sccm; Sputtering condition 2: ITO ceramic target and Zr-Nb2O5 target were used for co-sputtering; the weight ratio of indium oxide to tin oxide in the front target was 9:1, and the DC sputtering power was 40-60W; the weight ratio of zirconium to niobium pentoxide in the rear target was 3:1, and the RF sputtering power was 8-10.5W; the vacuum degree was 10 -4 Pa; working pressure is 0.48-0.52Pa; argon flow rate is 45sccm; oxygen flow rate is 0.3sccm.

2. The method for preparing the ITO transparent conductive film glass according to claim 1, characterized in that: A silicon dioxide barrier coating is also provided between the glass substrate and the first film layer, and the thickness of the coating is 20-25 nm.

3. The method for preparing the ITO transparent conductive film glass according to claim 1, characterized in that: The annealing temperature is 250-300°C and the time is 2-3 minutes.

4. The method for preparing the ITO transparent conductive film glass according to claim 1, characterized in that: The temperature of the glass substrate during sputtering is 250-300°C.

5. The method for preparing the ITO transparent conductive film glass according to claim 1, characterized in that: In S1, when cleaning the glass substrate, it is first wiped, then ultrasonically cleaned with deionized water and then ultrasonically cleaned with ethanol, and then dried for use.

6. The method for preparing the ITO transparent conductive film glass according to claim 1, characterized in that: The glass substrate is made of soda-lime glass.

7. The method for preparing the ITO transparent conductive film glass according to claim 1, characterized in that: After the third film layer is grown, the surface of the film layer is also treated with 13-16% phosphoric acid for 10-15 minutes, and then rinsed with deionized water and dried.