High haze conductive film and single process preparation method thereof

Abstract

The application relates to a high-haze conductive film and a single-process preparation method thereof, which comprises the following steps: step S1, cleaning float high-transparency glass by adopting alkali liquor, acid liquor or an ion beam etching method; step S2, preparing an AZO seed crystal by adopting a magnetron sputtering method and using high-purity AZO target material in a certain concentration air atmosphere; step S3, closing the sputtering power supply, performing high-vacuum pumping, and removing oxygen existing in the cavity; step S4, performing film plating by adopting the magnetron sputtering method and using the high-purity AZO target material after pre-sputtering in an oxygen-free environment; and step S5, naturally cooling the film-plated glass to room temperature, so that a high-haze AZO conductive film is obtained. The application provides a simple and fast process method for producing and manufacturing the high-haze AZO conductive film, and controllable adjustment of the haze can be realized through simple adjustment of process parameters; and the application only adopts the film plating mode of the magnetron sputtering to realize construction of a microstructure, and is suitable for automatic continuous production.

Description

Technical Field

[0001] This invention belongs to the field of glass deep processing technology, and specifically relates to a high haze conductive film and its single-process preparation method. Background Technology

[0002] Transparent conductive glass can be used in fields such as liquid crystal dimming glass, solar panels, electrically heated glass, security glass, and electromagnetic shielding glass. However, with the expansion of its application areas, new demands have been placed on transparent conductive glass. As is well known, architectural window glass and solar photovoltaic cover glass, due to their high surface flatness, reflect light strongly under sunlight, causing glare and light pollution.

[0003] Traditional methods for preparing high-haze transparent conductive glass involve multiple complex processes and require templates. For example, patent CN111943520A reports a method of obtaining high-haze glass by reactive ion etching followed by treatment with hydrochloric acid and hydrofluoric acid solutions; patent CN110459368A reports the preparation of high-haze conductive films using PS microspheres as templates; patent CN102863156A reports the preparation of AZO transparent conductive films by first etching glass to create a texturized surface and then depositing a film; and patent CN104821192A reports the preparation of high-haze conductive films using silver nanowires, but the dip-coating method used is not conducive to industrial-scale production. Therefore, there is an urgent need to develop a relatively simple single-process method for preparing high-haze transparent conductive glass. Summary of the Invention

[0004] This invention addresses the shortcomings of existing technologies, such as complex manufacturing processes and the need for templates, in producing high-haze transparent conductive films. It provides a high-haze conductive film and a single-process preparation method thereof, the specific technical solution of which is as follows:

[0005] This invention provides a single-process method for preparing a high-haze conductive film, the method comprising the following steps:

[0006] Step S1: Clean the float glass using alkaline solution, acid solution, or ion beam etching.

[0007] Step S2: Using magnetron sputtering, high-purity AZO target material is used to prepare AZO seed crystals in an air atmosphere of a certain concentration.

[0008] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation to remove oxygen from the cavity;

[0009] Step S4: Using magnetron sputtering, high-purity AZO target material is used. The film is pre-sputtered in an oxygen-free environment before coating, and the film thickness is controlled by adjusting the coating time.

[0010] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film.

[0011] In the above method steps, step S1 is to clean the surface of the glass substrate; step S2 is to prepare seed crystals with a certain microstructure; step S3 is to adjust the atmosphere to complete the coating in step 4; step 4 is the rapid growth process of the seed crystal structure, which together with step 2 achieves roughness control; step 5 is to prevent the film from cracking due to rapid cooling.

[0012] As a preferred technical solution of the present invention, in step S1, the float glass is first soaked in a 10% sodium hydroxide / water / ethanol mixed solution for 5 minutes and then rinsed with deionized water; then it is soaked in a 10% hydrochloric acid solution for 5 minutes, rinsed with deionized water, and dried.

[0013] As a preferred embodiment of the present invention, the volume ratio of water to ethanol in a 10% sodium hydroxide / water / ethanol mixed solution is 1:5.

[0014] As a preferred technical solution of the present invention, in step S1, the surface activation treatment of the float glass is performed by ion beam etching.

[0015] As a preferred embodiment of the present invention, step S2 specifically involves placing the cleaned glass into a magnetron sputtering chamber; using a high-purity AZO (zinc aluminum oxide) target material with a purity of 99.99%, wherein the ZnO content is 97.2-98.3% and the Al2O3 content is 1.7-2.8%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶ Pa, the sputtering power is 6000-8000 W, and the voltage is 557-619 V;

[0016] The cleaned glass is introduced into the cavity. During ignition, the Ar (argon) flow rate is 200 sccm. After ignition, the Ar flow rate is 180-200 sccm, and air is introduced at 1-20 sccm to maintain a pressure of 3.0-3.5 x 10-3 torr. The glass reciprocates with the substrate holder at its bottom to reduce the film thickness difference caused by edge effects. The substrate holder is heated to 300-450℃ for seed crystal coating.

[0017] As a preferred technical solution of the present invention, the air flow rate is maintained to decrease linearly during the coating process, and the air volume is reduced to 0 sccm within 10 seconds. At the same time, the Ar flow rate is increased, and the increase of Ar is consistent with the decrease of air volume, so as to maintain the pressure balance in the cavity.

[0018] As a preferred technical solution of the present invention, in order to obtain an AZO conductive film with higher haze, the angle of the glass substrate can be adjusted; the angle adjustment method is to reciprocate the glass substrate and the target material at an angle of + / -10°.

[0019] As a preferred technical solution of the present invention, in step S3, the high vacuum pumping process adopts a reciprocating gas filling and pumping mode, that is, Ar is intermittently introduced and the pumping valve is closed, and then the Ar inlet valve is intermittently closed and the pumping valve is opened; after two or three cycles, the pumping state is maintained until a high vacuum is achieved.

[0020] As a preferred technical solution of the present invention, step S4 specifically involves introducing Ar gas at 200 sccm and maintaining it for 10 seconds, then igniting the sputtering power at 6000-8000 W and the voltage at 557-619 V to pre-sputter a composite AZO target of 97.2-98.3% ZnO and 1.7-2.8% Al2O3 for 5 seconds, followed by coating; and controlling the film thickness by adjusting the coating time.

[0021] The present invention also provides a high-haze conductive film, which is prepared by the method described above.

[0022] The beneficial effects of this invention are:

[0023] 1. This invention provides a simple and quick process for manufacturing high-haze AZO conductive films, and the haze can be controlled and adjusted by simply adjusting the process parameters;

[0024] 2. This invention abandons the traditional methods of constructing microstructures, such as photolithography and etching using large equipment and template methods, and only uses magnetron sputtering to deposit microstructures, making it suitable for automated continuous production;

[0025] 3. Compared with the existing technology that uses oxygen-free or fixed oxygen content for AZO coating, the present invention controls the change of oxygen content during the AZO coating process;

[0026] 4. Compared with existing high-haze conductive films which are made by combining multiple processes, this invention achieves the preparation of high-haze conductive films through a single two-step magnetron sputtering process. Attached Figure Description

[0027] Figure 1 The AFM image of the sample obtained in Embodiment 1 of this invention is shown;

[0028] Figure 2 The AFM image of the sample obtained in Embodiment 2 of this invention is shown;

[0029] Figure 3 The AFM image of the sample obtained in Example 3 of this invention is shown;

[0030] Figure 4 The AFM image of the sample obtained in Example 4 of this invention is shown;

[0031] Figure 5 The AFM image of the sample obtained in Example 5 of this invention is shown;

[0032] Figure 6 An AFM image of the sample obtained in Example 6 of this invention is shown. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0034] Example 1:

[0035] A single-process method for preparing a high-haze conductive film, the method comprising:

[0036] Step S1: Clean the float glass; first, soak it in a 10% sodium hydroxide / water / ethanol mixed solution for 5 minutes, where the volume ratio of water to ethanol is 1:5, and then rinse it with deionized water; then soak it in a 10% hydrochloric acid solution for 5 minutes, rinse it with deionized water, and dry it.

[0037] Step S2: Place the cleaned glass into the magnetron sputtering chamber; use a high-purity AZO target with a purity of 99.99%, of which ZnO content is 98.3% and Al2O3 content is 1.7%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6 The sputtering power was 7000W and the voltage was 600V. When the glass entered the cavity, the Ar flow rate was 200 sccm at ignition. After ignition, the Ar flow rate was 180 sccm, and air was introduced at 20 sccm to maintain a pressure of approximately 3.2 x 10⁻³ torr. The glass reciprocated 5 times with the substrate holder at its bottom. The substrate holder was heated to 400℃ for seed crystal deposition. During the deposition process, the air flow rate decreased linearly, reducing to 0 sccm in 10 seconds while simultaneously increasing the Ar flow rate to 200 sccm. The increase in Ar flow rate matched the decrease in air flow rate. During the deposition process, the glass substrate and the target circulated at an angle of + / -10°.

[0038] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation;

[0039] Step S4: Ar gas is introduced at 200 sccm and maintained for 10 seconds. Then, the sputtering power is 7000 W and the voltage is 600 V to pre-sputter a 98.3% ZnO, 1.7% Al2O3 composite AZO target for 5 seconds, followed by coating. The glass reciprocates 30 times with the substrate holder.

[0040] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film; the AFM image of the obtained sample is shown below. Figure 1 As shown, the sample has a haze of 10.94% and a sheet resistance of 9.9 Ω / □.

[0041] Example 2:

[0042] A single-process method for preparing a high-haze conductive film, the method comprising:

[0043] Step S1: Clean the float glass using ion beam etching; wherein the glass rotation speed is 10 rpm, the Ar flow rate is 18 sccm, the RF power supply power is 150 W, the ion source plate voltage is 300 V, the ion source acceleration voltage is 200 V, the neutralizer voltage is 15 V, and the cleaning time is 5 min.

[0044] Step S2: Place the cleaned glass into the magnetron sputtering chamber; use a high-purity AZO target with a purity of 99.99%, of which ZnO content is 98.3% and Al2O3 content is 1.7%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6 The sputtering power was 6000W and the voltage was 600V. When the glass entered the cavity, the Ar flow rate was 200 sccm at ignition. After ignition, the Ar flow rate was 180 sccm, and air was introduced at 20 sccm to maintain the pressure at about 3.0 x 10-3 torr. The glass reciprocated 5 times with the substrate holder at its bottom. The substrate holder was heated to 400℃ for seed coating. During the coating process, the air flow rate was linearly decreased. The air flow rate was reduced to 0 sccm in 10 seconds, while the Ar flow rate was increased to 200 sccm. The increase in Ar flow rate was consistent with the decrease in air flow rate.

[0045] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation;

[0046] Step S4: Introduce Ar gas at 200 sccm and maintain for 10 seconds. Then, ignite the sputtering power at 6000 W and voltage at 600 V and pre-sputter the 98.3% ZnO, 1.7% Al2O3 composite AZO target for 5 seconds, followed by coating. The glass reciprocates 30 times with the substrate holder.

[0047] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film; the AFM image of the obtained sample is shown below.Figure 2 As shown, the sample has a haze of 10.6% and a sheet resistance of 10.5 Ω / □.

[0048] Example 3:

[0049] A single-process method for preparing a high-haze conductive film, the method comprising:

[0050] Step S1: Clean the float glass; first, soak it in a 10% sodium hydroxide / water / ethanol mixed solution for 5 minutes, where the volume ratio of water to ethanol is 1:5, and then rinse it with deionized water; then soak it in a 10% hydrochloric acid solution for 5 minutes, rinse it with deionized water, and dry it.

[0051] Step S2: Place the cleaned glass into the magnetron sputtering chamber; use a high-purity AZO target with a purity of 99.99%, of which ZnO content is 98.3% and Al2O3 content is 1.7%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6 The sputtering power was 6000W and the voltage was 560V. When the glass entered the chamber, the Ar flow rate was 200 sccm at ignition. After ignition, the Ar flow rate was 190 sccm, and air was introduced at 10 sccm to maintain a pressure of approximately 3.2 x 10⁻³ torr. The glass reciprocated 5 times with the substrate holder, which was heated to 350℃ for seed coating. During the coating process, the air flow rate decreased linearly, reducing to 0 sccm in 10 seconds while simultaneously increasing the Ar flow rate to 200 sccm, ensuring the increase in Ar flow matched the decrease in air flow.

[0052] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation;

[0053] Step S4: Ar gas is introduced at 200 sccm and maintained for 10 seconds. Then, the sputtering power is 6000 W and the voltage is 560 V to pre-sputter a 98.3% ZnO, 1.7% Al2O3 composite AZO target for 5 seconds, followed by coating. The glass reciprocates 30 times with the substrate holder.

[0054] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film;

[0055] The AFM plot of the obtained sample is as follows Figure 3 As shown, the sample has a haze of 5.25% and a sheet resistance of 11.5 Ω / □.

[0056] Example 4:

[0057] A single-process method for preparing a high-haze conductive film, the method comprising:

[0058] Step S1: Clean the float glass; first, soak it in a 10% sodium hydroxide / water / ethanol mixed solution for 5 minutes, where the volume ratio of water to ethanol is 1:5, and then rinse it with deionized water; then soak it in a 10% hydrochloric acid solution for 5 minutes, rinse it with deionized water, and dry it.

[0059] Step S2: Place the cleaned glass into the magnetron sputtering chamber; use a high-purity AZO target with a purity of 99.99%, of which ZnO content is 97.2% and Al2O3 content is 2.8%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6 The sputtering power was 7000W and the voltage was 600V. When the glass entered the cavity, the Ar flow rate was 200sccm at ignition. After ignition, the Ar flow rate was 195sccm, and air was introduced at 5sccm to maintain the pressure at about 3.5x10-3 torr. The glass reciprocated 5 times with the substrate holder at its bottom. The substrate holder was heated to 350℃ for seed coating. During the coating process, the air flow rate was reduced linearly. The air flow rate was reduced to 0sccm in 10s, while the Ar flow rate was increased to 200sccm. The increase in Ar flow rate was consistent with the decrease in air flow rate.

[0060] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation;

[0061] Step S4: Ar gas is introduced at 200 sccm and maintained for 10 seconds. Then, the sputtering power is 7000 W and the voltage is 600 V to pre-sputter a 97.2% ZnO, 2.8% Al2O3 composite AZO target for 5 seconds, followed by coating. The glass reciprocates 30 times with the substrate holder.

[0062] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film;

[0063] The AFM plot of the obtained sample is as follows Figure 4 As shown, the sample has a haze of 2.85% and a sheet resistance of 12.0 Ω / □.

[0064] Example 5:

[0065] A single-process method for preparing a high-haze conductive film, the method comprising:

[0066] Step S1: Clean the float glass; first, soak it in a 10% sodium hydroxide / water / ethanol mixed solution for 5 minutes, where the volume ratio of water to ethanol is 1:5, and then rinse it with deionized water; then soak it in a 10% hydrochloric acid solution for 5 minutes, rinse it with deionized water, and dry it.

[0067] Step S2: Place the cleaned glass into the magnetron sputtering chamber; use a high-purity AZO target with a purity of 99.99%, of which ZnO content is 97.2% and Al2O3 content is 2.8%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6 The sputtering power was 6000W and the voltage was 560V. When the glass entered the cavity, the Ar flow rate was 200 sccm at ignition. After ignition, the Ar flow rate was 199 sccm, and air was introduced at 1 sccm to maintain the pressure at about 3.2 x 10-3 torr. The glass reciprocated 5 times with the substrate holder at its bottom. The substrate holder was heated to 350℃ for seed coating. After the air was continuously introduced for 10 seconds, the air flow rate was directly reduced to 0 sccm, while the Ar flow rate was increased to 200 sccm.

[0068] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation;

[0069] Step S4: Introduce Ar gas at 200 sccm and maintain for 10 seconds. Then, ignite the sputtering power at 6000 W and voltage at 560 V and pre-sputter the 97.2% ZnO, 2.8% Al2O3 composite AZO target for 5 seconds, followed by coating. The glass reciprocates 30 times with the substrate holder.

[0070] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film;

[0071] The AFM plot of the obtained sample is as follows Figure 5 As shown, the haze of the sample is 1.93%, and the sheet resistance is 12.7 Ω / □.

[0072] Example 6:

[0073] A single-process method for preparing a high-haze conductive film, the method comprising:

[0074] Step S1: Clean the float glass; first, soak it in a 10% sodium hydroxide water / ethanol mixed solution for 5 minutes, where the volume ratio of water to ethanol is 1:5, and then rinse it with deionized water; then soak it in a 10% hydrochloric acid solution for 5 minutes, rinse it with deionized water, and dry it.

[0075] Step S2: Place the cleaned glass into the magnetron sputtering chamber; use a high-purity AZO target with a purity of 99.99%, of which ZnO content is 97.2% and Al2O3 content is 2.8%; the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6The sputtering power was 8000W and the voltage was 619V. When the glass entered the cavity, the Ar flow rate was 200 sccm at ignition. After ignition, the Ar flow rate was 199 sccm, and air was introduced at 1 sccm to maintain the pressure at about 3.2 x 10-3 torr. The glass reciprocated 5 times with the substrate holder at its bottom. The substrate holder was heated to 400℃ for seed coating. After the air was continuously introduced for 10 seconds, the air flow rate was directly reduced to 0 sccm, while the Ar flow rate was increased to 200 sccm.

[0076] Step S3: Turn off the sputtering power supply and perform high vacuum evacuation;

[0077] Step S4: Introduce Ar gas at 200 sccm and maintain for 10 seconds. Then, ignite the sputtering power at 8000 W and the voltage at 619 V. Pre-sputter the 97.2% ZnO, 2.8% Al2O3 composite AZO target for 5 seconds, followed by coating. The glass reciprocates 30 times with the substrate holder.

[0078] Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film;

[0079] The AFM plot of the obtained sample is as follows Figure 6 As shown, the haze of the sample is 1.87%, and the sheet resistance is 11.2 Ω / □.

[0080] The haze, roughness, and sheet resistance data of the samples obtained in Examples 1 to 6 above are shown in Table 1 below:

[0081] Table 1

[0082]

[0083] pass Figures 1 to 6 The AFM (Atomic Force Microscopy) images show the state of the surface structure of the AZO conductive film prepared in various embodiments of the present invention, and also show the differences in the microstructure of the AZO conductive film between different embodiments.

[0084] As shown in Table 1, compared with the existing high-haze conductive films which generally have a haze value of less than 1%, the high-haze AZO conductive films prepared by this invention all have a haze value greater than 1%, and the haze values ​​of Examples 1 and 2 even exceed 10%. The haze value is directly proportional to the roughness, and the roughness is obtained by AFM morphology analysis and calculation.

[0085] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A single-process method for preparing a high-haze conductive film, characterized in that, The method includes the following steps: Step S1: Clean the float glass using alkaline solution, acid solution, or ion beam etching. Step S2: Using magnetron sputtering, high-purity AZO target material is used to prepare AZO seed crystals in an air atmosphere of a certain concentration. Step S3: Turn off the sputtering power supply and perform high vacuum evacuation to remove oxygen from the cavity; Step S4: Using magnetron sputtering, high-purity AZO target material is used. The film is pre-sputtered in an oxygen-free environment before coating, and the film thickness is controlled by adjusting the coating time. Step S5: Allow the coated glass to cool naturally to room temperature to obtain a high-haze AZO conductive film; Specifically, step S2 involves placing the cleaned glass into the magnetron sputtering chamber; using a high-purity AZO (zinc aluminum oxide) target with a purity of 99.99%, wherein the ZnO content is 97.2-98.3% and the Al2O3 content is 1.7-2.8%; and the minimum vacuum level of the chamber is 6.1 x 10⁻⁶. -6 Pa, sputtering power of 6000-8000 W, voltage of 557-619 V; The cleaned glass is introduced into the chamber. During ignition, the Ar (argon) flow rate is 200 sccm; after ignition, the Ar flow rate is 180-200 sccm, and air is introduced at 1-20 sccm, maintaining a pressure of 3.0-3.5 x 10⁻⁶. -3 The pressure of torr; the glass reciprocates with the substrate holder at its bottom to reduce the film thickness difference caused by edge effect; the substrate holder is heated to 300-450 ℃ for seed coating; During the coating process, the air flow rate is maintained to decrease linearly, and the air volume is reduced to 0 sccm within 10 seconds. At the same time, the Ar flow rate is increased, and the increase in Ar is consistent with the decrease in air volume in order to maintain the pressure balance in the cavity. To obtain an AZO conductive film with higher haze, the angle of the glass substrate can be adjusted; the angle adjustment method is to repeatedly cycle the glass substrate and the target material at an angle of + / -10°.

2. The method for preparing a high-haze conductive film using a single process according to claim 1, characterized in that: In step S1, the float glass is first soaked in a 10% sodium hydroxide / water / ethanol mixed solution for 5 minutes and then rinsed with deionized water; then it is soaked in a 10% hydrochloric acid solution for 5 minutes, rinsed with deionized water, and dried.

3. The method for preparing a high-haze conductive film using a single process according to claim 2, characterized in that: In a 10% sodium hydroxide / water / ethanol mixed solution, the volume ratio of water to ethanol is 1:

5.

4. The method for preparing a high-haze conductive film using a single process according to claim 1, characterized in that: In step S1, the surface activation treatment of the float glass is performed by ion beam etching.

5. The method for preparing a high-haze conductive film using a single process according to claim 1, characterized in that: In step S3, the high vacuum pumping process adopts a reciprocating pumping mode, that is, Ar is intermittently introduced and the pumping valve is closed, and then the Ar inlet valve is intermittently closed and the pumping valve is opened; after two or three cycles, the pumping state is maintained until a high vacuum is reached.

6. The method for preparing a high-haze conductive film using a single process according to claim 1, characterized in that: Specifically, step S4 involves introducing Ar gas at 200 sccm and maintaining it for 10 seconds, then igniting the sputtering power at 6000-8000 W and the voltage at 557-619 V to pre-sputter a composite AZO target containing 97.2-98.3% ZnO and 1.7-2.8% Al2O3 for 5 seconds, followed by film deposition; and controlling the film thickness by adjusting the deposition time.

7. A high-haze conductive film, characterized in that: It is prepared by the method described in any one of claims 1 to 6.

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