Visible light anti-reflection water vapor barrier film as well as preparation method and application thereof

Abstract

The invention provides a visible light anti-reflection water vapor barrier film and a preparation method and application thereof, and belongs to the technical field of photoelectric thin films, and the visible light anti-reflection water vapor barrier film comprises a flexible base material and a water vapor barrier layer; the water vapor blocking layer is arranged on the light receiving surface of the flexible base material, the water vapor blocking layer is a composite film layer, the composite film layer is composed of single film layers, the single film layers are made of SiO2, SiNxOy and Si3N4, and the ratio of x to y is 3: (1-3); the preparation method comprises the following steps: performing plasma surface activation treatment on the flexible substrate, and depositing the water vapor barrier layer on the surface of the activated flexible substrate through magnetron sputtering; the visible light anti-reflection water vapor barrier film is applied to an ITO film, and an ITO film water vapor barrier layer and an ITO conducting layer are located on the two sides of a flexible base material respectively. The invention provides a visible light anti-reflection water vapor barrier film as well as a preparation method and application thereof. The water vapor transmittance of an ITO (Indium Tin Oxide) film of a flexible substrate is reduced, and the visible light transmittance is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic thin films, and particularly relates to a water vapor barrier film for enhancing visible light transmittance, a preparation method thereof, and an application thereof. Background Art

[0002] Today, with the rapid development of technology, photovoltaic technology, as an important part of renewable energy, is constantly promoting the transformation and upgrading of the global energy structure. Among numerous photovoltaic devices, perovskite photovoltaic cells have gradually become the focus of attention in the scientific research community and the industrial community due to their unique advantages and huge development potential. As a new type of photovoltaic device, the structure of perovskite photovoltaic cells is complex and delicate, mainly including five key parts: a transparent conductive substrate, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, and a metal electrode.

[0003] As the cornerstone of perovskite photovoltaic cells, the transparent conductive substrate not only supports the growth of other layers of materials but also is responsible for collecting photoelectrons. It is usually made of indium tin oxide (ITO) thin film. ITO is an inorganic composite material, usually composed of 90% indium oxide (In2O3) and 10% tin oxide (SnO2), and has the characteristics of high visible light transmittance and low resistivity. Such transparent and conductive characteristics are difficult to be simultaneously possessed by other materials, making ITO the preferred material in the field of transparent conductive films. The characteristics of ITO thin films enable light to penetrate the substrate smoothly and enter the battery interior, while ensuring the efficient export of photoelectrons, providing a strong guarantee for the photoelectric conversion efficiency of the battery.

[0004] The substrates of flexible ITO thin films include PET materials, PMMA materials, TAC materials, etc. However, the water vapor transmittance of flexible substrates such as PET is high and cannot meet the weather resistance requirements of solar photovoltaic cells. After using encapsulation materials to improve weather resistance, the light transmittance will be reduced, thereby affecting the conversion efficiency of the components. Summary of the Invention

[0005] In view of this, the present invention provides a water vapor barrier film for enhancing visible light transmittance, a preparation method thereof, and an application thereof, which can reduce the water vapor transmittance of the ITO film on the flexible substrate and improve the visible light transmittance.

[0006] To achieve the above object, the present invention provides a water vapor barrier film for enhancing visible light transmittance, including a flexible substrate and a water vapor barrier layer; the water vapor barrier layer is disposed on the light-receiving surface of the flexible substrate, the water vapor barrier layer is a composite film layer, and the composite film layer is composed of single film layers. The materials of the single film layers are SiO2, SiN x O y and Si3N4, and x:y is 3:1 to 3.

[0007] Optionally, the thickness of the water vapor barrier layer is 100~300nm.

[0008] Optionally, the two side layers of the composite film layer are SiO2 layers, and the middle layer is a stack of SiN x O y layer and Si3N4 layer.

[0009] Optionally, the flexible substrate is one of PET, TAC, and PMMA.

[0010] To achieve the above object, the present invention also provides a method for preparing a water vapor barrier film with enhanced visible light transmittance, including the following steps: performing plasma surface activation treatment on a flexible substrate, and magnetron sputtering and depositing a water vapor barrier layer on the surface of the activated flexible substrate.

[0011] Optionally, the magnetron sputtering and depositing of the water vapor barrier layer includes magnetron sputtering and depositing a SiO2 layer, and the process conditions are that the sputtering power is 8~15kW, the working gas pressure is 0.1~0.3Pa, the reaction gas is an Ar / O2 mixed gas, and the film layer thickness is 50~150nm.

[0012] Optionally, the magnetron sputtering and depositing of the water vapor barrier layer includes magnetron sputtering and depositing a Si3N4 layer, and the process conditions are that the sputtering power is 20~35kW, the working gas pressure is 0.1~0.3Pa, the reaction gas is an Ar / N2 mixed gas, and the film layer thickness is 40~180nm.

[0013] Optionally, the magnetron sputtering and depositing of the water vapor barrier layer includes magnetron sputtering and depositing a SiN x O y layer, and the process conditions are that the sputtering power is 20~30kW, the working gas pressure is 0.1~0.3Pa, the reaction gas is an N2 / O2 mixed gas, and the film layer thickness is 30~70nm.

[0014] To achieve the above object, the present invention also provides a water vapor barrier film with enhanced visible light transmittance applied to an ITO film, where the water vapor barrier layer and the ITO conductive layer of the ITO film are respectively located on both sides of the flexible substrate.

[0015] The above technical solution of the present invention has at least the following beneficial effects: The technical solution provided by the present invention reduces the water vapor transmittance of the ITO film and simultaneously reduces the light loss on the ITO surface and improves the visible light transmittance by setting a water vapor barrier film in the ITO film on the flexible substrate and using a Si3N4 / SiO2 composite film layer to jointly block the water and oxygen penetration path. Description of the Drawings

[0016] Figure 1 It is a visible light transmittance diagram of the ITO film prepared in Example 6 and Comparative Example 1 of the present invention. Detailed implementation manners

[0017] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the following will describe the technical solutions of the embodiments of the present invention in conjunction with the attached Figure 1 , and describe the technical solutions of the embodiments of the present invention clearly and completely. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art belong to the scope protected by the present invention.

[0018] Embodiment 1 A preparation method of a water vapor barrier film with enhanced visible light transmittance includes the following steps: Take the flexible substrate PET for plasma surface activation treatment, that is, use an Ar / O2 mixed gas with a flow ratio of 1:1, a power supply power of 5 kW, and a treatment time of 1 minute to remove surface contaminants of PET and improve surface energy.

[0019] Magnetron sputter deposit a SiO2 layer on the PET substrate. The process conditions are an MF intermediate frequency power supply, a power of 8 kW, a frequency of 40 kHz, a duty cycle of 70%, use a high-purity silicon target (99.999%), a target-substrate distance of 60 mm; an Ar / O2 mixed gas, a flow ratio of 4:1, a total flow rate of 200 sccm, a working pressure of 0.3 Pa, a deposition rate of 8 nm / min, and a film thickness of 80 nm.

[0020] After the deposition of the SiO2 layer is completed, introduce N2 plasma under the conditions of a power of 10 kW and a time of 30 s to enhance the chemical bonding between the Si3N4 layer and the SiO2 layer, and then magnetron sputter deposit a Si3N4 layer on the SiO2 layer. The process conditions are an MF intermediate frequency power supply, a power of 20 kW, use a high-purity silicon target (99.999%), pre-sputter the target for 10 minutes to remove the surface oxide layer, an Ar / N2 mixed gas, a flow ratio of 2:1, a total flow rate of 400 sccm, a working pressure of 0.3 Pa, a deposition rate of 12 nm / min, and a film thickness of 120 nm.

[0021] After the deposition of the Si3N4 layer is completed, continue to magnetron sputter deposit a SiN x O y layer, where x:y is 3:1. The process conditions are an MF intermediate frequency power supply, a power of 20 kW, use a high-purity silicon target (99.999%), pre-sputter the target for 10 minutes to remove the surface oxide layer, an N2 / O2 mixed gas, a flow ratio of 3:1, a total flow rate of 300 sccm, a working pressure of 0.3 Pa, a deposition rate of 10 nm / min, and a film thickness of 50 nm.

[0022] Embodiment 2 A preparation method of a water vapor barrier film with enhanced visible light transmittance includes the following steps: The flexible substrate PET is subjected to plasma surface activation treatment, that is, an Ar / O2 mixed gas with a flow ratio of 1:1, a power supply power of 5 kW, and a treatment time of 1 minute is used to remove surface contaminants of PET and increase the surface energy.

[0023] A SiO2 layer is magnetron sputtered and deposited on the PET substrate. The process conditions are an MF intermediate frequency power supply, a power of 15 kW, a frequency of 40 kHz, a duty cycle of 70%, a high-purity silicon target (99.999%) is used, and the target-substrate distance is 70 mm; an Ar / O2 mixed gas with a flow ratio of 5:1, a total flow rate of 300 sccm, a working pressure of 0.2 Pa, a deposition rate of 10 nm / min, and a film thickness of 50 nm.

[0024] After the deposition of the SiO2 layer is completed, N2 plasma is introduced with the conditions of a power of 10 kW and a time of 30 s to enhance the chemical bonding between the Si3N4 layer and the SiO2 layer. Then, a Si3N4 layer is magnetron sputtered and deposited on the SiO2 layer. The process conditions are an MF intermediate frequency power supply, a power of 35 kW, a high-purity silicon target (99.999%) is used, the target is pre-sputtered for 10 minutes to remove the surface oxide layer, an Ar / N2 mixed gas with a flow ratio of 3:1, a total flow rate of 250 sccm, a working pressure of 0.1 Pa, a deposition rate of 15 nm / min, and a film thickness of 180 nm.

[0025] After the deposition of the Si3N4 layer is completed, SiN x O y layer is continuously magnetron sputtered and deposited with x:y being 3:2. The process conditions are an MF intermediate frequency power supply, a power of 20 kW, a high-purity silicon target (99.999%) is used, the target is pre-sputtered for 10 minutes to remove the surface oxide layer, an N2 / O2 mixed gas with a flow ratio of 3:2, a total flow rate of 300 sccm, a working pressure of 0.2 Pa, a deposition rate of 10 nm / min, and a film thickness of 70 nm.

[0026] Example 3 A method for preparing a visible light antireflection and water vapor barrier film includes the following steps: The flexible substrate TAC is subjected to plasma surface activation treatment, that is, an Ar / O2 mixed gas with a flow ratio of 1:1, a radio frequency power of 4 kW, and a treatment time of 1 minute is used to remove surface contaminants of PET and increase the surface energy.

[0027] A SiO2 layer is magnetron sputtered and deposited on the TAC substrate. The process conditions are an MF intermediate frequency power supply, a power of 12 kW, a frequency of 40 kHz, a duty cycle of 70%, a high-purity silicon target (99.999%) is used, and the target-substrate distance is 80 mm; an Ar / O2 mixed gas with a flow ratio of 6:1, a total flow rate of 260 sccm, a working pressure of 0.2 Pa, a deposition rate of 15 nm / min, and a film thickness of 150 nm.

[0028] After the deposition of the SiO2 layer is completed, N2 plasma is introduced under the conditions of a power of 10 kW and a time of 30 s to enhance the chemical bonding between the Si3N4 layer and the SiO2 layer. Then, the Si3N4 layer is magnetron sputtered and deposited on the SiO2 layer. The process conditions are an MF intermediate frequency power supply, a power of 30 kW, using a high-purity silicon target (99.999%), pre-sputtering the target for 10 minutes to remove the surface oxide layer, an Ar / N2 mixed gas, a flow ratio of 3:1, a total flow rate of 300 sccm, a working pressure of 0.1 Pa, a deposition rate of 20 nm / min, and a film thickness of 40 nm.

[0029] After the deposition of the Si3N4 layer is completed, the SiN x O y layer is continuously magnetron sputtered and deposited with an x:y ratio of 3:1. The process conditions are an MF intermediate frequency power supply, a power of 30 kW, using a high-purity silicon target (99.999%), pre-sputtering the target for 10 minutes to remove the surface oxide layer, an N2 / O2 mixed gas, a flow ratio of 3:1, a total flow rate of 300 sccm, a working pressure of 0.1 Pa, a deposition rate of 10 nm / min, and a film thickness of 60 nm.

[0030] Example 4 A method for preparing a water vapor barrier film with enhanced visible light transmittance includes the following steps: Take the flexible substrate PMMA for plasma surface activation treatment, that is, use an Ar / O2 mixed gas with a flow ratio of 1:1, a power supply power of 4 kW, and a treatment time of 1 minute to remove surface contaminants on the PET and improve the surface energy.

[0031] The SiO2 layer is magnetron sputtered and deposited on the PMMA substrate. The process conditions are an MF intermediate frequency power supply, a power of 9 kW, a frequency of 40 kHz, a duty cycle of 70%, using a high-purity silicon target (99.999%), a target-substrate distance of 80 mm; an Ar / O2 mixed gas, a flow ratio of 4:1, a total flow rate of 240 sccm, a working pressure of 0.1 Pa, a deposition rate of 14 nm / min, and a film thickness of 140 nm.

[0032] After the deposition of the SiO2 layer is completed, N2 plasma is introduced under the conditions of a power of 10 kW and a time of 30 s to enhance the chemical bonding between the Si3N4 layer and the SiO2 layer. Then, the Si3N4 layer is magnetron sputtered and deposited on the SiO2 layer. The process conditions are an MF intermediate frequency power supply, a power of 28 kW, using a high-purity silicon target (99.999%), pre-sputtering the target for 10 minutes to remove the surface oxide layer, an Ar / N2 mixed gas, a flow ratio of 3:1, a total flow rate of 350 sccm, a working pressure of 0.2 Pa, a deposition rate of 20 nm / min, and a film thickness of 80 nm.

[0033] After the deposition of the Si3N4 layer is completed, the SiN xO y Layer, with an x:y ratio of 3:1. The process conditions are an MF intermediate frequency power supply, a power of 25 kW, using a high-purity silicon target (99.999%), pre-sputtering the target for 10 minutes to remove the surface oxide layer, a N2 / O2 mixed gas, a flow ratio of 3:1, a total flow rate of 300 sccm, a working pressure of 0.2 Pa, a deposition rate of 10 nm / min, and a film thickness of 40 nm.

[0034] Example 5 A method for preparing a water vapor barrier film with enhanced visible light transmittance includes the following steps: Take the flexible substrate PET and perform plasma surface activation treatment, that is, use an Ar / O2 mixed gas with a flow ratio of 1:1, a radio frequency power of 4 kW, and a treatment time of 1 minute to remove surface contaminants on the PET and increase the surface energy.

[0035] Magnetron sputter deposit a SiO2 layer on the PET substrate. The process conditions are an MF intermediate frequency power supply, a power of 12 kW, a frequency of 40 kHz, a duty cycle of 70%, using a high-purity silicon target (99.999%), a target-substrate distance of 80 mm; an Ar / O2 mixed gas, a flow ratio of 5:1, a total flow rate of 280 sccm, a working pressure of 0.2 Pa, a deposition rate of 10 nm / min, and a film thickness of 90 nm.

[0036] After the deposition of the SiO2 layer is completed, introduce N2 plasma with the conditions of a power of 10 kW and a time of 30 s to enhance the chemical bonding between the Si3N4 layer and the SiO2 layer. Then, magnetron sputter deposit a Si3N4 layer on the SiO2 layer. The process conditions are an MF intermediate frequency power supply, a power of 34 kW, using a high-purity silicon target (99.999%), pre-sputtering the target for 10 minutes to remove the surface oxide layer, an Ar / N2 mixed gas, a flow ratio of 2:1, a total flow rate of 340 sccm, a working pressure of 0.1 Pa, a deposition rate of 12 nm / min, and a film thickness of 120 nm.

[0037] After the deposition of the Si3N4 layer is completed, continue to magnetron sputter deposit SiN x O y Layer, with an x:y ratio of 3:1. The process conditions are an MF intermediate frequency power supply, a power of 20 kW, using a high-purity silicon target (99.999%), pre-sputtering the target for 10 minutes to remove the surface oxide layer, a N2 / O2 mixed gas, a flow ratio of 3:1, a total flow rate of 240 sccm, a working pressure of 0.3 Pa, a deposition rate of 10 nm / min, and a film thickness of 30 nm.

[0038] Example 6 A water vapor barrier film with enhanced visible light transmittance is applied to an ITO film, and an ITO conductive layer is deposited on the water vapor barrier film prepared in Example 1.

[0039] Comparative Example 1 Compared with Example 6, the difference is only that the ITO film does not include a water vapor barrier layer and only includes a flexible substrate and an ITO conductive layer, and the remaining preparation steps and parameters are the same.

[0040] The visible light transmittance of the ITO films prepared in Example 6 and Comparative Example 1 was detected, and Figure 1 .

[0041] It can be seen from Figure 1 that the visible light transmittance of the ITO film prepared by the present invention is higher than that of the ITO film prepared in Comparative Example 1, and the visible light transmittance is increased by 3-5%.

[0042] The water vapor transmission rate of the ITO films prepared in Example 6 and Comparative Example 1 was detected. The water vapor transmission rate of Example 6 < 0.1 g / (m 2 ·24 h), and the water vapor transmission rate of Comparative Example 1 > 10 g / (m 2 ·24 h).

[0043] In summary, the water vapor barrier film provided by the present invention can reduce the water vapor transmission rate of the ITO film on the flexible substrate and at the same time improve the visible light transmittance of the ITO film.

[0044] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A water vapor barrier film for enhancing the transmittance of visible light, characterized in that: The invention comprises a flexible substrate and a water vapor barrier layer; the water vapor barrier layer is arranged on the light-receiving surface of the flexible substrate, the water vapor barrier layer is a composite film layer, the composite film layer is composed of a single film layer, and the materials of the single film layer are SiO2, SiN x O y And Si3N4, x:y is 3:1~3.

2. The water vapor barrier film for enhancing visible light transmittance according to claim 1, characterized in that: The thickness of the water vapor barrier layer is 100-300 nm.

3. The water vapor barrier film for enhancing visible light transmittance according to claim 1, characterized in that: The two side layers of the composite film layer are SiO2 layers, and the middle layer is SiN x O y The Si3N4 layer is stacked.

4. The water vapor barrier film for enhancing visible light transmittance according to claim 1, characterized in that: The flexible substrate is one of PET, TAC and PMMA.

5. A method for preparing a water vapor barrier film having an enhanced visible light transmittance as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: The flexible substrate is subjected to plasma surface activation treatment, and a water vapor barrier layer is deposited on the surface of the activated flexible substrate by magnetron sputtering.

6. The method for preparing a water vapor barrier film for enhancing visible light transmittance according to claim 5, characterized in that: The magnetron sputtering deposition of the water vapor barrier layer includes a magnetron sputtering deposition of a SiO2 layer, the process conditions are: a sputtering power of 8-15 kW, a working gas pressure of 0.1-0.3 Pa, a reaction gas of Ar / O2 mixed gas, and a film thickness of 50-150 nm.

7. The method for preparing a water vapor barrier film for enhancing visible light transmittance according to claim 5, characterized in that: The magnetron sputtering deposition of the water vapor barrier layer includes a magnetron sputtering deposition of a Si3N4 layer, the process conditions are a sputtering power of 20-35 kW, a working gas pressure of 0.1-0.3 Pa, a reaction gas of Ar / N2 mixed gas, and a film thickness of 40-180 nm.

8. The method for preparing a water vapor barrier film for enhancing visible light transmittance according to claim 5, characterized in that: The magnetron sputtering deposition of the water vapor barrier layer includes magnetron sputtering deposition of SiN x O y The process conditions are as follows: sputtering power of 20-30 kW, working pressure of 0.1-0.3 Pa, reaction gas of N2 / O2 mixed gas, and film thickness of 30-70 nm.

9. A visible light transmittance enhancing water vapor barrier film as claimed in any one of claims 1 to 4 applied to an ITO film, characterized in that: The ITO film water vapor barrier layer and the ITO conductive layer are respectively located on two sides of the flexible substrate.

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