Transparent conductive film

Abstract

The transparent conducting film comprises a base material layer, a first resin layer, a base layer and a composite conducting layer which are sequentially arranged in a stacked mode, and the composite conducting layer comprises a first ITO conducting layer and a second ITO conducting layer arranged on the face, away from the base layer, of the first ITO conducting layer. The mass ratio of indium oxide to tin oxide in the raw material indium tin oxide of the first ITO conducting layer is 90: 10, and the mass ratio of indium oxide to tin oxide in the raw material indium tin oxide of the second ITO conducting layer is 93: 7; the first ITO conducting layer and the second ITO conducting layer are both prepared through a magnetron sputtering process, the bombardment gas during magnetron sputtering is krypton, and the direct-current sputtering voltage is 350-400 v. The transparent conductive film provided by the invention has good conductivity and light transmission, and is low in cost.

Description

Technical Field

[0001] The invention belongs to the technical field of conductive films, and in particular relates to a transparent conductive film. Background Art

[0002] Flexible perovskite solar cells are a new type of solar cell technology that has the advantages of being thin, light, bendable, and foldable. They have excellent photoelectric conversion performance and can efficiently convert light energy into electrical energy, and are expected to occupy an important position in the future energy market. The preparation of perovskite solar cells on flexible substrates can make them suitable for more special application scenarios, bringing new possibilities for the widespread application of solar energy. For example, wearable devices, portable electronic devices, and flexible building integration. Conductive films are used as transparent electrodes in solar cells and play a vital role.

[0003] ITO conductive film is commonly used in transparent electrodes. Its transmittance and sheet resistance are in a contradictory relationship. The thickness of the conductive layer has a great impact on the sheet resistance and transmittance. Generally speaking, the thicker the film layer, the lower the sheet resistance, which means the better the conductivity. However, this will hinder the transmission of light to a certain extent, resulting in a decrease in transmittance. On the contrary, when pursuing higher transmittance, it is necessary to reduce the thickness of the film layer, which will lead to an increase in sheet resistance and poor conductivity.

[0004] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0005] The object of the present invention is to provide a transparent conductive film which has both good conductivity and light transmittance and has low cost.

[0006] In order to achieve the above-mentioned purpose, a technical solution provided by a specific embodiment of the present invention is as follows: a transparent conductive film comprises a substrate layer, a first resin layer, a primer layer and a composite conductive layer which are stacked in sequence, the composite conductive layer comprises a first ITO conductive layer, and a second ITO conductive layer which is arranged on a side of the first ITO conductive layer away from the primer layer, the mass ratio of indium oxide to tin oxide in indium tin oxide, a raw material of the first ITO conductive layer, is 90:10, and the mass ratio of indium oxide to tin oxide in indium tin oxide, a raw material of the second ITO conductive layer, is 93:7; the first ITO conductive layer and the second ITO conductive layer are both prepared by a magnetron sputtering process, wherein the bombardment gas during magnetron sputtering is krypton gas, and the DC sputtering voltage is 350-400V.

[0007] In one or more embodiments of the present invention, the refractive index of the first resin layer is 1.6-1.7, and the thickness of the first resin layer is 0.8-1.2 μm.

[0008] In one or more embodiments of the present invention, the base layer is a silicon dioxide layer, and the thickness of the base layer is 3 to 5 nm.

[0009] In one or more embodiments of the present invention, the thickness of the composite conductive layer is 200 nm, the thickness of the first ITO conductive layer is 120-130 nm, and the thickness of the second ITO conductive layer is 70-80 nm.

[0010] In one or more embodiments of the present invention, the transparent conductive film further comprises a second resin layer disposed on the substrate layer on a side away from the first resin layer, the refractive index of the second resin layer is 1.5 to 1.55, the thickness of the second resin layer is 2 to 3 μm, and the surface roughness Ra is less than 1 nm.

[0011] In one or more embodiments of the present invention, a water-blocking layer is provided on a side of the second resin layer facing away from the substrate layer. The water-blocking layer is a silicon oxide layer or a silicon nitride layer. The thickness of the water-blocking layer is 120-150 nm.

[0012] In one or more embodiments of the present invention, a third resin layer is provided on the side of the water-blocking layer facing away from the substrate layer, the refractive index of the third resin layer is 1.45-1.5, and the thickness of the third resin layer is 800-1000 nm.

[0013] In one or more embodiments of the present invention, an acid-base resistant layer is further provided between the first resin layer and the primer layer, and the thickness of the acid-base resistant layer is 0.5-1 nm.

[0014] In one or more embodiments of the present invention, the acid-alkali resistant layer is a single silicon layer.

[0015] In one or more embodiments of the present invention, the thickness of the substrate layer is 25-200 μm, and the substrate layer is any one of a PET layer, a CPI layer, and a PC layer.

[0016] Compared with the prior art, the transparent conductive film of the present invention forms a composite conductive layer by using an indium tin oxide raw material with different ratios of indium oxide and tin oxide to form a first ITO conductive layer and a second ITO conductive layer structure prepared by a sputtering process under the condition that the bombardment gas is krypton gas. The composite conductive layer replaces the single-layer ITO conductive layer in the prior art, so that the transparent conductive film of the present invention has both good conductivity and light transmittance, and has the advantage of low preparation cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 Schematic diagram of the structure of a transparent conductive film in an example of the present invention.

[0019] Description of main reference numerals:

[0020] 1. Base material layer; 2. First resin layer; 3. Primer layer; 4. Composite conductive layer; 41. First ITO conductive layer; 42. Second ITO conductive layer; 5. Second resin layer; 6. Water-blocking layer; 7. Third resin layer; 8. Acid and alkali resistant layer. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0022] As mentioned in the background technology, the ITO (indium tin oxide) conductive layer in the traditional ITO conductive film has an inverse relationship between the transmittance and square resistance of the ITO (indium tin oxide) itself. Therefore, the existing improvement scheme generally adopts a conductive composite layer formed by an ITO layer and a metal layer (such as a metal copper layer, etc.) to replace the traditional ITO conductive layer (containing only ITO), or selects an ITO / metal (such as copper, etc.) doped film to replace the traditional ITO conductive layer, so as to improve the conductivity. However, the above method has the problems of high cost, complicated preparation steps, poor stability and durability, etc.

[0023] like Figure 1As shown, a transparent conductive film in an example of the present invention comprises a substrate layer 1, a first resin layer 2, a primer layer 3 and a composite conductive layer 4 which are stacked in sequence, wherein the composite conductive layer 4 comprises a first ITO conductive layer 41, and a second ITO conductive layer 42 which is arranged on a side of the first ITO conductive layer 41 away from the primer layer 3, wherein the mass ratio of indium oxide to tin oxide in the raw material indium tin oxide of the first ITO conductive layer 41 is 90:10, and the mass ratio of indium oxide to tin oxide in the raw material indium tin oxide of the second ITO conductive layer 42 is 93:7; wherein the first ITO conductive layer 41 and the second ITO conductive layer 42 are both prepared by a magnetron sputtering process, wherein the bombardment gas during magnetron sputtering is krypton gas, direct current sputtering, and the voltage is 350-400V.

[0024] It can be understood that the transparent conductive film of the present invention is formed by using indium tin oxide raw materials with different ratios of indium oxide and tin oxide and a first ITO conductive layer 41 and a second ITO conductive layer 42 structure prepared by a sputtering process under the condition that the bombardment gas is krypton gas to form a composite conductive layer 4. The composite conductive layer 4 replaces the single-layer ITO conductive layer in the prior art, so that the transparent conductive film of the present invention has both good conductivity and light transmittance, and the preparation cost is low. In addition, the preparation method of the composite conductive layer 4 in the present invention is simpler and has lower cost than the preparation method of the existing improved solution; in addition, the stability of the composite conductive layer 4 in the present invention is also good.

[0025] The transparent conductive film of the present invention can be used in flexible perovskite solar cells. Specifically, the transparent conductive film can be used as a transparent electrode of the flexible perovskite solar cell.

[0026] Specifically, the DC sputtering current may be 25 to 34 A, and the DC sputtering power may be approximately 10 to 12 kW.

[0027] Specifically, the refractive index of the first resin layer 2 is 1.6 to 1.7, and the thickness of the first resin layer 2 is 0.8 to 1.2 μm. The first resin layer 2 may be an acrylic resin layer, which may contain titanium oxide particles, aluminum oxide particles, etc. For example, the first resin layer 2 may be formed by coating with a coating liquid of Harima Chemicals Co., Ltd. UVH-D-ZR-165-32 or Toyo Ink TYZ68-UVR01-CN. The first resin layer 2 mainly plays a hardening role and can be considered as a hardening layer.

[0028] Specifically, the bottom layer 3 is a silicon dioxide layer, and the thickness of the bottom layer 3 is 3-5 nm. The bottom layer 3 ensures the film bonding strength between the conductive composite layer and the substrate layer 1 (including the first resin layer 2).

[0029] Specifically, the composite conductive layer 4 has a thickness of 200 nm, the first ITO conductive layer 41 has a thickness of 120-130 nm, and the second ITO conductive layer 42 has a thickness of 70-80 nm. Within this thickness range, the composite conductive layer 4 can have both good conductivity and light transmittance.

[0030] Specifically, the transparent conductive film further includes a second resin layer 5 disposed on the substrate layer 1 on a side away from the first resin layer 2, the refractive index of the second resin layer 5 is 1.5-1.55, the thickness of the second resin layer 5 is 2-3 μm, and the surface roughness Ra is less than 1 nm. The second resin layer 5 may be an acrylic resin layer, which may contain silicon dioxide particles, etc.; for example, the second resin layer 5 may be formed by coating with DIC GRANDIC PC15-5311 coating liquid. The second resin layer 5 plays a role in preventing sticking and improving adhesion.

[0031] Specifically, a water-blocking layer 6 is provided on one side of the second resin layer 5 facing away from the substrate layer 1, and the water-blocking layer 6 is a silicon oxide layer or a silicon nitride layer, and the thickness of the water-blocking layer 6 is 120-150 nm. The preparation process of the water-blocking layer 6 can be: planar magnetic field silicon target purity 5N, travel speed 0.8-1.0 m / min, power 12-15 kW, krypton gas: 200-300 sccm, oxygen PID control, voltage ratio 85-90%, frequency 40 khz.

[0032] Specifically, a third resin layer 7 is provided on the side of the water-blocking layer 6 facing away from the substrate layer 1, the refractive index of the third resin layer 7 is 1.45-1.5, the thickness of the third resin layer 7 is 800-1000nm, and the surface roughness thereof is required to be greater than 1.5 for good winding. The third resin layer 7 may be an acrylic resin layer, which may contain silicon dioxide particles, etc.; for example, the third resin layer 7 may be formed by coating with Arakawa Chemical: CHT-X1 coating liquid. The third resin layer 7 plays a role in protecting the water-blocking layer 6 from being scratched and providing winding to prevent adhesion.

[0033] Specifically, an acid-base resistant layer 8 is provided between the first resin layer 2 and the primer layer 3, and the thickness of the acid-base resistant layer 8 is 0.5-1 nm. Preferably, the acid-base resistant layer 8 is a single silicon layer.

[0034] Specifically, the thickness of the substrate layer 1 is 25-200 μm, and the substrate layer 1 is any one of a PET layer, a CPI layer, and a PC layer.

[0035] The transparent conductive film of the present invention will be described in detail below in conjunction with specific embodiments and comparative examples.

[0036] In the following examples and comparative examples, the first resin layer, the second resin layer and the third resin layer are all made of the following grades:

[0037] First resin layer: Toyo Ink TYZ68-UVR01-CN.

[0038] Second resin layer: DIC Corporation GRANDIC PC15-5311.

[0039] Third resin layer: Arakawa Chemical CHT-X1.

[0040] The following embodiments are illustrated by taking the impedance of 8 ohm and the roughness of the second resin layer Ra=0.8 as an example.

[0041] Example 1

[0042] Preparation Figure 1 The transparent conductive film shown in the figure, wherein the substrate layer is a PET layer, and its thickness is 188μm; the first resin layer is formed by coating on the substrate layer, and its thickness is 900nm, and its refractive index is 1.65; the acid and alkali resistant layer is a single substance silicon formed on the first resin layer by a sputtering process, and its thickness is 1nm; the bottom layer is silicon dioxide formed on the acid and alkali resistant layer by a sputtering process (in the condition of krypton and oxygen), and its thickness is 4nm; the composite conductive layer includes a first ITO conductive layer and a second ITO conductive layer, and the first ITO conductive layer is formed by indium tin oxide (wherein the mass ratio of indium oxide to tin oxide is 90:10) by a magnetron sputtering process (the bombardment gas during magnetron sputtering is krypton, the DC sputtering power is 10kW, the voltage is 400V, and the current is 25A) It is formed on the base layer and has a thickness of 120nm. The second ITO conductive layer is formed on the first ITO conductive layer by using a magnetron sputtering process (the bombardment gas during magnetron sputtering is krypton, the DC sputtering power is 10kW, the voltage is 400v, and the current is 25A) to form indium tin oxide (the mass ratio of indium oxide to tin oxide is 93:7) and has a thickness of 80nm; the second resin layer is formed on the substrate layer by coating and has a thickness of 2.5μm, a refractive index of 1.52, and a roughness of Ra of 0.5; the water-blocking layer is silicon oxide formed on the second resin layer by a sputtering process (in the conditions of krypton and oxygen) and has a thickness of 140nm; the third resin layer is formed on the water-blocking layer by coating and has a thickness of 900nm and a refractive index of 1.48.

[0043] Example 2

[0044] Preparation Figure 1The transparent conductive film shown in the figure, wherein the substrate layer is a PET layer, and its thickness is 188μm; the first resin layer is formed by coating on the substrate layer, and its thickness is 800nm, and its refractive index is 1.60; the acid and alkali resistant layer is a single substance silicon formed on the first resin layer by a sputtering process, and its thickness is 0.5nm; the bottom layer is silicon dioxide formed on the acid and alkali resistant layer by a sputtering process (in the condition of krypton and oxygen), and its thickness is 3nm; the composite conductive layer includes a first ITO conductive layer and a second ITO conductive layer, and the first ITO conductive layer is formed by indium tin oxide (wherein the mass ratio of indium oxide to tin oxide is 90:10) by a magnetron sputtering process (the bombardment gas during magnetron sputtering is krypton, the DC sputtering power is 10.64kW, the voltage is 380V, and the current is 28 A) is formed on the base layer, and its thickness is 130nm; the second ITO conductive layer is formed on the first ITO conductive layer by using indium tin oxide (wherein the mass ratio of indium oxide to tin oxide is 93:7) by magnetron sputtering process (the bombardment gas during magnetron sputtering is krypton gas, the DC sputtering power is 10.64kW, the voltage is 380v, and the current is 28A), and its thickness is 70nm; the second resin layer is formed on the substrate layer by coating, and its thickness is 2μm, the refractive index is 1.50, and the roughness is Ra 0.5; the water-blocking layer is silicon oxide formed on the second resin layer by sputtering process (in the condition of krypton and oxygen), and its thickness is 120nm; the third resin layer is formed on the water-blocking layer by coating, and its thickness is 800nm, and the refractive index is 1.45.

[0045] Example 3

[0046] Preparation Figure 1The transparent conductive film shown in the figure, wherein the substrate layer is a PET layer, and its thickness is 125μm; the first resin layer is formed by coating on the substrate layer, and its thickness is 1.2μm, and its refractive index is 1.70; the acid and alkali resistant layer is a single substance silicon formed on the first resin layer by a sputtering process, and its thickness is 1nm; the bottom layer is silicon dioxide formed on the acid and alkali resistant layer by a sputtering process (in the condition of krypton and oxygen), and its thickness is 5nm; the composite conductive layer includes a first ITO conductive layer and a second ITO conductive layer, and the first ITO conductive layer is formed by indium tin oxide (wherein the mass ratio of indium oxide to tin oxide is 90:10) by a magnetron sputtering process (the bombardment gas during magnetron sputtering is krypton, the DC sputtering power is 10.5kW, the voltage is 350V, and the current is 30 A) is formed on the base layer, and its thickness is 120nm; the second ITO conductive layer is formed on the first ITO conductive layer by using indium tin oxide (wherein the mass ratio of indium oxide to tin oxide is 93:7) by magnetron sputtering process (the bombardment gas during magnetron sputtering is krypton gas, the DC sputtering power is 10.5kW, the voltage is 350v, and the current is 30A), and its thickness is 80nm; the second resin layer is formed on the substrate layer by coating, and its thickness is 3μm, the refractive index is 1.55, and the roughness is Ra is 0.5; the water-blocking layer is silicon oxide formed on the second resin layer by sputtering process (in the condition of krypton and oxygen), and its thickness is 150nm; the third resin layer is formed on the water-blocking layer by coating, and its thickness is 1μm, and the refractive index is 1.50.

[0047] Comparative Example 1:

[0048] The only difference between this comparative example and Example 1 is that the bombardment gas during magnetron sputtering of the first ITO conductive layer and the second ITO conductive layer included in the composite conductive layer is argon.

[0049] Comparative Example 2

[0050] The only difference between this comparative example and Example 1 is that the composite conductive layer only includes the first ITO conductive layer, and its film thickness is also 200 nm.

[0051] Comparative Example 3

[0052] The difference between this comparative example and Example 1 is that the composite conductive layer only includes the first ITO conductive layer, the impedance is also 8 ohm, and the thickness of the composite conductive layer is different.

[0053] Comparative Example 4

[0054] The only difference between this comparative example and Example 1 is that the composite conductive layer only includes the second ITO conductive layer, and its film thickness is also 200 nm.

[0055] Comparative Example 5

[0056] The difference between this comparative example and Example 1 is that the composite conductive layer only includes the second ITO conductive layer, the impedance is also 8 ohm, and the thickness of the composite conductive layer is different.

[0057] Comparative Example 6

[0058] The only difference between this comparative example and Example 1 is that the roughness Ra of the second resin layer is 2.0.

[0059] Comparative Example 7

[0060] The only difference between this comparative example and Example 1 is that the water-blocking layer and the third resin layer are missing.

[0061] The transparent conductive films in Examples 1 to 3 and Comparative Examples 1 to 6 were subjected to the following performance tests:

[0062] (1) Impedance test: Use a 4-probe detector to test according to standard ASTM D991.

[0063] (2) Transmittance test: Use a photometer to test according to ASTM D1003 standard.

[0064] (3) Flexibility test: refer to GB / T232-2010.

[0065] (4) Water vapor barrier performance test: refer to GB / T 1037-2021.

[0066] The data shown in the following table is obtained:

[0067]

[0068] Data Analysis:

[0069] It can be seen from the above test data that: Examples 1-3 are the technical solutions of the present invention, and their composite conductive layers can achieve an impedance of 8 ohm at 200 nm, and have good light transmittance, flexibility and water vapor barrier properties.

[0070] Comparative Example 1 uses conventional argon gas for bombardment, and the thickness of the composite conductive layer needs to reach 320nm to achieve an impedance of 8ohm, which results in very poor light transmittance and flexibility.

[0071] In Comparative Examples 2 and 3, the composite conductive layer uses indium oxide and tin oxide in a ratio of 90:10. Although the conductivity and light transmittance are good, the degree of crystallization is poor because the probability of non-crystallization is high at a ratio of 90:10.

[0072] In Comparative Examples 4 and 5, the composite conductive layer uses indium oxide and tin oxide in a ratio of 93:7. Since the crystallization performance of the ratio of 93:7 is too good, this leads to a denser lattice and thus poorer flexibility.

[0073] In Comparative Example 6, the roughness of the second resin layer is greater than 1.0. Since the roughness of the base of the water-blocking layer is large, the surface of the water-blocking layer is uneven, which leads to a slightly poor overall water-blocking effect.

[0074] Comparative Example 7 has a very poor water vapor barrier effect due to the lack of a water-blocking layer and a third resin layer.

[0075] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

[0076] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A transparent conductive film, characterized in that: The invention comprises a substrate layer, a first resin layer, a primer layer and a composite conductive layer which are sequentially stacked, wherein the composite conductive layer comprises a first ITO conductive layer and a second ITO conductive layer which is arranged on a side of the first ITO conductive layer away from the primer layer, wherein the mass ratio of indium oxide to tin oxide in indium tin oxide, which is a raw material of the first ITO conductive layer, is 90:10, and the mass ratio of indium oxide to tin oxide in indium tin oxide, which is a raw material of the second ITO conductive layer, is 93:7; The first ITO conductive layer and the second ITO conductive layer are both prepared by a magnetron sputtering process, wherein the bombardment gas during magnetron sputtering is krypton gas and the DC sputtering voltage is 350-400V.

2. The transparent conductive film according to claim 1, characterized in that: The refractive index of the first resin layer is 1.6-1.7, and the thickness of the first resin layer is 0.8-1.2 μm.

3. The transparent conductive film according to claim 1, characterized in that: The bottom layer is a silicon dioxide layer, and the thickness of the bottom layer is 3-5 nm.

4. The transparent conductive film according to claim 1, characterized in that: The thickness of the composite conductive layer is 200 nm, the thickness of the first ITO conductive layer is 120-130 nm, and the thickness of the second ITO conductive layer is 70-80 nm.

5. The transparent conductive film according to claim 1, characterized in that: The transparent conductive film further comprises a second resin layer disposed on a side of the substrate layer away from the first resin layer, the refractive index of the second resin layer is 1.5-1.55, the thickness of the second resin layer is 2-3 μm, and the surface roughness Ra is less than 1 nm.

6. The transparent conductive film according to claim 5, characterized in that: A water-blocking layer is provided on a side of the second resin layer away from the substrate layer. The water-blocking layer is a silicon oxide layer or a silicon nitride layer. The thickness of the water-blocking layer is 120-150 nm.

7. The transparent conductive film according to claim 6, characterized in that: A third resin layer is provided on the side of the water-blocking layer away from the substrate layer. The refractive index of the third resin layer is 1.45-1.5, and the thickness of the third resin layer is 800-1000 nm.

8. The transparent conductive film according to claim 1, characterized in that: An acid-base resistant layer is also provided between the first resin layer and the primer layer, and the thickness of the acid-base resistant layer is 0.5-1 nm.

9. The transparent conductive film according to claim 8, characterized in that: The acid and alkali resistant layer is a single substance silicon layer.

10. The transparent conductive film according to claim 1, characterized in that: The thickness of the substrate layer is 25-200 μm, and the substrate layer is any one of a PET layer, a CPI layer, and a PC layer.

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