Gas barrier films and photoelectric conversion devices

Abstract

This invention provides a gas barrier film capable of preventing the transmission of ultraviolet light below 380 nm, and a photoelectric conversion device equipped with this gas barrier film. [Solution] According to the embodiment, a gas barrier film 1 is provided, which includes a substrate 2 and a first layer 3 provided on at least one side 2a of the substrate 2. The gas barrier film 1 has shielding performance against ultraviolet light with a wavelength of 380 nm or less.

Description

[Technical Field]

[0001] Embodiments of the present invention relate to a gas barrier film and a photoelectric conversion device. [Background technology]

[0002] Gas barriers are widely used in applications such as electronic equipment and packaging. For example, water vapor barriers are used in photoelectric conversion elements such as perovskite solar cells and organic electroluminescent (OLED) elements, as well as in non-aqueous electrolyte batteries. In food and pharmaceutical packaging, oxygen barriers are used to prevent deterioration of the contents. As for gas barrier films, films containing a silicon oxide film obtained by modifying silicon compounds such as polysilazane in an oxidizing atmosphere as a gas barrier layer are known.

[0003] On the other hand, solar cells using perovskite-type materials as photoelectric conversion materials have issues with photodurability. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-137710 [Non-patent literature]

[0005] [Non-Patent Document 1] Solution-Processed Gas Barriers with Glass-Like Ultrahigh Barrier Performance, Advanced Materials Interfaces 2022, 9, 2201517, by Tatsuki Sasaki et al. [Overview of the project] [Problems that the invention aims to solve]

[0006] This invention provides a gas barrier film capable of preventing the transmission of ultraviolet light below 380 nm, and a photoelectric conversion device equipped with this gas barrier film. [Means for solving the problem]

[0007] According to one embodiment, a gas barrier film is provided comprising a substrate and a first layer provided on at least one side of the substrate. The gas barrier film has shielding performance against ultraviolet light with a wavelength of 380 nm or less.

[0008] Furthermore, according to the embodiment, a photoelectric conversion device is provided that includes a photoelectric conversion element and a gas barrier film of the embodiment provided on the photoelectric conversion element. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic cross-sectional view showing a first example of a gas barrier film according to the embodiment. [Figure 2] A schematic cross-sectional view showing a second example of the gas barrier film of the embodiment. [Figure 3] A schematic cross-sectional view showing a third example of the gas barrier film of the embodiment. [Figure 4] A schematic cross-sectional view showing a first example of a photoelectric conversion device according to an embodiment. [Figure 5] A schematic cross-sectional view showing a second example of a photoelectric conversion device according to the embodiment. [Figure 6] A schematic cross-sectional view showing a third example of a photoelectric conversion device according to the embodiment. [Figure 7] A graph showing the change in light transmittance when the wavelength of light is changed for the gas barrier film of the example. [Modes for carrying out the invention]

[0010] (First Embodiment) The gas barrier film of the first embodiment includes a base material and a first layer provided on at least one surface side of the base material. The gas barrier film has a shielding performance against ultraviolet rays with a wavelength of 380 nm or less. The shielding performance against ultraviolet rays with a wavelength of 380 nm or less may absorb the ultraviolet rays or scatter the ultraviolet rays.

[0011] The first layer may be a single layer or may include a plurality of films.

[0012] The first layer can be, for example, a gas barrier layer. The gas barrier layer can include, for example, at least one of a silicon nitride film (SiN x (x>0) film) or a film of a material excluding silicon nitride (SiN x (x>0)) (hereinafter referred to as a material film). Examples of the silicon nitride film include those obtained by modifying a polysilazane compound with vacuum ultraviolet rays in an N2 atmosphere, those formed by chemical vapor deposition, and the like. The first layer may have a shielding performance against ultraviolet rays with a wavelength of 380 nm or less. In this case, at least one of the silicon nitride film or the material film has a shielding performance against ultraviolet rays with a wavelength of 380 nm or less.

[0013] The first layer may not have a shielding performance against ultraviolet rays with a wavelength of 380 nm or less. In this case, it is desirable to provide the first layer on one surface side of the base material and provide a second layer having a shielding performance against ultraviolet rays with a wavelength of 380 nm or less on the other surface side of the base material.

[0014] Examples of the gas barrier film of the embodiment will be described with reference to FIGS. 1 to 3. The gas barrier layer of the gas barrier film shown in each figure includes a plurality of films. In each figure, it is assumed that the thickness direction of the gas barrier film is parallel to the z-axis direction. It is assumed that the plane direction of the gas barrier film is parallel to the plane defined by the x-axis direction and the y-axis direction. The x-axis direction, the y-axis direction, and the z-axis direction are perpendicular to each other. Also, in each figure, members that commonly exist in a plurality of drawings are denoted by the same reference numerals and the description thereof is omitted.

[0015] The gas barrier film shown in FIGS. 1 and 2 is an example in which the first layer is a gas barrier layer having a shielding performance against ultraviolet rays with a wavelength of 380 nm or less.

[0016] The gas barrier film 1 shown in FIG. 1 includes a substrate 2 and a first layer 3 as a gas barrier layer. The first layer 3 includes a plurality of silicon nitride films. The substrate 2 has a layer shape or a film shape. The substrate 2 has two surfaces intersecting in the thickness direction (z-axis direction) as main surfaces (main faces) 2a and 2b. Each surface 2a and 2b is a surface parallel to the xy plane. Also, it can be said that the other surface 2b is located on the opposite side of one surface 2a. The substrate 2 may have light transmissibility. Further, the substrate 2 can be formed from, for example, polyethylene terephthalate (PET), polycarbonate, ETFE (ethylene tetrafluoroethylene), PI (polyimide), PEN (polyethylene naphthalate), or the like. The type of material constituting the substrate 2 may be one type or two or more types.

[0017] The first layer 3 is provided on one surface side of the substrate 2. In the case of FIG. 1, the first layer 3 is laminated on one surface 2a of the substrate 2. The first layer 3 has a barrier performance against gases such as water vapor and oxygen. Also, the first layer 3 has a shielding performance against ultraviolet rays with a wavelength of 380 nm or less. The first layer 3 is substantially composed of, for example, a silicon nitride film 4 on the substrate side and a silicon nitride film 5 on the surface layer side. Each of the silicon nitride film 4 on the substrate side and the silicon nitride film 5 on the surface layer side has two surfaces intersecting in the thickness direction (z-axis direction) as main surfaces (main faces). Each surface is parallel to the xy plane. At least one of the silicon nitride film 4 on the substrate side or the silicon nitride film 5 on the surface layer side may have a shielding performance against ultraviolet rays with a wavelength of 380 nm or less. In FIG. 1, it is assumed that the silicon nitride film 5 on the surface layer side has a shielding performance against ultraviolet rays with a wavelength of 380 nm or less.

[0018] The silicon nitride film 4 on the substrate side is provided on one surface 2a of the substrate 2. The silicon nitride film 4 on the substrate side is obtained, for example, by modifying a film of a polysilazane compound with vacuum ultraviolet light in an N2 atmosphere. Specifically, it is obtained by a method that includes coating a perhydropolysilazane (PHPS) solution onto the substrate 2, for example by a spin coating method, removing the solvent by pre-baking, for example, and then irradiating it with vacuum ultraviolet light in an N2 atmosphere. By irradiating a PHPS film formed by coating and drying a PHPS solution with vacuum ultraviolet light at a wavelength of 172 nm in an N2 atmosphere at room temperature, SiN x An example of a reaction that forms a (x>0) film is shown in Chemical Formula 1 below. As shown in Chemical Formula 1, a Si-N bond is formed and SiN x As a result of this process, H2 is released.

[0019] [ka]

[0020] Since the PHPS film is formed on the substrate 2 by coating, a flat surface can be obtained even if the substrate 2 has irregularities due to the presence of particles, etc. Therefore, the silicon nitride film 4 on the substrate side also serves as a planarization film. Furthermore, forming the PHPS film by coating makes it possible to reduce the manufacturing cost of the film. The silicon nitride film 4 obtained by the modification treatment may have a refractive index that changes in the thickness direction of the gas barrier film (for example, in the z-axis direction). Since vacuum ultraviolet light mainly modifies the area near the surface of the film, the SiN conversion reaction occurs continuously from the surface towards the substrate side. Therefore, the silicon nitride film 4 has a gradient in which the silicon nitride concentration is higher on the surface side than on the substrate side. Therefore, the silicon nitride film 4 may have the characteristic of having a refractive index that increases from the substrate side towards the surface side.

[0021] The surface silicon nitride film 5 is provided on a plane parallel to the xy plane of the silicon nitride film 4. The surface silicon nitride film 5 has shielding performance against ultraviolet light with a wavelength of 380 nm or less. It is desirable that the molar ratio of Si atoms to N atoms (Si / N) of the surface silicon nitride film 5 is greater than 1. Si-Si bonds can enhance the effect of absorbing ultraviolet light with a wavelength of 380 nm or less. By making the molar ratio (Si / N) greater than 1, it is possible to obtain a first layer 3 with high visible light transmittance and high absorption capacity against ultraviolet light with a wavelength of 380 nm or less. In addition, the stress of the silicon nitride film 5 can be reduced, so the silicon nitride film 5 can be deposited at a low temperature. It is more preferable that the molar ratio (Si / N) be 2 or more. This can further improve the ultraviolet cut performance. The surface silicon nitride film 5 is deposited, for example, by chemical vapor deposition (CVD).

[0022] The gas barrier film 1 shown in Figure 1 exhibits excellent barrier performance against gases such as water vapor and oxygen. Furthermore, the gas barrier film 1 possesses visible light transmittance while also providing shielding performance against ultraviolet light with wavelengths below 380 nm. Moreover, because the first layer 3 contains multiple silicon nitride films 4 and 5, sufficient barrier function can be obtained even with thin films of each silicon nitride film 4 and 5. As a result, defects such as cracking in the silicon nitride films 4 and 5 can be avoided.

[0023] Figure 1 shows an example where the silicon nitride film 5 on the surface side has UV shielding performance against ultraviolet light with a wavelength of 380 nm or less. However, the silicon nitride film 4 on the substrate side may have UV shielding performance instead of the silicon nitride film 5 on the surface side. Alternatively, both the silicon nitride film 5 on the surface side and the silicon nitride film 4 on the substrate side may have UV shielding performance. In these cases, it is desirable to make the molar ratio (Si / N) of the silicon nitride film 4 on the substrate side greater than 1. A more preferable molar ratio (Si / N) is 2 or more. Also, although Figure 1 describes an example in which the first layer 3 is directly laminated on one side of the substrate 2, it is not limited to this, and another layer such as a planarization layer may be interposed between the substrate 2 and the first layer 3.

[0024] Next, the gas barrier film shown in Figure 2 will be described. The gas barrier film 6 shown in Figure 2 includes a substrate 2 and a first layer 3. The details of the substrate 2 are as described in Figure 1.

[0025] The first layer 3 is provided on one side of the substrate 2. In the case of Figure 2, the first layer 3 is laminated on one side 2a of the substrate 2. The first layer 3 has barrier properties against gases such as water vapor and oxygen. The first layer 3 also has shielding properties against ultraviolet light with a wavelength of 380 nm or less. The first layer 3 substantially consists of, for example, a material film 7 as a planarization film and a silicon nitride film 8. At least one of the material film 7 or the silicon nitride film 8 has shielding properties against ultraviolet light with a wavelength of 380 nm or less. The material film 7 and the silicon nitride film 8 each have two main surfaces that intersect with the thickness direction (z-axis direction). Each surface is parallel to the xy-plane.

[0026] The material film 7 is provided on one surface 2a of the substrate 2. The material film 7 is a film whose matrix is ​​a material excluding silicon nitride, but because it is in contact with the silicon nitride film 8, silicon nitride may be mixed in. The material film 7 can be obtained, for example, by applying a coating agent containing a material excluding silicon nitride to one surface 2a of the substrate 2 and drying it. Examples of coating agents include a solution containing a material excluding silicon nitride and a suspension containing a material excluding silicon nitride. When the material film 7 is formed by this coating method, it is easy to obtain a flat surface even if the substrate 2 has minute irregularities due to particles, etc. Examples of material films 7 include films of silicone compounds, silicon oxide films obtained by modifying silicone compounds, silicon oxide films obtained by modifying polysilazane compounds, organic-inorganic hybrid films, and organic films.

[0027] Silicon oxide films can also be obtained, for example, by modifying a polysilazane compound film with vacuum ultraviolet light in an O2 atmosphere. Specifically, a method is used in which a perhydropolysilazane (PHPS) solution is applied to a substrate 2, for example by spin coating, the solvent is removed, for example by pre-baking, and then vacuum ultraviolet (VUV) light is irradiated in an O2 atmosphere. By irradiating a PHPS film formed by applying and drying a PHPS solution with vacuum ultraviolet light at a wavelength of 172 nm in an O2 atmosphere at room temperature, SiO2 oxide films are obtained. x An example of a reaction that forms a (x>0) film is shown in Chemical Formula 2 below. As shown in Chemical Formula 2, a Si-O bond is formed and SiO x As a result of the formation of this substance, NH3 is released. A silicon oxide film can also be obtained by modifying the polysilazane compound film by heating it in an O2 atmosphere instead of by vacuum ultraviolet modification treatment.

[0028] [ka]

[0029] The material film 7 may or may not have shielding performance against ultraviolet light with a wavelength of 380 nm or less. An example of a material film 7 having shielding performance against ultraviolet light with a wavelength of 380 nm or less is a film containing a resin having a group capable of absorbing ultraviolet light with a wavelength of 380 nm or less. Examples of resins having a group capable of absorbing ultraviolet light include acrylic resins having at least one skeleton or group selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton, and a cyano group, and silicone resins having at least one skeleton or group selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton, and a cyano group. Furthermore, the material film 7 may also contain a UV-absorbing silicone rubber material for LIMS from Shin-Etsu Silicone® manufactured by Shin-Etsu Chemical Co., Ltd., or an ultraviolet-cutting coating agent (HALS Hybrid® UV-G) manufactured by Nippon Shokubai Co., Ltd. The material film 7 can be formed from one or more materials selected from the above types.

[0030] The silicon nitride film 8 is provided on a plane parallel to the xy plane of the material film 7. The silicon nitride film 8 is not particularly limited as long as it is a film containing silicon nitride, but for example, it can be obtained by modifying a polysilazane compound film with vacuum ultraviolet light in an N2 atmosphere. Details of the modification treatment are as described in the gas barrier film section with reference to Figure 1. The same silicon nitride film 8 as the silicon nitride film 4 can be used. The silicon nitride film 8 may also be formed by chemical vapor deposition (CVD). The silicon nitride film 8 may or may not have shielding performance against ultraviolet light with a wavelength of 380 nm or less. In order for the silicon nitride film 8 to have shielding performance against ultraviolet light with a wavelength of 380 nm or less, it is desirable that the molar ratio of Si atoms to N atoms (Si / N) is greater than 1. By making the molar ratio (Si / N) greater than 1, a first layer 3 can be obtained that has high transmittance of visible light and high absorption capacity against ultraviolet light with a wavelength of 380 nm or less. Furthermore, since the stress on the silicon nitride film 8 can be reduced, the silicon nitride film 8 can be deposited by CVD at low temperatures. A molar ratio (Si / N) of 2 or higher is more preferable. This further enhances the UV-blocking performance.

[0031] In the gas barrier film 6 described above, it is sufficient that at least one of the material film 7 or the silicon nitride film 8 has shielding performance against ultraviolet light with a wavelength of 380 nm or less. For example, if either the material film 7 or the silicon nitride film 8 has shielding performance against ultraviolet light with a wavelength of 380 nm or less, the other does not need to have shielding performance. It is also possible that both the material film 7 and the silicon nitride film 8 have shielding performance against ultraviolet light with a wavelength of 380 nm or less. In this case, the ultraviolet light blocking function of the first layer 3 with a wavelength of 380 nm or less can be further enhanced.

[0032] The gas barrier film 6 shown in Figure 2 exhibits excellent barrier performance against gases such as water vapor and oxygen. Furthermore, the gas barrier film 6 can provide shielding against ultraviolet light with wavelengths of 380 nm or less while maintaining visible light transmittance.

[0033] In Figure 2, an example is shown in which the first layer 3 is directly laminated to one side of the base material 2. However, this is not the only example; another layer, such as an adhesive layer, may be interposed between the base material 2 and the first layer 3.

[0034] Next, the gas barrier film shown in Figure 3 will be described. The gas barrier film 9 shown in Figure 3 includes a substrate 2, a first layer 3, and a second layer 10. The details of the substrate 2 are as described in Figure 1.

[0035] The first layer 3 is provided on one side of the substrate 2. In the case of Figure 3, the first layer 3 is laminated on one side 2a of the substrate 2. The first layer 3 has barrier properties against gases such as water vapor and oxygen. The first layer 3 substantially consists of, for example, a material film 7 as a planarization film and a silicon nitride film 8. Details of the material film 7 and silicon nitride film 8 are as described in Figure 2. Note that the material film 7 and silicon nitride film 8 do not necessarily have shielding properties against ultraviolet light with a wavelength of 380 nm or less.

[0036] The second layer 10 is provided on the other side of the substrate 2. In the case of Figure 3, the second layer 10 is laminated on the other side 2b of the substrate 2. The second layer 10 may be light-transmitting. The second layer 10 has shielding performance against ultraviolet light with a wavelength of 380 nm or less. The second layer 10 can function as a planarization layer or planarization film. Furthermore, the second layer 10 can alleviate the difference between the stress applied to one side 2a of the substrate 2 and the stress applied to the other side 2b of the substrate 2. Therefore, the second layer 10 can suppress warping of the substrate 2 due to the stress difference. It is desirable that the second layer 10 has a matrix made of a material other than silicon nitride. An example of a material for forming the second layer 10 is a resin having a group capable of absorbing ultraviolet light with a wavelength of 380 nm or less. An example of a resin having a group capable of absorbing ultraviolet light is the same as that described in material film 7. The second layer 10 can be formed from one or more materials selected from the types described above.

[0037] The gas barrier film 9 shown in Figure 3 exhibits excellent barrier performance against gases such as water vapor and oxygen. Furthermore, the gas barrier film 9 can provide shielding performance against ultraviolet rays with wavelengths of 380 nm or less while maintaining visible light transmittance. In this gas barrier film 9, the first layer 3 is provided on one side of the substrate 2, and the second layer 10 is provided on the other side of the substrate 2. As a result, the difference between the stress on one side of the substrate 2 and the stress on the other side can be reduced, thereby suppressing warping of the substrate 2.

[0038] In Figure 3, an example is shown in which the first layer 3 and the second layer 10 are directly laminated to both surfaces of the substrate 2. However, the example is not limited to this, and another layer, such as an adhesive layer, may be interposed between the substrate 2 and the first layer 3 or the second layer 10.

[0039] The applications of the gas barrier film of the first embodiment are not particularly limited, but applications requiring gas barrier properties against water vapor or oxygen are preferable. The gas barrier film of the first embodiment can be used, for example, in photoelectric conversion devices. Examples of photoelectric conversion devices include solar cell devices and organic electroluminescent (organic EL) devices.

[0040] The gas barrier film of the first embodiment described above includes a substrate and a first layer provided on at least one side of the substrate. Furthermore, the gas barrier film of the first embodiment has shielding performance against ultraviolet rays with a wavelength of 380 nm or less. Therefore, the gas barrier film of the first embodiment has gas barrier performance while also having excellent UV cut performance against ultraviolet rays with a wavelength of 380 nm or less. (Second Embodiment) According to the second embodiment, a photoelectric conversion device is provided. The photoelectric conversion device includes a photoelectric conversion element and the gas barrier film of the first embodiment. The photoelectric conversion device may be, for example, a solar cell device, an organic electroluminescent (organic EL) device, and the like.

[0041] An example of applying the photoelectric conversion device of the embodiment to a solar cell device will be described with reference to Figures 4 to 6. In each figure, the thickness direction of the solar cell device is assumed to be parallel to the z-axis direction. The surface direction of the solar cell device is assumed to be parallel to the plane defined by the x-axis and y-axis directions. The x-axis, y-axis, and z-axis directions intersect perpendicularly to each other. In addition, in each figure, components that are common to multiple drawings are denoted by the same reference numeral and their description is omitted.

[0042] The solar cell device 100 shown in Figure 4 includes the gas barrier film 1 of the first embodiment and the solar cell element 11. The details of the gas barrier film 1 are as described in the first embodiment. The solar cell element 11 includes a transparent electrode 12 as the first electrode, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, a cathode 16 as the second electrode, an adhesive layer 17, and a back sheet 18. The transparent electrode 12, the hole transport layer 13, the photoelectric conversion layer 14, the electron transport layer 15, and the cathode 16 each have two surfaces that intersect with the thickness direction (z-axis direction) as their main surfaces. Each surface is parallel to the xy plane. The transparent electrode 12 is provided on a surface 5a of the silicon nitride film 5 on the surface side of the gas barrier film 1 that is parallel to the xy plane. One surface of the transparent electrode 12 that is parallel to the xy plane is in contact with surface 5a. On the other surface of the transparent electrode 12 parallel to the xy plane, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a cathode 16 are arranged in this order. A back sheet 18 is fixed to one surface of the cathode 16 parallel to the xy plane by an adhesive layer 17. Light such as sunlight or illumination light is irradiated, for example, from a first direction 19 to the other surface 2b of the substrate 2 of the gas barrier film 1.

[0043] Examples of transparent electrodes 12 as the first electrode include films made of materials that have light transmittance and conductivity, such as indium tin oxide (ITO), zinc oxide (ZnO), tin dioxide (SnO2), and fluorine-doped tin oxide (FTO).

[0044] The hole transport layer 13 has functions such as blocking electrons generated in the photoelectric conversion layer 14 and selectively and efficiently transporting holes to the cathode 16.

[0045] An example of a photoelectric conversion layer 14 is a perovskite layer. An example of a perovskite-type compound is methylammonium lead iodide (CH3NH3PbI3).

[0046] The electron transport layer 15 has functions such as blocking holes generated in the photoelectric conversion layer 14 and selectively and efficiently transporting electrons to the transparent electrode 12.

[0047] The cathode 16, which serves as the second electrode, is made of a material that is conductive and, in some cases, light-transmitting. An example of the cathode 16 is a layer containing Ti and / or Al. When light is shone onto the solar cell device 100 with the above structure, for example from a first direction 19 on the other side 2b of the substrate 2 of the gas barrier film 1, the photoelectric conversion layer 14 absorbs the shone light, generating electrons and their corresponding holes. Of the generated electrons and holes, for example, the electrons are collected at the cathode 16 via the electron transport layer 15. The holes are collected at the transparent electrode 12 via the hole transport layer 13. In this way, a photoelectric conversion reaction occurs.

[0048] The gas barrier film 1 can block ultraviolet light with a wavelength of 380 nm or less without obstructing the irradiation of visible light onto the solar cell element 11, thereby suppressing the degradation of the photoelectric conversion layer 14 due to ultraviolet light. As a result, the photodurability performance of the solar cell device 100 can be improved.

[0049] Next, the solar cell device 101 shown in Figure 5 will be described. The solar cell device 101 includes the gas barrier film 6 of the first embodiment and a solar cell element 11. The details of the gas barrier film 6 are as described in the first embodiment. The details of the solar cell element 11 are the same as those of the solar cell device 100 described with reference to Figure 4. The transparent electrode 12 of the solar cell element 11 is laminated on a surface 8a of the silicon nitride film 8 of the gas barrier film 6 that is parallel to the xy plane. Light such as sunlight or illumination light is irradiated, for example, from a first direction 19 to the other surface 2b of the substrate 2 of the gas barrier film 6. When light is shone onto the solar cell device 101 with the above structure, for example from a first direction 19, on the other side 2b of the substrate 2 of the gas barrier film 6, the gas barrier film 6 can cut out ultraviolet light with a wavelength of 380 nm or less without preventing visible light from being shone onto the solar cell element 11. As a result, degradation of the photoelectric conversion layer 14 due to ultraviolet light can be suppressed. Consequently, the photodurability performance of the solar cell device 101 can be improved.

[0050] Next, the solar cell device 102 shown in Figure 6 will be described. The solar cell device 102 includes the gas barrier film 9 of the first embodiment and a solar cell element 11. The details of the gas barrier film 9 are as described in the first embodiment. The details of the solar cell element 11 are the same as those of the solar cell device 100 described with reference to Figure 4. The transparent electrode 12 of the solar cell element 11 is laminated on a surface 8a of the silicon nitride film 8 of the gas barrier film 9 that is parallel to the xy plane. Light such as sunlight or illumination light is irradiated from, for example, the second layer 10 side of the gas barrier film 9 from the first direction 19. When light is shone onto the solar cell device 102 with the above structure, for example from the first direction 19 towards the second layer 10 side of the gas barrier film 9, the gas barrier film 9 can cut out ultraviolet light with a wavelength of 380 nm or less without obstructing visible light from being shone onto the solar cell element 11, thereby suppressing the degradation of the photoelectric conversion layer 14 due to ultraviolet light. As a result, the photodurability performance of the solar cell device 102 can be improved. In addition, since the second layer 10 of the gas barrier film 9 can suppress warping of the substrate 2, deformation such as warping can be avoided in the solar cell device 102.

[0051] In the example above, the first electrode (transparent electrode 12) is the anode and the second electrode is the cathode 16, but the arrangement of these electrodes can be reversed. That is, the first electrode (transparent electrode 12) may be the cathode and the second electrode may be the anode. In this case, the arrangement of the hole transport layer 13 and the electron transport layer 15 will also be swapped.

[0052] Although not illustrated, in addition to the first electrode side, a gas barrier film may also be provided on the second electrode side. The backsheet 18 may be omitted, and instead, a gas barrier film may be overlaid on the second electrode. If a light-transmissive electrode, that is, a transparent electrode, is used as the second electrode, light can also be taken in from the second electrode side. Therefore, it becomes possible to receive light on both sides of the solar cell device.

[0053] As described above, since the photoelectric conversion device of the second embodiment includes the gas barrier film of the first embodiment, it can cut off ultraviolet rays with a wavelength of 380 nm or less without preventing visible light from irradiating the photoelectric conversion element, and thus can suppress deterioration of the photoelectric conversion element due to ultraviolet rays. As a result, the light durability performance of the photoelectric conversion device can be improved.

Example

[0054] Hereinafter, an example of the gas barrier film will be described. The gas barrier film 1 described with reference to FIG. 1 was fabricated, and the light transmittance was measured.

[0055] A solution of PHPS (perhydropolysilazane) was spin-coated on a PET substrate as the substrate 2 so that the film thickness became 200 nm. After removing the solvent contained in the obtained film by pre-baking, vacuum ultraviolet rays with a wavelength of 172 nm were irradiated at 12 J / cm 2 in an N2 atmosphere, thereby forming a coating-type SiN x (x>0) film as the silicon nitride film 4 on the substrate side. Next, a SiN x film was formed on the upper layer of the coating-type SiN x film (the silicon nitride film 5 on the surface layer side) to a thickness of 1 μm. The gas ratio of SiH4 / NH3 / N2 was 2 / 1 / 33, and the film was formed at a pressure of 100 Pa, a power of 300 W, and 60°C. The molar ratio (Si / N) of Si atoms to N atoms in the SiN x film was 1.38. The molar ratio (Si / N) can be adjusted by changing the composition ratio of the gas. The water vapor transmission rate (WVTR) of the obtained gas barrier film 1 is 10 -4 Unit (g / m 2 The WVTR was less than or equal to / 24h. WVTR was evaluated using a gas / water vapor permeability analyzer (single chamber type (MAT), using the MA method) manufactured by MORESCO Corporation. From the obtained results, it can be said that the permeability of oxygen, which has a larger molecular size than water vapor, is also low. From these results, it was confirmed that the gas barrier film has barrier properties against water vapor and oxygen.

[0056] The obtained gas barrier film was irradiated with light of wavelengths from 200 nm to 800 nm, and its light transmittance was measured. The results are shown in Figure 7. In addition, a PET substrate alone was prepared as a comparative example, and the light transmittance of the PET substrate alone when irradiated with light of wavelengths from 200 nm to 800 nm was measured, and the results are also shown in Figure 7.

[0057] In Figure 7, the horizontal axis represents the wavelength of light (nm), and the vertical axis represents the light transmittance (%). The measurement results for the example are shown by the solid line, and the measurement results for the comparative example are shown by the dotted line. As shown in Figure 7, the gas barrier film of the example has a transmittance of 50% or less for ultraviolet light with wavelengths of 315-360 nm, and can reduce the transmission of ultraviolet light with wavelengths of 380 nm or less. In contrast, the comparative example, which consists of a PET substrate alone, had a transmittance of 60% or more for ultraviolet light with wavelengths of 315-360 nm.

[0058] A phototour durability test was conducted on the solar cell elements of the solar cell device of the embodiment by irradiating them with simulated sunlight through filters with different cut wavelengths. Specifically, a transparent electrode 12 made of an ITO film, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a cathode 16 made of a TiAl alloy layer were laminated on a PET substrate in this order. A perovskite layer containing methylammonium lead iodide was used as the photoelectric conversion layer 14. The filter was placed on the side of the PET substrate opposite to the solar cell elements. Simulated sunlight was irradiated from the filter side, and the maintenance rate of the conversion efficiency relative to the initial conversion efficiency after 485 hours of light irradiation was measured. The cut wavelength of the filter was varied to 370 nm and 380 nm. In the test solar cell irradiated with light without a UV cut filter, the conversion efficiency after 485 hours of light irradiation decreased by 20-30% from the initial conversion efficiency. In contrast, the test solar cells with 370nm and 380nm UV-cut filters showed a decrease in conversion efficiency of less than 10% from the initial conversion efficiency after 485 hours of light irradiation. Based on these results, the gas barrier film of this example can suppress the decrease in conversion efficiency of solar cell devices during light irradiation, and is expected to improve the photodurability of solar cell devices. According to at least one embodiment or example of these gas barrier films, the film comprises a substrate and a first layer provided on at least one side of the substrate, and has shielding performance against ultraviolet light with a wavelength of 380 nm or less. Therefore, it is possible to improve the cut performance against ultraviolet light with a wavelength of 380 nm or less while maintaining gas barrier performance.

[0059] While several embodiments of the present invention have been described, these embodiments are presented as examples only and are not intended to limit the scope of the invention. These novel embodiments can be carried out in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents. The invention described in the original claims of this application is listed below. [1] Substrate and It includes a first layer provided on at least one side of the base material, A gas barrier film that provides shielding against ultraviolet light with a wavelength of 380 nm or less. [2] The gas barrier film according to [1], wherein the first layer is a gas barrier layer having shielding performance against ultraviolet light with a wavelength of 380 nm or less. [3] The gas barrier film according to [2], wherein the gas barrier layer comprises at least one of a silicon nitride film having shielding performance against ultraviolet light with a wavelength of 380 nm or less, or a film (excluding the silicon nitride film) having shielding performance against ultraviolet light with a wavelength of 380 nm or less. [4] The silicon nitride film is a gas barrier film according to [3], wherein the molar ratio of Si atoms to N atoms is greater than 1. [5] The gas barrier film according to [3], wherein the silicon nitride film has a refractive index that changes in the thickness direction. [6] The gas barrier film according to [3], wherein the film having shielding performance against ultraviolet light with a wavelength of 380 nm or less (excluding the silicon nitride film) comprises at least one of an acrylic resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton and a cyano group, or a silicone resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton and a cyano group. [7] The first layer is a gas barrier layer provided on one side of the substrate, The gas barrier film according to [1], further comprising a second layer provided on the other side of the substrate and having shielding performance against ultraviolet light with a wavelength of 380 nm or less. [8] The gas barrier film according to [7], wherein the second layer comprises at least one of an acrylic resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton and a cyano group, or a silicone resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton and a cyano group. [9] Photoelectric conversion element and, A photoelectric conversion device comprising a gas barrier film provided on the photoelectric conversion element and described in any one of items [1] to [8]. [Explanation of Symbols]

[0060] 1,6,9...Gas barrier film, 2...Substrate, 2a,2b...Surface (main surface), 3...First layer, 4...Substrate-side silicon nitride film, 5...Front-side silicon nitride film, 5a...Surface (main surface), 7...Material film, 8...Silicon nitride film, 8a...Surface (main surface), 10...Second layer, 11...Solar cell element, 12...Transparent electrode, 13...Hole transport layer, 14...Photoelectric conversion layer, 15...Electron transport layer, 16...Cathode, 17...Adhesive layer, 18...Backsheet, 19...First direction, 100,101,102...Solar cell device.

Claims

1. Substrate and A first layer provided on at least one side of the substrate, The substrate and the first layer are provided with a planarization film made of a material film whose base material is a material other than silicon nitride, The aforementioned first layer is a gas barrier layer comprising a first silicon nitride film on the substrate side and a second silicon nitride film provided on the first silicon nitride film, wherein the molar ratio of Si atoms to N atoms is greater than 1. The first silicon nitride film is a planarized film having shielding performance against ultraviolet light with a wavelength of 380 nm or less. The second silicon nitride film is a gas barrier film for perovskite-type solar cells that has shielding performance against ultraviolet light in the entire wavelength range of 315-360 nm.

2. The gas barrier film for a perovskite solar cell according to claim 1, wherein the molar ratio of Si atoms to N atoms in the second silicon nitride film is greater than 1 and 1.38 or less.

3. The material film is a film (excluding silicon nitride film) having shielding performance against ultraviolet light with a wavelength of 380 nm or less, and comprises at least one of the following: an acrylic resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton and a cyano group, or a silicone resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton and a cyano group, as described in claim 1, for use as a gas barrier film for a perovskite solar cell.

4. The gas barrier film for a perovskite solar cell according to claim 1, wherein the first silicon nitride film has a refractive index that changes in the thickness direction.

5. The aforementioned layer is a gas barrier layer provided on one side of the substrate, The gas barrier film for a perovskite solar cell according to claim 1, further comprising a second layer provided on the other side of the substrate and having shielding performance against ultraviolet light with a wavelength of 380 nm or less.

6. The gas barrier film for a perovskite solar cell according to claim 5, wherein the second layer comprises at least one of an acrylic resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton, and a cyano group, or a silicone resin having at least one selected from the group consisting of a triazine skeleton, a benzophenone skeleton, a benzotriazole skeleton, a salicylate skeleton, and a cyano group.

7. Perovskite solar cell elements, A perovskite solar cell device comprising a perovskite solar cell element and a gas barrier film for perovskite solar cells according to any one of claims 1 to 6.

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