Electrochromic aperture, its manufacturing method, and lens module including same

Abstract

To provide an electrochromic diaphragm, its manufacturing method, and a lens module including the same.SOLUTION: In an electrochromic diaphragm including a first transparent base (11), a first transparent conductive layer (12), an ion storage layer (13), an ion transition layer (14), an electrochromic layer (15), a second transparent conductive layer (16), and a second transparent base (17) laminated successively, the ion transition layer (14) is a solid electrolyte layer. Further, a method for manufacturing the electrochromic diaphragm is provided. In the method, after completion of coating of the ion storage layer (13) and the electrochromic layer (15), etching is performed. A lens module including the electrochromic diaphragm is provided further.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present application relates to the technical field of photochromic diaphragms, and more particularly to electrochromic diaphragms, their manufacturing methods, and lens modules including the same. [Background technology]

[0002] With the development of mobile terminal technology, such as mobile phones and tablets, most mobile terminals are equipped with lens modules. Lens modules can be divided into two types: fixed aperture and adjustable aperture. Adjustable aperture lens modules typically use mechanical apertures and require the installation of complex aperture adjustment components, resulting in large lens module volumes and high manufacturing and installation process requirements. While fixed aperture lens modules have the advantage of simple structure, mobile terminals generally adopt fixed aperture lens modules due to size limitations. However, fixed aperture lens modules have a fixed light transmittance, which negatively impacts shooting resolution in strong and weak light, and cannot effectively control depth, making it difficult to capture background blur.

[0003] CN104903788A discloses an electro-optical diaphragm including a stack of a front transparent conductive medium, an electrolyte medium, an active electrochromic medium, and a rear transparent conductive medium, with the front and rear transparent conductive media directly connected to each other by a conductive sector located in the imaging path. CN108519657A discloses a lens module and a mobile terminal. The lens module includes a voltage application element. The voltage application element is electrically connected to an electrochromic film. The electrochromic film includes a first light-transmitting conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, and a second light-transmitting conductive layer, arranged in that order on a light-transmitting base. The electro-optical diaphragm or electrochromic film can change light transmittance and adjust light transmission by applying different electric fields. Furthermore, its small thickness allows it to be applied to imaging modules of portable consumer electronics devices without significantly increasing the Z-axis height of the lens module.

[0004] However, existing electrochromic apertures still have many deficiencies, such as: , concave Due to the non-discolored areas in the groove areas, light leaks or does not transmit through, further affecting imaging quality. thing The range of color change from the inside to the outside of the aperture is similar, and there is no obvious difference in the number of adjustable aperture steps. thing and the large thickness of the aperture limits its application in imaging modules of portable consumer electronic devices. thing Further issues need to be resolved. Summary of the Invention

[0005] The present application provides an electrochromic diaphragm, a manufacturing method thereof, and a lens module including the same. The manufacturing method of the present application ensures multi-stage adjustment of the diaphragm while effectively avoiding problems such as uneven discoloration caused by conventional etching methods. The electrochromic diaphragm with different structures of the present application achieves multi-stage adjustment of the diaphragm while avoiding problems such as light leakage or light imperfections caused by etching grooves, or enables adjustment of the diaphragm with a larger difference in the number of stages. The electrochromic diaphragm with a curved surface structure can be combined with an achromatic lens combination, allowing the lens module to be made thinner.

[0006] Existing electrochromic apertures typically have annular grooves etched into the transparent conductive layer, which are divided into multiple regions from the inside to the outside. Voltages are applied to each region independently, allowing for multi-stage adjustment of the electrochromic aperture. The ion storage layer and electrochromic layer are applied after the transparent conductive layer is etched. However, this can result in uneven ion storage layer and electrochromic layer in the grooves, which can lead to uneven discoloration of the aperture and potentially adversely affect imaging quality. Note that "from the inside to the outside" in this application refers to the radial direction from the center of the film surface to the edge.

[0007] In a first aspect, the present application provides an electrochromic diaphragm, the structure of which includes a first transparent base, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer, and a second transparent base, which are stacked in order, and the ion transition layer is a solid electrolyte layer.

[0008] In one preferred embodiment, a plurality of annular grooves are etched in the ion storage layer and the first transparent conductive layer, and / or in the electrochromic layer and the second transparent conductive layer, each centered on the central axis of the electrochromic diaphragm.

[0009] In another preferred embodiment, a plurality of annular grooves are etched in both the first transparent base and the first transparent conductive layer, or in the triple layer of the first transparent base, the first transparent conductive layer, and the ion storage layer, with the center being the central axis of the electrochromic diaphragm; and / or a plurality of annular grooves are etched in both the second transparent base and the second transparent conductive layer, or in the triple layer of the second transparent base, the second transparent conductive layer, and the electrochromic layer, with the center being the central axis of the electrochromic diaphragm.

[0010] In a specific embodiment of the present application, a plurality of annular grooves are etched in the first transparent conductive layer and the ion storage layer, the center of which is the central axis of the electrochromic diaphragm. In another specific embodiment of the present application, a plurality of annular grooves are etched in the second transparent conductive layer and the electrochromic layer, the center of which is the central axis of the electrochromic diaphragm. In another specific embodiment of the present application, a plurality of annular grooves are etched in the first transparent base and the first transparent conductive layer, the center of which is the central axis of the electrochromic diaphragm. In another specific embodiment of the present application, a plurality of annular grooves are etched in the second transparent base and the second transparent conductive layer, the center of which is the central axis of the electrochromic diaphragm. In another specific embodiment of the present application, a plurality of annular grooves are etched in the first transparent base, the first transparent conductive layer, and the ion storage layer, the center of which is the central axis of the electrochromic diaphragm. In another specific embodiment of the present application, a plurality of annular grooves are etched in the second transparent base, the second transparent conductive layer, and the electrochromic layer, the center of which is the central axis of the electrochromic diaphragm.

[0011] In a second aspect, the present application provides a method for producing a pharmaceutical composition comprising: (1) forming a first transparent conductive layer on a first transparent base and a second transparent conductive layer on a second transparent base; (2) forming an ion storage layer on the first transparent conductive layer and forming an electrochromic layer on the second transparent conductive layer; (3) etching a plurality of annular grooves centered on the central axis of the electrochromic diaphragm in the ion storage layer and the first transparent conductive layer, and / or in the electrochromic layer and the second transparent conductive layer; and (4) combining the ion storage layer with the electrochromic layer and the ion transition layer, such that the ion transition layer is disposed between the ion storage layer and the electrochromic layer, to obtain the electrochromic aperture; Or, (1) forming a first transparent conductive layer on a first transparent base and a second transparent conductive layer on a second transparent base; (2) forming an ion storage layer on the first transparent conductive layer and an electrochromic layer on the second transparent conductive layer; (3) combining the ion storage layer with the electrochromic layer and the ion transition layer such that the ion transition layer is disposed between the ion storage layer and the electrochromic layer; and (4) Etching is performed from the first transparent base side, and a plurality of annular grooves are etched in both the first transparent base and the first transparent conductive layer, or in the three layers of the first transparent base, the first transparent conductive layer, and the ion storage layer, with the center being the central axis of the electrochromic diaphragm; and / or and etching from the second transparent base side to etch a plurality of annular grooves centered on the central axis of the electrochromic diaphragm in both the second transparent base and the second transparent conductive layer, or in the three-layer structure of the second transparent base, the second transparent conductive layer, and the electrochromic layer.

[0012] In the present application, the etching method is not particularly limited, and laser etching may be used, for example.

[0013] In this method, etching is performed after the application of the ion storage layer and the electrochromic layer is completed, thereby ensuring the realization of multi-stage aperture adjustment while effectively avoiding problems such as uneven discoloration caused by conventional etching methods.

[0014] Although the manufacturing method of the second embodiment can effectively avoid the problems of uneven discoloration caused by the conventional etching method, the groove etching method, while realizing the multi-stage discoloration of the electrochromic aperture, still leaves non-discolored areas in the groove area, which causes light leakage or light impermeability, further affecting the imaging quality, and therefore requires further improvement.

[0015] To solve this problem, the present application provides an electrochromic diaphragm in the following third aspect, in which the projection of the electrochromic layers of different electrochromic units in a direction along the central axis of the electrochromic diaphragm is seamlessly continuous, and the color change process of different electrochromic units can be controlled independently, thereby realizing multi-stage adjustment of the diaphragm while avoiding the problems of light leakage or light imperfections caused by etching of the grooves.

[0016] In a third aspect, the present application provides an electrochromic aperture, which includes at least two stacked, independent electrochromic units, each of which includes a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, and a second transparent conductive layer, stacked in order, and wherein adjacent electrochromic units are separated by a transparent base.

[0017] The electrochromic layer and the ion storage layer have a circular or annular shape centered on the central axis of the electrochromic aperture, and the ion storage layer and the electrochromic layer in the same electrochromic unit coincide with each other, and the projections of the electrochromic layers in different electrochromic units in the direction along the central axis of the electrochromic aperture do not overlap, and their boundaries coincide with each other.

[0018] In this application, "the ion storage layer and the electrochromic layer in the same electrochromic unit coincide with each other" means that, in the same electrochromic unit, the projections of the ion storage layer and the electrochromic layer in the direction along the central axis of the electrochromic aperture overlap with each other.

[0019] In the present application, the method for producing the ion storage layer and the electrochromic layer having the above-mentioned shapes is not particularly limited, and the following two methods may be mentioned as examples.

[0020] 1. First, a transparent conductive layer is coated using an openwork annular shielding substrate, and an electrochromic layer or ion storage layer is applied on the transparent conductive layer. After removing the shielding substrate, a ring-shaped electrochromic layer or ion storage layer is obtained.

[0021] 2. The transparent conductive layer coated with the electrochromic layer or ion storage layer is subjected to laser etching, and then a ring-shaped electrochromic layer or ion storage layer is obtained by chemical corrosion or physical wiping.

[0022] To solve the problem of light leakage or light impermeability due to groove etching, the present application provides an electrochromic diaphragm in the following fourth aspect. The electrochromic diaphragm is divided into three regions from the inside to the outside, and the voltages at which each region begins to brighten are 0.4, 0.8, and 1.2 V. For example, when the voltage is between 0.4 and 0.8 V, only the innermost region begins to brighten. When the voltage is between 0.8 and 1.2 V, the innermost and middle regions begin to brighten. When the voltage is greater than 1.2 V, the innermost, middle, and outermost regions all begin to brighten. When the voltage at which the diaphragm begins to darken gradually decreases from the inside to the outside, applying a reverse voltage causes the outer periphery of the diaphragm to become darker than the inner periphery. Because each region of the diaphragm is continuous from the inside to the outside, the diaphragm can be adjusted in multiple stages while avoiding the problem of light leakage or light impermeability due to groove etching.

[0023] In a fourth aspect, the present application provides an electrochromic aperture including, in order, a first transparent base, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer, and a second transparent base.

[0024] When the electrochromic diaphragm starts to brighten, the voltage gradually increases from the inside to the outside, and when the electrochromic diaphragm starts to darken, the voltage gradually decreases from the inside to the outside.

[0025] In the present application, the method for realizing "the voltage gradually increasing from the inside to the outside when the electrochromic diaphragm starts to brighten, or the voltage gradually decreasing from the inside to the outside when the electrochromic diaphragm starts to darken" is not particularly limited, and the following two methods may be mentioned as examples.

[0026] 1. Before the ionic transition layer is cured with ultraviolet light, different areas are shielded with materials with different ultraviolet transmittances, so that the cross-linking degree of the ionic transition layer gradually increases from the inside to the outside.

[0027] 2. By applying electrochromic materials with different voltages when they start to brighten or darken on the transparent conductive layer, the voltage when the electrochromic material starts to brighten gradually increases or the voltage when it starts to darken gradually decreases from the inside to the outside.

[0028] To solve the problem of light leakage or non-transmission caused by etching of grooves, the present application provides an electrochromic diaphragm according to the fifth aspect. By using the electrochromic diaphragm according to the fifth aspect, a high voltage is applied to the center and a low voltage is applied to the edges, so that the voltage across the diaphragm can be gradually reduced from the inside to the outside. Because the grooves in the diaphragm are not etched and the transmittance at any point on the diaphragm is related to the voltage at that point, when the voltage across the diaphragm is gradually reduced from the inside to the outside, the transmittance also gradually decreases from the inside to the outside. Therefore, by changing the voltage, it is possible to control the changes in the transmittance of the diaphragm at different levels, thereby achieving multi-stage adjustment of the diaphragm and avoiding the problem of light leakage or non-transmission caused by etching of grooves.

[0029] In a fifth aspect, the present application provides an electrochromic aperture including, stacked in sequence, a first transparent base, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer, and a second transparent base.

[0030] The electrochromic diaphragm is made of the same material from the inside to the outside, and has no grooves.

[0031] In a sixth aspect, the present application provides a method for performing multi-stage adjustment on the electrochromic diaphragm according to the fifth aspect, which uses the electrochromic diaphragm according to the fifth aspect and achieves multi-stage adjustment by applying different voltages to the center and edges of the electrochromic diaphragm, with the voltage at the center being greater than the voltage at the edges.

[0032] In this application, the voltage applied to the aperture refers to the potential difference between the electrochromic layer and the ion storage layer. If the potential difference is positive, the applied voltage is a positive voltage, and if the potential difference is negative, the applied voltage is a negative voltage. The phrase "the voltage at the center is greater than the voltage at the edge" refers to the center voltage being greater than the edge voltage. For example, the center may be a positive voltage and the edge may be a negative voltage, or both the center and the edge may be positive voltages with the absolute value of the center voltage being greater than the absolute value of the edge voltage, or both the center and the edge may be negative voltages with the absolute value of the center voltage being smaller than the absolute value of the edge voltage.

[0033] The excessive thickness of the aperture has always limited its application in imaging modules for portable consumer electronic devices. The electrochromic aperture according to the seventh and eighth aspects of the present application has flexible and bendable characteristics due to the selection of materials for each layer. The aperture can be designed with a curved surface structure that matches the curvature of the convex or concave lens in an achromatic lens assembly. By attaching the aperture to the surface of the concave or convex lens in the achromatic lens assembly, the aperture and lens can be integrated into the lens module, further reducing the thickness of the lens module. Alternatively, the aperture can be designed with a structure similar to the shape of the concave or convex lens in the achromatic lens assembly, replacing the concave or convex lens, thereby achieving the aperture and lens integration in the lens module, further reducing the thickness of the lens module. The electrochromic aperture exhibits minimal change in refractive index during the color change process, so the achromatic function is not affected.

[0034] In a seventh aspect, the present application provides an electrochromic aperture including, stacked in sequence, a first transparent base, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer, and a second transparent base.

[0035] The electrochromic diaphragm has a curved surface structure, and the curvature is the same as that of the surface of the concave or convex lens in the achromatic lens combination.

[0036] In an eighth aspect, the present application provides an electrochromic aperture including, stacked in sequence, a first transparent base, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer, and a second transparent base.

[0037] The electrochromic diaphragm has a shape similar to that of a concave or convex lens in an achromatic lens combination.

[0038] Existing electrochromic iris diaphragms are basically two-stage adjustable, meaning that there are only two stages of iris adjustment. Even if there are three stages, if the color change ranges of the three circles are the same (assuming the color change range of each circle is 20-90%), the overall transmittance of the minimum pupil is still large, which not only affects the imaging effect but also makes the difference in the number of adjustable stages of the iris unclear. In other words, the ratio between the maximum and minimum pupil transmittance is small and needs to be improved.

[0039] To address this issue, the present application provides an electrochromic aperture in the following ninth aspect: By changing the thickness of the electrochromic layer in different regions, the color change range of each region can be changed (for example, the electrochromic layer is divided into three regions from the inside to the outside, and the color change ranges in each region are 20-90%, 10-80%, and 5-70%, respectively), which significantly increases the ratio of maximum pupil transmittance to minimum pupil transmittance, allowing for aperture adjustment with a larger number of different stages, and meeting the needs of multiple shooting scenes.

[0040] In a ninth aspect, the present application provides an electrochromic aperture based on the electrochromic aperture according to the first, third, fourth, fifth, seventh and eighth aspects of the present application, wherein the thickness of the electrochromic layer, or the thickness of the electrochromic layer and the ion storage layer, gradually increases from the inside to the outside.

[0041] The edge to center thickness ratio may be between 1.1 and 10:1, such as 1.1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.

[0042] It should be noted that the thickness of the ion transition layer is on the order of microns, and the change in thickness of the electrochromic layer is on the order of nanometers, so the actual change in thickness of the ion transition layer does not need to be taken into consideration.

[0043] In the present application, the thickness of the electrochromic layer is configured to gradually increase from the inside to the outside, so that the aperture has different color change ranges from the inside to the outside, and the number of different steps can be adjusted to achieve greater aperture adjustment, which can meet the needs of multiple shooting scenes.

[0044] In the present application, the method for achieving the above-mentioned thickness change is not particularly limited, and for example, a film layer with a uniform thickness is first manufactured and then laser etching is performed, or the thickness of the film layer is controlled when manufacturing the film layer (for example, by controlling it in the form of coating each layer).

[0045] In one embodiment of the present application, the materials of the first transparent conductive layer and the second transparent conductive layer are each independently made of indium-tin oxide (ITO), aluminum zinc oxide (AZO), fluorine-doped tin oxide (FTO), silver nanowires, graphene, carbon nanotubes, metal grids, or silver nanoparticles.

[0046] In one embodiment of the present application, the thickness of the first transparent conductive layer and the second transparent conductive layer is each independently 1 to 1000 nm, and may be, for example, 1 nm, 3 nm, 5 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 800 nm, or 1000 nm.

[0047] The first and second transparent conductive layers are electrodes of the electrochromic diaphragm. In practical applications, the electrodes may be connected to lead wires.

[0048] In one embodiment of the present application, the material of the ion storage layer is one or a combination of at least two of oxides or complexes of metal elements from groups IIIB, IVB, VB, VIB, VIIB, VIII, IB, and IIB that can store ions during an electrochemical reaction. For example, the material may be a metal oxide, a combination of two or more metal oxides, a metal complex, a combination of two or more metal complexes, or a combination of a metal complex and a metal oxide. When two or more metal oxides are selected, the metal oxides may be doped, such as NbO doped with 5 wt% TiO.

[0049] Preferably, the metal is selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu and Zn.

[0050] Preferably, the complex is Prussian green, Prussian white, Prussian brown, Prussian blue, KFeFe(CN)6, FeNiHCF, FeHCF, NiHCF or iron compound X m Y n {Fe(CN)6}, where X is Na + or K + or other metal ions mentioned in the literature, and Y is Fe 3+ , Co 3+ , Ni + , Mn 2+ , Zn 2+or Cu 2+ or other metal ions mentioned in the literature.

[0051] Preferably, the material of the ion storage layer further comprises a polymer having redox activity.

[0052] The polymer having redox activity may be a polymer made of pyrrole and a pyrrole derivative, a polymer made of thiophene and a thiophene derivative, a polymer containing TEMPO (tetramethylpiperidine nitroxide) and a derivative thereof, a polymer containing violet and a derivative thereof, or the like.

[0053] In one embodiment of the present application, the ion storage layer may be a mixed system of a transition metal complex and a metal oxide, a mixed system of a transition metal complex and a polymer having redox activity, or a mixed system of a metal oxide and a polymer having redox activity.

[0054] In one embodiment of the present application, the thickness of the ion storage layer is 1 to 10,000 nm, and may be, for example, 1 nm, 3 nm, 5 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 800 nm, 1000 nm, 2000 nm, 5000 nm, 8000 nm, or 10,000 nm.

[0055] The ion storage layer is mainly used to store ions. When an electric current is applied, the ions in the ion storage layer are transferred to the electrochromic layer, and the electrochromic layer absorbs these ions and changes color.

[0056] In one embodiment of the present application, the ionic transition layer is a flexible solid electrolyte layer.

[0057] In one embodiment of the present application, the weight percent content of the neutral organic small molecules contained in the ionic transition layer is 30 wt% or less, such as 25 wt%, 20 wt%, 15 wt%, 10 wt%, 5 wt%, etc., and the molecular weight of the neutral organic small molecules is 3000 or less, such as 2500, 2000, 1500, 1000, 500, etc.

[0058] In one embodiment of the present application, the polymer in the solid electrolyte layer is a solid electrolyte polymer having covalently linked plasticizing groups.

[0059] In one embodiment of the present application, the solid electrolyte polymer is a copolymer of a monomer or oligomer and an ion-conductive polymer, and the monomer or oligomer has a plasticizing group in a side chain thereof. Further, the composition of the solid electrolyte layer includes a monomer or oligomer segment having a crosslinking group in a side chain thereof.

[0060] The term "further" as used herein means that, in the above definition, the composition of the solid electrolyte layer preferably contains a copolymer of a monomer or oligomer and an ion-conductive polymer, and further contains a monomer or oligomer segment having a crosslinking group in its side chain. The same interpretation is also applied to the following "further" terms.

[0061] The plasticizing group and the plasticizing group refer to a group that can weaken the interaction between polymers and reduce polymer crystallinity.

[0062] In one embodiment of the present application, the solid electrolyte polymer is a plasticized linear polymer and an ionically conductive polymer linked by a chemical bond. The glass transition temperature of the plasticized linear polymer is below -20°C. Furthermore, the composition of the solid electrolyte layer further includes a monomer or polymer having a crosslinking group in a side chain. The monomer or polymer having a crosslinking group in a side chain, the plasticized linear polymer, and the ionically conductive polymer are linked by a chemical bond.

[0063] In one embodiment of the present application, the solid electrolyte polymer is a polymer having a plasticizing group in a side chain and a glass transition temperature of below −20° C. and an ion-conductive polymer, which are chemically bonded together. Furthermore, the composition of the solid electrolyte layer further includes a monomer or polymer having a crosslinking group in a side chain, and the monomer or polymer having a crosslinking group in a side chain, the polymer having a plasticizing group in a side chain and a glass transition temperature of below −20° C., and the ion-conductive polymer are chemically bonded together.

[0064] In one embodiment of the present application, the solid electrolyte polymer is a brush-like polymer having a flexible polymer backbone, ion-conductive side chains, and immiscible phase side chains. Furthermore, the composition of the solid electrolyte layer further includes a monomer or oligomer having a crosslinking group in its side chain. The monomer or oligomer having a crosslinking group in its side chain is chemically bonded to the brush-like polymer in the form of a block copolymer.

[0065] The term "immiscible phase side chains" used herein refers to side chains that are significantly different from other side chains or polymers and therefore cannot be effectively blended with other polymers. The term "brush polymers" used herein refers to polymers with flexible main chains. There are two types of side chains: one type is used to conduct ions, and the other type is a different type of side chain whose performance is significantly different from that of ion-conducting side chains and therefore cannot be effectively blended with other polymers. In this application, the introduction of these unblendable side chains reduces the crystallinity of the polymer, creating a disordered state within the polymer, thereby improving the ion-conducting ability and transparency of the entire polymer.

[0066] In one embodiment of the present application, the ionic transition layer is a flexible solid electrolyte layer, and the polymer of the flexible solid electrolyte layer may be selected from the following four types of polymers:

[0067] In one specific embodiment, x, y, and z are each independently selected from integers equal to or greater than 0. The rectangle in the formula represents a polymer block having ion-conducting properties (ion-conductive polymer block), and the oval represents a monomer or polymer having a side chain of PR (plasticizing group), or CL (crosslinking group), or NM (non-mixed phase group), or IC (ion-conductive group). [ka]

[0068] A block copolymer (represented as PEGPRCL) formed by copolymerization of an ion-conducting polymer block y (e.g., polyethylene glycol, or other materials reported in the literature), a monomer or polymer block x having a side chain plasticizing group (PR), and a monomer or polymer block z having a side chain crosslinking group (CL), or a block copolymer (represented as PEGPR) formed by copolymerization of an ion-conducting polymer block y (e.g., polyethylene glycol, or other materials reported in the literature) and a monomer or polymer block x having a side chain plasticizing group (PR). [ka]

[0069] A block copolymer (represented by PEGSPCL) is formed by copolymerizing an ion-conducting polymer block y (e.g., polyethylene glycol or other materials reported in the literature), a linear plasticized polymer (SP) block x (e.g., polyethylene, polybutene, polyisobutene, siloxane, or other materials reported in the literature) having a glass transition temperature below -20°C, and a monomer or polymer block z having a crosslinking group (CL) in the side chain. Alternatively, a block copolymer (represented by PEGSP) is formed by chemically linking an ion-conducting polymer block y (e.g., polyethylene glycol or other materials reported in the literature) and a linear plasticized polymer (SP) block x (e.g., polyethylene, polybutene, polyisobutene, siloxane, or other materials reported in the literature) having a glass transition temperature below -20°C. [ka]

[0070] A block copolymer (represented by PEGSP-PRCL) in which an ion-conducting polymer block y (e.g., polyethylene glycol or other materials reported in the literature) and a plasticizing polymer (SP-PR) block x having plasticizing side chains are linked by a chemical reaction and copolymerized with a monomer or oligomer (CL) block z having a crosslinking group in the side chain (represented by PEGSP-PRCL), or a block copolymer (represented by PEGSP-PR) in which an ion-conducting polymer block y (e.g., polyethylene glycol or other materials reported in the literature) and a plasticizing polymer (SP-PR) block x having plasticizing side chains are linked by a chemical reaction. [ka]

[0071] Comb block copolymers (ICNMCL) comprise flexible polymer blocks x having ion-conducting oligomers or polymers (e.g., polyethylene glycol or other materials reported in the literature) as side chains and flexible polymer blocks y having side chains that do not blend with ion-conducting polymers (e.g., alkyl, aromatic, or mixed alkyl and aromatic side chains), linked by a chemical reaction, and copolymerized with a monomer or oligomer (CL) block z having a crosslinking group in the side chain. Alternatively, comb block copolymers (ICNM) comprise flexible polymer blocks x having ion-conducting oligomers or polymers (e.g., polyethylene glycol or other materials reported in the literature) as side chains and flexible polymer blocks y having side chains that do not blend with ion-conducting polymers (e.g., alkyl, aromatic, or mixed alkyl and aromatic side chains), linked by a chemical reaction.

[0072] The polymer material used in the ionic transition layer must be blended with a certain amount of organic and / or inorganic salt to form an electrolyte precursor. The inorganic salts include, but are not limited to, lithium, sodium, potassium, magnesium, calcium, and aluminum salts, and the organic salts include, but are not limited to, ionic liquids such as EMITFSI and EMIOTF. An initiator must also be added to blend the materials together to form the electrolyte precursor. The electrolyte precursor can be crosslinked by heating, photoinitiation, or other methods to form the final all-solid-state electrolyte.

[0073] As used herein, plasticizing groups (PR) include, but are not limited to, the following structures: [ka]

[0074] Bridging groups (CL) include, but are not limited to, the following structures: [ka]

[0075] The backbone of the comb block copolymer includes, but is not limited to, the following structure: [ka]

[0076] Ion-conducting groups (IC) include, but are not limited to, the following structures: [ka]

[0077] In one embodiment of the present application, the thickness of the ion transition layer is 0.1 to 200 μm, such as 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 150 μm, 160 μm, 180 μm, or 200 μm. The ion transition layer is a transition passage for ions.

[0078] In one embodiment of the present application, the material of the electrochromic layer is selected from the group consisting of electrochromic metal oxides such as tungsten oxide, polydecylviologen and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, polythieno[3,4-b][1,4]dioxaheptane and its derivatives, polyfuran and its derivatives, polyfluorene and its derivatives, and polycarbazole and its derivatives, and / or a combination of one or at least two of the above polymers and a copolymer of a monomer or oligomer of the above polymer and an electron-deficient monomer.

[0079] In one embodiment of the present application, the electron-deficient monomer includes, but is not limited to, one or a combination of at least two selected from benzothiadiazole, benzoselenadiazole, benzoxazole, benzotriazole, benzimidazole, quinoxaline, and diketopyrrolopyrrole.

[0080] The color change of the electrochromic layer can be adjusted according to the type of electrochromic material, and may be, for example, a change between black and transparent, a change between black and red, a change between black and yellow, or the like.

[0081] In one embodiment of the present application, the thickness of the electrochromic layer is 1 to 10,000 nm, and may be, for example, 1 nm, 3 nm, 5 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 800 nm, 1000 nm, 2000 nm, 5000 nm, 8000 nm, or 10,000 nm.

[0082] In one embodiment of the present application, the materials of the first transparent base and the second transparent base are each independently glass or a flexible base material.

[0083] The flexible base material includes, but is not limited to, PET, cycloolefin copolymer, triacetyl cellulose, and the like.

[0084] In one embodiment of the present application, the total thickness of the electrochromic diaphragm is 1 mm or less.

[0085] The total thickness of the electrochromic aperture of the present invention can be controlled to 5 mm or less. The low thickness (also called Z-axis height) contributes to zooming and adjustment.

[0086] In a tenth aspect, the present application provides a method for producing a method for manufacturing a pharmaceutical composition comprising: A combination of a concave lens and a convex lens for achromatization, and an electrochromic diaphragm according to the seventh aspect attached to the surface of the concave lens or the convex lens. or There is provided an aperture lens combination including a combination of an achromatic concave lens and a convex lens, wherein the concave lens is an electrochromic aperture according to the eighth aspect.

[0087] In an eleventh aspect, the present application provides a method for producing a composition comprising: an achromatic lens combination, an electrochromic diaphragm according to the second, third, fourth, fifth, seventh, eighth or ninth aspect of the present application, an exposure controller, an image sensor, a pulse voltage controller, a light intensity sensor, a photosensitive element, a wiring substrate and a chip; The centers of the achromatic lens combination, the electrochromic aperture, the exposure controller and the image sensor are aligned on the same optical axis; Or, The diaphragm lens combination according to the tenth aspect includes an exposure controller, an image sensor, a pulse voltage controller, a light intensity sensor, a photosensitive element, a wiring substrate, and a chip; The lens module includes the aperture lens assembly, the electrochromic aperture, the exposure controller and the image sensor, and the centers of the aperture lens assembly, the electrochromic aperture, the exposure controller and the image sensor are aligned on the same optical axis.

[0088] In one specific embodiment, the achromatic lens combination includes a front lens and a rear lens. The front lens and the rear lens each independently include one or more lenses. Examples of lens materials include one or more resins that can be processed in a form such as UV curing, heat curing, or room temperature curing, such as polycarbonate, polyester, or polyurethane. The combination of the front lens and the rear lens is mainly used for achromatization.

[0089] The electrochromic diaphragm is mainly used to adjust the amount of light entering the lens module by adjusting the size of a diaphragm through which light can pass.

[0090] The pulse voltage controller is mainly used to act on the electrochromic diaphragm by applying a pulse voltage to change the light transmittance of the electrochromic diaphragm, and is influenced by a light intensity sensor, an exposure controller, a lens movement button, etc.

[0091] The image sensor controls the pulse voltage controller according to environmental parameters to adjust the diaphragm of the electrochromic iris, and controls the exposure controller to control the exposure parameters and exposure time. The environmental parameters include factors such as pixel integration time, ambient illumination, flash lamp, and whether the flash lamp is enabled. The image sensor may be any conventional solid-state imaging sensor capable of capturing a focused optical image, such as a complementary metal-oxide semiconductor (CMOS) sensor chip.

[0092] The photosensitive element converts the light beam into an electric charge, which can then be converted into a digital signal by an analog-to-digital converter chip. The digital signal is compressed and then stored in the camera's internal flash memory or built-in hard disk card (including charge-coupled device (CCD) and complementary metal-oxide semiconductor (CMOS)).

[0093] In this application, the entire manufacturing process of the lens module for adjusting the light amount and imaging effect may include the following steps:

[0094] (1) Manufacture electrochromic apertures.

[0095] (2) The achromatic lens combination is molded and cured to form an electrochromic aperture lens together with the electrochromic aperture.

[0096] (3) Debugging and installation of image sensors, pulse voltage controllers, and photosensitive elements.

[0097] Through precise testing, the electrochromic diaphragm, achromatic lens combination, and image sensor are controlled to be positioned on the same optical axis. The image sensor detects the ambient light illuminance, converts it into an electrical signal, and outputs it to the control chip. The pulse voltage controller then controls the corresponding current output to change the light transmittance of the electrochromic diaphragm, while the voice coil motor changes the corresponding focal length to the most suitable imaging parameter. The exposure controller then controls the exposure, and the image signal is converted from the CCD into an electrical signal, which is then processed and output as an image.

[0098] (4) A lens module is formed by combining the electrochromic aperture lens with other components.

[0099] After careful testing, the electrochromic aperture lens and other components, such as the exposure controller, CCD, and voice coil motor, are installed to form a lens module. [Effects of the Invention]

[0100] Compared with the prior art, the present application has the following beneficial effects:

[0101] The method for manufacturing an electrochromic diaphragm according to the first aspect of the present application can effectively avoid problems such as uneven discoloration that occur with conventional etching methods, while ensuring that multi-stage adjustment of the diaphragm can be achieved.

[0102] The electrochromic diaphragm according to the third and fourth aspects of the present application can achieve multi-stage adjustment of the diaphragm while avoiding the problems of light leakage or light impermeability caused by etching of the recessed grooves.

[0103] The method of performing multi-stage adjustment on the electrochromic diaphragm according to the fifth aspect and the electrochromic diaphragm according to the sixth aspect of the present application can achieve multi-stage adjustment of the diaphragm while avoiding the problems of light leakage or light imperfections caused by etching of the grooves.

[0104] The electrochromic diaphragm according to the seventh aspect of the present application has a curved surface structure, and its curvature is the same as that of the surface of the concave or convex lens in the achromatic lens combination. It can be attached to the surface of the concave or convex lens in the achromatic lens combination, thereby realizing the integration of the diaphragm and the lens in the lens module and further enabling the lens module to be made thinner.

[0105] The electrochromic diaphragm according to the eighth aspect of the present application has a curved structure and a shape similar to that of a concave or convex lens in an achromatic lens combination, and can replace the concave or convex lens in an achromatic lens combination, thereby realizing the integration of the diaphragm and the lens in the lens module and further enabling the lens module to be made thinner.

[0106] The electrochromic aperture according to the ninth aspect of the present application has different color change ranges from the inside to the outside, and different numbers of steps can realize greater aperture adjustment, which can meet the needs of multiple types of shooting scenes. [Brief explanation of the drawings]

[0107] [Figure 1] FIG. 2 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 1-1 of the present application. [Figure 2] FIG. 2 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 1-2 of the present application. [Figure 3] FIG. 2 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 1-3 of the present application. [Figure 4] FIG. 2 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 1-4 of the present application. [Figure 5] FIG. 2 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 1-5 of the present application. [Figure 6] FIG. 4 is a schematic cross-sectional view of an electrochromic diaphragm according to Example 2 of the present application. [Figure 7]FIG. 3 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 3-1 of the present application. [Figure 8] FIG. 3 is a schematic cross-sectional view of an electrochromic diaphragm according to Example 3-2 of the present application. [Figure 9] FIG. 10 is a schematic diagram of a method for performing multi-stage adjustment on an electrochromic diaphragm in Example 4 of the present application. [Figure 10] FIG. 5 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 5-1 of the present application. [Figure 11] FIG. 5 is a schematic cross-sectional view of the electrochromic diaphragm according to Example 5-2 of the present application. [Figure 12] FIG. 6 is a schematic cross-sectional view of a curved electrochromic diaphragm according to Example 6-1 of the present application. [Figure 13] FIG. 6 is a structural schematic diagram of an aperture lens combination according to Example 6-1 of the present application. [Figure 14] FIG. 6 is a structural schematic diagram of an aperture lens combination according to Example 6-2 of the present application. [Figure 15] FIG. 6 is a structural schematic diagram of an aperture lens combination according to Example 6-3 of the present application. [Figure 16] FIG. 6 is a structural schematic diagram of an aperture lens combination according to Example 6-4 of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0108] The technical solution of the present application will be further described below in conjunction with the drawings and specific embodiments. Those skilled in the art should understand that the specific embodiments are only for understanding the present application and should not be considered as specifically limiting the present application.

[0109] In the examples of the present application, the method for preparing polymer A (a type of solid electrolyte polymer belonging to PEGPRCL) is as follows. [ka]

[0110] To a suitable organic solvent, bromoisobutyric acid-terminated PEG (polyethylene glycol), acrylate with a plasticizing group, a crosslinking group with two acrylic acid groups, a monovalent copper catalyst, and PMDETA (N,N,N',N",N"-pentamethyldiethylenetriamine) ligand were added. The resulting mixture (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication) was reacted at 100°C for 12 hours, filtered through diatomaceous earth, and the solvent was removed under reduced pressure to obtain Polymer A.

[0111] The preparation method of polymer B (a type of solid electrolyte polymer belonging to PEGPR) is as follows. [ka]

[0112] PEG diamine (polyethylene glycol diamine) and phthaloyl chloride were added to a suitable organic solvent. Polymerization was carried out directly under alkaline conditions to obtain a polymer electrolyte (the mixture without the addition of solvent may be used directly as an electrolyte precursor for device fabrication). After washing with water, separation, and drying, the solvent was removed to obtain Polymer B.

[0113] The preparation method of polymer C (a type of solid electrolyte polymer belonging to PEGSPCL) is as follows. [ka]

[0114] PEG (polyethylene glycol), polysiloxane diamine, tetramine (a crosslinking agent), and carbonyldiimidazole (CDI) (a condensing agent) were added to a suitable organic solvent (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication). The mixture was reacted at 90°C to obtain a polymer. After washing with water, separation, and drying, the solvent was removed to obtain Polymer C.

[0115] The preparation method of polymer D (a type of solid electrolyte polymer belonging to PEGSP) is as follows. [ka]

[0116] PEG (polyethylene glycol), polysiloxane diamine, and a condensing agent, CDI (carbonyldiimidazole), were added to a suitable organic solvent (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication). The mixture was reacted at 120°C to obtain a polymer. After washing with water, separation, and drying, the solvent was removed to obtain Polymer D.

[0117] The preparation method of polymer E (a type of solid electrolyte polymer belonging to PEGSP-PRCL) is as follows. [ka]

[0118] PEG (polyethylene glycol), polysiloxanediol, a tetraol crosslinker, and carbonyldiimidazole (CDI) condensing agent were added to a suitable organic solvent (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication). The mixture was reacted at 100°C to obtain a polymer. After washing with water, separation, and drying, the solvent was removed to obtain polymer E.

[0119] The preparation method of polymer F (a type of solid electrolyte polymer belonging to PEGSP-PR) is as follows. [ka]

[0120] PEG (polyethylene glycol), polysiloxanediol, and a condensing agent, CDI (carbonyldiimidazole), were added to a suitable organic solvent (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication). The mixture was reacted at 100°C to obtain a polymer. After washing with water, separation, and drying, the solvent was removed to obtain Polymer F.

[0121] The preparation method of polymer G (a type of solid electrolyte polymer belonging to ICNMCL) is as follows. [ka]

[0122] To a suitable organic solvent, acrylic acid alkyl ester, polyethylene glycol acrylate, ethylene glycol diacrylate, and AIBN (azobisisobutylcyanide) were added (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication). The mixture reacted with irradiation to obtain a polymer. After washing with water, separation, and drying, the solvent was removed to obtain polymer G.

[0123] The preparation method of polymer H (a type of solid electrolyte polymer belonging to ICNM) is as follows. [ka]

[0124] Acrylic acid alkyl ester, polyethylene glycol acrylate, and AIBN (azobisisobutylcyanide) were added to a suitable organic solvent (the mixture without the solvent may be used directly as an electrolyte precursor for device fabrication). The mixture reacted with irradiation to obtain a polymer. After washing with water, separation, and drying, the solvent was removed to obtain polymer H.

[0125] Example 1-1

[0126] This embodiment provides an electrochromic diaphragm that realizes multi-stage control by shading, and a manufacturing method thereof.

[0127] As shown in FIG. 1, the structure of the electrochromic aperture includes a first transparent base 11, a first transparent conductive layer 12, an ion storage layer 13, an ion transition layer 14, an electrochromic layer 15, a second transparent conductive layer 16, and a second transparent base 17, which are stacked in this order.

[0128] Among these, in the electrochromic layer 15 and the second transparent conductive layer 16, a plurality of annular grooves are etched, each centered on the central axis of the electrochromic diaphragm.

[0129] In this example, the electrochromic diaphragm is manufactured as follows.

[0130] (1) Fabrication of the electrochromic layer 15 500 mg of poly(3-hexylthiophene) (P3HT) was dissolved in 10 mL of o-xylene and stirred for 10 h using a magnetic stirrer. The resulting solution was then dropped onto an ITO layer (second transparent conductive layer 16) plated on a glass substrate (second transparent base 17). A P3HT coating was formed by spin coating. As shown in Figure 1, multiple circular grooves were laser-etched in the P3HT coating and the second transparent conductive layer, resulting in an electrochromic layer 15.

[0131] (2) Manufacturing the ion storage layer 13 500 mg of tungsten trioxide was dissolved in 20 mL of deionized water. After stirring and filtering, the resulting solution was dropped onto an ITO layer (first transparent conductive layer 12) plated on a glass substrate (first transparent base 11), and a tungsten trioxide coating was formed by spin coating to obtain an ion storage layer 13.

[0132] (3) Manufacturing of electrochromic apertures 10 wt% lithium perchlorate, 89.9 wt% precursor of polymer H, and 0.1 wt% perazobisisobutyronitrile were mixed and applied to the ion storage layer 13 to form an electrolyte coating. Then, the electrochromic layer 15 (together with the ITO layer and the glass substrate) was coated on the electrolyte coating, and the electrolyte coating was cured by UV light to form an all-solid polymer electrolyte layer (ionic transition layer 14), thereby obtaining an electrochromic aperture.

[0133] Example 1-2

[0134] This embodiment provides an electrochromic diaphragm that realizes multi-stage control by shading, and a manufacturing method thereof.

[0135] As shown in FIG. 2, the structure of the electrochromic aperture includes a first transparent base 21, a first transparent conductive layer 22, an ion storage layer 23, an ion transition layer 24, an electrochromic layer 25, a second transparent conductive layer 26, and a second transparent base 27, which are stacked in this order.

[0136] Among these, in the ion storage layer 23 and the first transparent conductive layer 22, a plurality of annular grooves are simultaneously etched, each centered on the central axis of the electrochromic diaphragm.

[0137] In this example, the manufacturing method of the electrochromic diaphragm is the same as that of Example 1-1, except that after the application of the ion storage layer 23 is completed, the ion storage layer 23 and the first transparent conductive layer 22 are laser etched.

[0138] Examples 1-3

[0139] This embodiment provides an electrochromic diaphragm that realizes multi-stage control by shading, and a manufacturing method thereof.

[0140] The structure of the electrochromic diaphragm includes a first transparent base 31, a first transparent conductive layer 32, an ion storage layer 33, an ion transition layer 34, an electrochromic layer 35, a second transparent conductive layer 36 and a second transparent base 37, which are stacked in this order as shown in FIG.

[0141] Among these, a plurality of annular grooves are etched in the second transparent base 37, the second transparent conductive layer 36 and the electrochromic layer 35, with the center being the central axis of the electrochromic diaphragm.

[0142] In this embodiment, the manufacturing method of the electrochromic diaphragm is the same as that in Example 1-1, except that in step (3), laser etching is performed after the ultraviolet curing of the ion transition layer is completed, and the etching is performed from the second transparent base 37 side, so that the annular groove is simultaneously etched in the three layers of the second transparent base 37, the second transparent conductive layer 36, and the electrochromic layer 35.

[0143] Examples 1-4

[0144] This embodiment provides an electrochromic diaphragm that realizes multi-stage control by shading, and a manufacturing method thereof.

[0145] As shown in FIG. 4, the structure of the electrochromic aperture includes a first transparent base 41, a first transparent conductive layer 42, an ion storage layer 43, an ion transition layer 44, an electrochromic layer 45, a second transparent conductive layer 46, and a second transparent base 47, which are stacked in order.

[0146] Among them, a plurality of annular grooves are etched in the first transparent base 41, the first transparent conductive layer 42 and the ion storage layer 43, each centered on the central axis of the electrochromic diaphragm.

[0147] In this embodiment, the manufacturing method of the electrochromic diaphragm is the same as that in Example 1-1, except that in step (3), laser etching is performed after the ultraviolet curing of the ion transition layer is completed, and the etching is performed from the first transparent base 41 side, so that the annular groove is simultaneously etched in the three layers of the first transparent base 41, the first transparent conductive layer 42, and the ion storage layer 43.

[0148] Examples 1-5

[0149] This embodiment provides an electrochromic diaphragm that realizes multi-stage control by shading, and a manufacturing method thereof.

[0150] As shown in FIG. 5, the structure of the electrochromic aperture includes a first transparent base 51, a first transparent conductive layer 52, an ion storage layer 53, an ion transition layer 54, an electrochromic layer 55, a second transparent conductive layer 56, and a second transparent base 57, which are stacked in order.

[0151] Among these, a plurality of annular grooves are etched in the second transparent base 57 and the second transparent conductive layer 56, with the center being the central axis of the electrochromic diaphragm.

[0152] In this embodiment, the manufacturing method of the electrochromic diaphragm is the same as that in Example 1-1, except that in step (3), laser etching is performed after the ultraviolet curing of the ion transition layer is completed, and the etching is performed from the second transparent base 57 side, and the annular groove is etched simultaneously in both the second transparent base 57 and the second transparent conductive layer 56.

[0153] The manufacturing method used in Examples 1-1 to 1-5 performs etching after the application of the ion storage layer and the electrochromic layer is completed, thereby ensuring that multi-stage adjustment of aperture can be achieved while effectively avoiding problems such as uneven discoloration caused by conventional etching methods.

[0154] Example 2

[0155] In this embodiment, a multi-stage electrochromic diaphragm is provided by stacking multiple electrochromic units. As shown in Figure 6, the electrochromic diaphragm is formed by stacking two independent electrochromic units, and includes a transparent base 61, a transparent conductive layer 61-1, an ion storage layer 61-2, an ion transition layer 61-3, an electrochromic layer 61-4, a transparent conductive layer 61-5, a transparent base 62, a transparent conductive layer 62-1, an ion storage layer 62-2, an ion transition layer 62-3, an electrochromic layer 62-4, a transparent conductive layer 62-5, and a transparent base 63.

[0156] The ion storage layers 61-2 and 62-2 and the electrochromic layers 61-4 and 62-4 have annular shapes centered on the central axis of the electrochromic aperture. The ion storage layer 61-2 and the electrochromic layer 61-4 have similar shapes and are aligned with each other. The ion storage layer 62-2 and the electrochromic layer 62-4 have similar shapes and are aligned with each other. The outer diameter of the electrochromic layer 61-4 is the same as the inner diameter of the electrochromic layer 62-4.

[0157] In this embodiment, the projection in the direction along the central axis of the electrochromic aperture of the electrochromic layer 61-4 and the electrochromic layer 62-4 is seamless and continuous, thereby realizing multi-stage adjustment of the aperture while avoiding the problems of light leakage or light imperfections caused by etching of the grooves.

[0158] In this embodiment, there are two methods for manufacturing the annular electrochromic layer and the annular ion storage layer: 1. First, a hollow annular shielding substrate is used to coat the transparent conductive layer, and then the electrochromic layer or ion storage layer is applied to the transparent conductive layer. After removing the shielding substrate, the annular electrochromic layer or ion storage layer is obtained. 2. The annular electrochromic layer and ion storage layer are obtained by laser etching, chemical etching, or physical wiping on the transparent conductive layer on which the electrochromic layer or ion storage layer has been applied.

[0159] The layering method for each layer is as follows: First, the corresponding transparent conductive layers are applied to the three transparent substrates, and then the annular electrochromic layer and annular ion storage layer are formed on the transparent conductive layers. Then, the ion transition layer material is applied, compounded, and then cured with UV light. The materials for each layer are the same as in Example 1.

[0160] Example 3-1

[0161] This embodiment provides an electrochromic aperture that can be adjusted in multiple stages by controlling the voltage at which the color begins to change. As shown in FIG. 7 , the aperture includes a first transparent base 71, a first transparent conductive layer 72, an ion storage layer 73, an ion transition layer 74 with a different cross-linking degree, an electrochromic layer 75, a second transparent conductive layer 76, and a second transparent base 77, which are stacked in this order.

[0162] The ionic transition layer 74 is divided into three circular or annular regions from the inside to the outside, each centered on the central axis of the electrochromic aperture, and the degree of cross-linking of the ionic transition layer 74 gradually increases from the inside to the outside.

[0163] The specific method is as follows: Before UV curing of the ionic transition layer, different areas are shielded with materials with different UV transmittances, so that the cross-linking degree of the material in the ionic transition layer in different areas is different, resulting in different brightening or darkening voltages in different layers. The specific steps are as follows:

[0164] (1) Fabrication of the electrochromic layer 75 500 mg of poly(3-hexylthiophene) (P3HT) was dissolved in 10 mL of o-xylene and stirred for 10 h using a magnetic stirrer. The resulting solution was then added dropwise to an ITO layer (second transparent conductive layer 76) plated on a glass substrate (second transparent base 77). A P3HT coating was formed by spin coating to obtain an electrochromic layer.

[0165] (2) Fabrication of the ion storage layer 73 500 mg of tungsten trioxide was dissolved in 20 mL of deionized water, stirred, and filtered. The resulting solution was then dropped onto an ITO layer (first transparent conductive layer 72) plated on a glass substrate (first transparent base 71). A tungsten trioxide coating was formed by spin coating to obtain an ion storage layer 73.

[0166] (3) Manufacturing of electrochromic apertures A mixture of 10 wt% lithium bistrifluoromethanesulfonimide, 89.9 wt% polymer G precursor, and 0.1 wt% perazobisisobutyronitrile was applied to the ion storage layer to form an electrolyte coating. The electrochromic layer 75 (together with the ITO layer and glass substrate) was then coated onto the electrolyte coating. On the outside of the transparent base, the outermost ring of the ion transition layer 74 was covered and shielded with a surface-coated PET film with a UV transmittance of 10% that matched the shape of the outermost ring. The middle ring of the ion transition layer 74 was covered and shielded with a surface-coated PET film with a UV transmittance of 50% that matched the shape of the middle ring. The innermost ring of the ion transition layer 74 was covered and shielded with a PET film with a UV transmittance of 90% that matched the shape of the innermost ring. After heat curing, an electrochromic aperture was obtained.

[0167] The degree of cross-linking of the ionic transition layer material gradually increases from the inside to the outside, and the voltage at which brightness begins to increase gradually from the inside to the outside, so when a forward voltage is applied, the inner periphery of the aperture becomes brighter than the outer periphery. The aperture regions are continuous from the inside to the outside, allowing for multi-stage aperture adjustment while avoiding the problems of light leakage or light imperfections caused by etching the grooves.

[0168] Example 3-2

[0169] This embodiment provides an electrochromic diaphragm that can achieve multi-stage adjustment by controlling the voltage at which the color starts to change. As shown in FIG. 8 , the electrochromic diaphragm includes a first transparent base 81, a first transparent conductive layer 82, an ion storage layer 83, an ion transition layer 84, an electrochromic layer 85, a second transparent conductive layer 86, and a second transparent base 87, which are stacked in this order.

[0170] The electrochromic layer 85 is divided from the inside to the outside into three circular or annular regions centered on the central axis of the electrochromic aperture, and each region contains a different electrochromic material. From the inside to the outside, the voltage at which the electrochromic material begins to brighten gradually increases, and the voltage at which it begins to darken gradually decreases.

[0171] A specific method for achieving this is as follows: By applying electrochromic materials with different brightening and darkening voltages, such as WO3, polydecyl viologen and its derivatives, polyaniline and its derivatives, poly(3-hexylthiophene) and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, and polythieno[3,4-b][1,4]dioxaheptane and its derivatives, to the transparent conductive layer, different brightening and darkening voltages are achieved for different layers. The specific steps are as follows:

[0172] (1) Fabrication of the electrochromic layer 85 500 mg of poly(3,4-ethylenedioxythiophene) with ethylhexyl alkyl side chains was dissolved in 10 mL of chloroform and stirred for 10 h using a magnetic stirrer. 500 mg of polythieno[3,4-b][1,4]dioxaheptane with ethylhexyl alkyl side chains was dissolved in chlorobenzene and stirred for 10 h using a magnetic stirrer. 500 mg of poly(3-hexylthiophene) (P3HT) was dissolved in 10 mL of o-xylene and stirred for 10 h using a magnetic stirrer. A solution of poly(3,4-ethylenedioxythiophene) was inkjet printed onto an ITO layer (second transparent conductive layer 86) plated on a glass substrate (second transparent base 87) to form the innermost poly(3,4-ethylenedioxythiophene) coating. A solution of polythieno[3,4-b][1,4]dioxaheptane was inkjet printed onto the ITO layer (second transparent conductive layer 86) plated on the glass substrate (second transparent base 87) to form a second polythieno[3,4-b][1,4]dioxaheptane coating. A solution of poly(3-hexylthiophene) was inkjet printed onto the ITO layer (second transparent conductive layer 86) plated on the glass substrate (second transparent base 87) to form an outermost poly(3-hexylthiophene) coating, completing the fabrication of the electrochromic layer 85.

[0173] (2) Manufacturing of the ion storage layer 83 500 mg of tungsten trioxide was dissolved in 20 mL of deionized water, stirred, and filtered. The resulting solution was then dropped onto an ITO layer (first transparent conductive layer 82) plated on a glass substrate (first transparent base 81). A tungsten trioxide coating was formed by spin coating to obtain an ion storage layer 83.

[0174] (3) Manufacturing of electrochromic apertures 10 wt% lithium perchlorate, 79.9 wt% precursor of polymer G, and 0.1 wt% perazobisisobutyronitrile were mixed and applied to the ion storage layer to form an electrolyte coating. Then, the electrochromic layer 85 (together with the ITO layer and the glass substrate) was coated on the electrolyte coating, and after heat curing at 80°C, an electrochromic aperture was obtained.

[0175] The three-layer material of the electrochromic layer 85 has a gradually increasing voltage from the inside to the outside when the light begins to brighten, and a gradually increasing voltage when the light begins to darken. When a forward voltage is applied, the inner periphery of the iris becomes brighter than the outer periphery. Because each region of the iris is continuous from the inside to the outside, the iris can be brightened in multiple stages while avoiding the problems of light leakage or opacity caused by etching the grooves. When the light begins to darken, the three layers can be simultaneously restored to the dark state by simply shorting the two transparent conductive layers or applying a reverse voltage with an absolute value of less than 2V, thereby satisfying the needs of the iris without the need for multiple stages of darkening.

[0176] Example 4

[0177] This embodiment provides a method for the electrochromic iris to provide multi-stage adjustment to the electrochromic iris.

[0178] The electrochromic aperture includes a first transparent substrate, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer and a second transparent substrate stacked in order.

[0179] The electrochromic diaphragm is made of the same material from the inside to the outside, and has no grooves.

[0180] The method of multi-stage adjustment is as follows: By using the electrochromic diaphragm according to this embodiment and applying different voltages to its center and edge, the voltage at the center is greater than the voltage at the edge, thereby realizing multi-stage adjustment.

[0181] FIG. 9 is a schematic diagram of the multi-stage adjustment method for the electrochromic diaphragm in this embodiment (the electrochromic layer is located on top and the ion storage layer is located on the bottom). As shown in FIG. 9, the voltage at the center is +2V and the voltage at the edge is -2V. Under the action of these voltages, the voltage from the center to the edge changes spontaneously and gradually, forming a distribution in which the voltage gradually decreases from the inside to the outside. By changing the voltage at the center and the edge, it is possible to control the change in the transmittance of the diaphragm. Because the diaphragm is continuous from the inside to the outside, it is possible to achieve multi-stage adjustment of the diaphragm while avoiding the problems of light leakage or light imperfections caused by etching the grooves.

[0182] Example 5-1

[0183] This embodiment provides an electrochromic aperture control device that achieves multi-stage adjustment by using electrochromic layers with varying thicknesses. As shown in FIG. 10, the electrochromic aperture control device includes a first transparent substrate 101, a first transparent conductive layer 102, an ion storage layer 103, an ion transition layer 104, an electrochromic layer 105, a second transparent conductive layer 106, and a second transparent substrate 107, which are stacked in this order.

[0184] Among them, a plurality of annular grooves centered on the central axis of the electrochromic aperture are etched in the second transparent conductive layer 106. The thicknesses of the electrochromic layer 105 and the ion storage layer 103 gradually increase from the inside to the outside (the ratio of the edge thickness to the center thickness is 1.1:1).

[0185] The electrochromic diaphragm of this embodiment has a gradually increasing thickness of the electrochromic layer from the inside to the outside, so that the diaphragm has different color change ranges from the inside to the outside. Compared to an diaphragm in which the thickness of the electrochromic layer remains constant from the inside to the outside, the electrochromic diaphragm of this embodiment can achieve a larger number of different stages of diaphragm adjustment, and can meet the needs of various shooting scenes.

[0186] Manufacturing method:

[0187] The differences from Example 1-1 are as follows: After the application of the electrochromic layer is completed, the electrochromic layer is laser-etched, so that its thickness gradually increases from the inside to the outside. Then, multiple annular grooves centered on the central axis of the electrochromic aperture are etched in the second transparent conductive layer. After the application of the ion storage layer is completed, the ion storage layer is laser-etched (the thickness of the ion transition layer is on the order of microns, and the thickness changes of the electrochromic layer and the ion storage layer are on the order of nanometers, so the actual thickness changes of the ion transition layer are negligible), so that its thickness gradually increases from the inside to the outside.

[0188] Example 5-2

[0189] This embodiment provides an electrochromic aperture that achieves multi-stage adjustment by using electrochromic layers with varying thicknesses, and includes, as shown in FIG. 11 , a first transparent base 111, a first transparent conductive layer 112, an ion storage layer 113, an ion transition layer 114, an electrochromic layer 115, a second transparent conductive layer 116, and a second transparent base 117, which are stacked in sequence.

[0190] Among them, a plurality of annular grooves centered on the central axis of the electrochromic aperture are etched in the second transparent conductive layer 116. The thickness of the electrochromic layer 115 gradually increases from the center to the outside (the ratio of edge to center thickness is 1.1:1).

[0191] The electrochromic diaphragm of this embodiment has a gradually increasing thickness of the electrochromic layer from the inside to the outside, so that the diaphragm has different color change ranges from the inside to the outside. Compared to an diaphragm in which the thickness of the electrochromic layer remains constant from the inside to the outside, the electrochromic diaphragm of this embodiment can achieve a larger number of different stages of diaphragm adjustment, and can meet the needs of various shooting scenes.

[0192] Manufacturing method:

[0193] The differences from Example 1-1 are as follows: After the application of the electrochromic layer is completed, the electrochromic layer is laser-etched, so that its thickness gradually increases from the center to the outside. Then, multiple annular grooves centered on the central axis of the electrochromic aperture are etched in the second transparent conductive layer. (Since the thickness of the ion transition layer is on the order of microns and the change in thickness of the electrochromic layer is on the order of nanometers, the actual change in thickness of the ion transition layer does not need to be taken into account.)

[0194] Example 6-1

[0195] This embodiment provides a curved electrochromic iris and iris lens combination.

[0196] As shown in FIG. 12, the structure of the curved electrochromic aperture includes a first transparent substrate 121, a first transparent conductive layer 122, an ion storage layer 123, an ion transition layer 124, an electrochromic layer 125, a second transparent conductive layer 126 and a second transparent substrate 127, which are stacked in order.

[0197] The curvature of the electrochromic diaphragm is similar to that of the surface of a convex lens in an achromatic lens combination. A plurality of annular grooves are etched into the second transparent conductive layer 126, each centered on the central axis of the electrochromic diaphragm. The thickness of the electrochromic layer 125 gradually increases from the center to the outside.

[0198] 13, the structure of the aperture lens combination includes an achromatic lens combination and a curved electrochromic aperture 132 according to this embodiment. The achromatic lens combination includes a convex lens 131 and a concave lens 133, and the curved electrochromic aperture 132 is attached to the surface of the convex lens 131 by an optical adhesive such as OCA or LOCA.

[0199] In this embodiment, the curved electrochromic diaphragm is manufactured as follows.

[0200] (1) Fabrication of the electrochromic layer 125 500 mg of poly(3-dodecyl)thiophene (PDT) was dissolved in 10 mL of o-xylene and stirred for 10 hours using a magnetic stirrer. The resulting solution was then added dropwise to an ITO layer (second transparent conductive layer 126) plated on a PET substrate (second transparent substrate 127). A PDT coating (electrochromic layer 125) was formed by spin coating. The electrochromic layer 125 was then etched with a laser, forming a structure in which the etching depth gradually decreased from the center to the outside and the thickness gradually increased from the center to the outside. Nine circular grooves centered on the central axis of the electrochromic aperture were then laser-etched in the electrochromic layer 125 and second transparent conductive layer 126.

[0201] (2) Fabrication of the ion storage layer 123 500 mg of tungsten trioxide was dissolved in 20 mL of deionized water, stirred, and filtered. The resulting solution was then added dropwise to an ITO layer (first transparent conductive layer 122) plated on a PET (first transparent base 121). A tungsten trioxide coating, the ion storage layer 123, was formed by spin coating.

[0202] (3) Manufacturing of electrochromic apertures 5 wt% lithium perchlorate, 94.9 wt% polymer G, and 0.1 wt% tert-butyl peroxyneodecanoate were mixed and applied to the ion storage layer 13 to form an electrolyte coating. Then, the electrochromic layer 125 (together with the ITO layer and glass substrate) was coated on the electrolyte coating, and the electrolyte coating was cured with UV light to form an all-solid polymer electrolyte (ionic transition layer 124), resulting in an electrochromic aperture.

[0203] (4) Manufacturing of curved electrochromic apertures After one layer of OCA was attached to the surface of the convex lens, the electrochromic diaphragm was attached and fixed to the OCA to obtain a curved electrochromic diaphragm.

[0204] The electrochromic diaphragm according to this embodiment is characterized by being flexible and bendable, and can therefore be designed as a curved structure with a curvature similar to that of a convex lens in an achromatic lens combination, thereby enabling the diaphragm and lens to be combined in the lens module, thereby making the lens module thinner.

[0205] Example 6-2

[0206] This embodiment provides a curved electrochromic iris and iris lens combination.

[0207] The curved electrochromic diaphragm is the same as that of Example 6-1, except that its curvature is the same as that of the surface of the concave lens in the achromatic lens combination. The manufacturing method is the same as that of Example 6-1, except that in step (4), the electrochromic diaphragm is attached to the surface of the concave lens with the OCA to obtain the curved electrochromic diaphragm.

[0208] 14, the structure of the aperture lens assembly includes an achromatic lens assembly and a curved electrochromic aperture 142 according to this embodiment. The achromatic lens assembly includes a convex lens 141 and a concave lens 143. The curved electrochromic aperture 142 is attached to the surface of the concave lens 143 with an OCA optical adhesive.

[0209] The electrochromic diaphragm according to this embodiment is characterized by being flexible and bendable, and can therefore be designed as a curved structure with a curvature similar to that of a convex lens in an achromatic lens combination, thereby enabling the diaphragm and lens to be combined in the lens module, thereby making the lens module thinner.

[0210] Example 6-3

[0211] This embodiment provides a curved electrochromic iris and iris lens combination.

[0212] Among them, the curved electrochromic diaphragm is the same as that in Example 6-1, except that its shape is the same as that of the concave lens in the achromatic lens combination.

[0213] 15, the structure of the diaphragm lens combination includes a combination of achromatic convex lens 151 and concave lens 152, and a holder 153, with concave lens 152 being interposed in holder 153. Concave lens 152 is the curved electrochromic diaphragm according to this embodiment.

[0214] The electrochromic diaphragm according to this embodiment is flexible and bendable, and can be designed to have a shape similar to that of a concave lens in an achromatic lens combination, thereby replacing the concave lens in an achromatic lens combination. This allows the diaphragm and lens in the lens module to be combined, thereby making the lens module thinner.

[0215] Example 6-4

[0216] This embodiment provides a curved electrochromic iris and iris lens combination.

[0217] Among them, the curved electrochromic diaphragm is the same as that in Example 6-1, except that its shape is the same as that of the convex lens in the achromatic lens combination.

[0218] 15, the structure of the diaphragm lens combination includes a combination of achromatic convex lens 162 and concave lens 163, and a holder 161, with the convex lens 162 sandwiched between the holders 161. The convex lens 162 is a curved electrochromic diaphragm according to this embodiment.

[0219] The electrochromic diaphragm according to this embodiment is characterized by being flexible and bendable, and can be designed to have a shape similar to that of a convex lens in an achromatic lens combination, thereby replacing the convex lens in an achromatic lens combination, thereby realizing the integration of the diaphragm and lens in the lens module and making the lens module thinner.

[0220] It should be noted that the voltage drivers in the drawings of this application are used to provide a driving voltage and are merely for the purpose of easily explaining the operating principle of the electrochromic diaphragm, and should not be understood as being a constituent part of the electrochromic diaphragm.

[0221] The applicant declares that the above is only a specific embodiment of the present application, and the scope of protection of the present application is not limited thereto. It should be understood that any changes or substitutions that can be easily made by those skilled in the art within the technical scope disclosed in the present application are all included in the scope of protection and disclosure of the present application. [Explanation of symbols]

[0222] 11...first transparent base, 12...first transparent conductive layer, 13...ion storage layer, 14...ion transition layer, 15...electrochromic layer, 16...second transparent conductive layer, 17...second transparent base, 21...first transparent base, 22...first transparent conductive layer, 23...ion storage layer, 24...ion transition layer, 25...electrochromic layer, 26...second transparent conductive layer, 27...second transparent base, 31...first transparent base, 32...first transparent conductive layer, 33...ion storage layer, 34...ion transition layer, 35...electrochromic layer, 36...second transparent conductive layer, 37...second transparent base , 41...first transparent base, 42...first transparent conductive layer, 43...ion storage layer, 44...ion transition layer, 45...electrochromic layer, 46...second transparent conductive layer, 47...second transparent base, 51...first transparent base, 52...first transparent conductive layer, 53...ion storage layer, 54...ion transition layer, 55...electrochromic layer, 56...second transparent conductive layer, 57...second transparent base, 61, 62, 63...transparent base, 61-1, 61-5, 62-1, 62-5...transparent conductive layer, 61-2, 62-2...ion storage layer, 61-3, 62-3...ion transition layer, 61-4,62-4...electrochromic layer, 71...first transparent base, 72...first transparent conductive layer, 73...ion storage layer, 74...ion transition layer, 75...electrochromic layer, 76...second transparent conductive layer, 77...second transparent base, 81...first transparent base, 82...first transparent conductive layer, 83...ion storage layer, 84...ion transition layer, 85...electrochromic layer, 86...second transparent conductive layer, 87...second transparent base, 101...first transparent base, 102...first transparent conductive layer, 103...ion storage layer, 104...ion transition layer, 105...electrochromic layer, 106...second transparent conductive layer, 107...second transparent base, 111...first transparent base, 112...first transparent conductive layer, 113...ion storage layer, 114...ion transition layer, 115...electrochromic layer, 116...second transparent conductive layer, 117...second transparent base, 121...first transparent base, 122...first transparent conductive layer, 123...ion storage layer, 124...ion transition layer, 125...electrochromic layer, 126...second transparent conductive layer, 127...second transparent base, 131...convex lens, 132...curved electrochromic diaphragm according to Example 6-1, 133...concave lens, 141...convex lens, 142...curved electrochromic diaphragm according to Example 6-2, 143...concave lens, 151...convex lens, 152...curved electrochromic diaphragm according to Example 6-3, 153...holder, 161...holder, 162...curved electrochromic diaphragm according to Example 6-4, 163...concave lens,

Claims

1. An electrochromic diaphragm including, in order, a first transparent base, a first transparent conductive layer, an ion storage layer, an ion transition layer, an electrochromic layer, a second transparent conductive layer, and a second transparent base, the ionic transition layer is a solid electrolyte layer; The electrochromic aperture has a voltage that gradually increases from the inside to the outside when it starts to lighten, or a voltage that gradually decreases from the inside to the outside when it starts to darken, the ionic transition layer has a degree of cross-linking that gradually increases from the inside to the outside, or The electrochromic layer is an electrochromic aperture in which the voltage gradually increases as the electrochromic material begins to lighten or gradually decreases as the electrochromic material begins to darken from the inside to the outside.

2. the thickness of the electrochromic layer gradually increases from the inside to the outside, or 10. The electrochromic diaphragm of claim 1, wherein the thickness of the electrochromic layer and the ion storage layer gradually increases from the inside to the outside.

3. the thickness of the ion storage layer is between 1 and 10,000 nm; and / or the thickness of the ionic transition layer is 0.1 to 200 μm; and / or the thickness of the electrochromic layer is between 1 and 10,000 nm; and / or 3. The electrochromic diaphragm according to claim 1, wherein the total thickness of the electrochromic diaphragm is 5 mm or less.

4. A combination of a concave lens and a convex lens for achromatization, and the electrochromic diaphragm according to any one of claims 1 to 3 attached to the surface of the concave lens or the convex lens. Or, An aperture lens combination comprising a combination of an achromatic concave lens and a convex lens, wherein the concave lens or the convex lens is the electrochromic aperture according to any one of claims 1 to 3.

5. 5. The aperture lens combination according to claim 4, wherein the electrochromic aperture has a curved surface structure, and the curvature is the same as the curvature of the surface of the concave lens or the convex lens, or the shape of the electrochromic aperture is the same as the shape of the concave lens or the convex lens.

6. an achromatic lens combination, the electrochromic diaphragm according to any one of claims 1 to 3, an exposure controller, an image sensor, a pulse voltage controller, a light intensity sensor, a photosensitive element, a wiring substrate, and a chip; the centers of the achromatic lens combination, the electrochromic diaphragm, the exposure controller and the image sensor are located on the same optical axis; Or, 6. An optical system including the aperture lens combination according to claim 4 or 5, an exposure controller, an image sensor, a pulse voltage controller, a light intensity sensor, a photosensitive element, a wiring board, and a chip; a lens module, wherein the centers of the iris lens combination, the electrochromic iris, the exposure controller and the image sensor are located on the same optical axis;

Images