Light-transmitting metal material and preparation method and application thereof

Abstract

The invention discloses a light-transmitting metal material and a preparation method and application thereof. The light-transmitting metal material comprises a first metal and a second metal, the first metal comprises at least one of Pt, Pd, Ir or Ru, and the second metal comprises silver. The second metal layer is prepared on the surface of the first metal layer through the atomic layer deposition technology, layered growth of the silver material can be achieved to form the second metal layer, the thickness of the film layer is accurately controlled, the second metal layer has high continuity under the ultra-low thickness, and the light transmittance performance of the obtained material is good.

Description

Technical Field

[0001] The present invention belongs to the technical field of conductive materials, and in particular relates to a light-transmitting metal material and a preparation method and application thereof. Background Art

[0002] Ag is one of the metals with high conductivity, and its reflectivity in the visible spectrum is as high as over 91%, which makes the application prospects of nano-Ag film in the field of optoelectronic devices broad. For example, Ag film can be used in anti-reflection film; in addition, it can also be used in flexible electronic devices as a transparent conductive layer. However, in order to achieve the above performance requirements, the thickness of the nano-Ag film usually needs to be reduced to less than 10nm to meet the light transmission requirements.

[0003] The traditional coating technology for nano-Ag film is physical vapor deposition (PVD). The film formation method of PVD is nucleation growth. It is usually difficult to form a continuous Ag film within an ultra-thin thickness range (such as below 10nm). Usually, only island-shaped discontinuous Ag particles can be formed, and the performance is poor. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a light-transmitting metal material, the second metal layer contained in the material has good continuity and good performance.

[0005] The present invention also proposes the application of the light-transmitting metal material.

[0006] The invention also provides a photoelectric device.

[0007] The invention also provides a flexible electronic device.

[0008] According to a first aspect of the present invention, a light-transmitting metal material is provided, comprising a first metal and a second metal, wherein the first metal comprises at least one of Pt, Pd, Ir or Ru, and the second metal comprises silver.

[0009] The light-transmitting metal material according to the embodiment of the present invention has at least the following beneficial effects: In the present invention, since the electronic configuration structures of the first metal and the second metal are similar and the properties are similar, the interface energy between the first metal and the second metal is low, thereby improving the wetting of the second metal on the surface, increasing the nucleation rate of silver, and enabling the formation of a silver layer with good continuity, thereby achieving both good electrical conductivity and light transmittance.

[0010] In some embodiments of the present invention, the light-transmitting metal material includes a first metal layer and a second metal layer arranged in sequence, the first metal layer includes at least one of Pt, Pd, Ir or Ru, and the second metal layer includes silver.

[0011] In some embodiments of the present invention, the light-transmitting metal material includes a mixed layer of a first metal and a second metal.

[0012] In some embodiments of the present invention, the light-transmitting metal material is prepared by atomic layer deposition technology.

[0013] In some embodiments of the present invention, the first metal layer and the second metal layer are prepared by atomic layer deposition technology.

[0014] In some embodiments of the present invention, the mixed layer is prepared by atomic layer deposition technology.

[0015] Atomic layer deposition technology is a method of forming a thin film by alternately introducing gas-phase precursors and reactants into the reaction chamber and performing surface chemical reactions on the substrate. By alternately saturating the precursors with self-limiting reactions, a thin film with highly controllable thickness, composition, morphology, and structure at the nanoscale can be obtained.

[0016] In the present invention, since the metal in the first metal layer has a similar electron arrangement structure and similar properties to metallic silver, the second metal layer is prepared on the surface of the first metal layer by atomic layer deposition technology. The metal-metal interface energy is low (much lower than the metal oxide-metal interface energy, for example). Using a metal primer can further improve the wetting of the second metal layer on the surface, increase the nucleation rate of silver, and thus improve the continuity of the second metal layer. Therefore, not only can the layered growth of the silver material be realized to form the second metal layer and the film thickness be precisely controlled, but also the second metal layer can have high continuity at an ultra-low thickness (such as a thickness < 5 nm). The second metal layer is composed of multiple atomic layers stacked, forming a dense structure with continuous coverage between layers. For example, a 1-2 nm ultra-thin second metal layer can be uniformly deposited, and the resulting material has good electrical conductivity and good light transmittance.

[0017] In some embodiments of the present invention, the surface roughness of the second metal layer is < 1 nm, and the light transmittance of the material is > 98% at a thickness < 4 nm.

[0018] In some embodiments of the present invention, the second metal layer is formed on the surface of the first metal layer by atomic layer deposition technology.

[0019] In some embodiments of the present invention, the thickness of the first metal layer is 20 nm or less, and can be selected to be 5 nm or less, for example.

[0020] In some embodiments of the present invention, the thickness of the first metal layer is 1 - 5 nm.

[0021] In some embodiments of the present invention, the thickness of the second metal layer is 20 nm or less, and can be selected to be 5 nm or less, for example.

[0022] In some embodiments of the present invention, the thickness of the second metal layer is 1 to 5 nm.

[0023] In some embodiments of the present invention, the raw materials for preparing the second metal layer include precursor I and reactant I.

[0024] In some embodiments of the present invention, the precursor I includes at least one of Ag(piv)PEt3, Ag(piv)PBu3, Ag(fod)PEt3, or Ag(hfac)COD.

[0025] In some embodiments of the present invention, the reactant I includes at least one of H2O, O2, O3, NH3, H2, NH3 plasma, H2 plasma, or O2 plasma.

[0026] In some embodiments of the present invention, the conductivity of the film layer formed by the first metal layer and the second metal layer is 20 μΩ·cm or less, and may be optionally 10 μΩ·cm.

[0027] In some embodiments of the present invention, the light transmittance of the film layer formed by the first metal layer and the second metal layer is 95% or more.

[0028] In some embodiments of the present invention, one or more first metal layers may be provided, such as one, two, three, four, five, etc.

[0029] In some embodiments of the present invention, the first metal layer includes at least one of a Pt layer, a Pd layer, an Ir layer, or a Ru layer.

[0030] In some embodiments of the present invention, the first metal layer is prepared by atomic layer deposition technology.

[0031] In some embodiments of the present invention, the raw materials for preparing the first metal layer include precursor II and reactant II.

[0032] In some embodiments of the present invention, the precursor II includes at least one of RuCp2, Ru(EtCp)2, (EtCp)Ru(MeCp), Ru(tBu-Me-amd)2(CO)2, Ru(DMPD)2, Ru(DMBD)CO3, Ir(acac)3, (MeCp)Ir(CHD), (EtCp)Ir(COD), MeCpPtMe3, Pt(acac)2, Pd(hfac)2, or Pd(thd)2.

[0033] In some embodiments of the present invention, the reactant II includes at least one of H2O, O2, O3, NH3, H2, NH3 plasma, H2 plasma, or O2 plasma.

[0034] In some embodiments of the present invention, the light-transmitting metal material further includes a base layer, and the first metal layer is disposed on the surface of the base layer.

[0035] The material of the base layer is not limited, and may be selected from transparent polymer materials, glass, etc. In some embodiments of the present invention, the base layer includes at least one of PET and glass. In the present invention, the first metal layer can enhance the adhesion on the surface of the substrate (such as polymer or glass), and is beneficial to the infiltration of the Ag film to form a continuous film.

[0036] In some embodiments of the present invention, the thickness of the base layer is not limited, and may be selected, for example, from 2 μm to 3 mm.

[0037] In some embodiments of the present invention, the base layer includes glass, and the thickness of the glass may be selected from 0.2 to 3 mm.

[0038] In some embodiments of the present invention, the base layer includes a transparent polymer material, and the thickness of the transparent polymer material may be selected from 2 to 200 μm. Optionally, the transparent polymer material may be selected as PET or the like.

[0039] In a second aspect of the present invention, a preparation material for a light-transmitting metal material is provided, including the following steps: a second metal layer is prepared on the surface of the first metal layer by atomic layer deposition technology to obtain the light-transmitting metal material.

[0040] In some embodiments of the present invention, the preparation method includes the following steps: S1, preparing a first metal layer on the surface of the substrate layer; S2, preparing a second metal layer on the surface of the first metal layer by atomic layer deposition technology to obtain the light-transmitting metal material.

[0041] In some embodiments of the present invention, in step S1, the first metal layer is prepared on the surface of the substrate layer by physical vapor deposition technology, chemical vapor deposition technology or atomic layer deposition technology.

[0042] In some embodiments of the present invention, in step S1, the deposition temperature of atomic layer deposition is 50 - 250 °C, and may be selected, for example, from 100 - 200 °C.

[0043] In some embodiments of the present invention, step S1 specifically includes the following operations: S1-1, activating the substrate layer by using plasma in the chamber of the atomic layer deposition system; S1-2, at 25 - 400 °C, introducing precursor II, and then introducing reactant II to form a first metal layer on the surface of the substrate layer.

[0044] In some embodiments of the present invention, in step S1-1, the plasma includes at least one of oxygen plasma or ozone plasma.

[0045] In some embodiments of the present invention, step S1-2 specifically includes the following operations: S1-2-1, within 100 - 200 °C, pulse precursor II into the chamber of the atomic layer deposition system, and introduce N2 for purging; S1-2-2, pulse reactant II into the chamber of the atomic layer deposition system, and introduce N2 for purging; S1-2-3, repeat steps S1-2-1 and S1-2-2 for m times to form a first metal layer on the surface of the substrate layer.

[0046] In some embodiments of the present invention, in step S1-2-3, m is an integer, and 0 < m < 200.

[0047] In some embodiments of the present invention, in step S2, the deposition temperature of atomic layer deposition is 50 - 250 °C, and can be optionally 100 - 200 °C.

[0048] In some embodiments of the present invention, step S2 includes: at 25 - 400 °C, introduce precursor I into the chamber of the atomic layer deposition system, and then introduce reactant I to form a second metal layer on the surface of the first metal layer.

[0049] In some embodiments of the present invention, step S2 specifically includes the following operations: S2-1, within 100 - 200 °C, pulse precursor I into the chamber of the atomic layer deposition system, and introduce N2 for purging; S2-2, pulse reactant I into the chamber of the atomic layer deposition system, and introduce N2 for purging; S2-3, repeat steps S2-1 and S2-2 for n times to form a second metal layer on the surface of the first metal layer.

[0050] In some embodiments of the present invention, in step S2-3, n is an integer, and 1000 ≥ n ≥ 0.

[0051] In a third aspect of the present invention, an ultra-low reflection and anti-reflection film is proposed, which includes the above-mentioned light-transmitting metal material. Specifically, the ultra-low reflection and anti-reflection film in the present invention can be used for an anti-reflection film lens to achieve an ultra-low reflectivity (<0.1%) and eliminate ghost images and glare of the lens. In some embodiments of the present invention, the ultra-low reflection and anti-reflection film further includes an anti-reflection film base layer.

[0052] In some embodiments of the present invention, the anti-reflection film base layer includes TiO2 and SiO2.

[0053] In some embodiments of the present invention, the ultra-low reflection and anti-reflection film includes an anti-reflection film base layer, a first metal layer, and a second metal layer arranged in sequence.

[0054] Through the above embodiments, the ultra-low reflection and anti-reflection film has excellent anti-reflection effect, achieving an ultra-low reflection effect with a reflectivity of <0.1% within the visible light range of 380 - 780 nm.

[0055] In a fourth aspect of the present invention, there is provided an application of the above-mentioned light-transmitting metal material or the above-mentioned ultra-low reflection and anti-reflection film in optical devices, optoelectronic devices, or flexible electronic devices.

[0056] In some embodiments of the present invention, the optical device includes the ultra-low reflection and anti-reflection film.

[0057] In some embodiments of the present invention, the optical device includes a lens, such as a lens applied to mobile phones, cameras, security monitoring, vehicles (such as cars), etc.

[0058] In a fifth aspect of the present invention, there is provided an optoelectronic device including the above-mentioned light-transmitting metal material.

[0059] In a sixth aspect of the present invention, there is provided a flexible electronic device including the above-mentioned light-transmitting metal material. The light-transmitting metal material can achieve conductivity without affecting light transmission, improving the performance of the flexible electronic device.

[0060] In some embodiments of the present invention, the flexible electronic device includes a flexible display device and a flexible support device, such as a charging mobile phone case, a flexible display screen, etc.

[0061] In some embodiments of the present invention, the flexible electronic device includes an overheat protection element, and the overheat protection element includes the above-mentioned light-transmitting metal material. Description of the Drawings

[0062] Figure 1 It is the test result of the reflectivity of incident light with different wavelengths in the embodiments of the present application. Among them, 1 - 6 are respectively 6 repetitions of Example 3. Detailed Embodiments

[0063] The following will clearly and completely describe the concept and technical effects generated by the present invention in combination with the embodiments, so as to fully understand the purpose, features, and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0064] For the experimental methods without specific conditions in the following examples and comparative examples, they are generally carried out under the conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as the conventional market.

[0065] Example 1 This example discloses a light-transmitting metal material, and its preparation process specifically includes: (Ⅰ)Place the PET polymer film on the sample stage in the chamber (reaction chamber) of the atomic layer deposition system (Exploiter 200SP), set the atomic layer deposition temperature at 115 °C, the Ag precursor at 80 °C, the Ru precursor at 60 °C, and preheat for 60 min.

[0066] (Ⅱ)Preparation of the Ru layer: (a)Use Ru (DMPD)2 as the gas-phase precursor (Ru precursor), with nitrogen as the carrier gas, controlled by the ALD valve, and enter the reaction chamber in a pulsed form. The valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 3 s. A gas-solid chemical reaction occurs on the surface of the exposed PET polymer film substrate (with a thickness of about 150 μm), so that the Ru precursor is adsorbed on the substrate surface.

[0067] (b)Purge the reaction chamber with 3000 sccm of N2 gas for 30 s to remove the excess precursor vapor and reaction by-products from the reaction chamber.

[0068] (c)Introduce water vapor into the chamber in a pulsed form, the valve is opened for 1 s, and it stays in the reaction chamber to continue reacting with the Ru precursor adsorbed on the surface of the PET polymer film.

[0069] (d)Purge with 3000 sccm of N2 gas for 60 s to remove the excess water vapor and reaction by-products from the reaction chamber.

[0070] After steps (a) to (d) are cycled 100 times, a 1-nm-thick Ru layer is formed on the surface of the PET polymer film.

[0071] (Ⅲ)Preparation of the Ag layer: (e)Use Ag(piv)PEt3 as the gas-phase precursor (Ag precursor), with nitrogen as the carrier gas, controlled by the ALD valve, and enter the reaction chamber in a pulsed form. The valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 5 s. A gas-solid chemical reaction occurs on the surface of the exposed Ru layer, so that the Ag precursor is adsorbed on the Ru layer surface.

[0072] (f)Purge the reaction chamber with 3000 sccm of N2 gas for 30 s to remove the excess precursor vapor and reaction by-products from the reaction chamber.

[0073] (g) Introduce NH3 plasma and continuously introduce it for 5 s to continue reacting with the Ag precursor adsorbed on the surface of the Ru layer.

[0074] (k) Purge with 3000 sccm of N2 gas for 10 s to remove the excess NH3 and reaction by-products from the reaction chamber.

[0075] After steps (e) to (k) are cycled 500 times, a 4-nm-thick Ag layer is formed on the surface of the Ru layer to obtain a light-transmitting metal material. Among them, the surface roughness of the Ag layer is <1 nm.

[0076] This embodiment also discloses an optoelectronic device, including the light-transmitting metal material prepared in this embodiment.

[0077] This embodiment also discloses a flexible electronic device, including the light-transmitting metal material prepared in this embodiment. Example 2 This embodiment discloses a light-transmitting metal material, and the difference from Example 1 is only that in I and II, the Ru precursor is replaced with a mixed precursor of Ru and Pt in a molar ratio of 1:1. The Pt precursor in the mixed precursor is MeCpPtMe3, and the rest is the same as in Example 1.

[0078] This embodiment also discloses an optoelectronic device, including the light-transmitting metal material prepared in this embodiment.

[0079] This embodiment also discloses a flexible electronic device, including the light-transmitting metal material prepared in this embodiment.

[0080] Example 3 This embodiment discloses a light-transmitting metal material, and its preparation process specifically includes: (I) Place the glass substrate (including the antireflection film base layer of TiO2-SiO2 formed by atomic layer deposition, and the reflectance in the visible light range of 380 nm - 780 nm is about 0.5%) on the sample stage in the chamber of the atomic layer deposition system (reaction chamber), set the deposition temperature to 200 °C, the Ag precursor to 95 °C, and the Pt precursor to 40 °C, and preheat for 60 min.

[0081] (II) Preparation of the Pt layer: (a) Use Me3Pt(MeCp) as the gas-phase precursor, use nitrogen as the carrier gas, control with the ALD valve, and enter the reaction chamber in a pulsed form. Among them, the valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 3 s. A gas-solid chemical reaction occurs on the surface of the exposed glass substrate (with a thickness of about 2 mm) to adsorb the Pt precursor on the substrate surface.

[0082] (b) Purge with 3000 sccm of N2 gas in the reaction chamber for 30 s to remove the excess precursor vapor and reaction by-products from the reaction chamber.

[0083] (c) Introduce O2 and continuously introduce it for 5 s to continue reacting with the Pt precursor adsorbed on the substrate surface.

[0084] (d) Purge with 3000 sccm of N2 gas for 10 s to carry out the excess O2 and reaction by-products out of the reaction chamber.

[0085] After steps (a) to (d) are cycled 100 times, a 1-nm-thick Pt layer is formed on the surface of the glass substrate.

[0086] (III) Preparation of the Ag layer: (e) Use Ag(fod)PEt3 as the gas-phase precursor, with nitrogen as the carrier gas, controlled by the ALD valve, and enter the reaction chamber in a pulsed form. The valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 5 s. A gas-solid chemical reaction occurs on the exposed Pt layer surface, causing the Ag precursor to be adsorbed on the Pt layer surface.

[0087] (f) Purge with 3000 sccm of N2 gas in the reaction chamber for 30 s to carry out the excess precursor vapor and reaction by-products out of the reaction chamber.

[0088] (g) Introduce H2 plasma and continuously introduce it for 5 s to continue reacting with the Ag precursor adsorbed on the Pt layer surface.

[0089] (k) Purge with 3000 sccm of N2 gas for 10 s to carry out the excess NH3 and reaction by-products out of the reaction chamber.

[0090] After steps (e) to (k) are cycled 500 times, a 4-nm-thick Ag layer is formed on the Pt layer surface to obtain a light-transmitting metal material.

[0091] This embodiment also discloses an optoelectronic device, including the light-transmitting metal material prepared in this embodiment.

[0092] This embodiment also discloses a flexible electronic device, including the light-transmitting metal material prepared in this embodiment. Example 4 This embodiment discloses a light-transmitting metal material, the difference from Example 3 is only that a 1-nm-thick Pt layer is prepared on the glass surface by evaporation coating, and the rest is the same as Example 3.

[0093] This embodiment also discloses an optoelectronic device, including the light-transmitting metal material prepared in this embodiment.

[0094] This embodiment also discloses a flexible electronic device, including the light-transmitting metal material prepared in this embodiment.

[0095] Comparative Example 1 This comparative example discloses a composite material, the difference from the transparent metal material in Example 1 being only that: it does not contain an Ru layer, and an Ag layer with a thickness of 5 nm is directly prepared on the surface of the PET polymer film by an evaporation coating method.

[0096] Comparative Example 2 This comparative example discloses a composite material, the difference from the transparent metal material in Example 1 being only that: it does not contain an Ru layer, and an Ag layer with a thickness of 80 nm is directly prepared on the surface of the PET polymer film by an evaporation coating method.

[0097] Comparative Example 3 This comparative example discloses a composite material, the difference from the transparent metal material in Example 1 being only that: it does not contain an Ru layer, and an Ag layer with a thickness of 5 nm is directly prepared on the surface of the PET polymer film, and the preparation process of the Ag layer is the same as that in Example 1.

[0098] Comparative Example 4 This comparative example discloses a transparent metal material, the difference from the transparent metal material in Example 1 being only that: it does not contain an Ag layer, and the thickness of Ru is 5 nm (the preparation process of the Ru layer is the same as that in Example 1).

[0099] Comparative Example 5 This comparative example discloses a transparent material, the difference from the transparent metal material in Example 3 being only that: it does not contain an Ru layer, and an Ag layer with a thickness of 5 nm is directly prepared on the surface of the glass substrate by an evaporation coating method.

[0100] Comparative Example 6 This comparative example discloses a transparent material, the difference from the transparent metal material in Example 3 being only that: it does not contain a Pt layer, and an Ag layer with a thickness of 5 nm is directly prepared on the glass surface, and the preparation process of the Ag layer is the same as that in Example 3.

[0101] Comparative Example 7 This comparative example discloses a transparent material, the difference from the transparent metal material in Example 3 being only that: it does not contain an Ag layer, and the thickness of Pt is 5 nm (the preparation process of the Pt layer is the same as that in Example 3).

[0102] Comparative Example 8 This comparative example discloses a transparent material, and its preparation process specifically includes: (I) Place the PET polymer film on the sample stage in the chamber (reaction chamber) of the atomic layer deposition system, set the deposition temperature at 115 °C, the Cu precursor at 80 °C, the Ag precursor at 60 °C, and preheat for 60 min.

[0103] (II) Preparation of the Cu layer: (a) Using Cu(hfac)2 as the gas-phase precursor, with nitrogen as the carrier gas, controlled by an ALD valve, it enters the reaction chamber in a pulsed form. The valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 1 s. A gas-solid chemical reaction occurs on the surface of the exposed PET polymer film, causing the Cu precursor to be adsorbed on the surface of the PET polymer film.

[0104] (b) Purge the reaction chamber with 3000 sccm of N2 gas for 30 s to remove the excess precursor vapor and reaction by-products from the reaction chamber.

[0105] (c) Introduce 1000 sccm of H2 plasma into the reaction chamber for 10 s to continue reacting with the Cu precursor adsorbed on the surface of the PET polymer film.

[0106] (d) Purge with 3000 sccm of N2 gas for 60 s to remove the excess H2 and reaction by-products from the reaction chamber.

[0107] After repeating steps (a) - (d) 20 times, a 1-nm-thick Cu layer is formed on the surface of the PET polymer film.

[0108] (III) Preparation of the Ag layer: (e) Using Ag(piv)PEt3 as the gas-phase precursor, with nitrogen as the carrier gas, controlled by an ALD valve, it enters the reaction chamber in a pulsed form. The valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 5 s. A gas-solid chemical reaction occurs on the surface of the exposed Cu layer, causing the Ag precursor to be adsorbed on the surface of the substrate.

[0109] (f) Purge the reaction chamber with 3000 sccm of N2 gas for 30 s to remove the excess precursor vapor and reaction by-products from the reaction chamber.

[0110] (g) Introduce NH3 plasma and continuously introduce it for 5 s to continue reacting with the Ag precursor adsorbed on the surface of the Cu layer.

[0111] (k) Purge with 3000 sccm of N2 gas for 10 s to remove the excess NH3 and reaction by-products from the reaction chamber.

[0112] After repeating steps (e) - (k) 500 times, a 4-nm-thick Ag layer is formed on the surface of the Cu layer, obtaining a light-transmitting metal material.

[0113] Comparative Example 9 This comparative example discloses a light-transmitting material, and the difference from Comparative Example 8 is only that: it does not contain an Ag layer, and the thickness of Cu is 5 nm (the Cu layer preparation process is the same as that of Comparative Example 8).

[0114] Comparative Example 10 This comparative example discloses a light-transmitting material, and its preparation process specifically includes: (Ⅰ)Place the PET polymer film on the sample stage in the chamber (reaction chamber) of the atomic layer deposition system, set the deposition temperature at 115 °C, the Cu precursor at 80 °C, the Ag precursor at 60 °C, and preheat for 60 min.

[0115] (Ⅱ)Preparation of the CuO layer: (a)Use Cu(hfac)2 as the gas-phase precursor (Cu precursor), use nitrogen as the carrier gas, control with the ALD valve, and enter the reaction chamber in a pulsed form. Among them, the valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 1 s. A gas-solid chemical reaction occurs on the surface of the exposed PET polymer film, so that the Cu precursor is adsorbed on the substrate surface.

[0116] (b)Purge the reaction chamber with 3000 sccm of N2 gas for 30 s to carry out the excess precursor vapor and reaction by-products out of the reaction chamber.

[0117] (c)Introduce 1000 sccm of O3 and introduce it into the reaction chamber for 10 s to continue reacting with the Cu precursor adsorbed on the surface of the PET polymer film.

[0118] (d)Purge with 3000 sccm of N2 gas for 60 s to carry out the excess H2 and reaction by-products out of the reaction chamber.

[0119] After steps (a) to (d) are cycled 20 times, a 1-nm-thick CuO layer is formed on the surface of the PET polymer film.

[0120] (Ⅲ)Preparation of the Ag layer: (e)Use Ag(piv)PEt3 as the gas-phase precursor, use nitrogen as the carrier gas, control with the ALD valve, and enter the reaction chamber in a pulsed form. Among them, the valve is opened for 1 s, and the gas-phase precursor stays in the reaction chamber for 5 s. A gas-solid chemical reaction occurs on the surface of the exposed CuO layer, so that the Ag precursor is adsorbed on the surface of the CuO layer.

[0121] (f)Purge the reaction chamber with 3000 sccm of N2 gas for 30 s to carry out the excess precursor vapor and reaction by-products out of the reaction chamber.

[0122] (g)Introduce NH3 plasma and continuously introduce it for 5 s to continue reacting with the Ag precursor adsorbed on the surface of the CuO layer.

[0123] (k)Purge with 3000 sccm of N2 gas for 10 s to carry out the excess NH3 and reaction by-products out of the reaction chamber.

[0124] After steps (e) to (k) are cycled 500 times, a 4-nm-thick Ag layer is formed on the surface of the CuO layer to obtain a light-transmitting metallic material.

[0125] Comparative Example 11 This comparative example discloses a light-transmitting material, and the difference from Comparative Example 10 is only that: in step (II), TDMATi is used instead of Cu(hfac)2. After steps (a) to (d) are cycled 20 times, a 1-nm-thick TiO2 layer is formed on the surface of the PET polymer film, and the rest is the same as in Comparative Example 10.

[0126] Comparative Example 12 This comparative example discloses a light-transmitting material, and the difference from Comparative Example 10 is only that: in step (II), TMA is used instead of Cu(hfac)2. After steps (a) to (d) are cycled 10 times, a 1-nm-thick Al2O3 layer is formed on the surface of the PET polymer film, and the rest is the same as in Comparative Example 10.

[0127] Test Example This test example conducts performance tests on the light-transmitting metallic materials, composite materials, and light-transmitting materials obtained in the examples and comparative examples, specifically including: conductivity test, light transmittance test, and reflectance test. The test results are shown in Tables 1 to 2 below. Among them, the test methods are as follows: Conductivity test: Using the four-probe test technique, four equally spaced probes are inserted into the surface of the sample. A small appropriate current I is provided to the two outer probes by a constant current source, and then the voltage V between the two middle probes is measured to obtain the experimental result of the resistivity.

[0128] Light transmittance test: Using the spectrophotometric method, based on the Lambert-Beer law, when a beam of parallel monochromatic light is perpendicularly incident on a uniform sample, the degree of light absorption is proportional to the concentration of the sample and the optical path length. By measuring the ratio of the light intensity transmitted through the sample to the incident light intensity at visible light wavelengths (380 - 780 nm), the light transmittance can be obtained.

[0129] Reflectance test: The light source is collimated into parallel light and focused on the surface of the sample through a microscope objective. The reflected light from the sample surface enters the imaging lens group and is finally divided into two light paths through a spectro prism. One light path forms a clear light spot on the CCD for focusing. The other light enters the sensor, and the analysis software calculates the ratio of the reflected energy to the reference energy based on the data received by the sensor to obtain the reflectance of the sample surface.

[0130] Table 1 Test result table of the film system on the PET substrate

[0131] As can be seen from Examples 1 to 2 and Comparative Examples 8 to 9, a Cu thin film with a thickness of 1 - 5 nm cannot form a continuous film on the surface of PET and cannot be used as a nucleation and underlayer for Ag to form an ultra-thin conductive layer.

[0132] As can be seen from Examples 1 to 2 and Comparative Examples 10 to 12, 1 nm CuO thin film, TiO2 thin film, and Al2O3 thin film cannot be used as the nucleation and underlayer for Ag, and the Ag layer cannot wet and be continuous on the surface of the oxide to form an ultra-thin conductive layer.

[0133] Table 2 Test results of the film system on the glass substrate

[0134] Figure 1 It is the reflectivity detection result of Example 3. In the above Examples 3 and 4, since there are insulating layers above and below the antireflection film, they do not have conductivity.

[0135] Unless otherwise specified, the "about" in the present invention actually means that the allowable error is within the range of ±2%. For example, about 100 is actually 100 ± 2% × 100. The "normal temperature" and "room temperature" in the present invention are about 20 - 30°C unless otherwise specified. The "between... and..." in the present invention includes the endpoints. For example, "between 2 and 3" includes the endpoint values 2 and 3.

[0136] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those of ordinary skill in the art. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A light-transmitting metal material, characterized in that: The method comprises a first metal and a second metal, wherein the first metal comprises at least one of Pt, Pd, Ir or Ru, and the second metal comprises silver.

2. The light-transmitting metal material according to claim 1, characterized in that: The light-transmitting metal material includes a first metal layer and a second metal layer arranged in sequence, the first metal layer includes at least one of Pt, Pd, Ir or Ru, and the second metal layer includes silver.

3. The light-transmitting metal material according to claim 2, characterized in that: The thickness of the first metal layer is less than 20 nm; and / or, the thickness of the second metal layer is less than 20 nm; and / or, the raw materials for preparing the second metal layer include a precursor I and a reactant I, the precursor I includes at least one of Ag(piv)PEt3, Ag(piv)PBu3, Ag(fod)PEt3 or Ag(hfac)COD, and the reactant I includes at least one of H2O, O2, O3, NH3, H2, NH3 plasma, H2 plasma or O2 plasma.

4. The light-transmitting metal material according to claim 2, characterized in that: The conductivity of the film formed by the first metal layer and the second metal layer is less than 20 μΩ·cm; and / or the transmittance of the film formed by the first metal layer and the second metal layer is more than 95%.

5. The light-transmitting metal material according to claim 2, characterized in that: The first metal layer includes at least one of a Pt layer, a Pd layer, an Ir layer or a Ru layer; and / or, the first metal layer is prepared by atomic layer deposition technology.

6. A method for preparing a light-transmitting metal material, characterized in that: The method comprises the following steps: preparing a second metal layer on the surface of a first metal layer by atomic layer deposition technology to obtain the light-transmitting metal material; the first metal layer comprises at least one of Pt, Pd, Ir or Ru, and the second metal layer comprises silver.

7. An ultra-low reflection anti-reflection film, characterized in that: The light-transmitting metal material comprises the light-transmitting metal material according to any one of claims 1 to 5 or the light-transmitting metal material prepared by the preparation method according to claim 6.

8. Use of the light-transmitting metal material according to any one of claims 1 to 5, the light-transmitting metal material obtained by the preparation method according to claim 6, or the ultra-low reflection anti-reflection film according to claim 7 in optical devices, optoelectronic devices or flexible electronic devices.

9. An optical device, characterized in that: The light-transmitting metal material comprises the light-transmitting metal material according to any one of claims 1 to 5 or the light-transmitting metal material prepared by the preparation method according to claim 6.

10. A flexible electronic device, characterized in that: The light-transmitting metal material comprises the light-transmitting metal material according to any one of claims 1 to 5 or the light-transmitting metal material prepared by the preparation method according to claim 6.

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