Ultra-black film structure with low deposition temperature and low reflectivity

Abstract

The invention belongs to the technical field of optical coating, and particularly relates to an ultra-black film structure with low deposition temperature and low reflectivity. The bonding layer is deposited on the surface of the base material through ALD, the ultra-black film layer is deposited on the surface of the bonding layer through ALD and is made of a low-temperature light absorption material, the porous structure layer is deposited on the surface of the ultra-black film layer through ALD, and the reflectivity of the ultra-black film structure is smaller than 0.1%. According to the method, the film layer structure with the ultralow reflectivity smaller than 0.1% can be deposited at the low temperature (25-150 DEG C) in an ALD atomic layer deposition mode, the deposition temperature and the deposition thickness are greatly reduced, and the effect of the ultralow reflectivity smaller than 0.1% can be achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical coating, and in particular relates to an ultra-black film structure with low deposition temperature and low reflectivity. Background Art

[0002] Ultra-black film is a thin film material with ultra-high absorption, absorbing over 99% of incident light. It is widely used in applications requiring reduced stray light or improved light absorption efficiency. For example, in optical instruments and imaging systems, it reduces internal reflections, suppresses stray light within lenses, improves imaging contrast, and reduces reflection losses on the surfaces of optical components. In aerospace and remote sensing, it is used in interior components such as sunshades to reduce interference from scattered sunlight, enhance infrared radiation absorption, and improve detection accuracy. In solar cells and thermophotovoltaic systems, it improves light absorption efficiency, enhances selective absorption, and optimizes energy conversion. In high-end consumer display devices, such as OLED screen shading layers, it improves display contrast, and in VR / AR devices, it reduces internal light reflections and enhances the user experience.

[0003] However, the existing ultra-black film preparation temperature is relatively high, generally above 400°C, and the process is cumbersome, severely limiting the choice of substrate materials. Furthermore, the deposition of ultra-black films on 3D structures using traditional PVD or CVD methods results in uneven thickness and difficulty in controlling thickness, which affects the optical properties of optical components and product performance. Furthermore, the reflectivity of traditional ultra-black films can only reach specifications below 1%. To further meet application requirements, the reflectivity needs to be controlled below 0.1%. A thickness of several microns is typically required to achieve ultra-low reflectivity.

[0004] In light of this, the present invention aims to provide an ultra-black film structure with low deposition temperature and low reflectivity. The present invention uses atomic layer deposition (ALD) to deposit a film structure with an ultra-low reflectivity of less than 0.1% at low temperatures (25-150°C). This not only significantly reduces the deposition temperature and the total thickness of the film, but also achieves an ultra-low reflectivity of less than 0.1%. Summary of the Invention

[0005] The present invention aims to address the shortcomings of existing technologies by providing an ultra-black film structure with low deposition temperature and low reflectivity. The present invention utilizes atomic layer deposition (ALD) to deposit a film structure with ultra-low reflectivity (less than 0.1%) at low temperatures (25-150°C). This significantly reduces the deposition temperature and achieves an ultra-low reflectivity of less than 0.1%.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A low-deposition-temperature, low-reflectivity ultra-black film structure comprises a substrate, a bonding layer deposited on the substrate surface using ALD, an ultra-black film layer composed of a low-temperature light-absorbing material deposited on the bonding layer surface using ALD, and a porous structure layer disposed on the surface of the ultra-black film layer. The ultra-black film structure has a reflectivity of less than 0.1%. The present invention uses a highly absorptive metal element that can be deposited at low temperatures as the absorption layer to reduce the overall deposition temperature. The porous structure of the outermost layer further reduces the equivalent refractive index, thereby achieving low-temperature high absorption and ultra-low reflection.

[0008] As an improvement of the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the material of the substrate is ceramic, metal, plastic or glass.

[0009] As an improvement of the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the deposition temperature of the bonding layer and the ultra-black film layer is 25°C-150°C, and ALD technology is used to achieve low-temperature deposition, thereby broadening the selection range of substrates.

[0010] As an improvement to the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the thickness of the bonding layer is 0.1nm-20nm, the thickness of the ultra-black film layer is 200-1000nm, and the thickness of the porous structure layer is 80nm-500nm. By using low-temperature ALD, the present invention can obtain a low-temperature ultra-low reflectivity, ultra-black film coating with excellent bonding strength while reducing the total thickness.

[0011] As an improvement to the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the porosity of the porous structure layer is 50%-85%. A porous structure with a porosity in this range can further reduce the equivalent refractive index, thereby achieving low-temperature high absorption and ultra-low reflection.

[0012] As an improvement to the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the bonding layer is made of at least one of an oxide or a single metal, wherein the oxide is one of TiO2, SiO2, Al2O3, ZrO2, HfO2, Ta2O5, Nb2O5, CuO, and ZnO; and the single metal is one of Cu, Co, Ag, Ni, Ru, Pt, Pd, and Ir. Depending on the substrate, the bonding strength between the substrate and the film can be enhanced based on the principle of element gradient variation and matching thermal expansion coefficients.

[0013] When the bonding layer is an oxide, the bonding layer is prepared by time-type ALD or space-type ALD, wherein the time-type ALD comprises at least the following steps:

[0014] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0015] In the second step, the precursor is introduced at 25°C-150°C to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0016] In the third step, the first reactant is added into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted first reactant and by-products;

[0017] Step 4: repeating step 2 and step 3 n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0;

[0018] Spatial ALD includes at least the following steps:

[0019] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0020] In the second step, the precursor and reactant are continuously introduced into the chamber at 25°C-150°C through a carrier gas and a diluent gas, to the reaction area of ​​the precursor and the first reactant, while an inert gas is introduced between the precursor and the reactant;

[0021] In the third step, the substrate passes through the precursor, isolation gas, first reactant and isolation gas areas in sequence to complete a deposition cycle;

[0022] Step 4: repeating Step 2 and Step 3 n times, cyclically depositing to form a bonding layer; n is a natural number greater than or equal to 0;

[0023] The carrier gas, diluent gas and inert gas are argon or nitrogen.

[0024] The precursor is at least one of an aluminum source, a titanium source, a tantalum source, a niobium source, a zinc source, a zirconium source, a hafnium source, a zinc source, a copper source, and a silicon source, and the first reactant is H2O, O3, or O2 plasma;

[0025] The aluminum source is at least one of trimethylaluminum, triethylaluminum and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetrakis(dimethylamino)titanium and tetraisopropyl titanate; the zinc source is at least one of diethylzinc, dimethylzinc and zinc chloride; the zirconium source is at least one of tetrakis(dimethylamino)zirconium, tetraethylmethylaminozirconium and zirconium tetrachloride; the hafnium source is one of tetrakisdimethylaminohafnium, tetraethylmethylaminohafnium and hafnium tetrachloride; the silicon source is bis(diethylaminosilane) The tantalum source is at least one of penta(dimethylamino)tantalum, tert-butyliminotris(ethylmethylamino)tantalum, and tert-butyliminotris(diethylamino)tantalum; the niobium source is at least one of penta(dimethylamino)tantalum, tert-butyliminotris(ethylmethylamino)tantalum, and tert-butyliminotris(diethylamino)tantalum; the zinc source is at least one of dimethylzinc and diethylzinc; and the copper source is at least one of di(dimethylamine-2-propanol)copper and bis(hexafluoroacetylacetonate)copper.

[0026] When the bonding layer is a single metal, the bonding layer is prepared by time-based ALD or space-based ALD, wherein the time-based ALD comprises at least the following steps:

[0027] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0028] In the second step, the precursor is introduced at 25°C-150°C to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0029] In the third step, the reactants are added to the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted reactants and by-products.

[0030] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0031] Spatial ALD includes at least the following steps:

[0032] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0033] In the second step, the precursor and reactant are continuously introduced into the chamber at 25°C-150°C through a carrier gas and a diluent gas, to the reaction area of ​​the precursor and reactant, while an inert gas is introduced between the precursor and reactant;

[0034] In the third step, the substrate passes through the precursor, isolation gas, reactant and isolation gas areas in sequence to complete a deposition cycle;

[0035] Step 4: Repeat step 2 and step 3 n times, cyclically depositing to form a metal layer in the super black layer; n is a natural number greater than or equal to 0.

[0036] The carrier gas, diluent gas and inert gas are argon or nitrogen.

[0037] The carrier gas, diluent gas and inert gas are argon or nitrogen.

[0038] The precursor is at least one of a Co source, a Cu source, an Ag source, a Pd source, an Ir source, a Ni source, an Au source and a Ru source, and the reactant is O2 or O3 and H2.

[0039] The Co source is 3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, the Cu source is bis(2,2,6,6-tetramethyl-3,5-heptanedione) copper, the Pt source is bis(acetylacetonate) platinum, the Pd source is bis(2,2,6,6-tetramethyl-3,5-heptanedione) palladium, the Ir source is 1-ethylcyclododecenyl-1,3-cyclohexairidium, the Ni source is bis(methylcyclopentadienyl) nickel, the Au source is dimethyl(trifluoroacetylacetonate) gold, the Ag source is triethylphosphine (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedioate) silver, and the Ru source is bis(ethylcyclopentadienyl)ruthenium or bis(cyclopentadienyl)ruthenium.

[0040] As an improvement to the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the ultra-black film layer is formed by alternating metals and oxides, wherein the metal is at least one of Co, Cu, Pt, Pd, Ir, and Ni, and the oxide is at least one of TiO2, SiO2, Al2O3, ZrO2, HfO2, Ta2O5, Nb2O5, and ZnO. The above-mentioned metal elements have high absorption properties. By arranging the stacking of high-absorption metal elements and oxides according to the principle of light interference, the reflection and transmission of the film layer are reduced to less than 1%. In detail, when ceramics are used as the substrate, the material of the bonding layer can be oxides or softer metals. When metals are used as the substrate, the material of the bonding layer can be metals or corresponding oxides to achieve element gradient changes. When plastics are used as the substrate, the material of the bonding layer can be oxides, and the stress of the bonding layer is designed to be close to 0.

[0041] The ultra-black film layer is a multilayer stack of metal elements and oxides. The oxides in the ultra-black film layer are prepared by time-based ALD or space-based ALD, where time-based ALD includes at least the following steps:

[0042] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0043] In the second step, the precursor is introduced at 25°C-150°C to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0044] In the third step, the reactants are added to the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted reactants and by-products.

[0045] Step 4: repeating step 2 and step 3 n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0;

[0046] Spatial ALD includes at least the following steps:

[0047] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0048] In the second step, the precursor and reactant are continuously introduced into the chamber at 25°C-150°C through a carrier gas and a diluent gas, to the reaction area of ​​the precursor and reactant, while an inert gas is introduced between the precursor and reactant;

[0049] In the third step, the substrate passes through the precursor, isolation gas, reactant and isolation gas areas in sequence to complete a deposition cycle;

[0050] Step 4: repeating Step 2 and Step 3 n times, cyclically depositing to form a bonding layer; n is a natural number greater than or equal to 0;

[0051] The carrier gas, diluent gas and inert gas are argon or nitrogen.

[0052] The precursor is at least one of an aluminum source, a titanium source, a tantalum source, a niobium source, a zinc source, a zirconium source, a hafnium source, a zinc source, and a silicon source, and the reactant is H2O, O3, or O2 plasma;

[0053] The aluminum source is at least one of trimethylaluminum, triethylaluminum and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetrakis(dimethylamino)titanium and tetraisopropyl titanate; the zinc source is at least one of diethylzinc, dimethylzinc and zinc chloride; the zirconium source is at least one of tetrakis(dimethylamino)zirconium, tetraethylmethylaminozirconium and zirconium tetrachloride; the hafnium source is one of tetrakisdimethylaminohafnium, tetraethylmethylaminohafnium and hafnium tetrachloride; the silicon source is bis(diethylaminosilane) , diisopropylamine silane, tris(dimethylamino)silane and bis(tert-butylamino)silane; the tantalum source is at least one of penta(dimethylamino)tantalum, tert-butyliminotris(ethylmethylamino)tantalum and tert-butyliminotris(diethylamino)tantalum, the niobium source is at least one of penta(dimethylamino)niobium, tert-butyliminotris(ethylmethylamino)niobium and tert-butyliminotris(diethylamino)niobium, and the zinc source is at least one of dimethylzinc and diethylzinc.

[0054] The metal in the ultra-black film layer is prepared by time-based ALD or space-based ALD, wherein the time-based ALD comprises at least the following steps:

[0055] In the first step, the substrate with the bonding layer attached is placed in an atomic layer deposition chamber under vacuum;

[0056] In the second step, the precursor is introduced at 25°C-150°C to chemically adsorb on the surface of the bonding layer; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0057] In the third step, the reactants are added to the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted reactants and by-products.

[0058] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0059] Spatial ALD includes at least the following steps:

[0060] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0061] In the second step, the precursor and reactant are continuously introduced into the chamber at 25°C-150°C through a carrier gas and a diluent gas, to the reaction area of ​​the precursor and reactant, while an inert gas is introduced between the precursor and reactant;

[0062] In the third step, the substrate passes through the precursor, isolation gas, reactant and isolation gas areas in sequence to complete a deposition cycle;

[0063] Step 4: repeating Step 2 and Step 3 n times, cyclically depositing, to form a metal layer in the super black layer; n is a natural number greater than or equal to 0;

[0064] The carrier gas, diluent gas and inert gas are argon or nitrogen.

[0065] The precursor is at least one of a Co source, a Cu source, a Pt source, a Pd source, an Ir source, and a Ni source, and the reactant is O2 or O3 and H2.

[0066] The Co source is 3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, the Cu source is bis(2,2,6,6-tetramethyl-3,5-heptanedione) copper, the Pt source is di(acetylacetonate) platinum, the Pd source is bis(2,2,6,6-tetramethyl-3,5-heptanedione) palladium, the Ir source is 1-ethylcyclododecenyl-1,3-cyclohexairidium, and the Ni source is bis(methylcyclopentadienyl) nickel.

[0067] As an improvement to the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the porous structure layer is porous Al2O3 or SiO2. Porous Al2O3 and SiO2 can further reduce the equivalent refractive index by taking advantage of the refractive index of air, n=1, thereby further reducing the reflectivity.

[0068] As an improvement to the ultra-black film structure with low deposition temperature and low reflectivity of the present invention, the porous structure layer is prepared by an ALD method to obtain the film layer and then treated with a water bath or a phosphoric acid solution.

[0069] The porous structure film is prepared by time-based ALD or space-based ALD, wherein the time-based ALD comprises at least the following steps:

[0070] In the first step, a precursor is introduced into an atomic layer deposition chamber at 25°C-150°C to chemically adsorb on the surface of the bonding layer; then an inert gas is introduced to purge unreacted precursors and by-products;

[0071] In the second step, the reactants are added to the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted reactants and by-products.

[0072] Step 3: Repeat Step 1 and Step 2 n times, cyclically depositing to form a light absorbing layer; n is a natural number greater than or equal to 0;

[0073] Spatial ALD includes at least the following steps:

[0074] In the first step, in an atomic layer deposition chamber at 25°C-150°C, the precursor and reactant are continuously introduced into the chamber through carrier gas and diluent gas, to the reaction area of ​​the precursor and reactant, while an inert gas is introduced between the precursor and reactant;

[0075] In the second step, the substrate with the transition layer deposited passes through the precursor, isolation gas, reactant and isolation gas areas in sequence to complete a deposition cycle;

[0076] Step 3: Repeat Step 1 and Step 2 n times, cyclically depositing to form a light absorbing layer; n is a natural number greater than or equal to 0;

[0077] Wherein, the carrier gas, diluent gas and inert gas are argon or nitrogen;

[0078] The precursors are an aluminum source and a silicon source, wherein the aluminum source is at least one of trimethylaluminum, triethylaluminum and aluminum trichloride; the silicon source is at least one of bis(diethylamino)silane, diisopropylaminesilane, tris(dimethylamino)silane and bis(tert-butylamino)silane; and the reactants are H2O, O3 or O2 plasma.

[0079] The specific steps of the water bath treatment are: placing the coated part in 60℃-90℃ ultrapure water for 1h-3h and then drying it in a high-temperature oven for 2h-5h to obtain a porous aluminum oxide or silicon oxide structure.

[0080] The specific steps of phosphoric acid solution treatment are: place the coated part in 85% phosphoric acid solution at 50°C-80°C for 0.5h-24h, then wash it in ethanol solution and blow dry it with N2 gun.

[0081] Equivalent to existing technologies, this method first uses ALD to deposit a bonding layer on substrates such as ceramics, metals, plastics, and glass, strengthening the bond between the coating and the substrate and preventing the film from detaching. ALD then deposits an ultra-absorbent, ultra-black film layer on top of the bonding layer. A porous structure is then constructed within the ultra-black film layer to further reduce the film's reflectivity. In other words, this method significantly reduces deposition temperatures, significantly reduces the overall film thickness compared to conventional microstructure-free methods, lowering costs and achieving ultra-low reflectivity below 0.1%.

[0082] The present invention also provides an application of the ultra-black film structure described in the present invention in mobile phone lenses, vehicle lenses, and AR / VR fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 It is a structural schematic diagram of the present invention.

[0084] Figure 2 This is the absorption effect and film stacking thickness diagram of Comparative Example 1.

[0085] Figure 3 Schematic diagram of the ultra-low reflectivity curve of Example 1. DETAILED DESCRIPTION

[0086] The following will provide a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0087] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the various components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0088] In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the fact that ordinary technicians in this field can implement them. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0089] Example 1

[0090] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0091] The material of the substrate 1 is ceramic.

[0092] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 100°C.

[0093] The bonding layer 2 is made of TiO2. The ultra-black film layer 3 is made of metal and oxide alternately stacked, wherein the metal is Co and the oxide is SiO2. The porous structure layer 4 is porous SiO2.

[0094] Specifically, the thickness of the bonding layer 2 is 10nm, and the ultra-black film layer 3 is composed of alternating layers of Co and SiO2, wherein Co is four layers and SiO2 is three layers. From the bonding layer 2 to the porous structure layer 4, the seven-layer structure is arranged in sequence, and the thicknesses of the seven-layer structure are Co (100nm), SiO2 (87.78nm), Co (11.6nm), SiO2 (98.58nm), Co (4.82nm), SiO2 (87.15nm) and Co (1.27nm) respectively. The total thickness of the ultra-black film layer is 391.2nm, and the thickness of the porous structure layer 4 is 202.5nm.

[0095] The porosity of the porous structure layer 4 is 75%.

[0096] The porous structure layer 4 is prepared by ALD-SiO2 plus water bath treatment.

[0097] The bonding layer 2 is prepared by time-type ALD, which includes at least the following steps:

[0098] In the first step, the substrate ceramic is placed in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr);

[0099] In the second step, the precursor titanium tetrachloride was introduced in pulse form at 100°C for 5 seconds to allow it to chemically adsorb on the substrate surface. Then, 4000 sccm of inert gas was introduced for 60 seconds to purge the unreacted precursor and by-products.

[0100] In the third step, O2 plasma was pulsed into the chamber for 5 seconds to form a monolayer with the titanium tetrachloride adsorbed on the surface. Then, an inert gas was introduced at 3000 sccm for 60 seconds to purge the unreacted O2 plasma and byproducts.

[0101] In the fourth step, the second and third steps are repeated for cyclic deposition to form a bonding layer 2.

[0102] The preparation method of the ultra-black film layer 3 is spatial ALD, which includes at least the following steps:

[0103] In the first step, the substrate with the bonding layer attached is placed in an atomic layer deposition chamber under vacuum;

[0104] In the second step, the precursor (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl) is introduced at 100°C to chemically adsorb on the surface of the bonding layer; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0105] In the third step, reactants (oxygen and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge unreacted reactants and by-products.

[0106] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0107] In the fourth step, diisopropylamine silane was introduced in pulses at 100°C for 3 seconds to allow it to chemically adsorb on the Co surface. Then, an inert gas was introduced at 4000 sccm to purge the unreacted diisopropylamine silane and by-products for 30 seconds.

[0108] In the fifth step, O2 plasma was introduced into the chamber in pulsed form and maintained for 20 seconds to form a monolayer with diisopropylamine silane adsorbed on the surface. Then, 4000 sccm of inert gas was introduced to purge the unreacted O2 plasma and byproducts for 10 seconds.

[0109] Step 6: Repeat steps 4 and 5, and perform cyclic deposition to form SiO2 in the ultra-black film layer.

[0110] Step 7: Repeat steps 3 and 6, and perform cyclic deposition to form an ultra-black film layer 3.

[0111] The preparation method of the porous structure layer is the same as the preparation method of SiO2 in the ultra-black film layer. After obtaining the film layer, a porous structure is manufactured on the film layer by water bath treatment. The specific steps of the water bath treatment are: placing the coated part in 80°C ultrapure water for 2 hours and then drying it in a high-temperature oven for 3 hours to obtain a porous silicon oxide structure.

[0112] Example 2

[0113] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0114] The material of the substrate 1 is copper.

[0115] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 120°C.

[0116] The bonding layer 2 is made of Au. The ultra-black film layer 3 is made of alternating metals and oxides, where the metal is Pt and the oxides are ZrO2 and SiO2. The porous structure layer 4 is porous Al2O3.

[0117] The thickness of the bonding layer 2 is 10 nm, the thickness of the ultra-black film layer 3 is 443.85 nm, and the thickness of the porous structure layer 4 is 210 nm. The ultra-black film layer includes a Pt layer (100 nm), a ZrO2 layer (55.41 nm), a Pt layer (10.42 nm), a SiO2 layer (112.51 nm), a Pt layer (8.34 nm), a ZrO2 layer (60.7 nm), a Pt layer (2.26 nm), a SiO2 layer (90.77 nm), a Pt layer (1.3 nm), and a SiO2 layer (2.14 nm), which are arranged in sequence from the bonding layer 2 to the porous structure layer 4.

[0118] The porosity of the porous structure layer 4 is 80%.

[0119] The porous structure layer 4 is prepared by ALD plus water bath treatment.

[0120] The bonding layer 2 is prepared by spatial ALD, which includes at least the following steps:

[0121] In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum;

[0122] In the second step, the precursor dimethyl(trifluoroacetylacetonate)gold and reactants (ozone and hydrogen) are continuously introduced into the chamber at 75°C through a carrier gas and a diluent gas, respectively, to the reaction area of ​​the precursor and reactants, while an inert gas is introduced between the precursor and reactants.

[0123] In the third step, the substrate passes through the precursor, isolation gas, reactant and isolation gas areas in sequence to complete a deposition cycle;

[0124] Step 4: repeating Step 2 and Step 3 n times, cyclically depositing, to form a metal layer in the super black layer; n is a natural number greater than or equal to 0;

[0125] Among them, the carrier gas, dilution gas and inert gas are argon.

[0126] The ultra-black film layer 3 is prepared by time ALD, wherein the preparation method of the Pt layer is time-type ALD, which at least includes the following steps:

[0127] In the first step, the substrate with the bonding layer attached is placed in an atomic layer deposition chamber under vacuum;

[0128] In the second step, the precursor di(acetylacetonate) platinum is introduced at 90°C to chemically adsorb on the surface of the binding layer (or the film layer of the ultra-black film); then an inert gas is introduced to purge the unreacted precursor and by-products;

[0129] In the third step, reactants (oxygen and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge unreacted reactants and by-products.

[0130] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0131] The preparation method of ZrO2 is:

[0132] In the first step, tetrakis(dimethylamino)zirconium was introduced into the atomic layer deposition chamber at 80°C in pulsed form for 3 seconds to allow it to chemically adsorb on the surface of the Pt layer. Then, 4000 sccm of inert gas was introduced for 30 seconds to purge unreacted tetrakis(dimethylamino)zirconium and byproducts.

[0133] In the second step, O2 plasma was pulsed into the chamber and maintained for 20 seconds to form a monolayer with the surface-adsorbed tetrakis(dimethylamino)zirconium. Unreacted O2 plasma and byproducts were then purged with 4000 sccm of inert gas for 10 seconds.

[0134] In the third step, the first and second steps are repeated, and the deposition is cyclic to form ZrO2.

[0135] The preparation method of SiO2 is:

[0136] In the first step, diisopropylamine silane was introduced into the atomic layer deposition chamber at 80°C in pulse form for 3 seconds to allow it to chemically adsorb on the surface of the bonding layer. Then, 4000 sccm of inert gas was introduced for 30 seconds to purge unreacted diisopropylamine silane and byproducts.

[0137] In the second step, O2 plasma was pulsed into the chamber and maintained for 20 seconds to form a monolayer with diisopropylamine silane adsorbed on the surface. Then, 4000 sccm of inert gas was introduced to purge the unreacted O2 plasma and byproducts for 10 seconds.

[0138] In the third step, the first and second steps are repeated, and the deposition is cyclic to form SiO2.

[0139] The preparation method of the Al2O3 film layer of the porous structure layer is as follows:

[0140] In the first step, triethylaluminum was introduced into the atomic layer deposition chamber at 90°C in pulsed form to chemically adsorb it on the surface of the ultra-black film. Then, 2000 sccm of inert gas was introduced to purge unreacted triethylaluminum and by-products for 20 seconds.

[0141] In the second step, distilled water was added to the chamber in a pulsed manner to form a monolayer with triethylaluminum adsorbed on the surface. Then, an inert gas was introduced at a flow rate of 1000 sccm for 30 seconds to purge the unreacted distilled water and byproducts.

[0142] In the third step, the first and second steps are repeated, and the deposition is cyclic to form Al2O3.

[0143] Then, a porous structure is formed on the surface of the Al2O3 film layer through water bath treatment. The specific process is as follows: the coated part is placed in 75°C ultrapure water for 1.5 hours and then dried in a high-temperature oven for 4 hours to obtain a porous silicon oxide structure.

[0144] Example 3

[0145] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0146] The material of the substrate 1 is metallic iron.

[0147] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 130°C.

[0148] The material of the bonding layer 2 is CuO. The ultra-black film layer 3 is formed by alternating metals and oxides, wherein the metal is Cu / Ir and the oxides are Ta2O5 and SiO2. The porous structure layer 4 is porous SiO2. The thickness of the bonding layer 2 is 15.54nm, the thickness of the ultra-black film layer 3 is 533.02nm, and the thickness of the porous structure layer 4 is 273nm. The ultra-black film layer includes a Cu layer (200nm), Ta2O5 (44.64nm), an Ir layer (9.39nm), a SiO2 layer (118.9nm), an Ir layer (8.41nm), a Ta2O5 layer (51.4nm), an Ir layer (1.97nm), a SiO2 layer (97.04nm) and an Ir layer (1.27nm) arranged in sequence from the bonding layer 2 to the porous structure layer 4.

[0149] The porosity of the porous structure layer 4 is 85%.

[0150] The bonding layer 2 is prepared by time-type ALD, which specifically includes the following steps:

[0151] In the first step, copper di(dimethylamine-2-propanol) was introduced into the atomic layer deposition chamber at 80°C in pulsed form to chemically adsorb it on the substrate surface. Then, an inert gas was introduced at 2000 sccm to purge the unreacted copper di(dimethylamine-2-propanol) and byproducts for 20 seconds.

[0152] In the second step, distilled water was added to the chamber in pulses to form a monolayer with the adsorbed copper di(dimethylamine-2-propanol) on the surface. Unreacted distilled water and byproducts were then purged by passing 1000 sccm of inert gas for 30 seconds.

[0153] In the third step, the first and second steps are repeated, and the deposition cycle is repeated to form CuO.

[0154] The preparation method of the Cu layer in the ultra-black film layer 3 is time-type ALD, which includes at least the following steps:

[0155] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0156] In the second step, the precursor copper bis(2,2,6,6-tetramethyl-3,5-heptanedione) is introduced at 70°C to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0157] In the third step, the reactants (ozone and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted reactants and by-products.

[0158] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0159] The preparation method of the Ir layer is time-type ALD, which includes at least the following steps:

[0160] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0161] In the second step, the precursor 1-ethylcyclododecenyl-1,3-cyclohexairidium is introduced at 60°C to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0162] In the third step, the reactants (ozone and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge the unreacted reactants and by-products.

[0163] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0164] The Ta2O5 layer is prepared as follows: first, tantalum penta(dimethylamino) is introduced into an atomic layer deposition chamber at 80°C in a pulsed manner to chemically adsorb it on the surface of the Cu layer or the Ir layer; then, an inert gas is introduced at a flow rate of 2000 sccm to purge the unreacted tantalum penta(dimethylamino) and by-products for 20 seconds;

[0165] In the second step, distilled water was added to the chamber in pulses to form a monolayer with the adsorbed tantalum penta(dimethylamino)imidazoline. Unreacted distilled water and byproducts were then purged with 1000 sccm of inert gas for 30 seconds.

[0166] In the third step, the first and second steps are repeated, and the deposition is cyclic to form Ta2O5.

[0167] The SiO2 layer was prepared as follows: first, tri(dimethylamino)silane was introduced into an atomic layer deposition chamber at 80°C in a pulsed manner to chemically adsorb it on the surface of the Ir layer; then, an inert gas was introduced at a flow rate of 2000 sccm for 20 seconds to purge unreacted tri(dimethylamino)silane and byproducts;

[0168] In the second step, distilled water was added to the chamber in a pulsed manner to form a monolayer with tris(dimethylamino)silane adsorbed on the surface. Then, an inert gas was introduced at 1000 sccm for 30 seconds to purge the unreacted distilled water and byproducts.

[0169] In the third step, the first and second steps are repeated, and the deposition is cyclic to form SiO2.

[0170] The preparation method of the SiO2 film layer in the porous structure layer is the same as that of the SiO2 layer in the ultra-black film layer. The preparation method of the porous structure is post-treated with 85% phosphoric acid solution. The specific steps are: place the coated part in an 85% phosphoric acid solution at 60°C for 12 hours, then wash it in an ethanol solution and blow it dry with an N2 gun.

[0171] Example 4

[0172] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0173] The material of the substrate 1 is glass.

[0174] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 120°C.

[0175] The thickness of the bonding layer 2 is 10.2 nm, the thickness of the ultra-black film layer 3 is 568.58 nm, and the thickness of the porous structure layer 4 is 217.5 nm.

[0176] The porosity of the porous structure layer 4 is 81%.

[0177] The material of the bonding layer 2 is TiO2. The ultra-black film layer 3 is composed of metal and oxide alternately stacked, wherein the metal is Pt or Ir and the oxide is SiO2. The ultra-black film layer includes a Pt layer (150nm), a SiO2 layer (95.8nm), an Ir layer (10.36nm), a SiO2 layer (107.14nm), an Ir layer (5.32nm), a SiO2 layer (106.63nm), an Ir layer (3.38nm), a SiO2 layer (88.49nm), and an Ir layer (1.46nm) arranged in sequence from the bonding layer 2 to the porous structure layer 4.

[0178] The porous structure layer 4 is porous Al2O3.

[0179] The porous structure layer 4 is prepared by ALD plus water bath treatment.

[0180] The bonding layer 2 is prepared by time-type ALD, which includes the following steps:

[0181] In the first step, tetraisopropyl titanate was introduced into the atomic layer deposition chamber at 90°C in pulsed form, causing it to chemically adsorb on the surface of the ultra-black film. Then, an inert gas was introduced at 2000 sccm to purge the unreacted tetraisopropyl titanate and by-products for 20 seconds.

[0182] In the second step, distilled water was added to the chamber in pulses to form a monolayer with tetraisopropyl titanate adsorbed on the surface. Unreacted distilled water and byproducts were then purged by passing 1000 sccm of inert gas for 30 seconds.

[0183] In the third step, the first and second steps are repeated, and the deposition is cyclic to form TiO2.

[0184] The preparation method of the Pt layer in the ultra-black film layer 3 is time-type ALD, which includes at least the following steps:

[0185] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0186] In the second step, the precursor platinum di(acetylacetonate) is introduced at 70° C. to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0187] In the third step, reactants (oxygen and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge unreacted reactants and by-products.

[0188] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0189] The preparation method of the Ir layer is the same as that of Example 3.

[0190] The preparation method of SiO2 layer is as follows:

[0191] In the first step, tri(dimethylamino)silane was introduced into the atomic layer deposition chamber at 85°C in pulsed form for 3 seconds to allow it to chemically adsorb on the surface of the bonding layer. Then, 4000 sccm of inert gas was introduced for 30 seconds to purge unreacted tri(dimethylamino)silane and byproducts.

[0192] In the second step, O2 plasma was pulsed into the chamber for 20 seconds to form a monolayer with tri(dimethylamino)silane adsorbed on the surface. Then, 4000 sccm of inert gas was introduced for 10 seconds to purge the unreacted O2 plasma and byproducts.

[0193] In the third step, the first and second steps are repeated, and the deposition is cyclic to form SiO2.

[0194] The preparation method of the porous structure layer is as follows:

[0195] In the first step, trimethylaluminum was introduced into the atomic layer deposition chamber at 90°C in pulsed form to chemically adsorb it on the surface of the ultra-black film. Then, 2000 sccm of inert gas was introduced to purge unreacted trimethylaluminum and by-products for 20 seconds.

[0196] In the second step, distilled water was added to the chamber in a pulsed manner to form a monolayer with trimethylaluminum adsorbed on the surface. Then, an inert gas was introduced at a flow rate of 1000 sccm for 30 seconds to purge the unreacted distilled water and byproducts.

[0197] In the third step, the first and second steps are repeated, and the deposition is cyclic to form an Al2O3 film layer. Then, a phosphoric acid solution treatment method is used to prepare a porous structure. The specific steps are as follows: the coated part is placed in a 75°C 85% phosphoric acid solution for 10 hours, then washed in an ethanol solution and blown dry with an N2 gun.

[0198] Example 5

[0199] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0200] The material of the substrate 1 is glass.

[0201] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 110°C.

[0202] The thickness of the bonding layer 2 is 15.81 nm, the thickness of the ultra-black film layer 3 is 527.87 nm, and the thickness of the porous structure layer 4 is 245.7 nm.

[0203] The porosity of the porous structure layer 4 was 83%.

[0204] The material of the bonding layer 2 is TiO2; the ultra-black film layer 3 is composed of alternating metals and oxides, wherein the metal is Pt and the oxide is SiO2. The porous structure layer 4 is porous SiO2. Among them, the ultra-black film layer 3 includes a Pt layer (123.81nm), a SiO2 layer (90.29nm), a Pt layer (11.68nm), a SiO2 layer (101.78nm), a Pt layer (6.07nm), a SiO2 layer (103.54nm), a Pt layer (3.64nm), a SiO2 layer (85.96nm), and a Pt layer (1.1nm) arranged in sequence from the bonding layer 2 to the porous structure layer 4.

[0205] The preparation method of bonding layer 2 is the same as that of Example 4.

[0206] The preparation method of the Pt layer in the ultra-black film layer 3 is the same as that in Example 4.

[0207] The preparation method of the SiO2 layer is the same as that of Example 4.

[0208] The preparation method of the membrane layer in the porous structure layer 4 is the same as that in Example 3. The porous structure is prepared by adding 85% phosphoric acid solution, specifically, placing the coated part in 85% phosphoric acid solution at 55°C for 16 hours, then washing it in ethanol solution and drying it with an N2 gun.

[0209] Example 6

[0210] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0211] The material of the substrate 1 is plastic.

[0212] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 110°C.

[0213] The thickness of the bonding layer 2 is 17 nm, the thickness of the ultra-black film layer 3 is 458.27 nm, and the thickness of the porous structure layer 4 is 210 nm.

[0214] The porosity of the porous structure layer 4 is 78%.

[0215] The material of the bonding layer 2 is ZrO2. The ultra-black film layer 3 is composed of alternating metals and oxides, wherein the metal is Ni and the oxides are ZrO2 and SiO2. The ultra-black film layer 3 includes a Ni layer (120nm), ZrO2 (51.18nm), a Ni layer (12.83nm), SiO2 (109.61nm), a Ni layer (10.72nm), ZrO2 (58.77nm), a Ni layer (3.05nm), SiO2 (90.4nm), and a Ni layer (1.71nm) arranged in sequence from the bonding layer 2 to the porous structure layer 4.

[0216] The porous structure layer 4 is porous Al2O3.

[0217] The bonding layer 2 was prepared as follows: first, tetraethylmethylamino zirconium was introduced into an atomic layer deposition chamber at 85°C in pulsed form for 5 seconds to allow it to chemically adsorb on the surface of the Pt layer; then, 4000 sccm of inert gas was introduced for 30 seconds to purge unreacted tetraethylmethylamino zirconium and byproducts;

[0218] In the second step, O3 was added into the chamber in pulse form and maintained for 20 seconds to form a monolayer with tetraethylmethylamino zirconium adsorbed on the surface. Then, 4000 sccm of inert gas was introduced to purge unreacted O3 and byproducts for 10 seconds.

[0219] In the third step, the first and second steps are repeated, and the deposition is cyclic to form ZrO2.

[0220] The preparation method of the Ni layer in the ultra-black film layer 3 is time-type ALD, and the specific steps are as follows:

[0221] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0222] In the second step, the precursor bis(methylcyclopentadienyl) nickel is introduced at 55° C. to chemically adsorb on the substrate surface; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0223] In the third step, reactants (oxygen and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge unreacted reactants and by-products.

[0224] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0225] The preparation method of ZrO2 is the same as that of the bonding layer.

[0226] The preparation method of the porous structure layer is the same as that of Example 4. The preparation method of the porous structure is water bath treatment, specifically the following steps: placing the coated piece in 68°C ultrapure water for 2.2 hours and then drying it in a high temperature oven for 4 hours to obtain porous aluminum oxide.

[0227] Example 7

[0228] like Figure 1 As shown, this embodiment provides an ultra-black film structure with low deposition temperature and low reflectivity, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, an ultra-black film layer 3 composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer 2 using ALD, and a porous structure layer 4 deposited on the surface of the ultra-black film layer 3 using ALD. The reflectivity of the ultra-black film structure is less than 0.1%.

[0229] The material of the substrate 1 is plastic.

[0230] The deposition temperature of the bonding layer 2 and the ultra-black film layer 3 is 100°C.

[0231] The thickness of the bonding layer 2 is 19 nm, the thickness of the ultra-black film layer 3 is 448.21 nm, and the thickness of the porous structure layer 4 is 262.08 nm.

[0232] The porosity of the porous structure layer 4 is 82%.

[0233] The material of the bonding layer 2 is TiO2.

[0234] The ultra-black film layer 3 is composed of alternating metals and oxides, where the metals are Pd and Pt, and the oxides are ZrO2 / HfO2 / SiO2. The ultra-black film layer 3 includes a Pt layer (100 nm), a ZrO2 layer (59.47 nm), a Pd layer (11.79 nm), a SiO2 layer (109.15 nm), a Pt layer (9.4 nm), a HfO2 layer (62.34 nm), a Pd layer (2.73 nm), a SiO2 layer (91.9 nm), and a Pt layer (1.43 nm), arranged in sequence from the bonding layer 2 to the porous structure layer 4.

[0235] The porous structure layer 4 is porous SiO2.

[0236] The preparation method of bonding layer 2 is the same as that of Example 4.

[0237] The preparation method of Pd in ​​the ultra-black film layer 3 is time-type ALD, and the preparation method includes the following steps:

[0238] In the first step, the substrate with the bonding layer attached is placed in an atomic layer deposition chamber under vacuum;

[0239] In the second step, the precursor bis(2,2,6,6-tetramethyl-3,5-heptanedione)palladium is introduced at 110°C to chemically adsorb on the surface of the binding layer; then an inert gas is introduced to purge the unreacted precursor and by-products;

[0240] In the third step, reactants (oxygen and hydrogen) are introduced into the chamber to form a monolayer with the surface-adsorbed precursor; then an inert gas is introduced to purge unreacted reactants and by-products.

[0241] Repeat n times, cyclic deposition, to form a bonding layer, where n is a natural number greater than or equal to 0.

[0242] The preparation method of Pt is the same as that in Example 4.

[0243] The preparation method of ZrO2 is the same as that of Example 2. The preparation method of SiO2 is the same as that of Example 4.

[0244] The preparation method of HfO2 layer is:

[0245] In the first step, a pulse of hafnium tetramethylamino was introduced into the atomic layer deposition chamber at 85°C for 3 seconds to allow it to chemically adsorb on the surface of the bonding layer. Then, an inert gas was introduced at 5000 sccm for 30 seconds to purge unreacted hafnium tetramethylamino and byproducts.

[0246] In the second step, O2 plasma was pulsed into the chamber and maintained for 20 seconds to form a monolayer with the surface-adsorbed hafnium tetradimethylamino. Unreacted O2 plasma and byproducts were then purged with inert gas at 5000 sccm for 10 seconds.

[0247] In the third step, the first and second steps are repeated, and HfO2 is formed by cyclic deposition.

[0248] The preparation method for the membrane layer in the porous structure layer is the same as in Example 4. The porous structure is prepared by ALD plus 85% phosphoric acid solution. The specific steps are as follows: the coated part is placed in 85% phosphoric acid solution at 52°C for 18 hours, then rinsed in ethanol solution and blown dry with an N2 gun.

[0249] Comparative Example 1

[0250] This comparative example provides a traditional ultra-black film structure. The black film layer material is the same as that in Example 1, the metal is Co, the oxide is SiO2, and the total stacking thickness is 2418.42nm. There is no design of a bonding layer and a porous structure layer. The absorption effect and the film layer stacking thickness are as follows. Figure 2 shown.

[0251] Figure 3 is a schematic diagram of the ultra-low reflectivity curve of Example 1, Figure 2 and Figure 3 It can be seen that the design of the present invention can effectively reduce the thickness of the film layer while achieving the purpose of ultra-low reflection.

[0252]

[0253] A spectrophotometer was used to test reflectivity, emissivity, and absorptivity. Adhesion was assessed using a 100-grid test. The specific test method involves cutting a regular grid (usually 1mm×1mm or 2mm×2mm squares) on the coating surface with a blade, then applying and peeling off adhesive tape to observe the coating's shedding to determine the adhesion level. (Level 0: Smooth edges, no shedding (best adhesion); Level 1: Shedding area <5%; Level 2: 5% to 15% shedding; Level 3: 15% to 35% shedding; Level 4: 35% to 65% shedding; Level 5: >65% shedding (worst adhesion)). A comparison of optical properties and adhesion evaluation is shown in Table 2.

[0254] Table 2: Comparison of optical properties and adhesion between 400-800nm

[0255]

[0256] Table 2 shows that compared to traditional ultra-black film designs, the coating system designed in this invention effectively reduces the total coating thickness and achieves an ultra-low reflectivity of less than 0.1%, saving production costs and time. Furthermore, the bonding layer significantly improves the coating's adhesion and prevents film delamination.

[0257] In short, the present invention can significantly reduce the deposition temperature; it can significantly reduce the total thickness of the film layer compared to the traditional microstructure-free film, reduce costs and achieve ultra-low reflectivity below 0.1%. The ultra-black film of the present invention can be widely used in the fields of mobile phone lenses, car lenses, AR / VR, etc. Among them, in the field of mobile phone lenses and car lenses, the present invention can greatly reduce internal reflections, suppress stray light inside the lens, improve imaging contrast, and reduce reflection losses on the surface of optical components. The use of the present invention in the field of VR / AR equipment can greatly reduce internal light reflections and improve user experience.

[0258] Based on the disclosure and teachings of the above description, those skilled in the art may also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and modifications and variations of the present invention should also fall within the scope of protection of the claims of the present invention. In addition, although certain specific terms are used in this description, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims

1. An ultra-black film structure with low deposition temperature and low reflectivity, characterized by: It includes a substrate, a bonding layer deposited on the surface of the substrate using ALD, an ultra-black film layer composed of a low-temperature light-absorbing material deposited on the surface of the bonding layer using ALD, and a porous structure layer arranged on the surface of the ultra-black film layer. The reflectivity of the ultra-black film structure is less than 0.1%.

2. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The substrate is made of ceramic, metal, plastic or glass.

3. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The deposition temperature of the bonding layer and the ultra-black film layer is 25° C.-150° C.

4. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The thickness of the bonding layer is 0.1-20 nm, the thickness of the ultra-black film layer is 200 nm-1000 nm, and the thickness of the porous structure layer is 80 nm-500 nm.

5. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The porosity of the porous structure layer is 50%-85%.

6. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The material of the bonding layer is at least one of an oxide or a metal element, wherein the oxide is one of TiO2, SiO2, Al2O3, ZrO2, HfO2, Ta2O5, Nb2O5, CuO and ZnO; the metal element is one of Cu, Co, Ag, Ni, Ru, Pt, Pd and Ir.

7. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The ultra-black film layer is formed by alternating superposition of metals and oxides, wherein the metal is at least one of Co, Cu, Pt, Pd, Ir and Ni, and the oxide is at least one of TiO2, SiO2, Al2O3, ZrO2, HfO2, Ta2O5, Nb2O5 and ZnO.

8. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The porous structure layer is porous Al2O3 or SiO2.

9. The ultra-black film structure with low deposition temperature and low reflectivity according to claim 1, characterized in that: The porous structure layer is prepared by an ALD method to obtain a membrane layer and then treated with a water bath or a phosphoric acid solution.

10. Application of the ultra-black film structure according to any one of claims 1 to 9 in mobile phone lenses, vehicle lenses, and AR / VR fields.

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