Super black nano-coating structure

Abstract

The application belongs to the technical field of nano coating, and particularly relates to a super-black nano coating structure, which comprises a substrate, a transition layer deposited on the surface of the substrate by ALD, a light-absorbing layer deposited on the surface of the transition layer by ALD, and an anti-corrosion layer deposited on the surface of the light-absorbing layer by ALD. Compared with the prior art, the application uses the ALD technology to realize the super-black film of the substrate / transition layer (increasing adhesion) / light-absorbing layer (multi-layer interference film layer) / anti-corrosion layer (single layer or multiple layers) with low temperature (50-250 DEG C), high coverage, ultra-low reflection (less than or equal to 0.5%), high absorption efficiency (greater than or equal to 99.00%) and good bonding force, effectively expands the selection range of the substrate material, solves the problem that the current super-black film manufacturing process has a great limitation on the substrate material, and is difficult to be compatible with the low-temperature control and high coverage, high absorption rate of the film.

Description

Technical Field

[0001] This invention belongs to the field of nano-coating technology, and in particular relates to an ultra-black nano-coating structure. Background Technology

[0002] The ultra-black nano-coating possesses extremely high absorptivity and extremely low reflectivity, effectively shielding and absorbing optical interference from visible and infrared light, reducing various unwanted reflected light, and eliminating harmful stray light. These properties can be widely applied in the field of optics, significantly improving the imaging quality and accuracy of optical products, thereby enhancing product performance.

[0003] Currently, commonly used industrial technologies for producing ultra-black films include chemical vapor deposition (CVD), physical vapor deposition (PVD), and carbon nanotube methods. However, these processes all have certain limitations on substrate materials. For example, 1) it is difficult to achieve uniform deposition on substrates with high aspect ratio structures; 2) the deposition temperature requirements are relatively high, which limits many substrate materials that are not resistant to high temperatures.

[0004] In view of this, the present invention aims to provide an ultra-black nanofilm structure, which is fabricated using a low-temperature ALD (Atomic Layer Deposition) process, allowing for precise control of the film thickness at the atomic level. This technology offers significant advantages in terms of precise control of film thickness, film thickness uniformity, and coverage of complex-shaped components. The ultra-black film obtained by this invention solves the problem of traditional ultra-black films struggling to achieve high coverage and high absorption efficiency (≥99.00%) at low temperatures, enabling compatibility with more substrate materials and application in a wider range of products. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by providing an ultra-black nanofilm structure. This structure is fabricated using a low-temperature ALD (Atomic Layer Deposition) process, allowing for precise atomic-level control of the film thickness. This technology offers significant advantages in terms of precise thickness control, film thickness uniformity, and coverage of complex shapes. The ultra-black film obtained by this invention solves the problem of traditional ultra-black films failing to achieve high coverage and high absorption efficiency (≥99.00%) at low temperatures, enabling compatibility with a wider range of substrate materials and applications in more products.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] An ultra-black nano-coating structure includes a substrate, a transition layer deposited on the surface of the substrate by ALD, a light-absorbing layer deposited on the surface of the transition layer by ALD, and an anti-corrosion layer deposited on the surface of the light-absorbing layer by ALD.

[0008] The transition layer enhances adhesion, preventing poor bonding between the substrate and the light-absorbing layer due to mismatched thermal expansion coefficients. The light-absorbing layer, a multi-layered interference film, effectively reduces light reflection on its surface, allowing more light to enter and be absorbed by the main light-absorbing layer, thus improving overall light absorption efficiency. The anti-corrosion layer creates a gradient refractive index, increasing the film's wear and corrosion resistance with minimal increase in reflection. ALD (Alternating Discharge Coating) is a high-precision coating preparation technology that allows for atomic-level control of film thickness. This technology offers significant advantages in precise thickness control, uniform thickness, and coverage of complex-shaped components.

[0009] As an improvement to the ultra-black nano-coating structure of the present invention, the thickness of the transition layer is 1-50nm, which needs to be sufficient to cover the defects of the substrate, but too thick a layer will increase stress. The thickness of the light-absorbing layer is 50-800nm, and multiple layers are stacked to achieve broadband low reflectance. The thickness of the anti-corrosion layer is 5-300nm, which needs to meet the requirements of medium barrier and mechanical strength.

[0010] As an improvement to the ultra-black nano-coating structure of the present invention, the substrate is made of at least one of polycarbonate, polymethyl methacrylate, polyimide, SiC or titanium alloy and BK7 optical glass.

[0011] As an improvement to the ultra-black nanofilm structure of this invention, the transition layer can be at least one of oxide, nitride, and organic-inorganic hybrid thin film. The oxide forms a strong bond with the metal or ceramic substrate through MO-Me (metal-oxygen-substrate) bonds, making it particularly suitable for oxygen-containing substrates (such as glass and stainless steel), and exhibiting better low-temperature compatibility, making it suitable for heat-sensitive substrates (such as plastics and organic semiconductors). The general chemical formula of the oxide is MO. x M is at least one of Ti, Al, V, Mn, Zn, Zr, Hf, Mg, and Si, and 1 ≤ x ≤ 5; the nitride has high hardness and enhances the bonding with the rough substrate through mechanical anchoring effect, making it more suitable for metals or alloys; the nitride is at least one of titanium nitride, aluminum nitride, silicon nitride, hafnium nitride, tantalum nitride, and zirconium nitride; the organic-inorganic hybrid film combines the flexibility of organic chains with the high strength of inorganic units, which can alleviate the thermal stress between the substrate and the functional layer, making it more suitable for flexible substrates; the film types include at least one of Alucone (aluminum-based hybrid film), Zincone (zinc-based hybrid film), Zircone (zircone-based hybrid film), Titanicone (titanium-based hybrid film), Hf-cone (hafnium-based hybrid film), Vanadicone (vanadium-based hybrid film), Magnesicone (magnesium-based hybrid film), and manganese-based hybrid film.

[0012] As an improvement to the ultra-black nano-coating structure of the present invention, the light-absorbing layer includes a titanium aluminum carbide (TiAlC) layer; it may also include a SiO2 layer and / or an Al2O3 layer. TiAlC can achieve an ultra-black film with high coverage, ultra-low reflectivity (≤0.20%), and high absorption efficiency (≥99.00%) at low temperatures (50-250℃).

[0013] As an improvement to the ultra-black nano-coating structure of the present invention, the anti-corrosion layer is an oxide and / or a nitride. The oxide has excellent chemical stability, high transmittance, and low optical influence, making it more suitable for applications in optically sensitive, low-temperature, and oxidation-resistant environments. The oxide is at least one of ZrO2, Al2O3, SiO2, and TiO2. The nitride performs better in terms of mechanical protection, acid and alkali resistance, and electrical conductivity. The nitride is at least one of titanium nitride (TiN), aluminum nitride (AlN), tantalum nitride, chromium nitride, and silicon nitride.

[0014] As an improvement to the ultra-black nanofilm structure of this invention, the transition layer can be prepared using either time-based ALD or space-based ALD deposition methods. Time-based ALD deposition allows for precise control of each layer thickness to optimize refractive index matching, provides better shape retention for high aspect ratio substrates, and offers greater flexibility in material selection. Space-based ALD deposition not only possesses the basic characteristics of precise film quality control and good shape retention but also enables rapid deposition, making it suitable for large-scale, large-size, and low-cost product deposition. The time-based ALD deposition method includes at least the following steps:

[0015] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0016] The second step involves introducing the first precursor in a pulsed manner at 50-250℃ for 0.1-10s to allow it to be chemically adsorbed onto the substrate surface; then, an inert gas of 500-5000 sccm is introduced to purge the unreacted first precursor and byproducts for 5-120s.

[0017] The third step involves adding the first reactant into the chamber in a pulsed manner and holding it for 0.1-10 seconds to allow it to form a monolayer with the first precursor adsorbed on the surface. Then, an inert gas of 500-5000 sccm is introduced to purge the unreacted first reactant and byproducts for 5-120 seconds.

[0018] The fourth step is to repeat steps two and three, cyclically depositing to form a transition layer; this step is optional, and when this step is not selected, a single-layer structure is obtained.

[0019] Spatial ALD deposition methods include at least the following steps:

[0020] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0021] The second step involves continuously introducing the first precursor and the first reactant into the cavity at 50-250°C through a carrier gas of 500-5000 sccm and a dilution gas of 500-10000 sccm, respectively, to the reaction zone of the first precursor and the first reactant. At the same time, an inert gas of 5000-20000 sccm is introduced between the first precursor and the first reactant.

[0022] The third step involves the substrate sequentially passing through the first precursor, the isolation gas, the first reactant, and the isolation gas region to complete one cycle of deposition.

[0023] The fourth step is to repeat steps two and three, cyclically depositing to form a transition layer; this step is optional, and when this step is not selected, a single-layer structure is obtained.

[0024] The carrier gas, dilution gas, and inert gas can be argon or nitrogen.

[0025] As an improvement to the ultra-black nano-coating structure of the present invention, when the transition layer is an oxide, the first precursor is at least one of aluminum source, titanium source, vanadium source, manganese source, zinc source, zirconium source, hafnium source, magnesium source and silicon source, and the first reactant is H2O, O3 or O2 plasma.

[0026] When the transition layer is a nitride, the first precursor is at least one of a titanium source, an aluminum source, a silicon source, a hafnium source, a tantalum source, and a zirconium source; the first reactant is at least one of a nitrogen plasma and an ammonia plasma.

[0027] When the transition layer is an organic-inorganic hybrid thin film, the first precursor is at least one of aluminum source, titanium source, vanadium source, manganese source, zinc source, zirconium source, hafnium source, and magnesium source, and the first reactant is at least one of EG (ethylene glycol), glycerol, 1,4-butanediol, HQ (hydroquinone), and ethanolamine.

[0028] The aluminum source is at least one of TMA (trimethylaluminum), TEA (triethylaluminum), and AlCl3 (aluminum trichloride); the titanium source is at least one of TiCl4 (titanium tetrachloride), TDMAT (tetra(dimethylamino)titanium), and TTIP (tetraisopropyl titanate); the vanadium source is at least one of V2O5 (vanadium pentoxide), VCl3 (vanadium trichloride), VCl4 (vanadium tetrachloride), and VOCl3 (vanadium oxychloride); the manganese source is at least one of MnCl2 (manganese dichloride), Mn3O4 (manganese trioxide), and Mn(Cp)2 (di(cyclopentadienyl)manganese); and the zinc source is DEZ (diethylzinc). The source is at least one of DMZ (dimethylzinc) and ZnCl2 (zinc chloride); the zirconium source is at least one of TDMAZr (tetra(dimethylamino)zirconium), TEMAZr (tetraethylmethylaminozirconium), and ZrCl4 (zirconium tetrachloride); the hafnium source is one of TDMAHf (tetramethylaminohafnium), TEMAHf (tetraethylmethylaminohafnium), and HfCl4 (hafnium tetrachloride); the magnesium source is at least one of Mg(Cp)2 (magnesium pyrocene), Mg(Et)2 (diethylmagnesium), and Mg(OMe)(tBu) (methylmagnesium tert-butoxy); the silicon source can be at least one of BDEAS (bis(diethylamino)silane), DIPAS (diisopropylaminosilane), 3DMAS (tris(dimethylamino)silane), and BTBAS (bis(tert-butylamino)silane).

[0029] As an improvement to the ultra-black nanofilm structure of the present invention, the light-absorbing layer is prepared by a time-dependent ALD or a spatial ALD deposition method, wherein the time-dependent ALD deposition method includes at least the following steps:

[0030] The first step involves introducing the second precursor in a pulsed manner in an atomic layer deposition chamber at 50-250°C for 0.1-10 seconds to allow it to be chemically adsorbed onto the surface of the transition layer. Then, an inert gas of 500-5000 sccm is introduced to purge the unreacted second precursor and byproducts for 5-120 seconds.

[0031] The second step involves adding the second reactant into the chamber in a pulsed manner, allowing it to form a monolayer with the second precursor adsorbed on the surface; then, an inert gas of 500-5000 sccm is introduced to purge unreacted second reactants and byproducts for 5-120 s.

[0032] The third step is to repeat the first and second steps to form a light-absorbing layer through cyclic deposition. This step is optional; if this step is not selected, a single-layer structure is obtained.

[0033] Spatial ALD methods include at least the following steps:

[0034] In the first step, in an atomic layer deposition chamber at 50-250°C, the second precursor and the second reactant are continuously introduced into the chamber through a carrier gas of 500-5000 sccm and a dilution gas of 500-10000 sccm, respectively, to the reaction zone of the second precursor and the second reactant. At the same time, an inert gas of 5000-20000 sccm is introduced between the second precursor and the second reactant.

[0035] In the second step, the substrate with the transition layer deposited passes through the second precursor, the isolation gas, the second reactant, and the isolation gas region in sequence to complete one cycle of deposition.

[0036] The third step is to repeat the first and second steps to form a light-absorbing layer through cyclic deposition. This step is optional; if this step is not selected, a single-layer structure is obtained.

[0037] Among them, the carrier gas, dilution gas, and inert gas can be argon or nitrogen;

[0038] The second precursor is an aluminum source and a titanium source, wherein the aluminum source is at least one of TMA, TEA (triethylaluminum), and AlCl3 (aluminum trichloride); the titanium source is at least one of TiCl4 (titanium tetrachloride), TDMAT (tetra(dimethylamino)titanium), and TTIP (tetraisopropyl titanate); and the second reactant is a methane plasma as the carbon source.

[0039] The preparation methods for the SiO2 layer and / or Al2O3 layer in the light-absorbing layer are the same as those for the oxides in the transition layer and the anti-corrosion layer.

[0040] As an improvement to the ultra-black nano-coating structure of the present invention, the method for preparing the anti-corrosion layer is a time-dependent ALD or spatial ALD deposition method, wherein the time-dependent ALD deposition method includes at least the following steps:

[0041] The first step involves introducing the third precursor in a pulsed manner in an atomic layer deposition chamber at 50-250℃ for 0.1-10s to allow it to be chemically adsorbed onto the surface of the light-absorbing layer. Then, an inert gas of 500-5000 sccm is introduced to purge the unreacted third precursor and byproducts for 5-120s.

[0042] The second step involves adding the third reactant into the chamber in a pulsed manner, allowing it to form a monolayer with the third precursor adsorbed on the surface; then, an inert gas of 500-5000 sccm is introduced to purge the unreacted third reactant and byproducts for 5-120 s.

[0043] The third step is to repeat the first and second steps to form an anti-corrosion layer through cyclic deposition. This step is optional; if this step is not selected, a single-layer structure is obtained.

[0044] Spatial ALD deposition methods include at least the following steps:

[0045] In the first step, in an atomic layer deposition chamber at 50-250℃, the third precursor and the third reactant are continuously introduced into the chamber through a carrier gas of 500-5000 sccm and a dilution gas of 500-10000 sccm, respectively, to the reaction zone of the third precursor and the third reactant. At the same time, an inert gas of 5000-20000 sccm is introduced between the third precursor and the third reactant.

[0046] The second step involves the substrate with the transition layer and light-absorbing layer deposited sequentially passing through the third precursor, isolation gas, third reactant, and isolation gas regions to complete one cycle of deposition.

[0047] The third step is to repeat the first and second steps to form an anti-corrosion layer through cyclic deposition. This step is optional; if this step is not selected, a single-layer structure is obtained.

[0048] Among them, the carrier gas, dilution gas, and inert gas can be argon or nitrogen;

[0049] When the anti-corrosion layer is an oxide, the third precursor is at least one of aluminum source, silicon source, titanium source and zirconium source; the third reactant is H2O, O3 or O2 plasma;

[0050] When the anti-corrosion layer is a nitride, the third reactant is at least one of aluminum source, titanium source, tantalum source, chromium source and silicon source, and the third reactant is at least one of nitrogen plasma and ammonia plasma;

[0051] The aluminum source is at least one of trimethylaluminum, triethylaluminum, and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetra(dimethylamino)titanium, and tetraisopropyl titanate; the silicon source is one of bis(diethylamino)silane, diisopropylaminosilane, tri(dimethylamino)silane, and bis(tert-butylamino)silane; the zirconium source is at least one of tetra(dimethylamino)zirconium, tetraethylmethylaminozirconium, and zirconium tetrachloride; and the tantalum source is at least one of penta(dimethylamino)tantalum, tert-butyliminotri(ethylmethylamino)tantalum, and tert-butyliminotri(diethylamino)tantalum.

[0052] Compared to existing technologies, this invention uses ALD technology to achieve the technical objective of low-temperature (50-250℃) deposition of ultra-black films. Under the premise of high film coverage, high absorption efficiency, and good adhesion, the process temperature is reduced, making it compatible with more substrate materials and applicable to more products. At the same time, this invention can also achieve uniform deposition on substrates with high aspect ratio structures, and the surface anti-corrosion layer can form a gradient refractive index, which increases the wear resistance and anti-corrosion performance of the film with almost no increase in reflection.

[0053] In summary, this invention utilizes ALD technology to achieve low-temperature (50-250℃) fabrication of ultra-black films with high coverage, ultra-low reflectivity (≤0.20%), high absorption efficiency (≥99.00%), and good adhesion. The film consists of a substrate / transition layer (to increase adhesion), a light-absorbing layer (multi-layer interference film), and an anti-corrosion layer (single or multiple layers). This effectively expands the range of substrate material choices and solves the problem that current ultra-black film fabrication processes have significant limitations on substrate materials, making it difficult to achieve low-temperature control and high coverage and high absorption rates. Attached Figure Description

[0054] Figure 1 This is a schematic diagram of the structure of the present invention. Detailed Implementation

[0055] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0056] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0057] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0058] Example 1

[0059] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0060] The substrate 1 is made of polycarbonate, the transition layer 2 is magnesium oxide, the light-absorbing layer 3 is a titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide layer, and the anti-corrosion layer 4 is titanium oxide, aluminum oxide and silicon oxide.

[0061] The thickness of transition layer 2 is 6nm, the thickness of light-absorbing layer 3 is 94.69nm, 197.9nm, 54.5nm, 33.07nm, and 13.67nm, and the thickness of anti-corrosion layer 4 is 5nm, 5nm, and 63.76nm.

[0062] The transition layer 2 is prepared by time-dependent ALD, and includes at least the following steps:

[0063] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0064] The second step involves introducing diethylmagnesium in a pulsed manner at 100°C for 5 seconds to allow it to chemically adsorb onto the surface of substrate 1. Then, an inert gas of 4000 sccm is introduced to purge the unreacted diethylmagnesium and byproducts for 60 seconds.

[0065] The third step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 5 seconds to allow it to form a monolayer with the diethylmagnesium adsorbed on the surface. Then, an inert gas of 3000 sccm is introduced to purge the unreacted O2 plasma and byproducts for 60 seconds.

[0066] Fourth step: Repeat steps two and three, cyclically depositing to form transition layer 2.

[0067] The light-absorbing layer 3 is prepared by a spatial ALD, and includes at least the following steps:

[0068] In the first step, in an atomic layer deposition chamber at 100°C, trimethylaluminum, titanium tetrachloride and methane plasmas are continuously introduced into the chamber through a carrier gas of 2000 sccm and a dilution gas of 3000 sccm, until they reach the reaction region of the trimethylaluminum, titanium tetrachloride and methane plasmas. At the same time, an inert gas of 4000 sccm is introduced between the trimethylaluminum, titanium tetrachloride and methane plasmas.

[0069] In the second step, the substrate with the transition layer 2 is deposited sequentially through the trimethylaluminum, titanium tetrachloride, and methane plasma and isolation gas regions to complete one cycle of deposition.

[0070] The third step involves repeating the first and second steps in a cyclic deposition process to form the TiAlC in the light-absorbing layer.

[0071] Fourth step: At 100°C, diisopropylamine silane is introduced in a pulsed manner and held for 3 seconds to allow it to be chemically adsorbed onto the TiAlC surface; then, an inert gas of 4000 sccm is introduced to purge unreacted diisopropylamine silane and byproducts for 30 seconds.

[0072] The fifth step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 20 seconds to allow it to form a monolayer with the diisopropylamine silane adsorbed on the surface. Then, an inert gas of 4000 sccm is introduced to purge the unreacted O2 plasma and byproducts for 10 seconds.

[0073] Step 6: Repeat steps 4 and 5 to form a light-absorbing layer of SiO2 through cyclic deposition.

[0074] Step 7: Repeat steps 3 and 6 to form a light-absorbing layer 3 through cyclic deposition.

[0075] Argon is used as the carrier gas, dilution gas, and inert gas.

[0076] The preparation method of anti-corrosion layer 4 is time-type ALD, which includes at least the following steps:

[0077] First, titanium tetrachloride was introduced in a pulsed manner in an atomic layer deposition chamber at 100°C, causing it to be chemically adsorbed onto the surface of the light-absorbing layer 3; then, an inert gas of 1000 sccm was introduced to purge the unreacted titanium tetrachloride and byproducts for 20 seconds.

[0078] The second step involves adding distilled water into the chamber in a pulsed manner to allow it to form a monolayer with the titanium tetrachloride adsorbed on the surface; then, an inert gas flow of 1000 sccm is introduced to purge unreacted nitrogen plasma and byproducts for 30 seconds.

[0079] The third step involves repeating the first and second steps to form a TiO2 anti-corrosion layer through cyclic deposition.

[0080] The fourth step involves introducing diethylaluminum in a pulsed manner into an atomic layer deposition chamber at 100°C, causing it to chemically adsorb onto the TiO2 surface; then, an inert gas flow of 2000 sccm is introduced to purge unreacted diethylaluminum and byproducts for 20 seconds.

[0081] The fifth step involves adding distilled water into the chamber in a pulsed manner to allow it to form a monolayer with the diethylaluminum adsorbed on the surface; then, an inert gas flow of 1000 sccm is introduced to purge unreacted distilled water and byproducts for 30 seconds.

[0082] Step six, repeat steps four and five, cyclically depositing to form Al2O3.

[0083] Step 7: At 100°C, diisopropylamine silane is introduced in a pulsed manner and held for 3 seconds to allow it to be chemically adsorbed onto the surface of the anti-corrosion layer Al2O3; then, an inert gas of 4000 sccm is introduced to purge unreacted diisopropylamine silane and byproducts for 30 seconds.

[0084] Step 8: O2 plasma is introduced into the chamber in a pulsed manner and held for 20 seconds to allow it to form a monolayer with the diisopropylamine silane adsorbed on the surface; then, 4000 sccm of inert gas is introduced to purge the unreacted O2 plasma and byproducts for 10 seconds.

[0085] Step 9: Repeat steps 7 and 8 to form SiO2 through cyclic deposition.

[0086] Example 2

[0087] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0088] The substrate 1 is made of polymethyl methacrylate, the transition layer 2 is an aluminum-based hybrid film, the light-absorbing layer 3 is a titanium aluminum carbide / alumina / titanium aluminum carbide / alumina / titanium aluminum carbide layer, and the anti-corrosion layer 4 is tantalum nitride / silicon oxide. The thickness of the transition layer 2 is 10 nm, the thicknesses of the light-absorbing layer 3 are 90 nm, 20 nm, 66.53 nm, 23.74 nm, and 1.56 nm, and the thicknesses of the anti-corrosion layer 4 are 23.86 nm and 66.68 nm.

[0089] The transition layer 2 is prepared by time-dependent ALD, and includes at least the following steps:

[0090] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0091] The second step involves introducing magnesium pyrocene in a pulsed manner at 105°C for 8 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2000 sccm is introduced to purge the unreacted magnesium pyrocene and byproducts for 50 seconds.

[0092] The third step involves adding O3 into the chamber in a pulsed manner and holding it for 5 seconds to allow it to form a monolayer with the magnesia adsorbed on the surface. Then, an inert gas flow of 4000 sccm is introduced to purge unreacted O3 and byproducts for 50 seconds.

[0093] Fourth step: Repeat steps two and three, cyclically depositing to form transition layer 2.

[0094] The light-absorbing layer 3 is prepared by time-dependent ALD, and includes at least the following steps:

[0095] In the first step, trimethylaluminum and titanium tetrachloride were introduced in a pulsed manner in an atomic layer deposition chamber at 105°C, so that they were chemically adsorbed on the surface of transition layer 2; then, an inert gas of 4000 sccm was introduced to purge unreacted trimethylaluminum, titanium tetrachloride and byproducts for 100 s.

[0096] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the trimethylaluminum and titanium tetrachloride adsorbed on the surface; then, an inert gas of 2000 sccm is introduced to purge the unreacted methane plasma and byproducts for 80 seconds.

[0097] The third step involves repeating the first and second steps in a cyclic deposition process to form titanium aluminum carbide.

[0098] The fourth step involves introducing dimethylaluminum in a pulsed manner into an atomic layer deposition chamber at 105°C, causing it to be chemically adsorbed onto the surface of titanium aluminum carbide; then, an inert gas of 3000 sccm is introduced to purge unreacted dimethylaluminum and byproducts for 20 seconds.

[0099] The fifth step involves adding distilled water into the chamber in a pulsed manner to allow it to form a monolayer with the dimethylaluminum adsorbed on the surface; then, an inert gas flow of 2000 sccm is introduced to purge unreacted distilled water and byproducts for 30 seconds.

[0100] Step six, repeat steps four and five, cyclically depositing to form Al2O3.

[0101] Step 7: Repeat steps 3 and 6 once each, and then repeat step 3 once more to form the light-absorbing layer.

[0102] The preparation method of anti-corrosion layer 4 is time-type ALD, which includes at least the following steps:

[0103] First, pentapentan(dimethylamino)tantalum is introduced in a pulsed manner in an atomic layer deposition chamber at 105°C, causing it to be chemically adsorbed on the surface of light-absorbing layer 3; then, an inert gas of 1500 sccm is introduced to purge unreacted pentapentan(dimethylamino)tantalum and byproducts for 30 s.

[0104] The second step involves introducing ammonia plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the adsorbed penta(dimethylamino)tantalum on the surface; then, an inert gas of 1500 sccm is introduced to purge unreacted oxygen plasma and byproducts for 40 seconds.

[0105] The third step involves repeating the first and second steps in a cyclic deposition process to form tantalum nitride.

[0106] Fourth step: At 105°C, bis(diethylamino)silane is introduced in a pulsed manner and held for 7 seconds to allow it to be chemically adsorbed onto the tantalum nitride surface; then, an inert gas of 2800 sccm is introduced to purge unreacted bis(diethylamino)silane and byproducts for 55 seconds.

[0107] The fifth step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 8 seconds to allow it to form a monolayer with the surface-adsorbed bis(diethylamino)silane. Then, an inert gas of 3800 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0108] Step 6: Repeat steps 4 and 5 to form a silicon dioxide layer through cyclic deposition.

[0109] Example 3

[0110] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0111] The substrate 1 is made of polyimide, the transition layer 2 is aluminum nitride, the light-absorbing layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide, and the anti-corrosion layer 4 is zirconium oxide / aluminum oxide / silicon oxide. The thickness of the transition layer 2 is 8.15 nm, the thickness of the light-absorbing layer 3 is 77.28 nm, 151.21 nm, 191.77 nm, 23.41 nm, and 13.59 nm, and the thickness of the anti-corrosion layer 4 is 7.2 nm, 13.88 nm, and 47.06 nm.

[0112] The transition layer 2 is prepared using a spatial ALD method, which includes at least the following steps:

[0113] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0114] The second step involves continuously introducing aluminum trichloride and nitrogen plasma into the cavity at 90°C through a carrier gas of 2500 sccm and a dilution gas of 5000 sccm, respectively, to the reaction area of ​​the first precursor and the first reactant. At the same time, an inert gas of 5000-20000 sccm is introduced between the first precursor and the first reactant.

[0115] The third step involves the substrate sequentially passing through aluminum trichloride, isolation gas, nitrogen plasma, and the isolation gas region to complete one cycle of deposition.

[0116] The fourth step involves repeating steps two and three, cyclically depositing to form a transition layer.

[0117] Argon is used as the carrier gas, dilution gas, and inert gas.

[0118] The light-absorbing layer 3 is prepared by a spatial ALD deposition method, which includes at least the following steps:

[0119] In the first step, in an atomic layer deposition chamber at 90°C, trimethylaluminum, titanium tetrachloride, and methane plasmas are continuously introduced into the chamber through a carrier gas of 2600 sccm and a dilution gas of 3500 sccm, until they reach the reaction zone of the trimethylaluminum, titanium tetrachloride, and methane plasmas. At the same time, an inert gas of 4800 sccm is introduced between the trimethylaluminum, tetra(dimethylamino)titanium, and methane plasmas.

[0120] In the second step, the substrate with the transition layer 2 is deposited sequentially through the trimethylaluminum, tetra(dimethylamino)titanium and methane plasma and isolation gas regions to complete one cycle of deposition;

[0121] The third step involves repeating the first and second steps in a cyclic deposition process to form titanium aluminum carbide.

[0122] The fourth step involves continuously introducing bis(diethylamino)silane and nitrogen plasma into the cavity at 90°C through a carrier gas of 2500 sccm and a dilution gas of 5000 sccm, respectively, to the reaction area of ​​the first precursor and the first reactant. At the same time, an inert gas of 5000-20000 sccm is introduced between the first precursor and the first reactant.

[0123] In the fourth step, the substrate sequentially passes through bis(diethylamino)silane, isolation gas, nitrogen plasma, and the isolation gas region to complete a cycle of deposition, forming silicon dioxide.

[0124] Among them, the carrier gas, dilution gas, and inert gas are argon or nitrogen;

[0125] The preparation method of the anti-corrosion layer 4 is a spatial ALD, which includes at least the following steps:

[0126] In the first step, in an atomic layer deposition chamber at 90°C, tetra(dimethylamino)zirconium and H2O are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, respectively, until they reach the reaction zone of tetra(dimethylamino)zirconium and H2O. At the same time, an inert gas of 10000 sccm is introduced between tetra(dimethylamino)zirconium and H2O.

[0127] In the second step, the substrate 1, with the transition layer 2 and the light-absorbing layer 3 deposited thereon passes through the tetra(dimethylamino)zirconium, the isolation gas, H2O and the isolation gas region in sequence to complete one cycle of deposition;

[0128] The third step involves repeating the first and second steps in a cyclic deposition process to form zirconium oxide.

[0129] In the fourth step, in the atomic layer deposition chamber at 90°C, diethylaluminum and H2O are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, respectively, to the reaction zone of diethylaluminum and H2O. At the same time, an inert gas of 10000 sccm is introduced between diethylaluminum and H2O.

[0130] The fifth step involves sequentially passing through the diethylaluminum, isolation gas, H2O, and isolation gas zones to complete one cycle of deposition.

[0131] Step 6: Repeat steps 4 and 5 in a cyclic deposition process to form alumina;

[0132] Step 7: In the atomic layer deposition chamber at 90°C, bis(diethylamino)silane and H2O are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, respectively, until they reach the reaction zone of bis(diethylamino)silane and H2O. At the same time, an inert gas of 10000 sccm is introduced between bis(diethylamino)silane and H2O.

[0133] The fifth step involves sequentially passing through the bis(diethylamino)silane, isolation gas, H2O, and isolation gas zones to complete one cycle of deposition.

[0134] Step six: Repeat steps one and two in a cycle to deposit silicon oxide.

[0135] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0136] Example 4

[0137] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0138] The substrate 1 is made of SiC, the transition layer 2 is aluminum nitride, the light-absorbing layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide; and the anti-corrosion layer 4 is titanium nitride / silicon oxide.

[0139] The thickness of transition layer 2 is 6.41 nm, the thickness of light-absorbing layer 3 is 74.88 nm, 186.95 nm, 191.75 nm, 28.09 nm, and 3.95 nm, and the thickness of anti-corrosion layer 4 is 16.13 nm and 62.01 nm.

[0140] The transition layer 2 is prepared by time-dependent ALD, and includes at least the following steps:

[0141] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0142] The second step involves introducing trimethylaluminum in a pulsed manner at 103°C for 10 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2500 sccm is introduced to purge unreacted trimethylaluminum and byproducts for 35 seconds.

[0143] The third step involves introducing ammonia plasma into the chamber in a pulsed manner and holding it for 10 seconds to allow it to form a monolayer with the trimethylaluminum adsorbed on the surface. Then, an inert gas of 4500 sccm is introduced to purge the unreacted ammonia plasma and byproducts for 35 seconds.

[0144] Fourth step: Repeat steps two and three, cyclically depositing to form transition layer 2.

[0145] The light-absorbing layer 3 is prepared by a time-dependent ALD deposition method, and the preparation method of the titanium aluminum carbide layer includes at least the following steps:

[0146] In the first step, triethylaluminum and tetra(dimethylamino)titanium were introduced in a pulsed manner in an atomic layer deposition chamber at 103°C, so that they were chemically adsorbed on the surface of transition layer 2; then, an inert gas of 4000 sccm was introduced to purge the unreacted triethylaluminum, tetra(dimethylamino)titanium and byproducts for 110 s.

[0147] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the triethylaluminum and tetra(dimethylamino)titanium adsorbed on the surface; then, an inert gas of 2200 sccm is introduced to purge the unreacted methane plasma and byproducts for 90 s.

[0148] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium aluminum carbide layer.

[0149] The method for preparing the silicon dioxide layer is as follows:

[0150] First, bis(diethylamino)silane was introduced in a pulsed manner at 103°C and held for 7 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2800 sccm was introduced to purge unreacted bis(diethylamino)silane and byproducts for 55 seconds.

[0151] The second step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 8 seconds to allow it to form a monolayer with the surface-adsorbed bis(diethylamino)silane. Then, an inert gas of 3800 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0152] The third step involves repeating steps two and three in a cyclic deposition process to form a silicon dioxide layer.

[0153] The anti-corrosion layer 4 is prepared by a time-dependent ALD deposition method, and the preparation method of titanium nitride includes at least the following steps:

[0154] First, tetraisopropyl titanate was introduced in a pulsed manner in an atomic layer deposition chamber at 103°C, causing it to be chemically adsorbed onto the surface of light-absorbing layer 3; then, an inert gas of 1500 sccm was introduced to purge unreacted tetraisopropyl titanate and byproducts for 30 seconds.

[0155] The second step involves introducing nitrogen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the tetraisopropyl titanate adsorbed on the surface; then, an inert gas of 1500 sccm is introduced to purge the unreacted nitrogen plasma and byproducts for 40 seconds.

[0156] The third step involves repeating the first and second steps in a cyclic deposition process to form titanium nitride.

[0157] The method for preparing silicon dioxide is as described in this embodiment for preparing silicon dioxide in the light-absorbing layer.

[0158] Example 5

[0159] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0160] Among them, the substrate 1 is made of titanium alloy, the transition layer 2 is a zinc-based hybrid film, the light-absorbing layer 3 is titanium aluminum carbide / alumina / titanium aluminum carbide / alumina / titanium aluminum carbide; and the anti-corrosion layer 4 is aluminum nitride / alumina / silicon oxide.

[0161] The thickness of transition layer 2 is 9nm, the thickness of light-absorbing layer 3 is 9.28nm, 173.5nm, 164.58nm, 24.53nm, and 13.44nm, and the thickness of anti-corrosion layer 4 is 7nm, 34.94nm, and 27.69nm.

[0162] The transition layer 2 is prepared by a spatial ALD deposition method, which includes at least the following steps:

[0163] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0164] The second step involves continuously introducing diethylzinc and glycerol into the chamber at 95°C through a carrier gas of 4500 sccm and a dilution gas of 8000 sccm, respectively, to the reaction zone of diethylzinc and glycerol. At the same time, an inert gas of 15000 sccm is introduced between diethylzinc and glycerol.

[0165] The third step involves the substrate sequentially passing through diethylzinc, isolation gas, glycerol, and the isolation gas region to complete one cycle of deposition.

[0166] The fourth step involves repeating steps two and three, cyclically depositing to form a transition layer.

[0167] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0168] The light-absorbing layer 3 is prepared by a time-dependent ALD deposition method, and the preparation method of the titanium aluminum carbide layer includes at least the following steps:

[0169] In the first step, trimethylaluminum and tetra(dimethylamino)titanium were introduced in a pulsed manner in an atomic layer deposition chamber at 95°C and held for 4 seconds to allow them to be chemically adsorbed on the surface of transition layer 2. Then, an inert gas of 4100 sccm was introduced to purge the unreacted trimethylaluminum, tetra(dimethylamino)titanium and byproducts for 100 seconds.

[0170] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the trimethylaluminum and tetra(dimethylamino)titanium adsorbed on the surface; then, an inert gas of 2800 sccm is introduced to purge the unreacted methane plasma and byproducts for 65 seconds.

[0171] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium aluminum carbide layer.

[0172] The method for preparing the alumina layer is as follows:

[0173] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0174] The second step involves introducing aluminum trichloride in a pulsed manner at 95°C for 7 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2800 sccm is introduced to purge unreacted aluminum trichloride and byproducts for 55 seconds.

[0175] The third step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 8 seconds to allow it to form a monolayer with the aluminum trichloride adsorbed on the surface. Then, an inert gas of 3800 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0176] Fourth, repeat steps two and three to form an alumina layer through cyclic deposition.

[0177] The anti-corrosion layer 4 is prepared by a spatial ALD deposition method:

[0178] The preparation method of aluminum nitride includes the following steps:

[0179] First, trimethylaluminum was introduced in a pulsed manner in an atomic layer deposition chamber at 95°C, causing it to be chemically adsorbed onto the surface of light-absorbing layer 3; then, an inert gas of 1800 sccm was introduced to purge unreacted trimethylaluminum and byproducts for 25 seconds.

[0180] The second step involves introducing nitrogen plasma into the chamber in a pulsed manner to form a monolayer with the trimethylaluminum adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted nitrogen plasma and byproducts for 25 seconds.

[0181] The third step involves repeating the first and second steps in a cyclic deposition process to form aluminum nitride.

[0182] The preparation method of alumina includes the following steps:

[0183] The first step involves introducing trimethylaluminum in a pulsed manner into an atomic layer deposition chamber at 95°C, causing it to chemically adsorb onto the surface of aluminum nitride; then, an inert gas at 1800 sccm is introduced to purge unreacted trimethylaluminum and byproducts for 25 seconds.

[0184] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the trimethylaluminum adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 25 seconds.

[0185] The third step involves repeating the first and second steps in a cyclical deposition process to form aluminum oxide.

[0186] Methods for preparing silicon dioxide:

[0187] The first step involves introducing tris(dimethylamino)silane in a pulsed manner into an atomic layer deposition chamber at 95°C, causing it to be chemically adsorbed onto the surface of alumina; then, an inert gas of 1800 sccm is introduced to purge unreacted tris(dimethylamino)silane and byproducts for 25 seconds.

[0188] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the tris(dimethylamino)silane adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 25 seconds.

[0189] The third step involves repeating the first and second steps in a cyclic deposition process to form silicon oxide.

[0190] Example 6

[0191] like Figure 1As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0192] The substrate 1 is made of optical glass, the transition layer 2 is zinc oxide, the light-absorbing layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide, and the anti-corrosion layer 4 is silicon nitride / aluminum oxide / silicon oxide. The thickness of the transition layer 2 is 6.86 nm, the thickness of the light-absorbing layer 3 is 9.28 nm, 191.79 nm, 164.58 nm, 30.47 nm, and 13.44 nm, and the thickness of the anti-corrosion layer 4 is 5.53 nm, 34.94 nm, and 28.45 nm.

[0193] The transition layer 2 is prepared by time-dependent ALD, and includes at least the following steps:

[0194] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0195] The second step involves introducing dimethyl zinc in a pulsed manner at 100°C for 5 seconds to allow it to be chemically adsorbed onto the surface of substrate 1; then, an inert gas of 4000 sccm is introduced to purge unreacted dimethyl zinc and byproducts for 60 seconds.

[0196] The third step involves adding O3 into the chamber in a pulsed manner and holding it for 6 seconds to allow it to form a monolayer with the dimethyl zinc adsorbed on the surface. Then, an inert gas of 8000 sccm is introduced to purge unreacted O3 and byproducts for 50 seconds.

[0197] Fourth step: Repeat steps two and three, cyclically depositing to form transition layer 2.

[0198] The light-absorbing layer 3 is prepared by time-dependent ALD, and includes at least the following steps:

[0199] The preparation method of titanium aluminum carbide includes the following steps:

[0200] In the first step, trimethylaluminum and titanium tetrachloride were introduced in a pulsed manner in an atomic layer deposition chamber at 100°C, so that they were chemically adsorbed on the surface of transition layer 2; then, an inert gas of 4000 sccm was introduced to purge unreacted trimethylaluminum, titanium tetrachloride and byproducts for 100 s.

[0201] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the trimethylaluminum and titanium tetrachloride adsorbed on the surface; then, an inert gas of 2000 sccm is introduced to purge the unreacted methane plasma and byproducts for 80 seconds.

[0202] The third step involves repeating the first and second steps to form a light-absorbing layer 3 through cyclic deposition.

[0203] The method for preparing the silicon dioxide layer is as follows:

[0204] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0205] The second step involves introducing bis(diethylamino)silane in a pulsed manner at 100°C for 7 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2800 sccm is introduced to purge unreacted bis(diethylamino)silane and byproducts for 55 seconds.

[0206] The third step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 8 seconds to allow it to form a monolayer with the bis(diethylamino)silane adsorbed on the surface. Then, an inert gas of 3800 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0207] Fourth, repeat steps two and three to form a silicon dioxide layer through cyclic deposition.

[0208] The preparation method of anti-corrosion layer 4 is time-type ALD:

[0209] Preparation method of silicon nitride: First, tris(dimethylamino)silane is introduced in a pulsed manner in an atomic layer deposition chamber at 100°C, so that it is chemically adsorbed on the surface of light-absorbing layer 3; then, an inert gas of 1800 sccm is introduced to purge unreacted tris(dimethylamino)silane and byproducts for 30 s.

[0210] The second step involves introducing ammonia plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the tris(dimethylamino)silane adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted ammonia plasma and byproducts for 30 seconds.

[0211] The third step involves repeating the first and second steps in a cyclic deposition process to form silicon nitride.

[0212] Preparation method of alumina: First, triethylaluminum is introduced in a pulsed manner in an atomic layer deposition chamber at 100°C, so that it is chemically adsorbed on the surface of silicon nitride; then, an inert gas of 1800 sccm is introduced to purge unreacted triethylaluminum and byproducts for 30 s.

[0213] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the triethylaluminum adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 30 seconds.

[0214] The third step involves repeating the first and second steps in a cyclical deposition process to form aluminum oxide.

[0215] Preparation method of silicon oxide: First, tris(dimethylamino)silane is introduced in pulse form in an atomic layer deposition chamber at 100°C, so that it is chemically adsorbed on the surface of light-absorbing layer 3; then, an inert gas of 1800 sccm is introduced to purge unreacted tris(dimethylamino)silane and byproducts for 30 s.

[0216] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the tris(dimethylamino)silane adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 30 seconds.

[0217] The third step involves repeating the first and second steps in a cyclic deposition process to form silicon oxide.

[0218] Example 7

[0219] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0220] The substrate 1 is made of polycarbonate, the transition layer 2 is a titanium-based hybrid film, the light-absorbing layer 3 is titanium aluminum carbide / alumina / titanium aluminum carbide / alumina / titanium aluminum carbide; and the anti-corrosion layer 4 is tantalum nitride / alumina / silicon oxide.

[0221] The thickness of transition layer 2 is 13.4 nm, the thickness of light-absorbing layer 3 is 9.28 nm, 173.5 nm, 164.58 nm, 24.53 nm and 9.76 nm, and the thickness of anti-corrosion layer 4 is 6.59 nm, 34.94 nm and 27.69 nm.

[0222] The transition layer 2 is prepared using a spatial ALD method, which includes at least the following steps:

[0223] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0224] The second step involves continuously introducing titanium tetrachloride and 1,4-butanediol into the chamber at 102°C through a carrier gas of 4500 sccm and a dilution gas of 8000 sccm, respectively, to the reaction zone of titanium tetrachloride and 1,4-butanediol. At the same time, an inert gas of 13000 sccm is introduced between titanium tetrachloride and 1,4-butanediol.

[0225] The third step involves the substrate sequentially passing through the titanium tetrachloride, isolation gas, 1,4-butanediol, and isolation gas regions to complete one cycle of deposition.

[0226] The fourth step involves repeating steps two and three, cyclically depositing to form a transition layer.

[0227] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0228] The light-absorbing layer 3 is prepared by a time-dependent ALD deposition method, and the preparation method of the titanium aluminum carbide layer includes at least the following steps:

[0229] In the first step, triethylaluminum and tetraisopropyl titanate were introduced in a pulsed manner in an atomic layer deposition chamber at 102°C and held for 4 seconds to allow them to be chemically adsorbed on the surface of transition layer 2. Then, an inert gas of 4800 sccm was introduced to purge the unreacted triethylaluminum, tetraisopropyl titanate and byproducts for 70 seconds.

[0230] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the triethylaluminum and tetraisopropyl titanate adsorbed on the surface; then, an inert gas of 3800 sccm is introduced to purge the unreacted methane plasma and byproducts for 65 seconds.

[0231] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium aluminum carbide layer.

[0232] The method for preparing the alumina layer is as follows:

[0233] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0234] The second step involves introducing triethylaluminum in a pulsed manner at 102°C for 7.5 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2500 sccm is introduced to purge unreacted triethylaluminum and byproducts for 55 seconds.

[0235] The third step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 3 seconds to allow it to form a monolayer with the triethylaluminum adsorbed on the surface. Then, an inert gas of 3300 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0236] Fourth, repeat steps two and three to form an alumina layer through cyclic deposition.

[0237] The preparation method of anti-corrosion layer 4 is time-type ALD, and the preparation method of tantalum nitride includes at least the following steps:

[0238] In the first step, in an atomic layer deposition chamber at 102°C, tert-butyliminotris(ethylmethylamino)tantalum and nitrogen plasma are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 3000 sccm, respectively, until they reach the reaction region of tert-butyliminotris(ethylmethylamino)tantalum and nitrogen plasma. At the same time, an inert gas of 11000 sccm is introduced between tert-butyliminotris(ethylmethylamino)tantalum and nitrogen plasma.

[0239] In the second step, the substrate with the transition layer 2 and the light-absorbing layer 3 is deposited sequentially through tert-butyliminotris(ethylmethylamino)tantalum, isolation gas, nitrogen plasma and isolation gas region to complete one cycle of deposition;

[0240] The third step involves repeating the first and second steps in a cyclic deposition process to form tantalum nitride.

[0241] The preparation method of alumina is the same as that of alumina in the light-absorbing layer in this embodiment, while the preparation method of silicon oxide is to replace the aluminum source with a silicon source.

[0242] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0243] Example 8

[0244] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0245] The transition layer 2 has a thickness of 6 nm, the light-absorbing layer 3 has thicknesses of 61.61 nm, 167.96 nm, 164.15 nm, 33.02 nm, and 15.01 nm, and the anti-corrosion layer 4 has thicknesses of 10.42 nm and 63.52 nm.

[0246] The substrate 1 is made of polyimide, the transition layer 2 is aluminum nitride, the light-absorbing layer 3 is composed of alternating titanium aluminum carbide and aluminum oxide, and the anti-corrosion layer 4 is composed of zirconium oxide and silicon oxide.

[0247] The transition layer 2 is prepared using a spatial ALD method, which includes at least the following steps:

[0248] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0249] The second step involves continuously introducing aluminum trichloride and nitrogen plasma into the cavity at 105°C through a carrier gas of 2500 sccm and a dilution gas of 5000 sccm, respectively, to the reaction area of ​​the first precursor and the first reactant. At the same time, an inert gas of 5000-20000 sccm is introduced between the first precursor and the first reactant.

[0250] The third step involves the substrate sequentially passing through aluminum trichloride, isolation gas, nitrogen plasma, and the isolation gas region to complete one cycle of deposition.

[0251] The fourth step involves repeating steps two and three, cyclically depositing to form a transition layer.

[0252] The carrier gas, dilution gas, and inert gas are all argon.

[0253] The light-absorbing layer 3 is prepared using a two-dimensional ALD, and the preparation method of titanium aluminum carbide includes the following steps:

[0254] In the first step, in an atomic layer deposition chamber at 105°C, trimethylaluminum, titanium tetrachloride, and methane plasmas are continuously introduced into the chamber through a carrier gas of 2600 sccm and a dilution gas of 3500 sccm, respectively, to the reaction zone of the trimethylaluminum, titanium tetrachloride, and methane plasmas. At the same time, an inert gas of 4800 sccm is introduced between the trimethylaluminum, tetra(dimethylamino)titanium, and methane plasmas.

[0255] In the second step, the substrate with the transition layer 2 is deposited sequentially through the trimethylaluminum, tetra(dimethylamino)titanium and methane plasma and isolation gas regions to complete one cycle of deposition;

[0256] The third step involves repeating the first and second steps in a cyclic deposition process to form titanium aluminum carbide.

[0257] Among them, the carrier gas, dilution gas, and inert gas are all argon;

[0258] The method for preparing the alumina layer includes the following steps: First, in an atomic layer deposition chamber at 105°C, diethylaluminum and H2O are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, respectively, to the reaction zone of diethylaluminum and H2O. At the same time, an inert gas of 10000 sccm is introduced between diethylaluminum and H2O.

[0259] The second step involves sequentially passing through the diethylaluminum, isolation gas, H2O, and isolation gas zones to complete one cycle of deposition.

[0260] The third step involves repeating the first and second steps in a cyclic deposition process to form aluminum oxide.

[0261] The anti-corrosion layer 4 is prepared by a spatial ALD, and the preparation of the zirconia layer includes the following steps:

[0262] In the first step, in an atomic layer deposition chamber at 105°C, tetra(dimethylamino)zirconium and H2O are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, respectively, until they reach the reaction zone of tetra(dimethylamino)zirconium and H2O. At the same time, an inert gas of 10000 sccm is introduced between tetra(dimethylamino)zirconium and H2O.

[0263] In the second step, the substrate 1, with the transition layer 2 and the light-absorbing layer 3 deposited thereon passes through the tetra(dimethylamino)zirconium, the isolation gas, H2O and the isolation gas region in sequence to complete one cycle of deposition;

[0264] The third step involves repeating the first and second steps in a cyclic deposition process to form a zirconium oxide layer.

[0265] The preparation method of silicon dioxide is as follows:

[0266] The first step involves introducing diisopropylamine silane in a pulsed manner into an atomic layer deposition chamber at 105°C, causing it to be chemically adsorbed onto the zirconium oxide surface; then, an inert gas of 1800 sccm is introduced to purge unreacted diisopropylamine silane and byproducts for 25 seconds.

[0267] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the diisopropylamine silane adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 25 seconds.

[0268] The third step involves repeating the first and second steps in a cyclic deposition process to form silicon oxide.

[0269] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0270] Example 9

[0271] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0272] The thickness of the transition layer 2 is 8.29 nm, the thickness of the light-absorbing layer 3 is 60.40 nm, 185.78 nm, 175.05 nm, 24.44 nm, and 13.04 nm, and the thickness of the anti-corrosion layer 4 is 8.69 nm and 58.85 nm.

[0273] The substrate 1 is made of SiC, the transition layer 2 is an aluminum-based hybrid film, the light-absorbing layer 3 is an alternating layer of titanium aluminum carbide and silicon dioxide; the anti-corrosion layer 4 is titanium oxide and silicon oxide.

[0274] The transition layer 2 is prepared by time-dependent ALD, and includes at least the following steps:

[0275] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0276] The second step involves introducing trimethylaluminum in a pulsed manner at 95°C for 10 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2500 sccm is introduced to purge unreacted trimethylaluminum and byproducts for 35 seconds.

[0277] The third step involves adding ethylene glycol into the chamber in a pulsed manner and holding it for 10 seconds to allow it to form a monolayer with the trimethylaluminum adsorbed on the surface. Then, an inert gas of 4500 sccm is introduced to purge unreacted ethylene glycol and byproducts for 35 seconds.

[0278] Fourth step: Repeat steps two and three, cyclically depositing to form transition layer 2.

[0279] The light-absorbing layer 3 is prepared by time-dependent ALD, and the preparation method of the titanium aluminum carbide layer includes at least the following steps:

[0280] In the first step, triethylaluminum and tetra(dimethylamino)titanium were introduced in a pulsed manner in an atomic layer deposition chamber at 95°C, so that they were chemically adsorbed on the surface of transition layer 2; then, an inert gas of 4000 sccm was introduced to purge the unreacted triethylaluminum, tetra(dimethylamino)titanium and byproducts for 110 s.

[0281] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the triethylaluminum and tetra(dimethylamino)titanium adsorbed on the surface; then, an inert gas of 2200 sccm is introduced to purge the unreacted methane plasma and byproducts for 90 s.

[0282] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium aluminum carbide layer.

[0283] The method for preparing the silicon dioxide layer is as follows:

[0284] First, bis(diethylamino)silane was introduced in a pulsed manner at 95°C and held for 7 seconds to allow it to be chemically adsorbed onto the surface of the titanium aluminum carbide layer. Then, an inert gas of 2800 sccm was introduced to purge unreacted bis(diethylamino)silane and byproducts for 55 seconds.

[0285] The second step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 8 seconds to allow it to form a monolayer with the surface-adsorbed bis(diethylamino)silane. Then, an inert gas of 3800 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0286] The third step involves repeating steps two and three in a cyclic deposition process to form a silicon dioxide layer.

[0287] The anti-corrosion layer 4 is prepared by time-dependent ALD, and the preparation method of titanium oxide includes at least the following steps:

[0288] First, tetraisopropyl titanate was introduced in a pulsed manner in an atomic layer deposition chamber at 95°C, causing it to be chemically adsorbed onto the surface of light-absorbing layer 3; then, an inert gas of 1500 sccm was introduced to purge unreacted tetraisopropyl titanate and byproducts for 30 seconds.

[0289] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the tetraisopropyl titanate adsorbed on the surface; then, an inert gas of 1500 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 40 seconds.

[0290] The third step involves repeating the first and second steps in a cyclic deposition process to form titanium oxide.

[0291] The method for preparing the silicon oxide layer is the same as the method for preparing the silicon dioxide layer of the light-absorbing layer in this invention.

[0292] Example 10

[0293] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0294] The thickness of the transition layer 2 is 7.31 nm, the thickness of the light-absorbing layer 3 is 39.99 nm, 168.07 nm, 159.74 nm, 22.11 nm, and 11.67 nm, and the thickness of the anti-corrosion layer 4 is 11.17 nm and 65.39 nm.

[0295] The substrate 1 is made of titanium alloy, the transition layer 2 is a zinc-based hybrid film, the light-absorbing layer 3 is an alternating layer of titanium aluminum carbide and aluminum oxide; the anti-corrosion layer 4 is silicon nitride and silicon oxide.

[0296] The transition layer 2 is prepared using a spatial ALD method, which includes at least the following steps:

[0297] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0298] The second step involves continuously introducing diethylzinc and glycerol into the chamber at 90°C through a carrier gas of 4500 sccm and a dilution gas of 8000 sccm, respectively, to the reaction zone of diethylzinc and glycerol. At the same time, an inert gas of 15000 sccm is introduced between diethylzinc and glycerol.

[0299] The third step involves the substrate sequentially passing through diethylzinc, isolation gas, glycerol, and the isolation gas region to complete one cycle of deposition.

[0300] The fourth step involves repeating steps two and three, cyclically depositing to form a transition layer.

[0301] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0302] The light-absorbing layer 3 is prepared by time-dependent ALD, and the preparation method of the titanium aluminum carbide layer includes at least the following steps:

[0303] In the first step, trimethylaluminum and tetra(dimethylamino)titanium were introduced in a pulsed manner in an atomic layer deposition chamber at 90°C and held for 4 seconds to allow them to be chemically adsorbed on the surface of transition layer 2. Then, an inert gas of 4100 sccm was introduced to purge the unreacted trimethylaluminum, tetra(dimethylamino)titanium and byproducts for 100 seconds.

[0304] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the trimethylaluminum and tetra(dimethylamino)titanium adsorbed on the surface; then, an inert gas of 2800 sccm is introduced to purge the unreacted methane plasma and byproducts for 65 seconds.

[0305] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium aluminum carbide layer.

[0306] The method for preparing the alumina layer is as follows:

[0307] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0308] The second step involves introducing aluminum trichloride in a pulsed manner at 90°C for 7 seconds to allow it to be chemically adsorbed onto the surface of substrate 1. Then, an inert gas of 2800 sccm is introduced to purge unreacted aluminum trichloride and byproducts for 55 seconds.

[0309] The third step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 8 seconds to allow it to form a monolayer with the aluminum trichloride adsorbed on the surface. Then, an inert gas of 3800 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0310] Fourth, repeat steps two and three to form an alumina layer through cyclic deposition.

[0311] The anti-corrosion layer 4 is prepared by a spatial ALD, and the preparation method of the silicon nitride layer includes at least the following steps:

[0312] First, tris(dimethylamino)silane was introduced in a pulsed manner in an atomic layer deposition chamber at 90°C, causing it to be chemically adsorbed onto the surface of the light-absorbing layer 3; then, an inert gas of 1800 sccm was introduced to purge unreacted tris(dimethylamino)silane and byproducts for 25 seconds.

[0313] The second step involves introducing nitrogen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the tris(dimethylamino)silane adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted nitrogen plasma and byproducts for 25 seconds.

[0314] The third step involves repeating the first and second steps in a cyclic deposition process to form a silicon nitride layer.

[0315] The preparation method of silicon dioxide is as follows:

[0316] The first step involves introducing diisopropylamine silane in a pulsed manner into an atomic layer deposition chamber at 90°C, causing it to chemically adsorb onto the silicon nitride surface; then, an inert gas of 1500 sccm is introduced to purge unreacted diisopropylamine silane and byproducts for 28 seconds.

[0317] The second step involves introducing oxygen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the diisopropylamine silane adsorbed on the surface; then, an inert gas of 1600 sccm is introduced to purge the unreacted oxygen plasma and byproducts for 28 seconds.

[0318] The third step involves repeating the first and second steps in a cyclic deposition process to form silicon oxide.

[0319] Example 11

[0320] like Figure 1As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0321] The thickness of the transition layer 2 is 5.91 nm, the thickness of the light-absorbing layer 3 is 85.92 nm, 129.69 nm, 175.05 nm, 25.49 nm, and 5.33 nm, and the thickness of the anti-corrosion layer 4 is 26.84 nm and 70.07 nm.

[0322] The substrate 1 is made of optical glass, the transition layer 2 is zinc oxide, the light-absorbing layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / aluminum oxide / titanium aluminum carbide layer; and the anti-corrosion layer 4 is tantalum nitride and silicon oxide.

[0323] The transition layer 2 is prepared by time-dependent ALD, and includes at least the following steps:

[0324] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0325] The second step involves introducing dimethyl zinc in a pulsed manner at 105°C for 5 seconds to allow it to be chemically adsorbed onto the surface of substrate 1; then, an inert gas of 4000 sccm is introduced to purge unreacted dimethyl zinc and byproducts for 60 seconds.

[0326] The third step involves adding O3 into the chamber in a pulsed manner and holding it for 6 seconds to allow it to form a monolayer with the dimethyl zinc adsorbed on the surface. Then, an inert gas of 8000 sccm is introduced to purge unreacted O3 and byproducts for 50 seconds.

[0327] Fourth step: Repeat steps two and three, cyclically depositing to form transition layer 2.

[0328] The light-absorbing layer 3 is prepared by time-dependent ALD, and the preparation method of titanium aluminum carbide includes the following steps:

[0329] In the first step, trimethylaluminum and titanium tetrachloride were introduced in a pulsed manner in an atomic layer deposition chamber at 105°C, so that they were chemically adsorbed on the surface of transition layer 2; then, an inert gas of 4000 sccm was introduced to purge unreacted trimethylaluminum, titanium tetrachloride and byproducts for 100 s.

[0330] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the trimethylaluminum and titanium tetrachloride adsorbed on the surface; then, an inert gas of 2000 sccm is introduced to purge the unreacted methane plasma and byproducts for 80 seconds.

[0331] The third step involves repeating the first and second steps in a cyclic deposition process to form titanium aluminum carbide.

[0332] The method for preparing the silicon oxide layer is as follows: First, bis(diethylamino)silane is introduced in a pulsed manner at 105°C and held for 9s to allow it to be chemically adsorbed onto the surface of the titanium aluminum carbide layer; then, an inert gas of 3800 sccm is introduced to purge the unreacted bis(diethylamino)silane and byproducts for 55s.

[0333] The second step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 9 seconds to allow it to form a monolayer with the surface-adsorbed bis(diethylamino)silane. Then, an inert gas of 4200 sccm is introduced to purge the unreacted O2 plasma and byproducts for 40 seconds.

[0334] The third step involves repeating steps two and three in a cyclic deposition process to form a silicon oxide layer.

[0335] The preparation method of the alumina layer is the same as that of the silicon oxide layer, except that bis(diethylamino)silane is replaced with triethylaluminum.

[0336] The preparation method of the anti-corrosion layer 4 is time-type ALD, and the preparation method of the tantalum nitride layer includes at least the following steps:

[0337] First, pentapentanyl(dimethylamino)tantalum is introduced in a pulsed manner in an atomic layer deposition chamber at 105°C, causing it to be chemically adsorbed onto the surface of light-absorbing layer 3; then, an inert gas of 1800 sccm is introduced to purge unreacted pentapentanyl(dimethylamino)tantalum and byproducts for 30 s.

[0338] The second step involves introducing nitrogen plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the adsorbed penta(dimethylamino)tantalum on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted nitrogen plasma and byproducts for 30 seconds.

[0339] The third step involves repeating the first and second steps in a cyclic deposition process to form tantalum nitride.

[0340] The method for preparing the silicon oxide layer is the same as the method for preparing the silicon oxide in the light-absorbing layer in this embodiment.

[0341] Example 12

[0342] like Figure 1 As shown, this embodiment provides an ultra-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light-absorbing layer 3 deposited on the surface of the transition layer 2 by ALD, and an anti-corrosion layer 4 deposited on the surface of the light-absorbing layer 3 by ALD.

[0343] The transition layer 2 has a thickness of 11 nm, the light-absorbing layer 3 has thicknesses of 177.49 nm, 193.43 nm, 98.5 nm, 25.37 nm, and 15.29 nm, and the anti-corrosion layer 4 has thicknesses of 18.86 nm, 14.33 nm, and 69.13 nm.

[0344] The substrate 1 is made of polycarbonate, the transition layer 2 is a titanium-based hybrid film, the light-absorbing layer 3 is an alternating layer of titanium aluminum carbide and aluminum oxide; the anti-corrosion layer 4 is composed of titanium oxide, aluminum oxide and silicon oxide.

[0345] The transition layer 2 is prepared using a spatial ALD method, which includes at least the following steps:

[0346] The first step is to place the substrate in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0347] The second step involves continuously introducing titanium tetrachloride and 1,4-butanediol into the chamber at 100°C through a carrier gas of 4500 sccm and a dilution gas of 8000 sccm, respectively, into the reaction zone of titanium tetrachloride and 1,4-butanediol. At the same time, an inert gas of 13000 sccm is introduced between titanium tetrachloride and 1,4-butanediol.

[0348] The third step involves the substrate sequentially passing through the titanium tetrachloride, isolation gas, 1,4-butanediol, and isolation gas regions to complete one cycle of deposition.

[0349] The fourth step involves repeating steps two and three, cyclically depositing to form a transition layer.

[0350] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0351] The light-absorbing layer 3 is prepared by time-dependent ALD, and the preparation method of the titanium aluminum carbide layer includes at least the following steps:

[0352] In the first step, triethylaluminum and tetraisopropyl titanate were introduced in a pulsed manner in an atomic layer deposition chamber at 100°C for 4 seconds to allow them to be chemically adsorbed onto the surface of transition layer 2. Then, an inert gas of 4800 sccm was introduced to purge the unreacted triethylaluminum, tetraisopropyl titanate and byproducts for 70 seconds.

[0353] The second step involves introducing methane plasma into the chamber in a pulsed manner, allowing it to form a monolayer with the triethylaluminum and tetraisopropyl titanate adsorbed on the surface; then, an inert gas of 3800 sccm is introduced to purge the unreacted methane plasma and byproducts for 65 seconds.

[0354] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium aluminum carbide layer.

[0355] The method for preparing the alumina layer is as follows:

[0356] The first step is to place substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr);

[0357] The second step involves introducing triethylaluminum in a pulsed manner at 100°C for 7.5 seconds to allow it to chemically adsorb onto the surface of substrate 1. Then, an inert gas of 2500 sccm is introduced to purge unreacted triethylaluminum and byproducts for 55 seconds.

[0358] The third step involves introducing O2 plasma into the chamber in a pulsed manner and holding it for 3 seconds to allow it to form a monolayer with the triethylaluminum adsorbed on the surface. Then, an inert gas of 3300 sccm is introduced to purge the unreacted O2 plasma and byproducts for 50 seconds.

[0359] Fourth, repeat steps two and three to form an alumina layer through cyclic deposition.

[0360] The anti-corrosion layer 4 is prepared by time-type ALD, and the preparation method of the titanium oxide layer includes at least the following steps:

[0361] In the first step, in an atomic layer deposition chamber at 100°C, tetra(dimethylamino)titanium and H2O are continuously introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 3000 sccm, respectively, to the reaction zone of tetra(dimethylamino)titanium and H2O. At the same time, an inert gas of 11000 sccm is introduced between tetra(dimethylamino)titanium and H2O.

[0362] In the second step, the substrate with the transition layer 2 and the light-absorbing layer 3 deposited sequentially passes through the tetrakis(dimethylamino)titanium, the isolation gas, H2O and the isolation gas region to complete one cycle of deposition;

[0363] The third step involves repeating the first and second steps in a cyclic deposition process to form a titanium oxide layer.

[0364] The carrier gas, dilution gas, and inert gas are all nitrogen.

[0365] The preparation method of the alumina layer is the same as that of the alumina layer in this embodiment. For the silicon oxide, the aluminum source is replaced with the silicon source bis(tert-butylamino)silane.

[0366] Comparative Example 1

[0367] This comparative example provides an ultra-black nanofilm structure, including a substrate and a light-absorbing layer deposited on the substrate surface using ALD. The thickness and preparation method of the light-absorbing layer are the same as in Example 1.

[0368] Comparative Example 2

[0369] This comparative example provides an ultra-black nanofilm structure, including a substrate and a light-absorbing layer deposited on the substrate surface using chemical vapor deposition. The thickness of the light-absorbing layer is the same as in Example 1.

[0370] Comparative Example 3

[0371] This comparative example provides an ultra-black nanofilm structure, including a substrate, a light-absorbing layer deposited on the substrate surface using ALD, and an anti-corrosion layer deposited on the light-absorbing layer using ALD. The thickness and preparation method of the light-absorbing layer and the anti-corrosion layer are the same as in Example 1.

[0372] Comparative Example 4

[0373] This comparative example provides an ultra-black nano-coating structure, including a substrate, a light-absorbing layer deposited on the substrate surface by chemical vapor deposition, and an anti-corrosion layer deposited on the light-absorbing layer by chemical vapor deposition. The thicknesses of the light-absorbing layer and the anti-corrosion layer are the same as in Example 1.

[0374] Comparative Example 5

[0375] This comparative example provides an ultra-black nanofilm structure, including a substrate, a transition layer deposited on the substrate surface using ALD, and a light-absorbing layer deposited on the surface of the transition layer using ALD. The thickness and preparation method of the transition layer and the light-absorbing layer are the same as in Example 1.

[0376] Comparative Example 6

[0377] This comparative example provides an ultra-black nanofilm structure, including a substrate, a transition layer deposited on the surface of the substrate by chemical vapor deposition, and a light-absorbing layer deposited on the surface of the transition layer by chemical vapor deposition. The thicknesses of the transition layer and the light-absorbing layer are the same as in Example 1.

[0378] Performance testing

[0379] The products obtained from Examples 1-12 and Comparative Examples 1-6 were tested as follows, and the results are shown in Table 1.

[0380] 1. Test the absorption efficiency of the sample.

[0381] The reflectivity and absorption efficiency of the products were tested using a BCSP-Pro autofocus reflectance spectrometer. As shown in Table 1, the absorption efficiency of the ultra-black film with light-absorbing layer, ultra-black film with light-absorbing layer and anti-corrosion layer, and ultra-black film with transition layer and light-absorbing layer made by ALD and PVD was significantly reduced. The lowest was 87.50%@400-700nm for the ultra-black film with transition layer and light-absorbing layer made by ALD in Comparative Example 5. Adding a transition layer and anti-corrosion layer can reduce reflection and optimize light transmission, effectively improving the absorption efficiency to above 99.05%@400-700nm.

[0382] 2. Adhesion test

[0383] The adhesion of the product is tested using the cross-cut adhesion test method. The specific method is as follows: Apply even pressure to the cross-cut cutter, making 6-11 horizontal and 11 vertical cuts on the coating surface (forming 25-100 squares), penetrating the coating to the substrate. Then, apply tape tightly to the grid area, press to remove air bubbles, and quickly peel it off at a 60° angle. Repeat 2-3 times. Observe the coating peeling within the squares under a light source and score it according to a standard rating chart (e.g., ISO 2409 is divided into 0-5 levels, where level 0 is no peeling; level 1 is peeling area <5%; level 2 is peeling area <5%, >15%; level 3 is peeling area <15%, >35%; level 4 is peeling area <35%, >65%; and level 5 is peeling area >65%).

[0384] As shown in Table 1, the ultra-black films with light-absorbing layers, ultra-black films with light-absorbing and anti-corrosion layers, and ultra-black films with transition layers and light-absorbing layers produced by ALD and PVD exhibit significant film delamination. The most serious case is the ultra-black film with only a light-absorbing layer produced by PVD in Comparative Example 2. Compared with the ALD film, the film layer is not dense enough and is more prone to delamination, with a delamination area of ​​>65%. Adding transition layers and anti-corrosion layers effectively increases the adhesion and corrosion resistance of the film layers, and no film delamination occurs.

[0385] 3. Boiling water test

[0386] The samples were boiled in 100℃ water for 10 minutes, and the area of ​​film peeling was rated according to the cross-cut adhesion test method. As shown in Table 1, there are obvious film peeling issues in the ultra-black films with light-absorbing layers, ultra-black films with light-absorbing and anti-corrosion layers, and ultra-black films with transition and light-absorbing layers made by ALD and PVD. The most serious cases are in Comparative Examples 1, 2, and 6: ultra-black films with only light-absorbing layers made by ALD and PVD, and ultra-black films with transition and light-absorbing layers made by PVD, with peeling areas >65%. Adding transition and anti-corrosion layers effectively increases the adhesion and corrosion resistance of the film, and no film peeling occurs.

[0387] Table 1: Performance Test of Ultra-Black Film

[0388]

[0389] Note: The 100-grip test and boiling water test ratings are as follows: (0-5, where 0 means no shedding; 1 means shedding area <5%; 2 means shedding area <5% and >15%; 3 means shedding area <15% and >35%; 4 means shedding area <35% and >65%; and 5 means shedding area >65%).

[0390] Based on the disclosure and teachings of the foregoing specification, those skilled in the art can make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention. Furthermore, although some specific terms are used in this specification, these terms are only for convenience of explanation and do not constitute any limitation on the present invention.

Claims

1. An ultra-black nano-coating structure, characterized in that: It includes a substrate, a transition layer deposited on the surface of the substrate using ALD, a light-absorbing layer deposited on the surface of the transition layer using ALD, and an anti-corrosion layer deposited on the surface of the light-absorbing layer using ALD; The transition layer is at least one of organic-inorganic hybrid films, which is at least one of aluminum-based hybrid films, zinc-based hybrid films, zirconium-based hybrid films, titanium-based hybrid films, hafnium-based hybrid films, vanadium-based hybrid films, magnesium-based hybrid films, and manganese-based hybrid films. The light-absorbing layer comprises a titanium aluminum carbide layer and an oxide layer, wherein the oxide is SiO2 and / or Al2O3; The light-absorbing layer is prepared by a time-type ALD or a spatial-type ALD, wherein the time-type ALD includes at least the following steps: The first step involves introducing a second precursor into an atomic layer deposition chamber at 50-250°C, causing it to be chemically adsorbed onto the surface of the transition layer; then, an inert gas is introduced to purge unreacted second precursors and byproducts. The second step involves adding the second reactant into the chamber to form a monolayer with the second precursor adsorbed on the surface; then, an inert gas is introduced to purge unreacted second reactant and byproducts. The third step involves repeating the first and second steps n times, cyclically depositing to form a light-absorbing layer; where n is a natural number greater than or equal to 0. Spatial ALD includes at least the following steps: The first step involves continuously introducing the second precursor and the second reactant into the atomic layer deposition chamber at 50-250°C through a carrier gas and a dilution gas, respectively, to the reaction zone of the second precursor and the second reactant. At the same time, an inert gas is introduced between the second precursor and the second reactant. In the second step, the substrate with the transition layer deposited passes through the second precursor, the isolation gas, the second reactant, and the isolation gas region in sequence to complete one cycle of deposition. The third step involves repeating the first and second steps n times, cyclically depositing to form a light-absorbing layer; where n is a natural number greater than or equal to 0. Among them, the carrier gas, dilution gas, and inert gas are argon or nitrogen; The second precursor is an aluminum source and a titanium source, wherein the aluminum source is at least one of trimethylaluminum, triethylaluminum and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetra(dimethylamino)titanium and tetraisopropyl titanate; and the second reactant is a carbon source methane plasma. This coating structure uses ALD technology to produce an ultra-black film with high coverage, reflectivity ≤0.20%, and absorption efficiency ≥99.00% at temperatures ranging from 50-250℃.

2. The ultra-black nano-coating structure according to claim 1, characterized in that: The thickness of the transition layer is 1-50 nm, the thickness of the light-absorbing layer is 50-800 nm, and the thickness of the anti-corrosion layer is 5-300 nm.

3. The ultra-black nano-coating structure according to claim 1, characterized in that: The substrate is made of at least one of polycarbonate, polymethyl methacrylate, polyimide, SiC, titanium alloy, and optical glass.

4. The ultra-black nano-coating structure according to claim 1, characterized in that: The anti-corrosion layer is an oxide and / or a nitride, wherein the oxide is at least one of ZrO2, Al2O3, SiO2 and TiO2; and the nitride is at least one of TiN, AlN, tantalum nitride, chromium nitride and silicon nitride.

5. The ultra-black nano-coating structure according to claim 1, characterized in that: The transition layer is prepared by either a time-type ALD or a spatial-type ALD, wherein the time-type ALD includes at least the following steps: The first step is to place the substrate in an atomic layer deposition chamber under vacuum; The second step involves introducing the first precursor at 50-250°C to allow it to chemically adsorb onto the substrate surface; then, an inert gas is introduced to purge unreacted first precursor and byproducts. The third step involves adding the first reactant into the chamber to form a monolayer with the first precursor adsorbed on the surface; then, an inert gas is introduced to purge unreacted first reactant and byproducts. The fourth step is to repeat steps two and three n times, cyclically depositing to form a transition layer, where n is a natural number greater than or equal to 0; Spatial ALD includes at least the following steps: The first step is to place the substrate in an atomic layer deposition chamber under vacuum; The second step involves continuously introducing the first precursor and the first reactant into the cavity through a carrier gas and a dilution gas at a temperature of 50-250°C, to the reaction zone of the first precursor and the first reactant, while an inert gas is introduced between the first precursor and the first reactant. The third step involves the substrate sequentially passing through the first precursor, the isolation gas, the first reactant, and the isolation gas region to complete one cycle of deposition. The fourth step involves repeating steps two and three n times, creating a cyclic deposition process to form a transition layer; where n is a natural number greater than or equal to 0. The carrier gas, dilution gas, and inert gas are argon or nitrogen.

6. The ultra-black nano-coating structure according to claim 5, characterized in that: When the transition layer is an oxide, the first precursor is at least one of aluminum source, titanium source, vanadium source, manganese source, zinc source, zirconium source, hafnium source, magnesium source and silicon source, and the first reactant is H2O, O3 or O2 plasma. When the transition layer is a nitride, the first precursor is at least one of a titanium source, an aluminum source, a silicon source, a hafnium source, a tantalum source, and a zirconium source; the first reactant is at least one of a nitrogen plasma and an ammonia plasma. When the transition layer is an organic-inorganic hybrid thin film, the first precursor is at least one of aluminum source, titanium source, vanadium source, manganese source, zinc source, zirconium source, hafnium source, and magnesium source, and the first reactant is at least one of ethylene glycol, glycerol, 1,4-butanediol, hydroquinone, and ethanolamine. The aluminum source is at least one of trimethylaluminum, triethylaluminum, and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetra(dimethylamino)titanium, and tetraisopropyl titanate; the vanadium source is at least one of vanadium pentoxide, vanadium trichloride, vanadium tetrachloride, and vanadium oxychloride; the manganese source is at least one of manganese dichloride, manganese trioxide, and di(cyclopentadienyl)manganese; the zinc source is at least one of diethylzinc, dimethylzinc, and zinc chloride; the zirconium source is at least one of tetra(dimethylamino)zirconium, tetraethylmethylaminozirconium, and zirconium tetrachloride; the hafnium source is one of tetradimethylaminohafnium, tetraethylmethylaminohafnium, and hafnium tetrachloride; the magnesium source is at least one of magnesia ceratolide, diethylmagnesium, and methylmagnesium tert-butoxy; and the silicon source is bis(diethylamino)silane, diisopropylaminesilane, etc. At least one of 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.

7. The ultra-black nano-coating structure according to claim 4, characterized in that: The method for preparing the anti-corrosion layer is either time-type ALD or space-type ALD, wherein the time-type ALD includes at least the following steps: The first step involves introducing a third precursor into an atomic layer deposition chamber at 50-250°C, causing it to be chemically adsorbed onto the surface of the light-absorbing layer; then, an inert gas is introduced to purge unreacted third precursors and byproducts. The second step involves adding the third reactant into the chamber to form a monolayer with the third precursor adsorbed on the surface; then, an inert gas is introduced to purge unreacted third reactant and byproducts. The third step involves repeating the first and second steps n times, creating a cyclic deposition process to form an anti-corrosion layer; where n is a natural number greater than or equal to 0. Spatial ALD includes at least the following steps: The first step involves continuously introducing the third precursor and the third reactant into the atomic layer deposition chamber at 50-250℃ through a carrier gas and a dilution gas, respectively, to the reaction zone of the third precursor and the third reactant. At the same time, an inert gas is introduced between the third precursor and the third reactant. The second step involves depositing a substrate with a transition layer and a light-absorbing layer, which then passes through the third precursor, the isolation gas, the third reactant, and the isolation gas region in sequence to complete one cycle of deposition. The third step involves repeating the first and second steps n times, creating a cyclic deposition process to form an anti-corrosion layer; where n is a natural number greater than or equal to 0. Among them, the carrier gas, dilution gas, and inert gas are all argon or nitrogen; When the anti-corrosion layer is an oxide, the third precursor is at least one of aluminum source, silicon source, titanium source and zirconium source; the third reactant is H2O, O3 or O2 plasma; When the anti-corrosion layer is a nitride, the third reactant is at least one of aluminum source, titanium source, tantalum source, chromium source and silicon source, and the third reactant is at least one of nitrogen plasma and ammonia plasma; The aluminum source is at least one of trimethylaluminum, triethylaluminum, and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetra(dimethylamino)titanium, and tetraisopropyl titanate; the silicon source is one of bis(diethylamino)silane, diisopropylaminosilane, tri(dimethylamino)silane, and bis(tert-butylamino)silane; the zirconium source is at least one of tetra(dimethylamino)zirconium, tetraethylmethylaminozirconium, and zirconium tetrachloride; and the tantalum source is at least one of penta(dimethylamino)tantalum, tert-butyliminotri(ethylmethylamino)tantalum, and tert-butyliminotri(diethylamino)tantalum.

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