Ultra-black nano coating structure

Abstract

The invention belongs to the technical field of nano coating, and particularly relates to an ultra-black nano coating structure which comprises a substrate, a transition layer deposited on the surface of the substrate through ALD, a light absorption layer deposited on the surface of the transition layer through ALD and an anti-corrosion layer deposited on the surface of the light absorption layer through ALD. Compared with the prior art, the ALD technology is adopted for manufacturing the ultra-black film with the high coverage rate, the ultra-low reflection rate (smaller than or equal to 0.5%), the high absorption efficiency (larger than or equal to 99.00%) and the good binding force at the low temperature (50-250 DEG C), the selection range of substrate materials is effectively expanded, and the ultra-black film with the high coverage rate, the ultra-low reflection rate (smaller than or equal to 0.5%), the high absorption efficiency (larger than or equal to 99.00%) and the good binding force is obtained. The problems that an existing ultra-black film manufacturing process has large limitation on a substrate material and is difficult to be compatible with low-temperature control, high coverage rate and high absorptivity of a thin film are solved.

Description

Technical Field

[0001] The invention belongs to the technical field of nano coating, and in particular relates to an ultra-black nano coating structure. Background Art

[0002] Ultra-black nano-coating has ultra-high absorption rate and extremely low reflectivity, which can effectively shield and absorb optical interference of visible light and infrared light, reduce various useless reflected light, and eliminate harmful stray light. These characteristics can be widely used in the field of optics, greatly improving the imaging quality and accuracy of optical products, thereby improving product performance.

[0003] The technologies commonly used in the industry to produce ultra-black films include chemical vapor deposition (CVD), physical vapor deposition (PVD), carbon nanotube method, etc., but the above processes 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 is 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 nano-coating structure, which adopts the ALD (atomic layer deposition) low-temperature process to produce the ultra-black nano-coating structure, and the film thickness can be precisely controlled at the atomic level. This technology has significant advantages in terms of precise control of film thickness, uniformity of film thickness, and coverage of complex-shaped components. The ultra-black film obtained by the present invention solves the problem that traditional ultra-black films are difficult to achieve high coverage and high absorption efficiency (≥99.00%) at low temperatures, so as to be compatible with more substrate materials and applied to more products. Summary of the invention

[0005] The purpose of the present invention is to provide an ultra-black nano-coating structure to address the deficiencies of the prior art. The ultra-black nano-coating structure is made using an ALD (atomic layer deposition) low-temperature process, and the film thickness can be precisely controlled at the atomic level. This technology has significant advantages in terms of precise control of film thickness, uniformity of film thickness, and coverage of complex-shaped components. The ultra-black film obtained by the present invention solves the problem that traditional ultra-black films are difficult to achieve high coverage and high absorption efficiency (≥99.00%) at low temperatures, so that it is compatible with more substrate materials and can be applied to more products.

[0006] In order to achieve the above object, the present invention adopts the following technical solution: An ultra-black nano-coating structure 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.

[0007] Among them, the transition layer can increase the adhesion force and avoid poor bonding between the substrate and the light-absorbing layer due to the mismatch of the thermal expansion coefficients; the light-absorbing layer is a multi-layer interference film layer, and the optical interference layer can effectively reduce the reflection of light on the film surface, enabling more light to enter the main light-absorbing layer and be absorbed, thereby improving the overall light absorption efficiency; the anti-corrosion layer can form a gradient refractive index and increase the wear and corrosion resistance of the thin film with almost no increase in reflection. ALD is a technology for preparing high-precision coatings, and the film thickness of the thin film can be precisely controlled at the atomic level. This technology has significant advantages in aspects such as precise control of the thin film thickness, film thickness uniformity, and coverage of complex-shaped components.

[0008] As an improvement to the ultra-black nano-coating structure of the present invention, the thickness of the transition layer is 1 - 50 nm, which needs to sufficiently cover the defects of the substrate, but being too thick will increase stress. The thickness of the light-absorbing layer is 50 - 800 nm, and multiple layers of thickness are stacked to achieve wide-spectrum low reflection; the thickness of the anti-corrosion layer is 5 - 300 nm, which needs to meet the requirements of dielectric barrier and mechanical strength.

[0009] As an improvement to the ultra-black nano-coating structure of the present invention, the material of the substrate is at least one of polycarbonate, polymethyl methacrylate, polyimide, SiC, titanium alloy, and BK7 optical glass.

[0010] As an improvement to the ultra-black nano-coating structure of the present invention, the transition layer can be at least one of oxides, nitrides, and organic-inorganic hybrid thin films. Among them, the oxide forms a strong bond with the metal or ceramic substrate through the M - O - Me (metal - oxygen - substrate) bond, especially suitable for the surface of oxygen-containing substrates (such as glass, stainless steel), and has better low-temperature compatibility and is suitable for heat-sensitive substrates (such as plastics, organic semiconductors). The chemical general formula of the oxide is MO x , where 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 the mechanical anchoring effect, and is 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 thin film combines the flexibility of the organic chain and the high strength of the inorganic unit, can relieve the thermal stress between the substrate and the functional layer, and is more suitable for flexible substrates. The types of thin films include at least one of Alucone (aluminum-based hybrid film), Zincone (zinc-based hybrid film), Zircone (zirconium-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.

[0011] 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 SiO 2 layer and / or an Al 2 O 3 layer. TiAlC can achieve an ultra-black film with high coverage, ultra-low reflectance (≤0.20%), and high absorption efficiency (≥99.00%) at low temperatures (50 - 250°C).

[0012] 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. Among them, the oxide has excellent chemical stability, high transmittance, and low optical impact, and is more suitable for applications in scenarios that are optically sensitive, low-temperature, and oxidation-resistant; the oxides are: ZrO 2 、Al 2 O 3 、SiO 2 and TiO 2 at least one of them; the nitride performs better in mechanical protection, acid and alkali resistance, and conductive requirements; the nitride is at least one of titanium nitride (TiN), aluminum nitride (AlN), tantalum nitride, chromium nitride, and silicon nitride.

[0013] As an improvement to the ultra-black nano-coating structure of the present invention, the preparation method of the transition layer can adopt a time-based ALD or a spatial ALD deposition method. The time-based ALD deposition method can precisely control the thickness of each layer to optimize refractive index matching, has better conformal coating on substrates with high aspect ratio structures, and has a wider variety of deposition materials to choose from; the spatial ALD deposition method not only has the basic characteristics of precise film quality control and good conformal coating, but also can achieve rapid deposition, which is suitable for the deposition of large-scale, large-size, and low-cost products. Among them, the time-based ALD deposition method at least includes the following steps: The first step is to place the substrate in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). The second step is to introduce the first precursor in the form of pulses at 50 - 250°C for 0.1 - 10 s to chemically adsorb it on the surface of the substrate; then introduce an inert gas of 500 - 5000 sccm to purge the unreacted first precursor and by-products, and the purge duration is 5 - 120 s. The third step is to add the first reactant to the chamber in the form of pulses for 0.1 - 10 s to form a monolayer growth with the first precursor adsorbed on the surface; then introduce an inert gas of 500 - 5000 sccm to purge the unreacted first reactant and by-products, and the purge duration is 5 - 120 s. The fourth step is to repeat the second and third steps for cyclic deposition to form the transition layer; this step is an optional step. When this step is not selected, a single-layer structure is obtained.

[0014] The spatial ALD deposition method at least includes the following steps: In the first step, place the substrate in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). In the second step, at 50 - 250 °C, continuously introduce the first precursor and the first reactant into the chamber through carrier gas at 500 - 5000 sccm and dilution gas at 500 - 10000 sccm to the reaction region of the first precursor and the first reactant. Meanwhile, introduce inert gas at 5000 - 20000 sccm between the first precursor and the first reactant. In the third step, the substrate sequentially passes through the regions of the first precursor, isolation gas, the first reactant, and isolation gas to complete one cycle of deposition. In the fourth step, repeat the second and third steps for cyclic deposition to form a transition layer; this step is an optional step. When this step is not selected, a single - layer structure is obtained.

[0015] Among them, the carrier gas, dilution gas, and inert gas can be argon or nitrogen.

[0016] As an improvement to the super - 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 H 2 O, O 3 or O 2 plasma; When the transition layer is a nitride, the first precursor is at least one of titanium source, aluminum source, silicon source, hafnium source, tantalum source, and zirconium source; the first reactant is at least one of nitrogen plasma and 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 EG (ethylene glycol), glycerol, 1,4 - butanediol, HQ (hydroquinone), and ethanolamine; Among them, the aluminum source is at least one of TMA (trimethylaluminum), TEA (triethylaluminum), and AlCl 3 (aluminum trichloride); the titanium source is at least one of TiCl 4 (titanium tetrachloride), TDMAT (tetrakis(dimethylamino)titanium), and TTIP (tetraisopropyl titanate); the vanadium source is V 2 O 5 (vanadium pentoxide), VCl 3 (vanadium trichloride), VCl 4 (vanadium tetrachloride), VOCl 3 (oxychloride vanadium); the manganese source is MnCl2 Manganese dichloride, Mn 3 O 4 Manganese tetraoxide, Mn(Cp) 2 (Manganese bis(cyclopentadienyl)), at least one of them; the zinc source is at least one of DEZ (diethylzinc), DMZ (dimethylzinc), ZnCl 2 (Zinc chloride); the zirconium source is at least one of TDMAZr (tetrakis(dimethylamino)zirconium), TEMAZr (tetraethylmethylaminozirconium), ZrCl 4 (Zirconium tetrachloride); the hafnium source is one of TDMAHf (tetrakis(dimethylamino)hafnium), TEMAHf (tetraethylmethylaminohafnium), HfCl 4 (Hafnium tetrachloride); the magnesium source is Mg(Cp) 2 (Magnesium bis(cyclopentadienyl)), Mg(Et) 2 (Diethylmagnesium), Mg(OMe)(tBu) (methylmagnesium tert-butoxide), at least one of them; the silicon source can be at least one of BDEAS (bis(diethylamino)silane), DIPAS (diisopropylaminesilane), 3DMAS (tris(dimethylamino)silane), BTBAS (bis(tert-butylamino)silane).

[0017] As an improvement to the super-black nano-coating structure of the present invention, the method for preparing the light-absorbing layer is a time-type ALD or a space-type ALD deposition method. The time-type ALD deposition method at least includes the following steps: First step, introduce the second precursor in pulse form into the atomic layer deposition chamber at 50 - 250 °C and keep it for 0.1 - 10 s to chemically adsorb it on the surface of the transition layer; then introduce an inert gas of 500 - 5000 sccm to purge the unreacted second precursor and by-products, and the purge duration is 5 - 120 s; Second step, add the second reactant into the chamber in pulse form to form a monolayer growth with the second precursor adsorbed on the surface; then introduce an inert gas of 500 - 5000 sccm to purge the unreacted second reactant and by-products, and the purge duration is 5 - 120 s; Third step, repeat the first step and the second step for cyclic deposition to form the light-absorbing layer; this step is an optional step. When this step is not selected, a monolayer structure is obtained.

[0018] The space-type ALD method at least includes the following steps: First step, in an atomic layer deposition chamber at 50 - 250 °C, continuously introduce a second precursor and a second reactant into the chamber successively through a carrier gas at 500 - 5000 sccm and a dilution gas at 500 - 10000 sccm to the reaction region of the second precursor and the second reactant. Meanwhile, introduce an inert gas at 5000 - 20000 sccm between the second precursor and the second reactant; Second step, the substrate deposited with the transition layer sequentially passes through the regions of the second precursor, isolation gas, second reactant, and isolation gas to complete one cycle of deposition; Third step, repeat the first step and the second step for cyclic deposition to form the light-absorbing layer; this step is an optional step. When this step is not selected, a single-layer structure is obtained.

[0019] Among them, the carrier gas, dilution gas, and inert gas can be argon or nitrogen; The second precursor is an aluminum source and a titanium source. The aluminum source is at least one of TMA, TEA (triethylaluminum), AlCl 3 (aluminum trichloride); the titanium source is at least one of TiCl 4 (titanium tetrachloride), TDMAT (tetrakis(dimethylamino)titanium), TTIP (tetraisopropyl titanate); the second reactant is a carbon source of methane plasma.

[0020] In the light-absorbing layer, the preparation method of the SiO 2 layer and / or the Al 2 O 3 layer is the same as the preparation method of the oxides in the transition layer and the anti-corrosion layer.

[0021] As an improvement of the super-black nano-coating structure of the present invention, the preparation method of the anti-corrosion layer is a time-type ALD or a space-type ALD deposition method. The time-type ALD deposition method at least includes the following steps: First step, introduce a third precursor into the atomic layer deposition chamber at 50 - 250 °C in a pulsed form and keep it for 0.1 - 10 s to chemically adsorb it on the surface of the light-absorbing layer; then introduce an inert gas at 500 - 5000 sccm to purge the unreacted third precursor and by-products, and the purge duration is 5 - 120 s; Second step, add a third reactant into the chamber in a pulsed form to form a monolayer growth with the third precursor adsorbed on the surface; then introduce an inert gas at 500 - 5000 sccm to purge the unreacted third reactant and by-products, and the purge duration is 5 - 120 s; Third step, repeat the first step and the second step for cyclic deposition to form the anti-corrosion layer; this step is an optional step. When this step is not selected, a single-layer structure is obtained.

[0022] The space-type ALD deposition method at least includes the following steps: First step: In an atomic layer deposition chamber at 50 - 250 °C, the third precursor and the third reactant are successively introduced into the chamber continuously through a carrier gas of 500 - 5000 sccm and a dilution gas of 500 - 10000 sccm to the reaction region of the third precursor and the third reactant. Meanwhile, an inert gas of 5000 - 20000 sccm is introduced between the third precursor and the third reactant. Second step: The substrate deposited with the transition layer and the light - absorbing layer successively passes through the regions of the third precursor, the isolation gas, the third reactant, and the isolation gas to complete one cycle of deposition. Third step: Repeat the first step and the second step for cyclic deposition to form an anti - corrosion layer; this step is an optional step. When this step is not selected, a single - layer structure is obtained.

[0023] Among them, the carrier gas, the dilution gas, and the inert gas can be argon or nitrogen. When the anti - corrosion layer is an oxide, the third precursor is at least one of an aluminum source, a silicon source, a titanium source, and a zirconium source; the third reactant is H 2 O, O 3 or O 2 plasma. When the anti - corrosion layer is a nitride, the third reactant is at least one of an aluminum source, a titanium source, a tantalum source, a chromium source, and a silicon source, and the third reactant is at least one of nitrogen plasma and ammonia plasma. Among them, the aluminum source is at least one of trimethylaluminum, triethylaluminum, and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetrakis(dimethylamino)titanium, and tetraisopropyl titanate; the silicon source is bis(diethylamino)silane, diisopropylamine silane, tris(dimethylamino)silane, or bis(tert - butylamino)silane; the zirconium source is at least one of tetrakis(dimethylamino)zirconium, tetraethylmethylaminozirconium, and zirconium tetrachloride; the tantalum source is at least one of pentakis(dimethylamino)tantalum, tert - butylimino tris(ethylmethylamino)tantalum, and tert - butylimino tris(diethylamino)tantalum.

[0024] Compared with the prior art, the present invention adopts the ALD technology, which can achieve the technical purpose of depositing a super - black film at a low temperature (50 - 250 °C). On the premise of high film coverage, high absorption efficiency, and good bonding strength, the process temperature is reduced, enabling compatibility with more substrate materials and application to more products. At the same time, the present 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, increasing the wear - resistance and anti - corrosion performance of the film with almost no increase in reflection.

[0025] In summary, the present invention uses ALD technology to fabricate a super-black film with a low temperature (50 - 250 °C), high coverage rate, ultra-low reflectance (≤0.20%), high absorption efficiency (≥99.00%), and good adhesion for the substrate / transition layer (increasing adhesion) / light-absorbing layer (multi-layer interference film layer) / anti-corrosion layer (single layer or multi-layers). This effectively expands the selection range of substrate materials and solves the problems that the current manufacturing process of super-black films has significant limitations on substrate materials and is difficult to be compatible with low-temperature control, high coverage rate, and high absorption rate of thin films. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic structural diagram of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0027] To make the above objects, features, and advantages of the present invention more obvious and understandable, the following will describe the detailed embodiments of the present invention in conjunction with the accompanying drawings.

[0028] In the following description, many specific details are set forth to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar generalizations without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0029] To make the purpose, technical solution, and advantages of the present invention clearer, the following will further describe the embodiments of the present invention in detail in conjunction with the accompanying drawings.

[0030] Embodiment 1

[0031] As Figure 1 shown, this embodiment provides a super-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.

[0032] Among them, the material of the substrate 1 is 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; the anti-corrosion layer 4 is titanium oxide, aluminum oxide, and silicon oxide.

[0033] The thickness of the transition layer 2 is 6 nm, the thickness of the light-absorbing layer 3 is 94.69 nm, 197.9 nm, 54.5 nm, 33.07 nm, 13.67 nm, and the thickness of the anti-corrosion layer 4 is 5 nm, 5 nm, 63.76 nm.

[0034] The preparation method of the transition layer 2 is time-based ALD, which at least includes the following steps: Step 1: Place the substrate 1 in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). Step 2: At 100 °C, introduce diethylmagnesium in the form of pulses for 5 s to allow it to chemisorb on the surface of the substrate 1; then introduce 4000 sccm of inert gas to purge the unreacted diethylmagnesium and by-products, and the purging duration is 60 s. Step 3: Add O 2 plasma into the chamber in the form of pulses for 5 s to form a monolayer growth with the diethylmagnesium adsorbed on the surface; then introduce 3000 sccm of inert gas to purge the unreacted O 2 plasma and by-products, and the purging duration is 60 s. Step 4: Repeat Step 2 and Step 3 for cyclic deposition to form the transition layer 2.

[0035] The preparation method of the light-absorbing layer 3 is spatial ALD, and it includes at least the following steps: Step 1: In an atomic layer deposition chamber at 100 °C, continuously introduce trimethylaluminum, titanium tetrachloride, and methane plasma into the chamber through 2000 sccm of carrier gas and 3000 sccm of dilution gas to the reaction regions of trimethylaluminum, titanium tetrachloride, and methane plasma. At the same time, introduce 4000 sccm of inert gas between trimethylaluminum, titanium tetrachloride, and methane plasma. Step 2: The substrate deposited with the transition layer 2 sequentially passes through the regions of trimethylaluminum, titanium tetrachloride, and methane plasma and the isolation gas region to complete one cycle of deposition. Step 3: Repeat Step 1 and Step 2 for cyclic deposition to form TiAlC in the light-absorbing layer. Step 4: At 100 °C, introduce diisopropylamine silane in the form of pulses for 3 s to allow it to chemisorb on the surface of TiAlC; then introduce 4000 sccm of inert gas to purge the unreacted diisopropylamine silane and by-products, and the purging duration is 30 s. Step 5: Add O 2 plasma into the chamber in the form of pulses for 20 s to form a monolayer growth with the diisopropylamine silane adsorbed on the surface; then introduce 4000 sccm of inert gas to purge the unreacted O 2 plasma and by-products, and the purging duration is 10 s. Step 6: Repeat Step 4 and Step 5 for cyclic deposition to form SiO 2 in the light-absorbing layer.

[0036] Step 7: Repeat Step 3 and Step 6 for cyclic deposition to form the light-absorbing layer 3.

[0037] Among them, the carrier gas, dilution gas, and inert gas are argon. The preparation method of the anti-corrosion layer 4 is time-based ALD, and at least includes the following steps: In the first step, titanium tetrachloride is introduced into the atomic layer deposition chamber at 100 °C in a pulsed manner, so that it is chemically adsorbed on the surface of the light absorption layer 3; then 1000 sccm of inert gas is introduced to purge unreacted titanium tetrachloride and by-products, and the purge duration is 20 s; In the second step, distilled water is added to the chamber in a pulsed manner to form a monolayer growth with the titanium tetrachloride adsorbed on the surface; then 1000 sccm of inert gas is introduced to purge unreacted nitrogen plasma and by-products, and the purge duration is 30 s; In the third step, the first step and the second step are repeated for cyclic deposition to form the anti-corrosion layer TiO 2 。

[0038] In the fourth step, diethylaluminum is introduced into the atomic layer deposition chamber at 100 °C in a pulsed manner, so that it is chemically adsorbed on the surface of TiO 2 ; then 2000 sccm of inert gas is introduced to purge unreacted diethylaluminum and by-products, and the purge duration is 20 s; In the fifth step, distilled water is added to the chamber in a pulsed manner to form a monolayer growth with the diethylaluminum adsorbed on the surface; then 1000 sccm of inert gas is introduced to purge unreacted distilled water and by-products, and the purge duration is 30 s; In the sixth step, the fourth step and the fifth step are repeated for cyclic deposition to form Al 2 O 3 。

[0039] In the seventh step, at 100 °C, diisopropylamine silane is introduced in a pulsed manner and maintained for 3 s, so that it is chemically adsorbed on the surface of the anti-corrosion layer Al 2 O 3 ; then 4000 sccm of inert gas is introduced to purge unreacted diisopropylamine silane and by-products, and the purge duration is 30 s; In the eighth step, O 2 plasma is added to the chamber in a pulsed manner and maintained for 20 s to form a monolayer growth with the diisopropylamine silane adsorbed on the surface; then 4000 sccm of inert gas is introduced to purge unreacted O 2 plasma and by-products, and the purge duration is 10 s; In the ninth step, the seventh step and the eighth step are repeated for cyclic deposition to form SiO 2 。

[0040] Example 2

[0041] Such as Figure 1As shown in the figure, this embodiment provides a super black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, an 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 absorbing layer 3 by ALD.

[0042] Among them, the material of the substrate 1 is polymethyl methacrylate, the transition layer 2 is an aluminum-based hybrid film, and the absorbing layer 3 is a titanium aluminum carbide / aluminum oxide / titanium aluminum carbide / aluminum oxide / titanium aluminum carbide layer; the anti-corrosion layer 4 is tantalum nitride / silicon oxide. The thickness of the transition layer 2 is 10 nm, and the thicknesses of the 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.

[0043] The preparation method of the transition layer 2 is time-based ALD, which at least includes the following steps: The first step is to place the substrate 1 in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). The second step is to introduce magnesium cyclopentadienide in the form of pulses at 105 °C and keep it for 8 s to chemically adsorb it on the surface of the substrate 1; then introduce 2000 sccm of inert gas to purge the unreacted magnesium cyclopentadienide and by-products, and the purge duration is 50 s. The third step is to add O 3 into the chamber in the form of pulses and keep it for 5 s to form a monolayer growth with the magnesium cyclopentadienide adsorbed on the surface; then introduce 4000 sccm of inert gas to purge the unreacted O 3 and by-products, and the purge duration is 50 s. The fourth step is to repeat the second step and the third step for cyclic deposition to form the transition layer 2.

[0044] The preparation method of the absorbing layer 3 is time-based ALD, which at least includes the following steps: The first step is to introduce trimethylaluminum and titanium tetrachloride in the form of pulses in an atomic layer deposition chamber at 105 °C to chemically adsorb them on the surface of the transition layer 2; then introduce 4000 sccm of inert gas to purge the unreacted trimethylaluminum, titanium tetrachloride and by-products, and the purge duration is 100 s. The second step is to add methane plasma into the chamber in the form of pulses to form a monolayer growth with the trimethylaluminum and titanium tetrachloride adsorbed on the surface; then introduce 2000 sccm of inert gas to purge the unreacted methane plasma and by-products, and the purge duration is 80 s. The third step is to repeat the first step and the second step for cyclic deposition to form titanium aluminum carbide. Step 4: Pulse-feed dimethylaluminum into the atomic layer deposition chamber at 105°C to chemically adsorb it on the surface of aluminum titanium carbide; then introduce 3000 sccm of inert gas to purge unreacted dimethylaluminum and by-products, with the purge duration being 20 s; Step 5: Pulse-feed distilled water into the chamber to form a monolayer growth with the dimethylaluminum adsorbed on the surface; then introduce 2000 sccm of inert gas to purge unreacted distilled water and by-products, with the purge duration being 30 s; Step 6: Repeat Step 4 and Step 5 for cyclic deposition to form Al 2 O 3 .

[0045] Step 7: Repeat Step 3 and Step 6 once each, and then repeat Step 3 once more to form the light-absorbing layer.

[0046] The preparation method of the anticorrosion layer 4 is time-based ALD, which at least includes the following steps: Step 1: Pulse-feed pentakis(dimethylamino)tantalum into the atomic layer deposition chamber at 105°C to chemically adsorb it on the surface of the light-absorbing layer 3; then introduce 1500 sccm of inert gas to purge unreacted pentakis(dimethylamino)tantalum and by-products, with the purge duration being 30 s; Step 2: Pulse-feed ammonia plasma into the chamber to form a monolayer growth with the pentakis(dimethylamino)tantalum adsorbed on the surface; then introduce 1500 sccm of inert gas to purge unreacted oxygen plasma and by-products, with the purge duration being 40 s; Step 3: Repeat Step 1 and Step 2 for cyclic deposition to form tantalum nitride; Step 4: At 105°C, pulse-feed bis(diethylamino)silane for 7 s to chemically adsorb it on the surface of tantalum nitride; then introduce 2800 sccm of inert gas to purge unreacted bis(diethylamino)silane and by-products, with the purge duration being 55 s; Step 5: Pulse-feed O 2 plasma into the chamber for 8 s to form a monolayer growth with the bis(diethylamino)silane adsorbed on the surface; then introduce 3800 sccm of inert gas to purge unreacted O 2 plasma and by-products, with the purge duration being 50 s; Step 6: Repeat Step 4 and Step 5 for cyclic deposition to form a silica layer.

[0047] Example 3

[0048] As Figure 1As shown in the figure, this embodiment provides a super-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, an 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 absorbing layer 3 by ALD.

[0049] Among them, the material of the substrate 1 is polyimide, the transition layer 2 is aluminum nitride, the absorbing layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide; 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 absorbing layer 3 is 77.28 nm, 151.21 nm, 191.77 nm, 23.41 nm, 13.59 nm, and the thickness of the anti-corrosion layer 4 is 7.2 nm, 13.88 nm, 47.06 nm.

[0050] The preparation method of the transition layer 2 is a spatial ALD method, which at least includes the following steps: First step, place the substrate in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). Second step, at 90 °C, pass aluminum trichloride and nitrogen plasma through a carrier gas of 2500 sccm and a dilution gas of 5000 sccm into the chamber continuously, to the reaction region of the first precursor and the first reactant, and at the same time, pass an inert gas of 5000 - 20000 sccm between the first precursor and the first reactant. Third step, the substrate passes through the regions of aluminum trichloride, isolation gas, nitrogen plasma, and isolation gas in sequence to complete one cycle of deposition. Fourth step, repeat the second step and the third step, and deposit cyclically to form the transition layer.

[0051] Among them, the carrier gas, dilution gas, and inert gas are argon.

[0052] The preparation method of the absorbing layer 3 is a spatial ALD deposition method, which at least includes the following steps: First step, in an atomic layer deposition chamber at 90 °C, pass trimethylaluminum, titanium tetrachloride, and methane plasma through a carrier gas of 2600 sccm and a dilution gas of 3500 sccm into the chamber continuously, to the reaction region of trimethylaluminum, titanium tetrachloride, and methane plasma, and at the same time, pass an inert gas of 4800 sccm between trimethylaluminum, tetra(dimethylamino)titanium, and methane plasma. Second step, the substrate deposited with the transition layer 2 passes through the regions of trimethylaluminum, tetra(dimethylamino)titanium, methane plasma, and isolation gas in sequence to complete one cycle of deposition. Third step, repeat the first step and the second step, and deposit cyclically to form titanium aluminum carbide. Step 4: At 90 °C, bis(diethylamino)silane and nitrogen plasma are successively introduced into the chamber through a carrier gas of 2500 sccm and a dilution gas of 5000 sccm, reaching the reaction region of the first precursor and the first reactant. Meanwhile, an inert gas of 5000 - 20000 sccm is introduced between the first precursor and the first reactant. Step 4: The substrate successively passes through the regions of bis(diethylamino)silane, isolation gas, nitrogen plasma, and isolation gas, completing one cycle of deposition to form silicon dioxide.

[0053] Among them, the carrier gas, dilution gas, and inert gas are argon or nitrogen. The preparation method of the anti-corrosion layer 4 is spatial ALD, including at least the following steps: Step 1: In an atomic layer deposition chamber at 90 °C, zirconium tetrakis(dimethylamino) and H 2 O are successively introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, reaching the reaction region of zirconium tetrakis(dimethylamino) and H 2 O. Meanwhile, an inert gas of 10000 sccm is introduced between zirconium tetrakis(dimethylamino) and H 2 O. Step 2: The substrate 1 deposited with the transition layer 2 and the light-absorbing layer 3 successively passes through the regions of zirconium tetrakis(dimethylamino), isolation gas, H 2 O, and isolation gas, completing one cycle of deposition. Step 3: Repeat Step 1 and Step 2, and deposit cyclically to form zirconia. Step 4: In an atomic layer deposition chamber at 90 °C, diethylaluminum and H 2 O are successively introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, reaching the reaction region of diethylaluminum and H 2 O. Meanwhile, an inert gas of 10000 sccm is introduced between diethylaluminum and H 2 O. Step 5: Successively pass through the regions of diethylaluminum, isolation gas, H 2 O, and isolation gas, completing one cycle of deposition. Step 6: Repeat Step 4 and Step 5, and deposit cyclically to form alumina. Step 7: In an atomic layer deposition chamber at 90 °C, bis(diethylamino)silane and H 2 O are successively introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, reaching the reaction region of bis(diethylamino)silane and H 2 O. Meanwhile, an inert gas of 10000 sccm is introduced between bis(diethylamino)silane and H 2 O. Step 5: Sequentially pass through bis(diethylamino)silane, purge gas, H 2 O, and the purge gas region to complete one cycle of deposition; Step 6: Repeat Step 1 and Step 2 for cyclic deposition to form silicon oxide.

[0054] Among them, the carrier gas, dilution gas, and inert gas are nitrogen.

[0055] Example 4

[0056] As Figure 1 shown, this example provides a super black nano - coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, an absorbent 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 absorbent layer 3 by ALD.

[0057] Among them, the material of the substrate 1 is SiC, the transition layer 2 is aluminum nitride, the absorbent layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide; the anti - corrosion layer 4 is titanium nitride / silicon oxide; The thickness of the transition layer 2 is 6.41 nm, the thickness of the absorbent layer 3 is 74.88 nm, 186.95 nm, 191.75 nm, 28.09 nm, 3.95 nm, and the thickness of the anti - corrosion layer 4 is 16.13, 62.01 nm.

[0058] The preparation method of the transition layer 2 is time - type ALD, which at least includes the following steps: Step 1: Place the substrate 1 in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr); Step 2: At 103 °C, introduce trimethylaluminum in the form of pulses and maintain for 10 s to chemically adsorb it on the surface of the substrate 1; then introduce 2500 sccm of inert gas to purge the unreacted trimethylaluminum and by - products, and the purge duration is 35 s; Step 3: Add ammonia plasma into the chamber in the form of pulses and maintain for 10 s to form a monolayer growth with the trimethylaluminum adsorbed on the surface; then introduce 4500 sccm of inert gas to purge the unreacted ammonia plasma and by - products, and the purge duration is 35 s; Step 4: Repeat Step 2 and Step 3 for cyclic deposition to form the transition layer 2.

[0059] The preparation method of the absorbent layer 3 is the time - type ALD deposition method, and the preparation method of the titanium aluminum carbide layer at least includes the following steps: First step, trimethylaluminum and titanium tetrakis(dimethylamido) are introduced in pulses into the atomic layer deposition chamber at 103 °C, and chemically adsorbed on the surface of the transition layer 2; then 4000 sccm of inert gas is introduced to purge unreacted trimethylaluminum, titanium tetrakis(dimethylamido), and by-products, and the purge duration is 110 s; Second step, methane plasma is added into the chamber in pulses, and a monolayer growth is formed with the trimethylaluminum and titanium tetrakis(dimethylamido) adsorbed on the surface; then 2200 sccm of inert gas is introduced to purge unreacted methane plasma and by-products, and the purge duration is 90 s; Third step, the first and second steps are repeated for cyclic deposition to form an aluminum titanium carbide layer.

[0060] The preparation method of the silicon dioxide layer is as follows: First step, bis(diethylamino)silane is introduced in pulses at 103 °C for 7 s, and chemically adsorbed on the surface of the substrate 1; then 2800 sccm of inert gas is introduced to purge unreacted bis(diethylamino)silane and by-products, and the purge duration is 55 s; Second step, O 2 plasma is added into the chamber in pulses for 8 s, and a monolayer growth is formed with the bis(diethylamino)silane adsorbed on the surface; then 3800 sccm of inert gas is introduced to purge unreacted O 2 plasma and by-products, and the purge duration is 50 s; Third step, the second step is repeated for cyclic deposition to form a silicon dioxide layer.

[0061] The preparation method of the anticorrosive layer 4 is a time-based ALD deposition method, and the preparation method of titanium nitride includes at least the following steps: First step, tetraisopropyl titanate is introduced in pulses into the atomic layer deposition chamber at 103 °C, and chemically adsorbed on the surface of the light absorption layer 3; then 1500 sccm of inert gas is introduced to purge unreacted tetraisopropyl titanate and by-products, and the purge duration is 30 s; Second step, nitrogen plasma is added into the chamber in pulses, and a monolayer growth is formed with the tetraisopropyl titanate adsorbed on the surface; then 1500 sccm of inert gas is introduced to purge unreacted nitrogen plasma and by-products, and the purge duration is 40 s; Third step, the first and second steps are repeated for cyclic deposition to form titanium nitride.

[0062] The preparation method of silicon dioxide is the same as that of the silicon dioxide in the light absorption layer in this embodiment.

[0063] Example 5

[0064] AsFigure 1 As shown in the figure, this embodiment provides a super-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.

[0065] Among them, the material of the substrate 1 is titanium alloy, the transition layer 2 is a zinc-based hybrid film, the light-absorbing layer 3 is titanium aluminum carbide / aluminum oxide / titanium aluminum carbide / aluminum oxide / titanium aluminum carbide; the anti-corrosion layer 4 is aluminum nitride / aluminum oxide / silicon oxide; The thickness of the transition layer 2 is 9nm, the thickness of the light-absorbing layer 3 is 9.28nm, 173.5nm, 164.58nm, 24.53nm, 13.44nm, and the thickness of the anti-corrosion layer 4 is 7nm, 34.94nm, 27.69nm.

[0066] The preparation method of the transition layer 2 is a spatial ALD deposition method, which at least includes the following steps: First step, place the substrate in an atomic layer deposition chamber under a vacuum state (pressure below 5mTorr); Second step, at 95°C, continuously introduce diethyl zinc and glycerol into the chamber through a carrier gas of 4500sccm and a dilution gas of 8000sccm until the reaction area of diethyl zinc and glycerol, and at the same time introduce an inert gas of 15000sccm between diethyl zinc and glycerol; Third step, the substrate passes through the diethyl zinc, isolation gas, glycerol, and isolation gas regions in sequence to complete one cycle of deposition; Fourth step, repeat the second step and the third step, and deposit cyclically to form the transition layer.

[0067] Among them, the carrier gas, dilution gas, and inert gas are nitrogen.

[0068] The preparation method of the light-absorbing layer 3 is a time-based ALD deposition method, and the preparation method of the titanium aluminum carbide layer at least includes the following steps: First step, in an atomic layer deposition chamber at 95°C, introduce trimethylaluminum and titanium tetrakis(dimethylamino) in pulse form and hold for 4s to chemically adsorb on the surface of the transition layer 2; then introduce an inert gas of 4100sccm to purge the unreacted trimethylaluminum, titanium tetrakis(dimethylamino), and by-products, and the purge duration is 100s; Second step, add methane plasma into the chamber in pulse form to form monolayer growth with the trimethylaluminum and titanium tetrakis(dimethylamino) adsorbed on the surface; then introduce an inert gas of 2800sccm to purge the unreacted methane plasma and by-products, and the purge duration is 65s; Third step, repeat the first step and the second step, and deposit cyclically to form the titanium aluminum carbide layer.

[0069] The preparation method of the aluminum oxide layer is as follows: First step, place the substrate 1 in an atomic layer deposition chamber under a vacuum state (the air pressure is below 5 mTorr); Second step, at 95 °C, introduce aluminum trichloride in the form of pulses and keep it for 7 s to chemically adsorb it on the surface of the substrate 1; then introduce 2800 sccm of inert gas to purge the unreacted aluminum trichloride and by-products, and the purge duration is 55 s; Third step, add O 2 plasma into the chamber in the form of pulses and keep it for 8 s to form a monolayer growth with the aluminum trichloride adsorbed on the surface; then introduce 3800 sccm of inert gas to purge the unreacted O 2 plasma and by-products, and the purge duration is 50 s; Fourth step, repeat the second step and the third step for cyclic deposition to form the aluminum oxide layer.

[0070] The preparation method of the anti-corrosion layer 4 is the spatial ALD deposition method: The preparation method of aluminum nitride includes the following steps: First step, introduce trimethylaluminum in the form of pulses in an atomic layer deposition chamber at 95 °C to chemically adsorb it on the surface of the light absorption layer 3; then introduce 1800 sccm of inert gas to purge the unreacted trimethylaluminum and by-products, and the purge duration is 25 s; Second step, add nitrogen plasma into the chamber in the form of pulses to form a monolayer growth with the trimethylaluminum adsorbed on the surface; then introduce 1800 sccm of inert gas to purge the unreacted nitrogen plasma and by-products, and the purge duration is 25 s; Third step, repeat the first step and the second step for cyclic deposition to form aluminum nitride.

[0071] The preparation method of aluminum oxide includes the following steps: First step, introduce trimethylaluminum in the form of pulses in an atomic layer deposition chamber at 95 °C to chemically adsorb it on the surface of the aluminum nitride; then introduce 1800 sccm of inert gas to purge the unreacted trimethylaluminum and by-products, and the purge duration is 25 s; Second step, add oxygen plasma into the chamber in the form of pulses to form a monolayer growth with the trimethylaluminum adsorbed on the surface; then introduce 1800 sccm of inert gas to purge the unreacted oxygen plasma and by-products, and the purge duration is 25 s; Third step, repeat the first step and the second step for cyclic deposition to form aluminum oxide.

[0072] The preparation method of silicon oxide: First step, pulse trimethylsilylamine into the atomic layer deposition chamber at 95°C to chemically adsorb it on the surface of alumina; then introduce 1800 sccm of inert gas to purge unreacted trimethylsilylamine and by-products, and the purge duration is 25 s; Second step, pulse oxygen plasma into the chamber to form a monolayer growth with the trimethylsilylamine adsorbed on the surface; then introduce 1800 sccm of inert gas to purge unreacted oxygen plasma and by-products, and the purge duration is 25 s; Third step, repeat the first and second steps for cyclic deposition to form silicon oxide.

[0073] Example 6

[0074] As Figure 1 shown, this example provides a super black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, an 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 absorbing layer 3 by ALD.

[0075] Among them, the material of the substrate 1 is an optical glass sheet, the transition layer 2 is zinc oxide, the absorbing layer 3 is titanium aluminum carbide / silicon oxide / titanium aluminum carbide / silicon oxide / titanium aluminum carbide; the anti-corrosion layer 4 is silicon nitride / aluminum oxide / silicon oxide. The thickness of the transition layer 2 is 6.86 nm, and the thicknesses of the absorbing layer 3 are 9.28 nm, 191.79 nm, 164.58 nm, 30.47 nm, and 13.44 nm, and the thicknesses of the anti-corrosion layer 4 are 5.53 nm, 34.94 nm, and 28.45 nm.

[0076] The preparation method of the transition layer 2 is time-based ALD, including at least the following steps: First step, place the substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr); Second step, at 100°C, pulse dimethylzinc and keep it for 5 s to chemically adsorb it on the surface of the substrate 1; then introduce 4000 sccm of inert gas to purge unreacted dimethylzinc and by-products, and the purge duration is 60 s; Third step, pulse O 3 into the chamber and keep it for 6 s to form a monolayer growth with the dimethylzinc adsorbed on the surface; then introduce 8000 sccm of inert gas to purge unreacted O 3 and by-products, and the purge duration is 50 s; Fourth step, repeat the second and third steps for cyclic deposition to form the transition layer 2.

[0077] The preparation method of the absorbing layer 3 is time-based ALD, including at least the following steps: The preparation method of aluminum titanium carbide includes the following steps: In the first step, trimethylaluminum and titanium tetrachloride are introduced into the atomic layer deposition chamber at 100 °C in a pulsed manner, and they are chemically adsorbed on the surface of the transition layer 2; then, 4000 sccm of inert gas is introduced to purge the unreacted trimethylaluminum, titanium tetrachloride, and by-products, and the purge duration is 100 s; In the second step, methane plasma is added to the chamber in a pulsed manner to form a monolayer growth with the trimethylaluminum and titanium tetrachloride adsorbed on the surface; then, 2000 sccm of inert gas is introduced to purge the unreacted methane plasma and by-products, and the purge duration is 80 s; In the third step, the first and second steps are repeated for cyclic deposition to form the light-absorbing layer 3.

[0078] The preparation method of the silicon dioxide layer is as follows: In the first step, the substrate 1 is placed in an atomic layer deposition chamber under a vacuum state (the pressure is reduced to below 5 mTorr); In the second step, at 100 °C, bis(diethylamino)silane is introduced in a pulsed manner and kept for 7 s to be chemically adsorbed on the surface of the substrate 1; then, 2800 sccm of inert gas is introduced to purge the unreacted bis(diethylamino)silane and by-products, and the purge duration is 55 s; In the third step, O 2 plasma is added to the chamber in a pulsed manner and kept for 8 s to form a monolayer growth with the bis(diethylamino)silane adsorbed on the surface; then, 3800 sccm of inert gas is introduced to purge the unreacted O 2 plasma and by-products, and the purge duration is 50 s; In the fourth step, the second and third steps are repeated for cyclic deposition to form the silicon dioxide layer.

[0079] The preparation method of the anti-corrosion layer 4 is time-based ALD: The preparation method of silicon nitride: In the first step, tris(dimethylamino)silane is introduced into the atomic layer deposition chamber at 100 °C in a pulsed manner to be chemically adsorbed on the surface of the light-absorbing layer 3; then, 1800 sccm of inert gas is introduced to purge the unreacted tris(dimethylamino)silane and by-products, and the purge duration is 30 s; In the second step, ammonia plasma is added to the chamber in a pulsed manner to form a monolayer growth with the tris(dimethylamino)silane adsorbed on the surface; then, 1800 sccm of inert gas is introduced to purge the unreacted ammonia plasma and by-products, and the purge duration is 30 s; In the third step, the first and second steps are repeated for cyclic deposition to form silicon nitride.

[0080] Method for preparing aluminum oxide: In the first step, trimethylaluminum is introduced in pulses into an atomic layer deposition chamber at 100 °C, so that it is chemically adsorbed on the surface of silicon nitride; then, 1800 sccm of inert gas is introduced to purge unreacted trimethylaluminum and by-products, and the purge duration is 30 s; In the second step, oxygen plasma is added to the chamber in pulses, so that it forms monolayer growth with the trimethylaluminum adsorbed on the surface; then, 1800 sccm of inert gas is introduced to purge unreacted oxygen plasma and by-products, and the purge duration is 30 s; In the third step, the first and second steps are repeated for cyclic deposition to form aluminum oxide.

[0081] Method for preparing silicon oxide: In the first step, tris(dimethylamino)silane is introduced in pulses into an atomic layer deposition chamber at 100 °C, so that it is chemically adsorbed on the surface of the light-absorbing layer 3; then, 1800 sccm of inert gas is introduced to purge unreacted tris(dimethylamino)silane and by-products, and the purge duration is 30 s; In the second step, oxygen plasma is added to the chamber in pulses, so that it forms monolayer growth with the tris(dimethylamino)silane adsorbed on the surface; then, 1800 sccm of inert gas is introduced to purge unreacted oxygen plasma and by-products, and the purge duration is 30 s; In the third step, the first and second steps are repeated for cyclic deposition to form silicon oxide.

[0082] Example 7 As Figure 1 shown, this example provides a super-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.

[0083] Among them, the material of the substrate 1 is polycarbonate, the transition layer 2 is a titanium-based hybrid film, the light-absorbing layer 3 is titanium aluminum carbide / aluminum oxide / titanium aluminum carbide / aluminum oxide / titanium aluminum carbide; the anti-corrosion layer 4 is tantalum nitride / aluminum oxide / silicon oxide.

[0084] The thickness of the transition layer 2 is 13.4 nm, the thickness of the 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 the anti-corrosion layer 4 is 6.59 nm, 34.94 nm, 27.69 nm.

[0085] The preparation method of the transition layer 2 is spatial ALD, including at least the following steps: In the first step, the substrate is placed in an atomic layer deposition chamber in a vacuum state (pressure below 5 mTorr); Step 2: At 102 °C, continuously introduce titanium tetrachloride and 1,4-butanediol into the chamber through a carrier gas of 4500 sccm and a dilution gas of 8000 sccm until the reaction zone of titanium tetrachloride and 1,4-butanediol. Meanwhile, introduce an inert gas of 13000 sccm between titanium tetrachloride and 1,4-butanediol; Step 3: The substrate sequentially passes through the regions of titanium tetrachloride, isolation gas, 1,4-butanediol, and isolation gas to complete one cycle of deposition; Step 4: Repeat Step 2 and Step 3 for cyclic deposition to form a transition layer.

[0086] Among them, the carrier gas, dilution gas, and inert gas are nitrogen.

[0087] The preparation method of the light-absorbing layer 3 is a time-based ALD deposition method. The preparation method of the titanium aluminum carbide layer at least includes the following steps: Step 1: In the atomic layer deposition chamber at 102 °C, introduce triethylaluminum and tetraisopropyl titanate in a pulsed manner and hold for 4 s to chemically adsorb them on the surface of the transition layer 2; then introduce an inert gas of 4800 sccm to purge the unreacted triethylaluminum, tetraisopropyl titanate, and by-products, and the purge duration is 70 s; Step 2: Add methane plasma into the chamber in a pulsed manner to form a monolayer growth with the triethylaluminum and tetraisopropyl titanate adsorbed on the surface; then introduce an inert gas of 3800 sccm to purge the unreacted methane plasma and by-products, and the purge duration is 65 s; Step 3: Repeat Step 1 and Step 2 for cyclic deposition to form a titanium aluminum carbide layer.

[0088] The preparation method of the aluminum oxide layer is as follows: Step 1: Place the substrate 1 in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr); Step 2: At 102 °C, introduce triethylaluminum in a pulsed manner and hold for 7.5 s to chemically adsorb it on the surface of the substrate 1; then introduce an inert gas of 2500 sccm to purge the unreacted triethylaluminum and by-products, and the purge duration is 55 s; Step 3: Add O 2 plasma into the chamber in a pulsed manner and hold for 3 s to form a monolayer growth with the triethylaluminum adsorbed on the surface; then introduce an inert gas of 3300 sccm to purge the unreacted O 2 plasma and by-products, and the purge duration is 50 s; Step 4: Repeat Step 2 and Step 3 for cyclic deposition to form an aluminum oxide layer.

[0089] The preparation method of the anti-corrosion layer 4 is time-based ALD. The preparation method of tantalum nitride at least includes the following steps: First step: In an atomic layer deposition chamber at 102 °C, tert-butylimido tris(ethylmethylamido)tantalum and nitrogen plasma are successively introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 3000 sccm until the reaction region of tert-butylimido tris(ethylmethylamido)tantalum and nitrogen plasma. Meanwhile, an inert gas of 11000 sccm is introduced between tert-butylimido tris(ethylmethylamido)tantalum and nitrogen plasma. Second step: The substrate deposited with the transition layer 2 and the light-absorbing layer 3 successively passes through the regions of tert-butylimido tris(ethylmethylamido)tantalum, isolation gas, nitrogen plasma, and isolation gas to complete one cycle of deposition. Third step: Repeat the first step and the second step for cyclic deposition to form tantalum nitride. The preparation method of alumina is the same as that of alumina in the light-absorbing layer in this embodiment, and the preparation method of silica is to replace the aluminum source with a silicon source.

[0090] Among them, the carrier gas, dilution gas, and inert gas are nitrogen.

[0091] Example 8

[0092] As Figure 1 shown, this embodiment provides a super-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.

[0093] Among them, the thickness of the transition layer 2 is 6 nm, the thickness of the light-absorbing layer 3 is 61.61 nm, 167.96 nm, 164.15 nm, 33.02 nm, 15.01 nm, and the thickness of the anti-corrosion layer 4 is 10.42 nm, 63.52 nm.

[0094] The material of the substrate 1 is polyimide, the transition layer 2 is aluminum nitride, the light-absorbing layer 3 is alternately arranged aluminum titanium carbide and alumina; the anti-corrosion layer 4 is zirconium oxide and silica.

[0095] The preparation method of the transition layer 2 is spatial ALD, which at least includes the following steps: First step: Place the substrate in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). Second step: At 105 °C, aluminum trichloride and nitrogen plasma are successively introduced into the chamber through a carrier gas of 2500 sccm and a dilution gas of 5000 sccm until the reaction region of the first precursor and the first reactant. Meanwhile, an inert gas of 5000 - 20000 sccm is introduced between the first precursor and the first reactant. In the third step, the substrate sequentially passes through the regions of aluminum trichloride, isolation gas, nitrogen plasma, and isolation gas to complete one cycle of deposition; In the fourth step, repeat the second and third steps for cyclic deposition to form a transition layer.

[0096] Among them, the carrier gas, dilution gas, and inert gas are all argon.

[0097] The preparation method of the light-absorbing layer 3 is spatial ALD. The preparation method of aluminum titanium carbide includes the following steps: In the first step, in an atomic layer deposition chamber at 105 °C, trimethylaluminum, titanium tetrachloride, and methane plasma are successively introduced into the chamber through a carrier gas of 2600 sccm and a dilution gas of 3500 sccm, reaching the reaction regions of trimethylaluminum, titanium tetrachloride, and methane plasma. Meanwhile, an inert gas of 4800 sccm is introduced between trimethylaluminum, tetra(dimethylamino)titanium, and methane plasma; In the second step, the substrate deposited with the transition layer 2 sequentially passes through the regions of trimethylaluminum, tetra(dimethylamino)titanium, methane plasma, and isolation gas to complete one cycle of deposition; In the third step, repeat the first and second steps for cyclic deposition to form aluminum titanium carbide.

[0098] Among them, the carrier gas, dilution gas, and inert gas are all argon; The preparation method of the aluminum oxide layer includes the following steps: In the first step, in an atomic layer deposition chamber at 105 °C, diethylaluminum and H 2 O are successively introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, reaching the reaction regions of diethylaluminum and H 2 O. Meanwhile, an inert gas of 10000 sccm is introduced between diethylaluminum and H 2 O; In the second step, sequentially pass through the regions of diethylaluminum, isolation gas, H 2 O, and isolation gas to complete one cycle of deposition; In the third step, repeat the first and second steps for cyclic deposition to form aluminum oxide; The preparation method of the anti-corrosion layer 4 is spatial ALD. The preparation of the zirconium oxide layer includes the following steps: In the first step, in an atomic layer deposition chamber at 105 °C, tetra(dimethylamino)zirconium and H 2 O are successively introduced into the chamber through a carrier gas of 4000 sccm and a dilution gas of 6000 sccm, reaching the reaction regions of tetra(dimethylamino)zirconium and H 2 O. Meanwhile, an inert gas of 10000 sccm is introduced between tetra(dimethylamino)zirconium and H 2 O; In the second step, the substrate 1 deposited with the transition layer 2 and the light-absorbing layer 3 sequentially passes through the regions of zirconium tetrakis(dimethylamino), isolation gas, H 2 O, and isolation gas to complete one cycle of deposition; In the third step, the first and second steps are repeated for cyclic deposition to form a zirconia layer.

[0099] The preparation method of silicon oxide is as follows: In the first step, diisopropylamine silane is introduced in a pulsed manner into an atomic layer deposition chamber at 105 °C to chemically adsorb it on the surface of zirconia; then, an inert gas of 1800 sccm is introduced to purge the unreacted diisopropylamine silane and by-products, and the purge duration is 25 s; In the second step, oxygen plasma is added to the chamber in a pulsed manner to form a monolayer growth with the diisopropylamine silane adsorbed on the surface; then, an inert gas of 1800 sccm is introduced to purge the unreacted oxygen plasma and by-products, and the purge duration is 25 s; In the third step, the first and second steps are repeated for cyclic deposition to form silicon oxide.

[0100] Among them, the carrier gas, dilution gas, and inert gas are all nitrogen.

[0101] Example 9

[0102] As Figure 1 shown, this example provides a super 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.

[0103] Among them, the thickness of the transition layer 2 is 8.29 nm, the thicknesses of the light-absorbing layer 3 are 60.40 nm, 185.78 nm, 175.05 nm, 24.44 nm, 13.04 nm, and the thicknesses of the anti-corrosion layer 4 are 8.69 nm, 58.85 nm.

[0104] The material of the substrate 1 is 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.

[0105] The preparation method of the transition layer 2 is time-based ALD, including at least the following steps: In the first step, the substrate 1 is placed in an atomic layer deposition chamber in a vacuum state (pressure below 5 mTorr); In the second step, at 95 °C, trimethylaluminum is introduced in a pulsed manner and held for 10 s to chemically adsorb it on the surface of the substrate 1; then, an inert gas of 2500 sccm is introduced to purge the unreacted trimethylaluminum and by-products, and the purge duration is 35 s; In the third step, ethylene glycol is added into the chamber in a pulsed manner and kept for 10 s to form monolayer growth with trimethylaluminum adsorbed on the surface; then an inert gas of 4500 sccm is introduced to purge unreacted ethylene glycol and by-products, and the purge duration is 35 s; In the fourth step, the second and third steps are repeated for cyclic deposition to form the transition layer 2.

[0106] The preparation method of the light absorption layer 3 is time-type ALD. The preparation method of the aluminum titanium carbide layer includes at least the following steps: In the first step, triethylaluminum and titanium tetrakis(dimethylamido) are introduced into the atomic layer deposition chamber at 95 °C in a pulsed manner to chemically adsorb on the surface of the transition layer 2; then an inert gas of 4000 sccm is introduced to purge unreacted triethylaluminum, titanium tetrakis(dimethylamido), and by-products, and the purge duration is 110 s; In the second step, methane plasma is added into the chamber in a pulsed manner to form monolayer growth with triethylaluminum and titanium tetrakis(dimethylamido) adsorbed on the surface; then an inert gas of 2200 sccm is introduced to purge unreacted methane plasma and by-products, and the purge duration is 90 s; In the third step, the first and second steps are repeated for cyclic deposition to form the aluminum titanium carbide layer.

[0107] The preparation method of the silicon dioxide layer is as follows: In the first step, bis(diethylamino)silane is introduced at 95 °C in a pulsed manner and kept for 7 s to chemically adsorb on the surface of the aluminum titanium carbide layer; then an inert gas of 2800 sccm is introduced to purge unreacted bis(diethylamino)silane and by-products, and the purge duration is 55 s; In the second step, O 2 plasma is added into the chamber in a pulsed manner and kept for 8 s to form monolayer growth with bis(diethylamino)silane adsorbed on the surface; then an inert gas of 3800 sccm is introduced to purge unreacted O 2 plasma and by-products, and the purge duration is 50 s; In the third step, the second step is repeated for cyclic deposition to form the silicon dioxide layer.

[0108] The preparation method of the anti-corrosion layer 4 is time-type ALD. The preparation method of titanium oxide includes at least the following steps: In the first step, tetraisopropyl titanate is introduced into the atomic layer deposition chamber at 95 °C in a pulsed manner to chemically adsorb on the surface of the light absorption layer 3; then an inert gas of 1500 sccm is introduced to purge unreacted tetraisopropyl titanate and by-products, and the purge duration is 30 s; In the second step, oxygen plasma is introduced into the chamber in the form of pulses to form a monolayer growth with the adsorbed tetraisopropyl titanate on the surface; then, an inert gas of 1500 sccm is introduced to purge the unreacted oxygen plasma and by-products, and the purging duration is 40 s. In the third step, the first and second steps are repeated for cyclic deposition to form titanium oxide.

[0109] The preparation method of the silicon oxide layer is the same as that of the silicon oxide layer of the light absorption layer in the present invention.

[0110] Example 10

[0111] As Figure 1 As shown in the figure, this example provides a super black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, a light absorption 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 absorption layer 3 by ALD.

[0112] Among them, the thickness of the transition layer 2 is 7.31 nm, the thicknesses of the light absorption layer 3 are 39.99 nm, 168.07 nm, 159.74 nm, 22.11 nm, 11.67 nm, and the thicknesses of the anti-corrosion layer 4 are 11.17 nm, 65.39 nm.

[0113] The material of the substrate 1 is titanium alloy, the transition layer 2 is a zinc-based hybrid film, the light absorption layer 3 is an alternating layer of titanium aluminum carbide and aluminum oxide; the anti-corrosion layer 4 is silicon nitride and silicon oxide.

[0114] The preparation method of the transition layer 2 is spatial ALD, which at least includes the following steps: In the first step, the substrate is placed in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). In the second step, diethyl zinc and glycerol are continuously introduced into the chamber through a carrier gas of 4500 sccm and a dilution gas of 8000 sccm at 90 °C to the reaction region of diethyl zinc and glycerol, and at the same time, an inert gas of 15000 sccm is introduced between diethyl zinc and glycerol. In the third step, the substrate passes through the regions of diethyl zinc, isolation gas, glycerol, and isolation gas in sequence to complete a cycle of deposition. In the fourth step, the second and third steps are repeated for cyclic deposition to form the transition layer.

[0115] Among them, the carrier gas, dilution gas, and inert gas are all nitrogen.

[0116] The preparation method of the light absorption layer 3 is time-based ALD, and the preparation method of the titanium aluminum carbide layer at least includes the following steps: First step: Pulse trimethylaluminum and titanium tetrakis(dimethylamido) into the atomic layer deposition chamber at 90 °C and hold for 4 s to allow chemisorption on the surface of the transition layer 2; then introduce 4100 sccm of inert gas to purge unreacted trimethylaluminum, titanium tetrakis(dimethylamido), and by-products, with a purge duration of 100 s. Second step: Pulse methane plasma into the chamber to form a monolayer growth with the trimethylaluminum and titanium tetrakis(dimethylamido) adsorbed on the surface; then introduce 2800 sccm of inert gas to purge unreacted methane plasma and by-products, with a purge duration of 65 s. Third step: Repeat the first and second steps for cyclic deposition to form an aluminum titanium carbide layer.

[0117] The preparation method of the alumina layer is as follows: First step: Place the substrate 1 in an atomic layer deposition chamber under vacuum (pressure below 5 mTorr). Second step: Pulse aluminum trichloride into the chamber at 90 °C and hold for 7 s to allow chemisorption on the surface of the substrate 1; then introduce 2800 sccm of inert gas to purge unreacted aluminum trichloride and by-products, with a purge duration of 55 s. Third step: Pulse O 2 plasma into the chamber and hold for 8 s to form a monolayer growth with the aluminum trichloride adsorbed on the surface; then introduce 3800 sccm of inert gas to purge unreacted O 2 plasma and by-products, with a purge duration of 50 s. Fourth step: Repeat the second and third steps for cyclic deposition to form an alumina layer.

[0118] The preparation method of the anticorrosion layer 4 is spatial ALD. The preparation method of the silicon nitride layer includes at least the following steps: First step: Pulse tris(dimethylamino)silane into the atomic layer deposition chamber at 90 °C to allow chemisorption on the surface of the light-absorbing layer 3; then introduce 1800 sccm of inert gas to purge unreacted tris(dimethylamino)silane and by-products, with a purge duration of 25 s. Second step: Pulse nitrogen plasma into the chamber to form a monolayer growth with the tris(dimethylamino)silane adsorbed on the surface; then introduce 1800 sccm of inert gas to purge unreacted nitrogen plasma and by-products, with a purge duration of 25 s. Third step: Repeat the first and second steps for cyclic deposition to form a silicon nitride layer.

[0119] The preparation method of silicon oxide is: First step, diisopropylamine silane is introduced in a pulsed manner into an atomic layer deposition chamber at 90 °C, allowing it to chemically adsorb on the surface of silicon nitride; then, 1500 sccm of inert gas is introduced to purge unreacted diisopropylamine silane and by-products, and the purge duration is 28 s; Second step, oxygen plasma is added to the chamber in a pulsed manner to form a monolayer growth with the diisopropylamine silane adsorbed on the surface; then, 1600 sccm of inert gas is introduced to purge unreacted oxygen plasma and by-products, and the purge duration is 28 s; Third step, the first and second steps are repeated for cyclic deposition to form silicon oxide.

[0120] Example 11

[0121] As Figure 1 shown, this example provides a super black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, an 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 absorbing layer 3 by ALD.

[0122] Among them, the thickness of the transition layer 2 is 5.91 nm, the thicknesses of the absorbing layer 3 are 85.92 nm, 129.69 nm, 175.05 nm, 25.49 nm, 5.33 nm, and the thicknesses of the anti-corrosion layer 4 are 26.84 nm, 70.07 nm.

[0123] The material of the substrate 1 is an optical glass sheet, the transition layer 2 is zinc oxide, the absorbing layer 3 is a titanium aluminum carbide / silicon oxide / titanium aluminum carbide / aluminum oxide / titanium aluminum carbide layer; the anti-corrosion layer 4 is tantalum nitride and silicon oxide.

[0124] The preparation method of the transition layer 2 is time-based ALD, which at least includes the following steps: First step, the substrate 1 is placed in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr); Second step, at 105 °C, dimethylzinc is introduced in a pulsed manner and held for 5 s to allow it to chemically adsorb on the surface of the substrate 1; then, 4000 sccm of inert gas is introduced to purge unreacted dimethylzinc and by-products, and the purge duration is 60 s; Third step, O3 is added to the chamber in a pulsed manner and held for 6 s to form a monolayer growth with the dimethylzinc adsorbed on the surface; then, 8000 sccm of inert gas is introduced to purge unreacted O3 and by-products, and the purge duration is 50 s; Fourth step, the second and third steps are repeated for cyclic deposition to form the transition layer 2.

[0125] The preparation method of the absorbing layer 3 is time-based ALD, and the preparation method of titanium aluminum carbide includes the following steps: First step: Pulse trimethylaluminum and titanium tetrachloride into the atomic layer deposition chamber at 105°C to chemically adsorb them on the surface of the transition layer 2; then introduce 4000 sccm of inert gas to purge unreacted trimethylaluminum, titanium tetrachloride, and by-products, and the purge duration is 100 s; Second step: Pulse methane plasma into the chamber to form a monolayer growth with the trimethylaluminum and titanium tetrachloride adsorbed on the surface; then introduce 2000 sccm of inert gas to purge unreacted methane plasma and by-products, and the purge duration is 80 s; Third step: Repeat the first and second steps for cyclic deposition to form aluminum titanium carbide.

[0126] The preparation method of the silicon oxide layer is as follows: First step: Pulse bis(diethylamino)silane into the chamber at 105°C and hold for 9 s to chemically adsorb it on the surface of the aluminum titanium carbide layer; then introduce 3800 sccm of inert gas to purge unreacted bis(diethylamino)silane and by-products, and the purge duration is 55 s; Second step: Pulse O 2 plasma into the chamber and hold for 9 s to form a monolayer growth with the bis(diethylamino)silane adsorbed on the surface; then introduce 4200 sccm of inert gas to purge unreacted O 2 plasma and by-products, and the purge duration is 40 s; Third step: Repeat the second and third steps for cyclic deposition to form the silicon oxide layer.

[0127] The preparation method of the aluminum oxide layer is the same as that of the silicon oxide layer, only need to replace bis(diethylamino)silane with triethylaluminum.

[0128] The preparation method of the anticorrosion layer 4 is time-based ALD. The preparation method of the tantalum nitride layer includes at least the following steps: First step: Pulse pentakis(dimethylamino)tantalum into the atomic layer deposition chamber at 105°C to chemically adsorb it on the surface of the light absorption layer 3; then introduce 1800 sccm of inert gas to purge unreacted pentakis(dimethylamino)tantalum and by-products, and the purge duration is 30 s; Second step: Pulse nitrogen plasma into the chamber to form a monolayer growth with the pentakis(dimethylamino)tantalum adsorbed on the surface; then introduce 1800 sccm of inert gas to purge unreacted nitrogen plasma and by-products, and the purge duration is 30 s; Third step: Repeat the first and second steps for cyclic deposition to form tantalum nitride.

[0129] The preparation method of the silicon oxide layer is the same as that of the silicon oxide in the light absorption layer in this embodiment.

[0130] Example 12 As Figure 1 shown, this embodiment provides a super-black nano-coating structure, including a substrate 1, a transition layer 2 deposited on the surface of the substrate 1 by ALD, an 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 absorbing layer 3 by ALD.

[0131] Among them, the thickness of the transition layer 2 is 11 nm, the thickness of the absorbing layer 3 is 177.49 nm, 193.43 nm, 98.5 nm, 25.37 nm, 15.29 nm, and the thickness of the anti-corrosion layer 4 is 18.86 nm, 14.33 nm, 69.13 nm.

[0132] The material of the substrate 1 is polycarbonate, the transition layer 2 is a titanium-based hybrid film, the absorbing layer 3 is an alternating layer of titanium aluminum carbide and alumina; the anti-corrosion layer 4 is titanium oxide, alumina and silica.

[0133] The preparation method of the transition layer 2 is spatial ALD, which at least includes the following steps: The first step is to place the substrate in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr); The second step is to continuously introduce 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 to the reaction region of titanium tetrachloride and 1,4-butanediol, and at the same time introduce an inert gas of 13000 sccm between titanium tetrachloride and 1,4-butanediol; The third step is that the substrate passes through the regions of titanium tetrachloride, isolation gas, 1,4-butanediol and isolation gas in sequence to complete one cycle of deposition; The fourth step is to repeat the second step and the third step, and deposit cyclically to form a transition layer.

[0134] Among them, the carrier gas, dilution gas and inert gas are all nitrogen.

[0135] The preparation method of the absorbing layer 3 is time-based ALD, and the preparation method of the titanium aluminum carbide layer at least includes the following steps: The first step is to pulse-feed triethylaluminum and titanium tetraisopropoxide into the atomic layer deposition chamber at 100 °C and keep for 4 s to chemically adsorb them on the surface of the transition layer 2; then introduce an inert gas of 4800 sccm to purge the unreacted triethylaluminum, titanium tetraisopropoxide and by-products, and the purge duration is 70 s; The second step is to pulse-feed methane plasma into the chamber to form a monolayer growth with the triethylaluminum and titanium tetraisopropoxide adsorbed on the surface; then introduce an inert gas of 3800 sccm to purge the unreacted methane plasma and by-products, and the purge duration is 65 s; In the third step, repeat the first and second steps, and deposit in a cycle to form an aluminum titanium carbide layer.

[0136] The preparation method of the aluminum oxide layer is as follows: In the first step, place the substrate 1 in an atomic layer deposition chamber under a vacuum state (pressure below 5 mTorr). In the second step, at 100 °C, introduce triethylaluminum in the form of pulses and keep it for 7.5 s to chemically adsorb it on the surface of the substrate 1; then introduce 2500 sccm of inert gas to purge the unreacted triethylaluminum and by-products, and the purge duration is 55 s. In the third step, add O 2 plasma into the chamber in the form of pulses and keep it for 3 s to form monolayer growth with the triethylaluminum adsorbed on the surface; then introduce 3300 sccm of inert gas to purge the unreacted O 2 plasma and by-products, and the purge duration is 50 s. In the fourth step, repeat the second and third steps, and deposit in a cycle to form an aluminum oxide layer.

[0137] The preparation method of the anti-corrosion layer 4 is time-based ALD, and the preparation method of the titanium oxide layer includes at least the following steps: In the first step, in an atomic layer deposition chamber at 100 °C, continuously introduce titanium tetrakis(dimethylamino) and H 2 O into the chamber successively through 4000 sccm of carrier gas and 3000 sccm of dilution gas until the reaction region of titanium tetrakis(dimethylamino) and H 2 O, and at the same time introduce 11000 sccm of inert gas between titanium tetrakis(dimethylamino) and H 2 O. In the second step, the substrate deposited with the transition layer 2 and the light absorption layer 3 sequentially passes through the regions of titanium tetrakis(dimethylamino), isolation gas, H2O, and isolation gas to complete one cycle of deposition. In the third step, repeat the first and second steps, and deposit in a cycle to form a titanium oxide layer. Among them, the carrier gas, dilution gas, and inert gas are all nitrogen.

[0138] The preparation method of the aluminum oxide layer is the same as the preparation method of the aluminum oxide of the light absorption layer in this embodiment. For silicon oxide, just replace the aluminum source with bis(tert-butylamino)silane.

[0139] Comparative Example 1 This comparative example provides a super black nano-coating structure, including a substrate and a light absorption layer deposited on the surface of the substrate by ALD. The thickness and preparation method of the light absorption layer are the same as those in Example 1.

[0140] Comparative Example 2 This comparative example provides a super-black nano-coating structure, including a substrate and a light-absorbing layer deposited on the surface of the substrate by chemical vapor deposition. The thickness of the light-absorbing layer is the same as that in Example 1.

[0141] Comparative Example 3 This comparative example provides a super-black nano-coating structure, including a substrate, a light-absorbing layer deposited on the surface of the substrate by ALD, and an anti-corrosion layer deposited on the light-absorbing layer by ALD. The thicknesses and preparation methods of the light-absorbing layer and the anti-corrosion layer are the same as those in Example 1.

[0142] Comparative Example 4 This comparative example provides a super-black nano-coating structure, including a substrate, a light-absorbing layer deposited on the surface of the substrate 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 those in Example 1.

[0143] Comparative Example 5 This comparative example provides a super-black nano-coating structure, including a substrate, a transition layer deposited on the surface of the substrate by ALD, and a light-absorbing layer deposited on the surface of the transition layer by ALD. The thicknesses and preparation methods of the transition layer and the light-absorbing layer are the same as those in Example 1.

[0144] Comparative Example 6 This comparative example provides a super-black nano-coating 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 those in Example 1.

[0145] Performance Test The products obtained from Examples 1 - 12 and Comparative Examples 1 - 6 were tested as follows, and the results are shown in Table 1.

[0146] 1. Absorption efficiency of the test samples Tested with a BCSP-Pro autofocus reflective spectrometer for the reflectivity and absorption efficiency of the products. It can be seen from Table 1 that the absorption efficiencies of the super-black films of the light-absorbing layer fabricated by ALD and PVD, the super-black films of the light-absorbing layer and the anti-corrosion layer, and the super-black films of the transition layer and the light-absorbing layer are all significantly reduced. The lowest is Comparative Example 5: the super-black film of the transition layer and the light-absorbing layer fabricated by ALD, with only 87.50% @ 400 - 700 nm. Adding a transition layer and an anti-corrosion layer can reduce reflection and optimize light transmission, effectively improving the absorption efficiency to above 99.05% @ 400 - 700 nm.

[0147] 2. Adhesion test The adhesion of the product was tested by the cross - hatch test. The specific method is as follows: Push the cross - hatch cutter evenly with force, draw 6 - 11 vertical and horizontal cuts (forming 25 - 100 squares) on the coating surface, and the depth should penetrate the coating to the substrate. Then stick the tape closely 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 situation within the squares under the light source and score according to the standard grade chart (for example, ISO 2409 is divided into grades 0 - 5, grade 0 means no peeling; grade 1 means the peeling area < 5%; grade 2 means the peeling area < 5% and > 15%; grade 3 means the peeling area < 15% and > 35%; grade 4 means the peeling area < 35% and > 65%; grade 5 means the peeling area > 65%). It can be seen from Table 1 that there is obvious film peeling in the light - absorbing layer ultra - black film, light - absorbing layer and anti - corrosion layer ultra - black film, and transition layer and light - absorbing layer ultra - black film made by ALD and PVD. The most serious one is Comparative Example 2: The ultra - black film with only a light - absorbing layer made by PVD is less dense than the ALD film layer and is more prone to film peeling, with a peeling area > 65%. Adding a transition layer and an anti - corrosion layer can effectively increase the adhesion and anti - corrosion ability of the film layer, and there is no film peeling phenomenon.

[0148] 3. Boiling water test The sample was placed in boiling water at 100 °C for 10 min, and the rating of the film peeling area was referred to the cross - hatch test method. It can be seen from Table 1 that there is obvious film peeling in the light - absorbing layer ultra - black film, light - absorbing layer and anti - corrosion layer ultra - black film, and transition layer and light - absorbing layer ultra - black film made by ALD and PVD. The most serious ones are Comparative Examples 1, 2, and 6: The ultra - black film with only a light - absorbing layer made by ALD and PVD, and the ultra - black film of the transition layer and light - absorbing layer made by PVD, with a peeling area > 65%. Adding a transition layer and an anti - corrosion layer can effectively increase the bonding force and anti - corrosion ability of the film layer, and there is no film peeling phenomenon.

[0149] Table 1: Performance test of ultra - black film

[0150] Note: Ratings for cross - hatch test and boiling water test: (0 - 5 grades, grade 0 means no peeling; grade 1 means the peeling area < 5%; grade 2 means the peeling area < 5% and > 15%; grade 3 means the peeling area < 15% and > 35%; grade 4 means the peeling area < 35% and > 65%; grade 5 means the peeling area > 65%).

[0151] According to the disclosure and teachings of the above - mentioned specification, those skilled in the art of the present invention can also make changes and modifications to the above - mentioned 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. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims

1. An ultra-black nano-coating structure, characterized in that: The invention 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.

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 absorption 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 material of the substrate is 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 transition layer is at least one of an oxide, a nitride and an organic-inorganic hybrid film, wherein the chemical formula of the oxide is MO x , wherein M is at least one of Ti, Al, V, Mn, Zn, Zr, Hf, Mg and Si, 1≤x≤5; the nitride is at least one of titanium nitride, aluminum nitride, silicon nitride, hafnium nitride, tantalum nitride and zirconium nitride, and the organic-inorganic hybrid film is at least one of an aluminum-based hybrid film, a zinc-based hybrid film, a zirconium-based hybrid film, a titanium-based hybrid film, a hafnium-based hybrid film, a vanadium-based hybrid film, a magnesium-based hybrid film and a manganese-based hybrid film.

5. The ultra-black nano-coating structure according to claim 1, characterized in that: The light absorbing layer comprises a titanium aluminum carbide layer and an oxide layer, and the oxide is SiO2 and / or Al2O3.

6. 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.

7. The ultra-black nano-coating structure according to claim 4, characterized in that: The preparation method of the transition layer is time-type ALD or space-type ALD, wherein the time-type ALD at least comprises the following steps: In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum; The second step is to introduce the first precursor at 50-250° C. to chemically adsorb it on the surface of the substrate; then introduce an inert gas to purge the unreacted first precursor and by-products; The third step is to add the first reactant into the chamber to form a monolayer growth with the first precursor adsorbed on the surface; then, an inert gas is introduced to purge the unreacted first reactant and by-products; Step 4, repeating Step 2 and Step 3 for n times, cyclic deposition, 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: In the first step, the substrate is placed in an atomic layer deposition chamber under vacuum; The second step is to continuously introduce the first precursor and the first reactant into the chamber at 50-250° C. through a carrier gas and a diluent gas to the reaction area of ​​the first precursor and the first reactant, and at the same time introduce an inert gas between the first precursor and the first reactant; In the third step, the substrate passes through the first precursor, isolation gas, first reactant and isolation gas regions in sequence to complete a cycle of deposition; Step 4, repeating Step 2 and Step 3 n times, cyclically depositing, to form a transition layer; n is a natural number greater than or equal to 0; The carrier gas, diluent gas and inert gas are argon or nitrogen.

8. The ultra-black nano-coating structure according to claim 7, characterized in that: When the transition layer is an oxide, the first precursor is at least one of an aluminum source, a titanium source, a vanadium source, a manganese source, a zinc source, a zirconium source, a hafnium source, a magnesium source and a 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 film, the first precursor is at least one of an aluminum source, a titanium source, a vanadium source, a manganese source, a zinc source, a zirconium source, a hafnium source, and a magnesium source, and the first reactant is at least one of ethylene glycol, glycerol, 1,4-butanediol, hydroquinone, and ethanolamine; wherein the aluminum source is at least one of trimethylaluminum, triethylaluminum and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetrakis(dimethylamino)titanium and tetraisopropyl titanate; the 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 tetraoxide 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 tetrakis(dimethylamino)zirconium, tetraethylmethylaminozirconium and zirconium tetrachloride; the hafnium source is one of tetrakis(dimethylamino)hafnium, tetraethylmethylaminohafnium and hafnium tetrachloride; the magnesium source is at least one of bis(diethylamino)magnesium, diethylmagnesium and methylmagnesium tert-butoxy; the silicon source is bis(diethylamino)silane, diisopropylaminesilane, 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.

9. The ultra-black nano-coating structure according to claim 5, characterized in that: The preparation method of the light absorbing layer is time-type ALD or space-type ALD, wherein the time-type ALD at least comprises the following steps: In the first step, a second precursor is introduced into an atomic layer deposition chamber at 50-250° C. to chemically adsorb the second precursor on the surface of the transition layer; then an inert gas is introduced to purge the unreacted second precursor and by-products; In the second step, a second reactant is added into the chamber to form a monolayer growth with the second precursor adsorbed on the surface; then an inert gas is introduced to purge the unreacted second reactant and by-products; Step 3: repeat the first and second steps n times, cyclically deposit, to form a light absorbing layer; n is a natural number greater than or equal to 0; Spatial ALD includes at least the following steps: The first step is to continuously introduce the second precursor and the second reactant into the chamber in an atomic layer deposition chamber at 50-250° C. through a carrier gas and a diluent gas to the reaction area of ​​the second precursor and the second reactant, and at the same time introduce an inert gas between the second precursor and the second reactant; In the second step, the substrate on which the transition layer is deposited passes through the second precursor, the isolation gas, the second reactant and the isolation gas area in sequence to complete a cycle of deposition; Step 3: repeat the first and second steps n times, cyclically deposit, to form a light absorbing layer; n is a natural number greater than or equal to 0; Wherein, the carrier gas, diluent 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, tetrakis(dimethylamino)titanium and tetraisopropyl titanate; and the second reactant is a carbon source, which is methane plasma.

10. The ultra-black nano-coating structure according to claim 5, characterized in that: The preparation method of the anti-corrosion layer is time-type ALD or space-type ALD, wherein the time-type ALD at least comprises the following steps: In the first step, a third precursor is introduced into an atomic layer deposition chamber at 50-250° C. to chemically adsorb the third precursor on the surface of the light absorbing layer; then an inert gas is introduced to purge the unreacted third precursor and by-products; In the second step, a third reactant is added into the chamber to form a monolayer growth with the third precursor adsorbed on the surface; then an inert gas is introduced to purge the unreacted third reactant and by-products; Step 3: repeat the first and second steps n times, cyclically deposit, and form an anti-corrosion layer; n is a natural number greater than or equal to 0; Spatial ALD includes at least the following steps: The first step is to continuously introduce a third precursor and a third reactant into the chamber in an atomic layer deposition chamber at 50-250° C. through a carrier gas and a diluent gas, to a reaction area of ​​the third precursor and the third reactant, and at the same time introduce an inert gas between the third precursor and the third reactant; In the second step, the substrate on which the transition layer and the light absorbing layer are deposited passes through the third precursor, the isolation gas, the third reactant and the isolation gas area in sequence to complete a cycle of deposition; Step 3: repeat the first and second steps n times, cyclically deposit, and form an anti-corrosion layer; n is a natural number greater than or equal to 0; Wherein, the carrier gas, diluent 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 an aluminum source, a silicon source, a titanium source and a 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 an aluminum source, a titanium source, a tantalum source, a chromium source and a silicon source, and the third reactant is at least one of nitrogen plasma and ammonia plasma; Among them, the aluminum source is at least one of trimethylaluminum, triethylaluminum and aluminum trichloride; the titanium source is at least one of titanium tetrachloride, tetrakis(dimethylamino)titanium and tetraisopropyl titanate; the silicon source is one of bis(diethylamino)silane, diisopropylamine silane, tri(dimethylamino)silane and bis(tert-butylamino)silane; the zirconium source is at least one of tetrakis(dimethylamino)zirconium, tetraethylmethylamino zirconium and zirconium tetrachloride; the tantalum source is at least one of penta(dimethylamino)tantalum, tert-butyliminotri(ethylmethylamino)tantalum and tert-butyliminotri(diethylamino)tantalum.

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