Oil-stain-resistant ultra-black film structure

Abstract

The invention belongs to the technical field of optical coating, and particularly relates to an oil-stain-resistant ultra-black film structure which comprises a base material, a bonding layer deposited on the surface of the base material through ALD, a light absorption layer deposited on the surface of the bonding layer through ALD and an oil-stain-resistant layer deposited on the surface of the light absorption layer through ALD. The oil-resistant layer is at least one of a fluorine-containing compound, a hydrophobic SiO2 nanostructure and an organic-inorganic hybrid layer, and the oil contact angle of the oil-resistant layer is gt; and 90 degrees. In order to solve the problem that the prior art is difficult to be compatible with the optical performance, the uniformity and the oil stain prevention function of the ultra-black film, the ultra-black film with a substrate / bonding layer / light absorption layer (single-layer or multi-layer) / oil stain prevention layer (single-layer or multi-layer) structure is prepared by adopting an atomic layer deposition technology. The technology has the remarkable advantages in the aspects of accurate control over the film thickness, film thickness uniformity, the coverage degree of components in complex shapes and the like, and the obtained ultra-black film can achieve the effects of high absorption efficiency (larger than or equal to 99%), high coverage rate and oil stain resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of optical coating, and in particular relates to an ultra-black film structure with oil-proof properties. Background Art

[0002] Ultra-black nano-coating can absorb all light in the ultraviolet, visible, near-infrared, mid-infrared and far-infrared bands incident on the surface of the material without reflection. The incident light absorption rate is over 99% and the reflectivity is less than 0.5%. It is widely used in the optical field.

[0003] Traditional methods for making ultra-black films include carbon nanotube method, chemical vapor deposition (CVD), physical vapor deposition (PVD), etc. However, as the market demands for the precision and quality of optical instruments and optoelectronic components, traditional black surface treatment technology is gradually unable to meet market demand at the same time: 1) It is difficult to achieve uniform deposition on substrates with complex three-dimensional structures; 2) It is susceptible to contamination and not resistant to oil stains. Existing oil-resistant coatings (such as fluorosilanes) are usually applied by spraying or spin coating, but it is difficult to evenly cover the nanostructure of the ultra-black film and may reduce its optical performance; 3) The bonding strength with the substrate is poor and it is easy to peel off.

[0004] Therefore, the present invention aims to provide an ultra-black film structure with anti-oil pollution, which adopts atomic layer deposition technology to prepare the ultra-black film structure with anti-oil pollution function. It is a film that can maintain ultra-black characteristics and has anti-oil pollution function. Summary of the Invention

[0005] The purpose of the present invention is to provide an ultra-black film structure with oil-proof function to address the shortcomings of the existing technology. The ultra-black film structure with oil-proof function is prepared by atomic layer deposition technology. It is a film that can maintain ultra-black characteristics and has oil-proof function.

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

[0007] An ultra-black film structure with oil repellency comprises a substrate, a bonding layer deposited on the substrate surface using ALD, a light-absorbing layer deposited on the bonding layer surface using ALD, and an oil repellency layer disposed on the light-absorbing layer surface. The oil repellency layer comprises at least one of a fluorine-containing compound, a hydrophobic SiO2 nanostructure, and an organic-inorganic hybrid layer, and has an oil contact angle greater than 90°. By utilizing ALD, a technology capable of precisely controlling thickness and achieving high step coverage, the present invention achieves a precise combination of an ultrathin oil repellency layer and an optical film, achieving excellent oil repellency with minimal impact on light transmittance. The oil contact angle of the oil repellency layer is greater than 90°, meeting oil repellency testing requirements.

[0008] As an improvement of the oil-proof ultra-black film structure of the present invention, the material of the substrate is one of silicon, glass, metal, polyethylene terephthalate (PET), polyimide (PI) and ceramic.

[0009] As an improvement to the oil-repellent ultra-black film structure of the present invention, the thickness of the bonding layer ranges from 1nm to 50nm. This thickness needs to be sufficient to cover the substrate and enhance bonding strength, but excessive thickness can lead to decreased optical performance. The thickness of the light-absorbing layer ranges from 200nm to 2000nm. This thickness needs to be sufficient to cover long-wavelength absorption and match the thickness of adjacent layers to reduce interfacial reflection. The thickness of the oil-repellent layer ranges from 5nm to 1000nm. A film layer that is too thin is susceptible to wear and pinhole defects, while a film layer that is too thick will fill structural gaps, resulting in increased reflectivity.

[0010] As an improvement of the oil-proof ultra-black film structure of the present invention, the material of the bonding layer is at least one of oxide, nitride, and metal element. The oxide film layer has a low refractive index, high optical compatibility, and can also reduce reflection. It is suitable for flexible substrates and is at least one of TiO2, SiO2, Al2O3, ZnO, MgO, HfO2, MnO2 and ZrO2; the nitride has high hardness and wear resistance, is suitable for matching metal substrates, has strong adhesion, and reduces the risk of interlayer delamination. It is at least one of titanium nitride, aluminum nitride, silicon nitride, hafnium nitride, tantalum nitride and zirconium nitride; the metal element forms chemical bonds with glass, metal and other substrates, has excellent adhesion, and is one of Ir, Au, Cu, Co, Ni, Ru, Al, Pt, Ta, V and W.

[0011] As an improvement to the oil-resistant ultra-black film structure of the present invention, the light-absorbing layer is made of TiAlC or alternating layers of a metal and an oxide. The metal is at least one of Ir, Au, Cu, Co, Ni, Ru, Al, Pt, Ta, V, and W, and the oxide is at least one of TiO2, SiO2, Al2O3, ZnO, MgO, HfO2, MnO2, and ZrO2. The synergistic effects of materials, thickness, and structure significantly improve optical absorptivity, mechanical strength, and environmental stability, achieving the ultimate performance of the ultra-black film.

[0012] As an improvement of the ultra-black film structure with oil-proof properties of the present invention, the fluorine-containing compound is at least one of AlF3, TiF4 and perfluoropolyether film, wherein the preparation method of AlF3 and TiF4 is: according to the four steps of precursor-purge-reactant-purge of the ALD process, metal precursors and fluorine sources are alternately introduced to achieve precise control at the single atomic layer level, the metal precursor is at least one of TMA, AlCl3, aluminum β-diketone complex, TiCl4, tetrakis(dimethylamino)titanium, and tetraisopropoxide titanium, and the fluorine source is at least one of HF, NH4F, TiF4, F2 plasma, and SF6 plasma; the perfluoropolyether film is prepared by molecular layer deposition using a fluorine-containing dicarboxylic acid and a diol precursor for gradual polymerization, wherein the fluorine-containing dicarboxylic acid is at least one of perfluoroadipic acid and perfluorosuccinic acid, and the diol precursor is at least one of perfluoropolyether diol, ethylene glycol, and hydroquinone. Specifically, AlF3 and TiF4 are deposited layer by layer through a four-step process: precursor pulse, inert gas purge, reactant pulse, and inert gas purge. Perfluoropolyether membranes are polymerized layer by layer using a small molecule perfluorinated monomer (such as perfluorodiacyl chloride) reacted with a diol. Both achieve oil repellency by forming a low-energy surface.

[0013] As an improvement to the oil-proof ultra-black film structure of the present invention, the hydrophobic SiO2 nanostructure is achieved by dry etching SiO2 with CF4 / O2 plasma. Specifically, the SiO2 substrate is placed in a vacuum atomic layer deposition chamber and continuously etched with CF4 / O2 plasma. The gas ratio is CF4:O2 = 1:1 to 10:1, and the etching time is 5-600 seconds at a power of 50-1000W. Finally, nitrogen is purged to remove residual gas. Vertical channels are formed through ion bombardment, avoiding the lateral drilling problem of wet etching. The porosity and depth can be precisely controlled to form a porous structure. This method has good material compatibility, and the underlying light-absorbing layer is not easily damaged. Oil-proofing is achieved through a dual mechanism of physical roughening and chemical modification.

[0014] As an improvement of the present invention's ultra-black film structure with anti-oil pollution, the organic-inorganic hybrid layer is specifically one of trimethylsiloxane-modified SiO2, octadecyl long-chain-modified Al2O3, and dimethylsiloxy-modified TiO2. The organic-inorganic hybrid layer is achieved by alternately introducing an inorganic precursor and an organosilane. Specifically, an inorganic component is first deposited by ALD, and then an organosilane layer is passed through for condensation, exposing a -CF3 group, repeating inorganic / organic deposition, and regulating hydrophobicity to achieve anti-oil pollution function, wherein the inorganic component can be one of SiO2, Al2O3, and TiO2, and the organosilane mainly introduces a hydrophobic group, which can be one of trimethylchlorosilane, octadecyltrimethoxysilane, and dimethyldimethoxysilane. Wherein the inorganic phase provides hardness, and the organic phase absorbs stress, which can avoid the brittle cracking of the pure inorganic layer; Introducing organic matter can reduce surface energy and achieve a super oleophobic effect.

[0015] As an improvement of the oil-proof ultra-black film structure of the present invention, the preparation methods of the bonding layer and the light-absorbing layer are: using the atomic layer deposition method, the precursor and the reactant are alternately introduced through four steps of precursor pulse-inert gas purge-reactant pulse-inert gas purge, and the thin film is deposited layer by layer on the surface of the substrate.

[0016] The present invention also provides an application of the oil-proof ultra-black film structure described in the present invention in mobile phone lenses, vehicle lenses, and AR / VR fields.

[0017] Compared to existing technologies, this invention addresses the difficulties of achieving consistent optical performance, uniformity, and oil-resistance in ultra-black films. By utilizing atomic layer deposition (ALD), the ultra-black film is fabricated with a substrate / bonding layer / light-absorbing layer (single or multi-layer) / oil-resistance layer (single or multi-layer) structure. This technology offers significant advantages in precise control of film thickness, uniformity, and coverage of complex-shaped components. The resulting ultra-black film achieves high absorption efficiency (≥99%), high coverage, and oil-resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a structural schematic diagram of the present invention. DETAILED DESCRIPTION

[0019] The following will provide a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0020] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the various components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0021] In addition, the descriptions of "first", "second", etc. in the present invention are for descriptive purposes only and should not be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of such features. In addition, the technical solutions between the various embodiments can be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in this field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0022] Example 1

[0023] like Figure 1 As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light absorbing layer 3 using ALD, wherein the anti-oil layer 4 is a fluorine-containing compound AlF3.

[0024] The material of the substrate 1 is glass, the material of the bonding layer 2 is ZnO, the thickness of the bonding layer 2 is 8nm, and the material of the light-absorbing layer 3 is an alternating superposition of Co and oxide SiO2, including Co layer / SiO2 layer / Co layer / SiO2 layer arranged in sequence from the bonding layer 2 to the anti-oil layer 4, with thicknesses of 179.72nm / 56.52nm / 22.24nm / 36.54nm respectively, and the thickness of the anti-oil layer 4 is 9.18nm.

[0025] The preparation method of the bonding layer 2 is as follows:

[0026] In the first step, a substrate 1 is placed in an atomic layer deposition chamber under a vacuum state;

[0027] In the second step, the precursor diethylzinc was introduced in pulse form at 100°C for 5 seconds to allow it to chemically adsorb on the substrate surface. Then, 4000 sccm of inert gas was introduced for 60 seconds to purge the unreacted precursor and by-products.

[0028] In the third step, H2O is added to the chamber in pulses for 5 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts are then purged with inert gas at 3000 sccm for 60 seconds.

[0029] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition to form a bonding layer ZnO film layer, where n is a natural number greater than or equal to 0.

[0030] The preparation method of Co in the light absorbing layer 3 is:

[0031] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0032] In the second step, the precursor, cobaltocene, was introduced in pulses at 100°C for 5 seconds to allow it to chemically adsorb on the substrate surface. Unreacted precursors and byproducts were then purged with 4000 sccm of inert gas for 60 seconds.

[0033] In the third step, H2 plasma is introduced into the chamber in pulsed form and maintained for 5 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas is introduced at 3000 sccm to purge unreacted reactants and byproducts for 60 seconds.

[0034] Step 4: Repeat step 2 and step 3 n times, cyclic deposition, to form a Co film layer, where n is a natural number greater than or equal to 0.

[0035] Diisopropylaminosilane and O3 are selected as precursors and reactants to continue depositing SiO2 film layers; Co / SiO2 / Co / SiO2 deposition is completed in sequence.

[0036] The preparation method of the anti-oil layer 4 is as follows:

[0037] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0038] In the second step, the precursor trimethylaluminum was introduced in pulse form at 100°C for 5 seconds to allow it to chemically adsorb on the substrate surface. Then, 4000 sccm of inert gas was introduced for 60 seconds to purge the unreacted precursor and by-products.

[0039] In the third step, titanium tetrafluoride was added to the chamber in pulse form and held for 5 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas was introduced at 3000 sccm to purge unreacted reactants and byproducts for 60 seconds.

[0040] Step 4: Repeat step 2 and step 3 n times, cyclically deposit, to form an AlF3 film layer, where n is a natural number greater than or equal to 0.

[0041] Example 2

[0042] like Figure 1As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light absorbing layer 3 using ALD, wherein the anti-oil layer 4 is a hydrophobic SiO2 nanostructure.

[0043] The material of the substrate 1 is polyethylene terephthalate (PET).

[0044] The material of the bonding layer 2 is TiO2, and the thickness of the bonding layer 2 is 4.65nm. The material of the light-absorbing layer 3 is an alternating superposition of metal element Cu and oxide Al2O3, including Cu / Al2O3 / Cu / Al2O3 / Cu / Al2O3 arranged in sequence from the bonding layer 2 to the anti-oil layer 4, and their thicknesses are 181.93nm / 26.21nm / 48.42nm / 42.65nm / 36.24nm / 25.37nm respectively. The thickness of the anti-oil layer 4 is 30.94nm.

[0045] The preparation method of the bonding layer 2 is as follows:

[0046] In the first step, a substrate 1 is placed in an atomic layer deposition chamber under a vacuum state;

[0047] In the second step, the precursor tetrakis(dimethylamino)titanium was introduced in pulse form at 120°C for 10 seconds to allow it to chemically adsorb on the substrate surface; then, 3000 sccm of inert gas was introduced to purge the unreacted precursor and by-products for 40 seconds.

[0048] In the third step, H2O is added to the chamber in pulses for 8 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts are then purged with inert gas at 4000 sccm for 70 seconds.

[0049] Step 4: Repeat step 2 and step 3 n times, cyclic deposition, to form a TiO2 film layer, where n is a natural number greater than or equal to 0.

[0050] The preparation method of the Cu film layer in the light absorbing layer 3 is as follows:

[0051] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0052] In the second step, the precursor Cu(I) amino group was introduced in pulse form at 130°C for 8 seconds to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and byproducts.

[0053] In the third step, H2 plasma is introduced into the chamber in pulsed form and maintained for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas is introduced at 4500 sccm to purge unreacted reactants and byproducts for 65 seconds.

[0054] Step 4: Repeat step 2 and step 3 n times, cyclically deposit, to form a Cu film layer, where n is a natural number greater than or equal to 0.

[0055] Similarly, aluminum chloride and H2O are selected as precursors and reactants to continue depositing the Al2O3 film layer; Cu / Al2O3 / Cu / Al2O3 / Cu / Al2O3 deposition is completed in sequence.

[0056] The preparation method of the anti-oil layer 4 is as follows:

[0057] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0058] In the second step, the precursor bis(diethylamino)silane was introduced in pulse form at 130°C for 8 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and byproducts.

[0059] In the third step, pulsed O2 plasma was introduced into the chamber for 7 seconds to allow it to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4500 sccm for 65 seconds.

[0060] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition to deposit a SiO2 film layer on the light absorbing layer, where n is a natural number greater than or equal to 0.

[0061] Then, CF4 / O2 plasma etching is continuously introduced with a CF4 and O2 flow rate of 50 sccm, a time of 15 s, and a power of 200 W. Finally, nitrogen is purged to remove residual gas to form a porous structure.

[0062] Example 3

[0063] like Figure 1 As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light absorbing layer 3 using ALD, the anti-oil layer 4 is an organic-inorganic hybrid layer: Al2O3 modified with a long chain of octadecyl.

[0064] The material of the substrate 1 is ceramic. The material of the bonding layer 2 is Ni, and the thickness of the bonding layer 2 is 7.14 nm.

[0065] The material of the light-absorbing layer 3 is an alternating stack of Au and ZrO2, including Au / ZrO2 / Au / ZrO2 arranged in sequence from the bonding layer 2 to the anti-oil layer 4, with thicknesses of 148.05nm / 18.07nm / 25.82nm / 24.13nm respectively. The thickness of the anti-oil layer 4 is 20.53nm.

[0066] The preparation method of the bonding layer 2 is as follows:

[0067] In the first step, a substrate 1 is placed in an atomic layer deposition chamber under a vacuum state;

[0068] In the second step, the precursor nickelocene was introduced in pulse form at 120°C for 8 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and by-products.

[0069] In the third step, H2 plasma is introduced into the chamber in pulsed form and maintained for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas is introduced at 4500 sccm to purge unreacted reactants and byproducts for 65 seconds.

[0070] Step 4: Repeat step 2 and step 3 n times, cyclic deposition, to form a Ni film layer, where n is a natural number greater than or equal to 0.

[0071] The preparation method of the Au film layer in the light absorbing layer 3 is as follows:

[0072] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0073] In the second step, the precursor gold acetylacetonate was introduced in pulse form at 120°C for 7 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and byproducts.

[0074] In the third step, H2 plasma is introduced into the chamber in pulsed form and maintained for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas is introduced at 4500 sccm to purge unreacted reactants and byproducts for 65 seconds.

[0075] Step 4: Repeat step 2 and step 3 n times, cyclically deposit, to form an Au film layer, where n is a natural number greater than or equal to 0.

[0076] Similarly, tri(dimethylamine)cyclopentadienyl zirconium and H2O are selected as precursors and reactants to continue depositing the ZrO2 film layer; and Au / ZrO2 / Au / ZrO2 deposition is completed in sequence.

[0077] The preparation method of the anti-oil layer 4 is as follows:

[0078] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0079] In the second step, the precursor trimethylaluminum was introduced in pulse form at 120°C for 7 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and byproducts.

[0080] In the third step, H2O was added to the chamber in pulses for 7 seconds to allow it to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4500 sccm for 65 seconds.

[0081] In the fourth step, the second and third steps are repeated n times, and the deposition is cyclic to form an Au film layer, where n is a natural number greater than or equal to 0, and an Al2O3 film layer is deposited on the light-absorbing layer; then octadecyltrimethoxysilane is selected to react with the hydroxyl groups on the surface of Al2O3 to form a chemical bond, thereby generating octadecyl long-chain modified Al2O3.

[0082] Example 4

[0083] like Figure 1 As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light absorbing layer 3 using ALD, wherein the anti-oil layer 4 is a fluorine-containing compound TiF4.

[0084] The material of the substrate 1 is silicon.

[0085] The material of the bonding layer 2 is aluminum nitride, and the thickness of the bonding layer 2 is 7nm. The material of the light-absorbing layer 3 is an alternating superposition layer of metal elements Cu and HfO2, including Cu / HfO2 / Cu / HfO2 / Cu / HfO2 arranged in sequence from the bonding layer 2 to the anti-oil layer 4, with thicknesses of 168.8 / 14.94 / 10.3 / 13.77 / 30.64 / 14.63nm respectively. The thickness of the anti-oil layer 4 is 25.65nm.

[0086] The preparation method of the bonding layer 2 is as follows:

[0087] In the first step, a substrate 1 is placed in an atomic layer deposition chamber under a vacuum state;

[0088] In the second step, the precursor aluminum triisopropoxide was introduced in pulse form at 120°C for 8 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and byproducts.

[0089] In the third step, N2 plasma was introduced into the chamber in a pulsed manner for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas was introduced at 4500 sccm to purge unreacted reactants and byproducts for 65 seconds.

[0090] Step 4: Repeat step 2 and step 3 n times, cyclically deposit, to form an aluminum nitride film layer, where n is a natural number greater than or equal to 0.

[0091] The preparation method of the Cu film layer in the light absorbing layer 3 is as follows:

[0092] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0093] In the second step, the precursor CuCl2 was introduced in pulse form at 118°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and by-products.

[0094] In the third step, H2 plasma is introduced into the chamber in pulsed form for 6 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas is introduced at 4000 sccm to purge unreacted reactants and byproducts for 65 seconds.

[0095] Step 4: Repeat step 2 and step 3 n times, cyclically deposit, to form a Cu film layer, where n is a natural number greater than or equal to 0.

[0096] Similarly, tetrakis(dimethylamino)hafnium and H2O are selected as precursors and reactants to continue depositing the HfO2 film layer; and Cu / HfO2 / Cu / HfO2 / Cu / HfO2 deposition is completed in sequence.

[0097] The preparation method of the anti-oil layer 4 is as follows:

[0098] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0099] In the second step, the precursor isopropyl titanate was introduced in pulse form at 115°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 42 seconds to purge the unreacted precursor and by-products.

[0100] In the third step, hexafluoroethane was introduced into the chamber in pulses for 6 seconds to allow it to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4000 sccm for 65 seconds.

[0101] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition to form a Cu film layer, where n is a natural number greater than or equal to 0, and deposit a TiF4 film layer on the light absorbing layer.

[0102] Example 5

[0103] like Figure 1 As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light-absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light-absorbing layer 3 using ALD, wherein the anti-oil layer 4 is trimethylsiloxane-modified silica.

[0104] The material of the substrate 1 is polyimide (PI).

[0105] The material of the bonding layer 2 is Au, and the thickness of the bonding layer 2 is 8.99nm. The material of the light-absorbing layer 3 is an alternating superposition layer of TiAlC and oxide HfO2, including TiAlC / HfO2 / TiAlC / HfO2 / TiAlC / HfO2 arranged in sequence from the bonding layer 2 to the anti-oil layer 4, and their thicknesses are 91.5nm / 21.92nm / 90.62nm / 21.67nm / 9.75nm / 17.48nm respectively. The thickness of the anti-oil layer 4 is 68.06nm.

[0106] The preparation method of the bonding layer 2 is as follows:

[0107] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0108] In the second step, the precursor trimethyl gold was introduced in pulse form at 118°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3500 sccm of inert gas was introduced for 45 seconds to purge the unreacted precursor and byproducts.

[0109] In the third step, H2 plasma is introduced into the chamber in pulsed form for 6 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas is introduced at 4000 sccm to purge unreacted reactants and byproducts for 65 seconds.

[0110] Step 4: Repeat step 2 and step 3 n times, cyclically deposit, to form an Au film layer, where n is a natural number greater than or equal to 0.

[0111] The preparation method of the light absorbing layer 3 is as follows:

[0112] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0113] In the second step, the precursor titanium tetrachloride was introduced in pulses at 118°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Unreacted precursors and byproducts were then purged with 3500 sccm of inert gas for 45 seconds.

[0114] In the third step, trimethylaluminum was added to the chamber in pulse form and held for 6 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4000 sccm for 65 seconds.

[0115] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition, where n is a natural number greater than or equal to 0, and deposit a TiAlC film layer on the upper surface of the bonding layer.

[0116] Similarly, tetrakis(ethylmethylamino)hafnium and H2O are selected as precursors and reactants to continue depositing the HfO2 film layer; TiAlC / HfO2 / TiAlC / HfO2 / TiAlC / HfO2 deposition is completed in sequence.

[0117] The preparation method of the anti-oil layer 4 is as follows:

[0118] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0119] In the second step, the precursor bis(diethylamino)silane was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced to purge the unreacted precursor and byproducts for 48 seconds.

[0120] In the third step, oxygen plasma was pulsed into the chamber for 7 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4200 sccm for 62 seconds.

[0121] The fourth step is to repeat the second and third steps n times in a cyclic deposition process, where n is a natural number greater than or equal to 0, and deposit SiO2 on the light-absorbing layer. Then, trimethylsilyl chloride is selected to react with the hydroxyl groups on the surface of SiO2 to form a chemical bond, thereby generating trimethylsiloxane-modified silica.

[0122] Example 6

[0123] like Figure 1As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light absorbing layer 3 using ALD, wherein the anti-oil layer 4 is a fluorine-containing compound AlF3.

[0124] The material of the substrate 1 is copper.

[0125] The bonding layer 2 is made of TiN and has a thickness of 5.23 nm. The light-absorbing layer 3 is made of alternating layers of TiAlC and SiO2, including TiAlC / SiO2 / TiAlC / SiO2 / / TiAlC / SiO2, arranged in the order from the bonding layer 2 to the anti-oil layer 4. The thicknesses are 21.68 nm / 18.69 nm / 183.32 nm / 50.62 nm / 12.83 nm / 33.74 nm, respectively. The anti-oil layer 4 has a thickness of 48.46 nm.

[0126] The preparation method of the bonding layer 2 is as follows:

[0127] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0128] In the second step, the precursor titanium trichloride was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced to purge the unreacted precursor and by-products for 48 seconds.

[0129] In the third step, N2 plasma was introduced into the chamber in a pulsed manner for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas was introduced at 4200 sccm to purge unreacted reactants and byproducts for 55 seconds.

[0130] The fourth step is to repeat the second and third steps n times, cyclically depositing, where n is a natural number greater than or equal to 0, and deposit a TiN film layer on the surface of the substrate.

[0131] The TiAlC film in the light absorbing layer 3 is prepared as follows:

[0132] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0133] In the second step, the precursor titanium trichloride was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced to purge the unreacted precursor and by-products for 48 seconds.

[0134] In the third step, triethanolamine was added to the chamber in pulses for 7 seconds to allow it to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4200 sccm for 55 seconds.

[0135] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition, where n is a natural number greater than or equal to 0, and deposit a TiAlC film layer on the upper surface of the bonding layer.

[0136] Similarly, tri(dimethylamino)silane and O2 plasma are selected as precursors and reactants to continue depositing SiO2 film layers; TiAlC / SiO2 / TiAlC / SiO2 / / TiAlC / SiO2 deposition is completed in sequence.

[0137] The preparation method of the anti-oil layer 4 is as follows:

[0138] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0139] In the second step, the precursor trimethylaluminum was introduced in pulse form at 128°C for 8 seconds to allow it to chemically adsorb on the substrate surface. Then, 3800 sccm of inert gas was introduced for 44 seconds to purge the unreacted precursor and byproducts.

[0140] In the third step, hydrogen fluoride was pulsed into the chamber for 6 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4800 sccm for 51 seconds.

[0141] The fourth step is to repeat the second and third steps n times, cyclically depositing, where n is a natural number greater than or equal to 0, and deposit an AlF3 film layer on the light-absorbing layer.

[0142] Example 7

[0143] like Figure 1 As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light-absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light-absorbing layer 3 using ALD, wherein the anti-oil layer 4 is an organic-inorganic hybrid layer of Al2O3 modified with a long chain of octadecyl.

[0144] Substrate 1 is made of titanium. Bonding layer 2 is made of MgO. The thickness of bonding layer 2 is 9.85 nm. Light-absorbing layer 3 is composed of alternating layers of Cu and ZrO2, including Cu / ZrO2 / Cu / ZrO2, arranged in the order from bonding layer 2 to anti-oil layer 4. The thicknesses are 252.6 nm, 26.22 nm, 42.07 nm, and 10.7 nm, respectively. The thickness of anti-oil layer 4 is 28.58 nm.

[0145] The preparation method of the bonding layer 2 is as follows:

[0146] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0147] In the second step, the precursor, bis(cyclopentadienyl)magnesium, was introduced in pulses at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Unreacted precursors and byproducts were then purged with 3200 sccm of inert gas for 48 seconds.

[0148] In the third step, H2O was added to the chamber in pulses for 7 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4200 sccm for 55 seconds.

[0149] The fourth step is to repeat the second and third steps n times, cyclically depositing, where n is a natural number greater than or equal to 0, and deposit a MgO film layer on the surface of the substrate.

[0150] The preparation method of the Cu film layer in the light absorbing layer 3 is as follows:

[0151] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0152] In the second step, the precursor copper hexafluoroacetylacetonate was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced for 48 seconds to purge the unreacted precursor and byproducts.

[0153] In the third step, H2 plasma was introduced into the chamber in pulsed form for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas was introduced at 4200 sccm to purge unreacted reactants and byproducts for 55 seconds.

[0154] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition, where n is a natural number greater than or equal to 0, and deposit a Cu film layer on the upper surface of the bonding layer.

[0155] Similarly, cyclopentadienyl tris(dimethylamino) zirconium and H2O are selected as precursors and reactants to continue depositing the ZrO2 film layer; and Cu / ZrO2 / Cu / ZrO2 deposition is completed in sequence.

[0156] The preparation method of the anti-oil layer 4 is as follows:

[0157] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0158] In the second step, the precursor aluminum chloride was introduced in pulses at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Unreacted precursors and byproducts were then purged with 3200 sccm of inert gas for 48 seconds.

[0159] In the third step, H2O was added to the chamber in pulses for 7 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4200 sccm for 55 seconds.

[0160] The fourth step is to repeat the second and third steps n times, and the deposition is cyclic, where n is a natural number greater than or equal to 0, and Al2O3 is deposited on the light-absorbing layer. Then, heptafluorodecyltrimethoxysilane is selected to react with the hydroxyl groups on the surface of Al2O3 to finally form Al-O-Si-C8F 17 Covalent bond, fluorocarbon chain (-C8F 17 ) are arranged outward to provide oleophobicity.

[0161] Example 8

[0162] like Figure 1 As shown, this embodiment provides an ultra-black film structure with anti-oil properties, including a substrate 1, a bonding layer 2 deposited on the surface of the substrate 1 using ALD, a light-absorbing layer 3 deposited on the surface of the bonding layer 2 using ALD, and an anti-oil layer 4 deposited on the surface of the light-absorbing layer 3 using ALD, wherein the anti-oil layer 4 is an organic-inorganic hybrid layer: trimethylsiloxane-modified silica.

[0163] The material of the substrate 1 is glass.

[0164] The bonding layer 2 is made of Al2O3 and has a thickness of 8.46 nm. The light-absorbing layer 3 is made of alternating layers of the metal elements Ni and SiO2, consisting of Ni / SiO2 / Ni / SiO2 arranged in the order from the bonding layer 2 to the oil-proof layer 4. The light-absorbing layer 3 has a thickness of 231.18 nm / 49.97 nm / 21.79 nm / 45.55 nm, while the oil-proof layer 4 has a thickness of 7.81 nm.

[0165] The preparation method of the bonding layer 2 is as follows:

[0166] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0167] In the second step, the precursor trimethylaluminum was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced for 48 seconds to purge the unreacted precursor and byproducts.

[0168] In the third step, H2O was added to the chamber in pulses for 7 seconds to form a monolayer with the surface-adsorbed precursor. Unreacted reactants and byproducts were then purged with inert gas at 4200 sccm for 55 seconds.

[0169] The fourth step is to repeat the second and third steps n times, cyclic deposition, where n is a natural number greater than or equal to 0, and deposit an Al2O3 film layer on the surface of the substrate.

[0170] The preparation method of the Ni film layer in the light absorbing layer 3 is as follows:

[0171] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0172] In the second step, the precursor dimethyl nickelocene was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced to purge the unreacted precursor and by-products for 48 seconds.

[0173] In the third step, H2 plasma was introduced into the chamber in pulsed form for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas was introduced at 4200 sccm to purge unreacted reactants and byproducts for 55 seconds.

[0174] The fourth step is to repeat the second and third steps n times, and perform cyclic deposition, where n is a natural number greater than or equal to 0, and deposit a Ni film layer on the upper surface of the bonding layer.

[0175] Similarly, bis(tert-butylamino)silane and O2 plasma are selected as precursors and reactants to continue depositing SiO2 film layers; and Ni / SiO2 / Ni / SiO2 deposition is completed in sequence.

[0176] The preparation method of the anti-oil layer 4 is as follows:

[0177] In the first step, the material is placed in an atomic layer deposition chamber under vacuum;

[0178] In the second step, the precursor BDIPADS (1,2-diisopropyldisilane) was introduced in pulse form at 128°C for 6 seconds to allow it to chemically adsorb on the substrate surface. Then, 3200 sccm of inert gas was introduced to purge the unreacted precursor and by-products for 48 seconds.

[0179] In the third step, O3 was added to the chamber in pulse form for 7 seconds to form a monolayer with the surface-adsorbed precursor. Then, an inert gas was introduced at 4200 sccm to purge unreacted reactants and byproducts for 55 seconds.

[0180] The fourth step is to repeat the second and third steps n times, and the deposition is cyclic, where n is a natural number greater than or equal to 0, and SiO2 is deposited on the light-absorbing layer. Then, octadecyltrichlorosilane is selected to react with the hydroxyl groups on the surface of SiO2 to form closely arranged -C 18 H 37 Alkyl chains provide oleophobicity.

[0181] Comparative Example 1

[0182] This comparative example provides an ultra-black film structure. Different from Example 1, this comparative example includes a substrate, a light-absorbing layer, and fluorosilanes prepared by a CVD process.

[0183] The absorbance of Examples 1 to 8 and Comparative Example 1 was measured using a BCSP-Pro autofocus reflectance spectrometer. The results are shown in Table 1. A contact angle meter was also used to evaluate the oleophobicity of the material surface by measuring the static contact angle (θ) formed by an oil droplet on the material surface: θ > 90°: oleophobic surface (good oil resistance); θ < 90°: oleophilic surface (easy oil adhesion).

[0184] Table 1: Absorption rate and oil resistance test results of Examples 1 to 8 and Comparative Example 1.

[0185] Group Absorption rate / % Oil resistance (°) Example 1 99.56 116.57 Example 2 99.07 104.18 Example 3 99.05 99.99 Example 4 99.42 110.73 Example 5 99.65 119.23 Example 6 99.15 103.61 Example 7 99.19 113.52 Example 8 99.45 111.37 Comparative Example 1 98.82 88.64

[0186] As can be seen from Table 1, the ultra-black film produced by the CVD process is not as dense as the ALD film layer, and the accuracy of film thickness control is lower. Therefore, the absorption efficiency and oil resistance of the ultra-black film are ultimately lower than those produced by the ALD process.

[0187] The ultra-black film of the present invention can be widely used in the fields of mobile phone lenses, vehicle lenses, AR / VR, etc. It has good oil resistance and high absorption rate.

[0188] Based on the disclosure and teachings of the above description, those skilled in the art may also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and modifications and variations of the present invention should also fall within the scope of protection of the claims of the present invention. In addition, although certain specific terms are used in this description, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims

1. An ultra-black film structure with oil-proof properties, characterized by: The invention comprises a substrate, a bonding layer deposited on the surface of the substrate by ALD, a light-absorbing layer deposited on the surface of the bonding layer by ALD, and an anti-oil-fouling layer arranged on the surface of the light-absorbing layer, wherein the anti-oil-fouling layer is at least one of a fluorine-containing compound, a hydrophobic SiO2 nanostructure, and an organic-inorganic hybrid layer, and the oil contact angle of the anti-oil-fouling layer is greater than 90°.

2. The ultra-black film structure with oil-proof properties according to claim 1, characterized in that: The substrate is made of one of silicon, glass, metal, polyethylene terephthalate (PET), polyimide (PI) and ceramics.

3. The ultra-black film structure with oil-proof properties according to claim 1, characterized in that: The thickness of the bonding layer is 1 nm to 50 nm, the thickness of the light absorbing layer is 200 nm to 2000 nm, and the thickness of the anti-oil layer is 5 nm to 1000 nm.

4. The ultra-black film structure with oil-proof properties according to claim 1, characterized in that: The material of the bonding layer is at least one of oxide, nitride, and metal element, the oxide is at least one of TiO2, SiO2, Al2O3, ZnO, MgO, HfO2, MnO2 and ZrO2; the nitride is at least one of titanium nitride, aluminum nitride, silicon nitride, hafnium nitride, tantalum nitride and zirconium nitride; the metal element is one of Ir, Au, Cu, Co, Ni, Ru, Al, Pt, Ta, V and W.

5. The ultra-black film structure with oil-proof properties according to claim 1, characterized in that: The material of the light-absorbing layer is TiAlC or alternating superimposed layers of metal elements and oxides, the metal element is at least one of Ir, Au, Cu, Co, Ni, Ru, Al, Pt, Ta, V and W, and the oxide is at least one of TiO2, SiO2, Al2O3, ZnO, MgO, HfO2, MnO2 and ZrO2.

6. The oil-proof ultra-black film structure according to claim 1, characterized in that: The fluorine-containing compound is at least one of AlF3, TiF4 and perfluoropolyether membrane, wherein the preparation method of AlF3 and TiF4 is: according to the four steps of precursor-purge-reactant-purge of the ALD process, metal precursors and fluorine sources are alternately introduced to achieve precise control at the single atomic layer level, the metal precursor is at least one of TMA, AlCl3, β-diketone complex of aluminum, TiCl4, tetrakis(dimethylamino)titanium, and tetraisopropoxide titanium, and the fluorine source is at least one of HF, NH4F, TiF4, F2 plasma, and SF6 plasma; the perfluoropolyether membrane is prepared by molecular layer deposition using a fluorine-containing dicarboxylic acid and a diol precursor for stepwise polymerization, wherein the fluorine-containing dicarboxylic acid is at least one of perfluoroadipic acid and perfluorosuccinic acid, and the diol precursor is at least one of perfluoropolyether diol, ethylene glycol, and hydroquinone.

7. The oil-proof ultra-black film structure according to claim 1, characterized in that: The hydrophobic SiO2 nanostructure is achieved by CF4 / O2 plasma dry etching of SiO2. Specifically, the SiO2 substrate is placed in an atomic layer deposition chamber under a vacuum state, and CF4 / O2 plasma is continuously introduced for etching. The gas ratio is: CF4:O2=1:1~10:1, the time is 5-600s, the power is 50-1000w, and finally nitrogen is used to purge to remove residual gas.

8. The oil-proof ultra-black film structure according to claim 1, characterized in that: The organic-inorganic hybrid layer is specifically one of trimethylsiloxane-modified SiO2, octadecyl long-chain-modified Al2O3, and dimethylsiloxy-modified TiO2 surface; it is achieved by alternately introducing inorganic precursors and organic silanes. Specifically, the inorganic component is first deposited by ALD, and then the organic silane layer is introduced for condensation to expose the -CF3 group, and the inorganic / organic deposition is repeated, wherein the inorganic component can be one of SiO2, Al2O3 and TiO2, and the organic silane is at least one of trimethylchlorosilane, octadecyltrimethoxysilane, and dimethyldimethoxysilane.

9. The ultra-black film structure with oil-proof properties according to claim 1, characterized in that: The preparation methods of the bonding layer and the light absorbing layer are both: using the atomic layer deposition method, alternately introducing precursors and reactants through four steps of precursor pulse-inert gas purge-reactant pulse-inert gas purge, and depositing thin films layer by layer on the surface of the substrate.

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

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