Zirconia optical coating, preparation method and application, and anti-reflection film

Abstract

The present invention relates to the field of optical coating technology, and discloses a zirconium oxide optical coating, a preparation method and application thereof, and an anti-reflection film. The zirconium oxide optical coating has a thickness of 1-1000 nm and a density of 5.99-6.23 g / cm 3 , the refractive index at a wavelength of 550nm is ≥2.1. The preparation method comprises: (1) thermally evaporating a zirconium oxide material to obtain a zirconium oxide pre-coating film attached to the surface of a substrate; (2) contacting the zirconium oxide pre-coating film with a gas containing water vapor in the presence of ion bombardment, and annealing the zirconium oxide pre-coating film to obtain a zirconium oxide optical coating film. Compared with conventional zirconium oxide thin films, the zirconium oxide optical coating film provided by the present invention has a higher refractive index and a low extinction coefficient, and has excellent optical properties, strength properties and UV resistance, and can be prepared together with a low refractive index film layer to form an anti-reflection film with excellent optical properties and strength properties.

Description

Technical Field

[0001] The invention relates to the field of optical coatings, and in particular to zirconium oxide optical coatings, preparation methods and applications thereof, and anti-reflection films. Background Art

[0002] Optical coating is a process of coating one or more thin and uniform dielectric layers on optical components or independent substrates. Its purpose is to use the principle of light interference to change the transmission, reflection or polarization properties of optical components. Common non-metallic optical coatings are mainly achieved by alternating high and low refractive index layers. Among them, high refractive index materials include TiO2, ZrO2, TaO2, etc., and low refractive index materials include SiO2, MgF2, etc.

[0003] Among them, TiO2 has the highest refractive index and strong resistance to chemical corrosion, so it is widely used in industrial mass production. However, since the Mohs hardness of TiO2 is only 5.5-6.0, and it is easy to undergo photocatalysis under ultraviolet irradiation, thereby changing the refractive index, it is severely limited in the fields of application requirements such as abrasion resistance and ultraviolet radiation. ZrO2, as a material with more stable physical and chemical properties, has good ultraviolet resistance and a Mohs hardness of 7-8 or even higher, showing its advantages as an optical coating material. The refractive index of ZrO2 optical coatings prepared by conventional coating processes is generally low (the refractive index at 550nm is only 1.9-2.05), which is difficult to meet the requirements of high-precision optical films. The currently reported processes for optimizing the refractive index, such as heating the substrate, will cause a simultaneous surge in the extinction coefficient of ZrO2, which is determined by the crystal properties of the ZrO2 material. This phenomenon has largely limited the application and development of ZrO2 materials in the field of optical coatings.

[0004] Therefore, it is of great significance to provide zirconium oxide optical coatings with further optimized comprehensive performance. Summary of the invention

[0005] Aiming at the problem that it is difficult to balance the improvement of refractive index and the suppression of extinction coefficient growth in zirconium oxide optical coatings prepared by existing processes, and the problem that the strength performance of the coatings is not ideal, the present invention provides zirconium oxide optical coatings, preparation methods and applications, and anti-reflection films.

[0006] In order to achieve the above object, the present invention provides a zirconium oxide optical coating in a first aspect, wherein the zirconium oxide optical coating has a thickness of 1-1000 nm and a density of 5.99-6.23 g / cm 3 , the refractive index at a wavelength of 550nm is ≥2.1.

[0007] A second aspect of the present invention provides a method for preparing a zirconium oxide optical coating, comprising:

[0008] (1) performing a thermal evaporation treatment on the zirconium oxide material to obtain a zirconium oxide pre-plating film attached to the surface of the substrate;

[0009] (2) In the presence of ion bombardment, a gas containing water vapor is brought into contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed to obtain a zirconium oxide optical coating film.

[0010] The third aspect of the present invention provides a zirconium oxide optical coating prepared by the method described in the second aspect.

[0011] The fourth aspect of the present invention provides the use of the method described in the second aspect to prepare an anti-reflection film on a glass, PC film or alloy substrate.

[0012] A fifth aspect of the present invention provides an anti-reflection film, the anti-reflection film comprising zirconium oxide films and silicon oxide films alternately stacked;

[0013] Wherein, the zirconium oxide film is the zirconium oxide optical coating film described in the first aspect or the third aspect.

[0014] Through the above scheme, on the basis of the traditional thermal evaporation process, after the coating is completed, the zirconium oxide film is cooled and annealed by gas containing water vapor, and the gas containing water vapor is ion-assisted bombarded during the annealing process, thereby obtaining a zirconium oxide optical coating with a greatly improved refractive index. The refractive index of the zirconium oxide optical coating at a wavelength of 550nm is ≥2.1, and the extinction coefficient is ≤8×10 -3 In addition, the density can reach 5.99-6.23g / cm 3 , Mohs hardness ≥ 8, ΔE ≤ 0.2 in the UV resistance test for 96h, and can have excellent optical properties, strength properties and UV resistance. Furthermore, the zirconium oxide optical coating can be alternately matched with a low refractive index film layer to form an anti-reflection film with excellent optical properties and strength properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0016] Figure 1 Schematic diagram of an anti-reflection film according to an embodiment of the present invention.

[0017] Description of Reference Numerals

[0018] 1. Base material 2. Zirconium oxide film 3. Silicon oxide film DETAILED DESCRIPTION

[0019] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0020] The first aspect of the present invention provides a zirconium oxide optical coating, wherein the thickness of the zirconium oxide optical coating is 1-1000nm and the density is 5.99-6.23g / cm 3 , the refractive index at a wavelength of 550nm is ≥2.1.

[0021] It is reported that the refractive index of the currently commercial zirconia optical coating is 1.9-2.05 (at a wavelength of 550nm), which is different from the theoretical refractive index value of the zirconia material. The refractive index of the zirconia optical coating provided by the present invention at a wavelength of 550nm is ≥2.1, which is much higher than the refractive index level of existing commercial zirconia optical coatings.

[0022] According to the present invention, preferably, the thickness of the zirconium oxide optical coating is 10-250 nm, and the density is 6.07-6.23 g / cm 3 , the refractive index at a wavelength of 550nm is ≥2.14.

[0023] In the present invention, the thickness of the coating is measured by a film thickness meter; the density of the coating is calculated by dividing the mass of the coating by the volume of the coating (volume of the coating = thickness of the coating × area of ​​the coating); and the refractive index of the coating is measured by a spectroscopic ellipsometer.

[0024] According to the present invention, the zirconium oxide optical coating has a high refractive index and a relatively low extinction coefficient, so that the zirconium oxide optical coating has excellent overall light transmission performance. Preferably, the extinction coefficient of the zirconium oxide optical coating is ≤8×e -3 .

[0025] In the present invention, the extinction coefficient is measured by using a spectroscopic ellipsometer.

[0026] According to the present invention, the zirconium oxide optical coating has a relatively high hardness. Preferably, the Mohs hardness of the zirconium oxide optical coating is ≥8, preferably >8.

[0027] In the present invention, the Mohs hardness is measured using a Mohs hardness tester.

[0028] According to the present invention, the zirconium oxide optical coating contains a tetragonal zirconium oxide crystal phase.

[0029] According to the present invention, the zirconium oxide optical coating has a higher compactness, which is manifested by the higher density value mentioned above. The higher density and hardness can bring higher wear resistance and strength performance to the zirconium oxide optical coating.

[0030] According to the present invention, the zirconium oxide optical coating has good UV resistance and is not prone to loss of refractive index under UV irradiation. In the UV resistance test, the zirconium oxide optical coating has a 96h ΔE (ΔE is the color difference value in the color difference test) ≤ 0.2, preferably ΔE ≤ 0.1.

[0031] In the present invention, the anti-ultraviolet test adopts a xenon lamp test chamber, the lamp tube irradiates at 340nm for 20 hours, and then turns off the solar radiation source for 4 hours, which is one cycle, and 4 cycles are performed for 96 hours; wherein, ΔE is calculated by the CIE2000 standard formula.

[0032] Compared with existing commercial zirconium oxide optical coatings, the zirconium oxide optical coating provided by the present invention has a significantly improved refractive index and a lower extinction coefficient, which can well meet the optical performance requirements of high-precision optical films, and has high density and hardness, good abrasion resistance and UV resistance. With the above-mentioned excellent comprehensive properties, it can be used as a high-refractive index film layer and can be alternately matched with low-refractive index silicon oxide film layers, magnesium fluoride film layers, aluminum oxide film layers, etc. to form an anti-reflection film with excellent optical properties and strength properties.

[0033] A second aspect of the present invention provides a method for preparing a zirconium oxide optical coating, comprising:

[0034] (1) performing a thermal evaporation treatment on the zirconium oxide material to obtain a zirconium oxide pre-plating film attached to the surface of the substrate;

[0035] (2) In the presence of ion bombardment, a gas containing water vapor is brought into contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed to obtain a zirconium oxide optical coating film.

[0036] According to the present invention, in step (1), the thermal evaporation treatment is a process for depositing thin films known in the art, which generally uses an electron beam or a resistance wire to heat and evaporate the source material into a gaseous state in a vacuum chamber, and the gaseous source material can directly adhere to the surface of the substrate to form a coating. In the preparation method of zirconium oxide optical coating of the present invention, the thermal evaporation treatment can be performed using a conventional device for thermal evaporation in the art, preferably an evaporation coating machine. The evaporation coating machine is configured with functional components including a chamber to be coated, an electron gun, an ion source, a crucible, a fixture, a refrigerator, and the like.

[0037] According to the present invention, in step (2), the "in the presence of ion bombardment, the gas containing water vapor is brought into contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed" specifically means that the zirconium oxide pre-coating film is first formed on the surface of the substrate by thermal evaporation, and after the coating is completed, the electron gun is turned off, the evaporated material is placed in the chamber to be coated, and the gas containing water vapor is immediately introduced into contact with the zirconium oxide pre-coating film, the latter is cooled and annealed, and during the annealing process, the ion source is simultaneously turned on to bombard the gas containing water vapor with ions until the annealing is completed.

[0038] According to the present invention, in step (2), the first ion source used for the ion bombardment can be selected from at least one of a Kaufman ion source, a Hall ion source and a radio frequency ion source, preferably a Kaufman ion source.

[0039] According to the present invention, in step (2), the average energy of the first ion source is 150-650 ev, preferably 400-500 ev.

[0040] According to the present invention, in step (2), the working gas of the first ion source is oxygen with a flow rate of 15-25 sccm.

[0041] According to the present invention, in step (2), the ion bombardment is carried out in a vacuum chamber, that is, the ion bombardment is carried out under vacuum conditions. Preferably, the vacuum degree of the vacuum chamber is ≤9×10 -3 Pa, and preferably the vacuum degree is ≤6×10 -3 Pa.

[0042] According to the present invention, in step (2), the water vapor content in the water vapor-containing gas is 10-35 g / m 3 (That is, the content of water vapor in each cubic meter of gas containing water vapor is 10-35 g). The present invention defines a wide range of the gas containing water vapor, as long as the water vapor content can meet the above definition and does not react with the zirconium oxide pre-coating film in a manner that is detrimental to the optical properties and strength properties. For example, it can be clean air containing water vapor, pure nitrogen containing water vapor, or pure argon containing water vapor.

[0043] According to the present invention, in step (2), during the process of the water vapor-containing gas contacting the zirconium oxide pre-coating film and performing annealing treatment, the flow rate of the water vapor-containing gas is 10-40 sccm, preferably 20-30 sccm.

[0044] According to the present invention, in step (2), the annealing treatment time is 10-50 min, preferably 25-35 min.

[0045] According to the present invention, by annealing the zirconium oxide pre-coating film obtained by thermal evaporation with a gas containing water vapor, and simultaneously assisting with ion bombardment of the gas containing water vapor, the zirconium oxide optical coating film finally obtained can have a significantly improved refractive index, and is beneficial to improving the crystalline stability and density of the zirconium oxide coating film.

[0046] According to the present invention, in step (1), the thermal evaporation treatment is carried out under vacuum conditions. In order to allow the gasified zirconium oxide to form a film on the substrate surface smoothly and ensure the film quality, preferably, the vacuum degree is 3×10 -3 -9×10 -3 Pa, more preferably 5×10 -3 -7×10 -3 Pa.

[0047] According to the present invention, in step (1), before the thermal evaporation treatment, the substrate is preferably heated to increase the substrate temperature to facilitate film growth during the thermal evaporation process. Preferably, the substrate temperature is 100-250°C, more preferably 150-200°C.

[0048] According to the present invention, in step (1), during the thermal evaporation treatment, the evaporation rate is preferably More preferably

[0049] According to the present invention, in step (1), the thermal evaporation treatment is performed in the presence of a second ion source.

[0050] In the present invention, the second ion source can be selected from at least one of a Kaufman ion source, a Hall ion source and a radio frequency ion source, and is preferably a Kaufman ion source.

[0051] In the present invention, during the thermal evaporation treatment, the average energy of the second ion source is 100-1100 ev, preferably 400-1000 ev.

[0052] In the present invention, the working gas of the second ion source is oxygen gas with a flow rate of 10-30 sccm.

[0053] According to the present invention, in step (1), preferably, the thickness of the zirconium oxide pre-coating film obtained by thermal evaporation treatment is 1-1000 nm.

[0054] According to the present invention, step (1) further includes: before the thermal evaporation treatment is performed, using the second ion source to perform ion cleaning on the surface of the substrate.

[0055] In the present invention, preferably, during the ion cleaning process, the average energy of the second ion source is 800-1100 eV.

[0056] In the present invention, preferably, the ion cleaning time is 2-5 minutes.

[0057] According to the present invention, the substrate can be selected from conventional materials in the art, for example, can be selected from at least one of glass, PC film (polycarbonate film) and alloy.

[0058] In the present invention, the alloy is preferably an aluminum alloy.

[0059] The third aspect of the present invention provides a zirconium oxide optical coating prepared by the method described in the second aspect.

[0060] According to the present invention, the zirconium oxide optical coating prepared by the method has the following performance indicators: thickness of 1-1000nm, preferably 10-250nm; density of 5.99-6.23g / cm 3 , preferably 6.07-6.23 g / cm 3 ; Refractive index at wavelength 550nm ≥ 2.1, preferably ≥ 2.14; Extinction coefficient ≤ 8×e -3 ; Mohs hardness ≥8, preferably >8; in the UV resistance test, ΔE≤0.2 for 96h, preferably ΔE≤0.1.

[0061] According to the above performance indicators, the zirconium oxide optical coating prepared by the method has a high refractive index, a low extinction coefficient, high density and hardness, and good wear resistance and UV resistance.

[0062] The fourth aspect of the present invention provides the use of the method described in the second aspect to prepare an anti-reflection film on a glass, PC film or alloy substrate.

[0063] A fifth aspect of the present invention provides an anti-reflection film, the anti-reflection film comprising zirconium oxide films and silicon oxide films alternately stacked;

[0064] Wherein, the zirconium oxide film is the zirconium oxide optical coating film described in the first aspect or the third aspect.

[0065] According to the present invention, the thickness of the anti-reflection film is 2-2500 nm.

[0066] According to the present invention, there is no particular limitation on the number of layers of the zirconium oxide film and the silicon oxide film in the anti-reflection film and the thickness of the silicon oxide film, and they can be adjusted according to different applications and performance requirements.

[0067] According to the present invention, the substrate of the anti-reflection film can be various conventional anti-reflection film substrates, preferably at least one of glass, PC film or alloy.

[0068] According to the present invention, the anti-reflection film has excellent optical properties, and its transmittance at a wavelength of 550 nm is ≥94.5%.

[0069] According to the present invention, the anti-reflection film has a relatively high hardness, and its Mohs hardness is greater than 8.

[0070] According to the present invention, the anti-reflection film has excellent anti-ultraviolet performance. In the anti-ultraviolet test, ΔE of 96h is ≤0.2.

[0071] According to the present invention, the anti-reflection film also has good wear resistance.

[0072] In the present invention, the transmittance is measured by a high-precision spectrophotometer, using a wavelength of 360-780 nm and a scanning step of 1 nm.

[0073] According to the present invention, the anti-reflection film can be prepared by alternately evaporating zirconium oxide film and silicon oxide film layer by layer from bottom to top on the surface of the substrate. Figure 1 As shown, there is no special limitation on the preparation method of the silicon oxide film, and the silicon oxide coating can be formed by the conventional thermal evaporation method in the art, and the zirconium oxide film is formed by the preparation method of the zirconium oxide optical coating described in the second aspect of the present invention, that is, after each layer of zirconium oxide pre-coating is formed, the zirconium oxide film is cooled and annealed by a gas containing water vapor, and the gas containing water vapor is ion bombarded during the annealing process to form the zirconium oxide optical coating described in the present invention, thereby alternately evaporated with the silicon oxide film and superimposed up and down to obtain the anti-reflection film described in the present invention.

[0074] According to the present invention, in the process of preparing the anti-reflection film, the preparation steps and parameter limitations of the zirconium oxide film are the same as the preparation method of the zirconium oxide optical coating described in the second aspect of the present invention, and will not be repeated here.

[0075] The present invention will be described in detail below by way of examples. In the following examples and comparative examples,

[0076] Evaporation coating machine: Japan Guangchi, Gener series.

[0077] Unless otherwise specified, all materials used are common commercially available products.

[0078] Example 1

[0079] This example is used to illustrate the preparation of zirconium oxide optical coating:

[0080] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0081] (1-2) The vacuum degree of the coating chamber reaches 6×10 -3Pa, and when the temperature of the glass substrate reaches 200°C, the second ion source (Kaufman ion source, average energy is 1000ev) is turned on to perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0082] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 200 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0083] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 450 eV. At the same time, pure air (flow rate of 30 sccm, water vapor content of 35 g / m) is introduced into the machine. 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes; during the annealing process, the first ion source continuously bombards the introduced pure air with ions;

[0084] (2-2) Stop supplying pure air, turn off the power of the first ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain a zirconium oxide optical coating (denoted as M1). The thickness of M1 is 200 nm.

[0085] The optical and physical indicators of M1 are shown in Table 1.

[0086] Example 2

[0087] This example is used to illustrate the preparation of zirconium oxide optical coating:

[0088] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0089] (1-2) The vacuum degree of the coating chamber reaches 5×10 -3 Pa, and when the temperature of the glass substrate reaches 175°C, turn on the second ion source (Kaufman ion source, average energy is 1000ev), and perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0090] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 200 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0091] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 20 sccm oxygen) and adjust the average energy to 500 eV. At the same time, pure air (flow rate of 25 sccm, water vapor content of 35 g / m 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 25 minutes; during the annealing process, the first ion source continuously bombards the introduced pure air with ions;

[0092] (2-2) Stop supplying pure air, turn off the power of the first ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain a zirconium oxide optical coating (denoted as M2). The thickness of M2 is 200 nm.

[0093] The optical and physical indicators of M2 are shown in Table 1.

[0094] Example 3

[0095] This example is used to illustrate the preparation of zirconium oxide optical coating:

[0096] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0097] (1-2) The vacuum degree of the coating chamber reaches 7×10 -3 Pa, and when the temperature of the glass substrate reaches 150°C, turn on the second ion source (Kaufman ion source, average energy is 1000ev), and perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0098] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 200 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0099] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 25 sccm oxygen) and adjust the average energy to 400 eV. At the same time, pure air (flow rate of 20 sccm, water vapor content of 35 g / m 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 35 minutes; during the annealing process, the first ion source continuously bombards the introduced pure air with ions;

[0100] (2-2) Stop supplying pure air, turn off the power of the first ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain a zirconium oxide optical coating (denoted as M3). The thickness of M3 is 200 nm.

[0101] The optical and physical indicators of M3 are shown in Table 1.

[0102] Example 4

[0103] This example is used to illustrate the preparation of zirconium oxide optical coating:

[0104] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0105] (1-2) The vacuum degree of the coating chamber reaches 9×10 -3 Pa, and when the temperature of the glass substrate reaches 100°C, turn on the second ion source (Kaufman ion source, average energy is 1000ev), and perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0106] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 200 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0107] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 600 eV. At the same time, pure air (flow rate of 40 sccm, water vapor content of 35 g / m 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes; during the annealing process, the first ion source continuously bombards the introduced pure air with ions;

[0108] (2-2) Stop supplying pure air, turn off the power of the first ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain a zirconium oxide optical coating (denoted as M4). The thickness of M4 is 200 nm.

[0109] The optical and physical indicators of M4 are shown in Table 1.

[0110] Example 5

[0111] This example is used to illustrate the preparation of zirconium oxide optical coating:

[0112] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0113] (1-2) The vacuum degree of the coating chamber reaches 9×10 -3 Pa, and when the temperature of the glass substrate reaches 100°C, turn on the second ion source (Kaufman ion source, average energy is 1000ev), and perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0114] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 200 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0115] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 600 eV. At the same time, pure air (flow rate of 10 sccm, water vapor content of 35 g / m 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes; during the annealing process, the first ion source continuously bombards the introduced pure air with ions;

[0116] (2-2) Stop supplying pure air, turn off the power of the first ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain a zirconium oxide optical coating (denoted as M5). The thickness of M5 is 200 nm.

[0117] The optical and physical indicators of M5 are shown in Table 1.

[0118] Example 6

[0119] This example is used to illustrate the preparation of zirconium oxide optical coating:

[0120] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0121] (1-2) The vacuum degree of the coating chamber reaches 9×10 -3 Pa, and when the temperature of the glass substrate reaches 100°C, turn on the second ion source (Kaufman ion source, average energy is 1000ev), and perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0122] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 200 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0123] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 150 eV. At the same time, pure air (flow rate of 40 sccm, water vapor content of 35 g / m) is introduced into the machine. 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 10 minutes; during the annealing process, the first ion source continuously bombards the introduced pure air with ions;

[0124] (2-2) Stop supplying pure air, turn off the power of the first ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain a zirconium oxide optical coating (denoted as M6). The thickness of M6 is 200 nm.

[0125] The optical and physical indicators of M6 are shown in Table 1.

[0126] Example 7

[0127] This example is used to illustrate the preparation of the anti-reflection film:

[0128] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0129] (1-2) The vacuum degree of the coating chamber reaches 6×10 -3 Pa, and when the temperature of the glass substrate reaches 200°C, the second ion source (Kaufman ion source, average energy is 1000ev) is turned on to perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0130] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 19 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0131] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 450 eV. At the same time, pure air (flow rate of 30 sccm, water vapor content of 35 g / m) is introduced into the machine. 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes (during the annealing process, the first ion source continuously bombards the introduced pure air with ions) to obtain a first coating layer (zirconium oxide film);

[0132] (3-1) Stop the introduction of pure air, turn off the power of the first ion source, wait for the crucible to rotate to the SiO2 material, and then turn on the electron gun to heat and evaporate the SiO2 crucible (the evaporation rate is ), setting the film thickness to 50nm, and obtaining the second coating layer (silicon oxide film);

[0133] (4-1) The electron gun is turned off, and the average energy of the second ion source (Kaufman ion source) is adjusted to 850 eV. After the crucible is rotated to ZrO2, the electron gun is turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen is introduced into the APC, and the evaporation rate is ), forming a 30nm thick zirconium oxide pre-coating film on the surface of the second coating layer;

[0134] (4-2) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 450 eV. At the same time, pure air (flow rate of 30 sccm, water vapor content of 35 g / m) is introduced into the machine. 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes (during the annealing process, the first ion source continuously bombards the introduced pure air with ions) to obtain a third coating (zirconium oxide film);

[0135] (5-1) Stop the introduction of pure air, turn off the power of the first ion source, wait for the crucible to rotate to the SiO2 material, and then turn on the electron gun to heat and evaporate the SiO2 crucible (the evaporation rate is ), setting the film thickness to 100 nm, and obtaining a fourth coating layer (silicon oxide film) on the surface of the third coating layer;

[0136] (6) Turn off the power of the electron gun and the ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain an anti-reflection film (denoted as AF1).

[0137] The optical and physical indicators of AF1 are shown in Table 2.

[0138] Example 8

[0139] This example is used to illustrate the preparation of the anti-reflection film:

[0140] (1-1) placing a glass substrate on a fixture of an evaporation coating machine and evacuating the substrate;

[0141] (1-2) The vacuum degree of the coating chamber reaches 9×10 -3Pa, and when the temperature of the glass substrate reaches 100°C, turn on the second ion source (Kaufman ion source, average energy is 1000ev), and perform ion cleaning on the surface of the glass substrate for 5 minutes;

[0142] (1-3) The average energy of the second ion source was adjusted to 850 eV, and the electron gun was turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen was introduced into the APC, and the evaporation rate was ), forming a 25 nm thick zirconium oxide pre-plating film on the surface of the glass substrate;

[0143] (2-1) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 600 eV. At the same time, pure air (flow rate of 40 sccm, water vapor content of 35 g / m 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes (during the annealing process, the first ion source continuously bombards the introduced pure air with ions) to obtain a first coating layer (zirconium oxide film);

[0144] (3-1) Stop the introduction of pure air, turn off the power of the first ion source, wait for the crucible to rotate to the SiO2 material, and then turn on the electron gun to heat and evaporate the SiO2 crucible (the evaporation rate is ), setting the film thickness to 40nm, and obtaining the second coating layer (silicon oxide film);

[0145] (4-1) The electron gun is turned off, and the average energy of the second ion source (Kaufman ion source) is adjusted to 850 eV. After the crucible is rotated to ZrO2, the electron gun is turned on to heat and evaporate the ZrO2 crucible (20 sccm of oxygen is introduced into the APC, and the evaporation rate is ), forming a 42nm thick zirconium oxide pre-coating film on the surface of the second coating layer;

[0146] (4-2) Turn off the power of the second ion source and the electron gun, turn on the first ion source (Kaufman ion source, APC with 15 sccm oxygen) and adjust the average energy to 600 eV. At the same time, pure air (flow rate of 40 sccm, water vapor content of 35 g / m 3 ) is in contact with the zirconium oxide pre-coating film, and the zirconium oxide pre-coating film is annealed for 30 minutes (during the annealing process, the first ion source continuously bombards the introduced pure air with ions) to obtain a third coating (zirconium oxide film);

[0147] (5-1) Stop the introduction of pure air, turn off the power of the first ion source, wait for the crucible to rotate to the SiO2 material, and then turn on the electron gun to heat and evaporate the SiO2 crucible (the evaporation rate is ), setting the film thickness to 105 nm, and obtaining a fourth coating layer (silicon oxide film) on the surface of the third coating layer;

[0148] (6) Turn off the power of the electron gun and the ion source, wait for the workpiece to cool down, turn on the refrigerator for defrosting, and finally inflate. After the pressure returns to atmospheric pressure, take out the workpiece to obtain an anti-reflection film (denoted as AF2).

[0149] The optical and physical indicators of AF2 are shown in Table 2.

[0150] Comparative Example 1

[0151] This comparative example is used to illustrate the preparation of zirconium oxide optical coating:

[0152] The method of Example 1 is followed, except that pure dry air without water vapor is introduced in step (2-1). Other conditions are the same as those of Example 1, and a zirconium oxide coating (denoted as D1) is obtained.

[0153] The optical and physical indicators of D1 are shown in Table 1.

[0154] Comparative Example 2

[0155] This comparative example is used to illustrate the preparation of zirconium oxide optical coating:

[0156] The method of Example 1 is followed, except that the first ion source is turned off in step (2-1), that is, no ion bombardment is performed. Other conditions are the same as those of Example 1, and a zirconium oxide coating (denoted as D2) is obtained.

[0157] The optical and physical indicators of D2 are shown in Table 1.

[0158] Comparative Example 3

[0159] This comparative example is used to illustrate the preparation of an anti-reflection film:

[0160] The method of Example 7 was followed, except that pure dry air without water vapor was introduced in both step (2-1) and step (4-2), and the total thickness of the film was controlled to be 210 nm. Other conditions were the same as those of Example 7, and an antireflection film (denoted as D3) was obtained.

[0161] The optical and physical indicators of D3 are shown in Table 2.

[0162] Comparative Example 4

[0163] This comparative example is used to illustrate the preparation of an anti-reflection film:

[0164] The method of Example 7 is followed, except that the first ion source is turned off in both step (2-1) and step (4-2), i.e., no ion bombardment is performed, and the total film thickness is controlled to be 220 nm. Other conditions are the same as those of Example 7, and an antireflection film (denoted as D4) is obtained.

[0165] The optical and physical indicators of D4 are shown in Table 2.

[0166] Table 1

[0167]

[0168] Note: The refractive index is the data under the condition of wavelength 550nm; the wear condition is evaluated by vibration friction test, and the test conditions include: speed 3000 rpm, test time 1h

[0169] Table 2

[0170]

[0171] Note: Transmittance is the data under the condition of wavelength 550nm; wear is evaluated by vibration friction test, the test conditions include: speed 3000 rpm, test time 1h

[0172] It can be seen from Table 1 that the zirconium oxide optical coatings M1-M6 prepared by the method of the present invention have a refractive index greater than 2.104 and an extinction coefficient less than 6.1×10 -3 , density>6.01, Mohs hardness greater than 8, ΔE of 96h in the UV resistance test is less than 0.1, showing a significantly improved refractive index compared to existing products, and at the same time, the extinction coefficient is low, which well solves the problem of difficulty in balancing the increase of the refractive index and the inhibition of the extinction coefficient, and at the same time shows high density, hardness, good UV resistance and wear resistance. Among them, the products M1-M3 prepared by Examples 1-3 have more outstanding optical properties and comprehensive effect advantages. Example 5 and Example 6 respectively adjust the flux of the gas containing water vapor and the energy of the ion source bombardment during the annealing process on the basis of the preparation method of Example 4, and the performance of the products is different, which shows that the introduction of gas containing water vapor for annealing and the ion bombardment during the annealing process play a vital role in the preparation method of the present invention. In particular, Comparative Example 1 does not introduce water vapor during the annealing process, and Comparative Example 2 does not use ion bombardment at the same time during the annealing process, resulting in a sharp decline in the optical properties of D1 and D2, and the effect of the present invention cannot be obtained.

[0173] It can be seen from Table 2 that the zirconium oxide optical coating provided by the preferred embodiment of the present invention can achieve an anti-reflection film AF1 with a transmittance of up to 95.4% and a thickness limited to 200 nm. The anti-reflection film AF2 prepared by the zirconium oxide optical coating provided by the non-preferred embodiment can still achieve a transmittance of 94.7% within the thickness range of 210 nm. The transmittance of the anti-reflection films D3 and D4 in the thickness range of 210-220 nm is low, and it is difficult to meet the requirements of higher precision lenses and optoelectronic display devices.

[0174] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A zirconium oxide optical coating, characterized in that: The thickness of the zirconium oxide optical coating is 1-1000nm and the density is 5.99-6.23g / cm 3 , the refractive index at a wavelength of 550nm is ≥2.1, Wherein, the preparation method of the zirconium oxide optical coating comprises: (1) Performing thermal evaporation treatment on the zirconium oxide material to obtain a zirconium oxide pre-coating film attached to the surface of the substrate; the conditions of the thermal evaporation treatment include: a vacuum degree of 3×10 -3 -9×10 -3 Pa, substrate temperature is 100-250°C, and evaporation rate is 0.5-3Å / s; (2) in the presence of ion bombardment, bringing the gas containing water vapor into contact with the zirconium oxide pre-coating film, annealing the zirconium oxide pre-coating film, and simultaneously bombarding the gas containing water vapor with ions to obtain a zirconium oxide optical coating, Wherein, the working gas of the first ion source used for the ion bombardment is oxygen.

2. The zirconium oxide optical coating according to claim 1, wherein: The thickness of the zirconium oxide optical coating is 10-250nm and the density is 6.07-6.23g / cm 3 , the refractive index at a wavelength of 550nm is ≥2.

14.

3. The zirconium oxide optical coating according to claim 1 or 2, wherein: The extinction coefficient of the zirconium oxide optical coating is ≤8×e -3 .

4. The zirconium oxide optical coating according to claim 3, wherein: The Mohs hardness of the zirconium oxide optical coating is ≥8.

5. The zirconium oxide optical coating according to claim 4, wherein: The Mohs hardness of the zirconium oxide optical coating is greater than 8.

6. The zirconium oxide optical coating according to claim 4 or 5, wherein: In the anti-ultraviolet test, the ∆E of the zirconium oxide optical coating is ≤0.2 for 96 hours.

7. The zirconium oxide optical coating according to claim 6, wherein: In the UV resistance test, the zirconium oxide optical coating has a ∆E of ≤0.1 for 96 hours.

8. A method for preparing a zirconium oxide optical coating, characterized in that: include: (1) thermally evaporating the zirconium oxide material to obtain a zirconium oxide pre-coating film attached to the surface of the substrate; The conditions of the thermal evaporation treatment include: a vacuum degree of 3×10 -3 -9×10 -3 Pa, substrate temperature is 100-250°C, and evaporation rate is 0.5-3Å / s; (2) in the presence of ion bombardment, bringing the gas containing water vapor into contact with the zirconium oxide pre-coating film, annealing the zirconium oxide pre-coating film, and simultaneously bombarding the gas containing water vapor with ions to obtain a zirconium oxide optical coating, Wherein, the working gas of the first ion source used for the ion bombardment is oxygen.

9. The method according to claim 8, wherein: The first ion source used for the ion bombardment is selected from at least one of a Kaufman ion source, a Hall ion source and a radio frequency ion source.

10. The method according to claim 9, wherein: The average energy of the first ion source is 150-650 eV.

11. The method according to claim 10, wherein: The average energy of the first ion source is 400-500 ev.

12. The method according to claim 11, wherein: The flow rate of the oxygen gas is 15-25 sccm.

13. The method according to any one of claims 8 to 12, wherein: The ion bombardment is carried out under vacuum conditions, with a vacuum degree of ≤9×10 -3 Pa.

14. The method according to claim 13, wherein: The ion bombardment is carried out under vacuum conditions, with a vacuum degree of ≤6×10 -3 Pa.

15. The method according to any one of claims 8 to 12, wherein: The water vapor content of the gas is 10-35 g / m 3 .

16. The method according to any one of claims 8 to 12, wherein: The flow rate of the gas containing water vapor is 10-40 sccm.

17. The method according to claim 16, wherein: The flow rate of the gas containing water vapor is 20-30 sccm.

18. The method according to any one of claims 8 to 12, wherein: The annealing treatment time is 10-50 minutes.

19. The method according to any one of claims 8 to 12, wherein: The annealing treatment time is 25-35 minutes.

20. The method according to any one of claims 8 to 12, wherein: The vacuum degree of the thermal evaporation process is 5×10 -3 -7×10 -3 Pa.

21. The method according to claim 20, wherein: The substrate temperature of the thermal evaporation treatment is 150-200°C.

22. The method according to claim 21, wherein: The evaporation rate of the thermal evaporation process is 1.5-2.5Å / s.

23. The method according to claim 22, wherein: The thermal evaporation process is performed in the presence of a second ion source.

24. The method according to claim 23, wherein: The second ion source is selected from at least one of a Kaufman ion source, a Hall ion source and a radio frequency ion source.

25. The method according to claim 24, wherein: The average energy of the second ion source is 100-1100 eV.

26. The method according to claim 25, wherein: The average energy of the second ion source is 400-1000 ev.

27. The method according to claim 26, wherein: The working gas of the second ion source is oxygen gas, and the flow rate is 10-30 sccm.

28. The method according to claim 27, wherein: Before the thermal evaporation treatment is performed, the surface of the substrate is ion cleaned by using the second ion source.

29. The method according to claim 28, wherein: The ion cleaning time is 2-5 minutes.

30. The method of claim 29, wherein: The substrate is selected from at least one of glass, PC film and alloy.

31. The method according to any one of claims 21 to 30, wherein: The thickness of the zirconium oxide pre-plating film is 1-1000nm.

32. A zirconium oxide optical coating prepared by the method according to any one of claims 8 to 31.

33. Use of the method according to any one of claims 8 to 31 in preparing an anti-reflection film on a glass, a PC film or an alloy substrate.

34. An anti-reflection film, characterized in that: The anti-reflection film comprises zirconium oxide films and silicon oxide films stacked alternately; Wherein, the zirconium oxide film is the zirconium oxide optical coating film as described in any one of claims 1-7 or 32.

35. The anti-reflection film according to claim 34, wherein: The thickness of the anti-reflection film is 2-2500nm.

36. The anti-reflection film according to claim 35, wherein: The substrate of the anti-reflection film is at least one of glass, PC film or alloy.

37. The anti-reflection film according to claim 36, wherein: The transmittance of the anti-reflection film at a wavelength of 550nm is ≥94.5%.

38. The anti-reflection film according to claim 37, wherein: The Mohs hardness of the anti-reflection film is greater than 8.

39. The anti-reflection film according to claim 38, wherein: In the anti-ultraviolet test, the anti-reflection film has a ∆E of ≤0.2 for 96 hours.

Images