阅读说明：本技术 一种带镧系氧化物疏水光学薄膜的光学镜片及其制备 (Optical lens with lanthanide oxide hydrophobic optical film and preparation thereof ) 是由 汪彦龙 李刚 张绍骞 邓淞文 向潜 于 2020-12-02 设计创作，主要内容包括：本发明公开了一种原子层沉积法制备的镧系氧化物疏水光学薄膜,其膜层材料采用镧系氧化物,该膜层镀于光学镜片基底表面时,不影响原镜片的光学性能。可应用于要求疏水性的光学器件表面,如防污染光学透射镜,反射镜等。本发明的镧系氧化物薄膜须采用原子层沉积镀膜工艺和设备进行制备,疏水性好,光学性能优良,应用广泛。(The invention discloses a lanthanide oxide hydrophobic optical film prepared by an atomic layer deposition method, wherein lanthanide oxide is adopted as a film material, and the film does not affect the optical performance of an original lens when being coated on the surface of the substrate of the optical lens. The method can be applied to the surfaces of optical devices which require hydrophobicity, such as anti-pollution optical transmission mirrors, reflecting mirrors and the like. The lanthanide oxide film is prepared by adopting an atomic layer deposition coating process and equipment, and has the advantages of good hydrophobicity, excellent optical performance and wide application.)

1. An optical lens with lanthanide oxide hydrophobic optical film, characterized in that: a lanthanide oxide hydrophobic optical film is arranged on a light receiving surface or a light incident surface of the optical lens, and the lanthanide oxide hydrophobic optical film layer is made of a lanthanide oxide material, and comprises the following components: CeO (CeO)₂,Pr₆O₁₁,Nd₂O₃,Sm₂O₃,Eu₂O₃,Gd₂O₃,Tb₄O₇,Dy₂O₃,Ho₂O₃,Er₂O₃,Tm₂O₃,Yb₂O₃And Lu₂O₃And one or more than two of 13 kinds.

2. The optical lens according to claim 1, wherein: the optical lens may be a bulk optical material or an optical lens as a substrate, or may be an optical lens with a single layer film or a multilayer film.

3. The optical lens according to claim 1, wherein: the lanthanide oxide hydrophobic optical film layer is preferably used in a thickness of 10-50nm, preferably 10-30nm, and most preferably 25 nm.

4. The optical lens according to claim 1, 2 or 3, characterized in that: the lanthanide oxide hydrophobic optical film has a film refractive index of 1.998 under a test wavelength of 1064 nm; the lanthanide oxide hydrophobic optical film plays a role in hydrophobic isolation and does not influence the optical performance of the original substrate.

5. The optical lens according to claim 1 or 2, characterized in that: the lanthanide oxide hydrophobic optical film layer is a film material with both hydrophobicity and high light transmittance, and is applied to an optical component with a surface hydrophobicity requirement, wherein the optical lens comprises a transmission lens, a reflection lens, a band-pass filter, a narrow-band filter or the surface of a light-transmitting layer of a solar cell.

6. A method for producing an optical lens according to any one of claims 1 to 5, characterized in that: preparing a lanthanide oxide hydrophobic optical film on the surface of the optical lens by adopting an atomic layer deposition coating process and equipment; when the preparation is carried out by adopting the atomic layer deposition coating process and equipment, the used precursor is Re_x(thmd)_yAnd ozone (with a volume concentration of 99.999% or more) or water; wherein Re is one or more of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, thmd is 2,2,6,6-tetramethyl-3, 5-heptaneedione, x is a positive integer of 1-10, and y is a positive integer of 1-10.

7. The method of claim 6, wherein: when the atomic layer deposition coating process and the equipment are adopted for preparation, the adopted preparation parameters are as follows: metal organic precursor Re_x(thmd)_yThe evaporation temperature is 100-130 ℃, the pulse duration is 0.5-2s, and the pulse interval is 1-3 s; the pulse duration of the ozone or the water is 0.5-2s, and the pulse interval is 1-3 s; high-purity nitrogen (with volume concentration more than or equal to 99.999%) is used as diluting and buffering gas; the growth temperature of the atomic layer deposition film is 200-500 ℃; the pressure in the reaction chamber is 1-6 mbar.

8. The production method according to claim 6 or 7, characterized in that: the preparation parameters preferably used are: the evaporation temperature of the metal organic matter precursor is 110 ℃, the pulse duration is 1s, and the pulse interval is 1.5 s; the pulse duration of ozone or water is 1.5s, and the pulse interval is 2 s; high-purity nitrogen (with volume concentration more than or equal to 99.999%) is used as a diluting and buffering gas; the growth temperature of the atomic layer deposition film is 220 ℃; the pressure in the reaction chamber is 2-3 mbar.

Technical Field

The invention relates to the field of coating, in particular to the field of lanthanide oxide hydrophobic optical films capable of ensuring dual properties of hydrophobicity and light transmittance.

Background

Hydrophobic and ultrahydrophobicWater coatings have become a focus of research in recent years. At first, people use the bionics principle to imitate the micro-nano structure of the lotus leaf surface to prepare the hydrophobic coating, the contact angle of water drops on the surface can reach 130 degrees to 160 degrees, and the hydrophobic coating has hydrophobic and even super-hydrophobic properties. Later, scientists developed low surface energy organic hydrophobic coatings such as polytetrafluoroethylene and the like. However, in some special fields, such as the surface of an optical component with hydrophobic requirement, the hydrophobic coating is required to be transparent in the working waveband, and can be applied to complex and severe environments, such as high temperature and high humidity, and the like, under special conditions. Amorphous materials of oxides in general, e.g. SiO₂，Al₂O₃And the like are hydrophilic materials and cannot meet the requirements. The lanthanide has high surface activity, so that the lanthanide is easy to adsorb hydrocarbon species in the atmosphere to further present a hydrophobic characteristic, can meet the requirements, and is applied to a hydrophobic coating on the surface of an optical component. Hydrophobic studies of lanthanide oxide ceramic bulk materials have been reported, but thin film materials are rarely reported, and are rarely reported particularly for application in optical films.

Disclosure of Invention

In order to solve the problems, the invention provides a lanthanide oxide hydrophobic optical film which is used for solving the requirement of surface hydrophobicity of certain optical components.

The hydrophobic coating of the invention is an amorphous transparent lanthanide oxide film with CeO₂,Pr₆O₁₁,Nd₂O₃,Sm₂O₃,Eu₂O₃,Gd₂O₃,Tb₄O₇,Dy₂O₃,Ho₂O₃,Er₂O₃,Tm₂O₃,Yb₂O₃And Lu₂O₃And 13 kinds in total.

The lanthanide oxide film of the present invention is prepared by an atomic layer deposition coating process.

The lanthanide oxide film has smooth surface and hydrophobic performance.

The light-transmitting wave band of the lanthanide oxide film can cover visible light and near infrared light wave bands; the refractive index can be matched with the existing optical film layer material.

The invention discloses a lanthanide oxide hydrophobic optical film prepared by an atomic layer deposition method, wherein lanthanide oxide is adopted as a film material, and the film does not affect the optical performance of an original lens when being coated on the surface of the substrate of the optical lens. The method can be applied to the surfaces of optical devices requiring hydrophobicity, such as anti-pollution optical transmission mirrors, reflectors, band-pass filters, narrow-band filters or the surfaces of solar cells. The lanthanide oxide film is prepared by adopting an atomic layer deposition coating process and equipment, and has the advantages of good hydrophobicity, excellent optical performance and wide application.

Drawings

FIG. 1: the atomic layer deposition film has a structure diagram, the thickness of the atomic layer deposition film is 10-30nm, the optimal thickness is 25nm, and the substrate can be bulk optical material or an optical lens, and can also be an optical lens with a single-layer film or a multi-layer film.

FIG. 2: atomic layer deposition of CeO₂The front and back hydrophobic properties of the film are compared, the film thickness is 25nm, the left picture is a picture of the residence of water drops on the surface of the original band-pass filter, and the static contact angle is 52 degrees; the right picture shows water drops in CeO plating₂The film had a static contact angle of 108 ° for the bandpass filter surface dwell photograph.

FIG. 3: the solid line is the transmitted light spectrum of the band-pass filter designed to work at 710-720nm, and the dotted line is CeO grown by atomic layer deposition and having a thickness of 25nm₂Transmission spectrum of bandpass filter of film. It can be seen that a layer of 25nm thick CeO is added₂The film has little effect on the optical performance of the original band-pass filter.

Detailed Description

In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example (c): coating a film on the surface of the light incidence side of the band-pass filter;

when the preparation is carried out by the atomic layer deposition coating process and equipment (model No9000, Ensure Nanotech), the adopted preparationThe preparation parameters are as follows: ce (thmd)₄The evaporation temperature of the precursor is 110 ℃, the pulse duration is 1s, and the pulse interval is 1.5 s; the pulse duration of the ozone is 1.5s, and the pulse interval is 2 s; high purity nitrogen (99.999%) is used as dilution and buffer gas; the growth temperature of the atomic layer deposition film is 220 ℃; the pressure in the reaction chamber is 2-3 mbar.

Prepared CeO₂The film is tested for surface wettability by a GBX-HTECH contact angle instrument, deionized water is used as a wetting liquid, the volume of a liquid drop is 3 mu l, and the static contact angle of the water drop on the film reaches 108 degrees.

Prepared CeO₂The film adopts a J.A.Woollam Co., Inc. ellipsometer to measure the thickness and the refractive index of the film, the scanning wavelength is 300-2100nm, the scanning step length is 10nm, and the incident angle is 55 degrees, 60 degrees and 65 degrees. The thickness was found to be 25nm and the refractive index was found to be [email protected] nm.

Prepared CeO₂The thin film was scanned with an atom probe microscope over a 5 × 5 μm scanning range, indicating that the surface roughness was well controlled and Rms was 2.3 nm.

The experimental data are as follows:

TABLE 1 bandpass Filter deposition of CeO₂The properties before and after the film were compared.

And (4) conclusion: as shown in the example, 25nm CeO was grown on the surface of the original band-pass filter₂After the film is formed, the surface hydrophobicity can be greatly improved (see table 1 and fig. 2), and the static contact angle of a water drop on the surface of the lens can be increased from 52 degrees to 108 degrees, and the water drop is changed from hydrophilicity to hydrophobicity. At the same time, the optical properties of the lens, such as surface roughness (see table 1) and transmittance (fig. 3), were not affected.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.