CN113960705B - Broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing and preparation method thereof - Google Patents
Broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001723 curing Methods 0.000 title description 20
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000007747 plating Methods 0.000 claims abstract description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 13
- 238000010849 ion bombardment Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000005566 electron beam evaporation Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000007602 hot air drying Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000006213 oxygenation reaction Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 65
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/0825—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
- G02B5/0833—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising inorganic materials only
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/10—Glass or silica
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0891—Ultraviolet [UV] mirrors
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Abstract
The invention belongs to the field of ultraviolet reflectors, and particularly relates to a broadband high-reflection all-dielectric film ultraviolet reflector for ultraviolet curing and a preparation method thereof, wherein the ultraviolet reflector comprises a glass substrate and a reflecting film; the reflecting film is made of high refractive index HfO 2 Film layer and low refractive index SiO 2 The film layers are sequentially and alternately deposited, and the deposited first layer and the deposited last layer are high-refractive index HfO 2 The film layer has the film system structure as follows: s| (HL) n H|A; wherein: s is a glass substrate; h is a high refractive index film layer; l is a low refractive index film layer; n is the number of membrane stack cycles; a is air. The preparation method comprises the steps of substrate cleaning, high-energy ion bombardment, multilayer film plating and aging treatment. The dielectric film layer has high density, stable spectral performance and long replacement period, and can reduce the scattering of the multilayer film, improve the utilization rate of ultraviolet light energy from short wave to long wave and ensure the ultraviolet curing quality.
Description
Technical Field
The invention belongs to the field of ultraviolet reflectors, and particularly relates to a broadband high-reflection full-dielectric film ultraviolet reflector for ultraviolet curing and a preparation method thereof.
Background
The ultraviolet curing technology has the advantages of high efficiency, energy saving, environmental protection, economy and the like, and is widely applied to various industries such as optical fiber cables, printed circuit boards, household electrical appliances, panel industries, automobile industries, printing and packaging and the like.
The ultraviolet reflector is an important key element of an ultraviolet curing system, and has the function of collecting and reflecting ultraviolet light emitted by a converging ultraviolet light source, so that the ultraviolet irradiation intensity of a working surface of the ultraviolet curing system is effectively increased, and the curing rate is further improved. Technical indexes such as reflectivity, reflection bandwidth, film layer environment adaptability and the like of the reflecting film on the surface of the reflecting mirror can directly influence the using effect of the ultraviolet reflecting mirror. The reflectivity of the reflecting film determines the illuminance of the reflected ultraviolet, and the higher the reflectivity is, the higher the illuminance of the ultraviolet reflected light is, and the faster the curing speed is; short wavelength uv light has a greater impact on the surface layer cure of the coating and insufficient short wave energy can cause the coating surface to be tacky. The long wave ultraviolet plays a dominant role in deep curing and adhesion of the coating, and poor adhesion can be caused by insufficient long wave energy. Therefore, the reflection bandwidth of the reflection film determines the width of the ultraviolet band wavelength range of the reflection light source, and directly influences the quality of the ultraviolet cured product; the reflector needs to continuously work under the environment of long-time high-temperature and high-intensity ultraviolet irradiation, and the firmness, the spectral stability and the like of the reflecting film determine the use and replacement period of the reflector; for photo-cured workpieces that are more sensitive to temperature effects or less resistant to temperature, the IR radiant heat carried by the uv light source is a serious hazard or even fatal. Therefore, the ultraviolet reflecting film needs to have high reflection in the ultraviolet band and high transmission in the near infrared band at the same time, so that the light splitting function is realized.
The current general ultraviolet reflecting film is an aluminum film and a dielectric film protecting layer, but the aluminum film has serious absorption and scattering and low reflectivity. The aluminum film totally reflects in the ultraviolet to infrared band, and near infrared light harmful to ultraviolet curing is also reflected to the working surface together, so that the curing effect is affected. The mechanical strength of the aluminum film is not high, the film layer is easy to damage during daily use and maintenance, the service cycle is relatively short, and the production cost is increased; the reflection band of the ultraviolet dielectric film reflection film which is commonly used at present mainly comprises a near ultraviolet wave band, and short-medium wave ultraviolet is not covered. At present, a preparation method of a dielectric film reflector capable of realizing broadband high reflection in the ultraviolet band from short waves to long waves is not available.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the broadband high-reflection all-dielectric film ultraviolet reflecting mirror for ultraviolet curing, which has the advantages of high density of a dielectric film layer, no falling of the film layer, stable spectral performance and long replacement period, can reduce the scattering of a multilayer film, improve the utilization rate of ultraviolet light energy from short waves to long waves, and ensure the ultraviolet curing quality, and the preparation method thereof.
In order to solve the technical problems, the invention is realized as follows:
the broadband high-reflection full-dielectric film ultraviolet reflector for ultraviolet curing comprises a glass substrate and a reflecting film; the reflecting film is made of high refractive index HfO 2 Film layer and low refractive index SiO 2 The film layers are sequentially and alternately deposited, and the deposited first layer and the deposited last layer are high-refractive index HfO 2 The film layer has the film system structure as follows: s| (HL) n H|A; wherein: s is a glass substrate; h is a high refractive index film layer; l is a low refractive index film layer; n is the number of membrane stack cycles; a is air.
Further, the HfO of the invention 2 Film layer and SiO 2 The film layer is a non-periodic multilayer film; the HfO 2 The physical thickness of the film layer is changed within the range of 14-55 nm; the SiO is 2 The physical thickness of (2) varies in the range of 30 to 130 nm.
Further, the glass substrate of the present invention is JGS1.
The preparation method of the broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing comprises the following steps:
(1) Cleaning a substrate: carrying out ultrasonic cleaning, slow-pull dehydration and hot air drying treatment on a substrate needing coating;
(2) High energy ion bombardment: placing the substrate treated in the step (1) into a vacuum chamber, heating to 220 ℃, wherein the vacuum degree is more than or equal to 3.0X10 -3 After Pa, starting an ion source, and bombarding substrate ions for 10 minutes;
(3) Plating a multilayer film: hfO using electron beam evaporation with ion assist 2 Film layer and SiO 2 Film layers are alternately evaporated layer by layer; control of HfO using quartz crystal monitoring 2 And Si (Si)O 2 Plating physical thickness of the two film materials;
(4) Aging: and (3) placing the plated reflecting mirror into a high-temperature oven, performing film aging treatment, baking at a high temperature of 400 ℃ for 2 hours, cooling to room temperature, and taking out the reflecting mirror.
Further, the HfO in the step (3) of the present invention 2 The film layer adopts HfO on the basis of electron beam evaporation and ion assistance 2 The plating is carried out by an enhanced oxidation method.
Further, the HfO of the invention 2 The enhanced oxidation method is to vapor deposit HfO on an electron gun 2 In the process, oxygen is additionally supplemented, and the oxygenation pressure is controlled to be 2.0X10 -2 Pa。
Further, in the step (1) of the invention, the substrate is ultrasonically cleaned by adopting neutral washing liquid, and the hot air drying temperature is 130 ℃.
Further, in the step (2) of the present invention, the ion source voltage is 250V, and the current is 5A; the ion source working gas is a mixed gas of oxygen and argon in a volume ratio of 4:1.
Further, in the step (3) of the present invention, the ion assist adopts a voltage of 200V, a current of 5A, and the ion source working gas is a mixed gas of oxygen and argon in a volume ratio of 1:1.
Further, in the aging treatment in the step (4), the time period for the temperature of the oven to rise from the room temperature to 350 ℃ is set to be 1 hour, and the temperature of the oven is kept constant for 2 hours after reaching 400 ℃.
The invention has the following beneficial effects:
compared with the existing aluminum film, the invention adopts the electron beam evaporation and ion auxiliary process, improves the density of the dielectric film layer, improves the interface of the film layer and reduces the scattering of the multilayer film. The ultraviolet reflecting mirror not only realizes high reflection and near infrared high transmission in the ultraviolet region, but also continuously works under the environment of long-time high-temperature and high-intensity ultraviolet irradiation, and the film layer has the advantages of no falling, stable spectral performance, convenience in maintenance, long replacement period and the like.
Compared with the existing ultraviolet dielectric film, the invention selects HfO 2 The plating process adopts HfO for high refractive index material 2 Enhanced oxidation process, effective reduction of HfO 2 The ultraviolet region of the film layer is absorbed, and high reflection in the wavelength range of 260-450nm is realized. Compared with the existing ultraviolet dielectric film, the reflection bandwidth is expanded by 70nm in the ultraviolet short wave direction. The requirements of the ultraviolet band broadband high reflection spectrum of the reflecting mirror are met, the energy utilization rate of the ultraviolet light source from short wave to long wave ultraviolet light is improved, and the ultraviolet curing quality is ensured.
Drawings
FIG. 1 is a schematic diagram of a broadband high reflection dielectric film reflector structure of the present invention;
FIG. 2 is a schematic diagram of a method for manufacturing a broadband high reflection dielectric film reflector according to the present invention;
FIG. 3 is a graph showing the measured reflectance spectrum of the broadband high-reflectance dielectric film reflector of the present invention.
In the figure: 1. a glass substrate; 2. HfO (HfO) 2 A film layer; 3. SiO (SiO) 2 And (3) a film layer.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
Thus, the following detailed description of the embodiments of the invention, as provided, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
As shown in the figure, the broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing comprises a glass substrate and a reflecting film; the reflecting film is made of high refractive index HfO 2 Film layer and low refractive index SiO 2 The film layers are sequentially and alternately deposited, and the deposited first layer and the deposited last layer are high-refractive index HfO 2 The film layer has the film system structure as follows: s| (HL) n H|A; wherein: s is a glass substrate; h is a high refractive index film layer; l isA low refractive index film layer; n is the number of membrane stack cycles; a is air.
HfO of the present invention 2 Film layer and SiO 2 The film layer is a non-periodic multilayer film; the HfO 2 The physical thickness of the film layer is changed within the range of 14-55 nm; the SiO is 2 The physical thickness of (2) varies in the range of 30 to 130 nm. The glass substrate of the present invention is JGS1.
The preparation method of the broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing comprises the following steps:
(1) Cleaning a substrate: carrying out ultrasonic cleaning, slow-pull dehydration and hot air drying treatment on a substrate needing coating;
(2) High energy ion bombardment: placing the substrate treated in the step (1) into a vacuum chamber, heating to 220 ℃, wherein the vacuum degree is more than or equal to 3.0X10 -3 After Pa, starting an ion source, and bombarding substrate ions for 10 minutes;
(3) Plating a multilayer film: hfO using electron beam evaporation with ion assist 2 Film layer and SiO 2 Film layers are alternately evaporated layer by layer; control of HfO using quartz crystal monitoring 2 And SiO 2 Plating physical thickness of the two film materials;
(4) Aging: and (3) placing the plated reflecting mirror into a high-temperature oven, performing film aging treatment, baking at a high temperature of 400 ℃ for 2 hours, cooling to room temperature, and taking out the reflecting mirror.
The HfO in the step (3) of the present invention 2 The film layer adopts HfO on the basis of electron beam evaporation and ion assistance 2 The plating is carried out by an enhanced oxidation method.
HfO of the present invention 2 The enhanced oxidation method is to vapor deposit HfO on an electron gun 2 In the process, oxygen is additionally supplemented, and the oxygenation pressure is controlled to be 2.0X10 -2 Pa. In the step (1), the neutral washing liquid is adopted to carry out ultrasonic washing on the substrate, and the drying temperature of hot air is 130 ℃. In the step (2), the voltage of the ion source is 250V and the current is 5A; the ion source working gas is a mixed gas of oxygen and argon in a volume ratio of 4:1. The ion assistance in the step (3) of the invention adopts the voltage of 200V and the current of 5A,the ion source working gas is a mixed gas of oxygen and argon in a volume ratio of 1:1. In the aging treatment in the step (4), the time length for the temperature of the oven to rise from the room temperature to 350 ℃ is set to be 1 hour, and the temperature of the oven is kept for 2 hours after reaching 400 ℃.
In a specific design, the broadband high-reflection full-dielectric film ultraviolet reflector for ultraviolet curing comprises a JGS1 glass substrate 1 and a reflecting film, wherein the reflecting film consists of a high-refractive index HfO 2 Film layer 2 and low refractive index SiO 2 The film layers 3 are sequentially and alternately deposited, and the deposited first layer and the deposited last layer are high refractive index HfO 2 And a film layer 2. Wherein HfO is 2 Film layer 2 and SiO 2 The film layer 3 is an aperiodic multilayered film with optimized design, hfO 2 The physical thickness of the film layer 2 varies in the range of 14-55nm, siO 2 The physical thickness of the film layer 3 varies in the range of 30 to 130 nm. The number of the two high-low refractive index material film layers is 39-42.
The preparation method of the broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing comprises the following steps:
(1) Cleaning a substrate: placing a substrate to be coated in neutral washing liquid for ultrasonic cleaning, slowly drawing and dehydrating, and finally placing in a 130-DEG drying box for hot air drying treatment;
(2) High energy ion bombardment: placing the cleaned substrate into a vacuum chamber, when the heating temperature of the vacuum chamber reaches 220 ℃, the vacuum degree is better than 3.0X10 -3 And after Pa. Starting an ion source, wherein the working gas of the ion source is mixed gas of oxygen and argon in a volume ratio of 1:1, the voltage of the ion source is 250V, the current is 5A, bombarding clean substrate ions for 10 minutes, removing impurities adsorbed on the surface of the substrate, improving the surface quality and improving the adhesion of a plating film layer and the substrate.
(3) Plating a multilayer film: after ion bombardment is completed, multi-layer film plating is performed. Due to HfO 2 And SiO 2 The film layer is an aperiodic multilayer film with optimized design, so that the physical thickness of plating of two film materials is controlled by using a quartz crystal monitoring mode. HfO (HfO) 2 And SiO 2 The two materials are evaporated layer by adopting electron beam evaporation and ion auxiliary process, and the ion auxiliary voltage is applied200V, 5A current and 1:1 mixed gas of oxygen and argon by volume ratio. And an electron beam evaporation and ion auxiliary process is adopted, so that the density of the dielectric film layer is improved, and the scattering loss caused by film layer loosening is effectively reduced. The stress between the film layers and the substrate are matched, and the mechanical strength and the optical performance of the film layer plated by the process are stable. Solves the problems of film firmness and spectrum stability of the ultraviolet reflecting film in the environment of long-time high-temperature and high-intensity ultraviolet irradiation; wherein the HfO 2 The film layer adopts HfO based on electron beam evaporation and ion-assisted process 2 Plating by enhanced oxidation method, specifically by vapor plating HfO in electron gun 2 In the process, oxygen is additionally supplemented to provide sufficient oxygen atoms to ensure HfO 2 The film layer can be fully oxidized, thereby effectively reducing HfO 2 And (5) absorbing the film layer. The oxygenation pressure of the pressure gauge is controlled to be 2.0x10 -2 About Pa. The plating of the broadband high-reflection full-medium ultraviolet reflecting film is realized, and the plating spectrum curve is shown in figure 3.
(4) Aging: and (5) placing the plated reflecting mirror into a high-temperature oven for ageing treatment of the film. Setting the temperature rising process of the aging treatment, setting the time length of the oven from room temperature to 400 ℃ to be 1 hour, and keeping the oven at the constant temperature for 2 hours after the temperature of the oven reaches 400 ℃. And taking out the reflector after the temperature of the oven is reduced to room temperature. The high-temperature aging treatment can change the crystal form of the film layer microscopically, eliminate the internal defects of the film layer, reduce the stress of the film layer and improve the spectral stability of the ultraviolet reflecting mirror of the broadband high-reflection dielectric film.
The foregoing is merely illustrative and explanatory of the invention as it is claimed, as modifications and additions may be made to, or similar to, the particular embodiments described, without the benefit of the inventors' inventive effort, and as alternatives to those of skill in the art, which remain within the scope of this patent.
Claims (5)
1. The preparation method of the broadband high-reflection full-dielectric film ultraviolet reflecting mirror for ultraviolet curing is characterized by comprising the following steps of:
(1) Cleaning a substrate: carrying out ultrasonic cleaning, slow-pull dehydration and hot air drying treatment on a substrate needing coating;
(2) High energy ion bombardment: placing the substrate treated in the step (1) into a vacuum chamber, heating to 220 ℃, wherein the vacuum degree is more than or equal to 3.0X10 -3 After Pa, starting an ion source, and bombarding substrate ions for 10 minutes;
(3) Plating a multilayer film: hfO using electron beam evaporation with ion assist 2 Film layer and SiO 2 Film layers are alternately evaporated layer by layer; control of HfO using quartz crystal monitoring 2 And SiO 2 Plating physical thickness of the two film materials; the HfO 2 The film layer adopts HfO on the basis of electron beam evaporation and ion assistance 2 Plating by an enhanced oxidation method; the HfO 2 The enhanced oxidation method is to vapor deposit HfO on an electron gun 2 In the process, oxygen is additionally supplemented, and the oxygenation pressure is controlled to be 2.0X10 -2 Pa；
(4) Aging: placing the plated reflecting mirror into a high-temperature oven, performing film aging treatment, baking at 400 ℃ for 2 hours, cooling to room temperature, and taking out the reflecting mirror;
the broadband high-reflection full-dielectric film ultraviolet reflector for ultraviolet curing comprises a glass substrate and a reflecting film; the reflecting film is made of high refractive index HfO 2 Film layer and low refractive index SiO 2 The film layers are sequentially and alternately deposited, and the deposited first layer and the deposited last layer are high-refractive index HfO 2 The film layer has the film system structure as follows: s| (HL) n H|A; wherein: s is a glass substrate; h is a high refractive index film layer; l is a low refractive index film layer; n is the number of membrane stack cycles; a is air; the HfO 2 Film layer and SiO 2 The film layer is a non-periodic multilayer film; the HfO 2 The physical thickness of the film layer is changed within the range of 14-55 nm; the SiO is 2 The physical thickness of (2) varies in the range of 30-130 nm; the glass substrate is JGS1.
2. The method for preparing the broadband high-reflection all-dielectric film ultraviolet reflecting mirror for ultraviolet curing according to claim 1, which is characterized in that: in the step (1), the substrate is ultrasonically cleaned by adopting neutral washing liquid, and the hot air drying temperature is 130 ℃.
3. The method for preparing the broadband high-reflection all-dielectric film ultraviolet reflecting mirror for ultraviolet curing according to claim 2, which is characterized in that: the ion source voltage in the step (2) is 250V, and the current is 5A; the ion source working gas is a mixed gas of oxygen and argon in a volume ratio of 4:1.
4. The method for preparing the broadband high-reflection all-dielectric film ultraviolet reflecting mirror for ultraviolet curing according to claim 3, wherein the method is characterized in that: in the step (3), the ion assistance adopts a mixed gas of oxygen and argon with the voltage of 200V and the current of 5A and the volume ratio of the ion source working gas of 1:1.
5. The method for preparing the broadband high-reflection all-dielectric film ultraviolet reflecting mirror for ultraviolet curing according to claim 4, wherein the method is characterized in that: in the aging treatment of the step (4), the time period for the temperature of the oven to rise from the room temperature to 350 ℃ is set to be 1 hour, and the temperature of the oven is kept constant for 2 hours after reaching 400 ℃.
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