CN115016052B - Laser omnidirectional reflecting film and application thereof in wearable laser protection field - Google Patents

Laser omnidirectional reflecting film and application thereof in wearable laser protection field Download PDF

Info

Publication number
CN115016052B
CN115016052B CN202210752787.1A CN202210752787A CN115016052B CN 115016052 B CN115016052 B CN 115016052B CN 202210752787 A CN202210752787 A CN 202210752787A CN 115016052 B CN115016052 B CN 115016052B
Authority
CN
China
Prior art keywords
layer
laser
omni
omnidirectional
refractive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210752787.1A
Other languages
Chinese (zh)
Other versions
CN115016052A (en
Inventor
陶光明
刘超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Baijun City Software Park Development Co ltd
Huazhong University of Science and Technology
Original Assignee
Wuhan Baijun City Software Park Development Co ltd
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Baijun City Software Park Development Co ltd, Huazhong University of Science and Technology filed Critical Wuhan Baijun City Software Park Development Co ltd
Priority to CN202210752787.1A priority Critical patent/CN115016052B/en
Publication of CN115016052A publication Critical patent/CN115016052A/en
Application granted granted Critical
Publication of CN115016052B publication Critical patent/CN115016052B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • G02B5/0841—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
    • 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
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • C23C14/0623—Sulfides, selenides or tellurides
    • C23C14/0629—Sulfides, selenides or tellurides of zinc, cadmium or mercury
    • 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
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • 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
    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C23C16/306—AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Landscapes

  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a laser omnidirectional reflecting film and a wearable CO (carbon monoxide) thereof in a wave band of 9.3-11 mu m 2 Application in the field of laser protection, the CO 2 The laser omnidirectional reflective film includes: a base layer; an omni-directional reflecting layer located on one side of the substrate layer. The omnidirectional reflecting layer comprises at least two refractive layers with different refractive indexes, and the omnidirectional reflecting layer formed by alternately arranging the refractive layers with different refractive indexes can reflect light omnidirectionally. The omnidirectional reflecting film has flexibility and can realize omnidirectional reflection of 9.3-11 mu m laser, and is applied to wearable CO 2 Laser protection field.

Description

Laser omnidirectional reflecting film and application thereof in wearable laser protection field
Technical Field
The invention relates to the technical field of laser reflection films, in particular to a laser omnidirectional reflection film and application thereof in the field of wearable laser protection.
Background
Because of the excellent monochromaticity, coherence, directivity and high energy density, lasers are widely used in the fields of industrial production, scientific and technological detection, medical health, national defense construction and the like. Compared with the traditional contact type industrial processing technology, the laser processing technology has the advantages of high efficiency, safety, no contact, no abrasion, easy control and processing and the like. In particular in the field of minimally invasive surgery, the laser scalpel technology is gradually replacing the traditional operation modes such as a metal scalpel, an electrotome, an ultrasonic scalpel and the like, and is an efficient, non-contact, non-infection and low-damage surgical operation mode. CO 2 The laser has special working wave band (9.3-11 μm) and super-high adjustable laser intensity, compared with other laser sources, can efficiently and accurately process biological tissues, steel, plastics and other materials, and is the first choice laser source in the fields of laser industrial processing and minimally invasive medical treatment.
However, high energy CO 2 The laser is used for a large amount ofThe use of the optical instrument poses a threat to the exposed human body. In case of accident, CO with power higher than 5W 2 Laser irradiation on normal human cornea or skin will result in vision loss and serious burns. In addition, high energy CO 2 The laser light impinges on the optical element and causes damage to the optical properties of the element. Currently common CO 2 The laser irradiation protection device is usually a reflecting mirror based on a rigid glass substrate, and has the problems of low power threshold, low reflectivity and poor flexibility, and complicated and huge rigid devices increase the operation burden and accidental risk of personnel related to laser processing or surgery, so that the CO can not be realized 2 The wearable body-fitting protection of laser. For example, chinese patent publication No. CN114002763a discloses a middle-far infrared and laser compatible stealth film and its design scheme, which uses a one-dimensional photonic crystal structure to have ultra-wide reflection band by superposition of photonic crystals with two forbidden bands in different wavelength ranges, but the substrate material is glass, the mechanical properties of the reflection film are poor, and the film only satisfies the condition that the incident light is perpendicular to the film surface, and does not realize omnidirectional reflection. The Chinese patent publication No. CN113589415A discloses an ultra-wideband laser reflecting film and a preparation method thereof, wherein the ultra-wideband reflection is realized by plating a film system on one side surface of a glass substrate or a silicon wafer through the design of the film system and the improvement of the process, but the existence of a metal film limits the reflection to occur in a near infrared band, and CO cannot be reflected 2 The laser, the substrate is glass or silicon chip simultaneously, and there is the metal film, and whole reflection film pliability is poor, is difficult to realize wearable laser protection. The Chinese patent publication No. CN104561908A discloses a preparation method of multiband high-reflection film, in which quartz glass is used As substrate, and the high-low refractive index materials are ZnS and As respectively 2 O 3 The single-sided reflectivity of the film layer is achieved at the same time in the near infrared and the mid infrared>95%, the high reflectivity needs more cycle numbers (more than 15 cycles), the coating time is long, the large-batch preparation is difficult, the flexibility of the film layer is poor, the omnidirectional reflection cannot be realized, and the wearable laser protection is difficult to realize. Chinese patent publication No. CN213581640U discloses a laser protective lens and a pair of laser protective glasses, wherein the light absorption layer is arranged to transmit light of a corresponding laser bandThe rate is reduced to less than or equal to 0.5%, the protection effect can be better, the eyes are prevented from being damaged, but the two stiffening layers cause the device to lack flexibility.
The chalcogenide glass is a novel photonic device matrix material, has excellent mid-far infrared transmission performance (the transmission range varies from 0.5 mu m to 25 mu m according to different compositions), extremely high linear refractive index (2.0-3.5) and extremely high nonlinear refractive index (2 Xl 0) -18 ～20×l0 -18 m 2 W is 100-1000 times of quartz material), smaller two-photon absorption coefficient alpha 2 (especially, the optical band gap of the chalcogenide glass is about 2.5eV, which is far greater than the two-photon absorption energy corresponding to the optical communication wavelength, the ultra-fast nonlinear response (response time is less than 200 fs) and other unique optical properties, the optical properties of the material can be regulated and controlled by glass components, and the preparation process (photoetching, etching and the like) compatible with the silicon-based semiconductor (CMOS) manufacturing can be adopted.) therefore, the research and development of a unit or an integrated photon function device based on the chalcogenide glass optical material are greatly focused in recent years, and the chalcogenide glass optical material is one of the most active front-end fields for the research and development of the international photon device at present.
Chalcogenide glass-based wearable CO capable of simultaneously realizing high flexibility, high reflectivity and omnidirectional reflection 2 The laser protective garment will be CO 2 New choices of protective equipment in laser industrial processing and minimally invasive medical. CO 2 The problems of high rigidity, low reflectivity, poor flexibility and inconvenient wearing of the laser protection equipment are solved by the laser omnidirectional reflecting film as a new generation of high-efficiency, high-precision and low-cost processing mode.
Disclosure of Invention
In view of the above, the invention provides a laser omnidirectional reflective film and application thereof in the field of wearable laser protection, solving the problem of the existing CO 2 The problems of insufficient flexibility of a transmission medium, high rigidity of the protective equipment, low reflectivity, insufficient flexibility and inconvenient wearing in the laser protective equipment.
To achieve the above object, in a first aspect, the present invention provides a laser omni-directional reflecting film comprising:
a base layer;
the omnidirectional reflecting layer is positioned on one side of the basal layer, and comprises at least two refractive layers with different refractive indexes, wherein the refractive layers with different refractive indexes are alternately arranged in sequence.
Preferably, the omnidirectional reflecting film further comprises a protective layer, and the protective layer is located on one side of the omnidirectional reflecting layer, which is far away from the substrate layer.
Preferably, the refractive index difference between the refractive layer with the highest refractive index and the refractive layer with the lowest refractive index of the omnidirectional laser reflecting film is 0.1-2.
Preferably, the material of the refraction layer of the omnidirectional laser reflection film is chalcogenide glass; the number of the refraction layers is 4-30 in turn.
Preferably, the sulfur-based glass comprises As-S, as-Se, as-Sb, as-Te, sb-S, sb-Se, ge-Se-Te, ge-As-Se-Te, ge-As-Se, ge-Sb-Se, ge-S, ga-S, ge-Se, ga-Se, cd-Se, ge-Ga-Te, ge-S-I, ge-S-Sb, ge-Te-Ag, ge-Ga-Te-Cu, ge-Se-Sn, geSe 2 -Ga 2 Se 3 -KI、Ge-Te-BiI 3 At least one of Ge-Te-AgI, ge-Te-CuI and Ge-Te-Ag.
Preferably, the material of the base layer of the omnidirectional laser reflecting film is thermoplastic polymer or ultraviolet curing resin, and the thickness of the base layer is 10-1000 mu m;
and/or the thermoplastic polymer comprises at least one of carbonate polymer, sulfone polymer, etherimide polymer, acrylic polymer, cycloolefin copolymer, polystyrene, polycarbonate, polyethylene, polypropylene, ABS and fluorine-containing polymer.
Preferably, the thickness of the protective layer is 0.5-100 μm, the protective layer is used for protecting the omnidirectional reflecting layer, and the material of the protective layer is polymer, metal oxide or ultraviolet curing resin;
and/or the polymer comprises at least one of carbonate polymer, sulfone polymer, etherimide polymer, acrylic polymer, cycloolefin copolymer, polystyrene, polycarbonate, polyethylene, polypropylene, ABS and fluorine-containing polymer;
and/or the thickness of the omnidirectional reflecting layer is 5-100 mu m, and the thicknesses of the refractive layers with different refractive indexes are all 0.7-2 mu m.
In a second aspect, the invention also provides a preparation method of the omnidirectional reflecting film for laser, which comprises the following steps:
providing at least two materials having different refractive indices;
sequentially and alternately preparing materials with different refractive indexes on the substrate layer to form an omnidirectional reflecting layer;
if the laser omni-directional reflecting film further comprises a protective layer, the preparation method of the laser omni-directional reflecting film further comprises the following steps:
and preparing a protective layer on one side of the omni-directional reflecting layer away from the basal layer.
Preferably, the preparation method of the laser omni-directional reflecting film adopts any one of a magnetron sputtering method, a chemical vapor deposition method, a sol-gel method, a pulse laser deposition method and a thermal evaporation method to prepare the omni-directional reflecting layer;
the protective layer is prepared by any one of spin coating, knife coating, spray coating, and roll coating.
In a third aspect, the invention also provides a laser omnidirectional reflecting film or the laser omnidirectional reflecting film prepared by the preparation method, which can realize omnidirectional reflection of 9.3-11 μm laser and is applied to wearable CO 2 Laser protection field.
The laser omnidirectional reflecting film of the invention and the wearable CO thereof in the wave band of 9.3-11 mu m 2 The application in the laser protection field has the following beneficial effects compared with the prior art:
1. the omnidirectional reflecting film of the invention comprises at least two refractive layers with different refractive indexes, the omnidirectional reflecting layers formed by alternately arranging the refractive layers with different refractive indexes can reflect light omnidirectionally, and the omnidirectional reflecting film can reflect light omnidirectionally when being used for CO 2 Laser with high reflectivityWhen in use, the reflective film has high flexibility and omnidirectional reflectivity and can be applied to wearable CO with the wave band of 9.3-11 mu m 2 The field of laser protection;
2. according to the laser omnidirectional reflecting film, the substrate layer adopts the thermoplastic polymer or the ultraviolet curing resin, has good elasticity, flexibility and high impact resistance, has good flexibility and can provide mechanical support for the whole omnidirectional reflecting film;
3. the preparation method of the laser omnidirectional reflecting film has simple process, can efficiently prepare the film in large batch, can adjust the laser protection wave band by regulating and controlling the thickness of each layer, and can be used in the field of wearable laser protection in large scale.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
Fig. 1 is a schematic structural diagram of a laser omni-directional reflective film according to one embodiment of the present invention;
fig. 2 is an energy band characteristic diagram of the omni-directional reflecting film of laser light prepared in example 1 of the present invention;
fig. 3 is a reflection characteristic diagram of the omni-directional reflecting film of laser light prepared in example 1 of the present invention;
fig. 4 is a cross-sectional SEM image of the omni-directional reflecting layer of laser light prepared in example 1 of the present invention;
fig. 5 is a physical diagram of the omni-directional reflecting film of the laser according to the embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, 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 those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present invention, it should be understood that, for the convenience of description and simplification of the description, it is not necessary to indicate or imply that the apparatus or elements referred to have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the invention, it is that the relation of orientation or position indicated as "upper" is based on the orientation or position relation shown in the drawings, or the orientation or position relation that is conventionally put when the inventive product is used, or the orientation or position relation that is conventionally understood by those skilled in the art.
Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The embodiment of the application provides a laser omnidirectional reflecting film, as shown in fig. 1, including:
a base layer 1;
the omnidirectional reflecting layer 2 is positioned on one side of the basal layer, and comprises at least two refractive layers with different refractive indexes, wherein the refractive layers with different refractive indexes are alternately arranged in sequence.
It should be noted that, the omnidirectional reflecting film of the laser has flexibility and can realize the omnidirectional reflection of 9.3-11 μm laser, and the omnidirectional reflecting film in the application refers to: the reflection of the laser with higher reflectivity can be realized within the range of 0-90 degrees of the incident angle of the laser. Specifically, the CO 2 The laser omnidirectional reflecting film comprises a substrate layer 1 and an omnidirectional reflecting layer 2, wherein the omnidirectional reflecting layer 2 comprises at least two refractive layers with different refractive indexes, for example, 2, 3, 4, 5 and … … refractive layers with different refractive indexes are arranged alternately in sequence; specifically, taking three refractive layers with different refractive indexes as examples, the three refractive layers with different refractive indexes are respectively a first refractive layer, a second refractive layer and a third refractive layer, and the alternate arrangement means that: the refractive indexes of any two adjacent refractive layers are different, for example, specific alternate arrangements may be a first refractive layer, a second refractive layer, a third refractive layer, and the like. CO of the present application 2 The laser omni-directional reflecting film has omni-directional reflecting layer comprising at least two kinds of refractive layers with different refractive indexes, and the omni-directional reflecting layer comprising alternately arranged refractive layers with different refractive indexes can reflect light in omni-direction to CO 2 The reflective film has high flexibility and omnidirectional reflectivity at the same time of high reflectivity of laser, and is suitable for wearable CO 2 The laser protection production and scientific research fields have wide application values.
In some embodiments, a protective layer 3 is further included, the protective layer 3 being located on the side of the omni-directional reflective layer 2 remote from the substrate layer 1. The protective layer 3 may not only play a role in protecting the omni-directional reflecting layer 2, preventing the omni-directional reflecting layer 2 from being broken and oxidized, but may also play a role in providing mechanical support for the entire omni-directional reflecting film.
In some embodiments, the refractive index difference between the refractive layer of the highest refractive index and the refractive layer of the lowest refractive index is 0.1 to 2.
In some embodiments, the omni-directional reflective layer comprises two refractive layers having different refractive indices, and in particular, the material of the refractive layers is chalcogenide glass. It will be appreciated that any chalcogenide glass material having two different refractive indices is possible. For example, the chalcogenide glass material includes As-S, as-Se, as-Sb, as-Te, sb-S, sb-Se, ge-Se-Te, ge-As-Se-Te, ge-As-Se, ge-Sb-Se, ge-S, ga-S, ge-Se, ga-Se, cd-Se, ge-Ga-Te, ge-S-I, ge-S-Sb, ge-Te-Ag, ge-Ga-Te-Cu, ge-Se-Sn, geSe 2 -Ga 2 Se 3 -KI、Ge-Te-BiI 3 At least one of Ge-Te-AgI, ge-Te-CuI and Ge-Te-Ag; it is apparent that the chalcogenide glass material may be a blend of any combination of the chalcogenide glasses described above.
Specifically, the chalcogenide glass material having the high refractive index refractive layer 21 includes Ge 20 As 20 Se 18 Te 42 、Te 20 As 30 Se 50 、As 2 Se 3 Any one of them; the chalcogenide glass material having the low refractive index refractive layer 22 includes As 2 S 3 、As 3 S 7 Any one of them.
Specifically, in the above embodiment, ge 20 As 20 Se 18 Te 42 With As 2 S 3 Is 0.698 and Te 20 As 30 Se 50 With As 3 S 7 Is 0.68 and As 2 Se 3 With As 2 S 3 Is 0.41; the refractive layers with high refractive index and the refractive layers with low refractive index are alternately arranged in sequence, the number of alternating layers can be determined according to practical situations, and for example, the number of alternating layers can be 4-30, specifically, the number of alternating layers is 4, 5, 6, 7, 8, … …, and the like.
In some embodiments, the material of the base layer 1 is a thermoplastic polymer or an ultraviolet curable resin, and the thickness of the base layer is 10 to 1000 μm. The substrate layer 1 adopts thermoplastic polymer or ultraviolet curing resin, has good stretching property and flexibility, and the substrate layer 1 not only has good flexibility, but also can provide mechanical support for the whole omnidirectional reflecting film. Specifically, the thermoplastic polymer adopted by the substrate layer 1 comprises at least one of carbonate polymers, sulfone polymers, etherimide polymers, acrylic polymers, cycloolefin copolymers, polystyrene, polycarbonate, polyethylene, polypropylene, ABS and fluorine-containing polymers; obviously, the thermoplastic polymer may be a blend of any combination of the above polymers.
In some embodiments, the material of the protective layer 3 is a metal, a metal oxide, a polymer, or an ultraviolet curable resin; specifically, the material of the protective layer 3 is thermoplastic polymer or ultraviolet curing resin with low absorption and high permeability in the wave band of 9.3-11 mu m, so that the protective layer is prevented from being damaged by high-energy laser; the thickness of the protective layer 3 is 0.5 to 100 μm. Specifically, the thermoplastic polymer used for the protective layer 3 includes a carbonate polymer (such as polycarbonate PC), a sulfone polymer (such as polyethersulfone PES, polyphenylenesulfone resin PPSU), an etherimide polymer (such as polyetherimide PEI), an acrylate polymer (such as polymethyl methacrylate PMMA, styrene dimethyl methacrylate copolymer SMMA), a Cyclic Olefin Copolymer (COC), polystyrene, polycarbonate, polyethylene, polypropylene, ABS, a fluoropolymer, or a blend of any one of the above, and the above polymers are used to provide the protective layer 3 with good elasticity and flexibility.
Specifically, in some embodiments, the material of the base layer 1 is PPSU or PEI, and the thickness is 10-200 μm; the protective layer 3 is PMMA or PEI, and has a thickness of 1-20 μm.
In some embodiments, the total reflection layer 2 has a thickness of 5 to 100 μm, and the refractive layers of different refractive indices each have a thickness of 0.2 to 10 μm.
Specifically, in the above embodiment, the thicknesses of the base layer 1, the total reflection layer 2, the protective layer 3, and the refractive layers of different refractive indices are defined so as to satisfy the requirement of CO 2 The laser is used in the 9.3-11 μm band.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the omnidirectional reflecting film, which comprises the following steps:
s1, providing at least two materials with different refractive indexes;
s2, materials with different refractive indexes are sequentially and alternately prepared on the substrate layer to form an omnidirectional reflecting layer 2;
if the laser omni-directional reflecting film further comprises a protective layer 3, the preparation method of the laser omni-directional reflecting film further comprises the following steps:
and S3, preparing a protective layer 3 on one side of the omni-directional reflecting layer, which is far away from the basal layer.
Specifically, the omni-directional reflecting layer 2 is prepared by any one of a magnetron sputtering method, a chemical vapor deposition method, a sol-gel method, a pulse laser deposition method and a thermal evaporation method;
the protective layer 3 is prepared by any one of spin coating, knife coating, spray coating, and roll coating.
Specifically, materials with different refractive indexes can be sequentially and alternately evaporated onto the substrate layer 1 by adopting a thermal evaporation method to form the omnidirectional reflecting layer 2; if the material of the protective layer 3 is thermoplastic polymer, the laser total reflection film is prepared by scraping and coating the thermoplastic polymer solution on one side of the omnidirectional reflection layer 2.
Specifically, adding a thermoplastic polymer to an organic solvent, such as Dimethylformamide (DMF), to form a thermoplastic polymer solution; and then scraping the thermoplastic polymer solution on the total reflection layer, and then placing the total reflection layer in an oven for curing, namely preparing the protective layer on the omnidirectional reflection layer.
In particular, when the material of the refractive layer having a high refractive index is Ge 20 As 20 Se 18 Te 42 The material of the low refractive index refraction layer is As 2 S 3 The material of the basal layer is PPSU; at this time, the preparation method of the omni-directional reflecting layer specifically includes: chalcogenide glass Ge by agate mortar 20 As 20 Se 18 Te 42 And As 2 S 3 Grinding into particles, and mixing Ge 20 As 20 Se 18 Te 42 And As 2 S 3 Filling the material into a crucible of a coating machine, simultaneously selecting an evaporation cover matched with the caliber of the crucible, and attaching a required PPSU polymer on an evaporation rollerA substrate film, sealing the whole film coating chamber, and loading Ge 20 As 20 Se 18 Te 42 And As 2 S 3 The glass is alternately and evenly evaporated on the PPSU polymer film to obtain the PPSU-As 2 S 3 -Ge 20 As 20 Se 18 Te 42 -As 2 S 3 -Ge 20 As 20 Se 18 Te 42 -…-Ge 20 As 20 Se 18 Te 42 The total reflection layer is prepared on the substrate layer.
When the material of the refractive layer with high refractive index is Te 20 As 30 Se 50 Or As 2 Se 3 When the material of the refractive layer with low refractive index is As 30 S 70 Or As 40 S 60 In the process, the preparation of the total reflection layer is carried out by adopting the evaporation plating method.
Wherein the chalcogenide glass Ge 20 As 20 Se 18 Te 42 、Te 20 As 30 Se 50 、As 2 Se 3 、As 30 S 70 、As 40 S 60 The preparation method comprises the steps of placing the glass into a clean quartz glass tube according to the weight ratio of simple substances in required chalcogenide glass components in a vacuum glove box, carrying out high Wen Yaobai homogenization synthesis and quenching annealing after vacuum treatment to obtain corresponding chalcogenide glass; for example chalcogenide glass Ge 20 As 20 Se 18 Te 42 The preparation method of (2) comprises the following steps: placing Ge simple substance, as simple substance, se simple substance and Te simple substance into quartz glass tube according to the weight ratio of simple substance, 100gGe 20 As 20 Se 18 Te 42 14.93g of Ge simple substance, 15.40g of As simple substance, 14.60g of Se simple substance and 58.13g of Te simple substance in chalcogenide glass, and carrying out high Wen Yaobai homogeneous synthesis, quenching and annealing after vacuum treatment to obtain the Ge 20 As 20 Se 18 Te 42 A chalcogenide glass.
The preparation method of the laser omnidirectional reflecting film has simple process, can prepare efficiently and in large batch, and can adjust the laser protection wave band by adjusting and controlling the thickness of each layer.
The laser omnidirectional reflecting film provided by the application has flexibility, can realize omnidirectional reflection of 9.3-11 mu m laser and is applied to wearable CO 2 Laser protection field.
The following further describes the laser omnidirectional reflective film of the present application with specific examples, and the preparation method and application thereof. This section further illustrates the summary of the invention in connection with specific embodiments, but should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The application provides a laser omnidirectional reflecting film, specifically, this laser omnidirectional reflecting film includes:
a base layer;
the omnidirectional reflecting layer is positioned on one side of the basal layer and comprises two refractive layers with different refractive indexes, and the refractive layers with different refractive indexes are alternately arranged in sequence;
the protective layer is positioned on one side of the omnidirectional reflecting layer, which is far away from the basal layer;
wherein the base layer is made of PPSU, and the thickness of the base layer is 45 mu m;
the material of the protective layer is PMMA, and the thickness of the protective layer is 5 mu m;
the omni-directional reflecting layer comprises two refractive layers with different refractive indexes, and the material of the refractive layer with high refractive index is Ge 20 As 20 Se 18 Te 42 The material of the refractive layer with low refractive index is As 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the high refractive index refractive layer is 0.864 mu m, the thickness of the low refractive index refractive layer is 1.118 mu m, the number of alternating layers of the high refractive index refractive layer and the low refractive index refractive layer is 4, and the thickness of the omnidirectional reflecting layer is 15.856 mu m;
the preparation method of the laser omnidirectional reflecting film comprises the following steps:
s1, preparing an omnidirectional reflecting layer on a PPSU polymer substrate film: chalcogenide glass Ge by agate mortar 20 As 20 Se 18 Te 42 And As 2 S 3 Grinding into particles, and mixing Ge 20 As 20 Se 18 Te 42 And As 2 S 3 Filling the material into a crucible of a coating machine, selecting an evaporation cover matched with the caliber of the crucible, attaching a PPSU polymer substrate film on an evaporation roller, sealing the whole coating chamber, and loading Ge 20 As 20 Se 18 Te 42 And As 2 S 3 The glass is alternately and evenly evaporated on the PPSU polymer film to obtain the PPSU-As 2 S 3 -Ge 20 As 20 Se 18 Te 42 -As 2 S 3 -Ge 20 As 20 Se 18 Te 42 -…-Ge 20 As 20 Se 18 Te 42 The multi-layer film structure of the (2) is prepared to obtain an omnidirectional reflecting layer; wherein As 2 S 3 The glass was charged at 50g, as 2 S 3 Vacuum degree in chamber is 8 x 10 during glass vapor deposition - 4 Pa，As 2 S 3 The glass vapor deposition temperature is 370 ℃, and the vapor deposition rate isThe vapor deposition thickness is 1.118 mu m; ge (gallium nitride) 20 As 20 Se 18 Te 42 The glass was charged at 50g, ge 20 As 20 Se 18 Te 42 Vacuum degree in chamber is 2 x 10 during glass vapor deposition -3 Pa，Ge 20 As 20 Se 18 Te 42 The glass vapor deposition temperature is 470 ℃, and the vapor deposition rate is +.>The vapor deposition thickness is 0.864 mu m, ge 20 As 20 Se 18 Te 42 And As 2 S 3 The glass alternate evaporation process needs to be circulated for 8 times; the PPSU polymer substrate film is scrubbed by alcohol before coating, and is cleaned by a radio frequency power supply before coating, the power of the power supply is 49W, and when the radio frequency is cleaned, the air pressure in a cavity is stabilized to be 5.0Pa after argon is introduced; PPSU aggregationThe rotating speed of the roller fixed by the object substrate film is 30rad/min;
s2, preparing a protective layer on the omnidirectional reflecting layer; placing PMMA particles in a Dimethylformamide (DMF) solution, and preparing according to the concentration of 0.3g/mL, wherein the preparation process is carried out in a water bath kettle at 75 ℃ to obtain a completely transparent PMMA solution; fixing the PPSU polymer substrate film with the omni-directional reflecting layer prepared in the step S1 on a hard substrate, and vertically and uniformly dripping 3mL of PMMA solution on the omni-directional reflecting layer through a pipette; and (3) moving a scraper to enable the solution to uniformly form a film on the omnidirectional reflecting layer according to the required thickness of the protective layer, placing the scraped film in a drying box, setting the temperature to 120 ℃, and baking for 1 hour to enable the PPSU film to be completely solidified, namely preparing the protective layer on the omnidirectional reflecting layer.
Example 2
The application provides a laser omnidirectional reflecting film, specifically, this laser omnidirectional reflecting film includes:
a base layer;
the omnidirectional reflecting layer is positioned on one side of the basal layer and comprises two refractive layers with different refractive indexes, and the refractive layers with different refractive indexes are alternately arranged in sequence;
the protective layer is positioned on one side of the omnidirectional reflecting layer, which is far away from the basal layer;
wherein the base layer is made of PPSU, and the thickness of the base layer is 20 mu m;
the material of the protective layer is PMMA, and the thickness of the protective layer is 8 mu m;
the omni-directional reflecting layer comprises two refractive layers with different refractive indexes, and the material of the refractive layer with high refractive index is Te 20 As 30 Se 50 The material of the refractive layer with low refractive index is As 30 S 70 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the high refractive index refractive layer is 0.911 μm, the thickness of the low refractive index refractive layer is 1.183 μm, the number of alternating layers of the high refractive index refractive layer and the low refractive index refractive layer is 12, and the thickness of the omnidirectional reflecting layer is 25.188 μm;
the preparation method of the laser omnidirectional reflecting film comprises the following steps:
s1, atPreparing an omnidirectional reflecting layer on a PPSU polymer substrate film: chalcogenide glass Te with agate mortar 20 As 30 Se 50 And As 30 S 70 Grinding into particles, and mixing Te 20 As 30 Se 50 And As 30 S 70 Filling the material into a crucible of a coating machine, selecting an evaporation cover matched with the caliber of the crucible, applying a PPSU polymer substrate film on an evaporation roller, sealing the whole coating chamber, and loading Te 20 As 30 Se 50 And As 30 S 70 The glass is alternately and evenly evaporated on the PPSU polymer film to obtain the PPSU-As 30 S 70 -Te 20 As 30 Se 50 -As 30 S 70 -Te 20 As 30 Se 50 -…-Te 20 As 30 Se 50 The multi-layer film structure is used for preparing the omnidirectional reflecting layer; wherein As 30 S 70 The glass was charged at 50g, as 30 S 70 Vacuum degree in chamber is 8 x 10 during glass vapor deposition -4 Pa，As 30 S 70 The glass vapor deposition temperature is 340 ℃, and the vapor deposition rate isThe vapor deposition thickness is 1.188 mu m; te (Te) 20 As 30 Se 50 The glass charge was 50g, te 20 As 30 Se 50 Vacuum degree in chamber is 7×10 during glass vapor deposition -4 Pa, te is described as 20 As 30 Se 50 The glass vapor deposition temperature is 340 ℃, and the vapor deposition rate is +.>The vapor deposition thickness is 0.911 mu m, te 20 As 30 Se 50 And As 30 S 70 The glass alternate evaporation process needs to be circulated for 12 times; the PPSU polymer substrate film is scrubbed by alcohol before coating, and is cleaned by a radio frequency power supply before coating, the power of the power supply is 49W, and when the radio frequency is cleaned, the air pressure in a cavity is stabilized to be 5.0Pa after argon is introduced; the rotating speed of the roller fixed by the PPSU polymer substrate film is 30rad/min;
s2, preparing a protective layer on the omnidirectional reflecting layer; placing PMMA particles in a Dimethylformamide (DMF) solution, and preparing according to the concentration of 0.5g/mL, wherein the preparation process is carried out in a water bath kettle at 75 ℃ to obtain a completely transparent PMMA solution; fixing the PPSU polymer substrate film with the omni-directional reflecting layer prepared in the step S1 on a hard substrate, placing the hard substrate film on a sucker through vacuum adsorption, and vertically and uniformly dripping 6mL of PMMA solution on the omni-directional reflecting layer through a pipette gun; and moving a scraper to enable the solution to uniformly form a film on the omnidirectional reflecting layer, placing the film after the scraping and coating in a drying box, setting the temperature to 120 ℃, and baking for 1 hour to enable the PPSU film to be completely solidified, namely preparing a protective layer on the omnidirectional reflecting layer.
Example 3
The application provides a laser omnidirectional reflector film and, specifically, this laser omnidirectional reflector film includes:
a base layer;
the omnidirectional reflecting layer is positioned on one side of the basal layer and comprises two refractive layers with different refractive indexes, and the refractive layers with different refractive indexes are alternately arranged in sequence;
wherein the base layer is made of PEI, and the thickness of the base layer is 100 mu m;
the omni-directional reflecting layer comprises two refractive layers with different refractive indexes, and the material of the refractive layer with high refractive index is As 2 Se 3 The material of the refractive layer with low refractive index is As 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the high refractive index refractive layer is 0.953 μm, the thickness of the low refractive index refractive layer is 1.118 μm, the number of alternating layers of the high refractive index refractive layer and the low refractive index refractive layer is 10, and the thickness of the omnidirectional reflecting layer is 20.71 μm;
the preparation method of the laser omnidirectional reflecting film comprises the following steps:
s1, preparing an omnidirectional reflecting layer on a PEI polymer substrate film: chalcogenide glass As using agate mortar 2 Se 3 And As 2 S 3 Grinding into particles, and adding As 2 Se 3 And As 2 S 3 Filling the material into a crucible of a coating machine, and simultaneously selecting a material matched with the caliber of the crucibleThe evaporation cover is used for coating a PEI polymer substrate film required by the evaporation roller, sealing the whole coating chamber and loading As 2 Se 3 And As 2 S 3 The glass is alternately and evenly evaporated on the PEI polymer film to obtain PEI-As 2 S 3 -As 2 Se 3 -As 2 S 3 -As 2 Se 3 -…-As 2 Se 3 The multi-layer film structure is used for preparing the omnidirectional reflecting layer; wherein As 2 S 3 The glass was charged at 50g, as 2 S 3 Vacuum degree in chamber is 8 x 10 during glass vapor deposition -4 Pa，As 2 S 3 The glass vapor deposition temperature is 370 ℃, and the vapor deposition rate isThe vapor deposition thickness is 1.118 mu m; as As 2 Se 3 The glass was charged at 50g, as 2 Se 3 Vacuum degree in chamber is 5×10 during glass vapor deposition -4 Pa，As 2 Se 3 The glass vapor deposition temperature is 450 ℃, and the vapor deposition rate is +.>The vapor deposition thickness is 0.953 mu m, as 2 Se 3 And As 2 S 3 The glass alternate evaporation process needs to be circulated for 10 times; the PEI polymer substrate film is scrubbed by alcohol before coating, and is cleaned by a radio frequency power supply before coating, the power of the power supply is 49W, and when the radio frequency is cleaned, the air pressure in a cavity is stabilized to be 5.0Pa after argon is introduced; the rotating speed of the roller fixed by the PPSU polymer substrate film is 30rad/min;
example 4
The application provides a laser omnidirectional reflecting film, specifically, this laser omnidirectional reflecting film includes:
a base layer;
the omnidirectional reflecting layer is positioned on one side of the basal layer and comprises two refractive layers with different refractive indexes, and the refractive layers with different refractive indexes are alternately arranged in sequence;
the protective layer is positioned on one side of the omnidirectional reflecting layer, which is far away from the basal layer;
wherein the base layer is made of PPSU, and the thickness of the base layer is 100 mu m;
the material of the protective layer is Al 2 O 3 The thickness of the protective layer is 5 μm;
the omni-directional reflecting layer comprises two refractive layers with different refractive indexes, and the material of the refractive layer with high refractive index is As 2 Se 3 The material of the refractive layer with low refractive index is As 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the high refractive index refractive layer is 0.953 μm, the thickness of the low refractive index refractive layer is 1.118 μm, the number of alternating layers of the high refractive index refractive layer and the low refractive index refractive layer is 10, and the thickness of the omnidirectional reflecting layer is 20.71 μm;
the CO mentioned above 2 The preparation method of the laser omnidirectional reflecting film comprises the following steps:
s1, preparing an omnidirectional reflecting layer on a PPSU polymer substrate film: chalcogenide glass As using agate mortar 2 Se 3 And As 2 S 3 Grinding into particles, and adding As 2 Se 3 And As 2 S 3 Filling the material into a crucible of a coating machine, selecting an evaporation cover matched with the caliber of the crucible, attaching a required PPSU polymer substrate film on an evaporation roller, sealing the whole coating chamber, and loading As 2 Se 3 And As 2 S 3 The glass is alternately and evenly evaporated on the PPSU polymer film to obtain the PPSU-As 2 S 3 -As 2 Se 3 -As 2 S 3 -As 2 Se 3 -…-As 2 Se 3 The multi-layer film structure is used for preparing the omnidirectional reflecting layer; wherein As 2 S 3 The glass was charged at 50g, as 2 S 3 Vacuum degree in chamber is 8 x 10 during glass vapor deposition -4 Pa，As 2 S 3 The glass vapor deposition temperature is 370 ℃, and the vapor deposition rate isThe vapor deposition thickness is 1.118 mu m; as As 2 Se 3 The glass was charged at 50g, as 2 Se 3 Vacuum degree in chamber is 5×10 during glass vapor deposition - 4 Pa，As 2 Se 3 The glass vapor deposition temperature is 450 ℃, and the vapor deposition rate is +.>The vapor deposition thickness is 0.953 mu m, as 2 Se 3 And As 2 S 3 The glass alternate evaporation process needs to be circulated for 10 times; the PPSU polymer substrate film is scrubbed by alcohol before coating, and is cleaned by a radio frequency power supply before coating, the power of the power supply is 49W, and when the radio frequency is cleaned, the air pressure in a cavity is stabilized to be 5.0Pa after argon is introduced; the rotating speed of the roller fixed by the PPSU polymer substrate film is 30rad/min;
s2, preparing a protective layer on the omnidirectional reflecting layer; magnetron sputtering of Al 2 O 3 And uniformly evaporating the powder on the omnidirectional reflecting layer, namely preparing a protective layer on the omnidirectional reflecting layer.
The laser omni-directional reflecting film prepared in the embodiment 1 of the application is a flexible omni-directional reflecting film with a reflecting band gap in the range of 9.8-11.4 μm, and can be applied to CO with a wave band of 9.8-11.4 μm 2 The band characteristics of the laser are shown in fig. 2. In fig. 2: the ordinate is normalized frequency (ratio of lattice constant to wavelength), the abscissa is the bloch wave vector, the left side in fig. 2 is the Transverse Magnetic (TM) mode state, the right side is the Transverse Electric (TE) mode state, the electric field is perpendicular to the plane for TE mode, the magnetic field is perpendicular to the plane for TM mode, the hatched area indicates the propagation state, the white area indicates the evanescent state, and the black area indicates the omnidirectional reflection range.
The reflection characteristics of the omni-directional reflection film prepared in example 1 are shown in fig. 3. In FIG. 3, the ordinate is the reflectance, the abscissa is the wavelength, the unit is μm, and θ is the incident angle, it can be seen from FIG. 3 that the omni-directional reflective film prepared in example 1 has a normal incidence reflectance of 85% or more in the 9.8-11.7 μm band, an incident angle varying from 0 to 80 °, and a reflectance of 98% or more in the vicinity of the 10.6 μm band, and can achieve CO alignment 2 High refractive index total angle reflection of the laser.
Fig. 4 shows a cross-sectional SEM image of the omni-directional reflective layer prepared in example 1.
Fig. 5 is a physical diagram of the laser omni-directional reflecting film in embodiment 1 of the present application, and as can be seen from fig. 5, the laser omni-directional reflecting film prepared by the present application can be easily wound on a glass rod with a diameter of 5mm, has good flexibility, and can be applied to the field of wearing laser protection films.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (5)

1. Omnidirectional reflection of 9.3-11 mu m laser can be realized by using laser omnidirectional reflection film and applied to wearable CO 2 Laser protection field, laser omnidirectional reflector film includes:
a base layer;
an omni-directional reflecting layer positioned on one side of the substrate layer,
the omnidirectional reflecting layer comprises two refractive layers with different refractive indexes, and the material of the refractive layer with high refractive index is Ge 20 As 20 Se 18 Te 42 The material of the refractive layer with low refractive index is As 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the high refractive index refractive layer is 0.864 mu m, the thickness of the low refractive index refractive layer is 1.118 mu m, and the number of alternating layers of the high refractive index refractive layer and the low refractive index refractive layer is 4;
the base layer is made of thermoplastic polymer or ultraviolet curing resin, and the thickness of the base layer is 10-1000 mu m;
the thermoplastic polymer comprises at least one of carbonate polymer, sulfone polymer, etherimide polymer, acrylic polymer, cycloolefin copolymer, polystyrene, polycarbonate, polyethylene, polypropylene, ABS and fluorine-containing polymer.
2. The laser omni-directional reflective film according to claim 1, further comprising a protective layer on a side of the omni-directional reflective layer remote from the substrate layer.
3. The laser omni-directional reflecting film according to claim 2, wherein the thickness of the protective layer is 0.5-100 μm, the protective layer is used for protecting the omni-directional reflecting layer, and the material of the protective layer is polymer, metal oxide or ultraviolet curing resin;
and/or the thickness of the omni-directional reflecting layer is 5-100 mu m.
4. A method for preparing the omni-directional reflecting film of laser according to claim 1-3, comprising the following steps:
providing at least two materials having different refractive indices;
sequentially and alternately preparing materials with different refractive indexes on the substrate layer to form an omnidirectional reflecting layer;
if the laser omni-directional reflecting film further comprises a protective layer, the preparation method of the laser omni-directional reflecting film further comprises the following steps:
and preparing a protective layer on one side of the omni-directional reflecting layer away from the basal layer.
5. The method for preparing the omni-directional reflecting film according to claim 4, wherein the omni-directional reflecting layer is prepared by any one of a magnetron sputtering method, a chemical vapor deposition method, a sol-gel method, a pulse laser deposition method and a thermal evaporation method;
the protective layer is prepared by any one of spin coating, knife coating, spray coating, and roll coating.
CN202210752787.1A 2022-06-29 2022-06-29 Laser omnidirectional reflecting film and application thereof in wearable laser protection field Active CN115016052B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210752787.1A CN115016052B (en) 2022-06-29 2022-06-29 Laser omnidirectional reflecting film and application thereof in wearable laser protection field

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210752787.1A CN115016052B (en) 2022-06-29 2022-06-29 Laser omnidirectional reflecting film and application thereof in wearable laser protection field

Publications (2)

Publication Number Publication Date
CN115016052A CN115016052A (en) 2022-09-06
CN115016052B true CN115016052B (en) 2023-07-28

Family

ID=83079191

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210752787.1A Active CN115016052B (en) 2022-06-29 2022-06-29 Laser omnidirectional reflecting film and application thereof in wearable laser protection field

Country Status (1)

Country Link
CN (1) CN115016052B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3643774B2 (en) * 1998-10-14 2005-04-27 マサチューセッツ インスティテュート オブ テクノロジー Omnidirectional multilayer device for optical waveguides
CA2454177A1 (en) * 2001-07-16 2003-01-30 Massachusetts Institute Of Technology Method of forming reflecting dielectric mirrors
US8861087B2 (en) * 2007-08-12 2014-10-14 Toyota Motor Corporation Multi-layer photonic structures having omni-directional reflectivity and coatings incorporating the same
JP2009086533A (en) * 2007-10-02 2009-04-23 Sumitomo Electric Hardmetal Corp Infrared multilayered film, infrared antireflection film, and infrared laser reflecting mirror
CN103543482B (en) * 2013-10-31 2015-09-02 武汉邮电科学研究院 The full polarizing mirror of the insensitive full angle of heat of communication band and manufacture method thereof
CN113885114A (en) * 2021-11-10 2022-01-04 洛阳司派特科技有限公司 Light-weight reflecting mirror blank and preparation method thereof

Also Published As

Publication number Publication date
CN115016052A (en) 2022-09-06

Similar Documents

Publication Publication Date Title
CN107942540B (en) Phase-change-material-based optical modulation device with dynamic color display and preparation method thereof
Lohmüller et al. Biomimetic interfaces for high-performance optics in the deep-UV light range
Nagaraja et al. Effect of annealing on the structural and nonlinear optical properties of ZnO thin films under cw regime
JP6351858B2 (en) Flexible substrate coated with sapphire thin film
TWI661066B (en) Sapphire thin film coated substrate
Elsayed et al. Transmission investigation of one-dimensional Fibonacci-based quasi-periodic photonic crystals including nanocomposite material and plasma
Spoorthi et al. Investigations on nonlinear optical properties of electron beam treated Gd: ZnO thin films for photonic device applications
Yue et al. Photo-oxidation-modulated refractive index in Bi2Te3 thin films
CN115016052B (en) Laser omnidirectional reflecting film and application thereof in wearable laser protection field
Taha et al. Textured concave anti-reflecting coating and convex back reflector to enhance the absorbance of amorphous Si solar cells
TWI653266B (en) Sapphire film coated substrate
Singh et al. Temperature tunable optical transmission using IR based 1D photonic crystals of VO2 nanostructures
WO2022037312A1 (en) Heating component having infrared anti-reflective property
CN100362973C (en) Method for preparing filmy intraocular lens
TWI710535B (en) Sapphire coated substrate with a flexible, anti-scratch and multi-layer coating and a method for preparing the same
CN114879282A (en) Laser protective film based on medium super surface and preparation method thereof
Ozer et al. Broadband asymmetric light transmission based on all-dielectric metasurfaces in the visible spectrum
Tang et al. Flexible, double-sided broadband optical absorber based on tapered concave nanostructure
US3493289A (en) Coated optical devices
US20190249292A1 (en) Sapphire Coated Substrate With A Flexible, Anti-Scratch And Multi-Layer Coating
Liu et al. Tunable, large-scale and low-cost Si infrared absorbers
Wu et al. NbN superconducting nanowire single-photon detector fabricated on MgF2 substrate
CN110133841A (en) The adjustable film of light transmittance and light transmittance regulating device
Xiao et al. All dissolvable and transient plasmonic device enabled by nanoimprint lithography
Ab Rahman et al. Passive optoelectronic elements

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant