CN113589408A - Lens capable of converting infrared rays into visible light waveband images and preparation method thereof - Google Patents
Lens capable of converting infrared rays into visible light waveband images and preparation method thereof Download PDFInfo
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- CN113589408A CN113589408A CN202110789516.9A CN202110789516A CN113589408A CN 113589408 A CN113589408 A CN 113589408A CN 202110789516 A CN202110789516 A CN 202110789516A CN 113589408 A CN113589408 A CN 113589408A
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- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 21
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- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 3
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- 239000002105 nanoparticle Substances 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
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- UNUKKGWFZVEVMP-UHFFFAOYSA-J sodium europium(3+) tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Eu+3].[Na+] UNUKKGWFZVEVMP-UHFFFAOYSA-J 0.000 claims description 3
- MJFMPUWWRLQGOR-UHFFFAOYSA-J sodium samarium(3+) tetrafluoride Chemical compound [F-].[Na+].[Sm+3].[F-].[F-].[F-] MJFMPUWWRLQGOR-UHFFFAOYSA-J 0.000 claims description 3
- OWFHVHWXOGAVRB-UHFFFAOYSA-J sodium;gadolinium(3+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Gd+3] OWFHVHWXOGAVRB-UHFFFAOYSA-J 0.000 claims description 3
- HPDGNIYVUYITCX-UHFFFAOYSA-J sodium;ytterbium(3+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Yb+3] HPDGNIYVUYITCX-UHFFFAOYSA-J 0.000 claims description 3
- HQHVZNOWXQGXIX-UHFFFAOYSA-J sodium;yttrium(3+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Y+3] HQHVZNOWXQGXIX-UHFFFAOYSA-J 0.000 claims description 3
- CVKJXWOUXWRRJT-UHFFFAOYSA-N technetium dioxide Chemical compound O=[Tc]=O CVKJXWOUXWRRJT-UHFFFAOYSA-N 0.000 claims description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 3
- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 claims description 3
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
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- Health & Medical Sciences (AREA)
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Health & Medical Sciences (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a lens for converting infrared rays into visible light waveband images and a preparation method thereof. The preparation method of the lens for converting infrared rays into visible light waveband images is characterized in that in the process of producing and preparing the plated film, the adjustment of an optical equivalent admittance value is introduced, a strict coupling wave method is adopted, a zinc oxide film layer prepared by an up-conversion infrared imaging machine and a two-dimensional square nano silver metal crystal periodic array super-surface film layer for carrying out multi-resonance coupling field enhanced luminescence are optimized, and the prepared film has the characteristics of compact film layer structure, corrosion resistance, good environmental stability and the like.
Description
Technical Field
The invention belongs to the technical field of up-conversion luminescence mechanism combined surface plasmon multi-resonance coupling field enhancement, and particularly relates to a lens for converting infrared rays into visible light waveband images and a preparation method thereof.
Background
For example, the anti-counterfeiting mark on the RMB is an up-conversion luminescent material, and emits a visible image of a visible light wave band under the irradiation of infrared light in an anti-counterfeiting identification machine, so that the anti-counterfeiting mark has been widely applied to the aspects of currency, credit cards, certificates, trademarks and the like at present; infrared imaging is a key technology in a number of applications, including night vision, autonomous vehicle navigation, optical tomography, and food quality control. There is an increasing demand for detecting Infrared (IR) light invisible to the human eye, from food quality control, remote sensing, to various applications of night vision devices, lidar. Commercial infrared cameras require that infrared light be first converted into electrons and the resulting image projected onto a display screen that blocks the transmission of visible light, thereby interfering with normal visible band vision. In addition, due to the low energy of infrared photons, such infrared detectors typically require extensive cryogenic cooling techniques and associated equipment, which greatly increases the overall weight and volume of the detector, making the infrared detector cumbersome.
Glasses lenses which emit high-energy short-wave visible light band images based on the ion energy step transition of an up-conversion luminescence machine mechanism are not developed in the international market, so any glasses lens in the market does not have the night vision function of infrared visible images. In addition, commercial infrared imaging detectors must rely on the absorption of incident photons and the release of electrons that are detected by electrons in narrow bandgap semiconductors, and because of the low energy of infrared photons, such infrared detection schemes require even cryogenic cooling, contain a very large variety of complex electronic components for photon-to-electron conversion, and are bulky and heavy.
Disclosure of Invention
In order to solve the problems in the prior art, the application provides a lens for converting infrared rays into visible light waveband images and a preparation method thereof.
In a first aspect, an embodiment of the invention provides a lens for converting infrared rays into visible light band images, which comprises a lens substrate, wherein a silicon dioxide film protective layer, an up-conversion luminescent infrared imaging material film layer doped with rare earth ions, a silicon dioxide film intermediate isolation layer, a two-dimensional square nano silver metal crystal periodic array super-surface film layer and a silicon dioxide film priming layer are sequentially arranged on the surface of the lens substrate from top to bottom.
In a preferred embodiment, the thickness of the silicon dioxide film protective layer is 2nm to 5nm, the deposition rate is 0.2nm/s to 3.0nm/s, the thickness of the rare earth ion doped up-conversion luminescence infrared imaging material film layer is 10nm to 50nm, the thickness of the middle isolation layer of the silicon dioxide film is 15nm to 30nm, the deposition rate is 0.2nm/s to 3.0nm/s, the thickness of the two-dimensional square nano silver metal crystal periodic array super-surface film layer is 10nm to 15nm, the thickness of the silicon dioxide film priming layer is 2nm to 5nm, the deposition rate is 0.2nm/s to 3.0nm/s, and the thickness range of the total film stacking layer deposited on the lens substrate is 30nm to 110 nm.
In a preferred embodiment, the rare earth ion doped upconversion luminescent infrared imaging material film layer comprises an upconversion substrate, an upconversion sensitizer ion and an upconversion activator ion.
In a preferred embodiment, the upconverting substrate includes, but is not limited to, at least one of a sodium yttrium tetrafluoride crystal, a sodium neodymium tetrafluoride crystal, a sodium samarium tetrafluoride crystal, a sodium europium tetrafluoride crystal, a sodium gadolinium tetrafluoride crystal, a sodium terbium tetrafluoride crystal, a lanthanum trifluoride crystal, a scandium trifluoride crystal, a lithium lutetium tetrafluoride crystal, a sodium ytterbium tetrafluoride crystal, a rubidium manganese trichloride crystal, a cesium lutetium bromide crystal, a calcium sulfide crystal, a neodymium tungstate crystal, an yttrium aluminum garnet crystal, an yttrium gallium garnet crystal, an yttrium barium oxide crystal, a lutetium trioxide crystal, a lithium tantalate crystal, a lithium niobate crystal, an yttrium vanadate crystal, a technetium dioxide crystal, an yttrium trioxide crystal, and a zinc oxide crystal, and further preferably a zinc oxide crystal.
In a preferred embodiment, the upconverting sensitizer ion comprises, but is not limited to Yb3+、Nd3+、Pr3+、Ce3+And Os4+Further, Yb is preferable3+。
In a preferred embodiment, the transition activator ion includes, but is not limited to Er3+、Tm3+、Ho3+、Sm3+、Re4 +、Tb3+、Eu3+、Gd3+、Mn2+And Mo3+Further, Er is preferable3+。
In a second aspect, an embodiment of the present invention provides a method for manufacturing a lens for converting infrared rays into images in a visible light band, including the following steps:
step S1: carrying out ion-assisted bombardment electron beam evaporation deposition on the lens substrate to deposit a silicon dioxide priming layer;
step S2: clamping a mask plate on each lens substrate, and performing electron beam evaporation deposition on the silicon dioxide base layer to deposit a two-dimensional square nano silver metal crystal periodic array super-surface thin film layer;
step S3: removing the mask plate, and then performing ion beam assisted deposition and electron beam evaporation to deposit a silicon dioxide film intermediate isolation layer;
step S4: continuously performing ion beam assisted deposition and electron beam evaporation deposition on the intermediate isolation layer of the silicon dioxide film to deposit an up-conversion luminescence infrared imaging material film layer doped with rare earth ions; and
step S5: and finally, carrying out ion beam assisted deposition and electron beam evaporation deposition to deposit a silicon dioxide film protective layer.
In a preferred embodiment, the mask plate adopts a two-dimensional square nano periodic array nano-sized open-area hollow structure with a sub-wavelength scale of laser interference direct writing, the pixel size of the open-area hollow structure is 30 microns multiplied by 30 microns, and the pixel pitch is 30 microns.
In a preferred embodiment, the vapor deposition rate of the two-dimensional square nano-silver metal crystal periodic array super-surface thin film layer in the step S2 is 0.1nm/S to 1.0 nm/S.
In a preferred embodiment, the vapor deposition rate of the rare earth ion doped upconversion luminescence infrared imaging material film layer in the step S4 is 0.3nm/S to 1.0 nm/S.
The lens for converting infrared rays into visible light waveband images adopts a special combination system of dual principle SPR-UCNPs surface plasmon resonance-up-conversion nano material ion energy step transition luminescence, so that the lens absorbs the intensity of visible light converted and emitted by an infrared light source in the process of using an ultrathin film to enhance the up-conversion ion energy step transition luminescence mechanism, has a night vision color visible image visual field in a dark environment, generates a visible light source image which can be seen at a dark night, and can replace a heavy and power-consuming electronic night vision device/electronic night vision mirror used by police or security personnel. In the aspect of life application, for example, the super-surface structure film can be safer to drive at night or walk home after dark, has huge market prospect with the characteristics of higher sensitivity, stronger penetrating power, no damage to eyeball tissues and the like which are incomparable to other fluorescent materials, and is transparent in visible light and infrared spectrum ranges due to the fact that the two-dimensional square nano silver metal crystal periodic array super-surface structure film layer is transparent, and further can transmit and transmit visible light to realize a normal visual effect when infrared imaging is carried out. The method technically combines the effect of enhancing the luminous intensity of a two-dimensional square nano silver metal crystal periodic array super surface plasmon polariton structure multi-resonance coupling field and an up-conversion infrared imaging mechanism (SPR-UCNPs special combination system), and has huge application and development potentials in the fields of national economy and national defense construction.
Drawings
The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and together with the description serve to explain the principles of the invention. Other embodiments and many of the intended advantages of embodiments will be readily appreciated as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale relative to each other. Like reference numerals designate corresponding similar parts.
FIG. 1 is a schematic diagram of the morphology of the total film layer of a lens for converting infrared rays into visible light band images according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of the energy level principle of an upconversion infrared imaging mechanism of a lens for converting infrared rays into visible band images according to an embodiment of the present invention;
FIG. 3 is a flowchart of a method for manufacturing a lens for converting infrared light into visible band images according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a size structure of a hollow area above a mask plate in a lens manufacturing method for converting infrared rays into visible band images according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a two-dimensional square nanocrystal periodic array super-surface thin film layer designed for deposition on a lens for infrared conversion into visible light band images according to an embodiment of the invention;
FIG. 6 is an optical microscopic partial magnified view of a two-dimensional square nanocrystal periodic array super-surface thin film layer actually deposited on a lens for infrared conversion to visible band images according to an embodiment of the invention;
fig. 7 is a schematic diagram of the lens for converting infrared rays into visible light band images according to the embodiment of the present invention, which is respectively transformed into (c) a spectrum of transmitted visible light after the incident (d) infrared different light source wavelengths are subjected to an up-conversion infrared imaging mechanism and (a) a multi-resonance coupling field enhancement effect of a super-surface two-dimensional square nano silver metal periodic array structure;
fig. 8 is a schematic diagram of curves of the converted visible light according to the variation of the incident infrared with the variation of different wavelengths in the process of the up-conversion infrared imaging (SFG) and frequency generation mechanism of the lens for converting the infrared into the visible light band image and the multi-resonance coupling field enhancement effect according to the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention will be described in detail with reference to the accompanying drawing 1, and the lens for converting infrared rays into visible light waveband images comprises a lens substrate, wherein a silicon dioxide film protective layer, an up-conversion luminescent infrared imaging material film layer doped with rare earth ions, a silicon dioxide film intermediate isolation layer, a two-dimensional square nano silver metal crystal periodic array super-surface film layer and a silicon dioxide film priming layer are sequentially arranged on the surface of the lens substrate from top to bottom.
The working principle of the lens for converting infrared rays into visible light waveband images is as follows: the infrared band is incident to pass through the zinc oxide film layer of the up-conversion infrared imaging material to generate ion energy step transition of an up-conversion luminescence mechanism and simultaneously emit high-energy visible photon energy to form a visible image of a visible light band.
Fig. 2 is a schematic diagram of the energy level principle of an Upconversion infrared imaging mechanism of a lens for converting infrared rays into visible light band images, as shown in fig. 2, the Upconversion infrared imaging mechanism contains 3 important Upconversion luminescence principles, namely, Ground State Absorption (GSA)/Excited State Absorption (ESA), Ground State Absorption (GSA)/energy Cross Relaxation Upconversion (ETU), and Photon Avalanche Cross Relaxation Upconversion (PAU), and so-called Cross Relaxation (CR) refers to two types of ions simultaneously located on an excited state, wherein one ion transfers energy to another different type of ion to make the ion transition to a higher energy level, and the ion itself relaxes to a lower energy level without radiation. The energy level widths of one ground state GS and two metastable excited states ES1, ES2 are substantially the same, and an intermediate metastable state ES1 is necessary for infrared up-conversion. Figure two presents the 3 most important upconversion light-emitting mechanisms: (1) ground State Absorption (GSA)/Excited State Absorption (ESA): the process of absorbing one photon to the metastable excited state ES1 by the GS ground state ions is the first step of the upconversion luminescence mechanism, and then the ions in the metastable state ES1 absorb one photon to the higher-order excited state ES 2; (2) ground State Absorption (GSA)/energy cross relaxation upconversion (ETU): two metal ions in the metastable state of ES1 are subjected to energy transfer in a CR cross relaxation mode through nonradiative coupling, one returns to the ground state of GS, and the other transits to a higher-order excited state ES 2; (3) photon Avalanche cross relaxation Upconversion (Photon Avalanche Upconversion): the process is characterized in that ions do not absorb light in a ground state, but do absorb ESA excited states and CR cross relaxation among ions, so that the population of ES1 metastable states with middle and long service life is increased, effective up-conversion luminescence is generated, the conversion process is that one ion on ES1 metastable state energy absorbs the energy and is excited to ES2 excited state energy level, the ES2 excited state energy level and ES1 metastable state energy level generate CR cross relaxation, and the ions are accumulated on ES1 metastable state energy level, so that the particle number on ES1 metastable state energy level is increased like avalanche, and the process is called photon avalanche.
In a specific embodiment, the thickness of the silicon dioxide film protective layer is 2 nm-5 nm, the deposition rate is 0.2 nm/s-3.0 nm/s, the thickness of the rare earth ion doped up-conversion luminescence infrared imaging material film layer is 10 nm-50 nm, the thickness of the intermediate isolation layer of the silicon dioxide film is 15 nm-30 nm, the deposition rate is 0.2 nm/s-3.0 nm/s, the thickness of the two-dimensional square nano silver metal crystal periodic array super-surface film layer is 10 nm-15 nm, the thickness of the silicon dioxide film priming layer is 2 nm-5 nm, the deposition rate is 0.2 nm/s-3.0 nm/s, and the thickness range of the total film stacking layer deposited on the lens substrate is 30 nm-110 nm.
In a specific embodiment, the rare earth ion doped upconversion luminescent infrared imaging material film layer comprises an upconversion substrate, an upconversion sensitizer ion and an upconversion activator ion. The upconversion substrate includes, but is not limited to, a sodium yttrium tetrafluoride crystal, a sodium neodymium tetrafluoride crystal, a sodium samarium tetrafluoride crystal, a sodium europium tetrafluoride crystal, a sodium gadolinium tetrafluoride crystal, a sodium terbium tetrafluoride crystal, a lanthanum trifluoride crystal, a scandium trifluoride crystal, a lithium lutetium tetrafluoride crystal, a sodium ytterbium tetrafluoride crystal, a rubidium manganese trichloride crystal, a cesium lutetium bromide crystal, a calcium sulfide crystal, a tungsten sulfide crystal, a cerium fluoride crystal, a lithium lutetium fluoride crystal, a lithium fluoride crystal, a lithium fluoride crystal, a lithium fluoride, aAt least one of neodymium acid crystal, yttrium aluminum garnet crystal, yttrium gallium garnet crystal, yttrium barium oxide crystal, lutetium trioxide crystal, lithium tantalate crystal, lithium niobate crystal, yttrium vanadate crystal, technetium dioxide crystal, yttrium trioxide crystal, and zinc oxide crystal, and further, zinc oxide crystal is preferable. Up-converting sensitizer ions include, but are not limited to Yb3+、Nd3+、pr3+、Ce3+And Os4+Further, Yb is preferable3+. Transition activator ions include, but are not limited to Er3+、Tm3+、Ho3+、Sm3+、Re4+、Tb3+、Eu3+、Gd3+、Mn2+And Mo3+Further, Er is preferable3+. The up-conversion substrate adopts zinc oxide crystals, the rare earth can be doped singly, doubly and multiply, the luminous efficiency of the single-doped up-conversion substrate is relatively low, and the single-doped up-conversion substrate is commonly doubly doped. In the double doped rare earth ions, one rare earth ion acts as an up-conversion sensitizer by absorbing photon energy and transferring it to the rare earth activator ion. The upconversion sensitizer ion of the present invention is preferably Yb3+The upconversion activator ion is preferably Er3+，Yb3+The special energy level structure can sensitize the luminescence of other rare earth ions; er3+ acts as an up-conversion activator ion, providing a luminescent center with abundant energy levels. The upconversion sensitizer ions have excellent infrared band absorption capacity and can efficiently transfer absorbed energy to the upconversion activator ions, and the upconversion activator ions radiate short-wave visible spectrum. The invention adopts rare earth ion Er3+-Yb3+Co-doping with zinc oxide film, wherein the total expression is (ZnO: Yb/Er), Er3+And Yb3+The optimum doping mole fraction of (a) is 4%, the performance of the upconversion luminescent film is optimum. In order to obtain higher conversion efficiency, the conversion of the up-conversion luminescence mechanism depends on the multi-resonance coupling field enhancement effect of the nonlinear crystal super surface, so that a mask plate method is simultaneously combined and developed for carrying out electron beam evaporation deposition on the two-dimensional square nano silver metal crystal periodic array super surface structureThe method comprises the steps of performing line multi-resonance coupling field enhanced luminescence effect, forming a special combination system of SPR-UCNPs surface plasmon resonance-up-conversion nano material ion energy step transition luminescence, and using an ultrathin super surface with a nano structure to have multi-resonance under all interaction wavelengths, so that a visible light waveband image emitted by a near-field enhanced visible spectrum is formed by performing field enhanced coupling frequency in the multi-resonance super surface. The optical response of the meta-surface is determined by the collective scattering of the individual nano-antennas and the mutual coupling between adjacent nano-antennas. Such a super-surface may exhibit enhanced frequency conversion of the resonant coupling field due to excitation of optical multi-resonances and good coupling to free space. By adopting an up-conversion infrared light-emitting imaging technology and combining a field-enhanced nonlinear crystal super-surface two-dimensional square nanocrystal periodic array film layer (SPR-UCNPs special combination system), the whole night vision infrared imaging has the advantages of higher spatial resolution, wider color adjustment range, better color reproducibility and stability and the like, so that spectacle lenses with the night vision color visual field characteristic are developed, and the spectacle lenses have great application value.
Fig. 3 is a flowchart of a method for manufacturing a lens with an image converted from infrared light to visible light, and as shown in fig. 3, the present invention further provides a method for manufacturing a lens with an image converted from infrared light to visible light, including the following steps:
step S1: firstly, carrying out ion-assisted bombardment electron beam evaporation deposition on a lens substrate to form a silicon dioxide priming coat, wherein the thickness of the silicon dioxide film priming coat is 2 nm-5 nm, the deposition rate is 0.2 nm/s-3.0 nm/s, the ion bombardment time is 1 min-5 min, the background vacuum degree is 1 multiplied by 10-3Pa～9×10-3Pa, oxygen pressure 1X 10-2Pa～8×10-2Pa；
Step S2: then, clamping a mask plate on each lens substrate by adopting a mask plate technical method, and when carrying out electron beam evaporation deposition on the two-dimensional square nano silver metal crystal periodic array super-surface film layer, after the silver metal film material evaporation beam penetrates through the area of the two-dimensional square nano periodic array type hollow open area on the mask plate, depositing the two-dimensional square nano silver metal crystal periodic array super-surface film layer on the silicon dioxide priming layer, wherein the thickness of the two-dimensional square nano silver metal crystal periodic array super-surface film layer is 10-15 nm, and the deposition rate of the evaporation beam is 0.1-1.0 nm/s;
step S3: removing the mask plate, and then carrying out ion beam assisted deposition and electron beam evaporation to deposit an isolation layer in the silicon dioxide film, wherein the thickness of the isolation layer is 15 nm-30 nm, and the deposition rate is 0.2 nm/s-3.0 nm/s;
step S4: continuously carrying out ion beam assisted deposition and electron beam evaporation deposition on the intermediate isolation layer of the silicon dioxide film to deposit the rare earth ion-doped up-conversion luminescence infrared imaging material film layer, wherein the deposition rate of the evaporation beam is 0.3-1.0 nm/s, and the thickness of the film layer is 10-50 nm; and
step S5: finally, carrying out ion beam assisted deposition and electron beam evaporation deposition to deposit a silicon dioxide film protective layer, wherein the thickness of the silicon dioxide film protective layer is 2-5 nm, the deposition rate is 0.2-3.0 nm/s, cooling for half an hour after the plating is stopped, and taking out the lens from the air-filled vacuum chamber.
In a specific embodiment, the distance between the lens substrate and the evaporation source is 40-90 cm, the crystal growth temperature of the lens substrate is 40-80 ℃, the beam current density is 100-120 mA, and the vacuum degree is 1 multiplied by 10 when the lens substrate works-3Pa～9×10-3Pa, the power of the electron gun is 50-80%, the anode voltage of the electron gun is 100-130V, the anode current is 3-10A, the cathode voltage is 20-50V and the cathode current is 12-20A.
In particular embodiments, the lens substrate includes, but is not limited to, the following: at least one of an optical lens, a glass substrate of a sunglass lens, a polycarbonate PC substrate, a nylon PA substrate, a CR-39 substrate, a PMMA substrate, an AC acrylic substrate, an MR-7 substrate, an MR-8 substrate, an MR-10 substrate, an MR-174 substrate and a TAC polarizer substrate.
Fig. 4 is a schematic diagram of a size structure of a square hollowed-out area on a mask plate in a lens preparation method for converting infrared rays into visible light band images, as shown in fig. 4, the mask plate adopts a two-dimensional square nano periodic array nano-sized open-area hollowed-out structure with a sub-wavelength scale by laser interference direct writing, the pixel size of the open-area hollowed-out structure is 30 μm × 30 μm, the pixel pitch is 30 μm, and a black area is the hollowed-out area of the mask plate.
FIG. 5 is a schematic diagram of a two-dimensional square nano-crystal periodic array super-surface thin film layer designed and deposited on a lens for converting infrared rays into visible light band images, FIG. 6 is an optical microscopic partial enlarged view of a two-dimensional square nano-crystal periodic array super-surface thin film layer actually deposited on a lens for converting infrared rays into visible light band images, and as shown in FIGS. 5 and 6, a two-dimensional square nano-silver metal crystal periodic array super-surface thin film layer deposited by electron beam evaporation is formed, when a Surface Plasmon Resonance (SPR) frequency is generated and is overlapped with an up-conversion luminescence band, a special combination system of SPR-UCNPs surface plasmon resonance-up-conversion nano material ion energy step transition luminescence is formed, and the photon local state density near the surface of a metal nano structure is increased by multi-resonance coupling of the emitted light and the Surface Plasmon Resonance (SPR), thereby enhancing the intensity of the emitted light during the upconversion luminescence mechanism.
Fig. 7 is a schematic diagram showing that the lenses for converting infrared rays into visible light band images are respectively converted into (c) transmitted visible light spectrums along with the change of incident (d) infrared different light source wavelengths after the up-conversion infrared imaging mechanism and (a) the multi-resonance coupling field enhancement effect of the super-surface two-dimensional square nano-silver metal periodic array structure, as shown in fig. 7, the lenses are respectively converted into (c) transmitted visible light spectrums along with the change of incident (d) infrared different light source wavelengths after the up-conversion infrared imaging mechanism and (a) the multi-resonance coupling field enhancement effect of the super-surface two-dimensional square nano-silver metal periodic array super-surface structure, and the multi-resonance coupling field enhancement effect enhancement of the super-surface realizes simultaneous multi-color infrared imaging of multiple wavelengths.
FIG. 8 is a schematic diagram of an up-conversion infrared imaging (SFG) sum frequency generation mechanism of a lens for converting infrared rays into visible light band images and a visible light curve converted along with the change of different wavelengths of incident infrared during the multi-resonance coupling field enhancement effect, as shown in FIG. 8, the incident wavelengths of different infrared source bands are respectively changed along with the change of different wavelengths of incident infrared through the up-conversion infrared imaging (SFG) sum frequency generation mechanism and the two-dimensional square nano silver metal crystal periodic array super-surface thin film layer with super-surface multi-resonance coupling field enhancement effect, the visible light curves converted along with the change of different wavelengths of incident infrared are generated by SFG sum frequency, the emitted spectrum is dependent on signal beams of different wavelengths, the stronger nonlinear intensity of the super-surface is related to the near-field enhancement of fundamental waves, and the efficiency nonlinear frequency mixing is also dependent on the spatial mode overlap of interacting waves, multiple color imaging is exhibited at room temperature.
The invention relates to a method for preparing a lens for converting infrared rays into visible light wave band images, which comprises the steps of firstly carrying out electron beam evaporation deposition on a silicon dioxide film bottom layer; then, carrying out electron beam evaporation deposition to generate a two-dimensional square nano silver metal crystal periodic array super-surface thin film layer with Surface Plasmon Resonance (SPR) frequency; then, carrying out electron beam evaporation to deposit a silicon dioxide film intermediate isolation layer; continuing to perform electron beam evaporation deposition on the rare earth ion-doped up-conversion luminescent infrared imaging material film layer; and finally, performing electron beam evaporation to deposit silicon dioxide as an external protective layer. The up-conversion infrared imaging material film zinc oxide thin film (UCNPs) converts incident infrared spectrum into visible images of visible light wave bands, the process of absorbing infrared long wave and then radiating a short wave visible light source is called as an up-conversion luminescence mechanism, the up-conversion luminescence phenomenon is Anti-Stokes (Anti-Stokes) effect, namely the energy emitted by radiation is larger than the absorbed energy, the up-conversion luminescence mechanism mainly utilizes the metastable state energy level characteristic of ion energy level, can absorb a plurality of long wave radiations with low energy, and emits a high-energy short wave radiation light source after multi-photon sum frequency, thereby converting infrared light invisible to visible light; on the other hand, a mask plate method is also developed and used for carrying out electron beam evaporation deposition on the two-dimensional square nano silver metal crystal periodic array super-surface structure to carry out resonance coupling field enhanced luminescence effect, so that the spectacle lens with the night vision color visual field characteristic is developed.
While the principles of the invention have been described in detail in connection with the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing embodiments are merely illustrative of exemplary implementations of the invention and are not limiting of the scope of the invention. The details of the embodiments are not to be interpreted as limiting the scope of the invention, and any obvious changes, such as equivalent alterations, simple substitutions and the like, based on the technical solution of the invention, can be interpreted without departing from the spirit and scope of the invention.
Claims (10)
1. The lens is characterized by comprising a lens substrate, wherein a silicon dioxide film protective layer, an up-conversion luminescence infrared imaging material film layer doped with rare earth ions, a silicon dioxide film middle isolation layer, a two-dimensional square nano silver metal crystal periodic array super-surface film layer and a silicon dioxide film priming layer are sequentially arranged on the surface of the lens substrate from top to bottom.
2. The lens for converting infrared rays into visible light band images according to claim 1, wherein the thickness of the silica thin film protective layer is 2nm to 5nm, the thickness of the rare earth ion-doped up-conversion luminescence infrared imaging material film layer is 10nm to 50nm, the thickness of the silica thin film intermediate isolation layer is 15nm to 30nm, the thickness of the two-dimensional square nano silver metal crystal periodic array super-surface thin film layer is 10nm to 15nm, the thickness of the silica thin film priming layer is 2nm to 5nm, and the thickness of the total film stack layer deposited on the lens substrate is 30nm to 110 nm.
3. The lens for converting infrared light into visible light band images according to claim 1, wherein the rare earth ion doped upconversion luminescent infrared imaging material film layer comprises an upconversion substrate, an upconversion sensitizer ion, and an upconversion activator ion.
4. The lens for infrared conversion into visible band images according to claim 3, wherein the up-conversion substrate comprises at least one of a sodium yttrium tetrafluoride crystal, a sodium neodymium tetrafluoride crystal, a sodium samarium tetrafluoride crystal, a sodium europium tetrafluoride crystal, a sodium gadolinium tetrafluoride crystal, a sodium terbium tetrafluoride crystal, a lanthanum trifluoride crystal, a scandium trifluoride crystal, a lithium lutetium tetrafluoride crystal, a sodium ytterbium tetrafluoride crystal, a rubidium manganese trichloride crystal, a cesium lutetium bromide crystal, a calcium sulfide crystal, a neodymium tungstate crystal, an yttrium aluminum garnet crystal, an yttrium gallium garnet crystal, an yttrium barium oxide crystal, a lutetium trioxide crystal, a lithium tantalate crystal, a lithium niobate crystal, an yttrium vanadate crystal, a technetium dioxide crystal, an yttrium oxide crystal, and a zinc oxide crystal.
5. The lens of claim 3 wherein the upconverting sensitizer ions include but are not limited to Yb3+、Nd3+、Pr3+、Ce3+And Os4+At least one of (1).
6. The lens of claim 3, wherein the conversion activator ions include but are not limited to Er3+、Tm3+、Ho3+、Sm3+、Re4+、Tb3+、Eu3+、Gd3+、Mn2+And Mo3+At least one of (1).
7. A preparation method of a lens for converting infrared rays into visible light waveband images is characterized by comprising the following steps:
step S1: carrying out ion-assisted bombardment electron beam evaporation deposition on the lens substrate to deposit a silicon dioxide priming layer;
step S2: clamping a mask plate on each lens substrate, and performing electron beam evaporation deposition on the silicon dioxide base layer to deposit a two-dimensional square nano silver metal crystal periodic array super-surface film layer;
step S3: removing the mask plate, and then carrying out ion beam assisted deposition and electron beam evaporation deposition to deposit a silicon dioxide film intermediate isolation layer;
step S4: continuing to perform ion beam assisted deposition electron beam evaporation deposition on the intermediate isolation layer of the silicon dioxide film to deposit an up-conversion luminescence infrared imaging material film layer doped with rare earth ions; and
step S5: and finally, carrying out ion beam assisted deposition and electron beam evaporation deposition to deposit a silicon dioxide film protective layer.
8. The method for manufacturing a lens capable of converting infrared rays into visible light waveband images according to claim 7, wherein the mask plate adopts a two-dimensional square nano periodic array nano-sized open-area hollow structure with a sub-wavelength scale of laser interference direct writing, the pixel size of the open-area hollow structure is 30 μm x 30 μm, and the pixel pitch is 30 μm.
9. The method for preparing a lens capable of converting infrared rays into visible light waveband images according to the claim 7, wherein the vapor deposition rate of the two-dimensional square nano-silver metal crystal periodic array super-surface thin film layer in the step S2 is 0.1 nm/S-1.0 nm/S.
10. The method of claim 7, wherein the deposition rate of the rare earth ion doped upconversion luminescence infrared imaging material film in step S4 is 0.3nm/S to 1.0 nm/S.
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