Design method and preparation method of chalcogenide glass substrate 8-12 [mu] m wave band high-transmittance film color controllable thin film

Abstract

The invention provides a design method and a preparation method of a chalcogenide glass substrate 8-12 [mu] m wave band high-transmittance film color controllable film. The design method of the 8-12 [mu] m waveband high-transmittance film color controllable thin film on the chalcogenide glass substrate comprises the steps that Sa, 550 nm serves as the reference wavelength of optical thin film design, a film stack formula Sub / M0.5 (L2HL) 50.5 (KL) 5 / AIR is used, the two faces are plated with the same film system, Sub is IRG chalcogenide glass, AIR represents air, H represents Ge, L represents ZnS, K represents YbF3, and M represents IDA; sb, generating a Sub / IDA / ZnS / Ge / ZnS / Ge / ZnS / YbF3 / ZnS / Air film layer structure through a film stack formula; sc, the optimization target is a film color target and a transmittance target, the film color target is one or two adjacent colors of red, orange, yellow, green, cyan, blue and purple light colors of visible light, and the to-be-designed spectral reflection peak value is located at the wavelength of the corresponding light color if the film color of one or two adjacent light colors needs to be designed; sd, the thickness of the film layer is optimized, the optimal thickness of the film layer is obtained, the transmittance of the optimized film layer structure reaches the target, and the film color is controllable; and Se, the optimal film layer thickness is input into a film plating machine.

Description

Technical Field

[0001] The present disclosure relates to the field of infrared optical film technology, and more specifically to a design method and a preparation method of a chalcogenide glass substrate 8-12 μm band high-transmittance color-controllable film. Background Art

[0002] 8-12μm is a common application band for long-wave infrared. Lenses in this band have strong detection capabilities for low-temperature objects and are suitable for temperature measurement and thermal imaging of low-temperature objects. They are widely used in infrared thermal imagers, infrared thermometers, infrared thermal imaging, night vision security equipment and other fields. Secondly, long-wave infrared can penetrate many common materials, such as smoke, haze, plastic, etc., and can be used to see through and detect heat sources or hidden objects in objects. Due to different requirements for film performance in application scenarios and different preferences for film color by customers, it is more difficult to select coating materials, design film systems, and improve the specific process of coating technology. Summary of the invention

[0003] In view of the problems existing in the background technology, an object of the present disclosure is to provide a design method and a preparation method of a chalcogenide glass substrate with high transmittance and controllable film color in the 8-12 μm band, which can make the designed and prepared chalcogenide glass substrate and the film system on both sides meet the requirements in the 8-12 μm band and the film color is controllable;

[0004] Another object of the present disclosure is to provide a design method and a preparation method for a high-transmittance, color-controllable thin film in the 8-12 μm band on a chalcogenide glass substrate, which can enable the designed and prepared silicon substrate and the film systems on both sides to meet the requirements of different application scenarios.

[0005] Therefore, a design method for a chalcogenide glass substrate 8-12 μm band high transmittance color controllable film comprises the following steps:

[0006] Sa, the film system design uses 550nm as the reference wavelength for optical thin film design, and uses the film stack formula: Sub / M0.5(L2HL)^5 0.5(KL)^5 / AIR. The same film system is plated on both sides of Sub, where Sub is a chalcogenide glass substrate, which is IRG chalcogenide glass, and AIR represents air. In the film stack expression: H represents a high refractive index material Ge (germanium) with a thickness of 1 / 4 wavelength, L represents a medium refractive index material ZnS (zinc sulfide) with a thickness of 1 / 4 wavelength, K represents a low refractive index material YbF3 (ytterbium fluoride) with a thickness of 1 / 4 wavelength, and M represents a base material IDA (titanium) with a thickness of 1 / 4 wavelength. , praseodymium oxide mixture); Sb, generate the film structure of Sub / IDA / ZnS / Ge / ZnS / Ge / ZnS / YbF3 / ZnS / Air through the input film stack formula; Sc, set the optimization target, the optimization target is the film color target and the transmittance target, the film color target is one or two adjacent colors of the red, orange, yellow, green, cyan, blue and purple of visible light. If you want to design a film color for one or two adjacent colors, the spectral reflection peak that needs to be designed is located at the wavelength of the corresponding light color.

[0007] Light Color Wavelength (nm) Frequency (Hz) Central wavelength (nm) red 780-622 <![CDATA[3.8×10 14 -4.8×10 14 ]]> 660 orange 622-597 <![CDATA[4.8×10 14 -5.0×10 14 ]]> 610 yellow 597-577 <![CDATA[5.0×10 14 -5.4×10 14 ]]> 580 green 577-492 <![CDATA[5.4×10 14 -6.1×10 14 ]]> 540 green 492-470 <![CDATA[6.1×10 14 -6.4×10 14 ]]> 480 blue 470-455 <![CDATA[6.4×10 14 -6.6×10 14 ]]> 460 purple 455-380 <![CDATA[6.6×10 14 -7.9×10 14 ]]> 430

[0008] ; Sd, the film thickness is optimized through thin film design software to obtain the best film thickness. The transmittance of the optimized film structure in the 8-12μm band reaches the target and the film color is controllable; Se, the optimized best film thickness is input into the control computer of the coating machine.

[0009] A method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance film color controllable film, characterized in that it includes the following steps: S1, cleaning the chalcogenide glass substrate product as a lens and the accompanying coating sheet before plating, and preparing four film materials of IDA, ZnS, Ge and YbF3, wherein the film material of the IDA film layer is Ida (Ti-Pr-Oxide) particles with a diameter of 0.7-3.5 mm and a brand number of 0484519 purchased from umicore, USA; S2, configuration of the coating process conditions and process files, wherein the configuration of the coating process conditions and process files includes the coating temperature, the background vacuum before plating, the film thickness, the evaporation mode of the film material, the deposition rate of the film material, and the ion source assisted deposition. Use and parameters, wherein the film thickness is based on the optimal film thickness stored in the control computer of the coating machine in the design method of the aforementioned chalcogenide glass substrate 8-12μm band high-transmittance film color controllable film; S3, the cleaned lens is placed in a fixture, the fixture with the lens placed is hung in the cavity of the coating machine, and the door is closed to evacuate and heat; S4, film material pre-melting; S5, ion source pre-cleaning; S6, film coating and monitoring, according to the coating process conditions of step S2 and the configuration of the process file, the film is coated on the first side of the lens; S7, constant temperature is maintained after coating; S8, cooling and taking out the parts; S9, repeating steps S1 to S8, and coating the second side of the lens.

[0010] The beneficial effects of the present disclosure are as follows.

[0011] In the design method of a chalcogenide glass substrate 8-12μm band high transmittance color controllable film according to the present disclosure, IDA is used as a primer layer and as a connecting layer between the chalcogenide glass substrate and the ZnS film layer, which plays a role in enhancing the bonding force between the chalcogenide glass substrate and the film layer, Ge is used as a high refractive index material, YbF3 is used as a low refractive index material, and ZnS is used as a medium refractive index material and also serves as the outermost protective layer. Therefore, not only the transmittance of the designed film structure in the 8-12μm band can meet the requirements, but also the combination of the primer layer and the silicon substrate in the film system on both sides, the blister test, salt spray test, adhesion test, moderate friction test, constant temperature and humidity test, low temperature test and high temperature test in the testing process of the two-sided film system are taken into consideration, so as to meet the requirements of different application scenarios.

[0012] In the method for preparing a high-transmittance, color-controllable film in the 8-12 μm band on a chalcogenide glass substrate according to the present disclosure, based on steps S1 to S9 and based on the optimal film thickness stored in the control computer of the coating machine in the aforementioned design method for a high-transmittance, color-controllable film on a chalcogenide glass substrate in the 8-12 μm band, as verified by the test, the transmittance of the prepared chalcogenide glass substrate together with the film systems on both sides in the 8-12 μm band can meet the requirements, and at the same time can meet the requirements of a blister test, a salt spray test, an adhesion test, a moderate friction test, a constant temperature and humidity test, a low temperature test, and a high temperature test, thereby meeting the requirements of different application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic structural diagram of the film layer structure according to the design method and preparation method of the 8-12 μm band high-transmittance color-controllable film on the chalcogenide glass substrate disclosed in the present invention.

[0014] Figure 2 This is a transmittance curve diagram designed by the design method of the 8-12 μm band high-transmittance color-controllable thin film on a chalcogenide glass substrate in Example 1.

[0015] Figure 3 This is a transmittance curve diagram of the accompanying coating sheet and the film system on both sides after the coating is completed in the method for preparing a high-transmittance color-controllable film in the 8-12 μm band on a chalcogenide glass substrate of Example 1.

[0016] Figure 4 These are photos of the method for preparing a high-transmittance, color-controllable thin film in the 8-12 μm band on a chalcogenide glass substrate of Example 1, after coating, of the product together with the films on both sides before and after the adhesion test.

[0017] Figure 5 These are photos of the method for preparing a high-transmittance, color-controllable thin film in the 8-12 μm band on a chalcogenide glass substrate of Example 1 after coating is completed, and before and after a constant temperature and humidity test of the film system on both sides.

[0018] Figure 6 These are photos of the accompanying coating sheet and the film systems on both sides after coating is completed according to the preparation methods of Example 1 and Comparative Example 1, wherein the left photo corresponds to Example 1 and the right photo corresponds to Comparative Example 1. DETAILED DESCRIPTION

[0019] It is understood that the disclosed embodiments are merely examples of the present disclosure, which may be implemented in various forms, and therefore, the specific details disclosed herein should not be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one of ordinary skill in the art to variously implement the present disclosure.

[0020] [Design method of high transmittance color-controllable thin films in the 8-12μm band on chalcogenide glass substrate]

[0021] Reference Figure 1 and Figure 2 According to the disclosed method, the design method of the 8-12 μm band high-transmittance color-controllable thin film on the chalcogenide glass substrate comprises the following steps:

[0022] Sa, the film system design uses 550nm as the reference wavelength for optical thin film design, and uses the film stack formula: Sub / M0.5(L2HL)^5 0.5(KL)^5 / AIR. The same film system is plated on both sides of Sub, where Sub is a chalcogenide glass substrate, which is an IRG chalcogenide glass, and AIR represents air. In the film stack expression:

[0023] H represents the high refractive index material Ge (germanium) with a thickness of 1 / 4 wavelength.

[0024] L represents the medium refractive index material ZnS (zinc sulfide) with a thickness of 1 / 4 wavelength.

[0025] K represents the low refractive index material YbF3 (ytterbium fluoride) with a thickness of 1 / 4 wavelength.

[0026] M represents the base material IDA (titanium and praseodymium oxide mixture) with a thickness of 1 / 4 wavelength;

[0027] Sb, through the input film stack formula, generates the film layer structure of Sub / IDA / ZnS / Ge / ZnS / Ge / ZnS / YbF3 / ZnS / Air;

[0028] Sc, set the optimization target, the optimization target is the film color target and the transmittance target, the film color target is one or two adjacent colors of the red, orange, yellow, green, cyan, blue and purple colors of visible light, and the film color of which one or two adjacent colors you want to design needs to have the spectral reflectance peak at the wavelength of the corresponding color;

[0029] Light Color Wavelength (nm) Frequency (Hz) Central wavelength (nm) red 780-622 <![CDATA[3.8×10 14 -4.8×10 14 ]]> 660 orange 622-597 <![CDATA[4.8×10 14 -5.0×10 14 ]]> 610 yellow 597-577 <![CDATA[5.0×10 14 -5.4×10 14 ]]> 580 green 577-492 <![CDATA[5.4×10 14 -6.1×10 14 ]]> 540 green 492-470 <![CDATA[6.1×10 14 -6.4×10 14 ]]> 480 blue 470-455 <![CDATA[6.4×10 14 -6.6×10 14 ]]> 460 purple 455-380 <![CDATA[6.6×10 14 -7.9×10 14 ]]> 430

[0030] Sd, the film thickness is optimized by thin film design software to obtain the best film thickness. The optimized film structure has the target transmittance in the 8-12μm band and the film color is controllable;

[0031] Se, the optimized best film thickness is input into the control computer of the coating machine.

[0032] In the design method of a chalcogenide glass substrate 8-12μm band high transmittance color controllable film according to the present disclosure, IDA is used as a primer layer and as a connecting layer between the chalcogenide glass substrate and the ZnS film layer, which plays a role in enhancing the bonding force between the chalcogenide glass substrate and the film layer, Ge is used as a high refractive index material, YbF3 is used as a low refractive index material, and ZnS is used as a medium refractive index material and is also used as the outermost protective layer. Therefore, not only the transmittance of the designed film layer structure in the 8-12μm band can meet the requirements, but also the combination of the primer layer and the silicon substrate in the film system on both sides, the blister test, salt spray test, adhesion test, moderate friction test, constant temperature and humidity test, low temperature test and high temperature test in the test process of the two-sided film system described later are taken into consideration, so as to meet the requirements of different application scenarios.

[0033] In one example, in step Sa, the IRG chalcogenide glass is IRG04, IRG06 or IRG09.

[0034] In one example, in step Sd, for each of the two sides of the lens, the optimal film thickness is expressed as a film structure as follows:

[0035] Sub / IDA(25) / ZnS(28.51) / Ge(19.42) / ZnS(632.92) / Ge(44.57) / ZnS(249.16) / YbF3(1517.1) / ZnS(60) / Air. The numbers in brackets are the film thickness. The unit of the film thickness is nm.

[0036] In one example, in step Sd, the transmittance of the optimized chalcogenide glass substrate in the 8-12 μm band is greater than 99.8% on average.

[0037] In one example, in step Sa to step Se, the design software is TFCalc or Essential Macleod.

[0038] [Preparation method of high-transmittance color-controllable thin film in the 8-12μm band on chalcogenide glass substrate]

[0039] The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable film according to the present disclosure comprises the following steps:

[0040] S1, cleaning of the chalcogenide glass substrate product and accompanying plating sheet as the lens before plating and preparation of four film materials: IDA, ZnS, Ge and YbF3. The film material of the IDA film layer is Ida (Ti-Pr-Oxide) particles with a diameter of 0.7-3.5 mm, purchased from Umicore, USA, with a brand number of 0484519;

[0041] S2, configuration of coating process conditions and process files, including coating temperature, background vacuum before coating, film thickness, film material evaporation mode, film material deposition rate, use and parameters of ion source assisted deposition, wherein the film thickness is based on the optimal film thickness stored in the control computer of the coating machine in the design method of the 8-12 μm band high-transmittance film color controllable film on the aforementioned chalcogenide glass substrate;

[0042] S3, the cleaned lens is placed in a fixture, the fixture with the lens is hung in the cavity of the coating machine, and the door is closed to evacuate and heat;

[0043] S4, pre-melting of film material;

[0044] S5, ion source pre-cleaning;

[0045] S6, coating and monitoring the film layer, coating the film layer on the first surface of the lens according to the coating process conditions and the configuration of the process file of step S2;

[0046] S7, constant temperature maintenance after coating;

[0047] S8, cooling and picking up;

[0048] S9, repeating steps S1 to S8 to perform film coating on the second surface of the lens.

[0049] In the method for preparing a high-transmittance, color-controllable film in the 8-12 μm band on a chalcogenide glass substrate according to the present disclosure, based on steps S1 to S9 and based on the optimal film thickness stored in the control computer of the coating machine in the aforementioned design method for a high-transmittance, color-controllable film on a chalcogenide glass substrate in the 8-12 μm band, as verified by subsequent tests, the transmittance of the prepared chalcogenide glass substrate together with the film systems on both sides in the 8-12 μm band can meet the requirements, and at the same time can meet the requirements of a water bubble test, a salt spray test, an adhesion test, a moderate friction test, a constant temperature and humidity test, a low temperature test, and a high temperature test, thereby meeting the requirements of different application scenarios.

[0050] In one example, in step S1 , the IRG chalcogenide glass is IRG04, IRG06 or IRG09.

[0051] In one example, in step S1, the product is a (50±0.1) mm×(10±0.1) mm convex mirror, and the accompanying plated sheet is a (25±0.1) mm×(2±0.1) mm round sheet.

[0052] The cleaning in step S1 makes the surface of the lens clean, which is conducive to the adhesion and bonding of the film layer. In one example, in step S1, the lens is cleaned using ultrasonic alcohol.

[0053] In one example, in step S2, the coating temperature is 130°C; the background vacuum before coating is 1.5×10 -3 Pa; the film thickness in the configuration of the coating process conditions and process files is based on the optimal film thickness stored in the control computer of the coating machine in the design method of the 8-12μm band high-transmittance film with controllable color on the aforementioned chalcogenide glass substrate; the evaporation mode of the film material is: ZnS and YbF3 are evaporated by resistance heating, and IDA and Ge are evaporated by electron beam heating; the deposition rate of the film material is: the deposition rate of the IDA film layer is The deposition rate of the Ge film is The deposition rate of ZnS film is The deposition rate of YbF3 film is The use of ion source assisted deposition is: the ion source is not turned on for all film layers.

[0054] In one example, in step S2, the coating machine is Leybold ARES1350.

[0055] In one example, in step S3, the vacuum is first evacuated to 5×10 -2 Pa, then the cavity of the coating machine starts heating, first heated to 130℃, then increased the temperature by 1℃ / min every 10℃ and maintained for 10min for gradient heating, increased to 190℃ and then decreased the temperature by 1℃ / min every 10℃ and maintained for 10min to 130℃, and then maintained for 2h. That is, after heating to 130°C, the temperature was increased to 140°C at 1°C / min and maintained for 10 min, then the temperature was increased to 150°C at 1°C / min and maintained for 10 min, then the temperature was increased to 160°C at 1°C / min and maintained for 10 min, then the temperature was increased to 170°C at 1°C / min and maintained for 10 min, then the temperature was increased to 180°C at 1°C / min and maintained for 10 min, then the temperature was increased to 190°C at 1°C / min and maintained for 10 min, then the temperature was decreased to 180°C at 1°C / min and maintained for 10 min, then the temperature was decreased to 170°C at 1°C / min and maintained for 10 min, then the temperature was decreased to 160°C at 1°C / min and maintained for 10 min, then the temperature was decreased to 150°C at 1°C / min and maintained for 10 min, then the temperature was decreased to 140°C at 1°C / min and maintained for 10 min, then the temperature was decreased to 130°C at 1°C / min and maintained for 2 h. In addition, in one example, in step S3, heating to 130°C first is heating from room temperature to 130°C at 5°C / min.

[0056] In step S4, the film material is pre-melted to release air and remove impurities to ensure the purity of the film material. In one example, in step S4, when the vacuum reaches (4.0-5.0)×10 -3Pa, the film material is pre-melted, and after the pre-melting of the film material is completed, the temperature of the cavity of the coating machine reaches 130°C and is kept constant for 10 minutes. Specifically, for example, in step S4, the pre-melting treatment adopts two methods: electron beam heating and resistance heating. For Ge film material, the current of electron beam heating is 260-290mA; for IDA film material, the current of electron beam heating is 420-480mA; for ZnS film material, the current of resistance heating is 720-760mA; for YbF3 film material, the current of resistance heating is 860-900mA.

[0057] The ion source cleaning in step S5 removes impurities on the surface of the chalcogenide glass substrate, making the surface of the chalcogenide glass substrate cleaner and increasing the adhesion of the film layer. In one example, the vacuum degree of the chamber reaches (1.5±0.1)×10 -3 Pa, start the ion source to clean the lens with ions, the ion source is an APS ion source, the parameters of the APS ion source are: ion source voltage is 700±50V, ion source current is 700±50mA, acceleration voltage is 500±50V, acceleration current is 700±50mA, the ion source uses pure argon gas, the ion source argon gas input is 60±5sccm, the neutralizer argon gas input is 8±0.13sccm, and the cleaning time is 300±2s.

[0058] In one example, in step S6, when coating each film layer, no gas is introduced into the cavity of the coating machine from outside the coating machine, and the cavity of the coating machine is evacuated and the coating temperature is maintained at 130°C; each film layer is plated at a cavity temperature of 130°C of the coating machine; the crystal oscillator method is used to monitor the film thickness using the corresponding crystal oscillator of the multiple crystal oscillators of the crystal controller, and after the ion source is cleaned, the crystal controller controls the corresponding operation of a new crystal oscillator among the multiple crystal oscillators, and the crystal oscillator frequency is not less than 5850Hz.

[0059] In one example, in step S7 , the chamber is kept at 130° C. for 40 minutes after plating is completed.

[0060] In one example, in step S8, after step S7 is completed, the temperature is first lowered to 110°C at 1°C / min and held for 5 minutes, then lowered to 90°C at 1°C / min and held for 5 minutes, and then lowered to below 60°C at 1°C / min, and the door is opened to take out the items.

[0061] [test]

[0062] Example 1

[0063] Part 1: Design method of high transmittance and color controllable thin films in the 8-12 μm band on chalcogenide glass substrate

[0064] The design method of the 8-12μm band high-transmittance color-controllable film on a chalcogenide glass substrate adopts the following steps:

[0065] Sa, the film system design uses 550nm as the reference wavelength for optical thin film design. In TFCalc, the film stack formula is used: Sub / M0.5(L2HL)^5 0.5(KL)^5 / AIR. The same film system is plated on both sides of Sub, where Sub is a chalcogenide glass substrate, which is IRG06 chalcogenide glass. AIR represents air. In the film stack expression:

[0066] H represents the high refractive index material Ge (germanium) with a thickness of 1 / 4 wavelength.

[0067] L represents the medium refractive index material ZnS (zinc sulfide) with a thickness of 1 / 4 wavelength.

[0068] K represents the low refractive index material YbF3 (ytterbium fluoride) with a thickness of 1 / 4 wavelength.

[0069] M represents the base material IDA (titanium and praseodymium oxide mixture) with a thickness of 1 / 4 wavelength.

[0070] Sb, through the input film stack formula, generates the film layer structure of Sub / IDA / ZnS / Ge / ZnS / Ge / ZnS / YbF3 / ZnS / Air;

[0071] Sc, set the optimization target, the optimization target is the film color target and the transmittance target, the film color target is one or two adjacent colors of the red, orange, yellow, green, cyan, blue and purple colors of visible light, and the film color of which one or two adjacent colors you want to design needs to have the spectral reflectance peak at the wavelength of the corresponding color;

[0072] Light Color Wavelength (nm) Frequency (Hz) Central wavelength (nm) red 780-622 <![CDATA[3.8×10 14 -4.8×10 14 ]]> 660 orange 622-597 <![CDATA[4.8×10 14 -5.0×10 14 ]]> 610 yellow 597-577 <![CDATA[5.0×10 14 -5.4×10 14 ]]> 580 green 577-492 <![CDATA[5.4×10 14 -6.1×10 14 ]]> 540 green 492-470 <![CDATA[6.1×10 14 -6.4×10 14 ]]> 480 blue 470-455 <![CDATA[6.4×10 14 -6.6×10 14 ]]> 460 purple 455-380 <![CDATA[6.6×10 14 -7.9×10 14 ]]> 430

[0073] Among them, the film color target of the film system is yellow-green light color, and the spectral reflection peak is set at 510-580nm;

[0074] Sd, the film thickness is optimized by thin film design software TFCalc to obtain the best film thickness. The optimized film structure has the target transmittance in the 8-12μm band and the film color is controllable.

[0075] In step Sd, for each of the two sides of the lens, the optimal film thickness is determined by the film thickness.

[0076] The layer structure is represented as:

[0077] Sub / IDA(25) / ZnS(28.51) / Ge(19.42) / ZnS(632.92) / Ge(44.57) / ZnS(249.1

[0078] 6) / YbF3(1517.1) / ZnS(60) / Air. The numbers in brackets are the film thickness.

[0079] The bit is nm;

[0080] Se, the optimized best film thickness is input into the control computer of the coating machine, the coating machine is Leybold ARES1350.

[0081] Part II: Preparation method of high transmittance and color controllable thin film in the 8-12 μm band on chalcogenide glass substrate

[0082] The preparation method of the 8-12 μm band high-transmittance color-controllable thin film on a chalcogenide glass substrate adopts the following steps:

[0083] S1, cleaning of the chalcogenide glass substrate product and the accompanying plating sheet as the lens before plating, and preparation of four film materials: IDA, ZnS, Ge and YbF3. The chalcogenide glass substrate is IRG06 chalcogenide glass, the product is a 50mm×10mm convex lens, the accompanying plating sheet is a 25mm×2mm round sheet, the lens is cleaned with ultrasonic alcohol, and the film material of the IDA film layer is Ida (Ti-Pr-Oxide) particles with a diameter of 0.7-3.5mm, purchased from Umicore, USA, with a brand number of 0484519;

[0084] S2, configuration of coating process conditions and process files, including coating temperature, background vacuum before coating, film thickness, film material evaporation mode, film material deposition rate, use and parameters of ion source assisted deposition, wherein the film thickness is based on the optimal film thickness stored in the control computer of the coating machine according to the design method of the 8-12 μm band high-transmittance film color controllable film on the chalcogenide glass substrate in the first part above;

[0085] In step S2,

[0086] The coating temperature is 130°C;

[0087] The background vacuum before plating is 1.5×10 -3 Pa;

[0088] The coating process conditions and the film thickness in the configuration of the process file are based on the optimal film thickness stored in the control computer of the coating machine as described in the design method of the 8-12 μm band high-transmittance film color controllable film on the chalcogenide glass substrate in the first part above;

[0089] The evaporation mode of the film materials is: ZnS and YbF3 are evaporated by resistance heating, and IDA and Ge are evaporated by electron beam heating;

[0090] The deposition rate of the film material is: The deposition rate of the IDA film layer is The deposition rate of the Ge film is The deposition rate of ZnS film is The deposition rate of YbF3 film is

[0091] The use of ion source assisted deposition is: the ion source is not turned on for all film layers;

[0092] S3, put the cleaned lens into the fixture, hang the fixture with the lens into the chamber of the coating machine, close the door, and first vacuumize to 5×10 -2 Pa, then the cavity of the coating machine starts heating, heating from room temperature to 130℃ at 5℃ / min, then heating to 140℃ at 1℃ / min and keeping for 10min, then heating to 150℃ at 1℃ / min and keeping for 10min, then heating to 160℃ at 1℃ / min and keeping for 10min, then heating to 170℃ at 1℃ / min and keeping for 10min, then heating to 180℃ at 1℃ / min and keeping for 10min, then heating to 190℃ at 1℃ / min and keeping for 10min, then heating to 110℃ at ... min to 190℃ and hold for 10min, then cool down to 180℃ and hold for 10min, then cool down to 170℃ and hold for 10min, then cool down to 160℃ and hold for 10min, then cool down to 150℃ and hold for 10min, then cool down to 140℃ and hold for 10min, then cool down to 130℃ and hold for 2h at 1℃ / min;

[0093] S4, film material pre-melting, when the vacuum reaches 5.0×10 -3 The film material is pre-melted at Pa. After the pre-melting of the film material is completed, the temperature of the cavity of the coating machine reaches 130°C and is kept constant for 10 minutes.

[0094] In step S4, the pre-melting process uses electron beam heating and resistance heating.

[0095] For Ge film material, the current of electron beam heating is 265mA;

[0096] For IDA film material, the current of electron beam heating is 450mA;

[0097] For ZnS film material, the current of resistance heating is 740mA;

[0098] For YbF3 film material, the current of resistance heating is 880mA;

[0099] S5, ion source pre-cleaning, chamber vacuum reaches 1.5×10 -3Pa, start the ion source to clean the lens with ions, the ion source is an APS ion source, the parameters of the APS ion source are: ion source voltage is 700V, ion source current is 700mA, acceleration voltage is 500V, acceleration current is 700mA, the ion source uses pure argon gas, the ion source argon gas flow rate is 60sccm, the neutralizer argon gas flow rate is 8sccm, and the cleaning time is 300s;

[0100] S6, coating and monitoring the film layer, coating the film layer on the first surface of the lens according to the coating process conditions and the configuration of the process file of step S2;

[0101] In step S6,

[0102] When coating each film layer, no gas is introduced into the cavity of the coating machine from outside the coating machine, and the cavity of the coating machine is kept evacuated and the coating temperature is kept at 130°C;

[0103] Each film layer is coated at a chamber temperature of 130°C in the coating machine;

[0104] The crystal oscillator method uses the corresponding crystal oscillator of the multiple crystal oscillators of the crystal controller to monitor the film thickness. After the ion source is cleaned, the crystal controller controls the corresponding operation of the new crystal oscillator among the multiple crystal oscillators.

[0105] The vibration frequency is 5990Hz;

[0106] S7,,After plating is completed, the cavity is kept at 130°C for 40 minutes;

[0107] S8, after step S7 is completed, the temperature is first lowered to 110°C at 1°C / min and held for 5 minutes, then lowered to 90°C at 1°C / min and held for 5 minutes, and then lowered to 60°C at 1°C / min, and the door is opened to take out the items;

[0108] S9, repeating steps S1 to S8 to perform film coating on the second surface of the lens.

[0109] Comparative Example 1

[0110] The process is the same as in Example 1 except that in step 3, the temperature is heated from room temperature to 130° C. at 5° C. / min and maintained for 2 h (ie, after heating to 130° C., no gradient heating or cooling is performed).

[0111] Comparative Example 2

[0112] In addition to introducing argon gas from the outside of the coating machine into the cavity of the coating machine when coating each film layer in step S6, the cavity of the coating machine is evacuated and the vacuum degree of the coating is maintained at 5×10 -3 Except for Pa, the rest is the same as in Example 1.

[0113] Figure 2 8-12 μm band high transmittance color controllable film of chalcogenide glass substrate designed by the design method of Example 1. Figure 2 It can be seen that the average transmittance of the chalcogenide glass substrate together with the films on both sides in the 8-12 μm band is 99.81% (ie, more than 99.8%).

[0114] Figure 3 This is a transmittance curve of the accompanying plate and the film system on both sides after the coating is completed in the method for preparing a high-transmittance color-controllable film in the 8-12 μm band of a chalcogenide glass substrate in Example 1. Figure 3 It can be seen that the average transmittance of the accompanying coating sheet and the film system on both sides is 98.1% (ie, more than 98%).

[0115] The products of Example 1 and Comparative Examples 1-2, together with the membrane systems on both sides, were subjected to the following overall performance test.

[0116] Water bubble test: Take tap water to conduct a water bubble test for 2 hours to observe whether the film layer on each surface falls off or cracks.

[0117] Salt spray test: neutral salt spray test for 24 hours, observe whether the film layer on each surface falls off or cracks.

[0118] Adhesion test: Use your hands to stick 3M tape on each side and pull the tape in the direction opposite to the sticking end to see if the film layer is pulled up.

[0119] Moderate friction test: The film layer is rubbed 50 times with a rubber friction head wrapped with degreased cloth at a pressure of 4.9N, and observe whether there are scratches or damage.

[0120] Constant temperature and humidity test: In a constant temperature and humidity chamber, at 50°C and 95% relative humidity for 24 hours, observe whether the film layers on each surface fall off or crack.

[0121] Low temperature test: In a low temperature box, at -40℃ for 24 hours, observe whether the film layers on each surface fall off or crack.

[0122] High temperature test: In a high temperature box, 85℃ for 24 hours, observe whether the film layers on each surface fall off or crack.

[0123] The product of Example 1 and the films on both sides passed all the water bubble tests, salt spray tests, adhesion tests, moderate friction tests, constant temperature and humidity tests, low temperature tests, and high temperature tests. Figure 4 These are photos of the method for preparing a high-transmittance, color-controllable thin film in the 8-12 μm band on a chalcogenide glass substrate of Example 1, after coating, of the product together with the films on both sides before and after the adhesion test. Figure 5These are photos of the method for preparing a high-transmittance, color-controllable thin film in the 8-12 μm band on a chalcogenide glass substrate of Example 1 after coating was completed, and before and after a constant temperature and humidity test of the product and the film systems on both sides. Figure 6 These are photos of the accompanying coating sheet and the film systems on both sides after coating is completed according to the preparation methods of Example 1 and Comparative Example 1, wherein the left photo corresponds to Example 1 and the right photo corresponds to Comparative Example 1.

[0124] Table 1 shows the average transmittance of Example 1 and Comparative Examples 1-2, the results of various tests, and the film colors.

[0125] Table 1 Average transmittance of Example 1 and Comparative Examples 1-2, results of various tests and film color

[0126]

[0127] The above detailed description is used to describe multiple exemplary embodiments, but this document is not intended to be limited to the explicitly disclosed combinations. Therefore, unless otherwise stated, the various features disclosed herein can be combined together to form multiple additional combinations that are not shown for the sake of simplicity.

Claims

1. A design method for a chalcogenide glass substrate 8-12 μm band high transmittance color controllable film, characterized in that: Includes steps: Sa, the film system design uses 550nm as the reference wavelength for optical thin film design, and uses the film stack formula: Sub / M0.5(L2HL)^5 0.5(KL)^5 / AIR. The same film system is plated on both sides of Sub, where Sub is a chalcogenide glass substrate, which is an IRG chalcogenide glass, and AIR represents air. In the film stack expression: H represents the high refractive index material Ge (germanium) with a thickness of 1 / 4 wavelength. L represents the medium refractive index material ZnS (zinc sulfide) with a thickness of 1 / 4 wavelength. K represents the low refractive index material YbF3 (ytterbium fluoride) with a thickness of 1 / 4 wavelength. M represents the base material IDA (titanium and praseodymium oxide mixture) with a thickness of 1 / 4 wavelength; Sb, through the input film stack formula, generates the film layer structure of Sub / IDA / ZnS / Ge / ZnS / Ge / ZnS / YbF3 / ZnS / Air; Sc, set the optimization target, the optimization target is the film color target and the transmittance target, the film color target is one or two adjacent colors of the red, orange, yellow, green, cyan, blue, and purple colors of visible light. If you want to design a film color for one or two adjacent colors, the spectral reflection peak of the design needs to be located at the wavelength of the corresponding color. ； Sd, the film thickness is optimized by thin film design software to obtain the best film thickness. The optimized film structure has the target transmittance in the 8-12μm band and the film color is controllable; Se, the optimized best film thickness is input into the control computer of the coating machine.

2. The design method of the 8-12 μm band high-transmittance color-controllable thin film on a chalcogenide glass substrate according to claim 1, characterized in that: In step Sa, the IRG chalcogenide glass is IRG04, IRG06 or IRG09; In step Sd, for each of the two sides of the lens, the optimal film thickness is expressed as a film structure: Sub / IDA(25) / ZnS(28.51) / Ge(19.42) / ZnS(632.92) / Ge(44.57) / ZnS(249.16) / YbF3(1517.1) / ZnS(60) / Air, the numbers in brackets are the film thickness, and the unit of the film thickness is nm; In step Sd, the transmittance of the optimized chalcogenide glass substrate in the 8-12 μm band is greater than 99.8% on average.

3. A method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable film, characterized in that: Includes steps: S1, cleaning of the chalcogenide glass substrate product and accompanying plating sheet as the lens before plating and preparation of four film materials: IDA, ZnS, Ge and YbF3. The film material of the IDA film layer is Ida (Ti-Pr-Oxide) particles with a diameter of 0.7-3.5 mm, purchased from Umicore, USA, with a brand number of 0484519; S2, configuration of coating process conditions and process files, the configuration of coating process conditions and process files includes coating temperature, background vacuum before coating, film thickness, evaporation mode of film material, deposition rate of film material, use and parameters of ion source assisted deposition, wherein the film thickness is based on the optimal film thickness stored in the control computer of the coating machine according to any one of claims 1-2; S3, the cleaned lens is placed in a fixture, the fixture with the lens is hung in the cavity of the coating machine, and the door is closed to evacuate and heat; S4, pre-melting of film material; S5, ion source pre-cleaning; S6, coating and monitoring the film layer, coating the film layer on the first surface of the lens according to the coating process conditions and the configuration of the process file of step S2; S7, constant temperature maintenance after coating; S8, cooling and picking up; S9, repeating steps S1 to S8 to perform film coating on the second surface of the lens.

4. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S1, IRG chalcogenide glass is IRG04, IRG06 or IRG09; The product is a (50±0.1)mm×(10±0.1)mm convex mirror, and the accompanying plate is a (25±0.1)mm×(2±0.1)mm round plate; The lenses are cleaned with ultrasonic alcohol.

5. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S2, The coating temperature is 130°C; The background vacuum before plating is 1.5×10 -3 Pa; Coating process conditions and film thickness in the configuration of process files Based on the optimal film thickness stored in the control computer of the coating machine according to claim 3; The evaporation mode of the film materials is: ZnS and YbF3 are evaporated by resistance heating, and IDA and Ge are evaporated by electron beam heating; The deposition rate of the film material is: The deposition rate of the IDA film layer is The deposition rate of the Ge film is The deposition rate of ZnS film is The deposition rate of YbF3 film is The use of ion source assisted deposition is: the ion source is not turned on for all film layers; In step S2, the coating machine is Leybold ARES1350.

6. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S3, the vacuum is first evacuated to 5×10 -2 Pa, then the coating machine cavity starts heating, first heated to 130℃, then increased by 1℃ / min for every 10℃ and maintained for 10min, gradually increased the temperature to 190℃, then decreased by 1℃ / min for every 10℃ and maintained for 10min to 130℃, and then maintained for 2h; In step S3, heating to 130°C is performed from room temperature to 130°C at a rate of 5°C / min.

7. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S4, when the vacuum reaches (4.0-5.0)×10 -3 The film material is pre-melted at Pa. After the pre-melting of the film material is completed, the temperature of the cavity of the coating machine reaches 130°C and is kept constant for 10 minutes. In step S4, the pre-melting process uses electron beam heating and resistance heating. For Ge film material, the current of electron beam heating is 260-290mA; For IDA film materials, the current of electron beam heating is 420-480mA; For ZnS film material, the current of resistance heating is 720-760mA; For YbF3 film material, the current of resistance heating is 860-900mA.

8. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S5, The vacuum degree of the cavity reaches 1.5±0.1)×10 -3 Pa, start the ion source to clean the lens with ions, the ion source is an APS ion source, the parameters of the APS ion source are: ion source voltage is 700±50V, ion source current is 700±50mA, acceleration voltage is 500±50V, acceleration current is 700±50mA, the ion source uses pure argon gas, the ion source argon gas input is 60±5sccm, the neutralizer argon gas input is 8±0.13sccm, and the cleaning time is 300±2s.

9. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S6, When coating each film layer, no gas is introduced into the cavity of the coating machine from outside the coating machine, and the cavity of the coating machine is kept evacuated and the coating temperature is kept at 130°C; Each film layer is coated at a chamber temperature of 130°C in the coating machine; The crystal oscillator method is used to monitor the film thickness using the corresponding crystal oscillator pieces of the multiple crystal oscillator pieces of the crystal controller. After the ion source is cleaned, the crystal controller controls the corresponding operation of the new crystal oscillator pieces among the multiple crystal oscillator pieces, and the crystal oscillator frequency is not less than 5850Hz.

10. The method for preparing a chalcogenide glass substrate 8-12 μm band high transmittance color controllable thin film according to claim 3, characterized in that: In step S7, after the plating is completed, the cavity is kept at 130° C. for 40 minutes; In step S8, after step S7 is completed, the temperature is first lowered to 110°C at 1°C / min and held for 5 minutes, then lowered to 90°C at 1°C / min and held for 5 minutes, and then lowered to below 60°C at 1°C / min, and the door is opened to take out the items.

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