Laser reflecting film system and its preparation method and application

Abstract

The application provides a laser reflection film system, which comprises film system structures symmetrically arranged on two sides of a substrate, and the film system structure is Sub / 0.5L(H0.5L)^4(G0.5L)^2(M0.5L)^3 / Air, wherein Sub is the substrate, Air is an air as an exit medium, L represents a low refractive index layer with one basic thickness, H represents a first high refractive index layer with one basic thickness, G represents a second high refractive index layer with one basic thickness, and M represents a medium refractive index layer with one basic thickness, wherein the basic thickness corresponding to one H or one L or one G or one M represents that the film layer has a 1 / 4 optical thickness at a reference wavelength. The laser reflection film system provided has high reflectivity, good adhesion of film layers, good resistance to moderate friction, good resistance to constant temperature and humidity, and excellent anti-laser loss performance, and can be used as a high reflection film of a laser element. The application also provides a preparation method and application of the laser reflection film system.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of laser film system structure, and particularly relates to a high-reflection film used for a laser element after laser film coating, and a design and preparation method of the film system structure resistant to laser damage threshold of the thin film in the use of laser equipment. BACKGROUND

[0002] With the increasing requirements of industry (laser marking machine, laser cutting machine), medical laser instrument and military on laser output optical power and spot quality, the damage threshold and surface shape of the high-reflection film of the laser cavity mirror are increasingly required, how to prepare a full dielectric laser reflection film with high laser damage threshold and high laser beam quality becomes a research focus of domestic and foreign scholars, and is also a pursuit goal of optical coating enterprises. Most enterprises and research institutions adopt the method of electron gun thermal evaporation, the film layer prepared by this method is relatively loose, and surface defects are serious, and a small number of enterprises select ion beam sputtering (IBS) coating, but stress is large, surface shape changes greatly, and output spot quality cannot meet the use requirements. Some enterprises and institutions adopt the method of post-processing after coating to improve the damage threshold, but the threshold is not obviously improved, the surface shape changes little by releasing stress by heating, and rebounds with the increase of use time. To design and prepare a high-quality high-reflection film for a laser system, not only the spectral characteristics, but also the laser damage resistance of the thin film need to be considered, and the material density of the laser film is required to be very strict, in addition, the film layer adhesion, moderate friction resistance and constant temperature and humidity requirements also need to be met. SUMMARY

[0003] In view of the above technical problems, the present application provides a laser reflection film system, a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0005] In a first aspect, a laser reflection film system is provided, comprising a substrate and a film system structure symmetrically arranged on both sides of the substrate, the film system structure being Sub / 0.5L(H0.5L)^4(G0.5L)^2(M0.5L)^3 / Air, wherein Sub is the substrate, Air is the exit medium air, L represents a low refractive index layer with a basic thickness, H represents a first high refractive index layer with a basic thickness, G represents a second high refractive index layer with a basic thickness, and M represents a medium refractive index layer with a basic thickness, wherein the basic thickness corresponding to one H or one L or one G or one M represents that the film layer has a 1 / 4 optical thickness at a reference wavelength.

[0006] Further, the low refractive index layer is a SiO2 layer, the first high refractive index layer is a Ta2O5 layer, the second high refractive index layer is a Ti3O5 layer, and the medium refractive index layer is a HfO2 layer.

[0007] Further, the material of the substrate is quartz.

[0008] Further, the reflectivity of the laser reflection film system to light of 355 nm wavelength is 99% or more.

[0009] Further, the film system structure comprises a first SiO2 layer, a first Ta2O5 layer, a second SiO2 layer, a second Ta2O5 layer, a third SiO2 layer, a third Ta2O5 layer, a fourth SiO2 layer, a fourth Ta2O5 layer, a fifth SiO2 layer, a first Ti3O5 layer, a sixth SiO2 layer, a second Ti3O5 layer, a seventh SiO2 layer, a first HfO2 layer, an eighth SiO2 layer, a second HfO2 layer, a ninth SiO2 layer, a third HfO2 layer and a tenth SiO2 layer arranged in sequence on the surface of the silicon substrate; the thickness of the first SiO2 layer is 42-44 nm, the thickness of the first Ta2O5 layer is 40.5-42.5 nm, the thickness of the second SiO2 layer is 38.5-40.5 nm, the thickness of the second Ta2O5 layer is 26.5-28.5 nm, the thickness of the third SiO2 layer is 50.5-52.5 nm, the thickness of the third Ta2O5 layer is 46.5-48.5 nm, the thickness of the fourth SiO2 layer is 78.5-80.5 nm, the thickness of the fourth Ta2O5 layer is 46.5-48.5 nm, the thickness of the fifth SiO2 layer is 68.5-70.5 nm, the thickness of the first Ti3O5 layer is 86.5-88.5 nm, the thickness of the sixth SiO2 layer is 68.5-70.5 nm, the thickness of the second Ti3O5 layer is 11.3-13.5 nm, the thickness of the seventh SiO2 layer is 41.5-43.5 nm, the thickness of the first HfO2 layer is 49.5-51.5 nm, the thickness of the eighth SiO2 layer is 63.5-65.5 nm, the thickness of the second HfO2 layer is 68.5-70.5 nm, the thickness of the ninth SiO2 layer is 77-79 nm, the thickness of the third HfO2 layer is 57-59 nm, and the thickness of the tenth SiO2 layer is 160-163 nm.

[0010] Further, the thickness of the first SiO2 layer is 43 nm, the thickness of the first Ta2O5 layer is 41.42 nm, the thickness of the second SiO2 layer is 39.41 nm, the thickness of the second Ta2O5 layer is 27.46 nm, the thickness of the third SiO2 layer is 51.62 nm, the thickness of the third Ta2O5 layer is 47.47 nm, the thickness of the fourth SiO2 layer is 79.7 nm, the thickness of the fourth Ta2O5 layer is 47.47 nm, the thickness of the fifth SiO2 layer is 69.72 nm, the thickness of the first Ti3O5 layer is 87.46 nm, the thickness of the sixth SiO2 layer is 69.72 nm, the thickness of the second Ti3O5 layer is 12.34 nm, the thickness of the seventh SiO2 layer is 42.5 nm, the thickness of the first HfO2 layer is 50.71 nm, the thickness of the eighth SiO2 layer is 64.4 nm, the thickness of the second HfO2 layer is 69.67 nm, the thickness of the ninth SiO2 layer is 77.91 nm, the thickness of the third HfO2 layer is 57.92 nm, and the thickness of the tenth SiO2 layer is 161.5 nm.

[0011] In a second aspect, a method for preparing the laser reflection film system is provided, comprising:

[0012] coating the film layers on the first surface of the substrate according to the film layer structure of the first surface of the substrate;

[0013] coating the same film layers on the second surface of the substrate as on the first surface;

[0014] cooling to room temperature to obtain the laser reflection film system.

[0015] Further, before coating the film layers on the first surface and the second surface of the substrate, each of the processes comprises: placing the substrate into a coating machine, vacuumizing to 2.0×10 -3 ±0.5×10 -3 Pa, preheating to 115-125℃, and performing ion source cleaning.

[0016] Further, the coating temperature of each film layer is 115-125℃.

[0017] Further, the vacuum degree in the cavity during coating of each film layer is 2.0×10 -3 ±0.5×10 -3 Pa.

[0018] Further, the deposition rate of the SiO2 layer is 7.6-8.8 Å / s, the deposition rate of the Ta2O5 layer is 4.5-5.5 Å / s, the deposition rate of the Ti3O5 layer is 3-4 Å / s, and the deposition rate of the HfO2 layer is 3.5-4.5 Å / s.

[0019] Further, the plating method of each film layer is vacuum electron beam evaporation plating.

[0020] Further, after the plating is completed, the temperature is first kept at 115-125℃ for 10-20 min, then the temperature is decreased to below 70℃, and then the product is taken out.

[0021] Further, the deposition of the SiO2 layer is performed under the assistance of an RF ion source; the RF ion source parameters are: voltage 800±5V, current 800±5mA, ACC voltage 600±5V, gas filling amount oxygen 50±5sccm, and neutralizer argon 8±5sccm.

[0022] Further, the deposition of the Ta2O5 layer is performed under the assistance of an RF ion source; the RF ion source parameters are: voltage 900±5V, current 900±2mA, ACC voltage 600±5V, gas filling amount oxygen 50±5sccm, and neutralizer argon 8±5sccm.

[0023] Further, the deposition of the Ti3O5 layer is performed under the assistance of an RF ion source; the RF ion source parameters are: voltage 800±5V, current 800±5mA, ACC voltage 600±5V, gas filling amount argon 60±5sccm, and neutralizer argon 10±5sccm.

[0024] Further, the deposition of the HfO2 layer is performed under the assistance of an RF ion source; the RF ion source parameters are: voltage 800±5V, current 800±2mA, ACC voltage 600±5V, gas filling amount argon 50±5sccm, and neutralizer argon 8±5sccm.

[0025] In a third aspect, a laser is provided, comprising the laser reflection film system prepared by the method described above.

[0026] Compared with the prior art, one or more of the above technical solutions can achieve at least one of the following beneficial effects:

[0027] The laser reflection film system provided has high reflectivity, good adhesion of the film layers, good resistance to moderate friction and constant temperature and humidity, and excellent anti-laser loss performance, and can be used as a high-reflection film for a laser element.

[0028] The laser reflection film system provided has high yield.

[0029] The plating structure design and the preparation method are simple and easy to implement, and the resulting high-reflection film has a reflectivity higher than 99% and high yield. BRIEF DESCRIPTION OF DRAWINGS

[0030] In order to make the technical solutions of the embodiments of the present application or the prior art clearer, the accompanying drawings needed in the embodiments or prior art description will be briefly introduced. Obviously, the accompanying drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort based on these drawings.

[0031] Figure 1 High reflectance spectrum of the laser reflecting film system designed for Example 1.

[0032] Figure 2 Measured high reflectance spectrum of the laser reflecting film system prepared for Example 1.

[0033] Figure 3 Measured high reflectance spectrum of the laser reflecting film system prepared for Comparative Example 1.

[0034] Figure 4 Measured high reflectance spectrum of the laser reflecting film system prepared for Comparative Example 3. DETAILED DESCRIPTION

[0035] Some embodiments of the present application provide a laser reflecting film system, which comprises film system structures symmetrically arranged on both sides of a substrate, and the film system structure is Sub / 0.5L(H0.5L)^4(G0.5L)^2(M0.5L)^3 / Air, i.e. Sub / 0.5L(H0.5LH0.5LH0.5LH0.5L)(G0.5LG0.5L)(M0.5LM0.5LM0.5L) / Air, wherein Sub is a substrate, Air is an exit medium air, L represents a low refractive index layer with a basic thickness, H represents a first high refractive index layer with a basic thickness, G represents a second high refractive index layer with a basic thickness, and M represents a medium refractive index layer with a basic thickness, wherein the basic thickness corresponding to one H or one L or one G or one M represents that the film layer has a 1 / 4 optical thickness at a reference wavelength.

[0036] In some preferred embodiments, the low refractive index layer is a SiO2 layer, the first high refractive index layer is a Ta2O5 layer, the second high refractive index layer is a Ti3O5 layer, and the medium refractive index layer is a HfO2 layer.

[0037] In some preferred embodiments, the material of the substrate is quartz.

[0038] In some preferred embodiments, the average reflectivity of the laser reflecting film system to light in the wavelength range of 355 nm is 98% or more, preferably 99% or more.

[0039] In some preferred embodiments, the film system comprises, in order, a first SiO2layer, a first Ta2O5layer, a second SiO2layer, a second Ta2O5layer, a third SiO2layer, a third Ta2O5layer, a fourth SiO2layer, a fourth Ta2O5layer, a fifth SiO2layer, a first Ti3O5layer, a sixth SiO2layer, a second Ti3O5layer, a seventh SiO2layer, a first HfO2layer, an eighth SiO2layer, a second HfO2layer, a ninth SiO2layer, a third HfO2layer, and a tenth SiO2layer disposed on the surface of the silicon substrate; the first SiO2layer has a thickness of 42-44 nm, the first Ta2O5layer has a thickness of 40.5-42.5 nm, the second SiO2layer has a thickness of 38.5-40.5 nm, the second Ta2O5layer has a thickness of 26.5-28.5 nm, the third SiO2layer has a thickness of 50.5-52.5 nm, the third Ta2O5layer has a thickness of 46.5-48.5 nm, the fourth SiO2layer has a thickness of 78.5-80.5 nm, the fourth Ta2O5layer has a thickness of 46.5-48.5 nm, the fifth SiO2layer has a thickness of 68.5-70.5 nm, the first Ti3O5layer has a thickness of 86.5-88.5 nm, the sixth SiO2layer has a thickness of 68.5-70.5 nm, the second Ti3O5layer has a thickness of 11.3-13.5 nm, the seventh SiO2layer has a thickness of 41.5-43.5 nm, the first HfO2layer has a thickness of 49.5-51.5 nm, the eighth SiO2layer has a thickness of 63.5-65.5 nm, the second HfO2layer has a thickness of 68.5-70.5 nm, the ninth SiO2layer has a thickness of 77-79 nm, the third HfO2layer has a thickness of 57-59 nm, and the tenth SiO2layer has a thickness of 160-163 nm.

[0040] In some preferred embodiments, the thickness of the first SiO2 layer is 43 nm, the thickness of the first Ta2O5 layer is 41.42 nm, the thickness of the second SiO2 layer is 39.41 nm, the thickness of the second Ta2O5 layer is 27.46 nm, the thickness of the third SiO2 layer is 51.62 nm, the thickness of the third Ta2O5 layer is 47.47 nm, the thickness of the fourth SiO2 layer is 79.7 nm, the thickness of the fourth Ta2O5 layer is 47.47 nm, the thickness of the fifth SiO2 layer is 69.72 nm, the thickness of the first Ti3O5 layer is 87.46 nm, the thickness of the sixth SiO2 layer is 69.72 nm, the thickness of the second Ti3O5 layer is 12.34 nm, the thickness of the seventh SiO2 layer is 42.5 nm, the thickness of the first HfO2 layer is 50.71 nm, the thickness of the eighth SiO2 layer is 64.4 nm, the thickness of the second HfO2 layer is 69.67 nm, the thickness of the ninth SiO2 layer is 77.91 nm, the thickness of the third HfO2 layer is 57.92 nm, and the thickness of the tenth SiO2 layer is 161.5 nm.

[0041] The application also provides a method for preparing the laser reflection film system as described above, comprising:

[0042] coating the film layers on the first surface of the substrate according to the film layer structure of the first surface of the substrate;

[0043] coating the same film layers on the second surface of the substrate as on the first surface;

[0044] cooling to room temperature to obtain the laser reflection film system.

[0045] In some preferred embodiments, before coating the film layers on the first surface and the second surface of the substrate, the method further comprises: placing the substrate into a coating machine, vacuumizing to 2.0×10 -3 ±0.5×10 -3 Pa, preheating to 115-125℃, and performing ion source cleaning.

[0046] Before the ion source cleaning, the method further comprises pre-melting and degassing the film material to ensure the purity of the film material.

[0047] The ion source ion cleaning can remove the oxidation layer and attached particles on the surface of the product and the accompanying coated piece, so that the surface is cleaner and the adhesion of the film layers is increased. The ion source can be an RF source, and the parameters can be voltage 700±2V, current 700±2mA, ACC voltage 600±2V, oxygen flow 50±1sccm, ion source argon flow 20sccm, and neutralizer argon flow 15ccm.

[0048] In some preferred embodiments, the coating temperature of each film layer is 115-125℃.

[0049] In some preferred embodiments, the deposition rate of the SiO2 layer is 7.6-8.8 Å / s; the deposition rate of the Ta2O5 layer is 4.5-5.5 Å / s; the deposition rate of the Ti3O5 layer is 3-4 Å / s; and the deposition rate of the HfO2 layer is 3.5-4.5 Å / s.

[0050] In some preferred embodiments, the plating method of each film layer is vacuum electron beam evaporation plating.

[0051] In some preferred embodiments, the deposition of the SiO2 layer is assisted by an RF ion source; the RF ion source parameters are: voltage 800±5 V, current 800±5 mA, ACC voltage 600±5 V, oxygen gas 50±5 sccm, and argon gas 8±5 sccm in the neutralizer.

[0052] In some preferred embodiments, the deposition of the Ta2O5 layer is assisted by an RF ion source; the RF ion source parameters are: voltage 900±5 V, current 900±5 mA, ACC voltage 600±5 V, oxygen gas 50±5 sccm, and argon gas 8±5 sccm in the neutralizer.

[0053] In some preferred embodiments, the deposition of the Ti3O5 layer is assisted by an RF ion source; the RF ion source parameters are: voltage 800±5 V, current 800±5 mA, ACC voltage 600±5 V, argon gas 60±5 sccm, and argon gas 10±5 sccm in the neutralizer.

[0054] In some preferred embodiments, the deposition of the HfO2 layer is assisted by an RF ion source; the RF ion source parameters are: voltage 800±5 V, current 800±5 mA, ACC voltage 600±5 V, argon gas 50±5 sccm, and argon gas 8±5 sccm in the neutralizer.

[0055] In some preferred embodiments, before the substrate is placed into the plating machine, the substrate is polished and cleaned. Back-reflection light control is used to monitor the film thickness during the plating process.

[0056] In some preferred embodiments, after the film plating on both sides of the substrate is completed, the substrate is removed after being stepwise cooled to below 70°C. Further preferably, after the film plating is completed, the substrate is removed after being stepwise cooled to below 70°C after being kept at 115-125°C for 10-20 min. Preferably, the stepwise cooling is: first cooled to 95-105°C and kept for 5 min, then cooled to 75-85°C and kept for 5 min, and finally cooled to below 70°C and opened to remove the substrate.

[0057] The present application also provides a laser comprising the aforementioned laser reflective film system or the laser reflective film system prepared by the aforementioned preparation method.

[0058] For the convenience of understanding the present application, the present application will be described more fully below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present application is not limited to the following specific embodiments.

[0059] Embodiment 1

[0060] The implementation process of the preparation method of the film system structure disclosed in this disclosure is as follows:

[0061] The film system design takes 355 nm as the center wavelength of optical thin film design, and the film stack formula is: Sub / 0.5L(H0.5L)^4(G0.5L)^2(M0.5L)^3 / Air, wherein Sub is the substrate material quartz, the substrate product is φ12.7*6.25mm, and the accompanying plating sheet is a quartz 77*77*0.5mm sheet. AIR represents air, and in the film stack expression:

[0062] L represents a low refractive index material SiO2 (silicon dioxide) with a 1 / 4 wavelength thickness.

[0063] H represents a high refractive index Ta2O5 (tantalum pentoxide) with a 1 / 4 wavelength thickness.

[0064] G represents a high refractive index Ti3O5 (trititanium pentoxide) with a 1 / 4 wavelength thickness.

[0065] M represents a medium refractive index material HfO2 (hafnium oxide) with a 1 / 4 wavelength thickness.

[0066] After generation and optimization, the final film thickness is as follows, with the unit being nm:

[0067] sub / SiO2(43) / Ta2O5(41.42) / SiO2(39.41) / Ta2O5(27.46) / SiO2(51.62) / Ta2O5(47.47) / SiO2(79.7) / Ta2O5(47.47) / SiO2(69.72) / Ti3O5(87.46) / SiO2(69.72) / Ti3O5(12.34) / SiO2(42.5) / HfO2(50.71) / SiO2(64.4) / HfO2(69.67) / SiO2(77.91) / HfO2(57.92) / SiO2(161.5) / AIR;

[0068] Step one: input the film thickness into the film plating file, and set the film plating temperature, evaporation rate, film plating vacuum, ion source voltage and current, and gas charging amount, etc.

[0069] Step two: clamp the pre-cleaned product and the accompanying plated piece, then put them into the umbrella frame of the coating machine, close the door and pump, set the coating temperature to 120±2℃; the pre-coating vacuum is 2.0×10 -3 ±0.1×10 -3 Pa; the deposition rate of Ta2O5 film layer is 5±0.2Å / s; the deposition rate of SiO2 film layer is 8±0.2Å / s; the deposition rate of Ti3O5 film layer is 3.5±0.2Å / s; the deposition rate of HfO2 film layer is 4±0.2Å / s;

[0070] Step three: pre-melt and degas the film material before coating to ensure the purity of the film material.

[0071] Step four: when the cavity vacuum reaches 2.0×10 -3 ±0.1×10 -3 Pa, start the RF source to ion-clean the lens and the accompanying plated piece, the cleaning time is 90±2s, the parameters are: voltage 700±2V, current 700±2mA, ACC voltage 600±2V, oxygen gas 50±1sccm, ion source argon 20sccm, neutralizer argon 15ccm.

[0072] Step five: after ion source cleaning, call the coating process to start coating, use back reflection light control to monitor film thickness. When depositing Ta2O5 film layer, the ion source parameters are: voltage 900±2V, current 900±2mA, ACC voltage 600±2V, oxygen gas 50±1sccm, neutralizer argon 8sccm. When depositing SiO2 film layer, the ion source parameters are: voltage 800±2V, current 800±2mA, ACC voltage 600±2V, oxygen gas 50±1sccm, neutralizer argon 8sccm. When depositing Ti3O5 film layer, the ion source parameters are: voltage 800±2V, current 800±2mA, ACC voltage 600±2V, argon gas 60±1sccm, neutralizer argon 10sccm. When depositing HfO2 film layer, the ion source parameters are: voltage 800±2V, current 800±2mA, ACC voltage 600±2V, argon gas 50±1sccm, neutralizer argon 8sccm.

[0073] Step six: turn over the quartz glass substrate and the accompanying plated piece, put them into the coating machine, repeat steps two to five to coat the same film layers on the other surface (sub / SiO2(43) / Ta2O5(41.42) / SiO2(39.41) / Ta2O5(27.46) / SiO2(51.62) /

[0074] Ta2O5(47.47) / SiO2(79.7) / Ta2O5(47.47) / SiO2(69.72) / Ti3O5(87.46) / SiO2(69.72) / Ti3O5(12.34) / SiO2(42.5) / HfO2(50.71) / SiO2(64.4) / HfO2(69.67) / SiO2(77.91) / HfO2(57.92) / SiO2(161.5) / AIR);

[0075] Step seven: after the film is plated, keep the temperature at 120±2℃ for 15 min, then step down to 100±2℃ for 5 min, to 80±2℃ for 5 min, and to 70±2℃ or below, open the door and take out the product.

[0076] After plating, the plated piece is subjected to spectral testing, and the durability of the quartz glass product is tested.

[0077] Constant temperature and humidity test: double 85 test (test in an environment with a temperature of 85℃ and a humidity of 85%) for 36h, and no film layer peeling or cracking is found on the quartz glass.

[0078] High and low temperature test: the temperature is from -40℃ to 71℃, and each gradient is kept for 2 hours. No film layer peeling or cracking is found on the quartz glass.

[0079] Moderate friction test: the film layer is subjected to a pressure of 4.9N, and the rubber friction head wrapped with a degreasing cloth is rubbed for 50 times, and no scratch or damage is found.

[0080] Adhesion test: after each test, the end face of the quartz glass is bonded with 3M tape, and the tape is pulled in the opposite direction of the bonded end, and the film layer is not pulled up.

[0081] Laser light source test: the product is installed in a 100W laser light source, and the laser breaks through the surface of the film layer, and no damage or penetration trace is found on the film layer.

[0082] The high reflectance spectrum of the designed laser reflection film system is shown in Figure 1 , and the actual measured high reflectance spectrum is shown in Figure 2 .

[0083] Example 2

[0084] Step one: input the film thickness into the plating file, and set the plating temperature, evaporation rate, plating vacuum, ion source voltage and current, and gas amount.

[0085] Step two: clamp the pre-cleaned product and plated piece, then put them into the umbrella frame of the plating machine, close the door, evacuate, set the plating temperature to 118±2℃, and the pre-plating base vacuum to 1.8×10 -3±0.1 x 10 -3 Pa; Ta2O5 film deposition rate is 4.8±0.2Å / s; SiO2 film deposition rate is 7.9±0.2Å / s; Ti3O5 film deposition rate is 3.3±0.2Å / s; HfO2 film deposition rate is 3.8±0.2Å / s;

[0086] Step three: before coating, the film material is pre-melted and degassed to remove impurities, ensuring the purity of the film material.

[0087] Step four: the cavity vacuum degree reaches 1.8 x 10 -3 ±0.1 x 10 -3 Pa, start RF source to clean the lens and the ion source of the accompanying coating piece, cleaning time is 90±2s, the parameter is voltage 698±2V, current 698±2mA, ACC voltage is 598±2V, the amount of gas is oxygen 48±1sccm, ion source argon 20sccm, neutralizer argon 15ccm.

[0088] Step five: after the ion source cleaning is completed, the coating process is called to start coating, using back reflection light control to monitor film thickness. When depositing Ta2O5 film, the ion source parameters are: voltage 898±2V, current 898±2mA, ACC voltage is 598±2V, the amount of gas is oxygen 48±1sccm, neutralizer argon 10sccm. When depositing SiO2 film, the ion source parameters are: voltage 798±2V, current 798±2mA, ACC voltage is 598±2V, the amount of gas is oxygen 48±1sccm, neutralizer argon 10sccm. When depositing Ti3O5 film, the ion source parameters are: voltage 798±2V, current 797±2mA, ACC voltage is 598±2V, the amount of gas is argon 58±1sccm, neutralizer argon 12sccm. When depositing HfO2 film, the ion source parameters are: voltage 798±2V, current 798±2mA, ACC voltage is 598±2V, the amount of gas is argon 48±1sccm, neutralizer argon 10sccm.

[0089] Step six: after turning over the quartz glass substrate and the accompanying coating piece, put them into the coating machine, repeat steps three to six, and coat the same film layer on the other surface (sub / SiO2(43) / Ta2O5(41.42) / SiO2(39.41) / Ta2O5(27.46) / SiO2(51.62) /

[0090] Ta2O5(47.47) / SiO2(79.7) / Ta2O5(47.47) / SiO2(69.72) / Ti3O5(87.46) / SiO2(69.72) / Ti3O5(12.34) / SiO2(42.5) / HfO2(50.71) / SiO2(64.4) / HfO2(69.67) / SiO2(77.91) / HfO2(57.92) / SiO2(161.5) / AIR);

[0091] Step seven: after the film plating is completed, keep at 120±2℃ for 15 min, then step down to 100±2℃ for 5 min, to 80±2℃ for 5 min, and open the door to take out the product when the temperature drops to below 70℃.

[0092] Example 3

[0093] Step one: input the film thickness into the film plating file, and set the film plating temperature, evaporation rate, film plating vacuum, ion source voltage and current, and gas charging amount, etc.

[0094] Step two: clamp the pre-cleaned product and the accompanying plating sheet, then put them into the umbrella frame of the film plating machine, close the door, evacuate, set the film plating temperature to 122±2℃; the pre-plating vacuum is 2.3×10 -3 ±0.1×10 -3 Pa; the Ta2O5 film layer deposition rate is 5.2±0.2Å / s; the SiO2 film layer deposition rate is 8.5±0.2Å / s; the Ti3O5 film layer deposition rate is 3.6±0.2Å / s; the HfO2 film layer deposition rate is 4.1±0.2Å / s;

[0095] Step three: pre-melt and degas the film material before film plating to ensure the purity of the film material.

[0096] Step four: when the cavity vacuum degree reaches 23×10 -3 ±0.1×10 -3 Pa, start the RF radio frequency source to ion clean the lens and the accompanying plating sheet, the cleaning time is 90±2s, the parameters are: voltage 702±2V, current 702±2mA, ACC voltage 602±2V, gas charging amount is oxygen 52±1sccm, ion source argon 20sccm, neutralizer argon 15ccm.

[0097] Step five: after the ion source cleaning is completed, a coating process is called to start coating, and a back reflection light control is used to monitor the film thickness. When depositing a Ta2O5 film layer, the ion source parameters are: voltage 902±2V, current 902±2mA, ACC voltage 601±2V, gas amount 52±1sccm of oxygen, and 5sccm of argon in the neutralizer. When depositing a SiO2 film layer, the ion source parameters are: voltage 801±2V, current 801±2mA, ACC voltage 602±2V, gas amount 52±1sccm of oxygen, and 6sccm of argon in the neutralizer. When depositing a Ti3O5 film layer, the ion source parameters are: voltage 802±2V, current 802±2mA, ACC voltage 602±2V, gas amount 62±1sccm of argon, and 8sccm of argon in the neutralizer. When depositing a HfO2 film layer, the ion source parameters are: voltage 802±2V, current 802±2mA, ACC voltage 602±2V, gas amount 52±1sccm of argon, and 5sccm of argon in the neutralizer.

[0098] Step six: after the quartz glass substrate and the accompanying plated sheet are turned over, they are placed into a coating machine, and steps three to six are repeated to coat the same film layers on the other surface (sub / SiO2(43) / Ta2O5(41.42) / SiO2(39.41) / Ta2O5(27.46) / SiO2(51.62) /

[0099] Ta2O5(47.47) / SiO2(79.7) / Ta2O5(47.47) / SiO2(69.72) / Ti3O5(87.46) / SiO2(69.72) / Ti3O5(12.34) / SiO2(42.5) / HfO2(50.71) / SiO2(64.4) / HfO2(69.67) / SiO2(77.91) / HfO2(57.92) / SiO2(161.5) / AIR);

[0100] Step seven: after the coating is completed, the temperature is kept at 123±2℃ for 15 min, then is decreased in steps to 103±2℃ for 5 min, to 83±2℃ for 5 min, and is decreased to below 70℃ to open the door and take out the product.

[0101] After multiple verifications, the laser film produced by the application is firm, resistant to laser, and 100 PCS of the coated products have a use rate as high as 90%.

[0102] Example 4

[0103] The difference between this example and example 1 is that the evaporation rate of HfO2 is different, and the evaporation rate is 5±0.2Å / S, and the rest remains unchanged.

[0104] Comparative example 1

[0105] The difference between the present comparative example and Example 1 is in the final film layer structure; the film layer structure on both sides of the final quartz substrate is as follows, unit: nm.

[0106] sub / SiO2(34) / Ta2O5(57.42) / SiO2(59.98) / Ta2O5(37.68) / SiO2(60.02) / Ta2O5(37.65) / SiO2(60.04) / Ta2O5(37.65) / SiO2(100.04) / Ta2O5(37.64) / SiO2(60.04) / Ta2O5(37.65) / SiO2(60.04) / Ta2O5(37.65) / SiO2(60.03) / Ta2O5(59.65) / SiO2(59.98) / Ta2O5(37.68) / SiO2(60.42) / AIR.

[0107] Comparative Example 2

[0108] The difference between the present comparative example and Example 1 is in the final film layer structure; the film layer structure on both sides of the final quartz substrate is as follows, unit: nm.

[0109] sub / SiO2(70) / Ti3O5(66.31) / SiO2(120.46) / Ti3O5(31.46) / SiO2(59.23) / Ti3O5(31.29) / SiO2(61) / Ti3O5(30.74) / SiO2(64.85) / Ti3O5(39.52) / SiO2(74.99) / Ti3O5(27.68) / SiO2(68.7) / HfO2(132.93) / SiO2(71.49) / HfO2(132.29) / SiO2(76.69) / HfO2(123.62) / SiO2(56.69) / AIR;

[0110] Comparative Example 3

[0111] The difference between the present comparative example and Example 1 is in the final film layer structure; the film layer structure on both sides of the final quartz substrate is as follows, unit: nm.

[0112] sub / SiO2(60) / Ta2O5(43.2) / SiO2(23.5) / Ta2O5(53.87) / SiO2(35.48) / Ta2O5(67.09) / SiO2(28.67) / Ta2O5(45.90) / SiO2(34.76) / Ta2O5(51.89) / SiO2(45.09) / Ta2O5(56.98) / SiO2(34.76) / HfO2(87.60) / SiO2(78.09) / HfO2(25.76) / SiO2(89.06) / HfO2(46.34) / SiO2(80) / AIR.

[0113] The plated pieces of Examples 2-4 and Comparative Examples 1-3 were subjected to spectral testing, quartz glass product durability testing, and the testing methods were the same as those of Example 1. The results are shown in Table 1. The high reflectance spectra of the film systems of Comparative Example 1 and Comparative Example 2 were measured, as shown in Figs. 1 and 2, respectively. Figure 3 、 Figure 4

[0114] As can be seen from Table 1, the film systems of the examples had a reflectance of 99% or more at 355 nm, and had strong film layer adhesion, good resistance to constant temperature and humidity, resistance to high and low temperatures, resistance to moderate friction, and a good product rate of 80% or more under a 100W laser light source. The reflectance of the film systems of Examples 1-3 was 84% or more.

[0115] The reflectance of the film systems of Comparative Examples 1-3 was less than 99% at 355 nm, and the film systems of Comparative Examples 1 and 2 had a very low good product rate under a 100W laser light source.

[0116] Table 1

[0117]

[0118] The above description is merely preferred embodiments of the present application, and it should be noted that those of ordinary skill in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of the present application.​

Claims

1. A laser reflecting film stack, characterized by, The film system structure is symmetrically arranged on both sides of the substrate, and the film system structure is Sub / 0.5L(H0.5L)^4(G0.5L)^2(M0.5L)^3 / Air, wherein Sub is the substrate, Air is the air as the exit medium, L represents a low refractive index layer with one basic thickness, H represents a first high refractive index layer with one basic thickness, G represents a second high refractive index layer with one basic thickness, and M represents a medium refractive index layer with one basic thickness, wherein the basic thickness corresponding to one H or one L or one G or one M represents that the film layer has 1 / 4 optical thickness at a reference wavelength; the low refractive index layer is a SiO2 layer, the first high refractive index layer is a Ta2O5 layer, the second high refractive index layer is a Ti3O5 layer, and the medium refractive index layer is a HfO2 layer.

2. The laser reflecting film of claim 1, wherein, The material of the substrate is quartz.

3. The laser reflecting film of claim 1, wherein, The reflectivity of the laser reflection film system to light with a wavelength of 355 nm is 99% or more.

4. The laser reflecting film of claim 2, wherein, The film system structure comprises a first SiO2 layer, a first Ta2O5 layer, a second SiO2 layer, a second Ta2O5 layer, a third SiO2 layer, a third Ta2O5 layer, a fourth SiO2 layer, a fourth Ta2O5 layer, a fifth SiO2 layer, a first Ti3O5 layer, a sixth SiO2 layer, a second Ti3O5 layer, a seventh SiO2 layer, a first HfO2 layer, an eighth SiO2 layer, a second HfO2 layer, a ninth SiO2 layer, a third HfO2 layer and a tenth SiO2 layer arranged in sequence on the surface of the silicon substrate; the thickness of the first SiO2 layer is 42-44 nm, the thickness of the first Ta2O5 layer is 40.5-42.5 nm, the thickness of the second SiO2 layer is 38.5-40.5 nm, the thickness of the second Ta2O5 layer is 26.5-28.5 nm, the thickness of the third SiO2 layer is 50.5-52.5 nm, the thickness of the third Ta2O5 layer is 46.5-48.5 nm, the thickness of the fourth SiO2 layer is 78.5-80.5 nm, the thickness of the fourth Ta2O5 layer is 46.5-48.5 nm, the thickness of the fifth SiO2 layer is 68.5-70.5 nm, the thickness of the first Ti3O5 layer is 86.5-88.5 nm, the thickness of the sixth SiO2 layer is 68.5-70.5 nm, the thickness of the second Ti3O5 layer is 11.3-13.5 nm, the thickness of the seventh SiO2 layer is 41.5-43.5 nm, the thickness of the first HfO2 layer is 49.5-51.5 nm, the thickness of the eighth SiO2 layer is 63.5-65.5 nm, the thickness of the second HfO2 layer is 68.5-70.5 nm, the thickness of the ninth SiO2 layer is 77-79 nm, the thickness of the third HfO2 layer is 57-59 nm, and the thickness of the tenth SiO2 layer is 160-163 nm.

5. The laser reflecting film of claim 4, wherein, The thickness of the first SiO2 layer is 43 nm, the thickness of the first Ta2O5 layer is 41.42 nm, the thickness of the second SiO2 layer is 39.41 nm, the thickness of the second Ta2O5 layer is 27.46 nm, the thickness of the third SiO2 layer is 51.62 nm, the thickness of the third Ta2O5 layer is 47.47 nm, the thickness of the fourth SiO2 layer is 79.7 nm, the thickness of the fourth Ta2O5 layer is 47.47 nm, the thickness of the fifth SiO2 layer is 69.72 nm, the thickness of the first Ti3O5 layer is 87.46 nm, the thickness of the sixth SiO2 layer is 69.72 nm, the thickness of the second Ti3O5 layer is 12.34 nm, the thickness of the seventh SiO2 layer is 42.5 nm, the thickness of the first HfO2 layer is 50.71 nm, the thickness of the eighth SiO2 layer is 64.4 nm, the thickness of the second HfO2 layer is 69.67 nm, the thickness of the ninth SiO2 layer is 77.91 nm, the thickness of the third HfO2 layer is 57.92 nm, and the thickness of the tenth SiO2 layer is 161.5 nm.

6. The method for producing a laser reflection film system according to any one of claims 1 to 5, wherein It comprises: coating film layers on the first surface of the substrate according to the film system structure of the first surface of the substrate; coating the same film layers on the second surface of the substrate as the first surface; cooling to room temperature to obtain the laser reflection film system.

7. The method of making a laser reflective film stack of claim 6, wherein, Before plating the film layer on the first surface and the film layer on the second surface of the substrate, each includes: placing the substrate into a plating machine, vacuumizing to 2.0*10 -3 Pa, preheating to 115~125℃, and performing ion source cleaning. -3 Pa, preheating to 115~125℃, and performing ion source cleaning.

8. The method of making a laser reflective film stack of claim 6, wherein, The coating temperature of each film layer is 115-125 DEG C; The vacuum degree in the cavity during plating of each film layer is 2.0 x 10 -3 ±0.5 x 10 -3 Pa; The deposition rate of the SiO2 layer is 7.6-8.8 angstrom / s, the deposition rate of the Ta2O5 layer is 4.5-5.5 angstrom / s, the deposition rate of the Ti3O5 layer is 3-4 angstrom / s, and the deposition rate of the HfO2 layer is 3.5-4.5 angstrom / s; The coating mode of each film layer is vacuum electron beam evaporation coating; After the coating is completed, first heat preservation at 115-125 DEG C for 10-20 min, then stepwise cooling to below 70 DEG C, and then taking out.

9. The method of making a laser reflective film stack of claim 6, wherein, The deposition of the SiO2 layer is carried out under the assistance of an RF ion source; the RF ion source parameters are: voltage 800±5V, current 800±5mA, ACC voltage 600±5V, gas filling amount oxygen 50±5sccm, and neutralizer argon 8±5sccm; The deposition of the Ta2O5 layer is carried out under the assistance of an RF ion source; the RF ion source parameters are: voltage 900±5V, current 900±2mA, ACC voltage 600±5V, gas filling amount oxygen 50±5sccm, and neutralizer argon 8±5sccm; The deposition of the Ti3O5 layer is carried out under the assistance of an RF ion source; the RF ion source parameters are: voltage 800±5V, current 800±5mA, ACC voltage 600±5V, gas filling amount argon 60±5sccm, and neutralizer argon 10±5sccm; The deposition of the HfO2 layer is carried out under the assistance of an RF ion source; the RF ion source parameters are: voltage 800±5V, current 800±2mA, ACC voltage 600±5V, gas filling amount argon 50±5sccm, and neutralizer argon 8±5sccm.

10. A laser characterized by, A laser reflection film system including the laser reflection film system according to any one of claims 1 to 5 or the laser reflection film system produced by the production method according to any one of claims 6 to 9.

Images