JGS1 substrate antireflection film and preparation method and application thereof

Abstract

The invention provides a JGS1 substrate antireflection film and a preparation method and application thereof. According to the JGS1 substrate antireflection film provided by the invention, the JGS1 quartz glass substrate with relatively high transmittance in a deep ultraviolet band is adopted to replace a calcium fluoride substrate, so that the cost is greatly reduced; meanwhile, a new film system design is adopted on the JGS1 quartz glass substrate: an F-SiO2 thin film layer is arranged on the JGS1 quartz glass substrate, and then an antireflection film layer is arranged; adding a protective layer on the antireflection film layer; according to the film system design, the adsorption force between the antireflection film layer and the JGS1 quartz glass substrate can be increased, and the mechanical strength of the film layer is improved; the deposition of organic matters is effectively prevented, and the JGS1 substrate antireflection film has a higher heat damage threshold value while the ultrahigh transmittance (greater than 99.5%) in a deep ultraviolet band (193nm) is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of optical thin films, and in particular to a JGS1 substrate anti-reflection film and a preparation method and application thereof. Background Art

[0002] In recent years, deep ultraviolet (DUV) lasers have gradually played an increasingly important role in laser precision processing, semiconductor manufacturing, material testing and other fields due to their excellent performance. In deep ultraviolet lasers, windows with high transmittance are extremely important core optical components, which usually use calcium fluoride (CaF2) as the substrate.

[0003] However, the high-precision calcium fluoride substrate itself is extremely expensive, and the window may be damaged due to a variety of situations: (1) Film shedding: The strength of optical thin films mainly depends on the adsorption force between the film layers. Under the irradiation of high-energy deep ultraviolet lasers, the parts with weak adsorption force between the film layers may fall off, causing component failure; (2) Chemical contamination: Organic matter in the deep ultraviolet system, the film layer of the window in contact with the air, will decompose and oxidize under the irradiation of high-energy deep ultraviolet lasers, which will cause the surface quality to deteriorate, thus seriously affecting its optical performance. If the anti-reflection layer is directly exposed to the outermost part, cleaning the contaminants may cause the anti-reflection layer to be damaged, thereby affecting the overall transmittance of the optical system.

[0004] Due to the defects of the current window piece designed based on the calcium fluoride substrate, it is necessary to improve it. Summary of the invention

[0005] In view of this, the present invention provides a JGS1 substrate anti-reflection film and a preparation method and application thereof, so as to solve or at least partially solve the defects existing in the prior art.

[0006] In a first aspect, the present invention provides a JGS1 substrate antireflection film, comprising:

[0007] JGS1 quartz glass substrate;

[0008] F-SiO2 thin film layer, located on the surface of the JGS1 quartz glass substrate;

[0009] An anti-reflection film layer, located on the surface of the F-SiO2 thin film layer away from the JGS1 quartz glass substrate, the anti-reflection film layer comprising a plurality of MgF2 thin film layers and GdF3 thin film layers arranged alternately in sequence;

[0010] The protective layer is located on the surface of the anti-reflection film layer away from the JGS1 quartz glass substrate.

[0011] Preferably, the protective layer is a SiO2 protective layer, and the roughness of the protective layer is less than 0.4 nm;

[0012] And / or, the F-doping mass concentration in the F-SiO2 thin film layer is 0.2% to 4%.

[0013] Preferably, the thickness of the JGS1 quartz glass substrate is 40 to 60 mm;

[0014] And / or, the thickness of the F-SiO2 thin film layer is 5 to 15 nm;

[0015] And / or, the thickness of the MgF2 thin film layer is 20 to 80 nm;

[0016] And / or, the thickness of the GdF3 thin film layer is 25 to 40 nm;

[0017] And / or, the protective layer has a thickness of 3 to 10 nm;

[0018] And / or, the MgF2 thin film layer and the GdF3 thin film layer are interlaced 1 to 20 times.

[0019] Preferably, the antireflection film layer includes a first MgF2 thin film layer, a first GdF3 thin film layer, a second MgF2 thin film layer, a second GdF3 thin film layer, a third MgF2 thin film layer, a third GdF3 thin film layer, a fourth MgF2 thin film layer, a fourth GdF3 thin film layer, and a fifth MgF2 thin film layer, which are located on the surface of the JGS1 quartz glass substrate and are stacked in sequence;

[0020] Wherein, the thickness of the first MgF2 thin film layer is 34-35 nm, and the thickness of the first GdF3 thin film layer is 36-37 nm;

[0021] The thickness of the second MgF2 thin film layer is 64-65 nm, and the thickness of the second GdF3 thin film layer is 30.5-31.5 nm;

[0022] The thickness of the third MgF2 thin film layer is 34-35 nm, and the thickness of the third GdF3 thin film layer is 31-32 nm;

[0023] The thickness of the fourth MgF2 thin film layer is 34-35 nm, and the thickness of the fourth GdF3 thin film layer is 31.5-32.5 nm;

[0024] The thickness of the fifth MgF2 thin film layer is 27.0-29.0 nm.

[0025] In a second aspect, the present invention further provides a method for preparing the JGS1 substrate antireflection film, comprising the following steps:

[0026] The F-SiO2 thin film layer was deposited on the surface of the JGS1 quartz glass substrate;

[0027] On the surface of the F-SiO2 thin film layer, a MgF2 thin film layer and a GdF3 thin film layer are sequentially and alternately deposited to obtain an anti-reflection film layer;

[0028] A protective layer is deposited on the surface of the anti-reflection film layer.

[0029] Preferably, F-SiO2 is used as a target material and a F-SiO2 thin film layer is deposited on the surface of a JGS1 quartz glass substrate by a magnetron sputtering method; wherein, during the deposition, the deposition temperature is 140 to 160°C.

[0030] Preferably, MgF2 and GdF3 particles are used as evaporation sources, respectively, and electron beam thermal evaporation is used to alternately deposit the MgF2 film layer and the GdF3 film layer on the surface of the F-SiO2 film layer in sequence;

[0031] When the MgF2 thin film layer and the GdF3 thin film layer are deposited, the temperature of the JGS1 quartz glass substrate is controlled to be 260-280° C., the deposition rate of the MgF2 thin film layer is 0.2-0.4 nm / s, and the deposition rate of the GdF3 thin film layer is 0.2-0.4 nm / s.

[0032] Preferably, before the MgF2 thin film layer and the GdF3 thin film layer are alternately deposited on the surface of the F-SiO2 thin film layer in sequence to obtain the thin film layer, the GS1 quartz glass substrate is also subjected to plasma treatment, wherein the plasma treatment gas includes oxygen and argon, the oxygen flow rate is 40 to 60 sccm, the argon flow rate is 5 to 10 sccm, the plasma treatment time is 60 to 120 s, the voltage is 690 to 710 V, and the current is 690 to 710 mA.

[0033] Preferably, the protective layer is a SiO2 protective layer; the SiO2 protective layer is prepared by sputtering coating method using Si as target material;

[0034] Among them, the sputtering gas is Ar, the ion source of the sputtering coater is O2 and Ar, the target sputtering power supply and the sputtering coater ion source work together to obtain a SiO2 protective layer, the flow rate of the sputtering gas Ar is 30-40sccm, the sputtering power of the sputtering coater is 1800-2200W, the ion source power of the sputtering coater is 2400-2600W, the O2 flow rate in the ion source is 50-60sccm, the Ar flow rate is 40-50sccm, and the temperature of the GS1 quartz glass substrate during sputtering is 140-160℃.

[0035] In a third aspect, the present invention further provides an application of the JGS1 substrate anti-reflection film or the JGS1 substrate anti-reflection film prepared by the preparation method in the preparation of a deep ultraviolet laser.

[0036] Compared with the prior art, the JGS1 substrate antireflection film and its preparation method and application of the present invention have the following advantages:

[0037] Beneficial effects:

[0038] 1. The JGS1 substrate anti-reflection film of the present invention adopts a JGS1 quartz glass substrate with high transmittance in the deep ultraviolet band to replace the calcium fluoride substrate, which greatly reduces the cost; at the same time, the present invention adopts a new film system design on the JGS1 quartz glass substrate: a F-SiO2 thin film layer is arranged on the JGS1 quartz glass substrate, and then an anti-reflection film layer is arranged; a protective layer is added on the anti-reflection film layer; this film system design can increase the adsorption force between the anti-reflection film layer and the JGS1 quartz glass substrate, and improve the mechanical strength of the film layer; effectively prevent the deposition of organic matter, and realize the JGS1 substrate anti-reflection film in the deep ultraviolet band (193nm) Ultra-high transmittance (> 99.5%) while having a higher thermal damage threshold;

[0039] 2. The JGS1 substrate antireflection film of the present invention has a smooth SiO2 protective layer with Ra < 0.4 nm, which can effectively prevent the JGS1 quartz glass substrate and the magnesium fluoride and gadolinium fluoride antireflection layers from being damaged by volatile organic compounds, thereby greatly improving the stability, thermal damage threshold and service life of the optical system of the JGS1 substrate antireflection film;

[0040] 3. The preparation method of the JGS1 substrate anti-reflection film of the present invention adopts ion sputtering deposition to form a dense and uniform nano-scale SiO2 protective layer by optimizing the deposition process. A smooth SiO2 protective layer with a surface roughness Ra < 0.4 nm can be obtained by ion sputtering deposition; the conventional high-temperature deposition (> 300°C), reverse mask deposition technology, in-situ or post-deposition plasma ion treatment and other complex process flows are overcome. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the prior art descriptions. Obviously, the drawings described below are only some embodiments of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0042] Figure 1 It is a schematic diagram of the structure of the JGS1 substrate anti-reflection film of the present invention;

[0043] Figure 2 It is a schematic flow chart of the method for preparing the anti-reflection film of the JGS1 substrate of the present invention;

[0044] Figure 3The average reflectivity diagram of the JGS1 substrate antireflection film at different incident angles in Example 1;

[0045] Figures 4 to 6 Atomic force microscope images of the SiO2 protective layer prepared according to the method in Example 1 at different positions. DETAILED DESCRIPTION

[0046] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0047] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0048] The following are described in detail. It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and simplicity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the numbered ranges, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated in this article, it is meant to include any quoted numbers (fractions or integers) within the indicated range.

[0049] The present invention provides a JGS1 substrate antireflection film, such as Figure 1 As shown, including:

[0050] JGS1 quartz glass substrate 1;

[0051] F-SiO2 thin film layer 2, located on the surface of JGS1 quartz glass substrate 1;

[0052] The anti-reflection film layer 3 is located on the surface of the F-SiO2 thin film layer 2 away from the JGS1 quartz glass substrate 1, and the anti-reflection film layer includes a plurality of MgF2 thin film layers 31 and GdF3 thin film layers 32 which are arranged alternately in sequence;

[0053] The protective layer 4 is located on the surface of the anti-reflection film layer 3 and away from the JGS1 quartz glass substrate 1 .

[0054] The JGS1 substrate anti-reflection film of the present invention comprises a JGS1 quartz glass substrate 1, an F-SiO2 thin film layer 2, an anti-reflection film layer 3 and a protective layer 4, wherein the anti-reflection film layer 3 comprises a plurality of MgF2 thin film layers 31 and GdF3 thin film layers 32 which are arranged alternately in sequence, i.e., MgF2 thin film layer 31 / GdF3 thin film layer 32 / MgF2 thin film layer 31 / GdF3 thin film layer 32..., which are arranged alternately in sequence. The existing invention is a film system design based on a calcium fluoride substrate, and the calcium fluoride substrate itself is expensive. The present invention adopts a JGS1 quartz glass substrate (i.e., a JGS1 quartz glass substrate) with a high transmittance in the deep ultraviolet band to replace the calcium fluoride substrate, thereby significantly reducing the cost. At the same time, the present invention adopts a new film system design on the JGS1 quartz glass substrate 1: 1) a F-SiO2 thin film layer 2 is arranged on the JGS1 quartz glass substrate 1, and then an anti-reflection film layer 3 is arranged; 2) a protective layer 4 is added on the anti-reflection film layer 3; this film system design can increase the adsorption force between the anti-reflection film layer 3 and the JGS1 quartz glass substrate 1, and improve the mechanical strength of the film layer; it can effectively prevent the deposition of organic matter, and achieve the ultra-high transmittance (>99.5%) of the JGS1 substrate anti-reflection film in the deep ultraviolet band (193nm) while having a higher thermal damage threshold.

[0055] Specifically, the JGS1 quartz glass substrate 1 is made of JGS1 quartz glass, namely, ultraviolet quartz glass, usually referred to as JGS1 quartz glass, which is a special material showing extremely low dispersion and very high transmittance in the ultraviolet spectrum.

[0056] In some embodiments, the F-SiO2 thin film layer 2 is an F-doped SiO2 thin film layer, wherein the F doping mass concentration in the F-SiO2 thin film layer is 0.2% to 4%; specifically, since the main component of the JGS1 quartz glass substrate 1 is SiO2, the SiO2 in the F-SiO2 thin film layer 2 is for improving the adsorption with the JGS1 quartz glass substrate 1; and the F ions in the F-SiO2 thin film layer 2 are for better coordination with the fluoride in the anti-reflection film layer 3, thereby playing the role of a bridge and improving the adsorption force and mechanical strength of the overall film system.

[0057] In some embodiments, the anti-reflection film layer 3 of the present invention is a fluoride anti-reflection film layer, and the MgF2 thin film layer 31 is a low refractive index (L) material, and the GdF3 thin film layer 32 is a high refractive index (H) material, that is, the anti-reflection film layer 3 of the present invention is an H / L anti-reflection film system.

[0058] In some embodiments, the protective layer 4 is a SiO2 protective layer, and the roughness of the protective layer is less than 0.4 nm. The present invention controls the surface roughness of the SiO2 protective layer, and the size of the surface roughness will affect the flux and service life of the optical system. The SiO2 protective layer of the present invention is a smooth SiO2 protective layer with Ra < 0.4 nm, which can effectively prevent the JGS1 quartz glass substrate 1 and the magnesium fluoride and gadolinium fluoride anti-reflection layer from a large amount of chemical pollution and damage by volatile organic compounds, thereby greatly improving the stability, thermal damage threshold and service life of the optical system of the JGS1 substrate anti-reflection film.

[0059] Further, preferably, the roughness of the SiO2 protective layer is ≤0.358 nm, for example, the roughness of the SiO2 protective layer is 0.298 nm, 0.305 nm, 0.358 nm, etc.

[0060] In some embodiments, the thickness of the JGS1 quartz glass substrate 1 is 40-60 mm, such as the thickness of the JGS1 quartz glass substrate 1 is 50 mm.

[0061] In some embodiments, the thickness of the F-SiO 2 thin film layer 2 is 5-15 nm, for example, the thickness of the F-SiO 2 thin film layer 2 is 9 nm.

[0062] In some embodiments, the thickness of the MgF 2 thin film layer 31 is 20-80 nm.

[0063] In some embodiments, the thickness of the GdF 3 thin film layer 32 is 25-40 nm.

[0064] In some embodiments, the thickness of the protective layer 4 is 3-10 nm, for example, the thickness of the protective layer 4 is 5 nm.

[0065] In some embodiments, the MgF 2 thin film layer 31 and the GdF 3 thin film layer 32 are interlaced 1 to 20 times.

[0066] In some embodiments, the anti-reflection film layer 31 includes a JGS1 quartz glass substrate surface, such as Figure 1 As shown, the first MgF2 thin film layer, the first GdF3 thin film layer, the second MgF2 thin film layer, the second GdF3 thin film layer, the third MgF2 thin film layer, the third GdF3 thin film layer, the fourth MgF2 thin film layer, the fourth GdF3 thin film layer, and the fifth MgF2 thin film layer are sequentially stacked from bottom to top;

[0067] Wherein, the thickness of the first MgF2 thin film layer is 34-35 nm, and the thickness of the first GdF3 thin film layer is 36-37 nm;

[0068] The thickness of the second MgF2 thin film layer is 64-65 nm, and the thickness of the second GdF3 thin film layer is 30.5-31.5 nm;

[0069] The thickness of the third MgF2 thin film layer is 34-35 nm, and the thickness of the third GdF3 thin film layer is 31-32 nm;

[0070] The thickness of the fourth MgF2 thin film layer is 34-35 nm, and the thickness of the fourth GdF3 thin film layer is 31.5-32.5 nm;

[0071] The thickness of the fifth MgF2 thin film layer is 27.0-29.0 nm.

[0072] Specifically, in the above embodiment, the antireflection film layer includes a first MgF2 thin film layer / a first GdF3 thin film layer / a second MgF2 thin film layer / a second GdF3 thin film layer / a third MgF2 thin film layer / a third GdF3 thin film layer / a fourth MgF2 thin film layer / a fourth GdF3 thin film layer / a fifth MgF2 thin film layer; wherein the first MgF2 thin film layer / the first GdF3 thin film layer is a first staggered MgF2 thin film layer and a GdF3 thin film layer; the second MgF2 thin film layer / the second GdF3 thin film layer is a second staggered MgF2 thin film layer. layer, and GdF3 thin film layer; the third MgF2 thin film layer / the third GdF3 thin film layer is the third staggered MgF2 thin film layer and GdF3 thin film layer; the fourth MgF2 thin film layer / the fourth GdF3 thin film layer is the fourth staggered MgF2 thin film layer and GdF3 thin film layer; the fifth MgF2 thin film layer is the fifth staggered MgF2 thin film layer (the fifth staggered arrangement has no GdF3 thin film layer); the above embodiment adopts a variable film thickness design that is not a quarter wavelength thick, which can effectively improve the transmittance of the JGS1 substrate anti-reflection film in the deep ultraviolet band.

[0073] Based on the same inventive concept, the present invention also provides a method for preparing the above-mentioned JGS1 substrate antireflection film, such as Figure 2 As shown, the following steps are included:

[0074] S1, depositing a F-SiO2 thin film layer on the surface of a JGS1 quartz glass substrate;

[0075] S2, alternately depositing a MgF2 thin film layer and a GdF3 thin film layer on the surface of the F-SiO2 thin film layer in sequence to prepare an anti-reflection film layer;

[0076] S3. Depositing a protective layer on the surface of the anti-reflection film layer.

[0077] In some embodiments, F-SiO2 is used as a target material and a F-SiO2 thin film layer is deposited on the surface of a JGS1 quartz glass substrate by magnetron sputtering; wherein, during deposition, the deposition temperature is 140 to 160°C.

[0078] Specifically, the preparation method of the F-SiO2 thin film layer is as follows:

[0079] S11, placing the JGS1 quartz glass substrate on the fixture plate of the sputtering coating machine, and selecting F-SiO2 as the sputtering target;

[0080] S12, use mechanical pump and molecular pump to pump the vacuum chamber of sputtering coating machine to less than 8×10 -4 Pa, use the heating wire to raise the temperature of the fixture plate to the set temperature (140-160°C);

[0081] S13, F-SiO2 target sputters Si ions and F ions in sputtering gas Ar, the ion source of the sputtering coating machine is filled with high-purity O2 and Ar to generate a plasma beam, the target sputtering power supply and the ion source of the sputtering coating machine work together to obtain an F-SiO2 thin film layer, and deposit it on the JGS1 quartz glass substrate; wherein, the flow rate of sputtering gas Ar is 30-40sccm, the sputtering power of the sputtering coating machine is 1800-2200W, the ion source power of the sputtering coating machine is 2400-2600W, the O2 flow rate in the ion source is 50-60sccm, and the Ar flow rate is 40-50sccm;

[0082] S14. After the deposition of the F-SiO2 thin film layer is completed, the vacuum chamber is cooled for 60 minutes and the sample is taken out.

[0083] Specifically, the above-mentioned F-SiO2 target material is a conventional commercially available F-SiO2 target material, and its preparation method can refer to the authorized patent of Al Qatar Company: CN1211303C-Production method of fluorine-doped silicon dioxide powder.

[0084] In some embodiments, MgF2 and GdF3 particles are used as evaporation sources, respectively, and electron beam thermal evaporation is used to sequentially and alternately deposit the MgF2 thin film layer and the GdF3 thin film layer on the surface of the F-SiO2 thin film layer;

[0085] When the MgF2 thin film layer and the GdF3 thin film layer are deposited, the temperature of the JGS1 quartz glass substrate is controlled to be 260-280° C., the deposition rate of the MgF2 thin film layer is 0.2-0.4 nm / s, and the deposition rate of the GdF3 thin film layer is 0.2-0.4 nm / s.

[0086] In some embodiments, before the MgF2 thin film layer and the GdF3 thin film layer are alternately deposited on the surface of the F-SiO2 thin film layer, the GS1 quartz glass substrate is also plasma treated, wherein the plasma treatment gas includes oxygen and argon, the oxygen flow rate is 40 to 60 sccm, the argon flow rate is 5 to 10 sccm, the plasma treatment time is 60 to 120 s, the voltage is 690 to 710 V, and the current is 690 to 710 mA.

[0087] Specifically, in some embodiments, the MgF2 thin film layer and the GdF3 thin film layer are obtained by alternately depositing them on the surface of the F-SiO2 thin film layer, comprising the following steps:

[0088] S21, select high-purity MgF2 and GdF3 particles and add them into different evaporation crucibles of the electron beam evaporation coating machine respectively, and place the JGS1 quartz glass substrate with a F-SiO2 thin film layer deposited on the surface on the coating umbrella of the electron beam evaporation coating machine;

[0089] S22, use mechanical pump and oil diffusion pump to pump the vacuum chamber of electron beam evaporation coating machine to less than 8×10 -4 Pa, use the heating wire to raise the temperature of the vacuum chamber to the set temperature (260-280°C);

[0090] S23, 40-60 sccm oxygen is introduced into the RF ion source of the electron beam evaporation coating machine, and 5-10 sccm argon is introduced into the ion source neutralizer to generate plasma for substrate cleaning;

[0091] S24, after the substrate is cleaned, alternately depositing MgF2 thin film layers and GdF3 thin film layers by electron beam thermal evaporation;

[0092] After the deposition of S25, MgF2 thin film layer and GdF3 thin film layer was completed, the vacuum chamber was cooled for 60 minutes and the sample was taken out;

[0093] Among them, the plasma treatment time is 60-120s, the voltage is 690-710V, and the current is 690-710mA; the deposition rate of the MgF2 thin film layer and the GdF3 thin film layer is 0.2-0.4nm / s, the electron gun that generates the electron beam is a 270-degree deflection electron gun, the high voltage is set to 6-7KV, and the current is controlled according to the real-time deposition rate.

[0094] In some embodiments, the protective layer is a SiO2 protective layer; the SiO2 protective layer is prepared by sputtering coating method using Si as a target;

[0095] Among them, the sputtering gas is Ar, the ion source of the sputtering coater is O2 and Ar, the target sputtering power supply and the sputtering coater ion source work together to obtain a SiO2 protective layer, the flow rate of the sputtering gas Ar is 30-40sccm, the sputtering power of the sputtering coater is 1800-2200W, the ion source power of the sputtering coater is 2400-2600W, the O2 flow rate in the ion source is 50-60sccm, the Ar flow rate is 40-50sccm, and the temperature of the GS1 quartz glass substrate during sputtering is 140-160℃.

[0096] Specifically, in some embodiments, the method for preparing the SiO2 protective layer includes the following steps:

[0097] S31, placing a JGS1 quartz glass substrate with an antireflection film layer deposited thereon on a fixture plate of a sputtering coating machine, and selecting high-purity elemental silicon as a sputtering target;

[0098] S32, use mechanical pump and molecular pump to pump the vacuum chamber of sputtering coating machine to less than 8×10 -4 Pa, use the heating wire to raise the temperature of the fixture plate to the set temperature (140-160°C);

[0099] S33, high-purity elemental silicon is sputtered out Si ions in the sputtering gas Ar, the ion source of the sputtering coating machine is filled with high-purity O2 and Ar to generate a plasma beam, the target material sputtering power supply and the ion source of the sputtering coating machine work together to obtain SiO2 thin film material, and deposit it on the anti-reflection film layer to obtain a SiO2 protective layer; the flow rate of the sputtering gas Ar is 30-40sccm, the sputtering power of the sputtering coating machine is 1800-2200W, the ion source power of the sputtering coating machine is 2400-2600W, the O2 flow rate in the ion source is 50-60sccm, and the Ar flow rate is 40-50sccm;

[0100] S34. After the deposition of the SiO2 protective layer is completed, the vacuum chamber is cooled for 60 minutes and the sample is taken out.

[0101] The present invention adopts ion sputtering deposition to form a dense and uniform nano-scale SiO2 protective layer by optimizing the deposition process. A smooth SiO2 protective layer with a surface roughness Ra < 0.4 nm can be obtained by ion sputtering deposition. The conventional complex process flow of high-temperature deposition (> 300°C), reverse mask deposition technology, in-situ or post-deposition plasma ion treatment, etc. is overcome.

[0102] Based on the same inventive concept, the present invention also provides an application of the above-mentioned JGS1 substrate anti-reflection film or the JGS1 substrate anti-reflection film prepared by the above-mentioned preparation method in the preparation of deep ultraviolet lasers.

[0103] The following further describes the JGS1 substrate antireflection film and its preparation method of the present application with specific examples. This section further describes the content of the present invention in conjunction with specific examples, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0104] Example 1

[0105] The embodiment of the present application provides a JGS1 substrate anti-reflection film, comprising:

[0106] JGS1 quartz glass substrate;

[0107] The F-SiO2 thin film layer is located on the surface of the JGS1 quartz glass substrate, and the F-doping mass concentration in the F-SiO2 thin film layer is 2%;

[0108] The anti-reflection film layer is located on the surface of the F-SiO2 thin film layer away from the JGS1 quartz glass substrate, and the anti-reflection film layer includes a plurality of MgF2 thin film layers and GdF3 thin film layers that are sequentially staggered; specifically, the anti-reflection film layer includes a plurality of sequentially stacked first MgF2 thin film layers, first GdF3 thin film layers, second MgF2 thin film layers, second GdF3 thin film layers, third MgF2 thin film layers, third GdF3 thin film layers, fourth MgF2 thin film layers, fourth GdF3 thin film layers, and fifth MgF2 thin film layers from bottom to top;

[0109] SiO2 protective layer, located on the fifth MgF2 thin film layer away from the surface of the JGS1 quartz glass substrate;

[0110] Among them, the thickness of each layer of JGS1 quartz glass substrate, F-SiO2 thin film layer, anti-reflection film layer, and SiO2 protective layer is shown in Table 1 below:

[0111] Table 1-Thickness of each layer of antireflection coating on JGS1 substrate

[0112] Each film layer thickness JGS1 Quartz Glass Substrate 50mm <![CDATA[F-SiO2 thin film layer]]> 9nm <![CDATA[First MgF2 thin film layer]]> 34.3nm <![CDATA[The first GdF3 thin film layer]]> 36.5nm <![CDATA[Second MgF2 thin film layer]]> 64.6nm <![CDATA[Second GdF3 thin film layer]]> 30.9nm <![CDATA[The third MgF2 thin film layer]]> 34.5nm <![CDATA[The third GdF3 thin film layer]]> 31.6nm <![CDATA[Fourth MgF2 thin film layer]]> 34.1nm <![CDATA[Fourth GdF3 thin film layer]]> 31.9nm <![CDATA[Fifth MgF2 thin film layer]]> 28.0nm <![CDATA[SiO2 protective layer]]> 5nm

[0113] The method for preparing the above-mentioned JGS1 substrate antireflection film comprises the following steps:

[0114] S1, depositing a F-SiO2 thin film layer on the surface of a JGS1 quartz glass substrate, specifically comprising the following steps:

[0115] S11, placing the JGS1 quartz glass substrate on the fixture plate of the sputtering coating machine, and selecting F-SiO2 as the sputtering target;

[0116] S12, use mechanical pump and molecular pump to pump the vacuum chamber of sputtering coating machine to less than 8×10 -4 Pa, use the heating wire to raise the temperature of the fixture plate to the set temperature (150°C);

[0117] S13, F-SiO2 target sputters Si ions in sputtering gas Ar, the ion source of the sputtering coater is filled with high-purity O2 and Ar to generate a plasma beam, the target sputtering power supply and the ion source of the sputtering coater work together to obtain an F-SiO2 thin film layer, and deposit it on the JGS1 quartz glass substrate; wherein, the flow rate of sputtering gas Ar is 35sccm, the sputtering power of the sputtering coater is 2000W, the ion source power of the sputtering coater is 2500W, the O2 flow rate in the ion source is 50sccm, and the Ar flow rate is 40sccm;

[0118] S14, after the deposition of the F-SiO2 thin film layer is completed, the vacuum chamber is cooled for 60 minutes, and the sample is taken out;

[0119] S2, alternately depositing a MgF2 thin film layer and a GdF3 thin film layer on the surface of the F-SiO2 thin film layer in sequence to prepare an anti-reflection film layer, specifically comprising the following steps:

[0120] S21, select high-purity MgF2 and GdF3 particles and add them into different evaporation crucibles of the electron beam evaporation coating machine respectively, and place the JGS1 quartz glass substrate with a F-SiO2 thin film layer deposited on the surface on the coating umbrella of the electron beam evaporation coating machine;

[0121] S22, use mechanical pump and oil diffusion pump to pump the vacuum chamber of electron beam evaporation coating machine to less than 8×10 -4 Pa, use the heating wire to raise the temperature of the vacuum chamber to the set temperature (270 °C);

[0122] S23, 55 sccm of oxygen is introduced into the RF ion source of the electron beam evaporation coating machine, and 8 sccm of argon is introduced into the ion source neutralizer to generate plasma for substrate cleaning;

[0123] S24, after the substrate is cleaned, MgF2 thin film layers and GdF3 thin film layers are alternately deposited by electron beam thermal evaporation, and a first MgF2 thin film layer, a first GdF3 thin film layer, a second MgF2 thin film layer, a second GdF3 thin film layer, a third MgF2 thin film layer, a third GdF3 thin film layer, a fourth MgF2 thin film layer, a fourth GdF3 thin film layer, and a fifth MgF2 thin film layer are deposited;

[0124] S25, after the film deposition is completed, the vacuum chamber is cooled for 60 minutes and the sample is taken out;

[0125] The plasma treatment time was 90s, the voltage was 700V, and the current was 700mA; the deposition rates of the MgF2 thin film layer and the GdF3 thin film layer were both 0.3nm / s;

[0126] S3, depositing a SiO2 protective layer on the surface of the fifth MgF2 thin film layer, specifically comprising the following steps:

[0127] S31, placing a JGS1 quartz glass substrate with an antireflection film layer deposited thereon on a fixture plate of a sputtering coating machine, and selecting high-purity elemental silicon as a sputtering target;

[0128] S32, use mechanical pump and molecular pump to pump the vacuum chamber of sputtering coating machine to less than 8×10 -4 Pa, use the heating wire to raise the temperature of the fixture plate to the set temperature (150°C);

[0129] S33, high-purity elemental silicon is sputtered out Si ions in the sputtering gas Ar, the ion source of the sputtering coating machine is filled with high-purity O2 and Ar to generate a plasma beam, the target material sputtering power supply and the ion source of the sputtering coating machine work together to obtain SiO2 thin film material, and deposit it on the fifth MgF2 thin film layer to obtain a SiO2 protective layer; the flow rate of the sputtering gas Ar is 35sccm, the sputtering power of the sputtering coating machine is 2000W, the ion source power of the sputtering coating machine is 2500W, the O2 flow rate in the ion source is 50sccm, and the Ar flow rate is 40sccm;

[0130] S34. After the deposition of SiO2 protective layer is completed, the vacuum chamber is cooled for 60 minutes, and the sample is taken out to obtain the JGS1 substrate antireflection film.

[0131] Performance Testing

[0132] Figure 3 This is a graph of the average reflectivity of the JGS1 substrate anti-reflection film in Example 1 at different incident angles (0-40°, specifically 0°, 10°, 20°, 30°, 40°). Figure 3 Ra is the average reflectivity, that is, s-light and p-light are not distinguished.

[0133] from Figure 3 It can be seen that at different incident angles, the JGS1 substrate anti-reflection film under this film system maintains a low average reflectivity for deep ultraviolet 193nm, which is less than 0.5%, and the transmittance (transmittance = 1-reflectivity) is greater than 99.5%.

[0134] Figures 4 to 6 Atomic force microscope images of the SiO2 protective layer prepared according to the method in Example 1 at different positions.

[0135] from Figures 4 to 6 It can be seen that in three different selected areas (each area is 1000nm×1000nm), the arithmetic average deviation (Ra) of the profile of the SiO2 protective layer is less than 0.4nm, which proves that an ultra-smooth surface is obtained. Figures 4 to 6 In the AFM data, LengthX and LengthY are the lengths of the AFM selected area in the X and Y directions respectively; Area is the selected area; Rz is the maximum profile height in the selected area; Rzjis is the ten-point average roughness in the selected area; Rq is the profile root mean square deviation; Rp is the maximum profile peak height in the selected area; Rv is the maximum profile valley depth in the selected area. In the surface roughness data, the profile arithmetic mean deviation Ra can best reflect the true situation of the profile surface roughness.

[0136] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A JGS1 substrate antireflection film, characterized in that: include: JGS1 quartz glass substrate; F-SiO2 thin film layer, located on the surface of the JGS1 quartz glass substrate; An anti-reflection film layer, located on the surface of the F-SiO2 thin film layer away from the JGS1 quartz glass substrate, the anti-reflection film layer comprising a plurality of MgF2 thin film layers and GdF3 thin film layers arranged alternately in sequence; The protective layer is located on the surface of the anti-reflection film layer away from the JGS1 quartz glass substrate.

2. The JGS1 substrate antireflection film according to claim 1, characterized in that: The protective layer is a SiO2 protective layer, and the roughness of the protective layer is less than 0.4 nm; And / or, the F-doping mass concentration in the F-SiO2 thin film layer is 0.2% to 4%.

3. The JGS1 substrate antireflection film according to claim 1, characterized in that: The thickness of the JGS1 quartz glass substrate is 40 to 60 mm; And / or, the thickness of the F-SiO2 thin film layer is 5 to 15 nm; And / or, the thickness of the MgF2 thin film layer is 20 to 80 nm; And / or, the thickness of the GdF3 thin film layer is 25 to 40 nm; And / or, the protective layer has a thickness of 3 to 10 nm; And / or, the MgF2 thin film layer and the GdF3 thin film layer are interlaced 1 to 20 times.

4. The JGS1 substrate antireflection film according to claim 1, characterized in that: The antireflection film layer includes a first MgF2 thin film layer, a first GdF3 thin film layer, a second MgF2 thin film layer, a second GdF3 thin film layer, a third MgF2 thin film layer, a third GdF3 thin film layer, a fourth MgF2 thin film layer, a fourth GdF3 thin film layer, and a fifth MgF2 thin film layer, which are located on the surface of the JGS1 quartz glass substrate and are stacked in sequence; The thickness of the first MgF2 thin film layer is 34-35 nm, and the thickness of the first GdF3 thin film layer is 36-37 nm; the thickness of the second MgF2 thin film layer is 64-65 nm, and the thickness of the second GdF3 thin film layer is 30.5-31.5 nm; the thickness of the third MgF2 thin film layer is 34-35 nm, and the thickness of the third GdF3 thin film layer is 31-32 nm; The thickness of the fourth MgF2 thin film layer is 34-35 nm, the thickness of the fourth GdF3 thin film layer is 31.5-32.5 nm; the thickness of the fifth MgF2 thin film layer is 27.0-29.0 nm.

5. A method for preparing a JGS1 substrate antireflection film as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: The F-SiO2 thin film layer was deposited on the surface of the JGS1 quartz glass substrate; On the surface of the F-SiO2 thin film layer, a MgF2 thin film layer and a GdF3 thin film layer are sequentially and alternately deposited to obtain an anti-reflection film layer; A protective layer is deposited on the surface of the anti-reflection film layer.

6. The method for preparing the JGS1 substrate antireflection film according to claim 5, characterized in that: With F-SiO2 as the target material, a F-SiO2 thin film layer is deposited on the surface of a JGS1 quartz glass substrate by a magnetron sputtering method; wherein, during the deposition, the deposition temperature is 140-160°C.

7. The method for preparing the antireflection film of JGS1 substrate according to claim 5, characterized in that: Using MgF2 and GdF3 particles as evaporation sources, the electron beam thermal evaporation method is used to alternately deposit the MgF2 film layer and the GdF3 film layer on the surface of the F-SiO2 film layer. When the MgF2 thin film layer and the GdF3 thin film layer are deposited, the temperature of the JGS1 quartz glass substrate is controlled to be 260-280° C., the deposition rate of the MgF2 thin film layer is 0.2-0.4 nm / s, and the deposition rate of the GdF3 thin film layer is 0.2-0.4 nm / s.

8. The method for preparing the JGS1 substrate antireflection film according to claim 7, characterized in that: Before the MgF2 thin film layer and the GdF3 thin film layer are alternately deposited on the surface of the F-SiO2 thin film layer, the GS1 quartz glass substrate is also subjected to plasma treatment, wherein the plasma treatment gas includes oxygen and argon, the oxygen flow rate is 40 to 60 sccm, the argon flow rate is 5 to 10 sccm, the plasma treatment time is 60 to 120 s, the voltage is 690 to 710 V, and the current is 690 to 710 mA.

9. The method for preparing the JGS1 substrate antireflection film according to claim 7, characterized in that: The protective layer is a SiO2 protective layer; the SiO2 protective layer is prepared by sputtering coating method using Si as target material; Among them, the sputtering gas is Ar, the ion source of the sputtering coater is O2 and Ar, the target sputtering power supply and the sputtering coater ion source work together to obtain a SiO2 protective layer, the flow rate of the sputtering gas Ar is 30-40sccm, the sputtering power of the sputtering coater is 1800-2200W, the ion source power of the sputtering coater is 2400-2600W, the O2 flow rate in the ion source is 50-60sccm, the Ar flow rate is 40-50sccm, and the temperature of the GS1 quartz glass substrate during sputtering is 140-160℃.

10. Use of the JGS1 substrate anti-reflection film according to any one of claims 1 to 4 or the JGS1 substrate anti-reflection film prepared by the preparation method according to any one of claims 5 to 9 in preparing deep ultraviolet lasers.

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