Anti-chip film as well as preparation method and application thereof

Abstract

The invention relates to the technical field of nano-film preparation, in particular to an anti-chip film and a preparation method and application thereof, and the preparation method comprises the following steps: mixing a nano-material with a solvent to obtain a nano-material solution; the method comprises the following steps: performing surface treatment on a substrate, performing first coating treatment by using a water-soluble sacrificial layer solution, and performing drying and annealing treatment to obtain a substrate with a water-soluble sacrificial layer; and carrying out second coating treatment on the water-soluble sacrificial layer by using a nano material solution, drying, and putting into deionized water to obtain the anti-chip film. The preparation method comprises the following steps: carrying out hydrophilic treatment on a substrate, coating a layer of water-soluble sacrificial layer solution, drying, coating a layer of nano material solution on the water-soluble sacrificial layer, drying to form a film, putting the double-layer film and the substrate into water, dissolving the water-soluble sacrificial layer in the water, and insoluble the anti-chip film in the water. Therefore, the chip-proof thin film can automatically fall off and float to the water surface, and preparation of the chip-proof thin film is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of nano film preparation, and in particular to an anti-debris film and a preparation method and application thereof. Background Art

[0002] In the extreme ultraviolet (EUV) lithography machine, the light source used is based on the plasma generated by laser-excited tin liquid, which contains EUV radiation with a wavelength of 13.5nm. When the laser bombards the tin droplets to excite the plasma, a large amount of debris will be generated. The high-speed moving debris enters the lithography and projection system without shielding, which will seriously contaminate the EUV mirror and optical mask, thereby affecting the performance, service life and yield of the optical components. Since the mirror in EUV is expensive, it is very easy to cause serious economic losses and reduce the working life of the EUV lithography machine. Therefore, using a thin film element with high mechanical stability and high transmittance for EUV light to be placed in front of the EUV mirror, the EUV mirror is protected from debris, which can improve the stability and life of the EUV light source. Fanghua film, as a high-transmittance, high-strength organic film, is widely used as a support film for transmission electron microscope grids and can also be used for debris protection.

[0003] The current methods for preparing Fanghua films have the following main disadvantages: using strong acid to treat the substrate has certain operational risks, is not suitable for large-scale processing, and is prone to residues that cause damage to the surface component structure of the Fanghua film; using mechanical methods to peel off the Fanghua film is not suitable for peeling off nano-level thin films and is prone to damage the film; using a copper mesh bracket with a honeycomb mesh has a small light-transmitting area, which is not conducive to the passage of EUV light.

[0004] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, an object of the present invention is to provide an anti-debris film and a preparation method and application thereof, aiming to solve the problems of substrate surface treatment contamination and peeling difficulty in the existing anti-debris film preparation process.

[0006] The technical solution of the present invention is as follows:

[0007] A method for preparing an anti-debris film comprises the steps of:

[0008] Mixing the nanomaterial with a solvent to obtain a nanomaterial solution;

[0009] After the substrate is subjected to hydrophilic treatment, a first coating treatment is performed using a water-soluble sacrificial layer solution, and after drying and annealing treatment, a substrate having a water-soluble sacrificial layer is obtained;

[0010] The nano material solution is subjected to a second coating treatment on the water-soluble sacrificial layer, and after drying, is placed in water to obtain an anti-chip film.

[0011] The method for preparing the anti-debris film, wherein the nano material is selected from one of polyvinyl formal, graphene, and carbon nanotubes; and / or the solvent is selected from one or more of ethylene dichloride, chloroform, and ethyl lactate.

[0012] In the method for preparing the anti-debris film, the volume fraction of the nano material in the nano material solution is 1%-5%.

[0013] In the method for preparing the anti-debris film, the water-soluble sacrificial layer material in the water-soluble sacrificial layer solution is selected from one or more of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polyethylene glycol, and polyacrylamide.

[0014] The method for preparing the anti-chip film, wherein the temperature of the annealing treatment is 20° C.-30° C., and the time of the annealing treatment is 15 min-25 min.

[0015] The method for preparing the anti-debris film, wherein the second coating treatment is a spin coating treatment; the spin coating speed of the spin coating treatment is 1800rpm-2500rpm, and the spin coating treatment time is 50s-70s.

[0016] An anti-debris film is prepared by using the preparation method of the anti-debris film.

[0017] The anti-debris film has a thickness of 25nm-35nm.

[0018] The invention discloses an application of an anti-debris film in an EUV light source debris protection element.

[0019] In the application, the EUV light source debris protection element includes a support carrier and an anti-debris film attached to the support carrier.

[0020] Beneficial effects: The present invention provides an anti-debris film and a preparation method and application thereof. The preparation method of the anti-debris film comprises the following steps: mixing a nano material with a solvent to obtain a nano material solution; performing a first coating treatment on a substrate using a water-soluble sacrificial layer solution after surface treatment, and obtaining a substrate having a water-soluble sacrificial layer after drying and annealing; performing a second coating treatment on the water-soluble sacrificial layer with the nano material solution, and placing the nano material solution in deionized water after drying to obtain an anti-debris film. The present invention performs a hydrophilic treatment on the substrate, first applies a layer of a water-soluble sacrificial layer solution, and then applies a layer of nano material solution on the water-soluble sacrificial layer after drying. After drying and forming a film, the double-layer film is placed in water together with the substrate, the water-soluble sacrificial layer dissolves in water, and the anti-debris film is insoluble in water, so that the anti-debris film automatically falls off in water and floats to the water surface, thereby realizing the preparation of the anti-debris film. The preparation method avoids the potential danger of using strong acid and the potential damage to the film; at the same time, the anti-debris film is peeled off from the substrate by utilizing the characteristic that the water-soluble sacrificial layer dissolves in water. Compared with the mechanical peeling method, the preparation method of the present invention has the advantages of being more gentle and less destructive, and can ensure the mechanical properties of the film, and can achieve batch peeling within a unit time. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A schematic diagram of a process for preparing an anti-debris film according to the present invention;

[0022] Figure 2 A schematic diagram of a tool structure for removing an anti-debris film from water;

[0023] Figure 3 for Figure 2 Exploded schematic diagram of the structure;

[0024] Figure 4 It is a schematic diagram of the structure of the supporting fixture;

[0025] Figure 5 The schematic diagram of the process flow of preparing Fanghua membrane in Example 1;

[0026] Figure 6 This is a comparison diagram of the Fanghua membrane solution prepared in Example 1 before and after stirring;

[0027] Figure 7 The microscopic images of the PEDOT:PSS film and the Fanghua film in Example 1 under a white light interference microscope;

[0028] Description of reference numerals: base 10 , handle 20 , connecting nut set 30 , main body base 40 , fixing hole 41 , slot 50 . DETAILED DESCRIPTION

[0029] The present invention provides an anti-debris film and a preparation method and application thereof. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0030] It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as generally understood by those skilled in the art in the art to which the present invention belongs. It should also be understood that terms such as those defined in general dictionaries should be understood to have meanings consistent with the meanings in the context of the prior art, and will not be interpreted with idealized or overly formal meanings unless specifically defined as herein.

[0031] The main steps of the current method for preparing Fanghua membrane are as follows: (1) dissolving Fanghua powder in a specific solvent, such as chloroform or dichloroethane, to prepare a solution of a certain concentration; (2) using silicon wafers, glass slides, etc. as substrates and using strong acid and deionized water for surface treatment; (3) coating the Fanghua solution on the substrate using a coating method (dip coating, slit coating); (4) evaporating the solvent and drying; (5) using a mechanical method to peel off the Fanghua membrane and place it on a copper mesh support with honeycomb mesh. However, there are problems such as substrate surface treatment contamination and difficulty in peeling.

[0032] Based on this, Figure 1 As shown, the present invention provides a method for preparing an anti-debris film, comprising the steps of:

[0033] Step S10: mixing the nanomaterial with the solvent to obtain a nanomaterial solution;

[0034] Step S20: After the substrate is subjected to hydrophilic treatment, a first coating treatment is performed using a water-soluble sacrificial layer solution, and after drying and annealing treatment, a substrate having a water-soluble sacrificial layer is obtained;

[0035] Step S30: performing a second coating process on the water-soluble sacrificial layer with the nano material solution, and placing the nano material solution in water after drying to obtain an anti-debris film.

[0036] In this embodiment, after the substrate is subjected to hydrophilic treatment, a layer of water-soluble sacrificial layer solution is first coated, and after drying, a layer of nanomaterial solution is coated on the water-soluble sacrificial layer. After drying to form a film, the double-layer film is placed in water together with the substrate. The water-soluble sacrificial layer dissolves in water, and the anti-debris film is insoluble in water, so it automatically falls off in water and floats to the water surface, thereby realizing the preparation of the anti-debris film. This preparation method avoids the potential danger of using strong acid and the potential damage to the film; at the same time, the anti-debris film is peeled off from the substrate by utilizing the characteristic that the water-soluble sacrificial layer dissolves in water. Compared with the mechanical peeling method, the preparation method of the present invention has the advantages of being more gentle and less destructive, and can ensure the mechanical properties of the film, and can achieve batch peeling within a unit time.

[0037] In some embodiments, the step of treating the substrate hydrophilically includes treating the substrate with plasma or ozone to improve the hydrophilicity of the substrate surface. Compared with the preparation of the traditional anti-chip film, since the present invention first coats a sacrificial layer on the substrate instead of directly coating the nanomaterial solution, there is no need to use a strong acid to modify the surface of the substrate hydrophilically and hydrophobically, but instead uses mild plasma cleaning or ozone irradiation to treat it, avoiding the potential danger of using strong acid and potential damage to the film.

[0038] In a preferred embodiment, the substrate is cleaned for 60 seconds using a plasma cleaning machine. The plasma treatment makes the treated surface of the substrate hydrophilic, which is conducive to the complete spreading of the first layer of water-soluble sacrificial layer solution on the substrate.

[0039] In some embodiments, before the substrate is subjected to hydrophilic treatment, the substrate needs to be cleaned and dried according to a cleaning procedure to obtain a clean substrate.

[0040] Specifically, the cleaning procedure is as follows: first, use deionized water with 1-2 drops of detergent to clean the substrate in an ultrasonic cleaning machine for 10 minutes to remove surface dust, oil stains and water-soluble substances; then use pure deionized water for ultrasonic cleaning for 10-15 minutes to remove the residual detergent in the previous step; then, use acetone for ultrasonic cleaning for 8-15 minutes to remove organic impurities on the surface of the substrate; finally, use isopropanol for ultrasonic cleaning for 8-15 minutes to remove organic impurities and acetone, and after cleaning, put it into a drying oven at 80°C for drying.

[0041] In some embodiments, the substrate is, but is not limited to, a glass sheet or the like.

[0042] In some embodiments, the nanomaterial is selected from one of polyvinyl formal, graphene, and carbon nanotubes; the anti-debris film made using the above material has higher EUV transmittance, excellent thermal conductivity and mechanical stability, and can improve higher debris protection effect.

[0043] In a preferred embodiment, the nanomaterial is polyvinyl formal (polyvinyl formal).

[0044] In some embodiments, the solvent is selected from one or more of dichloroethane, chloroform, and ethyl lactate. The above solvents can have good solubility for nanomaterials at room temperature.

[0045] In a preferred embodiment, the solvent is ethyl lactate, which is non-toxic and less volatile than ethylene dichloride and chloroform.

[0046] In some embodiments, the volume fraction of the nanomaterial in the nanomaterial solution is 1%-5%. The thickness of the anti-chip film can be controlled by controlling the volume fraction of the nanomaterial solution and combining the rotation speed and time of the coating treatment.

[0047] In a preferred embodiment, the volume fraction of the nanomaterial in the nanomaterial solution is 1%.

[0048] In some embodiments, the water-soluble sacrificial layer material in the water-soluble sacrificial layer solution is selected from one or more of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polyethylene glycol, and polyacrylamide. These water-soluble sacrificial layer materials are soluble in water. After the nanomaterial solution is coated on the water-soluble sacrificial layer, it is dried and placed in water, so that the water-soluble sacrificial layer is dissolved, thereby peeling the anti-debris film from the substrate, achieving gentle peeling and avoiding damage to the anti-debris film.

[0049] In a preferred embodiment, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) is selected as the water-soluble sacrificial layer material, and a 25μm hydrophilic filter head is used to filter the solution to remove tiny impurity particles. The parameters of the first coating treatment can be adjusted according to the required thickness of the water-soluble sacrificial layer.

[0050] In some embodiments, the annealing treatment is performed at a temperature of 20° C. to 30° C. and for a time of 15 min to 25 min. Through the annealing treatment, a water-soluble sacrificial layer can be prepared on the substrate.

[0051] In some embodiments, the second coating process is a spin coating process; the spin coating speed of the spin coating process is 1800rpm-2500rpm, and the spin coating time is 50s-70s. By controlling the spin coating speed and the spin coating time, the thickness of the anti-chip film can be precisely controlled.

[0052] Specifically, a 25 μm hydrophobic filter head is used to filter the nanomaterial solution to remove incompletely dissolved nanomaterials or other insoluble substances. A thin film with a thickness of about 30 nm can be obtained by spin coating at a speed of 2000 rpm for 60 seconds. Then, tweezers are used to transfer the substrate with the double-layer film to a water tank, and the water-soluble sacrificial layer is immersed to remove the water-soluble sacrificial layer. The upper anti-debris film automatically falls off from the surface of the substrate. The process is simple and avoids damage to the film surface by mechanical peeling.

[0053] In some embodiments, the first coating process and the second coating process can be selected from but not limited to spin coating, brush coating, blade coating, slit coating, spraying and the like.

[0054] In addition, the present invention also provides an anti-debris film, which is prepared by the method for preparing the anti-debris film.

[0055] In this embodiment, the anti-debris film prepared by the preparation method has good mechanical properties, and the shell can be peeled off in batches within a unit time.

[0056] In some embodiments, the thickness of the anti-debris film is 25nm-35nm. Through the above process, by adjusting the coating process parameters, an anti-debris film with controllable thickness can be obtained, and the anti-debris film within this thickness range has high light transmittance and good mechanical properties.

[0057] In addition, the present invention also provides an application of an anti-debris film in an EUV light source debris protection element.

[0058] In some embodiments, the EUV light source debris protection element includes a support carrier and an anti-debris film attached to the support carrier.

[0059] Specifically, the present invention also provides a tool for removing the anti-debris film from water, such as Figure 2 As shown, it includes a base 10, a handle 20 and a connecting nut set 30; the base adopts a three-level ladder design and is provided with a support carrier; the support carrier has a circular hole in the center and is placed in the second-level platform. When the anti-debris film floats on the water surface, the base and the support carrier are immersed in water, and their positions are adjusted so that the support carrier is located 5-10mm directly below the film, and lifted from bottom to top. The film is directly attached to the support carrier, and the debris protection element is obtained after drying at 50-60°C for 5-8 minutes. Using a unique ladder-type design tool, the square centimeter-level nanofilm can be directly coupled and advanced with the support carrier, and a large-area anti-debris element with high light transmittance can be prepared.

[0060] In some embodiments, the support carrier is a metal carrier, which has high strength and can provide better support for the anti-debris film.

[0061] In some embodiments, a circular hole is opened in the inner center of the base to prevent the anti-debris film from directly adhering to the base platform; the groove of the third step is used to remove the anti-debris film product supported by the support slide.

[0062] Specifically, Figure 3 As shown, the connection between the base, the handle and the connecting nut set adopts a trapezoidal meshing surface to achieve the rigid connection and angle adjustment function between the base and the handle, thereby enhancing the practicality of the tool.

[0063] In some embodiments, the EUV light source debris protection element is placed in a support fixture to form a debris protection device to prevent debris in the vacuum chamber. The structure of the support fixture is as follows: Figure 4 As shown, it includes a main base 40 and a slot 50; the slot is arranged at the front end of the main base, and the EUV light source debris protection element is tightly fixed through the slot; the rear end of the main base is provided with a fixing hole 41, which can be fixed to the optical rod by bolts to achieve precise adjustment of the three-dimensional position.

[0064] The following examples are further given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the scope of protection of the present invention.

[0065] Example 1

[0066] In this embodiment, polyvinyl formal is used as raw material to prepare Fanghua film, and its process flow is as follows: Figure 5 As shown, the specific steps are as follows:

[0067] (1) A 1.5 cm × 1.5 cm glass sheet was selected as the substrate, and the surface of the substrate was ultrasonically cleaned in detergent, deionized water, acetone, and isopropanol, respectively, and then placed in a drying oven for drying;

[0068] (2) polyvinyl formal was dissolved in ethyl lactate to prepare a solution with a volume fraction of 1%, and the polyvinyl formal was fully dissolved by rotating a magnetic stirrer on a magnetic heating stirrer to obtain a Fanghua membrane solution. The comparison of the solution before and after stirring was as follows: Figure 6 As shown, Figure 6 (a) is before stirring, and (b) is after stirring;

[0069] (3) Take a dried glass substrate, plasma clean the surface, and then spin-coat the first layer of PEDOT:PSS solution at a speed of 1600 rpm for 45 seconds, dry at 150°C, and anneal at room temperature for 20 minutes to obtain a PEDOT:PSS film. The surface of the film is observed by white light interference microscopy. Figure 7 As shown in (a);

[0070] (4) Spin coating a second layer of Fanghua film solution at a speed of 2000 rpm for 60 seconds and drying at room temperature to obtain a Fanghua film. The surface of the Fanghua film is observed under a white light interference microscope. Figure 7 As shown in (b);

[0071] (5) Using tweezers, place the glass slide with the double-layer film spin-coated in a square water tank filled with deionized water, and wait for the film to naturally fall off to the surface of the deionized water;

[0072] (6) Use Figure 2 The membrane removal tool shown is used to scoop up the Fanghua membrane from the water surface and directly install it on the supporting carrier. The preparation of the Fanghua membrane anti-debris element is completed.

[0073] The anti-debris element is placed in a support fixture to form a debris protection device that can be placed in a vacuum chamber of an EUV light source.

[0074] In summary, the present invention provides an anti-debris film and its preparation method and application. The preparation method of the anti-debris film includes the following steps: mixing nanomaterials with solvents to obtain a nanomaterial solution; performing a first coating treatment on a substrate using a water-soluble sacrificial layer solution, drying and annealing to obtain a substrate having a water-soluble sacrificial layer; performing a second coating treatment on the water-soluble sacrificial layer using the nanomaterial solution, and placing the nanomaterial solution in deionized water after drying to obtain an anti-debris film. The present invention performs a hydrophilic treatment on the substrate, first applies a layer of water-soluble sacrificial layer solution, and then applies a layer of nanomaterial solution on the water-soluble sacrificial layer after drying. After drying and forming a film, the double-layer film is placed in water together with the substrate. The water-soluble sacrificial layer dissolves in water, and the anti-debris film is insoluble in water, so that the anti-debris film automatically falls off in water and floats to the water surface, thereby realizing the preparation of the anti-debris film. The preparation method avoids the potential danger of using strong acid and the potential damage to the film; at the same time, the anti-debris film is peeled off from the substrate by utilizing the characteristic that the water-soluble sacrificial layer dissolves in water. Compared with the mechanical peeling method, the preparation method of the present invention has the advantages of being more gentle and less destructive, and can ensure the mechanical properties of the film, and can achieve batch peeling within a unit time.

[0075] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for preparing an anti-debris film, characterized in that: Includes steps: Mixing the nanomaterial with a solvent to obtain a nanomaterial solution; After the substrate is subjected to hydrophilic treatment, a first coating treatment is performed using a water-soluble sacrificial layer solution, and after drying and annealing treatment, a substrate having a water-soluble sacrificial layer is obtained; The nano material solution is subjected to a second coating treatment on the water-soluble sacrificial layer, and after drying, is placed in water to obtain an anti-chip film.

2. The method for preparing the anti-debris film according to claim 1, characterized in that: The nano material is selected from one of polyvinyl formal, graphene, and carbon nanotubes; and / or the solvent is selected from one or more of ethylene dichloride, chloroform, and ethyl lactate.

3. The method for preparing the anti-debris film according to claim 1, characterized in that: The volume fraction of the nano material in the nano material solution is 1%-5%.

4. The method for preparing the anti-debris film according to claim 1, characterized in that: The water-soluble sacrificial layer material in the water-soluble sacrificial layer solution is selected from one or more of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polyethylene glycol, and polyacrylamide.

5. The method for preparing the anti-debris film according to claim 1, characterized in that: The temperature of the annealing treatment is 20° C.-30° C., and the time of the annealing treatment is 15 min-25 min.

6. The method for preparing the anti-debris film according to claim 1, characterized in that: The second coating treatment is a spin coating treatment; the spin coating speed of the spin coating treatment is 1800rpm-2500rpm, and the spin coating treatment time is 50s-70s.

7. An anti-debris film, characterized in that: The anti-debris film is prepared by the method for preparing the anti-debris film according to any one of claims 1 to 6.

8. The anti-debris film according to claim 7, characterized in that: The thickness of the anti-debris film is 25nm-35nm.

9. Use of the anti-debris film according to any one of claims 7 to 8 in a debris protection element for an EUV light source.

10. The use according to claim 9, characterized in that: The EUV light source debris protection element includes a support carrier and an anti-debris film attached to the support carrier.

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