Mask surface anti-sticking treatment method and mask plate copying method

Abstract

The invention provides a mask surface anti-sticking treatment method and a mask plate copying method, and relates to the technical field of micro-nano machining, and the mask surface anti-sticking treatment method comprises the following steps: preparing a diluted solution required for forming an anti-sticking layer; the surface of the mask is treated, so that hydrophilic groups are generated on the surface of the mask; coating the surface of the mask on which the hydrophilic group is generated with a diluted solution to form an anti-sticking layer; and post-processing the mask with the anti-sticking layer formed on the surface, so that a chemical bond is formed between the anti-sticking layer and the surface of the mask, and the anti-sticking mask is obtained.

Description

Technical Field

[0001] The present invention relates to the field of micro-nano processing technology, and in particular to a mask surface anti-sticking treatment method and a mask plate replication method. Background Art

[0002] In the nanoimprint process, in order to make the mask better for demolding and pattern transfer, a hydrophobic coating needs to be applied to the mask surface to reduce its surface energy and ensure the complete peeling of the imprint adhesive structure. The anti-stick coating process determines the quality of the coating. Insufficient adhesion of the coating will cause the film layer to detach during the imprint process, and there is a risk of adhesive contamination of the mask. Too thick a coating will cause changes in the structural morphology and affect the imprint quality. Summary of the invention

[0003] In view of this, the embodiments of the present disclosure provide a method for anti-sticking treatment of a mask surface and a method for replicating a mask.

[0004] A first aspect of an embodiment of the present disclosure provides a method for anti-sticking treatment of a mask surface, comprising: preparing a dilute solution required for forming an anti-sticking layer; treating the mask surface to generate hydrophilic groups on the mask surface; coating the dilute solution on the mask surface with the hydrophilic groups to form an anti-sticking layer; post-treating the mask with the anti-sticking layer on the surface to form a chemical bond between the anti-sticking layer and the mask surface to obtain an anti-sticking mask.

[0005] According to an embodiment of the present disclosure, a dilute solution required for forming an anti-sticking layer is prepared, including: using at least one of decafluoropentane, hydrochlorofluorocarbons, perfluorocarbons, pentafluorobutane, heptafluoropropane, nonafluoropentyl ether, and nonafluorohexyl ether as a solvent, and at least one of perfluorooctyltrichlorosilane, perfluorodecyltrichlorosilane, perfluorooctyldimethylchlorosilane, polytetrafluoroethylene, polydimethylsiloxane, heptadecafluorodecyl phosphate, and perfluoroheptanoic acid as an effective ingredient to prepare the dilute solution.

[0006] According to an embodiment of the present disclosure, the mask surface is processed, including: using plasma equipment to physically bombard and chemically process the mask surface, so that hydrophilic groups are generated on the mask surface.

[0007] According to an embodiment of the present disclosure, the gases used in the plasma equipment include argon and oxygen, argon is used for physical bombardment, and oxygen is used for chemical treatment, and the volume ratio of argon to oxygen in the gas is 3:1~6:1; the power of the plasma equipment for treating the mask surface is 30 W~150 W, and the treatment time is 30 s~200 s.

[0008] According to an embodiment of the present disclosure, a dilute solution is coated on a mask surface formed with hydrophilic groups to form an anti-sticking layer, comprising: evenly spreading the dilute solution on the mask surface, and standing for a preset period of time to allow effective ingredients in the dilute solution to penetrate the mask surface; evenly dispersing the dilute solution on the mask surface at a first rotational speed to form a film layer; using a dilute solvent in the dilute solution required to form the anti-sticking layer, cyclically cleaning the mask surface at a second rotational speed, thinning the film layer into a monomolecular layer, and obtaining the anti-sticking layer; wherein the first rotational speed is greater than the second rotational speed.

[0009] According to an embodiment of the present disclosure, the first rotation speed is 2000 rpm~4000 rpm, the second rotation speed is 200 rpm~1000 rpm, the preset time period is 30 s~120 s, and the number of cycle cleaning is 3~5 times.

[0010] According to an embodiment of the present disclosure, the thickness of the anti-sticking layer is 8 nm to 20 nm.

[0011] According to an embodiment of the present disclosure, post-processing is performed on a mask having an anti-sticking layer formed on the surface, including: baking the mask having the anti-sticking layer formed on the surface, the baking temperature is 100° C. to 200° C., and the baking time is 300 s to 1200 s.

[0012] According to an embodiment of the present disclosure, the solid content of the diluted solution is 0.1%~0.5%.

[0013] A second aspect of the disclosed embodiments provides a mask replication method, comprising: performing anti-stick treatment on the surface of the mask using the above method to obtain an anti-stick mask; and using the anti-stick mask as a nanoimprint master to replicate a replication mask.

[0014] The mask surface anti-sticking treatment method and mask copying method provided by the embodiments of the present disclosure have at least the following technical effects:

[0015] The method firstly processes the mask surface to generate hydrophilic groups on the mask surface, thereby enhancing the adhesion of the mask surface. Then, combined with coating, especially spin coating process, an anti-sticking layer tightly adsorbed by chemical bonds can be quickly formed on the mask surface.

[0016] The plasma surface treatment process is used to hydrophilize the mask surface, find the boundary parameters of the surface treatment power without destroying the mask structure, and increase the service life of the anti-adhesive layer.

[0017] The anti-sticking layer is formed by coating, especially spin coating, a diluted solution, so that very little effective ingredient is consumed during each coating process, thereby reducing the coating cost; by adjusting the proportion of the diluted solution and the cleaning process, a uniform, dense, high-quality and ultra-thin single-molecular film layer can be achieved for masks with different structures. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The above and other objects, features and advantages of the present disclosure will become more apparent through the following description of the embodiments of the present disclosure with reference to the accompanying drawings, in which:

[0019] Figure 1 An optical microscope image of an anti-sticking layer on a mask surface in a conventional anti-sticking layer coating method is schematically shown.

[0020] Figure 2 The scanning electron microscope image of the anti-sticking layer on the mask surface of another example in the conventional anti-sticking layer coating method is schematically shown.

[0021] Figure 3 The flowchart of the anti-sticking treatment method for the mask surface according to the embodiment of the present disclosure is schematically shown.

[0022] Figure 4 The structural diagram corresponding to each operation in the anti-sticking treatment method for the mask surface according to an embodiment of the present disclosure is schematically shown.

[0023] Figure 5 The result of 5-point contact angle characterization of the coated mask according to Example 1 of the present disclosure is schematically shown.

[0024] Figure 6 The topography of the mask before and after imprinting according to Example 1 of the present disclosure is schematically shown.

[0025] Figure 7 The scanning electron microscope image of the mask imprint structure according to Example 1 of the present disclosure is schematically shown. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present disclosure more clearly understood, the present disclosure is further described in detail below in combination with specific embodiments and with reference to the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present disclosure, rather than all of the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present disclosure.

[0027] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise", "include", etc. used herein indicate the existence of the features, steps, operations and / or components, but do not exclude the existence or addition of one or more other features, steps, operations or components.

[0028] Similarly, in order to simplify the present disclosure and help understand one or more of the various disclosed aspects, in the above description of the exemplary embodiments of the present disclosure, the various features of the present disclosure are sometimes grouped together into a single embodiment, figure, or description thereof. The description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present disclosure. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0029] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the feature. In the description of the present disclosure, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0030] Figure 1 An optical microscope image of an anti-sticking layer on a mask surface in a conventional anti-sticking layer coating method is schematically shown. Figure 2 The scanning electron microscope image of the anti-sticking layer on the mask surface of another example in the conventional anti-sticking layer coating method is schematically shown.

[0031] like Figure 1 As shown in Figure 1, insufficient adhesion of the anti-sticking layer will cause the mask to stick during the imprint process. Figure 2 As shown, the anti-sticking layer is too thick, resulting in accumulation on the side walls and bottom of the structure.

[0032] In view of this, embodiments of the present disclosure provide a mask surface anti-sticking treatment method and a mask.

[0033] Figure 3 The flowchart of the anti-sticking treatment method for the mask surface according to the embodiment of the present disclosure is schematically shown.

[0034] like Figure 3 As shown, the mask surface anti-sticking treatment method provided in this embodiment may include operations S310 to S340.

[0035] In operation S310, a dilution solution required for forming an anti-sticking layer is prepared.

[0036] In operation S320, the surface of the mask is treated to generate hydrophilic groups on the surface of the mask.

[0037] In operation S330, a diluted solution is coated on the surface of the mask having the hydrophilic groups generated thereon to form an anti-sticking layer.

[0038] In operation S340, the mask with the anti-sticking layer formed on the surface is post-processed to form a chemical bond between the anti-sticking layer and the mask surface, thereby obtaining an anti-sticking mask.

[0039] According to the embodiments of the present disclosure, a dilution solvent and a stock solution of an anti-sticking active ingredient may be taken, and a dilution solution may be prepared according to the thickness requirement of the anti-sticking layer to form the anti-sticking layer.

[0040] In order to increase the hydrophilicity of the mask surface and increase the adhesion of the film layer, the mask surface is subjected to corresponding hydrophilic treatment according to the different mask materials, so that hydrophilic groups such as carboxyl and hydroxyl groups are generated on the substrate surface.

[0041] Based on the above embodiment, preparing the dilute solution required for forming the anti-sticking layer may include:

[0042] At least one of decafluoropentane (HFC), hydrochlorofluorocarbon (HCFC), perfluorocarbon (PFC), pentafluorobutane, heptafluoropropane, nonafluoropentyl ether, nonafluorohexyl ether (HFE) and the like is used as a solvent, and perfluorooctyl trichlorosilane (F 13 -OTCS), perfluorodecyltrichlorosilane (F 17 -DTCS), perfluorooctyldimethylsilyl chloride (F 13 -OMCS), polytetrafluoroethylene (PTFE), polydimethylsiloxane (PDMS), heptadecafluorodecyl phosphate, perfluoroheptanoic acid, etc. as an active ingredient to prepare a diluted solution.

[0043] On the basis of the above-mentioned embodiment, processing the mask surface may include: using plasma equipment to perform physical bombardment and chemical treatment on the mask surface to generate hydrophilic groups on the mask surface.

[0044] Furthermore, the gas used by the plasma equipment may include argon and oxygen. Argon can be used for physical bombardment to increase surface roughness, and oxygen can be used for chemical treatment to generate hydrophilic groups such as carboxyl and hydroxyl groups on the substrate surface. The volume ratio of argon to oxygen in the gas may be 3:1 to 6:1; the power of the plasma equipment for treating the mask surface is 30W to 150W, and the treatment time is 30 s to 200 s.

[0045] On the basis of the above embodiment, coating the dilute solution on the mask surface with hydrophilic groups to form an anti-sticking layer may include: spreading the dilute solution evenly on the mask surface, standing for a preset period of time to allow the effective components in the dilute solution to infiltrate the mask surface. Dispersing the dilute solution evenly on the mask surface at a first rotation speed to form a film layer; using a dilute solvent in the dilute solution required to form the anti-sticking layer, cyclically cleaning the mask surface at a second rotation speed to thin the film layer into a monomolecular layer to obtain the anti-sticking layer; wherein the first rotation speed is greater than the second rotation speed.

[0046] Furthermore, the first rotation speed can be 2000 rpm~4000 rpm, and high-speed spin coating makes the solution evenly dispersed. The second rotation speed can be 200 rpm~1000 rpm, and low-speed spin coating is conducive to better cleaning. The preset time period is 30 s~120 s. The surface of the mask can be repeatedly cleaned with a diluted solution for 3-5 cycles to further thin the film layer so that it forms a uniform monomolecular layer on the surface of the substrate as an anti-sticking layer with a thickness of 8 nm~20 nm.

[0047] Based on the above embodiment, post-processing the mask with the anti-sticking layer formed on the surface may include: baking the mask with the anti-sticking layer formed on the surface, the baking temperature is 100° C. to 200° C., and the baking time is 300 s to 1200 s.

[0048] After coating, the mask is post-baked to form a chemical bond between the film layer and the substrate, thereby forming a dense monomolecular film layer with good adhesion.

[0049] In order to more clearly illustrate the anti-sticking treatment method for the mask surface provided by the present disclosure, specific examples are listed below for illustration in conjunction with the accompanying drawings. Figure 4 The structural diagram corresponding to each operation in the anti-sticking treatment method for the mask surface according to an embodiment of the present disclosure is schematically shown.

[0050] The process of the anti-sticking treatment method for the mask surface in this embodiment 1 can be as follows:

[0051] Step 1: Take the dilution solvent and the stock solution of the anti-sticking active ingredient, select perfluoroheptanoic acid as the solute and a mixture of nonafluoropentyl ether and nonafluorohexyl ether (HFE) as the solvent according to the thickness requirement of the anti-sticking layer, and prepare a dilution solution with a solid content of 0.1%.

[0052] Step 2: Use plasma cleaning equipment to hydrophilize the mask surface. The gas type and volume ratio are Ar:O 2 =26:5, the processing power is 150 W, and the processing time is 100 s. Ar mainly plays a role in physical bombardment, increasing the surface roughness, and O 2The main function is chemical treatment, which generates hydrophilic groups such as carboxyl and hydroxyl groups on the substrate surface. The contact angle of the treated substrate surface is less than 10°. The structure corresponding to this step is as follows Figure 4 As shown in a.

[0053] Step 3: Evenly spread the diluted solution on the mask surface and let it stand for 60 seconds to allow the anti-sticking active ingredients to fully penetrate. The corresponding structure is as follows: Figure 4 As shown in b. The solution was evenly dispersed on the mask surface by high-speed spin coating at a speed of 2000 rpm; then the mask surface was cleaned back and forth for 3 cycles using a diluted solvent of a mixture of nonafluoropentyl ether and nonafluorohexyl ether (HFE) to further thin the film layer to form a uniform monolayer on the substrate surface with a thickness of 8 nm. The corresponding structure is shown in Figure 4 As shown in c.

[0054] Step 4: After coating, the mask is post-baked to form a chemical bond between the film layer and the substrate, thereby forming a dense monomolecular film layer with good adhesion. The baking temperature is 120 °C and the time is 1200 s. The structure corresponding to this step is as follows Figure 4 As shown in middle d.

[0055] It should be noted that the specific parameters, material types, processes, etc. involved in the above examples are for the purpose of more clearly illustrating the nanoimprint method provided by the embodiments of the present disclosure, and are not intended to limit the present disclosure.

[0056] Figure 5 The result of 5-point contact angle characterization of the coated mask according to Example 1 of the present disclosure is schematically shown.

[0057] like Figure 5 As shown in the figure, the contact angles are all between 107° and 112°. This is because the plasma surface treatment makes the substrate surface full of hydrophilic groups, and the spin coating method allows the anti-sticking active ingredients to be completely infiltrated, thus achieving a uniformly distributed dense monomolecular layer, indicating that the anti-sticking layer is successfully coated.

[0058] An embodiment of the present disclosure also provides a mask replication method, comprising:

[0059] The mask surface anti-sticking treatment method is used to perform anti-sticking treatment on the mask surface to obtain an anti-sticking mask. The anti-sticking mask is used as a nanoimprint master to replicate to obtain a replica mask.

[0060] After the anti-sticking layer is successfully coated, the anti-sticking mask is subjected to an imprinting process. The imprinting glue is evenly sprayed on the surface of the 4-inch silicon wafer. The anti-sticking mask is then brought into contact with the silicon wafer to allow the imprinting glue to completely soak the structure. After UV exposure and curing, the mold is demolded. The anti-sticking mask is smoothly peeled off from the silicon wafer, and the graphic results are completely transferred to the silicon wafer.

[0061] Figure 6 The topography of the mask before and after imprinting according to Example 1 of the present disclosure is schematically shown. Figure 7 The scanning electron microscope image of the mask imprint structure according to Example 1 of the present disclosure is schematically shown.

[0062] like Figure 6 As shown in the figure, the structure of the mask before and after imprinting has not changed at all, and there is no sticking. Figure 7 As shown, the structure after embossing is complete, and the morphology presents a uniformly distributed grating morphology, indicating that the mask after anti-stick coating has good hydrophobicity, and the film layer has no bottom accumulation and side wall adhesion, thereby completely reproducing the original morphology of the mask.

[0063] Through the processing method of the disclosed embodiment, anti-stick coating is performed by coating, especially spin coating, which is efficient and simple, and the entire coating process is short, which improves the efficiency of the entire process. After coating, the anti-stick layer of the mask can usually achieve dozens or even hundreds of reprint processes, and has a very long service life. The anti-stick coating and the mask substrate are connected by chemical bonds, and have excellent adhesion. At the same time, the side in contact with the embossing glue is usually fluorine-based and silicon-based side chains, and has a low surface energy. When the embossing filling, exposure curing and demolding molding process are performed, the embossing glue will not remain on the template, but will be completely separated from the embossing structure required for the formation process. The dilution process before the anti-sticking agent is applied and the cleaning process during the application process, by adjusting the solid content of the effective component and the flow rate and cleaning time of the solvent during the cleaning process, the thickness of the anti-sticking layer on the template is adjustable and the film layer is uniform. The optimal thickness and uniform film layer are adjusted for the template structure with different duty cycles, so that the template structure is uniformly attached to the anti-sticking coating, and the morphology will not change due to the accumulation of the effective component. In addition to the anti-adhesion coating on the surface of the mask, this method can also be used in the surface treatment of electronic screens, lenses, and glass, giving them excellent anti-fingerprint and anti-fouling properties.

[0064] The specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present disclosure in detail. It should be understood that the above are only preferred embodiments of the present disclosure and the technical principles used. Those skilled in the art will understand that the present disclosure is not limited to the specific embodiments described herein, and that various obvious changes, readjustments and substitutions can be made by those skilled in the art without departing from the protection scope of the present disclosure. Therefore, although the present disclosure is described in more detail through the above embodiments, the present disclosure is not limited to the above embodiments, and may also include more other equivalent embodiments without departing from the concept of the present disclosure, all of which belong to the protection scope of the present disclosure.

Claims

1. A method for anti-sticking treatment of a mask surface, characterized in that: include: preparing a dilute solution required for forming an anti-stick layer; Treating the surface of the mask to generate hydrophilic groups on the surface of the mask; Coating the diluted solution on the mask surface with hydrophilic groups to form the anti-sticking layer; The mask with the anti-sticking layer formed on the surface is post-processed to form a chemical bond between the anti-sticking layer and the mask surface, thereby obtaining an anti-sticking mask.

2. The method according to claim 1, characterized in that The dilution solution required for preparing the anti-sticking layer comprises: The diluted solution is prepared by using at least one of decafluoropentane, hydrochlorofluorocarbon, perfluorocarbon, pentafluorobutane, heptafluoropropane, nonafluoropentyl ether and nonafluorohexyl ether as a solvent, and at least one of perfluorooctyltrichlorosilane, perfluorodecyltrichlorosilane, perfluorooctyldimethylchlorosilane, polytetrafluoroethylene, polydimethylsiloxane, heptadecafluorodecyl phosphate and perfluoroheptanoic acid as an effective ingredient.

3. The method according to claim 1, characterized in that The processing of the mask surface comprises: The mask surface is physically bombarded and chemically treated by using plasma equipment to generate hydrophilic groups on the mask surface.

4. The method according to claim 3, characterized in that The gas used by the plasma equipment includes argon and oxygen, the argon is used for physical bombardment, and the oxygen is used for chemical treatment, and the volume ratio of argon to oxygen in the gas is 3:1 to 6:1; The power of the plasma equipment for treating the mask surface is 30 W to 150 W, and the treatment time is 30 s to 200 s.

5. The method according to claim 1, characterized in that The step of coating the diluted solution on the surface of the mask having the hydrophilic groups to form the anti-sticking layer comprises: Evenly spread the diluted solution on the surface of the mask, and let it stand for a preset time to allow the active ingredients in the diluted solution to penetrate the surface of the mask; Evenly dispersing the diluted solution on the surface of the mask at a first rotation speed to form a film layer; Using the diluent solvent in the diluent solution required for forming the anti-sticking layer, the surface of the mask is cyclically cleaned at a second rotation speed to thin the film layer into a monomolecular layer to obtain the anti-sticking layer; Wherein, the first rotation speed is greater than the second rotation speed.

6. The method according to claim 5, characterized in that The first rotation speed is 2000 rpm~4000 rpm, the second rotation speed is 200 rpm~1000 rpm, the preset time period is 30 s~120 s, and the number of cyclic cleaning is 3~5 times.

7. The method according to claim 1, 5 or 6, characterized in that: The thickness of the anti-sticking layer is 8 nm to 20 nm.

8. The method according to claim 1, characterized in that The post-processing of the mask having the anti-sticking layer formed on the surface comprises: The mask with the anti-sticking layer formed on the surface is baked at a temperature of 100° C. to 200° C. and a baking time of 300 s to 1200 s.

9. The method according to claim 1 or 2, characterized in that: The solid content of the diluted solution is 0.1% to 0.5%.

10. A mask replication method, characterized in that: include: Performing anti-stick treatment on the surface of the mask by the method described in any one of claims 1 to 9 to obtain an anti-stick mask; The anti-sticking mask is used as a nanoimprint master to replicate a replication mask.

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