Dismounting method of protective film assembly and pre-dismounting treatment device of protective film assembly

Abstract

Provided is a method for detaching a pellicle, comprising: a step for preparing a laminate provided with a photomask, a pellicle frame, and a pellicle arranged in this order; a step for forming only an adhesive layer on the self-supporting portion of the protective film in the laminate; a step for adhering a protective film to the adhesive layer; and a removal step of breaking the protective film and removing the protective film, the protective film, and the adhesive layer from the photomask in the laminate having the protective film and the adhesive layer.

Description

[0001] This application is a divisional application of the original Chinese patent application filed on December 10, 2020, with application number 202080076482.2, entitled "Method for disassembling a protective film assembly and a pre-treatment device for disassembling a protective film assembly". Technical Field

[0002] This disclosure relates to a method for disassembling a protective film assembly and a pre-treatment device for disassembling the protective film assembly. Background Technology

[0003] The integration and miniaturization of semiconductor devices are accelerating year by year.

[0004] For example, currently, stimulated excimer laser lithography (SEL) is used to form patterns with linewidths of around 45 nm. However, in recent years, with the further miniaturization of semiconductor devices, it has become necessary to form patterns with linewidths below 32 nm. Traditional SEL is insufficient for such fine-grained fabrication. Therefore, the study investigated replacing the exposure light with shorter wavelength EUV (Extreme Ultraviolet) light.

[0005] EUV light has the characteristic of being easily absorbed by any substance. In photolithography (hereinafter also referred to as "EUV lithography"), which uses EUV light as the exposure light, a reflective optical system is used for exposure. Specifically, EUV light is reflected by a photomask (such as an intermediate mask) that reflects the exposure pattern, and the resist is exposed by the EUV light as reflected light.

[0006] In the photolithography process, if a foreign object adheres to the photomask, the EUV light will be scattered because the foreign object absorbs the EUV light, and therefore the desired pattern may not be formed during exposure. Therefore, a protective film assembly is installed (i.e., assembled) on the EUV-irradiated side of the photomask to protect it.

[0007] The aforementioned protective film assembly comprises a protective film for protecting the EUV light irradiation surface of a photomask and a protective film assembly frame supporting the protective film.

[0008] Protective film assemblies mounted on photomasks are sometimes subjected to contamination from dust and other sources, as well as degradation caused by light. In such cases, it is sometimes necessary to replace the protective film assembly, and therefore, it is sometimes necessary to disassemble (i.e., remove) the protective film assembly mounted on the photomask.

[0009] As a conventional method for removing a protective film assembly from a photomask, for example, the method for removing a protective film assembly described in Patent Document 1 is known.

[0010] Patent Document 1 discloses a method for removing a protective film assembly by making at least the protective film of the protective film assembly disposed on a photomask fit tightly against the sheet, and removing the protective film assembly from the photomask.

[0011] Patent Document 1: Japanese Patent Application Publication No. 2016-206527 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] One embodiment of this disclosure aims to solve the problem of providing a method for removing a protective film assembly that effectively suppresses contamination of photomasks.

[0014] Solution for solving the problem

[0015] The solutions to the above problems include the following implementation methods.

[0016] <1> A method for disassembling a protective film assembly, comprising the following steps:

[0017] The process of preparing a laminate, wherein the laminate is configured in the following order, comprising a photomask, a protective film assembly frame, and a protective film;

[0018] The process of forming an adhesive layer on the protective film in the above-mentioned laminate; and

[0019] The removal process involves at least removing the protective film and the adhesive layer from the photomask in the laminate on which the adhesive layer is formed.

[0020] <2> According to the disassembly method of the protective film assembly described in <1>, in the process of forming the above-mentioned adhesive layer, the above-mentioned adhesive layer is formed by spray coating, spin coating, inkjet coating, screen printing or dip coating.

[0021] <3> According to the disassembly method of the protective film assembly described in <1>, in the process of forming the above-mentioned adhesive layer, the above-mentioned adhesive layer is formed by spray coating.

[0022] <4> The method for disassembling the protective film assembly according to any one of <1> to <3>, wherein the adhesive layer comprises at least one adhesive selected from the group consisting of silicone adhesives, acrylic adhesives, urethane adhesives, polyamide adhesives, polyester adhesives, ethylene vinyl acetate copolymers, olefin adhesives, polybutadiene adhesives, rubber adhesives and styrene adhesives.

[0023] <5> The disassembly method of the protective film assembly according to any one of <1> to <4> further includes a mask adhesive layer between the photomask and the protective film assembly frame.

[0024] <6> The method for disassembling the protective film assembly as described in <5>

[0025] When the above-mentioned laminate is set as the first laminate,

[0026] The above disassembly process includes:

[0027] By removing the protective film and the adhesive layer while leaving the protective film assembly frame in the photomask side of the first laminate in which the adhesive layer is formed, a second laminate including the photomask, the mask adhesive layer and the protective film assembly frame is obtained.

[0028] The second layer of the above-mentioned stack is subjected to heat treatment; and

[0029] Remove the protective film assembly frame from the photomask in the second layer of the above-mentioned stack.

[0030] <7> The method for disassembling the protective film assembly according to any one of <1> to <6> further includes a step of heat-treating the laminate before the above disassembly step.

[0031] <8> The method for disassembling the protective film assembly according to any one of <1> to <7> is provided with at least one of a recess and a cut on the outer peripheral surface of the protective film assembly frame.

[0032] <9> According to any one of <1> to <8>, the method for disassembling the protective film assembly is provided in the laminate, wherein a through hole is provided in the laminate to penetrate the protective film and the protective film assembly frame in the thickness direction.

[0033] <10> The method for removing the protective film assembly according to any one of <1> to <9> further includes, after the step of forming the adhesive layer and before the step of removing the assembly, a step of adhering a protective film to the adhesive layer in the laminate in which the adhesive layer is formed.

[0034] In the above disassembly process, at least the protective film, the adhesive layer, and the protective film are removed from the photomask in the above-mentioned laminate to which the protective film is adhered.

[0035] <11> A pre-treatment apparatus for removing a protective film assembly, which is a pre-treatment apparatus for removing a protective film assembly for performing the step of forming the above-mentioned adhesive layer in the method for removing a protective film assembly as described in any one of <1> to <10>, comprising:

[0036] The mounting portion, wherein the laminate is mounted with the protective film on the upper side and the photomask on the lower side; and

[0037] The discharge section is used to discharge adhesive onto the protective film placed in the laminated body of the aforementioned placement section.

[0038] <12> The pre-treatment device for disassembling the protective film assembly according to <11>,

[0039] The discharge method of the above-mentioned discharge section is a spray method.

[0040] The adhesive is applied by spray coating to form the adhesive layer.

[0041] <13> The pre-treatment device for disassembling the protective film assembly as described in <11>

[0042] The aforementioned mounting section has a rotation function.

[0043] The adhesive is applied by spin coating to form the adhesive layer.

[0044] The effects of the invention

[0045] According to this disclosure, a method for removing a protective film assembly that effectively inhibits contamination of a photomask is provided. Attached Figure Description

[0046] Figure 1 A schematic cross-sectional view of an example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly of this disclosure is shown for illustrative purposes.

[0047] Figure 2A The schematic cross-sectional view illustrates an example of an adhesive layer being formed on the protective film in the laminate through a process of forming an adhesive layer in the disassembly method of the protective film assembly disclosed herein.

[0048] Figure 2B To illustrate, from Figure 2A A schematic cross-sectional view of an example of removing the protective film and adhesive layer on a photomask in a laminate with an adhesive layer.

[0049] Figure 3 This is a schematic cross-sectional view illustrating an example of how the protective film assembly frame, protective film, and adhesive layer are removed from a photomask in a laminate with an adhesive layer formed by a removal process in the method for removing the protective film assembly disclosed herein.

[0050] Figure 4A This is a schematic plan view illustrating an example of a laminate with through holes extending through the protective film and the protective film assembly frame in the thickness direction.

[0051] Figure 4B This is a schematic cross-sectional view showing an example of a laminate with through holes extending through the protective film and the protective film assembly frame in the thickness direction.

[0052] Figure 5A This is a schematic plan view showing an example of a laminate containing a protective film assembly frame with recesses on its outer peripheral surface.

[0053] Figure 5B This is a schematic cross-sectional view showing an example of a laminate containing a protective film assembly frame with recesses on its outer peripheral surface.

[0054] Figure 5C This is a schematic cross-sectional view showing an example of a laminate containing a protective membrane assembly frame with cutouts on its outer peripheral surface.

[0055] Figure 6 A schematic cross-sectional view of another example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly of this disclosure is shown for illustrative purposes.

[0056] Figure 7 A schematic cross-sectional view of another example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly disclosed herein is shown for illustrative purposes.

[0057] Figure 8 A schematic cross-sectional view of another example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly disclosed herein is shown for illustrative purposes.

[0058] Figure 9 A schematic cross-sectional view is shown for the purpose of illustrating an example of a pre-removal treatment apparatus for a protective film assembly according to an embodiment of the present disclosure.

[0059] Figure 10 A schematic cross-sectional view is shown for the purpose of illustrating another example of a pre-removal treatment apparatus for a protective film assembly according to an embodiment of the present disclosure. Detailed Implementation

[0060] In this specification, the numerical range indicated by "~" refers to the range in which the values ​​before and after "~" are respectively the lower and upper limits. Within the numerical ranges described in stages in this specification, the upper or lower limit value described in a certain numerical range can be replaced by the upper or lower limit value of other numerical ranges described in stages. Furthermore, within the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range can also be replaced by the value shown in the embodiment.

[0061] In this specification, the preferred combination of methods is a more preferred method.

[0062] In this specification, the term "process" includes not only independent processes, but also processes that achieve the desired purpose of the process, even if they cannot be clearly distinguished from other processes.

[0063] In this specification, EUV (Extreme Ultra Violet) light refers to light with a wavelength of 5 nm to 30 nm. The preferred wavelength of EUV light is 5 nm to 13.5 nm.

[0064] In this specification, EUV light and light with wavelengths shorter than EUV light are sometimes collectively referred to as "EUV light, etc."

[0065] In this specification, the term "protective film assembly" refers to an assembly comprising:

[0066] Protective membrane assembly frame; and

[0067] A component of a protective membrane that is supported on one end face of the protective membrane assembly frame in the thickness direction.

[0068] Regarding the method of "protective membrane assembly",

[0069] The protective film can be supported directly (i.e., without via other elements) on one end face of the protective film assembly frame in the thickness direction (see reference). Figure 1 ),

[0070] Alternatively, the protective film can be supported on one end face of the protective film assembly frame in the thickness direction by other elements (e.g., protective film adhesive layer, protective film support frame, support frame adhesive layer, etc.).

[0071] In this specification, the term "method for removing the protective film assembly" refers to a method for removing (i.e., detaching) the protective film from a photomask on which the protective film assembly is mounted.

[0072] The concept of "method for removing protective membrane components" includes the following two aspects:

[0073] A method for removing the protective film while the protective film assembly frame remains on the photomask on which the protective film assembly is mounted; and

[0074] A method for removing the protective film and the protective film assembly frame (i.e., the protective film assembly as a whole) from a photomask on which the protective film assembly is mounted.

[0075] In addition, the concept of "method for removing protective film assembly" also includes: a method for removing only the protective film or the protective film and the protective film assembly frame, and other elements (e.g., adhesive layer, protective film, etc.).

[0076] In addition, the concept of "method for removing protective film assembly" also includes methods for removing the protective film assembly from the photomask while damaging it.

[0077] [Method for disassembling the protective membrane assembly]

[0078] The method for disassembling the protective membrane assembly disclosed herein includes the following steps:

[0079] The process of preparing a laminate, wherein the laminate is configured in the following order, comprising a photomask, a protective film assembly frame, and a protective film;

[0080] The process of forming an adhesive layer on a protective film in a laminate; and

[0081] The removal process involves at least the removal of the protective film and the adhesive layer from the photomask in the laminate containing the adhesive layer.

[0082] The protective film is an extremely thin film. For example, the protective film used in EUV lithography has a thickness on the nanometer scale. Therefore, when removing the protective film assembly from the photomask, damage to the protective film (including the concept of destruction, the same applies below) is easily caused, and sometimes the photomask is contaminated due to the protective film flakes generated by the damage. In particular, the self-supporting portion of the protective film (i.e., the portion located on the opening formed by the inner peripheral surface of the protective film assembly frame and not supported by the protective film assembly frame) is prone to damage.

[0083] Regarding these issues, in the method for removing the protective film assembly disclosed herein, before removing the protective film from the photomask in a laminate containing a photomask, a protective film assembly frame, and a protective film arranged in the following order, an adhesive layer is formed on the protective film in the laminate. Then, at least the protective film and the adhesive layer are removed from the photomask in the laminate where the adhesive layer is formed. Therefore, even if the protective film is damaged during removal, the protective film sheet resulting from the damage will be adhered to the adhesive layer, thereby suppressing the scattering of the protective film sheet. As a result, photomask contamination caused by the scattering of the protective film sheet can be suppressed.

[0084] In the method for disassembling the protective film assembly disclosed herein, an adhesive layer is pre-formed on the protective film before disassembly. This differs from the method for disassembling the protective film assembly described in Patent Document 1 (i.e., a method of disassembling the protective film assembly mounted on the photomask by ensuring at least the protective film is in close contact with the sheet, and then removing the protective film assembly from the photomask). Because of this difference, the method for disassembling the protective film assembly disclosed herein, compared to the method for disassembling the protective film assembly described in Patent Document 1, can suppress the scattering of the protective film sheet and the contamination of the photomask caused by the scattering of the protective film sheet.

[0085] The following example of this disclosure will be appropriately referenced, along with the appendix. Figure 1The explanation will be provided later.

[0086] However, this disclosure is not limited to the specific examples in the following figures, etc.

[0087] For elements common to all the figures, the same symbol is used, and sometimes repeated descriptions are omitted.

[0088] In addition, in the accompanying drawings, a portion of the hidden lines is sometimes omitted for easier observation of the structure.

[0089] Figure 1 A schematic cross-sectional view of an example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly of this disclosure is shown for illustrative purposes.

[0090] like Figure 1 As shown, the stacked body involved in this example is configured in the following order, including a photomask 105, a protective film assembly frame 103, and a protective film 102.

[0091] The laminate involved in this example can be obtained by mounting a protective film assembly 101, which includes a protective film 102 and a protective film assembly frame 103, onto a photomask 105.

[0092] The protective film assembly frame 103 supports the protective film 102 on one end face in its thickness direction. In other words, the portion of the protective film 102 that overlaps with the protective film assembly frame 103 when viewed from above is supported by the protective film assembly frame 103. The portion of the protective film 102 that overlaps with the opening defined by the inner circumferential surface of the protective film assembly frame 103 when viewed from above is not supported, but becomes a self-supporting portion (i.e., the portion where the film is not formed on the substrate, but exists as a separate film).

[0093] Figure 2A The schematic cross-sectional view illustrates an example of an adhesive layer being formed on the protective film in the laminate through a process of forming an adhesive layer in the disassembly method of the protective film assembly disclosed herein.

[0094] Figure 2A The photomask 205, the protective film assembly frame 203, and the protective film 202 shown are respectively related to... Figure 1 The photomask 105, the protective film assembly frame 103, and the protective film 102 shown are all substantially the same.

[0095] like Figure 2A As shown, in the process of forming the adhesive layer, the adhesive layer 200 is formed on the protective film 202 of the laminate.

[0096] Figure 2B To illustrate, from Figure 2A A schematic cross-sectional view of an example of removing the protective film and adhesive layer on a photomask in a laminate with an adhesive layer.

[0097] like Figure 2B As shown, in the disassembly process involved in this example, from Figure 2A On the photomask 205 in the laminate with the adhesive layer shown, the protective film 202 and the adhesive layer 200 are removed. Then, if necessary, the protective film assembly frame 203 is also removed from the photomask 205.

[0098] Figure 3 This is a schematic cross-sectional view illustrating an example of how the protective film assembly frame, protective film, and adhesive layer are removed from a photomask in a laminate with an adhesive layer formed by a removal process in the method for removing the protective film assembly disclosed herein.

[0099] Figure 3 One example shown is relative to Figure 2B A variation of the example shown.

[0100] Figure 3 The photomask 305, the protective film assembly frame 303, and the protective film 302 shown are respectively related to... Figure 2B The photomask 205, the protective film assembly frame 203, and the protective film 202 shown are all substantially the same.

[0101] like Figure 3 As shown, in the disassembly process involved in this example, the protective film assembly frame 303, the protective film 302 and the adhesive layer 300 are removed from the photomask 305 in the laminate in which the adhesive layer 300 is formed.

[0102] The following describes in more detail the steps that may be included in the disassembly method of the protective film assembly disclosed herein.

[0103] <Preparation process for laminated bodies>

[0104] The process of preparing the laminate is to prepare a laminate containing a photomask, a protective film assembly frame, and a protective film in the following order.

[0105] The process of preparing the laminate can be either the process of manufacturing the laminate or the process of simply preparing the pre-manufactured laminate.

[0106] For example, a laminate can be manufactured by mounting (i.e. assembling) a protective film assembly (more specifically, a protective film assembly comprising a protective film assembly frame and a protective film supported on one end face of the protective film assembly frame in the thickness direction) on a photomask.

[0107] (Protective film)

[0108] The laminates prepared in this process have a protective film.

[0109] As a protective film, a known protective film can be used.

[0110] There are no particular restrictions on the materials contained in the protective film; they can be organic materials, inorganic materials, or a mixture of organic and inorganic materials.

[0111] Examples of organic materials include fluorinated polymers.

[0112] Examples of inorganic materials include crystalline silicon (e.g., monocrystalline silicon, polycrystalline silicon), diamond-like carbon (DLC), graphite, amorphous carbon, graphene, silicon carbide, silicon nitride, and aluminum nitride.

[0113] The protective film may contain one of the above-mentioned materials alone, or it may contain two or more of them.

[0114] The protective film can be composed of a single layer or two or more layers.

[0115] The thickness of the protective film (total thickness when formed by two or more layers) is preferably 2nm to 200nm, more preferably 2nm to 100nm, even more preferably 2nm to 70nm, and particularly preferably 2nm to 50nm. The lower limit of the thickness of the protective film can be 5nm or 10nm.

[0116] Regarding the composition of the protective film, for example, one can appropriately refer to the composition of the protective film known in Japanese Patent Application Publication No. 2014-021217, International Publication No. 2015 / 174412, etc.

[0117] (Protective membrane assembly frame)

[0118] The laminate prepared in this process has a protective film assembly frame.

[0119] As a protective membrane assembly frame, a known protective membrane assembly frame that is a component having a frame shape can be used.

[0120] As the material for the protective film assembly frame, the usual materials used for protective film assembly frames can be applied.

[0121] Specifically, materials used for the protective membrane component frame include aluminum, aluminum alloys (5000 series, 6000 series, 7000 series, etc.), stainless steel, silicon, silicon alloys, iron, iron-based alloys, carbon steel, tool steel, ceramics, metal-ceramic composites, and resins. Among these, aluminum or aluminum alloys are preferred for their lightweight and rigidity.

[0122] In addition, the protective film assembly frame may have a protective film on its surface.

[0123] As a protective film, it is preferable to have a protective film that is resistant to hydrogen radicals and EUV light present in the exposure atmosphere.

[0124] Examples of protective films include oxide films. Oxide films can be formed by known methods such as anodizing. Furthermore, oxide films can be colored with black dyes. When the protective film assembly frame has an oxide film colored with a black dye, the detection of foreign matter on the protective film assembly frame becomes easier.

[0125] Regarding the structure of the protective film assembly frame, for example, one can appropriately refer to the known structure of the protective film assembly frame, such as Japanese Patent Application Publication No. 2014-021217 and Japanese Patent Application Publication No. 2010-146027.

[0126] Preferably, at least one of a recess and a cutout is provided on the outer peripheral surface of the protective film assembly frame. This makes it easier to remove the protective film assembly frame from the photomask. For example, by inserting or hooking a gripping device for operating the protective film assembly frame into the recess or cutout, the protective film assembly frame can be easily removed from the photomask.

[0127] The outer peripheral surface of the protective film assembly frame may have only one recess or multiple slits. When multiple recesses are provided, their shapes may be the same or different (the same applies to slits).

[0128] Figure 5A This is a schematic plan view illustrating an example of a laminate containing a protective film assembly frame with recesses on its outer peripheral surface. Figure 5B This is a simplified cross-sectional view to illustrate this example.

[0129] like Figure 5A and Figure 5B As shown, this example of the laminate includes a photomask 505 and a protective film assembly 501 comprising a protective film assembly frame 503 and a protective film 502. The photomask 505, the protective film assembly frame 503, and the protective film 502 are sequentially arranged in the laminate. Furthermore, an adhesive layer 500 is formed on the protective film 502.

[0130] On the outer peripheral surface of the protective film assembly frame 503, there are recesses 509 near each of the four corners when viewed from above. The recesses 509 extend from the outer peripheral surface of the protective film assembly frame in a direction parallel to the surface of the protective film 502.

[0131] In this example of the laminate, for example, by inserting or hooking a gripping device for operating the protective film assembly frame in the recess 509, the protective film assembly frame 503 can be easily removed from the photomask 505.

[0132] Figure 5C for Figure 5B The modified example of the laminate shown is a schematic cross-sectional view of an example of a laminate containing a protective film assembly frame with cutouts on its outer peripheral surface.

[0133] Figure 5C In the structure of the laminate shown, except that the recess 509 is changed to a cut 510, it is similar to... Figure 5B The structures shown are identical.

[0134] In this example of the stack, for example, by inserting or hooking a gripping device for operating the protective film assembly frame into the cutout 510, the protective film assembly frame 503 can be easily removed from the photomask 505.

[0135] Furthermore, a through hole can be provided in the protective film assembly frame, extending from the outer peripheral surface of the frame to the inner peripheral surface. This through hole, for example, functions as a vent to allow ventilation between the outside of the laminate and the inside of the laminate (i.e., the space surrounded by the inner peripheral surface of the protective film assembly frame, the protective film, and the photomask).

[0136] Furthermore, a through hole can be provided in the protective film assembly frame, extending through the thickness direction of the frame. This makes it easier to remove the protective film assembly frame from the photomask. For example, by inserting or hooking a gripping device for operating the protective film assembly frame into the through hole, the frame can be easily removed from the photomask.

[0137] Furthermore, through holes can be provided in the laminate, penetrating the protective film and the protective film assembly frame along the thickness direction. This makes it easier to remove the protective film and the protective film assembly frame from the photomask. For example, by inserting or hooking a gripping device for operating the protective film assembly frame into the through hole, the protective film and the protective film assembly frame can be easily removed from the photomask.

[0138] Figure 4A This is a schematic plan view illustrating an example of a laminate with through holes extending along the thickness direction through the protective film and the protective film assembly frame. Figure 4B This is a simplified cross-sectional view to illustrate this example.

[0139] like Figure 4A and Figure 4B As shown, the laminate in this example includes a photomask 405 and a protective film assembly 401 comprising a protective film assembly frame 403 and a protective film 402. The photomask 405, the protective film assembly frame 403, and the protective film 402 are arranged sequentially in the laminate.

[0140] The laminated body is provided with a through hole 409 that runs through the protective film 402 and the protective film assembly frame 403 along the thickness direction.

[0141] In this laminate, an adhesive layer 400 is further formed on the protective film 402 (specifically, in the area outside the through hole 409).

[0142] (Protective film adhesive layer)

[0143] The laminate prepared in this process can have a protective film adhesive layer between the protective film and the protective film assembly frame.

[0144] For example, a laminate in this manner can be fabricated by mounting a protective film assembly, which includes a protective film, a protective film adhesive layer, and a protective film assembly frame, onto a photomask.

[0145] Here, the so-called protective film adhesive layer refers to the layer between the protective film and the protective film assembly frame, which is used to bond the protective film to the protective film assembly frame.

[0146] The adhesive layer of the protective film can contain known adhesives.

[0147] Adhesives that can be included as the adhesive layer of the protective film include, for example, acrylic resin adhesives, epoxy resin adhesives, silicone resin adhesives, fluorinated silicone adhesives, and fluorinated ether adhesives.

[0148] (Photomask)

[0149] The laminate prepared in this process has a photomask.

[0150] As a photomask, there are no particular restrictions as long as it has a light-illuminating surface.

[0151] As a photomask, for example, a photomask comprising a support substrate, a reflective layer stacked on the support substrate, and an absorber layer formed on the reflective layer can be used.

[0152] In a photomask, the side with the reflective layer and the absorber layer is designated as the light-illuminating surface. When EUV light or similar light is irradiated onto the light-illuminating surface, the absorber layer on the light-illuminating surface absorbs at least a portion of the irradiated light, and the remaining portion of the light is reflected by the reflective layer. The reflected light then irradiates a sensing substrate (e.g., a semiconductor substrate with a photoresist film). Consequently, a desired image is formed on the sensing substrate.

[0153] As a reflective layer, a multilayer film of molybdenum (Mo) and silicon (Si) can be appropriately cited.

[0154] The absorber layer is preferably made of a material with high absorption of EUV light, such as chromium (Cr) or tantalum nitride.

[0155] (Mask bonding layer)

[0156] The laminate prepared in this process may further have a mask bonding layer between the photomask and the protective film assembly frame.

[0157] Such a laminate can be manufactured, for example, by mounting a protective film assembly having a protective film, a protective film assembly frame, and a mask adhesive layer in the following order onto a photomask with the mask adhesive layer in contact with the photomask.

[0158] Here, the so-called mask bonding layer refers to the layer located between the photomask and the protective film assembly frame, which is used to bond the photomask and the protective film assembly frame together.

[0159] The mask adhesive layer can contain known adhesives.

[0160] Adhesives that can be included as a mask adhesive layer include, for example, double-sided adhesive tape, silicone resin adhesives, acrylic adhesives, rubber adhesives, vinyl adhesives, epoxy adhesives, etc.

[0161] The laminate prepared in this process may have both the above-mentioned mask adhesive layer and the above-mentioned protective film adhesive layer.

[0162] Figure 6 To illustrate, another example of the laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly of this disclosure (i.e., with) Figure 1 A schematic cross-sectional view of one example different from another.

[0163] like Figure 6 As shown, the laminate involved in this example is configured in the following order, including a photomask 605, a photomask adhesive layer 607, a protective film assembly frame 603, a protective film adhesive layer 606, and a protective film 602.

[0164] In this example, the laminate can be manufactured using a protective film assembly 601 having a mask adhesive layer 607, a protective film assembly frame 603, a protective film adhesive layer 606, and a protective film 602 configured in the following order.

[0165] Figure 7 A schematic cross-sectional view of another example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly disclosed herein is shown for illustrative purposes.

[0166] Figure 7 In one example, the laminated body involves a protective film support frame 608 and a support frame adhesive layer 609 spaced between the protective film adhesive layer 606 and the protective film assembly frame 603 (here, the protective film support frame 608 is connected to the protective film adhesive layer 606, and the support frame adhesive layer 609 is connected to the protective film assembly frame 603). Apart from this, with... Figure 6The example shown involves a stacked body with the same structure.

[0167] In this example, the laminate can be manufactured using a protective film assembly 611 having a mask adhesive layer 607, a protective film assembly frame 603, a support frame adhesive layer 609, a protective film support frame 608, a protective film adhesive layer 606, and a protective film 602 arranged in the following order.

[0168] Figure 8 A schematic cross-sectional view of another example of a laminate prepared in the process of preparing the laminate in the disassembly method of the protective film assembly disclosed herein is shown for illustrative purposes.

[0169] Figure 8 In one example of the laminated structure shown, except for the absence of the protective film adhesive layer 606, it is consistent with... Figure 7 The example shown involves a stacked body with the same structure.

[0170] The laminate in this example can be manufactured using a protective film assembly 612, which comprises a mask adhesive layer 607, a protective film assembly frame 603, a support frame adhesive layer 609, a protective film support frame 608, and a protective film 602, configured in the following order.

[0171] As above Figures 6-8 As shown, within the scope of the protective film assembly in this disclosure,

[0172] This includes not only: the way in which the protective film is directly (i.e., without via other elements) supported on one end face of the protective film assembly frame in the thickness direction (see reference). Figure 1 ),

[0173] Furthermore, it includes: the way in which the protective film is supported on one end face of the protective film assembly frame in the thickness direction by other elements (e.g., protective film adhesive layer, protective film support frame, support frame adhesive layer, etc.). Figures 6-8 ).

[0174] <Process for forming the adhesive layer>

[0175] The process of forming the adhesive layer is the process of forming an adhesive layer on the protective film in the above-mentioned laminate.

[0176] From the viewpoint of further reducing the load applied to the protective film during the formation of the adhesive layer, the process of forming the adhesive layer is preferably a process of forming the adhesive layer by jet coating, spin coating, inkjet coating, screen printing, or dip coating.

[0177] More preferably, the process of forming the adhesive layer is by spray coating or spin coating.

[0178] The process of forming the adhesive layer by spray coating is particularly preferred.

[0179] The formation of the adhesive layer using the spray coating method can be carried out using known spray coating equipment.

[0180] Examples of spray coating devices include spray guns, ultrasonic spray coating devices, two-fluid spray coating devices, and one-fluid spray coating devices.

[0181] The adhesive layer preferably contains at least one adhesive.

[0182] From the viewpoint of suppressing photomask contamination, the adhesive layer preferably comprises at least one adhesive selected from the group consisting of silicone-based adhesives, acrylic adhesives, urethane-based adhesives, polyamide-based adhesives, polyester-based adhesives, ethylene-vinyl acetate copolymers, olefin-based adhesives, polybutadiene-based adhesives, rubber-based adhesives, and styrene-based adhesives.

[0183] More preferably, it includes at least one adhesive selected from the group consisting of acrylic adhesives, polybutadiene adhesives and rubber adhesives.

[0184] One type of adhesive can be used alone, or two or more types can be used together.

[0185] As a silicone-based adhesive, an adhesive with silicone resin as the main component is preferred. There are no particular limitations on silicone-based adhesives, and examples include addition-reaction type silicone-based adhesives, peroxide-curing type silicone-based adhesives, and condensation type silicone-based adhesives.

[0186] Among these, from the viewpoint of using adhesives to maintain the protective film, addition-curing silicone adhesives with high holding power are preferred.

[0187] In this disclosure, the term "main component of adhesive" refers to a component that accounts for more than 50% by mass relative to the total mass of the adhesive.

[0188] Acrylic adhesives are preferably adhesives in which acrylic resins are the main component. There are no particular limitations on the acrylic resins included in acrylic adhesives, and examples include alkyl (meth)acrylate adhesives, urethane (meth)acrylates, epoxy (meth)acrylates, etc.

[0189] Furthermore, acrylic adhesives can be adhesives that use acrylic rubber resins as the main component. Examples of acrylic rubber resins include, for instance, block copolymers of methyl methacrylate and butyl acrylate.

[0190] As a urethane-based adhesive, an adhesive with polyurethane resin as the main component is preferred. There are no particular limitations on the polyurethane included in the urethane-based adhesive; examples include polyester polyurethane and polycarbonate polyurethane.

[0191] Polyamide adhesives are preferably adhesives in which polyamide resin is the main component. There are no particular limitations on the polyamide resin included in the polyamide adhesive, and examples include polyamide (amide 11) in which undecylactam has undergone ring-opening condensation polymerization and polyamide (amide 12) in which laurylactam has undergone ring-opening condensation polymerization.

[0192] As a polyester-based adhesive, an adhesive with polyester resin as the main component is preferred. There are no particular limitations on the polyester resin; examples include condensation polymers of polycarboxylic acids and polyols.

[0193] Specific examples of the aforementioned polyesters include, for instance, polyethylene terephthalate and polybutylene terephthalate.

[0194] Olefin-based adhesives are preferably adhesives in which an olefin resin is the main component. There are no particular limitations on the olefin used; it can be a polymer homopolymerized from an olefin or a copolymer polymerized from an olefin and other monomers. Preferably, the olefin has 2 to 6 carbon atoms, and examples include ethylene, propylene, butene, methylpentene, and hexene. Examples of other monomers used in the copolymer include, for example, vinyl acetate.

[0195] Rubber-based adhesives are preferably adhesives containing rubber as the main component; for example, natural rubber-based adhesives and synthetic rubber-based adhesives can be appropriately cited. Examples of synthetic rubber-based adhesives include styrene-butadiene copolymers (SBR, SBS), styrene-isoprene copolymers (SIS), acrylonitrile-butadiene copolymers (NBR), chloroprene polymers, and isobutylene-isoprene copolymers (butyl rubber).

[0196] Among these, synthetic rubber-based adhesives are preferred from the viewpoint of easy formation of an adhesive layer and easy maintenance of a protective film. More preferably, adhesives with styrene-butadiene copolymer as the main component are preferred.

[0197] The polybutadiene-based adhesive is an adhesive other than the rubber-based adhesives mentioned above, and preferably an adhesive in which polybutadiene is the main component. As for the polybutadiene, there are no particular restrictions as long as it contains structural units formed of butadiene, and it can be a homopolymer or a copolymer with monomers other than butadiene.

[0198] Styrene-based adhesives are adhesives other than the aforementioned rubber-based adhesives, and are adhesives in which polystyrene resin is the main component. There are no particular limitations on the polystyrene resin; examples include homopolymers of styrene monomers (e.g., styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylxylene), and copolymers of styrene monomers and monomers capable of copolymerizing with styrene monomers.

[0199] Examples of monomers that can copolymerize with styrene-based monomers include, for example, vinyl monomers (e.g., acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, methyl methacrylate, maleic anhydride, butadiene).

[0200] From the viewpoint of suppressing contamination of photomasks, the glass transition temperature of the adhesive is preferably -60°C to -20°C, and more preferably -60°C to -40°C.

[0201] From the viewpoint of suppressing contamination of the photomask, the weight-average molecular weight of the base polymer used as the adhesive is preferably 10,000 to 1,500,000, more preferably 50,000 to 1,000,000. Alternatively, base polymers with different weight-average molecular weights can be mixed.

[0202] The amount of adhesive applied when applying the adhesive to the protective film to form an adhesive layer (e.g., the amount applied when applying the adhesive by spray coating) is preferably 1 g / m², based on the amount applied after drying. 2 ~1,000g / m 2 More preferably 50g / m 2 ~1,000g / m 2 .

[0203] An adhesive layer can be formed by applying an adhesive solution containing an adhesive and a solvent to a protective film.

[0204] As a solvent in the adhesive solution, known solvents can be used.

[0205] Examples of solvents used in adhesive solutions include acetone, methyl ethyl ketone (2-butanone), cyclohexane, ethyl acetate, vinyl dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 1-methoxy-2-propanol, 3-methoxy-1-propanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, etc.

[0206] The adhesive solution may contain only one solvent or two or more solvents.

[0207] The concentration of solid components in the adhesive solution (i.e., the content of adhesive relative to the total amount of adhesive solution) is preferably about 1% to 50% by mass.

[0208] From the viewpoint of further improving the adhesion between the protective film and the adhesive, the viscosity (25°C) of the adhesive solution is preferably 1 mPa·s to 1,000 mPa·s, and more preferably 100 mPa·s to 800 mPa·s.

[0209] The viscosity of the adhesive solution can be appropriately adjusted by the type and / or amount of the solvent mentioned above.

[0210] The thickness of the adhesive layer is more preferably 1 μm or more and 1 mm or less, and even more preferably 50 μm or more and 1 mm or less.

[0211] The thickness of the aforementioned adhesive layer can be adjusted using known methods.

[0212] For example, in the case of forming an adhesive layer by spray coating, the thickness of the adhesive layer can be adjusted by adjusting the amount of adhesive solution sprayed from the spray coating device (e.g., spray gun).

[0213] The thickness of the adhesive layer can be determined by cutting the laminate vertically and examining its cross-section using a scanning electron microscope.

[0214] The adhesive layer may have grooves with a lattice structure. By having grooves with a lattice structure, for example, when the protective film described later is laminated on the adhesive layer, gas entering between the protective films can easily be discharged to the outside through the lattice structure, thus preventing the protective film from breaking.

[0215] Apparatus for performing the process of forming an adhesive layer (e.g., the pre-treatment apparatus for removing the protective film assembly described later) may include a cover for preventing adhesive discharged onto the protective film from adhering to parts outside the protective film.

[0216] <Disassembly process>

[0217] The disassembly process is the process of removing at least the protective film and the adhesive layer from the photomask in the laminate in which the adhesive layer is formed.

[0218] There are no particular restrictions on the method for removing the protective film and adhesive layer. Removal can be performed using a holding tool or the protective film described later.

[0219] During the disassembly process, the protective film may be damaged when it is removed. Even if the protective film is damaged, the resulting film fragments will adhere to the adhesive layer and be secured, thus preventing the protective film fragments from scattering and consequently suppressing photomask contamination caused by the scattering of the protective film fragments.

[0220] During the disassembly process,

[0221] The protective film assembly frame, protective film, and adhesive layer can be removed from the photomask in the laminate containing the adhesive layer.

[0222] The protective film and adhesive layer can also be removed while the protective film assembly frame remains on the photomask side.

[0223] In the disassembly process, when the protective film assembly frame, protective film, and adhesive layer are removed from the photomask in the laminate containing the adhesive layer,...

[0224] The protective film assembly frame, protective film, and adhesive layer can all be disassembled together.

[0225] Alternatively, the protective film and adhesive layer can be removed while the protective film assembly frame remains on the photomask side, and then the protective film assembly frame can be removed.

[0226] (Heat treatment during disassembly)

[0227] When the laminate further includes a mask bonding layer between the photomask and the protective film assembly frame, and this laminate (i.e., a laminate comprising a photomask, a mask bonding layer, a protective film assembly frame, and a protective film arranged in the following order) is designated as the first laminate,

[0228] The disassembly process may include:

[0229] By removing the protective film and adhesive layer while the protective film assembly frame remains on the photomask side of the first laminate in which the adhesive layer is formed, a second laminate containing a photomask, a mask adhesive layer and a protective film assembly frame is obtained.

[0230] The second layer of the laminate was heat-treated;

[0231] Remove the protective film assembly frame from the photomask in the second layer stack.

[0232] According to this method, the adhesive force of the mask bonding layer can be reduced by heat treatment of the second layer stack, thereby making it easier to disassemble the protective film assembly frame.

[0233] During the heat treatment described above, the entire second laminate can be heat-treated, or a portion of the second laminate (e.g., the portion containing the adhesive layer) can be heat-treated.

[0234] There are no particular restrictions on the equipment used for heat treatment; heaters, hot plates, ovens, etc., can be used.

[0235] Examples of heat treatment temperatures include 50°C to 140°C.

[0236] Examples of heat treatment times include 10 to 300 seconds.

[0237] <Process of applying protective film>

[0238] An embodiment of the present disclosure relates to a method for removing a protective film assembly, which may be performed after the step of forming the adhesive layer and before the removal step, and further includes a step of adhering a protective film to the adhesive layer in a laminate in which the adhesive layer is formed.

[0239] In this case, the aforementioned disassembly process is preferably a process of removing at least the protective film, adhesive layer, and protective film from the photomask in the laminate to which the protective film is adhered. More preferably, this disassembly process is a process of removing the protective film, adhesive layer, protective film, and protective film assembly frame together, or a process of removing the protective film, adhesive layer, and protective film first, and then removing the protective film assembly frame.

[0240] When the method for removing the protective film assembly includes a step of adhering the protective film, even if the protective film is damaged, the protective film fragment resulting from the damage will be adhered to the adhesive layer and held on the protective film via the adhesive layer. This further suppresses the scattering of the protective film fragment and the contamination of the photomask caused by the scattering of the protective film fragment.

[0241] In this process, "adhering a protective film to the adhesive layer in a laminate with an adhesive layer" means adhering the adhesive layer and the protective film in the laminate with the adhesive layer. At this time, the adhesive layer can be pressed against the protective film to make them adhere, the protective film can be pressed against the adhesive layer to make them adhere, or the adhesive layer and the protective film can be pressed against each other to make them adhere.

[0242] There are no particular limitations on protective films; examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polycarbonate (PC) film.

[0243] If the protective film is transparent or semi-transparent, it is easy to apply while checking for air bubbles between the adhesive layer and the protective film. Therefore, a transparent or semi-transparent protective film is preferred, but the protective film is not limited to transparent or semi-transparent protective films.

[0244] There are no particular limitations on the thickness of the protective film, but from the viewpoint of having adequate strength, it is preferably 50 μm or more and 500 μm or less, and more preferably 100 μm or more and 200 μm or less.

[0245] From the viewpoint of easily venting the gas that enters when bonding with the adhesive to the outside, the protective film can have a lattice-like concave structure.

[0246] The process of attaching the protective film can also be: using a substrate with a protective film that includes a protective film and a substrate, attaching the protective film from the substrate with the protective film to the adhesive layer in a laminate in which an adhesive layer is formed.

[0247] Examples of substrates used in protective film substrates include glass substrates, metal substrates, and plastic substrates.

[0248] In the process of applying the protective film, there are no particular restrictions on the method of applying the protective film to the adhesive layer; for example:

[0249] Methods of applying external force to make a protective film adhere;

[0250] A method of making a protective film adhere without applying external force, relying on its own weight, intermolecular forces, electrostatic forces, and other attractive forces;

[0251] A method of bonding a protective film and an adhesive layer under reduced pressure by placing them in close proximity;

[0252] Methods such as introducing air into the space surrounded by the protective film, the inner peripheral surface of the protective film assembly frame, and the photomask in a laminate to make the pressure in that space positive, thereby causing the protective film with the adhesive layer to expand in the direction of the protective film to adhere it, etc.

[0253] When the protective film with the adhesive layer is expanded towards the protective film to adhere to it, the protective film can be intentionally damaged by expanding it. Even when the protective film is intentionally damaged, the resulting protective film fragment will be adhered to the adhesive layer and held in place by the adhesive layer. Therefore, the scattering of the protective film fragment and the contamination of the photomask caused by the scattering of the protective film fragment can be further suppressed.

[0254] Furthermore, in a laminate having through holes extending along the thickness direction through the adhesive layer, protective film, and protective film assembly frame (e.g., the above-mentioned...), Figure 4A and Figure 4B When a protective film is adhered to the adhesive layer of a laminate, a through-hole penetrating the protective film can be provided in the protective film at a position overlapping with the aforementioned through-hole. Thus, a through-hole (hereinafter also referred to as "through-hole X") penetrating the protective film, adhesive layer, protective film, and protective film assembly frame is formed in the laminate to which the protective film is adhered. By inserting or hooking a gripping device into the through-hole X, the protective film, adhesive layer, protective film, and protective film assembly frame can be easily removed from the laminate to which the protective film is adhered.

[0255] <Process for heat treatment of laminates>

[0256] The method for disassembling the protective film assembly disclosed herein may further include a step of heat treatment of the laminate (i.e., the laminate comprising a photomask, a protective film assembly frame, and a protective film) before the disassembly step (more preferably before the step of preparing the laminate and forming the adhesive layer).

[0257] When the laminate includes at least one of a protective film adhesive layer and a mask adhesive layer, the method of including a heat treatment process on the laminate is particularly effective. In this case, by heat treating the laminate, the adhesive force caused by at least one of the protective film adhesive layer and the mask adhesive layer can be reduced, thereby suppressing damage to the protective film and making disassembly easier.

[0258] During the heat treatment described above, the entire laminate can be heat-treated, or a portion of the laminate (e.g., a portion containing at least one of a protective film adhesive layer and a mask adhesive layer) can be heat-treated.

[0259] There are no particular restrictions on the equipment used for heat treatment; heaters, hot plates, ovens, etc., can be used.

[0260] Examples of heat treatment temperatures include 50°C to 140°C.

[0261] Examples of heat treatment times include 10 to 300 seconds.

[0262] The method for disassembling the protective membrane assembly disclosed herein may include other steps besides those described above, as needed.

[0263] The following describes embodiments 1 to 3 as specific implementations of the method for removing the protective film assembly of the present disclosure. However, the method for removing the protective film assembly of the present disclosure is not limited to the following embodiments.

[0264] <Implementation Method 1>

[0265] For implementation method 1, while referring to Figure 6 While explaining.

[0266] about Figure 6 As mentioned above.

[0267] In Implementation Method 1, firstly, a process for preparing a laminate is performed to prepare a laminate with the characteristics of... Figure 6 The laminate with the same structure as the laminate shown is subjected to a process of forming an adhesive layer on the laminate. An adhesive layer is formed on the protective film 602 to obtain a laminate with an adhesive layer (not shown).

[0268] Next, a heat treatment process is performed on the laminate with the adhesive layer (not shown). This reduces the adhesive strength of the mask adhesive layer and the protective film adhesive layer in the laminate.

[0269] Next, through the disassembly process, firstly, the adhesive layer (not shown) and the protective film 602 are removed from the heat-treated laminate with the adhesive layer. Then, the mask adhesive layer 607, the protective film assembly frame 603, and the protective film adhesive layer 606 are removed.

[0270] In Embodiment 1, the order of the steps of forming the adhesive layer and the steps of heat treating the laminate can be the reverse of the above order.

[0271] <Implementation Method 2>

[0272] Implementation method 2 is the same as implementation method 1 except for the following aspects.

[0273] Embodiment 2 further includes a step of attaching a protective film to the adhesive layer in the laminate containing the adhesive layer after the step of forming the adhesive layer and before the step of disassembly.

[0274] In Implementation 2, the disassembly process involves removing the photomask from the laminate with the protective film attached. First, the protective film, adhesive layer, and protective film are removed. Then, the mask adhesive layer, protective film assembly frame, and protective film adhesive layer are removed.

[0275] In Implementation Method 2, the heat treatment process of the laminate can be omitted.

[0276] <Implementation Method 3>

[0277] Implementation method 3 is the same as implementation method 1 except for the following aspects.

[0278] In Implementation Method 3, the heat treatment process of the laminate is not performed. Instead, the heat treatment process described later is performed.

[0279] Embodiment 3, after the step of forming the adhesive layer and before the step of disassembly, further includes a step of adhering a protective film to the adhesive layer of the first laminate in which the adhesive layer is formed (i.e., a laminate formed by forming an adhesive layer on a protective film of the first laminate in which the first laminate in which the adhesive layer is formed is arranged in the following order).

[0280] The disassembly process in Implementation Method 3 is as follows:

[0281] First, the protective film, adhesive layer, and protective film are removed from the photomask in the first laminate with the protective film attached, resulting in a second laminate containing the photomask, mask adhesive layer, protective film assembly frame, and protective film adhesive layer.

[0282] Next, the heat treatment process described above in the disassembly procedure is performed (i.e., the heat treatment of the second layer of the stack is performed).

[0283] Next, the photomask adhesive layer, protective film assembly frame, and protective film adhesive layer are removed from the photomask in the second layer stack.

[0284] [Pre-treatment device for disassembly of protective membrane assembly]

[0285] Next, an embodiment of the pre-removal treatment apparatus for the protective film assembly, which is suitable for the step of forming the adhesive layer in the above-described method for removing the protective film assembly, will be described.

[0286] here,

[0287] The term "pre-treatment before disassembly of the protective film assembly" refers to the operation of forming an adhesive layer in the disassembly method of the protective film assembly disclosed herein.

[0288] The so-called "pre-treatment device for disassembly of protective film assembly" refers to the device used to perform the above-mentioned "pre-treatment for disassembly of protective film assembly".

[0289] The pre-removal treatment apparatus for the protective film assembly according to this embodiment includes:

[0290] The mounting section holds the laminate (i.e., the laminate comprising a photomask, a protective film assembly frame, and a protective film arranged in the following order) from the disassembly method of the protective film assembly of this disclosure, with the protective film facing upwards and the photomask facing downwards; and

[0291] The discharge section is used to discharge the adhesive solution onto the protective film placed in the laminate.

[0292] The pre-treatment apparatus for disassembly of the protective film assembly according to this embodiment enables the step of forming an adhesive layer in the disassembly method of the protective film assembly disclosed herein. Specifically, an adhesive layer is formed by discharging and coating an adhesive solution onto the protective film.

[0293] Therefore, the pre-removal treatment apparatus for the protective film assembly according to this embodiment, like the removal method for the protective film assembly disclosed above, can achieve the effect of suppressing photomask contamination caused by the protective film.

[0294] In the pre-removal treatment apparatus for the protective film assembly according to this embodiment, an adhesive solution is discharged onto the protective film of a laminate placed with the protective film facing upwards and the photomask facing downwards to form an adhesive layer. Therefore, unevenness of the adhesive layer caused by dripping or the like is suppressed. From the viewpoint of obtaining such an effect more effectively, it is preferable to place the laminate on the mounting section in a manner that makes the surface of the protective film horizontal.

[0295] The pre-removal treatment device for the protective film assembly involved in this embodiment may also have other elements as needed.

[0296] Other elements include, for example, a cover to prevent the adhesive solution from scattering.

[0297] As a cover to prevent adhesive solution from scattering, for example, a cover can be used that covers a portion of the protective film assembly frame within the protective film, while exposing the self-supporting portion of the protective film. With such a cover, an adhesive layer can be formed on the self-supporting portion of the protective film while preventing the adhesive solution from scattering.

[0298] In addition, other elements include components for disassembling the protective film assembly (e.g., grippers, levers, etc. for operating the protective film assembly frame). In this case, the protective film assembly disassembly pretreatment apparatus according to this embodiment can perform both the pretreatment for disassembly of the protective film assembly (i.e., the formation of the adhesive layer) and the disassembly of the protective film assembly.

[0299] The following are two specific examples of the pre-removal treatment apparatus for the protective film assembly according to this embodiment; however, the pre-removal treatment apparatus for the protective film assembly according to this embodiment is not limited to the following two examples.

[0300] Figure 9 A schematic cross-sectional view is shown for the purpose of illustrating an example of the pre-removal treatment apparatus for the protective film assembly according to this embodiment.

[0301] In detail, Figure 9 One example shown is an apparatus for forming an adhesive layer by applying an adhesive solution using a spray coating method.

[0302] like Figure 9 As shown, the pre-removal treatment device 800 for the protective film assembly involved in this example is located in chamber 804 and includes:

[0303] The mounting portion 802, with the protective film on the upper side (i.e., the side opposite to the direction of gravity G) and the photomask on the lower side (i.e., the side facing the direction of gravity G), mounts the aforementioned laminate 101 (see reference). Figure 1 );as well as

[0304] The spray nozzle 806 (discharge section in spray mode) is used to discharge adhesive solution onto the protective film placed in the laminate of the mounting section.

[0305] The mounting section 802 may have a fixing function for fixing the laminate (e.g., a vacuum chuck).

[0306] In this example, an adhesive solution is supplied from an adhesive supply source (not shown) outside the chamber 804 in the direction of arrow X1, and the adhesive solution is ejected from the discharge port of the spray nozzle 806 introduced into the chamber 804 by spraying. The ejected adhesive solution is coated onto a protective film in a laminate placed on the mounting portion 802 (spray coating). Thus, an adhesive layer is formed on the protective film.

[0307] In this example, the adhesive solution is discharged from the spray nozzle 806 in a horizontal direction. This, when the discharge direction is horizontal, or upwards compared to a horizontal direction, further suppresses damage to the protective film caused by the discharge of the adhesive solution.

[0308] Figure 10 A schematic cross-sectional view is shown for the purpose of illustrating another example of the pre-removal treatment apparatus for the protective film assembly according to this embodiment.

[0309] In detail, Figure 10 One example shown is an apparatus for forming an adhesive layer by applying an adhesive solution using a spin coating method.

[0310] like Figure 10 As shown, the pre-removal treatment device 900 for the protective film assembly involved in this example is located in chamber 904 and includes:

[0311] The mounting portion 902, with the protective film on the upper side (i.e., the side opposite to the direction of gravity G) and the photomask on the lower side (i.e., the side facing the direction of gravity G), mounts the aforementioned laminate 101 (see reference). Figure 1 );as well as

[0312] Discharge section 906 is used to discharge adhesive solution onto the protective film placed in the laminate of the mounting section.

[0313] The mounting section 902 may have a fixing function for fixing the laminate (e.g., a vacuum chuck).

[0314] In this example, the mounting portion 902 has a rotation function. Through this rotation function, the laminate rotates in a plane that is horizontal relative to the surface of the protective film, thereby coating the adhesive solution discharged onto the protective film onto the protective film (rotation coating).

[0315] In this example, the discharge direction of the discharge section 906 is downward. The discharge position of the discharge section 906 is near the center of the protective membrane.

[0316] However, the discharge direction and discharge location of the discharge section 906 are not limited to this example.

[0317] Example

[0318] The following are embodiments of the present disclosure, but the present disclosure is not limited to the following embodiments.

[0319] [Example 1]

[0320] The protective membrane assembly is removed by performing the following steps. Details are shown below.

[0321] <Preparation process for laminated bodies>

[0322] Prepare a protective film assembly, the protective film assembly comprising:

[0323] SiN protective film;

[0324] A protective film assembly frame that supports the SiN film protective film on one end face;

[0325] The protective film adhesive layer between the SiN film protective film and the protective film assembly frame; and

[0326] A mask adhesive layer is provided on the end face of the protective film assembly frame, opposite to the end face of the protective film supporting the SiN film.

[0327] An operating hole, serving as a recess, is provided on the outer peripheral surface of the protective film assembly frame. This operating hole functions as the point of application when disassembling the assembly using a lever.

[0328] The protective membrane assembly frame is also provided with a through hole for ventilation that extends from the outer peripheral surface to the inner peripheral surface.

[0329] The aforementioned protective film assembly is pressed against the light-shielding film layer side of the photomask containing the light-shielding film layer for 30 seconds with a load of 98N, oriented so that the light-shielding film layer side of the photomask is in contact with the mask adhesive layer in the protective film assembly. Thus, the protective film assembly is mounted on the photomask, resulting in a laminate.

[0330] <Process for forming the adhesive layer>

[0331] On the self-supporting portion of the protective film of the above-mentioned laminate (i.e., the portion on the opening surrounded by the inner peripheral surface of the protective film assembly frame), a rubber-based adhesive solution (manufactured by 3M Corporation, product name: 3M Spray Adhesive 77) with styrene-butadiene rubber as the main component is sprayed and coated to form an adhesive layer with a thickness of about 100 μm, thereby obtaining a laminate with an adhesive layer.

[0332] In order to prevent the adhesive from adhering to the portion of the protective film other than the self-supporting portion during the formation of the adhesive layer, a PET film having an opening of substantially the same size as the self-supporting portion of the protective film is used to mask the portion of the protective film other than the self-supporting portion.

[0333] After the adhesive layer is formed, the PET film used for masking is removed.

[0334] <Process of applying protective film>

[0335] A 100μm thick transparent PET film, serving as a protective film, is overlapped onto a glass plate and fixed in place, preparing a glass plate with a PET film as a substrate with a protective film.

[0336] Next, the laminate with the adhesive layer is placed on a Z-axis driven precision platform (hereinafter also referred to as the "Z-drive platform") with the adhesive layer as the top layer.

[0337] Next, the glass plate with the PET film is fixed above the laminate with the adhesive layer placed on the Z-drive platform (i.e., above the adhesive layer), with the PET film in the glass plate with the PET film facing down (i.e., with the adhesive layer and the PET film facing each other). At this time, the adhesive layer and the PET film are adjusted to be parallel.

[0338] Next, the Z-drive platform is moved vertically upwards to bring the laminate with the adhesive layer into contact with the PET film in the glass plate with the PET film. At this point, visual inspection from the glass plate side confirms that no air bubbles are entangled at the interface between the PET film and the adhesive layer.

[0339] Next, a nitrogen inlet pipe is connected to the aforementioned through-hole (i.e., vent) of the protective film assembly frame in the laminate. Nitrogen gas is introduced through this pipe into the enclosed space surrounded by the inner circumferential surface of the protective film assembly frame, the protective film, and the photomask, creating a positive pressure of approximately 5 kPa in the enclosed space. This causes the protective film in the laminate with the adhesive layer to expand upwards, adhering the adhesive layer on the protective film to the PET film in the glass plate with the PET film.

[0340] <Disassembly process>

[0341] Next, the Z-drive platform is moved vertically downwards to pull the photomask side of the laminate with the adhesive layer away from the PET film in the glass plate with the PET film, thereby forcibly breaking the protective film in the laminate with the adhesive layer. This operation removes the protective film and adhesive layer from the laminate with the adhesive layer.

[0342] Next, the second laminate (i.e., the laminate containing the photomask, the mask adhesive layer, and the protective film assembly frame) remaining after the removal of the protective film and adhesive layer is placed on the hot plate along the direction in which the photomask contacts the hot plate, and the second laminate is heated at approximately 70°C for 5 minutes. This reduces the adhesive strength of the mask adhesive layer.

[0343] Next, using the operating hole on the outer periphery of the protective film assembly frame as the point of action, the protective film assembly frame is removed from the second layer stack using a lever.

[0344] The protective film assembly (i.e., the protective film assembly containing the protective film and the protective film assembly frame) is removed from the photomask in the laminate with the adhesive layer as described above.

[0345] <Confirmation of Photomask Contamination>

[0346] Next, the surface of the photomask after the protective film assembly was removed was visually inspected, and no foreign matter attachment (i.e., contamination) was confirmed.

[0347] [Comparative Example 1]

[0348] Perform the same operations as in the preparation of the laminate in Example 1 to prepare a laminate identical to that in Example 1 (i.e., a laminate comprising a photomask, a photomask adhesive layer, a protective film assembly frame, a protective film adhesive layer, and a protective film arranged in the following order). The steps of forming the adhesive layer and the adhesive protective film are not performed.

[0349] Next, the aforementioned laminate is placed on a hot plate along the direction in which the photomask contacts the hot plate, and the laminate is heated at approximately 70°C for 5 minutes. This reduces the adhesive strength of the mask bonding layer.

[0350] Next, using the operating hole on the outer periphery of the protective film assembly frame as the point of application, and employing a lever, the protective film assembly (i.e., the protective film assembly including the protective film assembly frame and the protective film) is removed from the laminate. During this removal operation, it was confirmed that the self-supporting portion of the protective film was destroyed.

[0351] Visual inspection of the photomask surface after the protective film assembly was removed confirmed that a protective film sheet was attached to the surface of the photomask due to the damage to the protective film (i.e., the photomask was contaminated).

[0352] The entire disclosure of Japanese Patent Application No. 2019-225699, filed on December 13, 2019, is incorporated herein by reference.

[0353] All documents, patent applications and technical standards described herein are incorporated herein by reference to the same extent that each document, patent application and technical standard is specifically described herein and incorporated herein by reference.

Claims

1. A method for disassembling a protective film assembly, comprising the following steps: The process of preparing a laminate, wherein the laminate is configured in the following order, comprising a photomask, a protective film assembly frame, and a protective film; The process of forming an adhesive-only layer on the self-supporting portion of the protective film in the laminate; The process of adhering a protective film to the adhesive layer; and The process of removing the protective film, the protective film, and the adhesive layer from the photomask in the laminate having the protective film and the adhesive layer involves breaking the protective film.

2. The method for disassembling the protective film assembly according to claim 1, wherein the adhesive layer is formed by spray coating, spin coating, inkjet printing, screen printing or dip coating in the process of forming the adhesive layer.

3. In the method for disassembling the protective film assembly according to claim 1, the adhesive layer is formed by spray coating.

4. The method for disassembling the protective film assembly according to claim 1, wherein the adhesive layer comprises at least one adhesive selected from the group consisting of silicone adhesives, acrylic adhesives, urethane adhesives, polyamide adhesives, polyester adhesives, ethylene vinyl acetate copolymers, olefin adhesives, polybutadiene adhesives, rubber adhesives, and styrene adhesives.

5. The method for disassembling the protective film assembly according to claim 1, wherein the laminate further comprises a mask adhesive layer between the photomask and the protective film assembly frame.

6. The method for disassembling the protective film assembly according to claim 1, further comprising a step of heat-treating the laminate before the disassembly step.

7. The method for disassembling the protective film assembly according to claim 1, wherein at least one of a recess and a cut is provided on the outer peripheral surface of the protective film assembly frame.

8. The method for disassembling the protective film assembly according to claim 1, wherein the laminate is provided with a through hole that penetrates the protective film and the protective film assembly frame along the thickness direction.

9. A pre-treatment apparatus for disassembling a protective film assembly, comprising: a pre-treatment apparatus for disassembling a protective film assembly for performing the step of forming the adhesive layer in the disassembly method of any one of claims 1 to 8; The mounting portion, which mounts the laminate with the protective film on the upper side and the photomask on the lower side; and The discharge section is used to discharge an adhesive solution onto the protective film placed in the laminate of the placement section.

10. The pre-disassembly treatment apparatus for the protective film assembly according to claim 9, The discharge method of the discharge section is a jet method. The adhesive solution is applied by spray coating to form the adhesive layer.

11. The pre-treatment apparatus for disassembly of the protective film assembly according to claim 9, The mounting section has a rotation function that allows the mounted laminate to rotate. The adhesive solution is applied by spin coating to form the adhesive layer.

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