TWI605304B - EUV reticle inorganic protective film assembly manufacturing method - Google Patents

Description

EUV reticle inorganic protective film assembly manufacturing method

The invention relates to a reticle inorganic protective film component, in particular to an EUV reticle inorganic protective film component manufacturing method which can be used in an extreme ultraviolet (EUV) lithography process, and the finished inorganic protective film component It may be a single layer of ruthenium crystal film or a layer of tantalum nitride (SiN) bonded to both sides of the ruthenium crystal film, and the ruthenium nitride layer may be replaced by a ruthenium metal (Ru) layer, so that the inorganic protective film has a single layer. Or a three-layer structure to increase structural stability.

The circuit pattern of the semiconductor element is a transfer of the circuit pattern to the surface of the germanium wafer by a lithography process using a photomask and an exposure technique. The defect of the mask may cause distortion or deformation of the circuit pattern on the surface of the wafer. One of the reasons for the known defect of the mask is that the surface of the mask is contaminated by contamination particles, so that the circuit pattern on the surface of the wafer is Distortion or distortion occurs in the presence of contaminating particles; in order to maintain the quality of the reticle during use, a known method is to provide a reticle protective film module on the surface of the reticle to prevent deposition of contaminating particles. Direct contact with the reticle surface; the construction of the reticle protective film assembly basically comprises a transparent protective film and a frame, and the protective film provides a physical barrier against external pollution for preventing escape from the environment and gas (outgassing) ) or other contaminant particles that contaminate the surface of the reticle.

Depending on the width of the circuit pattern, the wavelength of the light source used in the exposure technique is also different. For different wavelengths of exposure light, the protective film must have sufficient transmission to ensure the yield of the lithography process and protect the transmittance of the film. Depending on the thickness of the protective film, the type of anti-reflective coating, the light absorption of the material of the protective film, and the wavelength of the light source used in the wafer exposure machine or stepper, nitrocellulose was originally adopted. Film material, and this kind of protective film is Used in g-line (436nm) or i-line (365nm), the fluorinated polymer is used in KrF (248nm) or ArF (193nm) wafer exposure machines or broadband projection wafer steppers. With the miniaturization of circuit patterns, the lithography process using ultra-ultraviolet light (EUV) with a wavelength of only 13.5 nanometers (nm) as an exposure light source has begun to receive attention and actively develop related technologies, but the aforementioned for manufacturing protection The nitrocellulose material of the film absorbs a light source having a wavelength of less than 350 nm, and the fluorinated polymer absorbs a wavelength of less than 190 nm, so that a lithography process in which the wavelength of the light source is lower than 350 nm or 190 nm cannot be used.

Since the ruthenium crystal film is light for EUV, the light absorption coefficient is relatively low, especially the polycrystalline ruthenium film, which has a lower absorption coefficient than the amorphous ruthenium film or the single crystal ruthenium film, so that EUV can be easily satisfied. The light transmittance required for the protective film; in particular, the above-mentioned protective film for EUV using a ruthenium crystal film, there is still a problem that the ruthenium crystal film is not easily formed in the technique of ruthenium crystal film formation, and the published US patent 6,623,893, which proposes a protective film made of tantalum material, which can be formed by a chemical vapor deposition (CVD) technique on a screen made of tantalum material (such as ceria). The barrier layer is exposed by a etching process to remove the central portion of the protective film, but the process is complicated. Further, in the disclosed Chinese patent CN 101414118 A, a reticle protective film made of a single crystal ruthenium film and a method for producing the same are disclosed, which are produced by thinning an SOI substrate, specifically, thinning. A main surface of the SOI substrate forms a protective film of a single crystal germanium, and in the subsequent process, the SOI substrate is removed by an etching technique to expose the central portion of the single crystal germanium as a protective film.

In the disclosed Taiwan patent "Pneumatic film assembly for EUV" (Publication No. 201415157), a dust-proof film assembly for EUV which can reduce the reduction of incident EUV light and has high strength is proposed. An EUV dustproof film assembly through an EUV permeable film (which is a twin film) reinforced with an auxiliary structure of a mesh shape (for example, a honeycomb structure), but the auxiliary structure If it is not firmly adhered to the twin film, the separation of the auxiliary structure and the twin film will occur during the exposure process, which may cause damage to the twin film.

Regardless of the exposure of the illuminant protection film assembly, the material of the protective film must have appropriate uniformity, mechanical strength, penetration, and cleanliness to withstand the continual exposure of the reticle pattern to the wafer. Shadow processing, and overcoming the problem of contamination during storage and transportation or damage to the reticle protective film; in addition, the approved invention patent TW I398723 "Protective film assembly and its manufacturing method" has proposed a single crystal film. The protective film assembly of the protective film comprises a protective film formed on at least one side of the protective film, and the protective film can be SiO, SiO2, Si3N4, SiON, Y2O3, YN, Mo, Ru by gas cluster ion beam evaporation. And at least one material selected from the group consisting of Rh is made of the protective film.

The object of the present invention is to provide a method for manufacturing an EUV reticle inorganic protective film module, which can manufacture a reticle inorganic protective film module having an organic protective layer and can be used for EUV, thereby avoiding contamination of the inorganic protective film during storage and transportation. Or broken.

Another aspect of the present invention provides a method of manufacturing a photomask inorganic protective film module, which can easily form an inorganic protective film made of a twinned material on a frame, and form at least one organic layer for protecting the inorganic protective film. The protective layer.

An embodiment of the reticle inorganic protective film assembly of the present invention comprises: a first frame, an inorganic protective film, and a first organic protective layer interposed between the first frame and the inorganic protective film, wherein the first organic The protective layer is adhered to the upper surface of the first frame, and the first organic protective layer can form an inorganic protective film on the other side of the first frame with the support of the first organic protective layer, wherein the first organic protection The layer is removed until the reticle inorganic protective film component is mounted on the surface of the reticle, and the first organic protective layer can prevent the inorganic protective film of the reticle inorganic protective film component from being damaged during storage and transportation. Pollution or damage.

In an embodiment of the reticle inorganic protective film assembly of the present invention, the inorganic protective film is a ruthenium crystal film.

In an embodiment of the photomask inorganic protective film assembly of the present invention, the inorganic protective film comprises: a germanium crystal film and a tantalum nitride layer formed on opposite sides of the germanium crystal film to provide a relatively stable structure and avoid inorganic The protective film is brittle and damaged, and the tantalum nitride layer can be replaced by a metal (Ru).

In another embodiment of the reticle inorganic protective film assembly of the present invention, a second organic protective layer is formed on the other side of the inorganic protective film relative to the first organic protective layer, wherein the first organic protective layer and the second organic layer The protective layer is removed until the reticle inorganic protective film component is attached to the surface of the reticle, and the inorganic protective film of the reticle film assembly can be prevented from being stored and transported through the first organic protective layer and the second organic protective layer. It is contaminated or damaged during the process.

In another embodiment of the reticle inorganic protective film assembly of the present invention, comprising: a first organic protective layer, an inorganic protective film and a second frame, supported by the first organic protective layer, the first organic protection Forming the inorganic protective film on one side of the layer, the second frame directly adhering to the other side of the inorganic protective film relative to the first organic protective layer, and the inorganic protective film is interposed between the second frame and the first organic protective layer By using the first organic protective layer, the inorganic protective film of the reticle inorganic protective film assembly can be prevented from being contaminated or damaged during storage and transportation.

An embodiment of the method of the present invention comprises the steps of: providing a first frame, bonding an organic film on the upper surface of the first frame to form a first organic protective layer, and comparing the first organic protective layer with respect to the first The other side of a frame forms the step of forming an inorganic protective film. According to the above manufacturing method of the present invention, the inorganic protective film can be directly formed on the first frame as the inorganic protective film of the reticle inorganic protective film component under the support of the first organic protective layer, and the first organic protective layer is used in the inorganic protective film. The inner side provides protection and protection against contamination.

In an embodiment of the method of the present invention, the step of forming an organic protective layer on the inner side and the outer side of the inorganic protective film prevents the inner and outer sides of the inorganic protective film of the photomask module from being stored and transported during storage and transportation. It is contaminated or damaged.

A further embodiment of the method of the present invention comprises the steps of: providing a first frame, and bonding an organic film on the upper surface of the first frame to form a first organic protective layer, wherein the first organic protective layer is opposite to the first a step of forming an inorganic protective film on the other side of the frame; a step of directly bonding a second frame on the other side of the inorganic protective film with respect to the other side of the first organic protective layer; and cutting the inorganic protective film and the first organic protection The step of removing the first frame by the layer. According to the above manufacturing method of the present invention, the inorganic protective film can be directly formed on the first frame as the inorganic protective film of the reticle inorganic protective film component under the support of the first organic protective layer, and the first organic protective layer is used in the inorganic protective film. The outer side provides protection and protection against contamination.

Specific embodiments of the present invention and its technical features and effects will be described below in conjunction with the drawings.

(10) ‧ ‧ first frame

(11) ‧ ‧ upper surface

(12)‧‧‧ Lower surface

(20) ‧‧‧Inorganic protective film

(21)‧‧‧Central light transmission area

(22) ‧‧‧矽 Crystalline film

(23a) ‧‧‧First tantalum layer

(23b)‧‧‧Second tantalum layer

(31) ‧‧‧First organic protective layer

(32) ‧‧‧Second organic protective layer

(41) ‧‧‧film adhesive

(42)‧‧‧Viscos

(50) ‧‧‧second framework

(51) ‧ ‧ surface

(52) ‧ ‧ surface

(60)‧‧‧Steam degreasing unit

(61) ‧‧‧Organic solvents

(62) ‧‧‧Condenser

(M)‧‧‧Photomask

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the structure of an embodiment of a reticle inorganic protective film unit of the present invention.

2 is a flow chart showing the steps of the manufacturing method of the present invention, showing the steps for fabricating the mask inorganic protective film assembly of FIG. 1.

FIG. 3 is a schematic view showing the use of the mask inorganic protective film assembly of FIG. 1. FIG.

Figure 4 is a cross-sectional view showing the structure of another embodiment of the reticle inorganic protective film assembly shown in Figure 1.

Figure 5 is a flow chart showing the steps of the manufacturing method of the present invention, showing the steps for fabricating the mask inorganic protective film assembly of Figure 4.

Figure 6 is a schematic view showing the use of the mask inorganic protective film assembly of Figure 4.

FIG. 7 is a schematic view showing an embodiment of removing an organic protective layer of a photomask inorganic protective film assembly of the present invention.

Figure 8 is a cross-sectional view showing the structure of another embodiment of the photomask inorganic protective film module of the present invention (矽 crystal film + tantalum nitride film + first organic protective film).

Figure 9 is a cross-sectional view showing the structure of another embodiment of the photomask inorganic protective film assembly of the present invention (矽 crystal film + tantalum nitride film + first and second organic protective film)

Figure 10 is a flow chart showing the steps of the manufacturing method of the present invention, showing the steps for fabricating the mask inorganic protective film assembly of Figure 9.

Figure 11 is a cross-sectional view showing the structure of another embodiment of the reticle inorganic protective film assembly of the present invention.

Figure 12 is a flow chart showing the steps of the manufacturing method of the present invention, showing the steps for fabricating the mask inorganic protective film assembly of Figure 11.

Figure 13 is a schematic view showing the use of the mask inorganic protective film assembly of Figure 11.

Referring to FIG. 1 , an embodiment of a photomask inorganic protective film assembly of the present invention comprises: a first frame 10 , an inorganic protective film 20 , and a first between the first frame 10 and the inorganic protective film 20 . Organic protective layer 31 (Organic film).

The first frame 10 is an annular element. In an embodiment of the invention, the size of the first frame 10 is determined according to the size of the mask M. Specifically, the size of the first frame 10 can be attached to the mask. The surface of M becomes a frame (fram, see FIG. 3) of the reticle inorganic protective film assembly, and the first frame 10 can be made of any one of aluminum (Al) or bismuth (Si) or quartz glass.

The first organic protective layer 31 is bonded to the upper surface 11 of the first frame 10. The first organic protective layer 31 has a thickness of 1 to 10 μm. The first organic protective layer 31 may be a perfluoro polymer, or Any one of Nitrocellulose or Cellulose ester, and is produced by any one of spin coating and spray coating. In one embodiment of the present invention, the first organic protective layer 31 is adhered to the upper surface 11 of the first frame 10 by a film adhesive 41 (adhesive).

2 is a flow chart showing the steps of the manufacturing method of the present invention, and the steps for manufacturing the reticle inorganic protective film assembly of FIG. 1 include: providing a first frame 10; and preparing an organic film on the upper surface of the first frame 10. 11 bonding the organic film to form the first organic protective layer 31; and forming an inorganic protective film 20 on the other side of the first organic protective layer 31 with respect to the first frame 10, the inorganic protective film 20 may be chemical vapor deposited ( Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) is formed on the surface of an organic film; One embodiment of the inorganic protective film 20 is a germanium crystal film made of a twinned material. For an EUV exposure technique with a wavelength of only 13.5 nm, the light source of the wavelength band is relatively high, so it is highly suitable. As a material of the inorganic protective film 20 for EUV, the present invention forms the inorganic protective film 20 by forming a twinned material on the upper surface of the first organic protective layer 31, wherein the thickness of the germanium crystal film constituting the inorganic protective film 20 is between 20~200nm, wherein the germanium crystal material used for fabricating the germanium crystal film comprises germanium (Si), and the germanium crystal material can be subjected to chemical vapor deposition (CVD), electroplating (electroplating), atomic layer deposition (Atomic Layer Deposition). Or any of the vacuum deposition methods are formed on the first organic protective layer 31.

Through the manufacturing method of the present invention, the twinned material may be directly deposited under the support of the first organic protective layer 31 or grown on the upper surface of the first organic protective layer 31 to form the inorganic protective film 20 of the photomask inorganic protective film assembly. Therefore, an inorganic protective film 20 made of a twinned material can be easily formed on the first frame 10, and the first organic protective layer 31 is removed until the reticle inorganic protective film member is attached to the surface of the reticle M. In addition, one of the embodiments is to adhere to the inorganic protective film 20 by a technique of vapor degreasing using, for example, a perfluoro organic solvent 61 or other ketone ester solvent. The first organic protective layer 31 of the central light transmissive region 21 is removed, and as shown in FIG. 7, the aforementioned organic solvent is injected into the vapor degreasing device 60. 61. By heating the organic solvent 61 to form an organic solvent vapor and adhering to the surface of the first organic protective layer 31, a condenser 62 (for example, a heat dissipating fin or a cooling fan) is disposed outside the vapor degreasing device 60, and the organic solvent vapor is condensed. The solvent 61 is formed on the surface of the first organic protective layer 31, and the organic solvent 61 which is dissolved in the surface of the first organic protective layer 31 is dropped by gravity and the organic solvent 61, thereby removing For the purpose of the first organic protective layer 31, the lower surface 12 of the first frame 10 is then adhered to the surface of the mask M by using glue 42, and then used in the EUV exposure process, by the first organic protective layer. 31 can prevent the inorganic protective film 20 of the reticle inorganic protective film module from being contaminated or damaged during storage and transportation.

Please refer to FIG. 4 and FIG. 5 for another embodiment of the reticle inorganic protective film assembly of the present invention and a manufacturing method thereof. The difference from the embodiment of FIG. 1 is that the reticle inorganic protective film assembly of FIG. 4 includes a first The second organic protective layer 32 is formed on the other side of the inorganic protective film 20 with respect to the first organic protective layer 31; the manufacturing method includes the following steps (the manufacturing process can refer to FIG. 5): providing a first frame 10; preparing an organic a film, the organic film is bonded to the upper surface 11 of the first frame 10 to form a first organic protective layer 31; and a first crystalline film is formed on the other side of the first organic protective layer 31 with respect to the first frame 10 for inorganic protection. The film 20 is formed; and an organic material is formed on the other side of the inorganic protective film 20 with respect to the first organic protective layer 31 to form a second organic protective layer 32.

In an embodiment of the invention, the second organic protective layer 32 is formed by the same method as the first organic protective layer 31, and the first organic protective layer 31 and the second organic protective layer 32 are up to the reticle inorganic protective film assembly. It is removed before being applied to the surface of the mask M. One embodiment is the same as the aforementioned method for removing the first organic protective layer 31, using, for example, a fluorine-containing organic solvent or other ketone ester solvent. The first organic protective layer 31 attached to the central transparent region 21 of the inorganic protective film 20 is removed by a steam degreasing technique, and the second organic protective layer 32 is completely removed, and then the first adhesive layer 42 is used. The lower surface 12 of the frame 10 is attached to the surface of the reticle M (see Fig. 6), and is used in an EUV exposure process. The first organic protective layer is constructed by the above-described embodiment of the present invention and a manufacturing method thereof The 31 and the second organic protective layer 31 may provide a function of protecting and preventing contamination of the inner side surface (the side facing the mask M) and the outer side surface of the inorganic protective film 20.

Please refer to FIG. 8 , which is a configuration of another embodiment of the photomask inorganic protective film assembly of the present invention; FIG. 8 is different from the embodiment of FIG. 1 in that the inorganic protective film 20 of FIG. 8 includes: a germanium crystal film 22 and formation thereof. A first tantalum nitride (SiN) layer 23a and a second tantalum nitride layer 23b on opposite side surfaces of the germanium crystal film 22 can provide a relatively stable structure, so that the twinned film 22 is not easily broken and damaged; One embodiment of the invention is on either side of a twin film by chemical vapor deposition (CVD), electroplating, vacuum deposition, or atomic layer deposition (ALD). The first tantalum nitride layer 23a and the second tantalum nitride layer 23b are formed on the surface, and the first tantalum nitride layer 23a and the second tantalum nitride layer 23b have a thickness of 2-20 nm.

In addition, the first tantalum nitride (SiN) layer 23a and the second tantalum nitride layer 23b may be replaced by a first base metal (Ru) layer and a second base metal (Ru) layer, and a stable structure may be provided. The tantalum film 22 is not easily broken and damaged, and the first base metal (Ru) layer and the second base metal (Ru) layer have a thickness of 2-20 nm.

9 and 10 are flow charts showing the steps of another embodiment of the reticle inorganic protective film assembly of the present invention and a manufacturing method thereof. The reticle inorganic protective film assembly of FIG. 9 is different from the foregoing embodiment of FIG. Forming an organic material on the other side of the inorganic protective film 20 with respect to the other side of the first organic protective layer 31 to form a second organic protective layer 32. The manufacturing method includes the following steps (the manufacturing process can refer to FIG. 10): providing a first frame 10; preparing an organic film, bonding the organic film on the upper surface 11 of the first frame 10 to form a first organic protective layer 31; forming a first nitrogen on the other side of the first organic protective layer 31 with respect to the first frame 10 a ruthenium layer 23a; a tantalum crystal film 22 is formed on the other side of the first tantalum nitride layer 23a with respect to the first organic protective layer 31; and the other side surface of the tantalum crystal film 22 is opposite to the first tantalum nitride layer 23a. Forming the second tantalum nitride layer 23b such that the inorganic protective film 20 has a three-layer structure to increase structural stability; And forming an organic material on the other side of the second tantalum nitride layer 23b with respect to the tantalum crystal film 22 to form the second organic protective layer 32.

Further, the first tantalum nitride (SiN) layer 23a and the second tantalum nitride layer 23b may be replaced by a first base metal (Ru) layer and a second base metal (Ru) layer.

Please refer to FIG. 11 and FIG. 12 , which illustrate another embodiment of the reticle inorganic protective film assembly of the present invention and a manufacturing method thereof. The embodiment of the reticle inorganic protective film assembly disclosed in FIG. 8 includes: a first organic protection The layer 31, an inorganic protective film 20 and a second frame 50, the inorganic protective film 20 is also composed of a twinned material formed on one surface of the first organic protective layer 31, and is constructed in accordance with the foregoing embodiment of FIG. The difference is that the second frame 50 is directly attached to the other side of the inorganic protective film 20 relative to the first organic protective layer 31, so that the inorganic protective film 20 is interposed between the second frame 50 and the first organic protective layer 31, wherein One embodiment is to activate the twinned material of the edge of the inorganic protective film 20 (the region surrounding the central light-transmitting region 21 of the inorganic protective film 20) by an ion beam and the one side surface 51 of the second frame 50. Bonding together avoids the use of glue and contamination problems caused by the release of the gas from the glue.

In the embodiment of FIG. 11, the first organic protective layer 31 is removed until the reticle inorganic protective film assembly is attached to the surface of the reticle M (see FIG. 13), one embodiment and the foregoing for removal Like the first organic protective layer 31, the first organic protective layer 31 attached to the inorganic protective film 20 is removed by a technique such as fluorine-containing organic solvent or other ketone ester solvent by vapor degreasing. In the embodiment of FIG. 11, the first organic protective layer 31 is located on the outer side of the reticle inorganic protective film assembly, so that the first organic protective layer 31 can be completely removed, and then the second frame 50 is opposed to the inorganic by the adhesive 42. The other side surface 52 of the protective film 20 is attached to the surface of the mask M (see Fig. 13), and is used in an EUV exposure process.

12 illustrates an embodiment of a method of fabricating the reticle inorganic protective film assembly of FIG. 9 including: providing a first frame 10; preparing an organic film on the upper surface of the first frame 10. The first organic protective layer 31 is formed by laminating the organic film, and the inorganic protective film 20 is formed on the other side of the first organic protective layer 31 with respect to the other side of the first frame 10. The second frame 50 is provided. One side surface 51 of the second frame 50 is directly bonded to the other side of the inorganic protective film 20 with respect to the first organic protective layer 31; and the inorganic protective film 20 and the first organic protective layer 31 are cut for removal. A frame 10, a portion of the first organic protective layer 31 attached to the first frame 10, and a portion of the inorganic protective film 20 surrounding the second frame 50.

In the embodiment of the method illustrated in FIG. 12, the size of the second frame 50 is determined according to the size of the mask M. The size of the first frame 10 is larger than that of the second frame 50. Specifically, the size of the second frame 50 can be attached. After being combined with the surface of the mask M, it becomes a frame of the mask inorganic protective film assembly (see FIG. 13). The first frame 10 is wrapped around the second frame 50, and the first frame 10 is formed in the inorganic protective film 20. In the process for supporting the first organic protective layer 31 and the twinned material, an embodiment of the first frame 10 and the second frame 50 is made of the same material, for example, aluminum (Al) and bismuth (Si). Or any of the materials of quartz glass.

The embodiments and/or the embodiments described above are merely illustrative of preferred embodiments and/or implementations of the techniques of the present invention, and are not intended to limit the embodiments of the present invention in any way. The invention may be modified or modified to other equivalent embodiments without departing from the spirit and scope of the invention.

(10) ‧ ‧ first frame

(11) ‧ ‧ upper surface

(12)‧‧‧ Lower surface

(20) ‧‧‧Inorganic protective film

(21)‧‧‧Central light transmission area

(31) ‧‧‧First organic protective layer

(41) ‧‧‧film adhesive

Claims (12)

A method for manufacturing an EUV reticle inorganic protective film assembly, comprising: providing a first frame; preparing an organic film, bonding the organic film on an upper surface of the first frame to form a first organic protective layer; The protective layer forms an inorganic protective film with respect to the other side of the first frame; the first organic protective layer attached to the inorganic protective film is removed by a technique of vapor degreasing using an organic solvent, and only the inorganic protective film is retained; Forming a second organic protective layer on the other side of the first protective layer, wherein the first organic protective layer and the second organic protective layer have a thickness of 1 to 10 μm, the first The organic protective layer and the second organic protective layer are made of any one of a perfluoro polymer, a nitrocellulose, or a cellulose ester. The manufacturing method according to claim 1, wherein the inorganic protective film is a ruthenium crystal film, and the ruthenium crystal film has a thickness of 20 to 200 nm. The manufacturing method according to claim 1, wherein the inorganic protective film forms a first tantalum nitride layer and a second tantalum nitride layer on opposite side surfaces of the tantalum crystal film, and the tantalum crystal film is subjected to the first nitrogen. The plutonium layer and the second tantalum nitride layer are sandwiched to form a three-layer structure, and the first tantalum nitride layer and the second tantalum nitride layer have a thickness of 2-20 nm. The manufacturing method according to claim 1, wherein the inorganic protective film forms a first base metal layer and a second base metal layer on opposite side surfaces of the tantalum crystal film, so that the tantalum crystal film is subjected to the first base metal layer and The second tantalum metal layer is sandwiched to form a three-layer structure, and the first tantalum metal layer and the second tantalum metal layer have a thickness of 2-20 nm. The manufacturing method according to claim 1, 2, 3 or 4, wherein the inorganic protective film is formed by chemical vapor deposition (CVD), electroplating, vacuum deposition or Atomic Layer Deposition (ALD) is formed in any one of the first organic protective layers with respect to the other side of the first frame. A method for manufacturing an EUV reticle inorganic protective film assembly, comprising: providing a first frame; preparing an organic film, bonding the organic film on an upper surface of the first frame to form the first organic protective layer; The protective layer forms an inorganic protective film with respect to the other side of the first frame; the second frame is provided, and one side surface of the second frame is directly bonded to the inorganic protective film with respect to the first organic protective layer a side surface; the inorganic protective film and the first organic protective layer are cut to remove a portion including the first frame, the first organic protective layer is attached to the first frame, and the inorganic protective film is surrounded a portion around the second frame; the first organic protective layer attached to the inorganic protective film is removed by a technique of vapor degreasing using an organic solvent, and only the inorganic protective film formed of the ruthenium crystalline film is retained. The manufacturing method according to claim 6, wherein the size of the second frame is determined according to a size of the reticle, the first frame being larger in size than the second frame, the first frame being surrounds the second frame. The manufacturing method according to claim 6, wherein the first organic protective layer has a thickness of 1 to 10 μm, and the material of the first organic protective layer comprises a perfluoro polymer, a nitrocellulose or a fiber plastic. Any of the cellulose esters. The production method according to claim 6, wherein the inorganic protective film is a ruthenium crystal film having a thickness of 20 to 200 nm. The manufacturing method according to claim 6, wherein the inorganic protective film forms a first tantalum nitride layer and a second tantalum nitride layer on opposite side surfaces of the tantalum crystal film, so that the tantalum crystal film is subjected to the first The tantalum nitride layer and the second tantalum nitride layer are sandwiched to form a three-layer structure, and the first tantalum nitride layer and the second tantalum nitride layer have a thickness of 2-20 nm. The manufacturing method according to claim 6, wherein the inorganic protective film forms a first base metal layer and a second base metal layer on opposite side surfaces of the tantalum crystal film, so that the tantalum crystal film is subjected to the first base metal layer and The second tantalum metal layer is sandwiched to form a three-layer structure, and the first tantalum metal layer and the second tantalum metal layer have a thickness of 2-20 nm. The manufacturing method according to claim 6, wherein the inorganic protective film is produced by chemical vapor deposition (CVD), electroplating, vacuum deposition or atomic layer deposition (ALD). Either method is formed on the other side of the first organic protective layer with respect to the first frame.