JPH07176462A - Manufacture of x-ray mask structure, x-ray mask structure, x-ray exposure method using the structure, x-ray exposure device, and semiconductor device manufactured by applying the exposure method - Google Patents

Abstract

PURPOSE:To provide a method for manufacturing a mask structure having excellent positional accuracy of an X-ray absorber pattern and excellent flatness of a mask membrane. CONSTITUTION:A mask membrane 2 and an X-ray absorber layer 3 are formed on a board 1. A resist pattern 9 is formed on a surface of the membrane in a state that a mixture 7 of a binder and a heat conductive substance is disposed in contact with a rear surface side of the membrane 2, and the layer is etched with the pattern 9 as an etching resistant mask, thereby forming an X-ray absorber pattern 11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an X-ray mask structure used in X-ray lithography, the mask structure, an X-ray exposure method using the structure, an X-ray exposure apparatus, and the like. The present invention relates to a semiconductor device manufactured by using an X-ray exposure method.

[0002]

2. Description of the Related Art In recent years, X-ray lithography using SOR, that is, synchrotron radiation, has been attracting attention, and fine processing for forming line and space of 0.25 μm or less, which is originally difficult in optical lithography, has the same level. I am trying to demonstrate its power in the processing of tall patterns.

Conventionally, when manufacturing a mask structure for X-ray lithography, a mask membrane is formed by sticking an organic polymer thin film on an annular ring frame, and recently, a BN, SiN, SiC or the like is formed on a Si substrate. After the ceramic thin film is formed, the Si substrate in the portion corresponding to the mask region is removed by etching (back etching).

On the other hand, regarding the X-ray absorber, a metal mask pattern (X-ray absorber pattern) of Au, W, Ta or the like is formed on the surface of the mask membrane as described above by a method such as dry etching or plating. It is common to do so. Particularly when a mask membrane is formed on a Si substrate, the mask pattern is usually formed on the mask membrane as described above before the Si substrate in the mask region is removed by etching.

[0005]

However, a mask pattern is formed on the mask membrane by the above method, and X
Attempts to manufacture a line mask structure have the following problems.

First, when forming a mask pattern on a mask membrane in which an organic polymer thin film is attached to a ring frame, there are major problems of vibration of the membrane, flatness, heat dissipation and cooling in the mask pattern forming process.

Further, a membrane is formed on a Si substrate,
Further, after forming the mask pattern on the membrane, when the Si substrate in the portion corresponding to the mask region is back-etched and removed, the substrate is deformed due to the application of the membrane, the flatness of the mask membrane and the position of the mask pattern. Bring fluctuations.

On the other hand, Si with a membrane formed
A method of forming a mask pattern by performing plating or the like after removing a predetermined region of the substrate by back etching has been performed as being particularly useful in improving the pattern position accuracy. However, in this case, the mask membrane after the back etching has insufficient mechanical strength, and like the mask membrane in which the organic polymer thin film is attached to the ring frame, for example, the etching of the absorber, especially during the mask pattern formation process, is performed. There is a problem with heat dissipation and cooling. Furthermore, in this case, not only the defects during the mask pattern forming process but also the vibration of the membrane during the processing and formation of all the members on the surface side of the mask membrane,
There is a problem with respect to heat dissipation and cooling, and the positional accuracy of the final mask pattern is insufficient.

Various techniques have been disclosed in relation to the problems associated with the manufacture of the X-ray mask structure as described above.

For example, Japanese Unexamined Patent Publication (Kokai) No. 62-92437 discloses that a liquid metal is placed on the back side of the mask membrane and the front side of the mask membrane is processed while transferring heat from the mask. However, this technique has drawbacks such as toxicity of liquid metal and poor handleability.

Further, Japanese Unexamined Patent Publication No. 62-219924 discloses a technique for etching the front surface of the membrane while flowing a coolant such as helium gas on the back surface of the mask membrane. However, this technique has the drawback that it is difficult to seal the gas and control the pressure.

In addition to this, Japanese Patent Application Laid-Open No. 4-330712 discloses a technique in which PVA (polyvinyl alcohol) is placed on the back side of the mask membrane and etching is performed on the membrane front side. However, such a technique has drawbacks such as volume shrinkage of PVA and insufficient thermal conductivity of PVA.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a mask structure for X-ray lithography for forming at least a mask membrane and an X-ray absorber pattern on a substrate or a support material. A method for manufacturing an X-ray mask structure having excellent positional accuracy of an absorber pattern (mask pattern) without vibration or distortion of a mask membrane, and an X-ray mask having a fine pattern obtained by the method. A line mask structure is provided.

[0014]

The above object of the present invention is a method of manufacturing a mask structure for X-ray lithography, which comprises forming at least a mask membrane and an X-ray absorber pattern on a substrate or a support frame. Forming and / or processing a member constituting the mask structure on the substrate, the support frame, or the surface of the mask membrane, with a mixture of a binder and a heat conductive substance being in contact with the back surface of the mask membrane. And a method of manufacturing an X-ray mask structure characterized by the above.

In the method of manufacturing an X-ray mask structure of the present invention, the back surface side of the mask membrane (especially when the mask membrane is formed on the substrate, the portion corresponding to the mask region of the substrate is removed by etching (back etching). (It is not limited that the back surface side of the mask membrane after exposure, but the back surface of the mask membrane is exposed.)
In the state where the mixture of the above-mentioned specific composition, that is, the mixture consisting of the binder and the heat-conducting substance is placed in contact with,
Since the step of forming and / or processing the other member constituting the mask structure is performed, it is possible to efficiently dissipate the heat generated in the mask membrane or the like during the step, and improve the loading effect, and the mask membrane. Various loads on the board and substrate are reduced. Especially when plating or etching treatment is performed to form the X-ray absorber pattern on the mask membrane surface side after the above mixture is placed, the substrate temperature rises, the flatness of the mask membrane deteriorates, and the heat of other members is reduced. It is possible to reduce the damage caused by the above, and to significantly improve the positional accuracy of the formed pattern. It should be noted that the back surface side of the mask membrane is not limited to the membrane being exposed, and thus the membrane back surface mixture is not always directly touched.

Further, in the method for producing an X-ray mask structure of the present invention, handling and final removal of the above mixture at the time of contact placement on the back side of the mask membrane are easy.
The workability is improved, and since the mixture undergoes less change in state such as shrinkage during placement, that is, in the subsequent step, the above-mentioned properties such as heat dissipation are further improved.

Therefore, according to the method of manufacturing the X-ray mask structure of the present invention, the flatness of the mask membrane and the dimensional accuracy of other members are excellent, the X-ray absorber pattern is extremely fine, and the excellent performance is obtained. The X-ray lithography mask structure can be obtained.

The method of manufacturing the X-ray mask structure of the present invention will be described in detail below.

In the method, the mixture to be placed in contact with the back side of the mask membrane is preferably a substance that is solid at room temperature and easily softens by heating, for the purpose of further improving thermal conductivity. The medium is dispersed and compounded.

As the binder, for example, a wax such as a natural material and a paraffin such as a synthetic material can be used. Specific examples of the wax include stone wax, beeswax, sina wax, wood wax, cotton wax, lanolin and the like, and those having a melting point of about 40 to 80 ° C. and being hydrophobic and having excellent machinability are particularly preferable.

On the other hand, as the medium, that is, the heat conducting substance, for example, fine powder of a metal material, a ceramic material, a carbon material, a semiconductor material or the like can be used. Specific examples of metal materials include Ti, A1, Sn, Ag, and A.
u, W, Ta, Cu, Ni, Zn, Co, Mo, Pb,
And alloys such as duralumin, composites, and the like. Specific examples of ceramic materials include SiC, BN, and A1.
Examples thereof include N, SiN, and alumina. Specific examples of the carbon-based material include diamond, diamond-like carbon, and graphite. Specific examples of the semiconductor material include Si, Ge, TiO ₂ , and ZnO. Of these thermal conductive materials, the thermal conductivity is approximately 10W.
/ Mk or less, chemically stable and excellent in electrical conductivity,
Particularly preferred are those having a low specific gravity and good compatibility with the binder.

The combination and blending ratio of the components of the mixture are the kind of materials to be used, the condition of the step performed after the mixture is placed on the back surface of the mask membrane, for example,
It can be appropriately selected depending on the type of liquid used for plating or etching, temperature, atmospheric conditions, and the like.

The mixture is placed in contact with the back side of the mask membrane by the following method, for example. That is, first, the binder and the powder of the heat conductive material are mixed at a temperature higher than the melting point of the binder, and further thoroughly mixed. On the other hand, a substrate having a mask membrane formed on the surface thereof, in which the substrate portion corresponding to the mask region has been removed, or a support frame having a mask membrane formed on the surface of the substrate or the back side of the mask membrane on the side of the support frame The mixture is placed upward and the mixture is poured into a region surrounded by the substrate or the support frame and the mask membrane. Then, it is cooled and solidified at a predetermined temperature (which is appropriately set depending on the materials constituting the mixture).

The mixture overflowing from the above region can be easily removed by squeezing with a blade such as a cutter after cooling and solidifying.

Here, it is preferable that the mixture is completely filled and arranged in a region surrounded by the substrate or the support frame and the mask membrane, but if the back surface side of the mask membrane is completely covered, the mask membrane holding substrate and A large effect can be obtained if it is in contact with at least a part of the support frame.

In the method of manufacturing an X-ray mask structure of the present invention, the material of the mask membrane, the material of the X-ray absorber, and the material of the other members constituting the mask structure are commonly used as these materials. Any thing can be used. In particular, specific examples of the material of the mask membrane include Si and S
Examples of iN, SiC, BN, AlN, AlNO, diamond, diamond-like carbon and the organic film include polyimide, polyamide and polyester.

On the other hand, specific examples of the material of the X-ray absorber include noble metals such as gold, silver, platinum and rhodium, tungsten, heavy metals such as tantalum, nickel, cobalt and the like.

In the method of manufacturing an X-ray mask structure of the present invention, as described above, the mixture of the binder and the heat conducting material is placed in contact with the back side of the mask membrane, and then the substrate supporting the mask membrane in this state. Alternatively, a step of forming or processing another member constituting the mask structure is performed around the support frame or on the surface side of the mask membrane.

Specific examples of such steps include forming an X-ray absorber pattern on the surface of a mask membrane, forming an antireflection film, measuring and correcting the X-ray absorber pattern, and adhering a frame to a substrate or a support frame. Can be mentioned.

Of these, the X-ray absorber pattern is formed, for example, as follows. That is, a mask membrane is plated to form a layer made of an X-ray absorber material, a resist pattern is formed on the absorber layer, and then the absorber layer is etched using the pattern as a mask. To form. It is also possible to form the X-ray absorber layer on the back side of the mask membrane after forming the X-ray absorber layer, and form a resist pattern on the X-ray absorber layer and pattern the X-ray absorber layer by etching. . It is also possible to obtain an X-ray absorber pattern by placing the above mixture in contact with the back side of the mask membrane, subsequently forming a resist pattern on the front side of the mask membrane, and plating with this pattern as a mold.

After the above steps, the placed mixture is removed,
An X-ray mask structure having a predetermined fine X-ray absorber pattern is obtained.

The X-ray mask structure manufactured by the present invention is
It can be applied to an X-ray exposure method and X-ray lithography according to a conventional method. That is, a member to be exposed which is made of an X-ray sensitive layer such as a resist layer is exposed to X-rays through the X-ray mask structure by a prokinetic method or the like to transfer the pattern of the X-ray mask structure. Subsequently, development processing is performed to form a pattern of the exposed member.

Further, the X-ray mask structure manufactured by the present invention can be applied to an X-ray exposure apparatus for performing the above-mentioned X-ray exposure method in combination with a general X-ray source. Hereinafter, with reference to FIG. 3, an X-ray exposure apparatus for manufacturing a minute device (semiconductor device, thin-film magnetic head, micromachine, etc.) using synchrotron radiation (SOR) will be described as an example of the X-ray exposure apparatus. . In the figure, SOR
The sheet-beam-shaped synchrotron radiation 21 emitted from the radiation source 20 is expanded by a convex mirror 22 in a direction perpendicular to the orbital plane of the radiation. The radiated light reflected and expanded by the convex mirror 22 is adjusted by the shutter 23 so that the exposure amount in the irradiation area becomes uniform, and the radiated light passing through the shutter 23 is guided to the X-ray mask structure 24. The X-ray mask 24 is manufactured according to the method of the present invention described above. The exposure pattern (absorber pattern) formed on the X-ray mask structure 24 is exposed and transferred onto the wafer 25 by a step & repeat method, a scanning method, or the like.

Further, X-ray lithography using the X-ray mask structure manufactured according to the present invention can be applied to semiconductor devices such as
It can be widely applied to manufacturing processes of semiconductor chips such as ICs and LSIs, liquid crystal panels, CCDs and the like. That is, various semiconductor devices are manufactured by transferring a pattern of an X-ray mask structure by a member to be exposed on a substrate by the X-ray lithography and processing the substrate, for example, forming a wiring pattern or a contact hole. To do. The thus obtained semiconductor device has extremely high processing accuracy and high integration.

The manufacturing process of the semiconductor device, which is carried out by using the X-ray mask structure manufactured according to the present invention, will be described in more detail below with reference to FIGS. 4 and 5.

FIG. 4 shows an example of a semiconductor device manufacturing flow including the manufacture of the X-ray mask structure according to the present invention.

In step 1 (circuit design), a semiconductor device circuit is designed. In step 2 (mask making), an X-ray mask structure having a circuit pattern predesigned according to the present invention is manufactured. Meanwhile, step 3 (wafer manufacturing)
Then, a wafer is manufactured using a material such as silicon. Step 4 (wafer process) is called a pre-process, and an actual circuit is formed on the wafer by lithography using the X-ray mask structure and the wafer prepared above. The next step 5 (assembly) is called a post-process, and is a process of forming a semiconductor chip using the wafer manufactured in step 4, such as an assembly process (dicing, bonding), a packaging process (chip encapsulation), and the like. including. In step 6 (inspection), the semiconductor device manufactured in step 5 undergoes inspections such as an operation confirmation test and a durability test. Through these steps, the semiconductor device is completed and shipped (step 7).

FIG. 5 shows an example of the flow of the wafer process including the X-ray lithography technique using the X-ray mask structure according to the present invention. In step 11 (oxidation), the surface of the wafer is oxidized. Step 12 (CVD)
Then, an insulating film is formed on the wafer surface. In step 13 (electrode formation), electrodes are formed on the wafer by vapor deposition.
In step 14 (ion implantation), ions are implanted in the wafer. In step 15 (resist processing), a tourist agent is applied to the wafer. In step 16 (exposure), the circuit pattern of the mask is printed and exposed on the wafer by the above-described exposure method (X-ray lithography technique). In step 17 (development), the exposed wafer is developed. In step 18 (etching), parts other than the developed resist image are removed. In step 19 (resist stripping), the resist that is no longer needed after etching is removed. By repeating these steps, multiple fine circuit patterns are formed on the wafer.

According to this process, it is possible to manufacture a highly integrated semiconductor device which has been difficult to manufacture in the past.

[0040]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to the drawings. Note that these examples are made for the purpose of facilitating the understanding of the present invention, and do not particularly limit the present invention.

Example 1 (see FIG. 1) As a binder, 10 parts by weight of paraffin having a melting point of 50 ° C. was placed in a stainless beaker, and subsequently, A was used as a medium.
5 parts by weight of the fine powder (325 mesh) of 1 were added and the mixture was set in a Magnmix stirrer with a constant temperature bath at 80 ° C. After the paraffin was sufficiently dissolved, a stirrer unit was placed and the mixture was stirred by rotation. After mixing for about 2 hours, the mixture was left to stand in a thermostat for 2 hours.

On the other hand, as a mask membrane, a SiN film 2 was deposited to a thickness of about 2 μm on a single crystal Si substrate 1 having a diameter of 5 mm and a diameter of 3 inches and a crystal orientation of 100 by a low pressure CVD method. The SiN film 2 was removed using a dry etching (RIE) device with respect to the mask area 25 × 25 mm on the back surface. Then, a W film 3 which is an X-ray absorber is formed on the surface of the substrate by an RF sputtering device to a thickness of 0.8 μm, and a Cr film 4 is formed on the surface of the substrate.
It was laminated with a thickness of 05 μm. Next, the back surface was treated with a KOH 30% solution at 110 ° C. using a Si back etching device to remove Si, and thus a mask membrane 5 with an absorber layer was obtained. Next, the mask membrane 5 with the absorber layer was set on the flat table 6 kept at 80 ° C. with the back surface facing upward. Next, the mixture 7 left in the constant temperature bath was poured into the Si back etching hole, left for several hours, and then gradually cooled. After sufficiently cooled and fixed, the mixture was squeezed using a cutter to remove the mixture overflowing from the back surface of the substrate by cutting (FIG. 1 (a-1)). Here, the mixture does not have to be completely filled in the Si back etching hole, and if the back surface side of the mask membrane is covered, it only needs to contact a part of the substrate (FIG. 1 (a-2)). reference).

Next, the mask membrane 5 with the absorber layer
Was removed from the flat base, and the back surface was covered with aluminum foil 8 for better handling. (Filling Mask Membrane Unit) A COP resist having a thickness of 0.5 μm was applied to the surface of the filling mask membrane unit using a spin coater. Next, the mask pattern is exposed using an EB drawing device and a predetermined developing process is performed to form a resist pattern 9
Was formed (FIG. 1 (b)). Dry etching (RI
E) Using the apparatus, the Cr film was etched. Subsequently, the resist pattern 9 was removed by ashing with enzyme plasma to form a Cr pattern 10. Finally, the W film was etched using SF ₆ gas to form a W absorber pattern 11 (see FIG. 1).
(C)).

Next, peel off the aluminum foil on the cover,
The mixture was set face down in an atmosphere of 80 ° C. and the mixture was melted and removed. The residual was washed with chloroform to complete a mask structure for X-ray lithography.

Since the sample stage of the EB drawing device and the dry etching device was kept at a constant temperature, the temperature of the W film and Cr film during the drawing of the mask pattern and the temperature of the substrate during processing were not significantly changed depending on the arrangement of the mixture. It was possible to create a mask structure with extremely high pattern position accuracy.

Example-2 In Example-1, SiC (3
50 mesh), using wood wax as the binder material, 20 for each
Blended with 10 parts by weight. The same process as in Example-1 was performed, and a similar high precision X-ray mask structure could be created.

Example 3 (see FIG. 2) A 6 μm thick polyimide film 13 was stretched and bonded to a ring frame 12 having an outer diameter of 100 mm, an inner diameter of 50 mm, a height of 10 mm and an upper surface inclined outward by 15 °. An adhesive mask membrane was prepared with the agent.

A mixture was prepared in the same manner as in Example 1 except that tin powder (200 mesh) and lanolin were mixed in a ratio of 1: 1 (weight), and the back side of the mask membrane 12 was faced up. Cover with aluminum foil 8,
A filling mask membrane unit was created (Fig. 2-
(A)). Here, the mixture does not have to be completely filled in the region surrounded by the polyimide film 13 and the ring frame 12, and if it is completely in contact with the back surface side of the polyamide film 13, it is in contact with at least a part of the ring frame 12. All that is required is (see Figure 2- (b)).

A Cr film of 0.01 μm and an Au film of 0.05 μm were sequentially formed on the surface of the membrane by vapor deposition. The resist AZ-1350 is spin-coated to a thickness of 1.2 μm.
Coated Next, a Cr mask pattern and a transfer resist pattern on a quartz plate were formed using a contact printer (PLA).

Then, a 0.7 μm thick Au pattern (absorber pattern) was formed using the resist pattern as a mold by using a gold plating solution and an electrolytic plating method. The resist was removed by washing with acetone and then subjected to enzymatic plasma detreatment using dry etching (RIE) to remove Cr-Au. 70 ° C
The mixture on the back surface of the membrane was eluted in the atmosphere of 1 and the residue was washed and removed with hot alcohol to prepare an X-ray mask structure. The conventional method did not achieve the required performance because the contact and dry processing did not go well, but this time the contact was made evenly, the absorber pattern position accuracy was good, and the mask membrane flatness was also excellent. I was able to create a high quality mask.

Example 4 An X-ray mask structure was prepared in the same manner as in Example 3 except that beeswax was used as the binder and graphite was used as the medium, and the pattern position accuracy and the flatness of the mask membrane were excellent. It was

Example-5 In Example-3, the binder is paraffin wax and the medium is SiC.
(800 mesh) was mixed with 1 to 2 parts by weight to prepare a mixture, and an X-ray mask structure was created by the same method. To obtain a mask structure.

Example-6 In Example-1, the absorber pattern obtained by etching the W film (before removing the mixture on the back surface of the mask membrane) was changed to E.
A black defect was found in some patterns when measured using a B length measuring machine and SEM. When the sample table was kept at a low temperature and removed using an ion beam defect repair machine, the mask could be repaired accurately without damaging the membrane film. Next, SiO ₂ was further sputter-deposited as a light antireflection film, and a Pyrex ring frame was further adhered using an epoxy adhesive. After storing in a constant temperature bath kept at 70 ° C., the mixture was removed and the residue was washed off with chloroform to prepare a mask structure with a frame. In this example, the pattern is measured and corrected while the mixture is placed in contact with the back side of the mask membrane.
A mask structure having good pattern positional accuracy was obtained.

Example-7 The mask structure prepared in Example-6 was mounted on an X-ray stepper for SOR and X-ray (wavelength 10Å) exposure, and a gap of 10 was obtained.
resist (AZPF)
-100) to obtain a high resolution resist pattern at the submicron level.

[0055]

As described in detail above, according to the present invention,
A method for manufacturing a mask structure for X-ray lithography, which comprises forming at least a mask membrane and an X-ray absorber pattern on a substrate or a supporting frame, wherein the mask membrane and other members are not damaged by vibration, strain, or heat during the process. Provided is a method capable of producing an X-ray mask structure that is reduced in number, and finally has excellent positional accuracy of the X-ray absorber pattern and that has good parallelism of the mask membrane.

Further, according to the present invention, a high-performance X-ray mask structure obtained by the above method, an X-ray exposure method using the mask structure, and an X-ray exposure using the mask structure. A device, an X-ray lithography technique capable of forming a fine pattern, and a highly integrated semiconductor device which can be manufactured by applying the lithography technique are provided, and the industrial value thereof is extremely large.

[Brief description of drawings]

1A to 1C are cross-sectional views showing a method of manufacturing an X-ray mask structure according to an embodiment of the present invention along the steps thereof.

2 (a)-(b): X according to another embodiment of the present invention.
Sectional drawing which shows a mask membrane formation process in the manufacturing method of a line mask structure.

FIG. 3 is an explanatory view showing an example of an X-ray exposure apparatus using an X-ray mask structure according to the present invention.

FIG. 4 includes X-ray mask structure fabrication according to the present invention,
The block diagram which shows an example of the manufacturing flow of a semiconductor device.

FIG. 5 is a block diagram showing an example of a wafer process including an X-ray lithography technique using an X-ray mask structure according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Si substrate 2 SiN film (mask membrane) 3 W film (X-ray absorber layer) 4 Cr film 5 Mask membrane with absorber layer 6 Plane stand 7 Mixture 8 Aluminum foil 9 Resist pattern 10 Cr pattern 11 W film pattern (X Line absorber pattern) 12 Ring frame 13 Polyimide film (mask membrane) 20 SOR radiation source 21 Synchrotron radiation 22 Convex mirror 23 Shutter 24 X-ray mask structure 25 Wafer

Claims (9)

[Claims] 1. A method of manufacturing a mask structure for X-ray lithography, which comprises forming at least a mask membrane and an X-ray absorber pattern on a substrate or a support frame, wherein a back surface side of the mask membrane comprises a binder and a heat conductive material. A method for producing an X-ray mask structure, which comprises forming and / or processing a member constituting the mask structure on the surface of the substrate, the support frame or the mask membrane in a state where the mixture is arranged in contact. 2. The method according to claim 1, wherein the binder in the mixture is at least one hydrophobic substance selected from the group consisting of wax and paraffin. 3. The heat-conducting substance in the mixture is at least one unitary substance or a composite substance selected from the group consisting of metal materials, ceramic materials, carbon-based materials, and semiconductor materials. The method described in 1. 4. The method according to claim 1, wherein the mask membrane with which the mixture is placed in contact is formed by forming a film on a Si substrate and then removing the substrate portion corresponding to the mask region by etching to expose the back surface. 5. The steps on the substrate or the support frame after the mixture is placed in contact with the back side of the mask membrane are the steps of forming a pattern, the step of forming an antireflection film, and the measurement of the X-ray absorber pattern. The method according to claim 1, wherein the method is at least one step selected from the group consisting of a step of correcting and a step of adhering the frame. 6. An X-ray mask structure manufactured by the method according to claim 1. 7. An X-ray exposure method comprising the step of exposing a member to be exposed through X-ray exposure through the X-ray mask structure according to claim 6 to transfer a predetermined pattern. 8. An X-ray which comprises an X-ray source and the X-ray mask structure according to claim 6, and which exposes a member to be exposed to X-rays through the X-ray mask structure to transfer a predetermined pattern. Exposure equipment. 9. A semiconductor device manufactured by a process including the steps of transferring a pattern onto a member to be exposed on a substrate by the X-ray exposure method according to claim 7, and processing the substrate.