JPH0620929A - X-ray mask structure, manufacture of x-ray mask, x-ray exposure device, exposing method for x-ray and manufacture of semiconductor - Google Patents

Abstract

PURPOSE:To set stable alignment light transmittance without thick distribution, damage of an X-ray transmission film by forming a pattern on the transmission film as a metal oxide film having a special value or more of atomic number, and forming a part except the pattern as a metal oxide film having a special value or less of the atomic number. CONSTITUTION:Metal having an atomic number or 35 or less is more easily oxidized than that having an atomic number of 70. First, a desired fine resist pattern 15 is formed by an electron beam lithography. Then, gold to become an X-ray absorber 16 is formed, and the pattern 15 is peeled by a special purpose peeling solution. Peeling of a plated electrode 14 of a part having no absorber 16 is executed by an RIE. Further, an Si wafer is back etched, and a holding frame 11 is formed. Eventually, oxygen gas is supplied at 20 SCCM in the same RIE unit, 200W power is applied at 5X10<-2>Torr, a non-pattern forming part of a gold oxide 17 and a metal thin film 13 is formed on a surface of the absorber 16' by oxygen plasma as a chromium oxide 18.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention includes four interrelated inventions. Each invention will be described below. (First Invention) The present invention relates to an X-ray mask structure having a pattern to be transferred and a manufacturing method used in a semiconductor manufacturing X-ray exposure apparatus or the like. (Second invention) The present invention relates to an X-ray mask structure having a pattern to be transferred, which is used in an X-ray exposure apparatus for manufacturing a semiconductor, a manufacturing method thereof, an X-ray exposure apparatus, an X-ray exposure method and a semiconductor. It relates to a manufacturing method.

(Third Invention) The present invention relates to X for semiconductor manufacturing.
X-ray mask structure on which a pattern to be transferred is formed, used in a line exposure apparatus, etc., its manufacturing method, X-ray exposure apparatus,
The present invention relates to an X-ray exposure method and a semiconductor manufacturing method. (Fourth invention) The present invention relates to an X-ray mask structure having a pattern to be transferred, which is used in an X-ray exposure apparatus for semiconductor manufacturing, etc., a manufacturing method thereof, an X-ray exposure apparatus, an X-ray exposure method and a semiconductor. It relates to a manufacturing method.

[0003]

2. Description of the Related Art (First Invention) In recent years, as the density and speed of semiconductor integrated circuits have increased, the pattern line width of integrated circuits has tended to decrease by 70% in about three years. Due to the further integration of the large-capacity memory device, the printing apparatus is required to have higher performance, and the minimum line width capable of transfer is 0.3 μm or less. Therefore, a stepper using light in the X-ray region (2 to 20 Å) as an exposure wavelength is being developed. X used for the X-ray exposure apparatus
Conventionally, the line mask has a structure as shown in FIG. 10 (f) which is manufactured by the manufacturing process as shown in FIG.

The structure is such that nothing remains on the surface of the X-ray absorber and the non-patterned portion of the X-ray absorber on the X-ray transparent film. More specifically, reference numeral 61 is a substrate that serves as a holding frame.
Si wafers are often used. As the X-ray transparent film 62, a thin film of about 2 μmt having good X-ray transparency such as silicon nitride or silicon carbide is used. Chromium 50Å as the metal thin film 63 for depositing gold and 500Å gold as the plating electrode 64 for depositing the X-ray absorber are continuously vapor-deposited by EB vapor deposition, and as shown in FIG.
Becomes A desired fine resist pattern 65 is formed thereon by using an electron beam drawing apparatus, and is shown in FIG. The resist used may be a single layer or a multilayer. Next, gold to be the X-ray absorber 66 is formed by gold plating. The resist pattern 65 is peeled off, resulting in FIG.

Plating electrode 6 in a portion without X-ray absorber 66
The strip of 4 is etched using argon gas. Since both the plating electrode 64 and the X-ray absorber are made of gold, the X-ray absorber is evenly etched, and the X-ray absorber is as shown at 66 'in FIG. 10D. Further, the metal thin film 63 in the portion without the X-ray absorber 66 '
Although the chromium is removed, sputter etching using argon gas or etching using reactive gas (chlorine gas) is performed, resulting in FIG. Finally, the Si wafer is back-etched to form a holding frame 61, which is shown in FIG.

In the above conventional X-ray mask manufacturing process,
At the time of removing the chromium of the metal thin film 53 in the portion where the X-ray absorber 56 ′ is not present, in the sputter etching using argon gas,
Since chromium has a lower sputter rate than gold, the thickness of gold is greatly reduced and the contrast as an X-ray mask is reduced. The difficulty of the X-ray mask is the fine pattern (0.25 μm
It is necessary to form a pattern having a high aspect ratio of about 0.75 μmt (level) and obtain contrast. It is more difficult to form a thick gold film by taking into consideration the film thickness that decreases when etching chromium.

Further, in the etching using the reactive gas,
Since a chlorine-based gas is used, silicon nitride or silicon carbide, which is an X-ray transparent film, is etched, causing a film thickness distribution or damaging the film surface. Even sputter etching using argon gas causes a film thickness distribution and damages the film surface. Further, when the metal thin film remains, the X-ray transmittance is hardly affected, but the alignment light transmittance is greatly reduced. When Cr50Å remains, the X-ray transmittance is reduced by only 0.6%, but the alignment light transmittance (He-Ne laser) is reduced by 46% as compared with the substrate having only SiN 2 μm. Furthermore,
As a method of manufacturing an X-ray absorber, there is a method of forming W or Ta by etching, but a reactive gas (mainly fluorine type)
To use.

For many of these gases, silicon nitride and silicon carbide, which are X-ray transparent films, have a higher etching rate,
It causes the film thickness distribution and damages the film surface. Therefore, although a metal thin film for an etching stopper is provided, a similar problem occurs even though the film thickness distribution is thin and the amount of damage is small. Another problem of the X-ray mask is positional distortion of the pattern. One of the causes is the internal stress of the absorber. The conditions are set so that the stress becomes as small as possible when the absorber is manufactured, but it cannot be set to a sufficiently small value in consideration of the density and the film thickness distribution.

(Second Invention) In recent years, with the increase in density and speed of semiconductor integrated circuits, the pattern line width of the integrated circuits has become
It tends to be reduced by 70% in about 3 years. Due to the further integration of the large-capacity memory device, the printing apparatus is required to have higher performance, and the minimum line width capable of transfer is 0.3 μm or less. Therefore, a stepper using light in the X-ray region (2 to 20 Å) as an exposure wavelength is being developed. A cross-sectional view of an X-ray mask used in the X-ray exposure apparatus has a structure as shown in FIG. 10 (f) which is manufactured by the manufacturing process as shown in FIG.

An antireflection film is provided on the X-ray transmission film, and a mark for aligning the X-ray absorber and the mask with the wafer is formed on the antireflection film. The plan view is as shown in FIG. 10G, in which scribe lines are provided in the peripheral portion of the circuit pattern and marks for aligning the mask and the wafer are provided. Further, an antireflection film is provided on both the circuit pattern and the scribe line. More specifically, 61 is a substrate that serves as a holding frame, and a Si wafer is often used. As the X-ray transparent film 62, a thin film of about 2 μmt having good X-ray transparency is used such as silicon nitride or silicon carbide.

As the antireflection film 68, silicon oxide, polyimide, or the like is used as light for alignment (alignment light).
An appropriate thickness is formed depending on the wavelength. 10 nm of chromium as the metal thin film 63 for depositing gold and 50 nm of gold to be the plating electrode 64 for depositing the X-ray absorber are continuously vapor-deposited by EB vapor deposition. A desired fine resist pattern 65 is formed thereon by an electron beam drawing apparatus, and then, as shown in FIG.
(B). The resist used may be a single layer or a multilayer. Next, gold serving as the X-ray absorber 66 and the alignment mark 67 is formed by gold plating. The resist pattern 65 is peeled off, resulting in FIG.

X-ray absorber 66 and alignment mark 67
The peeling of the plated electrode 64 in the non-existing portion is etched using argon gas. Since the plating electrode 64, the X-ray absorber 66, and the alignment mark 67 are made of gold, they are uniformly etched, and the X-ray absorber 66 becomes 66 'in FIG. 10D.
It becomes like. Similarly, the alignment mark 67 is 67 '.
Becomes Further, the chromium of the metal thin film 63 in the portion where the X-ray absorber 66 'and the alignment mark 67' are not removed is removed, but is sputter-etched using argon gas or etched using a reactive gas (chlorine gas). 10
(E). Finally, the Si wafer is back-etched to form a holding frame 61, which is shown in FIG.

In the above-mentioned conventional X-ray mask structure, the antireflection film is formed on both the regions having the X-ray absorber 66 'used as a post-transfer circuit pattern and the alignment mark 67' used for alignment. . Positional distortion is one of the major problems in the X-ray mask. One of the factors is the stress of the X-ray transparent film, but it is difficult to control and its stability is a problem. If an X-ray transparent film alone is regarded as a problem and an antireflection film is provided, stress control for both is required.

In general, an oxide or the like is often used for the antireflection film, but X is more preferable than the material used for the X-ray transmission film.
Often the line resistance is weak. The X-rays that are irradiated when the X-ray mask is used for X-ray exposure cause the film to change with time and the stress value to change. However, in the case of only the X-ray transmission film without the antireflection film, the transmittance is 55 to 90% when there is a film thickness variation of 5% with respect to the substrate of SiN 2 μm, though it depends on the wavelength of the alignment light. The rate will change.

(Third Invention) In recent years, with the increase in density and speed of semiconductor integrated circuits, the pattern line width of the integrated circuits has become
It tends to be reduced by 70% in about 3 years. Due to the further integration of the large-capacity memory device, the printing apparatus is required to have higher performance, and the minimum line width capable of transfer is 0.3 μm or less. Therefore, a stepper using light in the X-ray region (2 to 20 Å) as an exposure wavelength is being developed. The cross-sectional view of the X-ray mask used in the X-ray exposure apparatus has a structure as shown in FIG. 17 (f) which is manufactured by the conventional manufacturing process as shown in FIG. The structure is such that nothing remains in the non-pattern forming portion of the X-ray absorber on the X-ray transparent film. The plan view is as shown in FIG. 17G, in which scribe lines are provided in the peripheral portion of the circuit pattern and marks for aligning the mask and the wafer are provided.

More specifically, 51 is a substrate that serves as a holding frame, and a Si wafer is often used. As the X-ray transparent film 52, silicon nitride, silicon carbide or the like having a good X-ray transparency of 2 μmt is used.
Some thin films are used. As shown in FIG. 17, chromium 50Å as the metal thin film 53 for depositing gold and 500Å gold as the plating electrode 54 for forming the X-ray absorber are continuously deposited by EB evaporation.
(A). A desired fine resist pattern 55 is formed on it by an electron beam drawing apparatus, and is shown in FIG. The resist used may be a single layer or a multilayer. Next, gold to be the X-ray absorber 56 and the alignment mark 57 is formed by gold plating. The resist pattern 55 is peeled off, resulting in FIG.

The plating electrode 5 in the portion without the X-ray absorber 56
The strip of 4 is etched using argon gas.
Since both the plating electrode 54 and the X-ray absorber are made of gold, they are uniformly etched, and the X-ray absorber becomes as shown at 56 'in FIG. 17 (d). Similarly, the alignment mark 57 becomes 57 '.
Furthermore, the X-ray absorber 56 'and the alignment mark 57'.
Although the chromium of the metal thin film 53 in the non-existing portion is removed, sputter etching using an argon gas or etching using a reactive gas (chlorine-based gas) is performed, resulting in FIG. Finally, the Si wafer is back-etched to form a holding frame 51, which is shown in FIG.

In the above conventional X-ray mask manufacturing process,
When removing the chromium of the metal thin film 53 in the portion where the X-ray absorber 56 ′ and the alignment mark 57 ′ are not present, in the sputter etching using argon gas, the sputtering rate of chromium is lower than that of gold. There is a large decrease, and the contrast as an X-ray mask is decreased (gold has a lower sputter rate among metals, so the sputter rate is lower than that of the metal normally used for deposition). The difficulty of the X-ray mask is that it is necessary to form a fine pattern (0.25 μm level) with a high aspect ratio of about 0.75 μmt to obtain contrast. It is more difficult to form a thick gold film by taking into consideration the film thickness that decreases when etching chromium. In addition, since chlorine-based gas is used in etching using a reactive gas, silicon nitride or silicon carbide, which is an X-ray transparent film, is etched, causing a film thickness distribution or damaging the film surface. Even in sputter etching using argon gas, it causes film thickness distribution,
Damages the film surface.

Further, when the metal thin film remains, the X-ray transmittance is hardly affected, but the alignment light transmittance is greatly reduced. Cr compared to a substrate with only 2 μm SiN
When 50Å remains, the X-ray transmittance is reduced only by 0.6%, but the alignment light transmittance (He-Ne laser) is reduced by 46%. Further, there is a method of forming W or Ta by etching as a method of manufacturing an X-ray absorber, but a reactive gas (mainly fluorine-based) is used. Many of these gases have a higher etching rate for silicon nitride and silicon carbide, which are X-ray transparent films, and cause film thickness distribution and damage the film surface. Therefore, although a metal thin film for an etching stopper is provided, a similar problem occurs even though the film thickness distribution is thin and the amount of damage is small.

Therefore, there has been a method of leaving the metal thin film in the circuit pattern portion and peeling off only the metal thin film in the range used for alignment (see Japanese Patent Laid-Open No. 58-93054). In this case, a reduction in the aspect ratio of the X-ray absorber can be prevented, but damage to the X-ray transparent film in the range used for alignment cannot be prevented. The transmittance of the alignment light causes a transmittance variation of 55 to 90% when a film thickness variation of 5% occurs on a substrate of SiN 2 μm. The X-ray transparent film in the range used for alignment is required to have film thickness accuracy higher than that of the circuit pattern portion. Further, the X-ray transparent film causes surface roughness due to the plasma used for peeling the metal thin film.

(Fourth Invention) In recent years, with the increase in density and speed of semiconductor integrated circuits, the pattern line width of the integrated circuits has become
It tends to be reduced by 70% in about 3 years. Due to the further integration of the large-capacity memory device, the printing apparatus is required to have higher performance, and the minimum line width capable of transfer is 0.3 μm or less. Therefore, a stepper using light in the X-ray region (2 to 20 Å) as an exposure wavelength is being developed. The X-ray mask used for the X-ray exposure apparatus has conventionally had a structure as shown in FIG. 25 (f), which is manufactured by the manufacturing process as shown in FIG. X on X-ray transparent film
This is a structure in which nothing exists in the non-pattern forming portion of the line absorber. More specifically, 71 is a substrate that serves as a holding frame, and a Si wafer is often used. The X-ray transparent film 72 is made of silicon nitride, silicon carbide or the like and has a good X-ray transparency of 2 μm.
A thin film of about t is used.

Chromium 5 as a metal thin film 73 for depositing gold
nm and X-ray absorber film forming plating electrode 74 50 n of gold
m is continuously vapor-deposited by EB vapor deposition, resulting in FIG.
A desired fine resist pattern 75 is formed thereon by using an electron beam drawing apparatus, and is shown in FIG. The resist used may be a single layer or a multilayer. Next, by gold plating, X
Gold that will become the line absorber 76 is formed. Resist pattern 7
5 is peeled off to obtain FIG. 25 (c).

The plating electrode 7 in the portion without the X-ray absorber 76
The strip of 4 is etched using argon gas. Since both the plating electrode 74 and the X-ray absorber are made of gold, the X-ray absorber is uniformly etched so that the X-ray absorber is as shown at 76 'in FIG. 25 (d). Further, the metal thin film 73 in the portion without the X-ray absorber 76 '
Although the chrome is removed, sputter etching using argon gas or etching using a reactive gas (chlorine gas) is performed, resulting in FIG. Finally, the Si wafer is back-etched to form a holding frame 71, and FIG.
And

In the above conventional X-ray mask manufacturing process,
The alignment light transmittance of the X-ray transparent film 72 is SiN2.
When the film thickness variation of 5% occurs for a substrate of μm 55-9
A 0% transmission variation is generated. 5 in normal film formation
% Film thickness variation occurs, and the X-ray transmission film causes surface roughness due to plasma used in processes such as metal stripping, resulting in film thickness unevenness in minute portions, and alignment light It causes fluctuations in transmittance. Further, when the chromium is removed from the metal thin film 73 in the portion where the X-ray absorber 76 'is not present, in the sputter etching using the argon gas, the sputtering rate of chromium is lower than that of gold, so that the gold film thickness is greatly reduced. The contrast as a line mask is reduced.

The difficulty of the X-ray mask is that fine patterns (0.
25 μm level), it is necessary to form a pattern having a high aspect ratio of about 0.75 μmt to obtain contrast. It is more difficult to form a thick gold film by taking into consideration the film thickness that decreases when etching chromium. In addition, since chlorine-based gas is used in etching using a reactive gas, silicon nitride or silicon carbide, which is an X-ray transparent film, is etched, causing a film thickness distribution or damaging the film surface. Even sputter etching using argon gas causes a film thickness distribution and damages the film surface.

Further, when the metal thin film remains, the X-ray transmittance is hardly influenced, but the alignment light transmittance is greatly reduced. Cr5 compared to a substrate with SiN 2 μm only
When 0Å remains, the X-ray transmittance is reduced only by 0.6%, but the alignment light transmittance (He-Ne laser) is reduced by 46%. Further, there is a method of forming W or Ta by etching as a method of manufacturing an X-ray absorber, but a reactive gas (mainly fluorine-based) is used. Many of these gases have a higher etching rate for silicon nitride and silicon carbide, which are X-ray transparent films, and cause film thickness distribution and damage the film surface. Therefore, although a metal thin film for an etching stopper is provided, a similar problem occurs even though the film thickness distribution is thin and the amount of damage is small.

[0027]

[Problems to be Solved by the Invention] (First invention)
Therefore, the object of the present invention is to solve the above-mentioned problems of the conventional example and to provide a metal thin film between the X-ray transmission film and the metal that plays a main role as an X-ray absorber, but reduce the X-ray absorber. X-ray mask that does not impede the film thickness distribution and damage of the X-ray transparent film and does not hinder the alignment light transmittance in the non-pattern forming portion of the metal thin film and minimizes the pattern position distortion. To provide an X-ray mask.

(Second invention) Accordingly, the object of the present invention is to
An X-ray mask which solves the problems of the conventional example and reduces the positional distortion of the X-ray mask without significantly changing the transmittance of alignment light, a method for manufacturing the same, an X-ray exposure apparatus,
An object is to provide an X-ray exposure method and a semiconductor manufacturing method.

(Third invention) Accordingly, the object of the present invention is to
An X-ray mask that solves the problems of the above-mentioned conventional example, does not reduce the X-ray absorber, does not cause the film thickness distribution and damage of the X-ray transmissive film, and does not hinder the alignment light transmittance, and its manufacture. A method, an X-ray exposure apparatus, an X-ray exposure method, and a semiconductor manufacturing method are provided.

(Fourth Invention) Accordingly, the object of the present invention is to:
An X-ray mask that solves the problems of the above-mentioned conventional example and can obtain a stable alignment light transmittance without reducing the X-ray absorber and causing the film thickness distribution and damage of the X-ray transmitting film, Manufacturing method thereof, X-ray exposure apparatus, X
An object is to provide a line exposure method and a semiconductor manufacturing method.

[0031]

The above object can be achieved by the present invention described below. (First invention) That is, the present invention provides an X-ray mask structure comprising an X-ray absorber having a desired pattern, an X-ray transmissive film supporting the absorber, and a holding frame for holding the X-ray mask structure. A metal oxide film having an atomic number of 70 or more is provided on a pattern portion on the X-ray transparent film, and a metal oxide film having an atomic number of 35 or less is provided on a portion other than the pattern portion on the X-ray transparent film. X-ray mask structure and manufacturing method thereof.

(Second Invention) That is, the present invention relates to an X-ray absorber having a desired circuit pattern, and an X supporting the absorber.
In an X-ray mask structure including a radiation transparent film and a holding frame holding the radiation transparent film, alignment marks are provided in the peripheral portion where the circuit pattern is formed, and the alignment marks are positioned on the X-ray transparent film. An X-ray mask structure characterized by having an antireflection film only in a range used for matching, a manufacturing method thereof, an X-ray exposure apparatus using the X-ray mask, an X-ray exposure method, and a semiconductor manufacturing method.

(Third Invention) That is, the present invention relates to an X-ray absorber having a desired circuit pattern, and an X supporting the absorber.
In an X-ray mask structure including a radiation transparent film and a holding frame holding the radiation transparent film, alignment marks are provided in the peripheral portion where the circuit pattern is formed, and the alignment marks are positioned on the X-ray transparent film. An X-ray mask structure characterized by having a metal oxide film in a range used for alignment and in a portion other than a pattern portion of an alignment mark, a method for manufacturing the same, an X-ray exposure apparatus using the X-ray mask, and X. A line exposure method and a semiconductor manufacturing method.

(Fourth Invention) That is, the present invention is an X-ray mask structure comprising an X-ray absorber having a desired pattern, an X-ray transmissive film for supporting the absorber, and a holding frame for holding them. In the X-ray transmission film, an X-ray mask structure having an antireflection film on a portion other than the pattern portion, a manufacturing method thereof, an X-ray exposure apparatus using the X-ray mask, and an X-ray exposure method. And a semiconductor manufacturing method.

[0035]

(First Invention) Since a thin metal film having an atomic number of 35 or less generally has a small X-ray absorption, it hardly affects the X-ray transmittance. It is oxidized without peeling off so as not to reduce the alignment light transmittance. Depending on the alignment light used, when 50 Å Cr was oxidized by oxygen plasma, the He-Ne laser (6328 Å) was 1.5%, and the semiconductor laser (8300
In Å), the transmittance decreases only by 0.5%. As the oxidation treatment method, any method such as oxygen plasma treatment, oxygen ion implantation treatment, and heat treatment in an oxygen atmosphere may be used. The metal thin film has an atomic number of 3 depending on its application.
Any metal may be used as long as it is 5 or less, but any metal oxide in a thin film state having a high visible or infrared light transmittance used for alignment may be used.

Generally, chromium, titanium, aluminum, zinc, copper or nickel is used. The thickness of the metal thin film is 1,000 Å or less, preferably 100 Å or less, which does not significantly reduce the X-ray transmittance, depending on its use. Also, the X-ray absorber has an atomic number of 7 which has a large X-ray absorption.
Zero or more metals are used. Generally, tantalum, tungsten, gold, platinum or the like is used. These metals are not easily oxidized, but if treated with high energy,
The pole surface is oxidized. It has been confirmed by ESCA that gold, which is a noble metal, is also oxidized. The amount of positional strain of the pattern is measured before the oxidation treatment, and the amount of positional strain is minimized by performing oxidation at the same time as the above oxidation treatment.

Metals with an atomic number of 35 or less have an atomic number of 70
Since the metal is more easily oxidized than the above metal, the amount that can minimize the positional strain of the absorber is prioritized as the amount of oxidation. For improving the translucency of alignment light by oxidizing the metal thin film in the non-patterned portion on the X-ray transparent film, see Canon File No. 2101029, 21
It has already been filed in 01027. A feature of the invention of this application is that the pattern positional distortion amount of the X-ray absorber is simultaneously reduced.

As described above, in the X-ray mask structure comprising the X-ray absorber having a desired pattern, the X-ray transmission film supporting the absorber, and the holding frame holding these, the pattern portion and the X-rays are formed. The above object of the present invention is achieved by an X-ray mask structure characterized by having a metal oxide film on a portion other than a pattern portion on a transmission film, and a manufacturing method thereof.

(Second invention) An antireflection film is formed only in the area used for alignment on the X-ray mask. The portion that will be the circuit pattern after transfer needs to have only X-ray transmittance,
Alignment light transmittance is not required. The range used for normal alignment is outside the circuit pattern, is a very narrow range, and is located substantially symmetrically. The stress value of the antireflection film is
It does not significantly affect the positional distortion of the entire X-ray mask.

As described above, an X-ray mask structure comprising an X-ray absorber having a desired pattern, an X-ray transmissive film supporting the absorber and a holding frame holding them usually has a circuit pattern. An alignment mark is provided on the formed peripheral portion, and an X-ray mask structure characterized by having an antireflection film only in a region used for alignment on the X-ray transparent film, and its manufacture. Method, X-ray exposure apparatus, X
The above object of the present invention is achieved by a line exposure method and a semiconductor manufacturing method.

(Third Invention) The metal thin film in the portion other than the alignment mark portion in the range used for alignment is oxidized without peeling so as not to reduce the alignant light transmittance. 50 depending on the alignment light used
When Å Cr is oxidized by oxygen plasma, SiN2μ
The He-Ne laser (6328Å) only reduces the transmittance by 1.5% and the semiconductor laser (8300Å) by 0.5% as compared with the substrate having only m. As the oxidation treatment method, any method such as oxygen plasma treatment, oxygen ion implantation treatment, and heat treatment in an oxygen atmosphere may be used.

As the metal thin film, any metal may be used depending on its application, but any metal oxide in a thin film state having a high visible or infrared light transmittance used for alignment may be used. Generally, chromium, titanium, tantalum, tungsten, aluminum, molybdenum, tin, zinc, copper, lead or nickel is used. The thickness of the metal thin film is 1,000 Å or less, preferably 100 Å or less, which does not significantly reduce the X-ray transmittance, depending on its use.

As described above, in the X-ray mask structure consisting of the X-ray absorber having a desired pattern, the X-ray transmitting film supporting the absorber, and the holding frame holding these, the X-ray transmitting film is formed on the X-ray transmitting film. X having a metal oxide film in addition to the alignment mark portion in the range used for alignment
The above object is achieved by a line mask structure, a manufacturing method thereof, an X-ray exposure apparatus, an X-ray exposure method, and a semiconductor manufacturing method. (Fourth invention)

In the X-ray mask, after forming the X-ray absorber pattern, an antireflection film is provided on a portion other than the pattern portion on the X-ray transmitting film. If only a stable alignment light transmittance is to be obtained, an antireflection film may be provided on the entire surface of the X-ray transmissive film, which is generally performed. The present invention is not only simpler in comparison with the case where an antireflection film is provided on the entire surface, but also has the problem that the film thickness of the absorber is reduced and the film thickness unevenness and damage of the transmissive film at the time of forming the absorber pattern at the same time. Can be resolved.

As described above, in the X-ray mask structure comprising the X-ray absorber having a desired pattern, the X-ray transmissive film supporting the absorber, and the holding frame holding them, the X-ray transmissive film is formed on the X-ray transmissive film. The object of the present invention is achieved by an X-ray mask structure characterized by having an antireflection film on a portion other than the absorber pattern portion, a method for manufacturing the same, an X-ray exposure apparatus, an X-ray exposure method, and a semiconductor manufacturing method. To be done.

[0046]

Embodiments of the present invention will be described below with reference to the drawings. (First Invention) First Embodiment FIG. 1 is a sectional view of an X-ray mask manufacturing process according to the first embodiment of the present invention. A Si wafer is often used as the substrate 11 that serves as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 11 is heated to 250 ° C. and the pressure is set to 5
A high-frequency power of 20 W was applied at × 10 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt, thereby forming an X-ray transparent film 12.

500 Å of gold to be the plating electrode 14 for depositing the X-ray absorber, and 50 Å of chromium as the metal thin film 13 for adhesion.
Is continuously vapor-deposited by EB vapor deposition, resulting in FIG. The metal thin film 13 may be a metal such as Ti, Al, or Zn that can improve the adhesive force. An electron beam resist PMMA (OEBR-1000, trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied thereon, and a desired fine resist pattern 15 is formed by an electron beam drawing apparatus, as shown in FIG. Next, a gold sulfite plating solution (Nutronex 309, trade name: EEJ
(Made by A), and plating is performed under the conditions of 50 ° C. and current density of 1 mA / cm ² to form gold to be the X-ray absorber 16.
The resist pattern 15 is stripped with a dedicated stripping solution,
(C). Peeling off of the plated electrode 14 in the portion where the X-ray absorber 16 is absent is performed by an RIE device. Back pressure 1 × 10 ^-5
After the pressure is reduced to Torr, 20 SCCM of argon gas is caused to flow, 200 W is applied at 5 × 10 ⁻² Torr, and etching is performed. Since both the plating electrode 14 and the X-ray absorber are made of gold, they are uniformly etched, and the X-ray absorber becomes as shown at 16 'in FIG. 1 (d).

Further, the Si wafer is back-etched with 30% by weight potassium hydroxide at 110 ° C., and the holding frame 11
To form FIG. 1 (e). At this time, the X-ray absorber 1
The pattern positional distortion amount of 6'was measured by a light wave interference coordinate measuring machine and found to be 0.3 μm. Oxidation conditions are selected according to this strain amount. Finally, 20 SCCM of oxygen gas was made to flow in the same RIE device, 200 W was applied at 5 × 10 ^-2 Torr, and X-ray absorber 16 ′ was formed by oxygen plasma.
1 (f) is obtained by forming the gold oxide 17 and the non-patterned portion of the metal thin film 13 on the surface of the chrome oxide 18 as chromium oxide 18. Gold is not easily oxidized, but if a large amount of energy is applied, only the pole surface is oxidized.

As described above, by oxidizing the chromium, which is the metal thin film for adhesion, without etching, the thickness of gold, which is the X-ray absorber 16 ', is reduced, and the thickness of silicon nitride, which is the X-ray transparent film, is reduced. It was possible to prevent the occurrence of distribution. In addition, due to the presence of the chromium oxide 18 in the non-patterned portion, the X-ray transmittance was reduced by 0.6%, and the transmittance of the He-Ne laser (6,328Å) used for alignment was reduced by only 1.5%, which is a problem. Absent. Further, when the positional distortion amount of the X-ray absorber 16 'was measured again by the light wave interference type coordinate measuring machine, the positional distortion amount was reduced to 0.03 μm (measurement limit), and it can be used as a high precision X-ray mask. .

Embodiment 2 FIG. 2 is a sectional view of the X-ray mask manufacturing process of the second embodiment of the present invention. A Si wafer is often used as the substrate 21 serving as the holding frame. This time, the one with 3 inches φ1 mmt was used. The substrate is set in the plasma CVD apparatus.
First, after the back pressure was reduced to 1 × 10 ⁻⁶ Torr, 10 SCCM of silane gas and 10 SCCM of methane gas diluted with hydrogen to 10% were supplied through the holes formed in the lower electrode. The temperature of the substrate 21 is heated to 650 ° C. and the pressure is set to 5 × 10.
^A high frequency power of 50 W was applied at ^-3 Torr to form a silicon carbide film having a thickness of 2 [mu] mt to form an X-ray transparent film 22.

Further, after setting it in a two-source sputtering apparatus and pulling back pressure to 2 × 10 ^-6 Torr, Ar gas 10 SC
CM pressure of 10 × 10 ^-2 Torr and substrate temperature of 150
C., high frequency power of 100 W is applied to form a film of chromium 200 Å to be the absorber etching stopper metal thin film 23, and further 500 W is continuously applied to form W of X-ray absorber 26 of 8,000 Å. It becomes FIG. 2 (a). The metal thin film 23 used may be any metal as long as it has a difference in etching rate from the metal used for the X-ray absorber.

The Si wafer is back-etched with 30% by weight potassium hydroxide at 110 ° C. to form a holding frame 21, which is shown in FIG. 2 (b). A two-layer resist lower layer PIQ (trade name: manufactured by Hitachi Chemical Co., Ltd.) and an upper layer Si-containing resist SNR (trade name: Toyo Soda Co., Ltd.) are applied thereon, and a desired fine resist pattern 25 is formed by an electron beam drawing apparatus. To form FIG. 2 (c). Then, etching of W to be the X-ray absorber 26 is performed by the RIE apparatus. Back pressure is 1 × 10 ^-5 T
After pulling to orr, flow 50 SCCM of CF ₄ gas,
200 W is applied at 5 × 10 ⁻² Torr to etch W.

Chromium is hardly etched by CF ₄ gas, so that it is not damaged and the X-ray absorber is as shown at 26 'in FIG. 2 (d). The resist pattern 25 is simultaneously etched during the etching of W, but the remaining pattern is stripped with a dedicated stripping solution. At this time, the X-ray absorber 2
When the pattern positional distortion amount of 6 ′ was measured by a light wave interference type coordinate measuring machine, the maximum distortion amount was 0.5 μm. Oxidation conditions are selected according to this strain amount. Oxygen gas 20SCCM is flown in the same RIE device and 5 × 10 ^-2 Tor is applied.
X-ray absorber 2 by applying 130 W at r and oxygen plasma
The tungsten oxide 27 and the non-patterned portion of the metal thin film 23 are chromium oxide 28 on the surface of 6 ', resulting in FIG. 2 (e).

As described above, by oxidizing the metal thin film of chromium that is the etching stopper without peeling it off, it was possible to prevent the occurrence of the film thickness distribution of silicon carbide that is the X-ray transparent film. Further, due to the presence of the chromium oxide 27 in the non-patterned portion, the X-ray transmittance is 2.3%, and the He-Ne laser (6328Å) used for alignment has a transmittance of 5.0%.
There is no problem because it has only decreased by%. Also, again the X-ray absorber 2
When the amount of positional distortion of 6'was measured by a light wave interference type coordinate measuring machine, the amount of positional distortion was reduced to 0.05 μm and it can be used as a high precision X-ray mask.

Embodiment 3 FIG. 3 is a sectional view of the X-ray mask manufacturing process of the third embodiment of the present invention. A Si wafer is often used as the substrate 31 that serves as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus.
First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 31 is heated to 250 ° C. and the pressure is set to 5 × 1.
A high-frequency power of 20 W was applied at 0 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt to form an X-ray transparent film 32. Then Si
The wafer is back-etched with 30 wt% potassium hydroxide at 110 ° C. to form a holding frame 31, which is shown in FIG.

Further, the back pressure was set to 2 × 10 ^-6 Torr by setting it in a two-way sputtering apparatus, and then Ar gas of 10 SC was used.
CM pressure of 10 × 10 ^-2 Torr and substrate temperature of 150
C., high frequency power of 100 W is applied to form a film of chromium 100 Å to be the metal thin film 33 for the absorber etching stopper, and 500 W is continuously applied to form film of 8,000 Å W to be the X-ray absorber 36. It becomes FIG.3 (b). The metal thin film 33 used may be any metal as long as it has a difference in etching rate from the metal used for the X-ray absorber. Then, electron beam resist PMMA (OEBR-1
000 product name: manufactured by Tokyo Ohka Co., Ltd., and a desired fine resist pattern 35 is formed by an electron beam drawing apparatus.
(C).

Next, etching of W to be the X-ray absorber 36 is performed by the RIE apparatus. Back pressure is 1 × 10 ^-5 Torr
After pulling up to 50, CF ₄ gas 50SCCM is made to flow, 5 × 1
200 W is applied at 0 ⁻² Torr to etch W.
Chromium is hardly etched by CF ₄ gas, so it is not damaged and the X-ray absorber is 3 in FIG. 3 (d).
It looks like 6 '. The resist pattern 35 is simultaneously etched during the etching of W, but the remaining one is stripped by a dedicated stripping solution.

At this time, when the pattern positional distortion amount of the X-ray absorber 36 'was measured by the light wave interference type coordinate measuring machine, the maximum distortion amount was 0.3 μm. Oxidation conditions are selected according to this strain amount. Next, heat treatment is performed at 100 ° C. in an oxygen atmosphere to form tungsten oxide 37 on the extreme surface of the absorber 36 ′ and chromium oxide 38 on the non-patterned portion of the metal thin film 33, resulting in FIG. 3 (e). . By oxidizing chromium, which is the metal thin film for adhesion, without peeling off, the thickness of gold, which is the X-ray absorber 36 ', is reduced, and the film thickness distribution of silicon nitride, which is the X-ray transparent film, is generated. I was able to prevent it. Further, due to the presence of chromium oxide 38 in the non-patterned portion, the X-ray transmittance is 0.3%, and He used for the alignment is used.
The transmittance of the -Ne laser (6328Å) was reduced by only 1.0%, and there was no problem at all. Also, again the X-ray absorber 3
When the amount of positional distortion of 6'was measured by a light wave interference type coordinate measuring machine, the amount of positional distortion was reduced to 0.05 μm and it can be used as a high precision X-ray mask.

Embodiment 4 FIG. 4 is a sectional view of the X-ray mask manufacturing process of the fourth embodiment of the present invention. A Si wafer is often used as the substrate 41 serving as a holding frame. Silicon nitride was added to 2 μm in the same manner as in Example 3.
The film was formed on mt to form an X-ray transparent film 42. Nickel 20 as a metal thin film 43 to be a plating electrode for X-ray absorber film formation
0Å is vapor-deposited by EB vapor deposition, resulting in FIG. An electron beam resist PMMA (OEBR-1000, trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied thereon, and a desired fine resist pattern 45 is formed by an electron beam drawing apparatus, as shown in FIG. 4 (b).

Next, using a gold sulfite plating solution (Nutronex 309, trade name: manufactured by EEJA), plating is performed under the conditions of 50 ° C. and a current density of 0.5 mA / cm ^2. Is formed, and the resist pattern 45 is peeled off with a dedicated peeling solution, as shown in FIG. Furthermore, Si
The wafer is back-etched with 30 wt% potassium hydroxide at 110 ° C. to form a holding frame 41, which is shown in FIG. At this time, when the pattern positional distortion amount of the X-ray absorber 46 was measured by a light wave interference type coordinate measuring machine, the maximum distortion amount was 0.2 μm. Oxidation conditions are selected according to this strain amount. Finally, the oxygen ion concentration is 1 in the ion implanter.
Implantation at 0 ¹⁶ to 10 ¹⁷ ions / cm ² 20 to 30 KV,
The gold oxide 47 is used as the extreme surface of the absorber 46, and the nickel oxide 48 is used as the non-patterned portion of the metal thin film 43.
Becomes If ion implantation is used, a relatively thick film can be oxidized by selecting an appropriate ion concentration and accelerating voltage. Therefore, a metal thin film may be formed so that the thickness of nickel oxide becomes an antireflection film (690 Å for He-Ne laser).

As described above, by oxidizing the metal thin film nickel without peeling it off, the film thickness of gold, which is the X-ray absorber 46, is reduced, and the film thickness distribution of silicon nitride, which is the X-ray transparent film, is generated. I was able to prevent it. Further, due to the presence of the nickel oxide 47 in the non-patterned portion, the X-ray transmittance is 4.2%, and the He-Ne laser (6,328) used for alignment is used.
The transmittance of Å) was reduced only by 5.0%, and there is no problem at all. Further, when the positional distortion amount of the X-ray absorber 46 was measured again by the light wave interference type coordinate measuring machine, the positional distortion amount was 0.03 μm.
m (measurement limit) and can be used as a high precision X-ray mask.

(Second Invention) Embodiment 1 FIG. 5 is a sectional view of an X-ray mask manufacturing process according to the first embodiment of the present invention. A Si wafer is often used as the substrate 11 serving as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus.
First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 11 is heated to 250 ° C. and the pressure is set to 5 × 1.
A high frequency power of 20 W was applied at 0 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt to form an X-ray transparent film 12.

Further, the substrate was set in a sputtering apparatus, and silicon oxide to be the antireflection film 18 was formed to a thickness of 111 nm, as shown in FIG. The thickness of silicon oxide is 17.5 for a He-Ne laser that is actually used for alignment.
The thickness at which the reflectance was minimized was selected during film formation at an angle of °. The resist is patterned in the form of scribe lines that correspond to the peripheral part of the circuit pattern, and RIE is performed.
Flowing CF ₄ gas 20SCCM in the equipment, 5 × 10 ^-2 T
100 W is applied at orrr and etching is performed to form an antireflection film 18 'in the form of a scribe line. If there is residual resist, it is peeled off, and the result is shown in FIG.

Gold 50 nm serving as the plating electrode 14 for forming the X-ray absorber and chromium 5 nm serving as the adhesion metal thin film 13
Is continuously vapor-deposited by EB vapor deposition, resulting in FIG. The metal thin film 13 may be a metal such as Ti, Al, or Zn that can improve the adhesive force. An electron beam resist PMMA (OEBR-1000, trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied thereon, and a desired fine resist pattern 15 is formed by an electron beam drawing apparatus, as shown in FIG. 5 (d). Next, a gold sulfite plating solution (Nutronex 309, trade name: EEJ
Using steel A), subjected to plating at 50 ° C., a current density of 1 mA / cm ² conditions, to form a gold comprising an X-ray absorber 16 and the alignment mark 17, the resist pattern 15 is peeled off by a dedicated stripping solution , FIG. 5 (e).

X-ray absorber 16 and alignment mark 1
Peeling of the plated electrode 14 in the area without 7 is performed by an RIE device. After back pressure is reduced to 1 × 10 ^-5 Torr, argon gas of 20 SCCM is flown and 5 × 10 ^-2 Torr is applied.
00 W is applied and etching is performed. Since the plating electrode 14, the X-ray absorber 16 and the alignment mark 17 are made of gold, they are uniformly etched, and the X-ray absorber has 16 'and the alignment mark 17', as shown in FIG. 5 (f). Further, 20 SCCM of CCl ₄ gas and 5 SCCM of oxygen gas are made to flow in the RIE device, and 200 W at 5 × 10 ^-2 Torr.
5G is applied to etch the metal thin film 13.
Becomes

Finally, the Si wafer was back-etched with 30% by weight potassium hydroxide at 110 ° C. to obtain a holding frame 1.
1 is formed and is referred to as FIG. FIG. 5 is a plan view.
As shown in (i), the antireflection film 18 'exists only on the scribe line. FIG. 11 is a simplified diagram of the X-ray exposure apparatus of the present invention, and 8 is an exposure chamber. 1 is a Be port, 9 is an exhaust port, and the exposure chamber 8
Is shielded from the X-ray source by Be, and the atmosphere in the chamber is
It is possible to perform exposure under various conditions such as vacuum and He atmosphere. 2 is a mask stage, 3 is an alignment detector, 4
Is a mask, 5 is a wafer (semiconductor substrate), 6 is a wafer chuck, and 7 is a wafer stage.

When the mask 4 is attracted to the mask stage 2, the mask 4 is mechanically set in a predetermined direction by using a positioning pin or an orientation flat.
The wafer 5 is also set on the wafer chuck 6 in the same manner,
The relative positional relationship between the mask 4 and the wafer 5 is determined by an instruction from the alignment detector 3 and then exposed by X-ray. As shown in FIG. 5 (h), by providing the silicon oxide as the antireflection film only on the scribe line, the reflection of the alignment light is prevented, the film thickness of gold as the X-ray absorber 16 ′ is reduced, and the oxidation is prevented. It is possible to prevent the displacement of gold, which is the X-ray absorber 16 ′, from occurring due to the stress of silicon and its change. Such a mask is set in the exposure chamber 8 and the He-Ne laser (633n
m) When alignment was performed using alignment light at an angle of 17.5 °, stable alignment light transmittance could be obtained, and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast can be obtained without reducing the film thickness of the X-ray absorber, and the occurrence of positional deviation can be prevented, so that a highly accurate semiconductor chip can be manufactured. Was completed.

Embodiment 2 FIG. 6 is a sectional view of the X-ray mask manufacturing process of the second embodiment of the present invention. A Si wafer is often used as the substrate 21 serving as the holding frame. This time, the one with 3 inches φ1 mmt was used. The substrate is set in the plasma CVD apparatus.
First, after the back pressure was reduced to 1 × 10 ⁻⁶ Torr, 10 SCCM of silane gas and 10 SCCM of methane gas diluted with hydrogen to 10% were supplied through the holes formed in the lower electrode. The temperature of the substrate 21 is heated to 650 ° C. and the pressure is set to 5 × 10.
^A high-frequency power of 50 W was applied at ^-3 Torr to form a silicon carbide film having a thickness of 2 μmt to form an X-ray transparent film 22.

Further, after setting in a two-source sputtering apparatus and pulling back pressure up to 2 × 10 ^-6 Torr, Ar gas 10 SC
CM pressure of 10 × 10 ^-2 Torr and substrate temperature of 150
At 50 ° C., a high frequency power of 100 W is applied to form a film of chromium having a thickness of 50 nm that becomes the absorber etching stopper metal thin film 23. a). The metal thin film 23 used may be any metal as long as it has a difference in etching rate from the metal used for the X-ray absorber. Si wafer is 110 with 30 wt% potassium hydroxide
Back etching is performed at ℃ to form a holding frame 21.
(B).

PIQ which is the lower layer of the two-layer resist
(Product name: manufactured by Hitachi Chemical Co., Ltd.), Si-containing resist SNR (product name: Toyo Soda Co., Ltd.), which is an upper layer, is applied, and a desired fine resist pattern 25 is formed by an electron beam drawing apparatus.
(C). Then, etching of W to be the X-ray absorber 26 is performed by the RIE apparatus. Back pressure is 1 × 10 ^-5 Tor
After pulling to r, CF ₄ gas 50SCCM is flowed, and 5 ×
200 W is applied at 10 ⁻² Torr to etch W. Chromium is hardly etched by CF ₄ gas, so it is not damaged and the X-ray absorber is shown in FIG. 6 (d).
26 'and the alignment mark 27. The resist pattern 25 is simultaneously etched during the etching of W, but the remaining pattern is stripped with a dedicated stripping solution. A protective film 29 is provided on the circuit pattern portion with a novolac resist (AZ
-1370SF product name: manufactured by Tokyo Ohka Co., Ltd., and becomes as shown in FIG. 6 (e).

Further, in the RIE apparatus, oxygen gas 20SC
By flowing CM and applying 200 W at 5 × 10 ^-2 Torr and irradiating oxygen plasma, the non-alignment mark forming portion of the metal thin film 23 in the range used for alignment is made of chromium oxide 63 nm which becomes the antireflection film 28, and 6 (f)
And The remaining protective film 29 is peeled off with a dedicated peeling liquid,
It becomes FIG.6 (g). As described above, the antireflection film is formed by oxidizing the metal thin film of chromium, which is the etching stopper of the non-alignment mark forming part in the range used for alignment, without peeling off, thereby preventing reflection of alignment light and oxidation. Without causing displacement of the tungsten that is the X-ray absorber 26 ′ due to the stress of chromium and its change, the thickness of the tungsten is reduced, and the thickness distribution of the silicon carbide that is the X-ray transparent film in the range used for alignment is reduced. It is also possible to prevent the occurrence of damage and damage to the film surface.

When such a mask is set in the exposure chamber 8 and alignment is performed using He-Ne laser (633 nm) alignment light, stable alignment light transmittance can be obtained, and highly accurate alignment is achieved. I was able to do it. Further, in exposure with X-rays, sufficient contrast can be obtained without reducing the film thickness of the X-ray absorber, and the occurrence of positional deviation can be prevented, so that a highly accurate semiconductor chip can be manufactured. Was completed.

Embodiment 3 FIG. 7 is a sectional view of the X-ray mask manufacturing process of the third embodiment of the present invention. A Si wafer is often used as the substrate 31 that serves as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus.
First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 31 is heated to 350 ° C. and the pressure is set to 5 × 1.
A high-frequency power of 20 W was applied at 0 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt to form an X-ray transparent film 32.

Nickel 55 nm as a metal thin film 33 to be a plating electrode for depositing the X-ray absorber is vapor-deposited by EB vapor deposition, resulting in FIG. Further, the Si wafer is back-etched with 30 wt% potassium hydroxide at 110 ° C.,
The holding frame 31 is formed and is shown in FIG. An electron beam resist PMMA (OEBR-1000, trade name: made by Tokyo Ohka Co., Ltd.) is applied thereon, and a desired fine resist pattern 35 is formed by an electron beam drawing apparatus, as shown in FIG. 7 (c). next,
Gold sulfite plating solution (Nutronex 309 product name:
(Manufactured by EEJA), 50 ° C, current density 0.5 mA / c
Plating is performed under the condition of m ² to form gold as the X-ray absorber 36 and the alignment mark 37, and the resist pattern 35 is peeled off with a dedicated peeling solution, as shown in FIG. 7 (d).

Finally, oxygen ion concentration of 10 ¹⁶ to 10 ¹⁷ ions / cm ² 60 to 70 KV is implanted in the focused ion implanter to remove the metal thin film 33 in the non-alignment mark forming portion in the range used for alignment. Nickel oxide 69 nm is formed as the antireflection film 38, and the result is shown in FIG. In this way, nickel, which is a metal thin film, is oxidized without forming only the non-alignment mark portion in the range used for alignment to form an antireflection film, thereby preventing the reflection of alignment light, and stress of nickel oxide and its change. As a result, the gold film thickness is reduced without causing displacement of the gold which is the X-ray absorber 36, the film thickness distribution of the silicon nitride which is the X-ray transparent film in the range used for alignment is generated, and the film surface is damaged. Can also be prevented.

When such a mask is set in the exposure chamber 8 and alignment is performed using He-Ne laser (633 nm) alignment light, stable alignment light transmittance can be obtained, and highly accurate alignment is achieved. I was able to do it. Further, in exposure with X-rays, sufficient contrast can be obtained without reducing the film thickness of the X-ray absorber, and the occurrence of positional deviation can be prevented, so that a highly accurate semiconductor chip can be manufactured. Was completed.

Embodiment 4 FIG. 8 is a sectional view of the X-ray mask manufacturing process of the fourth embodiment of the present invention. A Si wafer is often used as the substrate 41 serving as a holding frame. Silicon carbide was added to 2 μm in the same manner as in Example 2.
The film was formed on the mt to form the X-ray transparent film 42, which is shown in FIG. Further, the Si wafer is back-etched with 30 wt% potassium hydroxide at 110 ° C. to form a holding frame 41, which is shown in FIG. 8B. A polyimide film (PIQ-L100, trade name: manufactured by Hitachi Chemical Co., Ltd.) which becomes the antireflection film 48 is formed by 93.
nm is applied to both surfaces, and the result is shown in FIG.

A Si-containing resist (SNR product name: Toyo Soda Co., Ltd.) is patterned in the form of a scribe line corresponding to the peripheral portion of the circuit pattern, as shown in FIG. 8 (d). Next, it was set in the RIE apparatus, O ₂ gas 20SCCM was flowed, 100 W was applied at 5 × 10 ^-2 Torr, and etching was performed to form an antireflection film 48 ′ only on the scribe line. If there is residual resist, it is stripped with a dedicated stripping solution, and the result is shown in FIG. A dedicated stripping solution (PIQ etchant product name: manufactured by Hitachi Chemical Co., Ltd.) may be used for etching the polyimide. Furthermore, set it on the sputter device and set the back pressure to 2
Ar gas 10SCCM after drawing to × 10 ^-6 Torr
At a pressure of 10 × 10 ^-2 Torr, a substrate temperature of 150 ° C., a high frequency power of 500 W is applied to form a film of W serving as the X-ray absorber 46 to a thickness of 800 nm, as shown in FIG.

Polyimide (PIQ product name: manufactured by Hitachi Chemical), which is the lower layer of the two-layer resist, and Si, which is the upper layer, are formed thereon.
Apply the contained resist (SNR product name: Toyo Soda),
A desired fine resist pattern 45 is formed by an electron beam drawing apparatus, and the result is shown in FIG. Next, etching of W that becomes the X-ray absorber 46 and the alignment mark 47 is performed by the RIE apparatus. After pulling back pressure to 1 × 10 ^-5 Torr,
A CF ₄ gas of 50 SCCM is flown, 200 W is applied at 5 × 10 ⁻² Torr, and W is etched to obtain FIG. 8H.

As described above, by providing the polyimide as the antireflection film only on the cliff line, the reflection of the alignment light is prevented and the stress of the polyimide or its change causes X.
It is possible to prevent the displacement of the tungsten, which is the line absorber 46, from occurring. Such a mask is used for the exposure chamber 8
When it was set to, and alignment was performed using He-Ne laser (633 nm) alignment light, stable alignment light transmittance could be obtained, and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast can be obtained without reducing the film thickness of the X-ray absorber, and the occurrence of positional deviation can be prevented, so that a highly accurate semiconductor chip can be manufactured. Was completed.

Embodiment 5 FIG. 9 is a sectional view of an X-ray mask manufacturing process of the fifth embodiment of the present invention. A Si wafer is often used as the substrate 51 serving as a holding frame. Silicon nitride was added to 2 μm in the same manner as in Example 3.
The film was formed on mt to form an X-ray transparent film 52. Furthermore, after setting to a sputtering device and pulling back pressure to 2 × 10 ⁻⁶ Torr, pressure was 10 × 10 ⁻² Tor with Ar gas 10 SCCM.
r, substrate temperature of 120 ° C., and high-frequency power of 400 W were applied to form a Ta film of X-ray absorber 56 having a thickness of 800 nm.
(A). Polyimide (PIQ product name: Hitachi Chemical Co., Ltd.) that is the lower layer of the two-layer resist and S that is the upper layer
i-containing resist (SNR product name: Toyo Soda Co., Ltd.) is applied, and a desired fine resist pattern 4 is formed by an electron beam drawing apparatus.
5 is formed and is shown in FIG.

Next, Ta of the X-ray absorber 56 'and the alignment mark 57 is etched by the RIE apparatus. After pulling back pressure to 1 × 10 ^-5 Torr, CBrF
Flowing a ₃ gas 50 SCCM, 10 at 5 × 10 ^-2 Torr
By applying 0 W and etching Ta, the result is shown in FIG.
The resist pattern 55 is etched at the same time as Ta is etched, but the remaining pattern is stripped with a dedicated stripping solution. Further, the Si wafer is back-etched with 30 wt% potassium hydroxide at 110 ° C. to form a holding frame 51, which is shown in FIG. A protective film 59 is provided on the circuit pattern portion with a novolac resist (AZ-1370SF, trade name:
Formed in the shape of a scribe line by Tokyo Ohka)
It becomes like (e).

Further, the substrate was set in an EB vapor deposition apparatus, and silicon oxide to be the antireflection film 58 was formed to a thickness of 111 nm, as shown in FIG. 9 (f). The protective film 59 was lifted off with a dedicated stripping solution to obtain FIG. In this way, by providing the silicon oxide that is the antireflection film only on the clibrain, the reflection of the alignment light is prevented, and the Ta that is the X-ray absorber 56 ′ is prevented due to the stress of the silicon oxide and its change.
It is possible to prevent the occurrence of misalignment. When such a mask is set in the exposure chamber 8 and alignment is performed using He-Ne laser (633 nm) alignment light at an angle of 17.5 °, a stable alignment light transmittance can be obtained, which is high. We were able to perform accurate alignment. Further, in exposure with X-rays, sufficient contrast can be obtained without reducing the film thickness of the X-ray absorber, and the occurrence of positional deviation can be prevented, so that a highly accurate semiconductor chip can be manufactured. Was completed.

Embodiment 6 FIG. 12 is a sectional view of the X-ray mask manufacturing process of the sixth embodiment of the present invention. A Si wafer is often used as the substrate 81 serving as the holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 81 is heated to 250 ° C. and the pressure is set to 5
A high-frequency power of 20 W was applied at × 10 ⁻³ Torr to deposit silicon nitride to a thickness of 2 μmt to form an X-ray transparent film 82. Further, the substrate is set in a sputtering apparatus, and chromium oxide 88 which is a part of the antireflection film is formed to a thickness of 57 nm.
(A). The resist is patterned in the shape of a scribe line corresponding to the peripheral portion of the circuit pattern and etched to form a part 88 'of the antireflection film in the shape of the scribe line.
To form. If there is any remaining resist, it is peeled off and the result is shown in FIG.

Gold 50 nm serving as the X-ray absorber film-forming plating electrode 84 and chromium 5 nm serving as the adhesion metal thin film 83.
Is continuously vapor-deposited by EB vapor deposition, resulting in FIG. Electron beam resist PMMA (OEBR-1000)
A product name: manufactured by Tokyo Ohka Co., Ltd. is applied, and a desired fine resist pattern 85 is formed by an electron beam drawing apparatus, as shown in FIG. Next, a gold sulfite plating solution (Nutronex 30
9 Trade name: EEJA), 50 ℃, current density 1
The X-ray absorber 86 is plated under the condition of mA / cm ^2.
And gold to be the alignment mark 87 is formed, and the resist pattern 85 is peeled off with a dedicated peeling solution, as shown in FIG.
Becomes The peeling of the plating electrode 84 at the portion where the X-ray absorber 86 and the alignment mark 87 are not present is performed by an RIE device. After reducing the back pressure to 1 × 10 ^-5 Torr, argon gas of 20 SCCM is flown and the pressure is 5 × 10 ^-2 Torr to 200.
W is applied and etching is performed. Since both the plating electrode 84, the X-ray absorber 86 and the alignment mark 87 are made of gold, they are uniformly etched. The X-ray absorber has 86 'and the alignment mark has 87', as shown in FIG.

Further, in the RIE device, oxygen gas 20SC
CM was flown, 200 W was applied at 5 × 10 ⁻² Torr, and oxygen plasma was irradiated to form chromium oxide in the non-patterned portion of the metal thin film 83, which was previously formed 8
8'and chromium oxide 63 nm and an antireflection film 88 "are formed, which is shown in FIG. 12G. Finally, the Si wafer is back-etched with 30 wt% potassium hydroxide at 110 ° C. As shown in Fig. 12 (h), chromium oxide is formed on the entire non-patterned portion on the X-ray transparent film, unlike in Examples 1 to 5, as shown in Fig. 12 (h). Because of its extremely thin thickness, the stress of chromium oxide and its changes do not affect the positional shift of the X-ray absorber 86 '. It also functions as an antireflection film, and can prevent the reduction of the film thickness of gold which is the X-ray absorber 86 ′.

When such a mask is set in the exposure chamber 8 and alignment is performed using He-Ne laser (633 nm) alignment light, stable alignment light transmittance can be obtained, and highly accurate alignment is achieved. I was able to do it. Also, in the exposure with X-ray,
Since it is possible to obtain a sufficient contrast without reducing the film thickness of the X-ray absorber and prevent the occurrence of displacement, it is possible to manufacture a highly accurate semiconductor chip.

(Third Invention) Embodiment 1 FIG. 13 is a sectional view of an X-ray mask manufacturing process according to the first embodiment of the present invention. A Si wafer is often used as the substrate 11 serving as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 11 is heated to 250 ° C. and the pressure is set to 5
A high frequency power of 20 W was applied at × 10 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt to form an X-ray transparent film 12.

500 Å of gold which becomes the plating electrode 14 for X-ray absorber film formation, and 50 Å of chromium as the metal thin film 13 for adhesion.
Is continuously vapor-deposited by EB vapor deposition, resulting in FIG. The metal thin film 13 may be a metal such as Ti, Al, or Zn that can improve the adhesive force. An electron beam resist PMMA (OEBR-1000, trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied on top of this, and a desired fine resist pattern 15 is formed by an electron beam drawing apparatus, as shown in FIG. Next, a gold sulfite plating solution (Nutronex 309, trade name: EE
(Made by JA) at 50 ° C. and a current density of 1 mA / cm ² for plating to form gold that will serve as the X-ray absorber 16 and the alignment mark 17, and the resist pattern 15 is peeled off with a dedicated peeling solution. 13 (c).

X-ray absorber 16 and alignment mark 1
Peeling of the plated electrode 14 in the area without 7 is performed by an RIE device. After back pressure is reduced to 1 × 10 ^-5 Torr, argon gas of 20 SCCM is flown and 5 × 10 ^-2 Torr is applied.
00 W is applied and etching is performed. Since both the plating electrode 14 and the X-ray absorber are gold, they are uniformly etched, and the X-ray absorber has 16 'and the alignment mark has 17'.
It becomes like 3 (d). The protective film 18 is formed on the circuit pattern portion with a novolac-based resist (AZ-1370SF, trade name: manufactured by Tokyo Ohka Co., Ltd.), as shown in FIG. Furthermore,
Oxygen gas 20SCCM is made to flow in the RIE device and 5 × 1
200 W was applied at 0 ^-2 Torr, and the non-alignment mark forming portion of the metal thin film 13 on the scribe line was made to be chromium oxide 19 by oxygen plasma, resulting in FIG.

The protective film 18 is peeled off with a dedicated peeling solution,
It becomes 3 (g). An inorganic film such as SiO ₂ may be formed as the protective film 18 by sputtering or the like, and may be left as the protective film of the X-ray mask. Finally, the Si wafer was back-etched with 3% by weight potassium hydroxide at 110 ° C. to form a holding frame 1.
1 is formed to obtain FIG. FIG. 1 is a plan view.
It becomes like 3 (i). FIG. 18 is a simplified diagram of the X-ray exposure apparatus of the present invention, and 8 is an exposure chamber. 1 is a Be port, 9 is an exhaust port, and the exposure chamber 8
Is shielded from the X-ray source by Be, and the atmosphere in the chamber is
It is possible to perform exposure under various conditions such as vacuum and He atmosphere.

Reference numeral 2 is a mask stage, 3 is an alignment detector, 4 is a mask, 5 is a wafer (semiconductor substrate), 6 is a wafer chuck, and 7 is a wafer stage. When the mask 4 is attracted to the mask stage 2, the mask 4 is mechanically set in a direction determined to some extent by using a positioning pin or an orientation flat. The wafer 5 is similarly set on the wafer chuck 6, the relative positional relationship between the mask 4 and the wafer 5 is determined by an instruction from the alignment detection unit 3, and then exposed by X-ray.

The mask as shown in FIG. 13 (h) is formed by oxidizing chromium, which is a metal thin film for adhesion, without oxidizing only the non-alignment mark portion on the scribe line, thereby removing the gold of X-ray absorber 16 '. In order to prevent the film thickness from being reduced, the film thickness distribution of silicon nitride, which is an X-ray transmission film on the scribe line, and the film surface from being damaged, the exposure chamber 8 is used.
When the alignment was performed using He-Ne laser (633 nm) alignment light, stable alignment light transmittance could be obtained, and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 2 FIG. 14 is a cross-sectional view of the X-ray mask manufacturing process of the second embodiment of the present invention. A Si wafer is often used as the substrate 21 serving as the holding frame. This time, the one with 3 inches φ1 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 1 × 10 ⁻⁶ Torr, 10 SCCM of silane gas and 10 SCCM of methane gas diluted with hydrogen to 10% were supplied through the holes formed in the lower electrode. The temperature of the substrate 21 is heated to 650 ° C. and the pressure is 5 ×.
A high-frequency power of 50 W was applied at 10 ⁻³ Torr to form a silicon carbide film having a thickness of 2 μmt to form an X-ray transparent film 22.

Further, after setting in a two-source sputtering apparatus and pulling back pressure up to 2 × 10 ^-6 Torr, Ar gas 10 SC
CM pressure of 10 × 10 ^-2 Torr and substrate temperature of 150
C., high frequency power of 100 W is applied to form a film of chromium 200 Å which becomes the absorber etching stopper metal thin film 23, and further 500 W is continuously applied to form W of X-ray absorber 26 of 8,000 Å. It becomes FIG. 14 (a). The metal thin film 23 used may be any metal as long as it has a difference in etching rate from the metal used for the X-ray absorber. Si wafer 11 with 3 wt% potassium hydroxide
Back etching is performed at 0 ° C. to form a holding frame 21, which is shown in FIG. A two-layer resist lower layer PIQ (trade name: manufactured by Hitachi Chemical Co., Ltd.) and an upper layer Si-containing resist SNR (trade name: Toyo Soda Co., Ltd.) are applied thereon, and a desired fine resist pattern 25 is formed by an electron beam drawing apparatus. To form FIG. 14 (c).

Next, etching of W to be the X-ray absorber 26 is performed by the RIE apparatus. Back pressure is 1 × 10 ^-5 Torr
After pulling up to 50, CF ₄ gas 50SCCM is made to flow, 5 × 1
200 W is applied at 0 ⁻² Torr to etch W.
Since chromium is hardly etched by CF ₄ gas, it is not damaged, and the X-ray absorber becomes 26 'and alignment mark 27 in FIG. 14 (d). The resist pattern 25 is simultaneously etched during the etching of W, but the remaining pattern is stripped with a dedicated stripping solution.

A novolac-based resist (AZ-1370SF, trade name: manufactured by Tokyo Ohka) with a protective film 28 on the circuit pattern portion.
And is formed as shown in FIG. Further, 20 SCCM of oxygen gas was flown in the RIE apparatus to obtain 5 × 10 ^-2 To
14F by applying 200 W at rr and using chromium oxide 29 as the non-alignment mark forming portion of the metal thin film 23 in the range used for alignment by oxygen plasma. The protective film 28 is peeled off with a dedicated peeling liquid, and the result is shown in FIG.

As described above, by oxidizing the metal thin film of chromium, which is the etching stopper of the non-alignment mark forming portion in the range used for alignment, without peeling off, the film thickness distribution of silicon carbide, which is the X-ray transparent film, can be improved. In order to prevent generation and damage of the film surface, the He-Ne laser (633 nm) was set in the exposure chamber 8 in the same manner as in Example 1.
When alignment was performed using alignment light, stable alignment light transmittance could be obtained and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 3 FIG. 15 is a sectional view of the X-ray mask manufacturing process of the third embodiment of the present invention. A Si wafer is often used as the substrate 31 that serves as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 31 is heated to 350 ° C. and the pressure is set to 5
A high-frequency power of 20 W was applied at × 10 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt to form an X-ray transparent film 32.

500 Å of gold which becomes the plating electrode 34 for forming the X-ray absorber and 50 Å of titanium as the metal thin film 33 for adhesion.
Is continuously vapor-deposited by EB vapor deposition, resulting in FIG. Next, the Si wafer is treated with 3 wt% potassium hydroxide at 110 ° C.
Back etching is performed to form a holding frame 31, and then, as shown in FIG.
(B). Electron beam resist PMMA (OE
BR-1000 (trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied, and a desired fine resist pattern 35 is formed by an electron beam drawing apparatus, as shown in FIG. Next, using a gold sulfite plating solution (Nutronex 309, trade name: manufactured by EEJA), 5
Plating is performed under the conditions of 0 ° C. and a current density of 1 mA / cm ² to form gold to be the X-ray absorber 36 and the alignment mark 37, and the resist pattern 35 is peeled off with a dedicated peeling solution, as shown in FIG. Becomes

X-ray absorber 36 and alignment mark 3
The plating electrode 34 in the portion where there is no 7 is peeled off by the RIE device. After back pressure is reduced to 1 × 10 ^-5 Torr, argon gas of 20 SCCM is flown and 5 × 10 ^-2 Torr is applied.
00 W is applied and etching is performed. Since both the plating electrode 34, the X-ray absorber and the alignment mark are made of gold, they are uniformly etched, and the X-ray absorber 36 'and the alignment mark 37' are obtained, as shown in FIG. 15 (e). A protective film 38 is formed on the circuit pattern portion using a novolac resist (AZ-13).
70SF product name: manufactured by Tokyo Ohka)
It becomes like (f).

Further, heat treatment is performed at 100 ° C. in an oxygen atmosphere to form the titanium oxide 39 in the non-alignment mark forming portion of the metal thin film 33 in the range used for alignment.
(G). The protective film 38 is peeled off with a dedicated peeling solution, and the result is shown in FIG. An inorganic film such as SiO ₂ may be formed as the protective film 38 by sputtering or the like, and may be left as the protective film of the X-ray mask. Thus, by oxidizing the chromium, which is the adhesion metal thin film, without etching only the non-alignment mark portion in the range used for alignment, it is possible to reduce the film thickness of gold which is the X-ray absorber 36 ′ and to perform alignment. In order to prevent the occurrence of film thickness distribution of silicon nitride, which is the X-ray transparent film in the range used, and damage to the film surface, the He-Ne laser (633n) was set in the exposure chamber 8 as in Example 1.
m) When alignment is performed using alignment light, stable alignment light transmittance can be obtained,
Moreover, it was possible to perform highly accurate alignment. Also, X
In the exposure with rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 4 FIG. 16 is a sectional view of the X-ray mask manufacturing process of the fourth embodiment of the present invention. A Si wafer is often used as the substrate 41 serving as a holding frame. Silicon nitride was added in the same manner as in Example 3.
It was formed into a film having a thickness of μmt to form an X-ray transparent film 42. Nickel 2 as the metal thin film 43 to be the plating electrode for X-ray absorber film formation
16 nm is vapor-deposited by EB vapor deposition, resulting in FIG.
Electron beam resist PMMA (OEBR-1000)
The product name: manufactured by Tokyo Ohka Co., Ltd. is applied, and a desired fine resist pattern 45 is formed by an electron beam drawing apparatus, and FIG.
And Next, a gold sulfite plating solution (Nutronex 3
09 product name: manufactured by EEJA), plating is performed under the conditions of 50 ° C. and a current density of 0.5 mA / cm ² to form gold to be the X-ray absorber 46, and the resist pattern 45 is removed with a dedicated stripping solution. It peels and it becomes FIG.16 (c). Further, the Si wafer is back-etched with 3 wt% potassium hydroxide at 110 ° C. to form a holding frame 41, which is shown in FIG.

Finally, oxygen ion concentration of 10 ¹⁶ to 10 ¹⁷ ions / cm ² 40 to 50 KV is implanted in the focused ion implanter to remove the metal thin film 43 in the non-alignment mark forming portion in the range used for alignment. As shown in FIG. 16E, nickel oxide 49 is used. If the focused ion implantation method is used, the steps of forming and peeling the protective film can be omitted. Also, if ion implantation is used, a relatively thick film can be oxidized by selecting an appropriate ion concentration and accelerating voltage. Therefore, nickel oxide has a thickness (H
A metal thin film may be formed so as to be 690 Å) for the e-Ne laser.

Thus, by oxidizing the metal thin film nickel without peeling off only the non-alignment mark portion in the range used for the alignment, it is possible to reduce the film thickness of the gold as the X-ray absorber 46 and to perform the alignment. In order to prevent the film thickness distribution of silicon nitride, which is the X-ray transparent film in the range used, and the film surface from being damaged, the He-Ne laser (633 nm) alignment light was set in the exposure chamber 8 as in Example 1. When alignment was performed using the same, stable alignment light transmittance could be obtained and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

(Fourth Invention) Embodiment 1 FIG. 19 is a sectional view of an X-ray mask manufacturing process according to the first embodiment of the present invention. A Si wafer is often used as the substrate 11 serving as a holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 11 is heated to 250 ° C. and the pressure is set to 5
A high frequency power of 20 W was applied at × 10 ⁻³ Torr to form a silicon nitride film having a thickness of 2 μmt to form an X-ray transparent film 12.

50 nm of gold to be the plating electrode 14 for forming the X-ray absorber and 50 n of chromium as the metal thin film 13 for adhesion.
m is continuously vapor-deposited by EB vapor deposition, resulting in FIG.
The metal thin film 13 may be a metal such as Ti, Al, or Zn that can improve the adhesive force. An electron beam resist PMMA (OEBR-1000, trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied thereon, and a desired fine resist pattern 15 is formed by an electron beam drawing apparatus, as shown in FIG. Next, a gold sulfite plating solution (Nutronex 309, trade name: E
(Made by EJA) at 50 ° C. and a current density of 1 mA / cm ² , plating is performed to form gold to be the X-ray absorber 16, and the resist pattern 15 is peeled off with a dedicated peeling solution. c). Peeling off of the plated electrode 14 in the portion where the X-ray absorber 16 is absent is performed by an RIE device.

After reducing the back pressure to 1 × 10 ⁻⁵ Torr,
Argon gas 20SCCM is flown, 5 × 10 ^-2 Torr
Then, 200 W is applied for etching. Since both the plating electrode 14 and the X-ray absorber are made of gold, they are uniformly etched, and the X-ray absorber becomes as shown at 16 'in FIG. 19 (d). Furthermore, oxygen gas 20SCCM is flown in the same RIE device, and 5 ×
Applying 200 W at 10 ^-2 Torr, oxygen plasma is applied to the non-patterned portion of the metal thin film 13 to form chromium oxide 64 nm.
Then, the antireflection film 17 is formed, as shown in FIG.
Further, the Si wafer is treated with 3 wt% potassium hydroxide at 110%.
Back etching is performed at ℃ to form a holding frame 11,
9 (f). FIG. 24 is a simplified diagram of the X-ray exposure apparatus of the present invention, and 8 is an exposure chamber. 1 is a Be port, 9 is an exhaust port, and the exposure chamber 8 is B port.
Since the X-ray generation source is shielded by e, the inside of the chamber can be exposed in various conditions such as the atmosphere, vacuum, and He atmosphere.

Reference numeral 2 is a mask stage, 3 is an alignment detector, 4 is a mask, 5 is a wafer (semiconductor substrate), 6 is a wafer chuck, and 7 is a wafer stage. When the mask 4 is attracted to the mask stage 2, the mask 4 is mechanically set in a direction determined to some extent by using a positioning pin or an orientation flat. The wafer 5 is similarly set on the wafer chuck 6, the relative positional relationship between the mask 4 and the wafer 5 is determined by an instruction from the alignment detection unit 3, and then exposed by X-ray.

The mask as shown in FIG. 19 (f) is made into chromium oxide by oxidizing chromium, which is a metal thin film for adhesion, without etching only the non-patterned portion, and is used as the antireflection film 17, whereby X-rays are formed. In order to prevent the alignment light from being reflected from the transmission film 12, to reduce the film thickness of gold which is the X-ray absorber 16 ′, to prevent the film thickness distribution of silicon nitride which is the X-ray transmission film from occurring, and to prevent the film surface from being damaged. When the alignment was performed by setting in the exposure chamber 8 and using He-Ne laser (633 nm) alignment light at an angle of 17.5 °, stable alignment light transmittance can be obtained and highly accurate alignment is performed. I was able to do it.
Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 2 FIG. 20 is a sectional view of the X-ray mask manufacturing process of the second embodiment of the present invention. A Si wafer is often used as the substrate 21 serving as the holding frame. This time, the one with 3 inches φ1 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 1 × 10 ⁻⁶ Torr, 10 SCCM of silane gas and 10 SCCM of methane gas diluted with hydrogen to 10% were supplied through the holes formed in the lower electrode. The temperature of the substrate 21 is heated to 650 ° C. and the pressure is 5 ×.
A high-frequency power of 50 W was applied at 10 ⁻³ Torr to form a silicon carbide film having a thickness of 2 μmt to form an X-ray transparent film 22.

[0112] Further, the back pressure was set to 2 x 10 ^-6 Torr after setting in the two-source sputtering apparatus, and then Ar gas was 10 SC.
CM pressure of 10 × 10 ^-2 Torr and substrate temperature of 150
20 ° C., a high frequency power of 100 W is applied to form a film of chromium having a thickness of 50 nm, which will be the metal thin film 23 for the absorber etching stopper, and a continuous application of 500 W to form a film of W, which will be the X-ray absorber 26, having a thickness of 800 nm. a). The metal thin film 23 used may be any metal as long as it has a difference in etching rate from the metal used for the X-ray absorber.

The Si wafer is back-etched with 3 wt% potassium hydroxide at 110 ° C. to form a holding frame 21, which is shown in FIG. 20 (b). PIQ (trade name: manufactured by Hitachi Chemical), which is the lower layer of the two-layer resist, and Si, which is the upper layer.
The contained resist SNR (trade name: Toyo Soda Co., Ltd.) is applied, and a desired fine resist pattern 25 is formed by an electron beam drawing apparatus, and the result is shown in FIG.

Next, etching of W to be the X-ray absorber 26 is performed by the RIE apparatus. Back pressure is 1 × 10 ^-5 Torr
After pulling up to 50, CF ₄ gas 50SCCM is made to flow, 5 × 1
200 W is applied at 0 ⁻² Torr to etch W.
Chromium is hardly etched by CF ₄ gas, so that it is not damaged and the X-ray absorber is as shown at 26 ′ in FIG. 20 (d). The resist pattern 25 is simultaneously etched during the etching of W, but the remaining pattern is stripped with a dedicated stripping solution. Next, in an oxygen atmosphere, 300 ° C
20E, the non-patterned portion of the chromium that is the metal thin film 23 is oxidized to 63 nm of chromium oxide, and the antireflection film 27 is obtained.

The mask as shown in FIG. 20E is formed by oxidizing chromium, which is a metal thin film for the absorber etching stopper, without etching only the non-pattern forming portion to form chromium oxide, and by forming the antireflection film 27. ,
The alignment light of the X-ray transmissive film 22 is prevented from being reflected, the film thickness of W that is the X-ray absorber 26 ′ is reduced, the film thickness distribution of silicon carbide that is the X-ray transmissive film is prevented, and the film surface is not damaged. Therefore, like the first embodiment, the exposure chamber 8 is set and H
When alignment was performed using e-Ne laser (633 nm) alignment light, stable alignment light transmittance could be obtained, and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 3 FIG. 21 is a sectional view of the X-ray mask manufacturing process of the third embodiment of the present invention. An N type or a lightly doped P type Si wafer is used as the substrate 31 that serves as a holding frame. This time, the one with 3 inches φ2 mmt was used. On the substrate, boron was diffused to a depth of 2 μm from the surface so as to have a concentration of 10 ²⁰ cm ⁻³ to form a boron diffusion layer, which was used as an X-ray transparent film 32.
21 (a). Furthermore, after setting to a sputtering device and pulling back pressure to 2 × 10 ⁻⁶ Torr, Ar gas 10 SCCM was used to set the pressure to 10 × 10 ⁻² Torr, the substrate temperature to 150 ° C., and the high frequency power of 500 W was applied to absorb the absorption. 21B is formed by forming a W film for the body 36 to a thickness of 800 nm.

On top of that, electron beam resist PMMA (OEB
R-1000 (trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied, and a desired fine resist pattern 35 is formed by an electron beam drawing apparatus, as shown in FIG. Then, etching of W to be the X-ray absorber 36 is performed by the RIE apparatus. Back pressure 1 × 10 ^-5
After the pressure is reduced to Torr, 50 SCCM of CF ₄ gas is flown and 200 W is applied at 5 × 10 ^-2 Torr to etch W. The X-ray absorber is as shown at 36 'in FIG. The resist pattern 35 is simultaneously etched during the etching of W, but the remaining one is stripped by a dedicated stripping solution.

Further, the oxygen ion concentration of 10 ¹⁶ to 10 ¹⁷ ions / cm ^{2 is} 70 to 80 KV is implanted in the focused ion implanter to make the silicon of the X-ray transparent film 32 silicon oxide 111 nm and the antireflection film. 21 to form FIG.
(E). If ion implantation is used, a relatively thick film can be oxidized by selecting an appropriate ion concentration and accelerating voltage. However, this time, the thinnest antireflection condition is 111 nm. Finally, Si was etched with a mixed solution of ethylenediamine and pyrocatechol at 115 ° C. to form a holding frame 31, which was shown in FIG.

By thus oxidizing the silicon non-absorber pattern forming portion which is the X-ray transparent film, the X-ray transparent film 3 is formed.
It was possible to prevent the reflection of the alignment light of No. 2. When the alignment chamber was set in the exposure chamber 8 in the same manner as in Example 1 and He-Ne laser (633 nm) alignment light was used at an angle of 17.5 °, stable alignment light transmittance was obtained, and We were able to perform highly accurate alignment. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 4 FIG. 22 is a sectional view of the X-ray mask manufacturing process of the fourth embodiment of the present invention. A Si wafer is often used as the substrate 41 serving as a holding frame. Silicon nitride was added in the same manner as in Example 1.
It was formed into a film having a thickness of μmt to form an X-ray transparent film 42. Nickel 5 as a metal thin film 43 to be a plating electrode for X-ray absorber film formation
FIG. 22 (a) is obtained by depositing 5 nm by EB vapor deposition.
Electron beam resist PMMA (OEBR-1000)
Product name: manufactured by Tokyo Ohka Co., Ltd. is applied, and a desired fine resist pattern 45 is formed by an electron beam drawing apparatus, as shown in FIG.
And

Next, using a gold sulfite plating solution (Nutronex 309, trade name: manufactured by EEJA), plating is performed under the conditions of 50 ° C. and a current density of 0.5 mA / cm ² to form the gold to be the X-ray absorber 46. 22C is formed, and the resist pattern 45 is peeled off with a dedicated peeling solution, resulting in FIG. Furthermore, S
The i-wafer is back-etched with 3 wt% potassium hydroxide at 110 ° C. to form a holding frame 41, and FIG.
And Finally, oxygen ion concentration of 10 ¹⁶ to 10 ¹⁷ ions / cm ² 60 to 70 KV is implanted in the focused ion implanter, and the non-patterned portion of the metal thin film 43, which is a plating electrode, is made to have a nickel oxide of 69 nm and is reflected. The prevention film 48 is formed, and the structure shown in FIG.

By oxidizing the metal thin film, nickel, without peeling off, the alignment light of the X-ray transparent film 42 is prevented from being reflected, and the film thickness of gold, which is the X-ray absorber 46, is reduced, and Since it is possible to prevent the generation of the film thickness distribution of silicon nitride, which is a line-transmissive film, the He-Ne laser (633 nm) is set in the exposure chamber 8 as in the first embodiment.
When alignment was performed using alignment light, stable alignment light transmittance could be obtained and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 5 FIG. 23 is a sectional view of the X-ray mask manufacturing process of the fifth embodiment of the present invention. The substrate 51 serving as a holding frame is an N-type or lightly-doped P-type Si wafer. This time, the one with 3 inches φ2 mmt was used. A boron diffusion layer is formed by diffusing boron so as to have a concentration of 10 ^{20 cm −3} at a depth of 2 μm from the surface of the substrate to form an X-ray transparent film 52, as shown in FIG. Furthermore, after setting it in the sputtering device and pulling back pressure to 2 × 10 ⁻⁶ Torr, Ar
A pressure of 10 × 10 ^-2 Torr, a substrate temperature of 120 ° C., and a high frequency power of 400 W are applied with a gas of 10 SCCM to form a film of Ta serving as the absorber 56 to a thickness of 800 nm, and the result is shown in FIG. Next, Si was etched at 115 ° C. with a mixed solution of ethylenediamine and pyrocatechol to form a holding frame 51, as shown in FIG.

PIQ which is the lower layer of the two-layer resist
23 (trade name: manufactured by Hitachi Chemical Co., Ltd.), an upper layer Si-containing resist SNR (trade name: Toyo Soda Co., Ltd.) is applied, and a desired fine resist pattern 55 is formed by an electron beam drawing apparatus.
(D). Next, Ta that becomes the X-ray absorber 56 is etched by the RIE apparatus. Back pressure is 1 × 10 ^-5 T
After the pressure is reduced to orr, 50 SCCM of CBrF ₃ gas is flown and 100 W is applied at 5 × 10 ^-2 Torr to etch Ta. The X-ray absorber is as shown at 56 'in FIG. The resist pattern 55 is etched at the same time as Ta is etched, but the remaining pattern is stripped with a dedicated stripping solution.

Finally, implantation with a nitrogen ion concentration of 10 ¹⁶ to 10 ¹⁷ ions / cm ² 40 to 50 KV is carried out in the focused ion implanter to make the silicon of the X-ray transparent film 32 80 nm of silicon nitride to prevent reflection. Forming the membrane 57, FIG.
(F). In this way, by nitriding the silicon non-absorber pattern forming portion which is the X-ray transmission film, it was possible to prevent the reflection of alignment light of the X-ray transmission film 52. Set in the exposure chamber 8 in the same manner as in Example 1, and use He-Ne.
When alignment was performed using laser (633 nm) alignment light at an angle of 17.5 °, stable alignment light transmittance could be obtained and highly accurate alignment could be performed. Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

Embodiment 6 FIG. 26 is a sectional view of the X-ray mask manufacturing process of the sixth embodiment of the present invention. A Si wafer is often used as the substrate 81 serving as the holding frame. This time, the one with 3 inches φ2 mmt was used. The substrate is set in the plasma CVD apparatus. First, after the back pressure was reduced to 2 × 10 ⁻⁶ Torr, 5 SCCM of silane gas and 20 SCCM of ammonia gas diluted to 10% with hydrogen were supplied through the holes formed in the lower electrode. The temperature of the substrate 81 is heated to 250 ° C. and the pressure is set to 5
A high-frequency power of 20 W was applied at × 10 ⁻³ Torr to deposit silicon nitride to a thickness of 2 μmt to form an X-ray transparent film 82. Further, the substrate was set in a sputtering apparatus, and chromium oxide 57 nm was formed into a film having a thickness of 87, which is shown in FIG. FIG. 26B shows a case where 50 nm of gold to be the plating electrode 84 for forming the X-ray absorber and 5 nm of chromium as the metal thin film 83 for adhesion are continuously vapor-deposited by EB vapor deposition.

On top of that, electron beam resist PMMA (OEB
R-1000 (trade name: manufactured by Tokyo Ohka Co., Ltd.) is applied, and a desired fine resist pattern 85 is formed by an electron beam drawing apparatus, as shown in FIG. Next, using a gold sulfite plating solution (Nutronex 309, trade name: manufactured by EEJA), 50
Plating under conditions of ℃ and current density of 1mA / cm ² .
Forming gold to be the X-ray absorber 86, resist pattern 8
5 is peeled off with a dedicated peeling liquid, and FIG. 26 (d) is obtained. The peeling of the plating electrode 84 in the portion where the X-ray absorber 86 is not present is RI
Use the E device. After reducing the back pressure to 1 × 10 ^-5 Torr, 20 SCCM of argon gas was flowed and 5 × 10 ^-2 To
200 W is applied at rr for etching. Plating electrode 8
Since both 4 and the X-ray absorber 86 are gold, they are uniformly etched, and the X-ray absorber becomes as shown by 86 'in FIG. 26 (e).

Further, oxygen gas 20 is stored in the same RIE device.
SCCM is flown, 200 W is applied at 5 × 10 ⁻² Torr, and the non-patterned portion of the metal thin film 83 is made into chromium oxide by oxygen plasma, and combined with chromium oxide 87, only the non-patterned portion becomes the thickness of the antireflection film 87. 'Is formed, resulting in FIG. Further, the Si wafer was back-etched with 3 wt% potassium hydroxide at 110 ° C.,
The holding frame 11 is formed and is shown in FIG.

As described above, by oxidizing the metal thin film chromium without peeling it off, the antireflection film is formed together with the previously formed chromium oxide, and the alignment light of the X-ray transmission film 82 is reflected. Since it is possible to prevent the reduction of the film thickness of gold which is the X-ray absorber 86, the He-Ne laser (63) is set in the exposure chamber 8 as in the first embodiment.
When the alignment was performed using (3 nm) alignment light, a stable alignment light transmittance could be obtained and highly accurate alignment could be performed.
Further, in exposure with X-rays, sufficient contrast could be obtained without reducing the film thickness of the X-ray absorber, and a highly accurate semiconductor chip could be manufactured.

[0131]

As described above, the X-ray mask structure including the X-ray absorber having a desired pattern, the X-ray transmission film supporting the absorber, and the holding frame holding these films. An X-ray mask structure having a metal oxide film on a portion other than the pattern portion and the pattern portion on the X-ray transparent film, and a method for manufacturing the same.
The X-ray mask structure and the pattern are such that the metal thin film in the non-pattern forming portion does not hinder the alignment light transmittance without reducing the line absorber and causing the film thickness distribution and damage of the X-ray transparent film. It was possible to provide an X-ray mask with minimal positional distortion.

(Second Invention) In an X-ray mask having a positioning mark in the peripheral portion where the circuit pattern is formed, the antireflection film is provided only on the range used for the positioning on the X-ray transmissive film. By doing so, stable alignment light transmittance can be obtained without increasing the positional distortion of the X-ray mask due to the antireflection film, so that highly accurate alignment is performed and highly accurate exposure and highly accurate semiconductor fabrication are performed. Was able to do.

(Third invention) X having a desired pattern
In an X-ray mask structure including a radiation absorber, an X-ray transparent film that supports the absorber, and a holding frame that holds these,
By using a metal oxide film other than the alignment mark portion in the range used for alignment on the X-ray transparent film, the film thickness of the X-ray absorber is reduced and the film thickness of the X-ray transparent film in the range used for alignment. Since occurrence of distribution and damage to the film surface can be prevented and stable alignment light transmittance can be obtained, and sufficient contrast can be obtained during X-ray exposure,
High-precision alignment was performed, and high-precision exposure and high-precision semiconductor fabrication were possible.

(Fourth Invention) As described above, in an X-ray mask structure comprising an X-ray absorber having a desired pattern, an X-ray transmissive film supporting the absorber, and a holding frame holding these. An X-ray mask structure characterized by having an antireflection film on a portion other than a pattern portion on the X-ray transmission film, a method for manufacturing the same, an X-ray exposure apparatus, an X-ray exposure method, and a semiconductor manufacturing method. Prevents reduction of body thickness, X
Without causing the film thickness unevenness and damage of the wire permeable film,
Since a stable alignment light transmittance can be obtained, highly accurate alignment can be performed, and highly accurate exposure and highly accurate semiconductor manufacturing can be performed.

[0135]

[Brief description of drawings]

FIG. 1 is a process sectional view of an X-ray mask structure according to the present invention.

FIG. 2 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 3 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 4 is a process sectional view of an X-ray mask structure of another example according to the present invention.

[0136]

FIG. 5 is a process sectional view of an X-ray mask structure according to the present invention.

FIG. 6 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 7 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 8 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 9 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 10 is a process cross-sectional view of a conventional X-ray mask structure.

FIG. 11 is a simplified diagram of an X-ray exposure apparatus according to the present invention.

FIG. 12 is a process sectional view of an X-ray mask structure of another example according to the present invention.

[0137]

FIG. 13 is a process sectional view of an X-ray mask structure according to the present invention.

FIG. 14 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 15 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 16 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 17 is a process cross-sectional view of a conventional X-ray mask structure.

FIG. 18 is a simplified diagram of an X-ray exposure apparatus according to the present invention.

[0138]

FIG. 19 is a process sectional view of an X-ray mask structure according to the present invention.

FIG. 20 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 21 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 22 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 23 is a process sectional view of an X-ray mask structure of another example according to the present invention.

FIG. 24 is a simplified diagram of an X-ray exposure apparatus according to the present invention.

FIG. 25 is a process sectional view of a conventional X-ray mask structure.

FIG. 26 is a process sectional view of an X-ray mask structure of another example according to the present invention.

[0139]

[Explanation of symbols]

(FIGS. 1 to 4) 11, 21, 31, 41 ... Holding frame 12, 22, 32, 42 ... X-ray transparent film 13, 23, 33, 43 ... Metal thin film 14, 43 ... Plating electrode 15, 25, 35, 45 ... Resist 16, 26, 36, 46 ... X-ray absorber 16 ', 26', 36 '... X-ray absorber (after processing) 17, 27, 37, 47 ... Metal oxide (pattern portion) 18, 28 , 38, 48 ... Metal oxide (non-patterned portion on X-ray transparent film)

(FIGS. 5 to 12) 1 ... Be window port 2 ... Mask stage 3 ... Alignment detector 4 ... Mask 5 ... Wafer (semiconductor substrate) 6 ... Wafer chuck 7 ... Wafer stage 8 ... Exposure chamber 9 ... Exhaust Ports 11, 21, 31, 41, 51, 61, 81 ... Holding frame 12, 22, 32, 42, 52, 62, 82 ... X-ray transparent film 13, 23, 33, 63, 83 ... Metal thin film 14 , 33, 64, 84 ... Plating electrode 15, 25, 35, 45, 55, 65, 85 ... Resist 16, 26, 36, 46, 56, 66, 86 ... X-ray absorber 16 ', 26', 56 ' , 66 ', 86' ... X-ray absorber (after processing) 17, 27, 37, 47, 57, 67, 87 ... Alignment marks 18, 18 ', 28, 38, 48, 48', 58, 6
8, 88 "... Antireflection film 29, 59 ... Protective film

(FIGS. 13 to 18) 1 ... Be window port 2 ... Mask stage 3 ... Alignment detector 4 ... Mask 5 ... Wafer (semiconductor substrate) 6 ... Wafer chuck 7 ... Wafer stage 8 ... Exposure chamber 9 ... Exhaust Ports 11, 21, 31, 41, 51 ... Holding frame 12, 22, 32, 42, 52 ... X-ray transparent film 13, 23, 33, 43, 53 ... Metal thin film 14, 34, 43, 54 ... Plating Electrodes 15, 25, 35, 45, 55 ... Resist 16, 26, 36, 46, 56 ... X-ray absorber 16 ', 26', 36 ', 56' ... X-ray absorber (after processing) 17, 27, 37, 47, 57 ... Alignment mark 18, 28, 38 ... Protective film 19, 29, 39, 49 ... Metal oxide film (non-alignment pattern portion)

(FIGS. 19 to 26) 1 ... Be window port 2 ... Mask stage 3 ... Alignment detector 4 ... Mask 5 ... Wafer (semiconductor substrate) 6 ... Wafer chuck 7 ... Wafer stage 8 ... Exposure chamber 9 ... Exhaust Ports 11, 21, 31, 41, 51, 71, 81 ... Holding frame 12, 22, 32, 42, 52, 72, 82 ... X-ray transparent film 13, 23, 43, 73, 83 ... Metal thin film 14 , 43, 74, 84 ... Plating electrode 15, 25, 35, 45, 55, 75, 85 ... Resist 16, 26, 36, 46, 56, 76, 86 ... X-ray absorber 16 ', 26', 36 ' , 56 ', 76', 86 '... X
Line absorber (after processing) 17, 27, 37, 47, 57, 87 '... Antireflection film

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location G03F 7/20 503 9122-2H 521 9122-2H G11B 11/00 9075-5D 7352-4M H01L 21 / 30 331 E

Claims (31)

[Claims] 1. An X-ray mask structure comprising an X-ray absorber having a desired pattern, an X-ray transmissive film supporting the absorber, and a holding frame for holding these, wherein the pattern on the X-ray transmissive film. An X-ray mask structure having a metal oxide film having an atomic number of 70 or more in a portion and a metal oxide film having an atomic number of 35 or less in a portion other than the pattern portion on the X-ray transparent film. 2. The metal oxide film having an atomic number of 70 or more is an oxide of tantalum, tungsten, platinum, gold, or lead, and the metal oxide film having an atomic number of 35 or less is chromium, titanium, or aluminum. The X-ray mask structure according to claim 1, which is an oxide of any one of zinc, copper, and nickel. 3. An X-ray transparent film is provided on the holding frame,
In a method of manufacturing an X-ray mask having a metal thin film between a ray-transmissive film and a metal that plays a main role as an X-ray absorber,
After forming a metal that plays a main role as an X-ray absorber into a desired pattern, an oxidation treatment is performed to make the pattern portion and the non-pattern forming portion of the metal thin film a metal oxide. Method. 4. The method of manufacturing an X-ray mask according to claim 3, wherein the oxidation treatment of the metal thin film is an oxygen plasma treatment. 5. The method of manufacturing an X-ray mask according to claim 3, wherein the oxidation treatment of the metal thin film is an oxygen ion implantation treatment. 6. The method of manufacturing an X-ray mask according to claim 3, wherein the oxidation treatment of the metal thin film is a heat treatment in an oxygen atmosphere. 7. An X-ray mask structure comprising an X-ray absorber having a desired circuit pattern, an X-ray transmissive film supporting the absorber, and a holding frame for holding these, wherein the circuit pattern is formed. An X-ray mask structure, wherein an alignment mark is provided on a certain peripheral portion, and an antireflection film is provided only in a region used for alignment on the X-ray transmission film. 8. A peripheral portion on which a circuit pattern is formed,
A method of manufacturing an X-ray mask having an alignment mark, wherein an antireflection film is formed only in a range used for alignment. 9. The method of manufacturing an X-ray mask according to claim 8, wherein an antireflection film is formed after forming a metal that plays a main role as a pattern into a desired pattern. 10. An X-ray exposure apparatus comprising an X-ray generation source, an exposure chamber, a means for fixing an exposed material at a predetermined position, a means for fixing an X-ray mask at a predetermined position, an alignment and an alignment detection section. The mask includes an X-ray absorber having a desired pattern, an X-ray transmissive film that supports the absorber, and a holding frame that holds the X-ray absorber, and a positioning mark is provided on the peripheral portion where the circuit pattern is formed. An X-ray exposure apparatus, which is an X-ray mask provided with an antireflection film only in a range used for alignment on the X-ray transmission film. 11. An X-ray mask is superposed on the surface of the exposed material,
In an X-ray exposure method of aligning an X-ray mask with alignment light and exposing X-rays through the mask, the mask has an X-ray absorber having a desired pattern, and an X-ray transmissive film supporting the absorber. , And a holding frame for holding these, positioning marks are provided on the peripheral portion where the circuit pattern is formed, and the antireflection film is provided only on the range used for the positioning on the X-ray transmission film. An X-ray exposure method, which is an X-ray mask. 12. An X-ray mask having a pattern required for semiconductor manufacturing and a substrate coated with a material to be exposed are overlapped, alignment of the X-ray mask and the substrate is performed by alignment light, and X-rays are emitted through the mask. In a semiconductor manufacturing method for performing patterning by exposure, the mask includes an X-ray absorber, an X-ray transmissive film that supports the absorber, and a holding frame that holds these, and a periphery where a circuit pattern is formed. A semiconductor manufacturing method, characterized in that the X-ray mask is provided with an alignment mark on a portion thereof, and has an antireflection film only in a range used for alignment on the X-ray transmission film. 13. An X-ray mask structure comprising an X-ray absorber having a desired circuit pattern, an X-ray transmissive film supporting the absorber, and a holding frame for holding these, wherein the circuit pattern is formed. An alignment mark is provided in a certain peripheral portion, and a metal oxide film is provided on a portion of the X-ray transmission film that is used for alignment and in a portion other than the pattern portion of the alignment mark. X-ray mask structure. 14. The metal oxide film is chromium, titanium, tantalum, tungsten, molybdenum, tin, aluminum,
The X-ray mask structure according to claim 13, which is an oxide of any one of zinc, copper, nickel and lead. 15. The X-ray mask structure according to claim 13, wherein the metal oxide film has a thickness of 1,000 Å or less. 16. A method of manufacturing an X-ray mask having a circuit pattern and an alignment mark, wherein after a desired pattern is formed, an oxidation process is performed to apply a metal oxide to a non-pattern forming portion in a range used for alignment. A method for manufacturing an X-ray mask, which comprises: forming. 17. The method of manufacturing an X-ray mask according to claim 16, wherein the method of forming the metal oxide is oxygen plasma treatment. 18. The method of manufacturing an X-ray mask according to claim 16, wherein the method of forming the metal oxide is an oxygen ion implantation process. 19. The method for producing an X-ray mask according to claim 16, wherein the method for forming the metal oxide is a heat treatment in an oxygen atmosphere. 20. An X-ray exposure apparatus comprising an X-ray generation source, an exposure chamber, a means for fixing an exposed material at a predetermined position, a means for fixing an X-ray mask at a predetermined position, an alignment and an alignment detection section. The mask includes an X-ray absorber having a desired pattern, an X-ray transmissive film that supports the absorber, and a holding frame that holds the X-ray absorber, and a positioning mark is provided on the peripheral portion where the circuit pattern is formed. An X-ray exposure apparatus, which is an X-ray mask having a metal oxide film provided in a range used for alignment on the X-ray transparent film and in a portion other than the alignment mark pattern portion. 21. An X-ray mask is superposed on the surface of the exposed material,
In an X-ray exposure method of aligning an X-ray mask with alignment light and exposing X-rays through the mask, the mask has an X-ray absorber having a desired pattern, an X-ray transmissive film supporting the absorber, And a holding frame for holding these, a positioning mark is provided in the peripheral portion where the circuit pattern is formed, and the positioning mark pattern portion is used within the range used for the positioning on the X-ray transmission film. An X-ray exposure method, which is an X-ray mask having a metal oxide film on a portion other than the above. 22. An X-ray mask having a pattern required for semiconductor manufacturing and a substrate coated with a material to be exposed are superposed, alignment of the X-ray mask and the substrate is performed by alignment light, and X-rays are emitted through the mask. In a semiconductor manufacturing method for performing patterning by exposure, the mask includes an X-ray absorber, an X-ray transmissive film that supports the absorber, and a holding frame that holds these, and a periphery where a circuit pattern is formed. An X-ray mask having a metal oxide film in a portion used for alignment on the X-ray transmission film and in a portion other than the alignment mark pattern portion on the X-ray transparent film. Semiconductor manufacturing method. 23. An X-ray absorber having a desired pattern,
An X-ray mask structure comprising an X-ray transmissive film that supports the absorber and a holding frame that holds the X-ray transmissive film, wherein an antireflection film is provided on a portion other than the pattern portion on the X-ray transmissive film. X-ray mask structure. 24. The antireflection film comprises silicon, chromium, titanium, aluminum, zinc, copper, nickel, tantalum,
An oxide of tungsten, molybdenum or tin,
24. The X-ray mask structure according to claim 23, which is a nitride or a carbide. 25. An X having an X-ray transparent film provided on a holding frame.
In the method of manufacturing a X-ray mask, a metal that plays a main role as an X-ray absorber is formed into a desired pattern, and then the non-absorber pattern forming portion on the X-ray transmission film is used as an antireflection film. Line mask manufacturing method. 26. The X-ray mask manufacturing method according to claim 25, wherein the thin film processing method is ion implantation processing. 27. The X-ray mask manufacturing method according to claim 25, wherein the method of processing the metal thin film is plasma processing. 28. The X-ray mask manufacturing method according to claim 25, wherein the method of processing the metal thin film is heat treatment. 29. An X-ray exposure apparatus comprising an X-ray generation source, an exposure chamber, a means for fixing an exposed material at a predetermined position, a means for fixing an X-ray mask at a predetermined position, an alignment and an alignment detection unit. The mask comprises an X-ray absorber having a desired pattern, an X-ray transmissive film that supports the absorber, and a holding frame that holds these, and an antireflection film is provided on a portion other than the pattern portion on the X-ray transmissive film. With X
An X-ray exposure apparatus, which is a line mask. 30. An X-ray mask is superposed on the surface of the exposed material,
In an X-ray exposure method of aligning an X-ray mask with alignment light and exposing X-rays through the mask, the mask has an X-ray absorber having a desired pattern, an X-ray transmissive film supporting the absorber, An X-ray exposure method, which is an X-ray mask having an antireflection film on a portion other than the pattern portion on the X-ray transmission film, the X-ray exposure method comprising: 31. An X-ray mask having a pattern required for semiconductor manufacturing and a substrate coated with a material to be exposed are superposed, alignment of the X-ray mask and the substrate is performed by alignment light, and X-rays are emitted through the mask. In the semiconductor manufacturing method of patterning by exposure, the mask comprises an X-ray absorber, an X-ray transmissive film that supports the absorber, and a holding frame that holds these, and the pattern on the X-ray transmissive film. A method for manufacturing a semiconductor, which is an X-ray mask having an antireflection film on a portion other than the portion.