JP7195777B2 - Mask blank material film manufacturing apparatus, mask blank material film manufacturing method, phase shift mask blank manufacturing method, and phase shift mask manufacturing method - Google Patents

Description

The present invention relates to a mask blank material film manufacturing apparatus, a mask blank material film manufacturing method, a phase shift mask blank manufacturing method, and a phase shift mask manufacturing method, which are capable of coping with an increase in substrate size.

High integration and miniaturization in semiconductor integrated circuits are remarkable. Along with this, miniaturization of circuit patterns formed on a semiconductor substrate (hereinafter referred to as a wafer), which is an object to be processed, is also progressing rapidly.

Among them, photolithography technology is widely recognized as a basic technology in pattern formation. Therefore, various developments and improvements have been made to date. However, the miniaturization of patterns does not know where to stop, and the demand for improvement in pattern resolution is becoming stronger.

In recent years, as a technique to satisfy these demands, a phase shift exposure method using a phase shift mask has been researched and developed in various places, and many proposals have been disclosed. For example, techniques related to phase shift masks include "a phase shift mask, a manufacturing method thereof, and an exposure method using the phase shift mask (Patent Document 1)" and "phase shift photomask blanks manufacturing method, phase shift photomask Blanks and a Phase Shift Photomask (Patent Document 2)”, “Titanium Nitride Thin Film Forming Method (Patent Document 3)”, and the like.

Patent Documents 1 and 2 disclose a molybdenum silicide-based halftone phase shift mask and a manufacturing method thereof, and reactive sputtering using DC magnetron discharge is adopted as a method for forming a phase shifter film. ing.

In Patent Document 1, Ar is used as an inert gas, O ₂ or (O ₂ +N ₂ ) is used as a reactive gas, and a mixed gas system is adopted as a gas supply system.

In Patent Document 2, Ar is used as an inert gas, NO is used as a reactive gas, and a mixed gas system is adopted as in Patent Document 1 as a gas supply system.

Patent Literature 3 discloses a reactive low-pressure sputtering method and apparatus using DC magnetron discharge. The object of Patent Document 3 is to provide a titanium nitride thin film deposition method that allows a uniform film thickness distribution of the thin film on the substrate surface while maintaining good embedding characteristics inside the micropores.

In order to achieve this purpose, in Patent Document 3, the so ^- called long _- throw sputtering method (hereinafter referred to as LTS method) shown in FIG. In order to maintain the pressure at Pa (7.5×10 ⁻⁴ Torr) or less and obtain a uniform titanium nitride thin film distribution, the flow rate ratio of the mixed gas composition is 1/8≦Ar/N ₂ ≦1/3. The distance (T/S) between the target and the substrate is selected to be 140 mm to 200 mm.

Patent Document 4 discloses "a method for manufacturing a phase shifter film, a method for manufacturing a blank for a phase shift mask, and a method for manufacturing a phase shift mask". The manufacturing method of Patent Document 4 employs the LTS method of Patent Document 3 described above for forming the mask blank material film. In the manufacturing method of Patent Document 4, a gas separation method is proposed in which a reactive gas is blown to the substrate side and an inert gas is supplied to the vicinity of the target. Patent Document 4 describes that the distance (T/S) between the target and the substrate should be 100 mm or more, preferably 400 mm or more, in order to perform the gas separation method.
The mixed gas supply method has a problem that when the target surface is oxidized and the supply amount of the reactive gas increases, the deposition rate of the film on the substrate drops sharply, making it impossible to form a film. The production method of Patent Document 4 solves this problem by adopting a gas separation method.

Japanese Patent Laid-Open No. 2002-200000 discloses a "phase shift mask blank manufacturing method and phase shift mask blank manufacturing apparatus". The manufacturing method of Patent Document 5 employs a step of continuously forming a phase shift film on a transparent substrate using a sputtering method. It is described that the substrate is rotated during film formation, the target is placed obliquely above the substrate, and the target is angled with respect to the substrate. It is explained that this reduces variations in phase angle and transmittance between blanks and improves yield.

In recent years, there has been a demand for larger mask blanks in response to the increase in the area of wafers. In particular, when the size of a rectangular substrate is larger than 152 mm (6 inches), the uniformity of the film thickness within the substrate plane is remarkably reduced when there is only one target arranged substantially facing the substrate. For this reason, the problem that the quality as a mask blank material film cannot be achieved became apparent.

Therefore, a manufacturing apparatus for a mask blank material film, a method for manufacturing a mask blank material film, and a mask blank manufacturing are provided, which are capable of achieving uniform film thickness in the substrate surface even on a large rectangular substrate. It was hoped that a method would be developed.

Japanese Patent No. 3064769 Japanese Patent No. 3594659 Japanese Patent No. 3615801 Japanese Patent No. 4163331 JP-A-2002-090978

The present invention has been devised in view of such conventional circumstances, and provides a mask blank material film capable of achieving uniformity in film thickness within the substrate surface even for large rectangular substrates. An object of the present invention is to provide a manufacturing apparatus, a method for manufacturing a mask blank material film, a method for manufacturing phase shift mask blanks, and a method for manufacturing a phase shift mask.

An apparatus for manufacturing a mask blank material film according to claim 1 of the present invention is an apparatus for manufacturing a material film used for a mask blank by a reactive long-throw sputtering method,
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which serve as a base material of the material film, are arranged apart from each other,
Sputtered particles flying from each of the first and second targets are directed toward a rotating processing surface of a rectangular substrate,
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TSA connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate; A second tilt angle ΔB formed between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate is different for the first and second targets,
the first target having the first tilt angle ΔA of −22° to −19°;
the second target having the second tilt angle ΔB of −10° to −7°;
It is characterized in that the second target is moved in a direction away from the substrate more than the first target.
According to claim 2 of the present invention, there is provided an apparatus for manufacturing a mask blank material film according to claim 1, wherein a first gas supply means and a second A two gas supply means and an exhaust means for decompressing the film forming space,
The distance between the first and second targets and the substrate is set to 100 mm or more, the pressure in the film formation space is kept to 1.0 × 10 ^-1 Pa or less, and the reactive gas and the inert A means for controlling the first gas supply means, the second gas supply means, and the exhaust means so that the flow rate ratio with the gas satisfies 50% ≤ reactive gas / inert gas ≤ 80%, is preferred.
According to claim 3 of the present invention, there is provided an apparatus for manufacturing a mask blank material film according to claim 2, wherein the first gas supply means introduces the reaction gas to the substrate side, and the second gas supply means Preferably, an active gas is introduced to the first and second target sides.
According to a fourth aspect of the present invention, there is provided an apparatus for manufacturing a mask blank material film according to any one of the first to third aspects, wherein the material film is preferably oxynitride of molybdenum silicide.

A method for manufacturing a mask blank material film according to claim 5 of the present invention is a method for manufacturing a material film used for a mask blank by a reactive long-throw sputtering method, comprising:
The reactive long-throw sputtering method comprises:
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which serve as a base material of the material film, are arranged apart from each other,
The sputtered particles flying from each of the first and second targets are directed toward the rotating processing surface of the rectangular substrate, and
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TS A connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate ; and a second tilt angle ΔB between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate. , configured differently for the first and second targets, and
the first target having the first tilt angle ΔA of −22° to −19 ° ;
the second target having the second tilt angle ΔB of −10 ° to −7 °;
has
In a state in which the second target is arranged in a direction away from the substrate more than the first target,
Separately introducing the reactive gas and the inert gas,
pressure is 1.0 × 10 ^-1 Pa or less,
The distance between the first and second targets and the substrate is 100 mm or more,
A flow ratio of the reactive gas and the inert gas is 50%≦reactive gas/inert gas≦80%.
According to claim 6 of the present invention, there is provided a method for manufacturing a mask blank material film according to claim 5, wherein the reactive gas is introduced to the substrate side and the inert gas is introduced to the first and second target sides. preferably.
A method for manufacturing a mask blank material film according to claim 7 of the present invention is the mask blank material film manufacturing method according to claim 5 or 6, wherein the step of forming the material film is a step of performing heat treatment at 200° C. or higher after forming the material film. It is preferable to further include
According to claim 8 of the present invention, in the method of manufacturing a mask blank material film according to any one of claims 5 to 7, it is preferable that the material film is made of oxynitride of molybdenum silicide.

According to a ninth aspect of the present invention, there is provided a method of manufacturing blanks for a phase shift mask, comprising the step of forming a material film used for mask blanks as a phase shifter film on a transparent substrate using a reactive long-throw sputtering method . A method for manufacturing a blank for a phase shift mask, comprising:
The reactive long-throw sputtering method comprises:
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which serve as a base material of the material film, are arranged apart from each other,
The sputtered particles flying from each of the first and second targets are directed toward the rotating processing surface of the rectangular substrate, and
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TSA connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate; A second tilt angle ΔB formed between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate is configured differently for the first and second targets, and
the first target having the first tilt angle ΔA of −22° to −19°;
the second target having the second tilt angle ΔB of −10° to −7°;
has
In a state in which the second target is arranged in a direction away from the substrate more than the first target,
Separately introducing the reactive gas and the inert gas,
pressure is 1.0 × 10 ^-1 Pa or less,
The distance between the first and second targets and the substrate is 100 mm or more,
A flow ratio of the reactive gas and the inert gas is 50%≦reactive gas/inert gas≦80%.
According to claim 10 of the present invention, there is provided a method for manufacturing phase shift mask blanks according to claim 9, wherein the reactive gas is introduced to the substrate side, and the inert gas is introduced to the first and second target sides. preferably.
A method for manufacturing a phase shift mask blank according to claim 11 of the present invention is the method according to claim 9 or 10, wherein the step of forming the phase shift mask blank is performed after forming the phase shifter film using a sputtering method. , including a step of performing a heat treatment at 200° C. or higher.
According to claim 12 of the present invention, in the manufacturing method of blanks for a phase shift mask according to any one of claims 9 to 11, it is preferable that the phase shifter film is made of oxynitride of molybdenum silicide.
The method for manufacturing a phase shift mask blank according to claim 13 of the present invention is the method according to any one of claims 9 to 12, further comprising the step of forming a metal film after the step of forming the phase shifter film. is preferred.
A method for manufacturing a phase shift mask blank according to claim 14 of the present invention is characterized in that, in claim 13, the metal film is a film made of any one of molybdenum, chromium, tungsten, tantalum, titanium, silicon, and aluminum, Alternatively, it is preferably an alloy film made of any combination thereof.
A fifteenth aspect of the present invention is directed to a method for manufacturing a phase shift mask blank according to any one of the ninth to fourteenth aspects, wherein the step of forming a resist film after the step of forming the phase shifter film; and forming an antistatic film on the resist film after the film forming step.
According to the sixteenth aspect of the present invention, in the method of manufacturing a phase shift mask blank, in the fifteenth aspect, it is preferable that the antistatic film is made of a conductive polymer material.

A method for manufacturing a phase shift mask according to claim 17 of the present invention comprises the steps of forming a phase shifter film on a transparent substrate using a reactive long throw sputtering method, and forming a predetermined pattern on the phase shifter film. and a step of patterning the phase shifter film using the resist film as a mask, wherein
The reactive long-throw sputtering method comprises:
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which are base materials of the phase shifter film, are arranged apart from each other,
The sputtered particles flying from each of the first and second targets are directed toward the rotating processing surface of the rectangular substrate, and
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TS A connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate ; and a second tilt angle ΔB between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate. , configured differently for the first and second targets, and
the first target having the first tilt angle ΔA of −22° to −19 ° ;
the second target having the second tilt angle ΔB of −10 ° to −7 °;
has
In a state in which the second target is arranged in a direction away from the substrate more than the first target,
Separately introducing the reactive gas and the inert gas,
pressure is 1.0 × 10 ^-1 Pa or less,
The distance between the first and second targets and the substrate is 100 mm or more,
A flow ratio of the reactive gas and the inert gas is 50%≦reactive gas/inert gas≦80%.
The method of manufacturing a phase shift mask according to claim 18 of the present invention is the method according to claim 17, wherein the reaction gas is introduced to the substrate side, and the inert gas is introduced to the first and second target sides. is preferred.
According to claim 19 of the present invention, there is provided a method of manufacturing a phase shift mask according to claim 17 or 18, wherein the step of forming the phase shifter film is the step of performing heat treatment at 200° C. or higher after forming the phase shifter film. preferably includes
According to claim 20 of the present invention, in the method of manufacturing a phase shift mask according to any one of claims 17 to 19, it is preferable that the phase shifter film is made of oxynitride of molybdenum silicide.
According to claim 21 of the present invention, there is provided a method for manufacturing a phase shift mask according to claim 20, further comprising the step of forming a metal film between the step of forming the phase shifter film and the step of forming the resist film. It is preferable to further include.
The method for manufacturing a phase shift mask according to claim 22 of the present invention is characterized in that, in claim 21, the metal film is a film made of any one of molybdenum, chromium, tungsten, tantalum, titanium, silicon, and aluminum, or An alloy film made of any one of these combinations is preferred.
A twenty-third aspect of the present invention is directed to the method of manufacturing a phase shift mask according to any one of the twenty-first and twenty-second aspects, wherein the step of patterning the phase shifter film uses a mixed gas of fluorocarbon and oxygen. It is preferable to include a step of performing a dry etching method. The method for manufacturing a phase shift mask according to claim 24 of the present invention is the method according to any one of claims 17 to 23, further comprising forming an antistatic film on the resist film after the step of forming the resist film. It is preferable to further include a step.
In the twenty-fifth aspect of the present invention, it is preferable that the antistatic film is made of a conductive polymer material.
In the twenty-sixth aspect of the present invention, in the twenty-fourth aspect, it is preferable that the antistatic film is made of a molybdenum-based metal material.
A twenty-seventh aspect of the present invention is directed to the method of manufacturing a phase shift mask according to any one of the twenty-fourth to twenty-sixth aspects, wherein the step of forming the resist film having the predetermined pattern includes exposing the resist film. and removing the antistatic film before developing the resist film; and developing the resist film.
According to claim 28 of the present invention, in the method of manufacturing a phase shift mask according to claim 27, it is preferable that the step of removing the antistatic film uses water to remove the antistatic film.

The apparatus for manufacturing a mask blank material film of the present invention, when forming a material film on a surface to be processed that rotates (R: rotation direction) of a rectangular substrate by a reactive long-throw sputtering method, includes: A plurality of targets, which are the base materials of , are arranged in a single film-forming space. The tilt angle Δ between the vertical direction of each target with respect to the sputtering surface and the line segment TS connecting the center of the sputtering surface of the planar target serving as the base material of the material film and the center of the surface to be processed of the substrate is Each target is configured differently. As a result, the sputtered particles from the two or more targets are deposited at different angles on the rotating surface of the rectangular substrate to be processed, and deposited to form a material film having a desired thickness. be. As a result, it is possible to form a film having a uniform film thickness even on a large rectangular substrate. Therefore, the present invention contributes to the provision of a mask blank material film manufacturing apparatus capable of achieving uniformity of the film thickness in the substrate surface even on a large rectangular substrate.

The method for manufacturing a mask blank material film, the method for manufacturing a phase shift mask blank, and the method for manufacturing a phase shift mask according to the present invention are set conditions when using the above-described mask blank material film manufacturing apparatus. Among them, the reaction gas and the inert gas are introduced separately, the pressure is set to a predetermined value or less, the distance between the target and the substrate is set to a predetermined distance or more, and the flow rate ratio of the reaction gas and the inert gas. be within a predetermined range.
According to this definition, when sputtered particles are deposited at different angles from two or more targets on the surface to be processed which rotates (R: rotation direction) of a rectangular substrate, the transmittance is reduced. A uniform material film is obtained. Therefore, even with a large rectangular substrate, it is possible to form a film having uniform optical characteristics within the substrate surface. The present invention provides a method for manufacturing a mask blank material film, a method for manufacturing a phase shift mask blank, and a method for manufacturing a phase shift mask.

1 is a schematic diagram showing the configuration of a sputtering apparatus employing the LTS method according to the present invention; FIG. FIG. 2 is a bird's-eye view showing the arrangement of an object to be processed and a target viewed from above the apparatus of FIG. 1; 7 is a graph showing the relationship between the substrate radius and the normalized film thickness under different tilt angle conditions. A graph showing the result (SUM) of summing the normalized film thicknesses obtained under two conditions of tilt angles. FIG. 4 is a cross-sectional structural view of a phase shift mask according to Embodiment 2 of the present invention. FIG. 4 is a schematic diagram showing an electric field on the mask and an electric field on the wafer when using the phase shift mask according to the present invention; FIG. 8 is a cross-sectional view showing a first manufacturing process of Embodiment 2; FIG. 8 is a cross-sectional view showing a second manufacturing process of Embodiments 2 and 3; FIG. 11 is a cross-sectional view showing a third manufacturing process of Embodiments 2 and 3; Sectional drawing which shows a 4th manufacturing process. FIG. 11 is a cross-sectional view showing the first manufacturing process of Embodiment 3; FIG. 11 is a cross-sectional view showing a first manufacturing process of Embodiment 4; FIG. 11 is a cross-sectional view showing a second manufacturing process of Embodiment 4; FIG. 11 is a cross-sectional view showing a third manufacturing process of Embodiment 4; FIG. 12 is a cross-sectional view showing a fourth manufacturing process of Embodiment 4; FIG. 14 is a cross-sectional view showing a fifth manufacturing process of Embodiment 4; (a) and (b) are cross-sectional views of phase shift mask blanks of Embodiment 5. FIG. (a) and (b) are cross-sectional views showing a method for manufacturing a phase shift mask blank according to Embodiment 5. FIG. FIG. 4 is a cross-sectional view showing a method for correcting a defect of a phase shift mask; FIG. 4 is a schematic diagram showing a state of an exposure method using a phase shift mask; FIG. 1 is a schematic diagram showing the configuration of a conventional sputtering apparatus that employs the LTS method.

Each embodiment according to the present invention will be described below.

(Embodiment 1)
First, a sputtering apparatus for forming a mask blank material film according to the present invention using the LTS method will be described with reference to FIG.
FIG. 1 is a schematic diagram showing the configuration of a sputtering apparatus 100 employing the LTS method according to the present invention.

The sputtering apparatus 100 includes a low pressure vacuum chamber 103 . The vacuum chamber 103 has a reactive gas inlet 114a, an inert gas inlet 114b, and a mixed gas inlet 114c. It also has two evacuation ports 114d and 114e. Furthermore, it has two target electrodes 105A (105), a target electrode 105B (105), and a substrate holder 107. FIG.

A flat target 104A (104) serving as a base material for the material film is provided on the surface of the target electrode 105A, and a flat target 104B (104) serving as a base material for the material film is provided on the surface of the target electrode 105B. ing. The target electrodes 105A and 105B are arranged along the dome-shaped ceiling 102 that constitutes the vacuum chamber 103 .
That is, the sputtering apparatus 100 arranges a plurality of flat targets (two sets in the case of FIG. 1) spaced apart from each other in a single film formation space 103K formed by the vacuum chamber 103. This is a configuration example.

In the vacuum chamber 103 of the sputtering apparatus 100, the sputtered particles flying from the respective targets 104A and 104B are directed toward the surface 106u to be processed, which rotates (R: rotation direction) of the rectangular substrate 106. there is A line segment TS (TSA, TSB: solid arrows) connecting the vertical direction (dotted line arrow) to the sputtering surfaces 104As and 104Bs of the target and the center of the sputtering surface of the target and the center of the surface to be processed of the substrate. Tilt angles Δ(ΔA, ΔB) are different for each of the targets. Here, the line segment TS (TSA, TSB) is the so-called distance between the target and the substrate.

A vacuum pump (not shown) is connected to the evacuation port 114d and the evacuation port 114e. A magnet plate 109A (109) having two concentrically arranged magnets 110A (110) is provided on the back surface of the target electrode 105A. A high frequency power source 112A (112) is electrically connected to the target electrode 105A. Similarly, the back surface of the target electrode 105B is provided with a magnet plate 109B (109) having magnets 110B (110) arranged in double concentric circles. A high frequency power supply 112B (112) is electrically connected to the target electrode 105B.
A heater 111 is provided inside the substrate holder 107 .
In each of the following experimental examples, molybdenum silicide is used as a target during film formation.

(Experimental Examples 1 to 7)
In Experimental Examples 1 to 7, one target was used and a molybdenum silicide film was formed as a mask material film on a rectangular substrate.
Regarding the film thickness distribution of the mask material film, to reduce the influence on the line width, in the pattern process such as resist development, when the change monotonically increases (or monotonously decreases) from the center of the substrate toward the outer periphery, Some corrections are possible. However, when the film thickness change is not monotonous, the film thickness change directly appears as the pattern line width change.

FIG. 3 is a graph showing the relationship between the substrate radius and the normalized film thickness when the molybdenum silicide film is formed by changing the tilt angle conditions. In FIG. 3, the horizontal axis is the substrate radius, the vertical axis is the normalized film thickness, and the results of changing the tilt angle in the range of -9° to +9° are shown. Here, the tilt angle is −9° in Experimental Example 1, the tilt angle is −6° in Experimental Example 2, the tilt angle is −3° in Experimental Example 3, and the tilt angle is 0°. Experimental example 4, the tilt angle of +3° is referred to as experimental example 5, the tilt angle of +6° is referred to as experimental example 6, and the tilt angle of +9° is referred to as experimental example 7, respectively.

A blank substrate to which the present invention is directed is a rectangular substrate having a large area of 6 inches square (approximately 152 mm square) to 9 inches square (approximately 229 mm square).
If the substrate is 6 inches square (6 inches is converted to 152 mm), the maximum radius required to form a uniform film is about 108 mm (=152×√2/2). Since it can be read from FIG. 3 that the tilt angle with the smallest change in the normalized film thickness in the radial direction is “+9°”, it is found to be “(−16°+9°=)−7°”. rice field. Here, “−16°” is the basic tilt angle before change.

If the substrate is 9 inches square (9 inches is converted to 229 mm), the maximum radius required to form a uniform film is about 162 mm (=229×√2/2). Since it can be read from FIG. 3 that the tilt angle with the smallest change in the normalized film thickness in the radial direction is "-6°", it is "(-16°-6°=)-22°". I found out.

Considering the correction in the pattern process, the above conditions are the most preferable for the tendency of film thickness variation. However, when the tilt angle is "+9°" at the radial position of 108 mm, it can be read from FIG. 3 that the absolute value of the variation in the normalized film thickness is "about 0.85%". Similarly, when the tilt angle is "-6°" at the radial position of 162 mm, the absolute value of the variation in the normalized film thickness is "approximately 0.85%" from FIG. This "approximately 0.85%" variation is a problem in the pattern process.

Therefore, the present inventors performed sputtering film formation using a plurality of targets, superimposed film thicknesses, and studied improvement of film thickness variation.
In the bird's-eye view shown in FIG. 2, the film was formed using two targets (for example, target 104A and target 104D) at opposing positions (positions with different angles of 180 degrees). At that time, the tilt angle ΔA of the target 104A was set to "−22°", and the tilt angle ΔB of the target 104B was set to "−10°". In addition, the target 104B was moved 40 mm away from the substrate. That is, the TS distance was increased by 40 mm.

(Experimental Examples 11 to 13)
In Experimental Examples 11 to 13, the normalized film thickness obtained under one different tilt angle condition and the sum (SUM) of the normalized film thickness obtained under these two conditions of tilt angle were examined.
As a target, a molybdenum silicide film was formed as a mask material film on a rectangular substrate.
FIG. 4 is a graph showing the sum (SUM) of the normalized film thickness obtained under one different tilt angle condition and the normalized film thickness obtained under two different tilt angles conditions.

In the case of the plot "-6" (▽ mark) of the target 104A in FIG. are identical.

On the other hand, in the case of the plot "+6" (□ mark) of the target 104B in FIG. It is what I did. That is, at the position where the substrate radius is 0, the normalized film thickness has shifted about 0.25% to the + side (the normalized film thickness has moved from 1.0000 to 1.0025).

In the case of plot SUM (shaded circles) in FIG. is the result of superimposing As a result, the normalized film thickness at the outermost periphery of the substrate was slightly reduced, but the absolute value was improved to about 0.60%.

(Experimental Examples 21 to 26)
Based on the results of FIG. 4, various film properties (film thickness [nm], transmittance [%] @ 193 nm, phase difference [ °] @ 193 nm). In these four types of samples, only the "number of targets" and the "tilt angle" were changed as the deposition conditions, and the types and flow rates of the gases used were the same.

Experimental example 21 is a case where the number of targets is one (for example, target 104A) and the tilt angle is 0 degrees. That is, the surface 104As of one target 104A and the surface 106u of the substrate 106 were arranged to face each other to form a film by sputtering.

Experimental example 22 is a case where the number of targets is one (for example, the target 104A) and the tilt angle is -6 degrees. filmed.

Experimental example 23 is a case where the number of targets is one (for example, the target 104B) and the tilt angle is +6 degrees. did.

Experimental example 24 is a case where there are two targets (for example, target 104A and target 104B), and the tilt angles of each target are −6° and +6°. At the same time, a film was formed by sputtering with a different inclination angle from the surface 106u of .

Experimental example 25 is a case where there are two targets (for example, target 104A and target 104B) and the tilt angles of each target are −6° and +9°. At the same time, a film was formed by sputtering with a different inclination angle from the surface 106u of .

Experimental example 26 is a case where there are two targets (for example, target 104A and target 104B) and the tilt angles of each target are −3° and +6°. At the same time, a film was formed by sputtering with a different inclination angle from the surface 106u of .

The types and flow rates of gases used in Experimental Examples 21 to 26 were the same. That is, the gases and flow rates used are 5 sccm for argon gas (Ar), 40 sccm for helium gas (He), 23 sccm for nitrogen gas (N ₂ ), and 1 sccm for nitrogen monoxide gas (NO).
Table 1 shows the manufacturing conditions of six types of samples (Experimental Examples 21 to 26), and Table 2 shows various film properties (film thickness [nm], transmittance [% ] @ 193 nm, the phase difference [°] @ 193 nm), and the difference between the maximum value and the minimum value [max-min].

From Table 1, the following points became clear.
(A1) When the target and the substrate are arranged to face each other (Experimental Example 21), the distribution of the film thickness (14.8 nm) is large, so the distribution of the transmittance (4.6%) and the distribution of the phase difference (38. 17°) is also large.
(A2) When the tilt angle is −6 degrees (Experimental Example 22), the film thickness distribution (0.9 nm) is remarkably improved. As a result, the transmittance distribution (0.27%) and the phase difference distribution (2.29°) in Experimental Example 22 are less than one tenth of those in Experimental Example 21. FIG.
(A3) When the tilt angle is +6 degrees (Experimental Example 23), the film thickness distribution (0.7 nm) is remarkably improved. As a result, the transmittance distribution (0.27%) and the phase difference distribution (2.27°) in Experimental Example 23 are less than one tenth of those in Experimental Example 21. FIG. The characteristics of Experimental Example 23 are at the same level as those of Experimental Example 22.
(A4) Using two targets and different tilt angles (-6 degrees, +6 degrees), (-6 degrees, +9 degrees), (-3 degrees, +6 degrees) (Experimental Examples 24, 25, 26) is further improved in film thickness distribution (0.5 nm, 0.6 nm, 0.4 nm). As a result, the transmittance distributions (0.11%, 0.10%, 0.15%) and the phase difference distributions (1.36°, 1.63°, 1.11°) in Experimental Examples 24, 25, and 26 °) is about half that of Experimental Examples 22 and 23.

From the above results, it was confirmed that the apparatus for manufacturing a mask blank material film according to the present invention can form a film having a uniform film thickness even on a large rectangular substrate. rice field. This action/effect is not limited to the case where two targets are used. Even if three or more targets are used, the above functions and effects can be similarly obtained.
The mask blank material film manufacturing apparatus of the present invention is provided with a plurality of targets so that sputtered particles are deposited at different angles to form a material film with a desired thickness. . As a result, according to the apparatus for manufacturing a mask blank material film of the present invention, it is possible to form a film having a uniform film thickness even on a large rectangular substrate.
Therefore, the present invention provides a mask blank material film manufacturing apparatus capable of achieving uniformity of film thickness in the substrate surface even on a large rectangular substrate.

(Example 1)
Next, specific film forming conditions for the mask blank provided with the binary molybdenum silicide film are shown below.

T/S distance: 400mm
Tilt angle (basic angle): -16°
Tilt angle (ΔA) of target 104A: basic angle −6°=−22°
Tilt angle (ΔB) of target 104D: basic angle +6° = -10°
Offset angle (θA) of target 104A: 46°
Offset angle (θB) of target 104D: 46°
Target 104D: Moved 40 mm away from the substrate and placed Sputtering current: 0.5 A
Sputtering voltage: 520V-550V
Number of targets: 2 Target diameter: 160mmφ
Substrate temperature: 50°C to 120°C
Film thickness: 50 nm to 80 nm
Sputtering time: 8 min to 16 min (rotational deposition)
Gas separation method: Reactive gas is blown onto the substrate
Under the above conditions of supplying an inert gas to the target, the gas flow rate (sccm) and pressure (×10 ⁻¹ Pa) were appropriately selected, and “TR1, 2, 3”, which are samples formed, are shown in the table below. 3.

(Example 2)
Next, the specific film formation conditions for stationary film formation instead of rotation film formation are shown below. Other points were the same as in Example 1.
T/S distance: 400mm
Tilt angle (basic angle): -16°
Tilt angle (ΔA) of target 104A: basic angle −6°=−22°
Tilt angle (ΔB) of target 104D: basic angle +6° = -10°
Offset angle (θA) of target 104A: 46°
Offset angle (θB) of target 104D: 46°
Target 104D: Moved 40 mm away from the substrate and placed Sputtering current: 0.5 A
Sputtering voltage: 520V-550V
Number of targets: 2 Target diameter: 160mmφ
Substrate temperature: 50°C to 120°C
Film thickness: 50 nm to 80 nm
Sputtering time: 8min to 16min (static film formation)
Gas separation method: Reactive gas is blown onto the substrate
Under the above conditions of supplying an inert gas to the target, the gas flow rate (sccm) and pressure (×10 ⁻¹ Pa) were appropriately selected, and “TR1, 2, 3”, which are samples formed, are shown in the table below. 4.

(Example 3)
For reference, as Example 3, conditions for forming a molybdenum silicide film in the prior art (apparatus shown in FIG. 21) are shown below.
T/S distance: 400mm
Tilt angle (basic angle): -16°
Target tilt angle: 0°
Target offset angle: 0°
Sputter current: 0.5A
Sputtering voltage: 520V-550V
Number of targets: 1 Target diameter: 160mmφ
Substrate temperature: 50°C to 120°C
Film thickness: 50 nm to 80 nm
Sputtering time: 8 min to 16 min (rotational deposition)
: 8min to 16min (static film formation)
Gas separation method: Reactive gas is blown onto the substrate
Under the above conditions of supplying an inert gas to the target, the gas flow rate (sccm) and pressure (×10 ⁻¹ Pa) were appropriately selected, and “TR1, 2, 3”, which are samples formed, are shown in the table below. 5.

Next, Table 6 “ArF Laser (193 nm)” below shows the optical characteristics of each sample shown in Examples 1 to 3 (Tables 1 to 5) with respect to ArF laser (193 nm). All of these samples are in the "as deposition" state.

The following points have been clarified from the contents described in Table 6 above.
(B1) Using the manufacturing apparatus of the present invention, the samples (TR1 to TR3) prepared by rotary deposition and the samples (TX1 to TX3) prepared by stationary deposition were prepared by rotating deposition using a conventional manufacturing apparatus. Compared with the samples (SR1 to SR3) produced by the method and the samples (SX1 to SX3) produced by static film formation, the variation in optical constant and transmittance is small.
(B2) Using the manufacturing apparatus of the present invention, when comparing the samples (TR1 to TR3) produced by rotating deposition with the samples (TX1 to TX3) produced by stationary deposition, the rotation deposition has smaller variations in optical constants and transmittance than static film formation.
(B3) The tendency of (B2) above was the same when the conventional manufacturing apparatus was used. That is, rotational film formation can suppress variations in optical constants and transmittance more than stationary film formation.

From the results (B1) to (B3) described above, it was confirmed that the mask blank material film manufacturing apparatus of the present invention contributes to the uniformity of the film thickness within the substrate surface even for large rectangular substrates. . As a result, the apparatus for manufacturing a mask blank material film according to the present invention realizes film formation with uniform optical characteristics even on a large rectangular substrate.

In addition, among the setting conditions when using the mask blank material film manufacturing apparatus of the present invention, the reaction gas and the inert gas must be separately introduced, the pressure must be less than a predetermined value, and the distance between the target and the substrate is set at a predetermined distance or more, and the flow rate ratio of the reactive gas and the inert gas is set within a predetermined range. It becomes possible to form a film with a sufficient film thickness. As a result, it is possible to form a film with uniform optical properties even on a large rectangular substrate. The present invention provides a method for manufacturing a mask blank material film, a method for manufacturing a phase shift mask blank, and a method for manufacturing a phase shift mask.

(Embodiment 2)
Next, a phase shift mask including the phase shifter film and a method for manufacturing the same will be described below. First, referring to FIG. 5, the structure of the halftone phase shift mask according to the second embodiment will be described. This halftone type phase shift mask 200 comprises a transparent substrate 1 made of quartz that transmits exposure light, and a phase shift pattern 30 formed on the main surface of this transparent substrate 1 . In this phase shift pattern 30 , the first light transmitting portion 10 where the transparent substrate 1 is exposed and the phase and transmittance of the exposure light transmitted through the first light transmitting portion 10 are substantially equal to the phase of the exposure light transmitting through the first light transmitting portion 10 . and a second light transmitting portion 4 that converts 180° and has a required transmittance (for example, 1% to 40%) and is made of a single material.

Next, with reference to FIGS. 6A, 6B, and 6C, the electric field on the mask and the light intensity on the wafer of the exposure light passing through the phase shift mask 200 having the structure described above will be described.

Referring to FIG. 6(a), it is a cross-sectional view of the phase shift mask 200 described above. Referring to FIG. 6B, since the electric field on the mask is phase-inverted at the edges of the exposure pattern, the electric field at the edges of the exposure pattern is always zero. Therefore, referring to FIG. 6C, the difference in the electric field on the wafer between the light transmitting portion 10 and the phase shifter portion 4 of the exposure pattern becomes sufficient, and high resolution can be obtained.

Next, a method for manufacturing the phase shift mask 200 will be described in the case of using a molybdenum silicide film as the phase shifter film.

7 to 10 are cross-sectional structural diagrams showing manufacturing steps according to the cross-section of the phase shift mask 200 shown in FIG.

First, referring to FIG. 8, a phase shifter film 4 made of a molybdenum silicide film is formed on a transparent substrate 1 using the LTS method. Here, a phase shifter film 4 made of a single-layer molybdenum silicide film is formed to a thickness of about 1134 Å under the same film formation conditions as those of the sample TX1 in Table 1 described above. In this case, at a wavelength of 248 nm, a phase shift mask blank with a phase shift amount of about 180° could be obtained. A blank having the phase shifter film 4 formed on the transparent substrate 1 in this way is called a phase shift mask blank.

After that, in order to stabilize the transmittance of the phase shifter film 4, a heat treatment is performed at 200° C. or higher using a clean oven or the like.

As a result, it is possible to prevent the transmittance from fluctuating (0.5 to 1.0%) due to heat treatment (about 180° C.) such as a resist coating process for forming a conventional phase shifter film.

Next, on the phase shifter film 4, an electron beam resist film 5 (ZEP-810S (registered trademark) manufactured by Zeon Corporation) or the like is formed to a thickness of about 5000 Å. After that, since the molybdenum silicide oxynitride film does not have conductivity, an antistatic film 6 (Espacer 100 (registered trademark) manufactured by Showa Denko) or the like is formed to a thickness of about 100 Å in order to prevent electrification during electron beam exposure.

Next, referring to FIG. 8, electron beam resist film 5 is exposed to an electron beam and antistatic film 6 is removed by washing with water. Thereafter, resist film 5 having a predetermined resist pattern is formed by developing resist film 5 .

Next, referring to FIG. 9, phase shifter film 4 is etched using resist film 5 as a mask. At this time, a parallel plate type RF ion etching apparatus was used, the distance between the electrode substrates was 60 mm, the working pressure was 0.3 Torr, and the flow rate was about 95 sccm and about 5 sccm using the reaction gas CF ₄ +O ₂ . , and an etching time of about 11 minutes.

Next, referring to FIG. 10, resist film 5 is removed. With the above, the phase shift mask in the second embodiment is completed.

(Embodiment 3)
The present invention can also be applied when two phase shifters form a laminated structure as shown in FIG. For example, on a quartz substrate (#6025) 1, a lower layer phase shifter film 4L made of a molybdenum silicide oxynitride film having a film thickness of about 818 Å is formed.

Thereafter, an upper phase shifter film 4U made of a molybdenum silicide oxynitride film having a thickness of about 300 Å is formed on the lower phase shifter film 4L. The phase shifter film 4 is composed of the lower phase shifter film 4L and the upper phase shifter film 4U.

Next, the phase shifter film 4 having the two-layer structure is subjected to an annealing treatment at 350° C. for 3 hours in the air to complete a phase shift mask blank.

The optical properties of the phase shift mask blank thus obtained were a transmittance of about 6% and a phase difference of about 180° C. at a wavelength of 193 nm.

The phase difference was evaluated by a phase difference meter for ArF wavelength manufactured by Lasertech and calculation from optical constants. The transmittance at the defect inspection wavelength of 365 nm was 36%.

Using the obtained halftone phase shift mask blanks for ArF laser exposure, a predetermined pattern is formed on the phase shifter film 4 by the same steps as in the first embodiment.

In the first to third embodiments, the T/S distance is 400 mm, but it can be applied in the range of 100 mm to 600 mm depending on the field of application.

Moreover, in the first to third embodiments, N ₂ O is used as the reaction gas, but NO, N ₂ +O ₂ or a mixture of these gases can also be used. Also, although Ar is used as the inert gas, other inert gases (gases belonging to Group 0 of the periodic table) such as He, Ne, Kr, etc. can also be used.

In each of the above embodiments, the _LTS method is applied to the molybdenum _silicide -based halftone phase shifter film. Examples include silicide oxides and metal silicide _oxynitrides such as _ZrSiOxNy .

(Embodiment 4)
Next, Embodiment 4 based on this invention will be described. In the fourth embodiment, a metal film is formed on the phase shifter film to prevent electrification during exposure by electron beams or laser light in the manufacturing process of the phase shift mask.

The phase shifter film manufacturing process will be described below with reference to FIGS. 12 to 16 are sectional structural diagrams corresponding to the sectional structure of the phase shift mask shown in FIG.

First, referring to FIG. 12, a phase shifter film 4 made of an oxynitride film of molybdenum silicide is formed on a transparent substrate 1 in the same manner as in the first or second embodiment.

After that, an antistatic film 6 having a film thickness of about 100 to 500 Å is formed on the phase shifter film 4 . As the film quality of the antistatic film 6, a molybdenum film is formed because the film quality of the phase shifter film is Mo-based. This is because the phase shifter film 4 made of oxynitride of molybdenum silicide, which is formed by the method described above, does not have conductivity. Thereafter, an electron beam resist film 5 is formed on the antistatic film 6 to a thickness of about 5000 Å.

Next, referring to FIG. 13, a predetermined portion of electron beam resist film 5 is exposed to electron beams and developed to form resist film 5 having a desired resist pattern.

Next, referring to FIG. 14, when the antistatic film 6 is Mo-based, the electron beam resist film 5 is used as a mask to dry the antistatic film 6 and the phase shifter film 4 with CF ₄ +O ₂ gas. Etch continuously by etching.

Next, referring to FIG. 15, resist film 5 is removed using O ₂ plasma or the like. Thereafter, referring to FIG. 16, the power failure prevention film 6 is etched and removed using an etchant (mixed solution of ceric ammonium nitrate/perchloric acid) or the like.

This completes the phase shift mask.
In the etching of the phase shift mask, when the phase shift mask is MoSi-based, an antistatic film made of a molybdenum film is formed. A MoSi film may be used as the antistatic film, and similar effects can be obtained by using a Cr-based antistatic film instead of the Mo-based phase shifter film.

As described above, by providing the molybdenum film during the manufacturing process of the phase shift mask, it becomes possible to prevent electrification during electron beam exposure, and it also serves as a light reflecting film for the optical position detector. can be fulfilled.

In the present embodiment, a molybdenum film is used as the antistatic film, but a metal film that provides the same effect, such as W, Ta, Ti, Si, Al, or an alloy thereof, may also be used. .

(Embodiment 5)
The structure of the phase shift mask blanks used in the above embodiments will be described as Embodiment 5 with reference to the drawings.

As for the structure of the phase shift mask blanks used in the above embodiments, there are two types of structures shown in FIGS. 17(a) and 17(b). The structure shown in FIG. 17A has a phase shifter film 4 formed on a transparent substrate 1, and the structure shown in FIG. A metal film 6 is formed on the phase shifter film 4 .

When a phase shift mask is produced using these phase shift mask blanks, the production procedure differs depending on the drawing apparatus that exposes the resist film 4 . For example, (1) the electron beam is used to expose the resist film, and (2) the laser is used to expose the resist film.

(1) Exposing a Resist Film Using an Electron Beam First, a case of exposing a resist film using an electron beam will be described with reference to FIGS. 18(a) and 18(b).

When the electron beam is used to expose the resist film, the preparation procedure differs whether the acceleration voltage is 10 keV or 20 keV or more.

<For 10 keV>
As shown in FIG. 18(a), a phase shift film 4 is formed on a transparent substrate 1, a resist film 5 is formed on the phase shift film 4, and a highly conductive film is formed on the resist film 5. As shown in FIG. An antistatic film 6 composed of molecules is formed.

Next, the resist film 5 is exposed with an electron beam. After that, the antistatic film 6 is removed by washing with water.

Next, the resist film 5 is developed. After that, etching of the phase shifter film is performed. After that, the resist film is removed.

Alternatively, as shown in FIG. 18B, a phase shift film 4 is formed on a transparent substrate 1, a metal film 6b is formed on this phase shift film 4, and a resist film is formed on this metal film 6b. A film 5 is formed, and on this resist film 5 an antistatic film 6a made of a conductive polymer is formed.

Next, the resist film 5 is exposed with an electron beam. After that, the antistatic film 6 is removed by washing with water.
Next, the resist film 5 is developed. Thereafter, etching of metal film 6b is performed.

Next, etching of the phase shifter film is performed. After that, the resist film is removed. After that, the metal film is removed.

Alternatively, in the case shown in FIG. 18B, after the resist film is removed, the following manufacturing method can be adopted as an advanced manufacturing method.

After the resist film is removed, a resist film is formed. After that, a conductive film is formed on this resist film.

Next, the resist film is exposed with an electron beam (resist is left in the portions where light should not be transmitted when exposing the substrate).

Next, the antistatic film is removed by washing with water. After that, the resist film is developed. After that, the metal film is etched. After that, the resist film is removed.

<For 20 keV or more>
In the case of the phase shift mask blank structure shown in FIG. 18A, the phase shift mask is formed by the same procedure as in the case of 10 keV.

In the case of the phase shift mask blank structure shown in FIG. 18(b), the metal film 6b functions as an antistatic film, so the formation of the antistatic film 6a made of a conductive polymer becomes unnecessary. However, in the case of the above advanced manufacturing method, the antistatic film 6a made of a conductive polymer is necessary.

(2) When a resist film is exposed using a laser In the case of the phase shift mask blank structure shown in FIG.
In the case of the phase shift mask blank structure shown in FIG. 18(b), it is not necessary to form the antistatic film 6b made of a conductive polymer. Further, in this case, the formation of the antistatic film 6 is unnecessary even in the case of the above-described advanced manufacturing method.

(Embodiment 6)
Next, as shown in FIG. 18, in the phase shift mask according to the first to fifth embodiments, a defect inspection method when a residual defect (black defect) 50 or a pinhole defect (white defect) 51 occurs. and the defect correction method will be described.

First, the manufactured phase shift mask is subjected to chip comparison type defect inspection using a light transmission type defect inspection apparatus (Model 239HR manufactured by KLA).

This defect inspection apparatus performs inspection using light from a mercury lamp as a light source.
As a result of the inspection, residual defects where the phase shifter film remains where the pattern should be etched and pinhole defects where where the phase shifter film should remain do not have the shape of a pinhole or chip are detected.

Then fix these defects. Remaining defects are corrected by using a YAG laser-based laser blow repair apparatus, which is used for conventional photomasks.

As another method, it can be removed by assist etching by introduction of gas for sputter etching by FIB.

In addition, although the defect inspection apparatus described above performs inspection with light from a mercury lamp as a light source, remaining defects can be repaired by a similar method even when inspection is performed with light from a laser as a light source.

Next, the pinhole defect is repaired by burying the pinhole defect portion by depositing a carbon-based film 52 by the FIB assisted deposition method, which is used for conventional photomasks.

In this manner, even when the corrected phase shift mask is washed, a good phase shift mask can be obtained without peeling of the carbon-based film 52 .

The apparatus for manufacturing a mask blank material film, the method for manufacturing a mask blank material film, the method for manufacturing a phase shift mask blank, and the method for manufacturing a phase shift mask according to the present invention have been described above. It is not limited to this, and can be changed as appropriate without departing from the gist of the invention.

INDUSTRIAL APPLICABILITY The present invention is widely applicable to a mask blank material film manufacturing apparatus, a mask blank material film manufacturing method, a phase shift mask blank manufacturing method, and a phase shift mask manufacturing method. Although a large rectangular substrate has been described as an example, the present invention is also suitable for a large circular substrate, a wide sheet-like substrate, and the like. Moreover, the present invention is applicable regardless of the material of the substrate.

Δ (ΔA, ΔB) tilt angle, θ (θA, θB) offset angle, TS (TSA, TSB) line segment connecting the center of the sputtering surface of the target and the center of the processed surface of the substrate, R rotation direction of the substrate, 100 sputtering apparatus, 102 ceiling, 103 vacuum chamber, 104 (104A, 104B) target, 104As, 104Bs sputtering surface, 105 (105A, 105B) target electrode, 106 substrate, 106u surface to be processed, 107 substrate holder, 109 (109A, 109B) magnet plate, 110 (110A, 110B) magnet, 111 heater, 112 (112A, 112B) high-frequency power supply, 114a reaction gas introduction port, 114b inert gas introduction port, 114c mixed gas introduction port, 114d, 114e vacuum exhaust port .

Claims (28)

An apparatus for manufacturing a material film used for a mask blank by a reactive long-throw sputtering method,
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which serve as a base material of the material film, are arranged apart from each other,
Sputtered particles flying from each of the first and second targets are directed toward a rotating processing surface of a rectangular substrate,
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TSA connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate; A second tilt angle ΔB formed between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate is different for the first and second targets,
the first target having the first tilt angle ΔA of −22° to −19°;
the second target having the second tilt angle ΔB of −10° to −7°;
moving the second target in a direction further away from the substrate than the first target;
A mask blank material film manufacturing apparatus characterized by: a first gas supply means and a second gas supply means for respectively separating a reactive gas and an inert gas and introducing them into the film formation space;
and an exhaust means for depressurizing the film formation space,
setting the distance between the first and second targets and the substrate to 100 mm or more;
While maintaining the pressure in the film formation space at 1.0×10 ⁻¹ Pa or less,
The first gas supply means, the second gas supply means, and the exhaust means are arranged such that the flow ratio of the reactive gas and the inert gas satisfies 50%≦reactive gas/inert gas≦80%. comprising means for controlling
The apparatus for manufacturing a mask blank material film according to claim 1, characterized in that: The first gas supply means introduces the reactive gas toward the substrate, and the second gas supply means introduces the inert gas toward the first and second targets.
3. The apparatus for manufacturing a mask blank material film according to claim 2, wherein: 4. The apparatus for manufacturing a mask blank material film according to claim 1, wherein said material film is an oxynitride of molybdenum silicide. A method for producing a material film used for a mask blank by a reactive long-throw sputtering method, comprising:
The reactive long-throw sputtering method comprises:
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which serve as a base material of the material film, are arranged apart from each other,
The sputtered particles flying from each of the first and second targets are directed toward the rotating processing surface of the rectangular substrate, and
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TSA connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate; A second tilt angle ΔB formed between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate is configured differently for the first and second targets, and
the first target having the first tilt angle ΔA of −22° to −19°;
the second target having the second tilt angle ΔB of −10° to −7°;
has
In a state in which the second target is arranged in a direction away from the substrate more than the first target,
Separately introducing the reactive gas and the inert gas,
pressure is 1.0 × 10 ^-1 Pa or less,
The distance between the first and second targets and the substrate is 100 mm or more,
A method of manufacturing a mask blank material film, wherein a flow ratio of the reactive gas and the inert gas is 50%≦reactive gas/inert gas≦80%. 6. The method of manufacturing a mask blank material film according to claim 5, wherein said reactive gas is introduced to the substrate side, and said inert gas is introduced to said first and second target sides. The step of forming the material film includes:
7. The method of manufacturing a mask blank material film according to claim 5, further comprising the step of performing heat treatment at 200[deg.] C. or higher after forming said material film. 8. The method of manufacturing a mask blank material film according to claim 5, wherein said material film is made of oxynitride of molybdenum silicide. A method for manufacturing a phase shift mask blank, comprising the step of forming a material film used for a mask blank as a phase shifter film on a transparent substrate using a reactive long-throw sputtering method ,
The reactive long-throw sputtering method comprises:
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which serve as a base material of the material film, are arranged apart from each other,
The sputtered particles flying from each of the first and second targets are directed toward the rotating processing surface of the rectangular substrate, and
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TSA connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate; A second tilt angle ΔB formed between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate is configured differently for the first and second targets, and
the first target having the first tilt angle ΔA of −22° to −19°;
the second target having the second tilt angle ΔB of −10° to −7°;
has
In a state in which the second target is arranged in a direction away from the substrate more than the first target,
Separately introducing the reactive gas and the inert gas,
pressure is 1.0 × 10 ^-1 Pa or less,
The distance between the first and second targets and the substrate is 100 mm or more,
A method of manufacturing blanks for a phase shift mask, wherein a flow ratio of the reactive gas and the inert gas is 50%≦reactive gas/inert gas≦80%. 10. The method of manufacturing blanks for a phase shift mask according to claim 9, wherein said reactive gas is introduced to the substrate side, and said inert gas is introduced to said first and second target sides. The step of forming the phase shift mask blanks includes:
11. The method of manufacturing a phase shift mask blank according to claim 9, further comprising the step of performing a heat treatment at 200[deg.] C. or higher after forming the phase shifter film using a sputtering method. 12. The method of manufacturing a phase shift mask blank according to claim 9, wherein said phase shifter film is made of oxynitride of molybdenum silicide. 13. The method of manufacturing a phase shift mask blank according to claim 9, further comprising the step of forming a metal film after the step of forming the phase shifter film. 14. The phase according to claim 13, wherein the metal film is a film made of one of molybdenum, chromium, tungsten, tantalum, titanium, silicon, aluminum, or an alloy film made of any combination thereof. A method for manufacturing shift mask blanks. forming a resist film after the step of forming the phase shifter film;
15. The method of manufacturing a phase shift mask blank according to any one of claims 9 to 14, further comprising: forming an antistatic film on the resist film after the step of forming the resist film. 16. The method of manufacturing a phase shift mask blank according to claim 15, wherein said antistatic film is made of a conductive polymer material. forming a phase shifter film on a transparent substrate using a reactive long-throw sputtering method; forming a resist film having a predetermined pattern on the phase shifter film; and using the resist film as a mask. and a step of patterning the phase shifter film, comprising:
The reactive long-throw sputtering method comprises:
In a single film formation space, a first molybdenum silicide plate-like target and a second target of molybdenum silicide, which are base materials of the phase shifter film, are arranged apart from each other,
The sputtered particles flying from each of the first and second targets are directed toward the rotating processing surface of the rectangular substrate, and
a first tilt angle ΔA between a direction perpendicular to the sputtering surface of the first target and a line segment TSA connecting the center of the sputtering surface of the first target and the center of the surface to be processed of the substrate; A second tilt angle ΔB formed between a vertical direction to the sputtering surface of the second target and a line segment TSB connecting the center of the sputtering surface of the second target and the center of the surface to be processed of the substrate is configured differently for the first and second targets, and
the first target having the first tilt angle ΔA of −22° to −19°;
the second target having the second tilt angle ΔB of −10° to −7°;
In a state in which the second target is arranged in a direction away from the substrate more than the first target,
Separately introducing the reactive gas and the inert gas,
pressure is 1.0 × 10 ^-1 Pa or less,
The distance between the first and second targets and the substrate is 100 mm or more,
A method for manufacturing a phase shift mask, wherein a flow ratio of the reactive gas and the inert gas is 50%≦reactive gas/inert gas≦80%. 18. The method of manufacturing a phase shift mask according to claim 17, wherein the reactive gas is introduced to the substrate side, and the inert gas is introduced to the first and second target sides. The step of forming the phase shifter film includes:
19. The method of manufacturing a phase shift mask according to claim 17, further comprising the step of performing heat treatment at 200[deg.] C. or higher after forming said phase shifter film. 20. The method of manufacturing a phase shift mask according to claim 17, wherein said phase shifter film is made of oxynitride of molybdenum silicide. 21. The method of manufacturing a phase shift mask according to claim 20, further comprising forming a metal film between the step of forming the phase shifter film and the step of forming the resist film. 22. The phase according to claim 21, wherein the metal film is a film made of one of molybdenum, chromium, tungsten, tantalum, titanium, silicon, aluminum, or an alloy film made of any combination thereof. A method for manufacturing a shift mask. The step of patterning the phase shifter film includes:
23. The method of manufacturing a phase shift mask according to claim 21, comprising a step of dry etching using a mixed gas of fluorocarbon and oxygen. After the step of forming the resist film,
Further comprising the step of forming an antistatic film on the resist film,
24. The method of manufacturing a phase shift mask according to any one of claims 17 to 23. 25. The method of manufacturing a phase shift mask according to claim 24, wherein said antistatic film is made of a conductive polymeric material. 25. The method of manufacturing a phase shift mask according to claim 24, wherein said antistatic film is made of a molybdenum-based metal material. The step of forming the resist film having a predetermined pattern includes:
exposing the resist film;
removing the antistatic film before developing the resist film;
a step of developing the resist film;
27. The method of manufacturing a phase shift mask according to any one of claims 24 to 26, comprising: 28. The method of manufacturing a phase shift mask according to claim 27, wherein the step of removing the antistatic film uses water to remove the antistatic film.

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