JP4816197B2 - Gradation mask and manufacturing method thereof - Google Patents

Description

  The present invention relates to a gradation mask suitably used for halftone exposure in a manufacturing process of a display device or the like and a manufacturing method thereof.

  The gradation mask uses a light-shielding film that substantially shields exposure light and a semi-transparent film that transmits exposure light at a desired transmittance, a light-transmitting region, a light-shielding region that does not transmit light, This is a mask for producing gradation by having a translucent region in which the amount of transmitted light is adjusted (see Patent Document 1).

  As a method for manufacturing the gradation mask, various methods can be exemplified. For example, (1) a method of using a mask blank having a light shielding film formed on a transparent substrate, patterning the light shielding film, forming a semitransparent film on the light shielding film pattern, and further patterning, (2) transparent Examples include a method of patterning twice using a mask blank in which a translucent film and a light shielding film are laminated on a substrate (see Patent Document 2).

  In the method (1), the gradation mask can be produced by etching the light shielding film by the first patterning and etching the translucent film and the light shielding film at the same time by the second patterning. The gradation mask can also be produced by etching the light shielding film by the first patterning and etching only the semitransparent film by the second patterning.

  In the method (2), the gradation mask can be produced by etching the light-shielding film and the semi-transparent film at a time in the first patterning and etching only the light-shielding film in the second patterning. Further, the gradation mask can be manufactured by etching only the light shielding film in the first patterning and etching the light shielding film and the translucent film at the same time in the second patterning.

  However, in such a method of manufacturing a gradation mask that requires multiple times of patterning, the alignment of each pattern is shifted during the second patterning, and it is difficult to maintain the relative positional accuracy of each pattern. is there.

  In Patent Document 2, in the method (1), the light shielding film is etched by the first patterning and only the semitransparent film is etched by the second patterning. Are separately etched, and therefore, a gradation mask is disclosed in which the positions of the end portions of the light-shielding film pattern and the end portions of the semitransparent film pattern are different due to the deviation of the alignment positional accuracy. However, a specific gradation mask configuration and manufacturing method are not described in detail.

JP 2002-189280 A JP 2006-18001 A

  The present invention has been made in view of the above problems, and provides a method of manufacturing a gradation mask capable of manufacturing a gradation mask with high accuracy, and a high-accuracy gradation mask obtained thereby. The main purpose.

  In order to achieve the above object, the present invention provides a light shielding region in which a light shielding film and a translucent film having a transmittance adjusting function are stacked in this order on a transparent substrate, and the light shielding film is provided on the transparent substrate. A gradation mask having a translucent region in which only the translucent film is provided on the transparent substrate and a transmissive region in which neither the light-shielding film nor the translucent film is provided on the transparent substrate. The light-shielding region and the semi-transparent region have at least a boundary portion that contacts at least one side, and at least one side of the pattern of the semi-transparent film is disposed on the pattern of the light-shielding film in the vicinity of the boundary portion. And providing a gradation mask characterized in that the light-shielding film and the translucent film contain different kinds of metals.

  In the gradation mask of the present invention, the light-shielding region and the semi-transparent region are in contact with each other at least on one side, and at least one side of the semi-transparent film pattern is the light-shielding film in the vicinity of the boundary portion where the light-shielding region and the semi-transparent region are in contact with each other. Since it is arranged on the pattern, it can be said that the end of the pattern of the light shielding film and the end of the pattern of the semi-transparent film do not match. In such a gradation mask manufacturing process, it is assumed that a process of patterning only the semitransparent film is performed. Since the light shielding film and the semi-transparent film contain different kinds of metals, only the semi-transparent film can be selectively etched. Therefore, even if the alignment is shifted during patterning of the semitransparent film, only the semitransparent film is etched and the light shielding film is not etched, so that the pattern shape of the light shielding film does not change. Therefore, the dimensional accuracy of the pattern of the light shielding film can be guaranteed.

  In the said invention, it is preferable that the said semi-transparent film | membrane has an etching selectivity with respect to the said light shielding film. This is because only the semi-transparent film can be easily and selectively etched when manufacturing the gradation mask. In addition, since only the semitransparent film can be selectively etched, it may cause misalignment, particles during the semitransparent film formation, or peeling, dirt adhesion, patterning unevenness, etc. during patterning of the semitransparent film. This is because even if a defect occurs in the pattern of the semitransparent film, only the semitransparent film can be removed and recycled.

  According to the present invention, a light-shielding film and a translucent film having a transmittance adjusting function are laminated in random order on a transparent substrate, the light-shielding region in which the light-shielding film is provided on the transparent substrate, and the above-mentioned on the transparent substrate. A semi-transparent region provided with only a semi-transparent film, and a transmissive region where neither the light-shielding film nor the semi-transparent film is provided on the transparent substrate, wherein the light-shielding region and the semi-transparent region are at least A method of manufacturing a gradation mask having at least a boundary part in contact with one side, wherein the light shielding film and the translucent film contain different types of metals, applying a resist on the light shielding film, exposing, A first patterning step of patterning the light shielding film by etching the light shielding film, applying a resist on the light shielding film and the translucent film, and exposing at least one side of the light shielding film on the light shielding film. And a second patterning step of patterning only the semi-transparent film by exposing so as to be disposed on the screen, and etching only the semi-transparent film. To do.

  According to the present invention, since only the translucent film is patterned in the second patterning step, the light shielding region in the obtained gradation mask is defined by the pattern of the light shielding film formed in the first patterning step. Therefore, even if the alignment is shifted in the second patterning step, the dimensional accuracy of the light shielding region is guaranteed, so that the gradation mask can be manufactured with high accuracy. Moreover, since the light shielding film and the semitransparent film contain different metals, only the semitransparent film can be selectively etched. For this reason, the alignment is shifted, or particles are generated when the semitransparent film is formed, or the semitransparent film is peeled off during patterning of the semitransparent film, or the semitransparent film is contaminated. Even if unevenness occurs, only the semitransparent film can be removed after the second patterning step, and recycling is possible.

  In the above invention, the first patterning step is a step of patterning the light shielding film using a mask blank in which the light shielding film is formed on the transparent substrate. The first patterning step and the second patterning step are performed. Between the patterning step, a semi-transparent film forming step for forming the semi-transparent film on the entire surface of the transparent substrate on which the light shielding film pattern is formed may be performed. In this case, since only the etching selectivity in the second patterning process needs to be considered, the gradation mask can be manufactured by a relatively simple process.

  Further, the first patterning step may be a step of patterning only the light shielding film using a mask blank in which the translucent film and the light shielding film are formed in this order on the transparent substrate. In this case, it is not necessary to perform a semitransparent film forming step in the middle of the manufacturing process of the gradation mask, so that risks (defects, dirt, etc.) at the time of forming the semitransparent film can be reduced.

  According to the present invention, since only the translucent film is patterned in the second patterning step, the light shielding region in the obtained gradation mask is defined by the pattern of the light shielding film formed in the first patterning step. For this reason, even if the alignment is shifted in the second patterning step, it is possible to ensure the dimensional accuracy of the pattern of the light shielding film and the light shielding region, and it is possible to obtain a highly accurate gradation mask.

  Hereinafter, the gradation mask of the present invention and the manufacturing method thereof will be described in detail.

A. Gradation mask The gradation mask of the present invention includes a light shielding region in which a light shielding film and a translucent film having a transmittance adjusting function are stacked in this order on a transparent substrate, and the light shielding film is provided on the transparent substrate, A gradation mask having a translucent region in which only the translucent film is provided on the transparent substrate, and a transmissive region in which neither the light-shielding film nor the translucent film is provided on the transparent substrate. The light-shielding region and the semi-transparent region have at least a boundary part that contacts at least one side, and at least one side of the pattern of the semi-transparent film is disposed on the pattern of the light-shielding film in the vicinity of the boundary part. The light-shielding film and the translucent film contain different types of metals.

The gradation mask of the present invention will be described with reference to the drawings.
FIG. 1 is a plan view showing an example of the gradation mask of the present invention, and FIG. 2 is a cross-sectional view taken along line AA of FIG. As illustrated in FIGS. 1 and 2, in the gradation mask 1, a light shielding film 3 and a semitransparent film 4 are laminated in this order on a transparent substrate 2, and the light shielding film 3 is formed in a rectangular and concave pattern. The translucent film 4 is formed in a concave pattern. The light shielding film 3 substantially does not transmit exposure light, and the translucent film 4 has a transmittance adjusting function. Further, the light shielding film and the semi-transparent film contain different metals. In FIG. 1, a part of the light shielding film is indicated by a broken line.

  In the gradation mask 1, a light shielding region 11 in which a light shielding film 3 is provided on a transparent substrate 2, a semitransparent region 12 in which only a semitransparent film 4 is provided on the transparent substrate 2, and a semi-transparent region on the transparent substrate 2. A transparent region 4 in which neither the transparent film 4 nor the light shielding film 3 is provided is mixed. The light shielding region 11 has a rectangular shape and a concave shape, and the translucent region 12 has a concave shape. The concave translucent region 12 is in contact with the rectangular and concave light-shielding regions 11, specifically, three sides of the concave translucent region 12 and three of the concave light-shielding regions 11. The sides are in contact, and the three sides of the concave translucent region 12 are in contact with the three sides of the rectangular light-shielding region 11. Then, in the vicinity of the boundary portion b where the light shielding region 11 and the semitransparent region 12 are in contact, the three sides of the pattern of the concave translucent film 4 are arranged on the pattern of the concave light shielding film 3 to form the concave shape. Three sides of the pattern of the semi-transparent film 4 are arranged on the pattern of the rectangular light-shielding film 3. That is, the end of the pattern of the semitransparent film 4 and the end of the pattern of the light shielding film 3 do not match.

An example of a method for manufacturing a gradation mask according to the present invention is shown in FIGS. 4A to 4E are cross-sectional views taken along the line BB of FIGS. 3A to 3E, respectively.
In order to manufacture the gradation mask 1 illustrated in FIG. 1, first, a mask blank having a light shielding film 3a formed on a transparent substrate 2 is prepared, and a first resist film 21 is formed on the light shielding film 3a. Pattern exposure is performed, and development and etching of the light-shielding film 3a are performed (FIGS. 3A and 4A). As a result, rectangular and concave light-shielding film patterns 3b are formed on the transparent substrate 2 (FIGS. 3B and 4B). Next, a semi-transparent film 4a is formed on the transparent substrate 2 so as to cover the rectangular and concave light-shielding film patterns 3b (FIGS. 3C and 4C). Then, a second resist film 25 is formed on the semitransparent film 4a, pattern exposure is performed, and development and etching of the semitransparent film 4a are performed (FIGS. 3D and 4D). Thereby, a concave translucent film pattern 4b is formed on the transparent substrate 2 and the light shielding film 3 (FIGS. 3E and 4E).
In FIG. 3, the first resist film and the second resist film are omitted, and a part of the light shielding film is indicated by a broken line.

  In general, when pattern exposure is performed twice as described above in the process of manufacturing a gradation mask, the first patterning (patterning of a light shielding film in the example shown in FIG. 3) and the second patterning (FIG. 3). In the example shown in (2), alignment is difficult due to the patterning of the translucent film.

An example of a conventional gradation mask manufacturing method is shown in FIGS. FIGS. 6A to 6E are cross-sectional views taken along the line BB of FIGS. 5A to 5E, respectively.
First, a mask blank having a light shielding film 53a formed on a transparent substrate 52 is prepared, a first resist film 61 is formed on the light shielding film 53a, pattern exposure is performed, and development and etching of the light shielding film 53a are performed (FIG. 5 (a) and FIG. 6 (a)). As a result, a light shielding film pattern 53b having a concave opening is formed on the transparent substrate 2 (FIGS. 5B and 6B). Next, a semi-transparent film 54a is formed on the transparent substrate 52 so as to cover the light shielding film pattern 53b (FIGS. 5C and 6C). Then, a second resist film 65 is formed on the semitransparent film 54a, pattern exposure is performed, and development and etching of the semitransparent film 54a and the light shielding film pattern 53b are performed (FIGS. 5D and 6D). As a result, rectangular and concave light-shielding film patterns 53c and convex semi-transparent film patterns 54b are formed on the transparent substrate 2 (FIGS. 5E and 6E).
In FIG. 5, the first resist film and the second resist film are omitted, and a part of the light shielding film is indicated by a broken line.

  In the manufacturing process of such a gradation mask, a part of the light shielding film is etched at the time of the first patterning, and the translucent film and the light shielding film are etched at the time of the second patterning. When the exposure region 68 (outside the bold frame) at the time of the second patterning as shown in (d) shifts from front to back and from side to side, for example, the shape of the light shielding film pattern 53c is changed as shown in FIGS. As shown in FIGS. 7C and 7D, the shape of the light shielding region 71 is also changed. In FIGS. 7A and 7B, the light shielding film is indicated by a broken line. In FIGS. 7C and 7D, the transparent substrate, the light shielding film, and the semitransparent film are omitted, and the light shielding region and the semitransparent film are omitted. Regions and transmissive regions are shown.

  For example, when the exposure area at the time of the second patterning as shown in FIG. 5D is shifted to the left in the figure, the light shielding film pattern 53c is connected in a rectangular shape and a concave shape as shown in FIG. 7A. It becomes the shape that was done. In this case, as shown in FIG. 7C, the shape of the light shielding region 71 also changes. Further, for example, when the exposure area at the time of the second patterning as shown in FIG. 5D is shifted upward in the figure, the light shielding film pattern 53c is shifted from the two rectangles as shown in FIG. 7B. It becomes a shape that is connected and a concave shape that partially differs in line width. In this case, as shown in FIG. 7D, the shape of the light shielding region 71 also changes. In either case of FIGS. 7C and 7D, the shapes of the semi-transparent region 72 and the transmissive region 73 hardly change, but the shape of the light-shielding region 71 changes greatly, so that correction is necessary.

  On the other hand, in the manufacturing process of the gradation mask of the present invention, the pattern of the light shielding film is formed in advance at the time of the first patterning, and only the translucent film is etched at the time of the second patterning. Even if the exposure region 28 (outside the thick frame) at the time of the second patterning as shown in (d) is shifted from front to back and from side to side, for example, as shown in FIGS. The shape of the pattern 3b does not change, and the shape of the light shielding region 11 does not change as shown in FIGS. In addition, since exposure is performed so that at least one side of the exposure region 28 is disposed on the light shielding film pattern 3b in the second patterning, the exposure region 28 in the second patterning as shown in FIG. Even when the position is shifted from front to back and from side to side, for example, as shown in FIGS. 8D to 8F, the shape of the translucent region 12 hardly changes. 8A to 8C, a part of the light shielding film is indicated by a broken line. In FIGS. 8D to 8F, the transparent substrate, the light shielding film, and the semitransparent film are omitted, and the light shielding region is omitted. A translucent region and a transmissive region are shown.

  For example, even if the exposure area in the second patterning as shown in FIG. 3D is shifted to the right in the figure, the shape of the light shielding film pattern 3b does not change as shown in FIG. 8A. As shown in FIG. 8D, the shape of the light shielding region 11 does not change. Further, for example, even if the exposure area in the second patterning as shown in FIG. 3D shifts to the left in the figure, the shape of the light shielding film pattern 3b changes as shown in FIG. 8B. In addition, the shape of the light shielding region 11 does not change as shown in FIG. Furthermore, for example, even if the exposure area at the time of the second patterning as shown in FIG. 3D shifts upward in the figure, the shape of the light shielding film pattern 3b changes as shown in FIG. 8B. In addition, the shape of the light shielding region 11 does not change as shown in FIG. In the case of FIGS. 8D and 8E, the shape of the semi-transparent region 12 slightly changes, but it is considered that it does not become a big problem as compared with the cases of FIGS. 7C and 7D.

  Therefore, the gradation mask of the present invention has an advantage that the dimensional accuracy of the pattern of the light shielding film and the light shielding region is guaranteed, and is highly accurate.

In the present invention, since the light shielding film and the translucent film contain different types of metals, the etching selectivity can be improved. For this reason, it is possible to effectively prevent the light shielding film from being etched when the semitransparent film is etched in the process of manufacturing the gradation mask of the present invention.
Hereinafter, each configuration of the gradation mask will be described.

1. Light-shielding region, translucent region, and transmissive region The gradation mask of the present invention has a transmittance that changes stepwise in three stages, and has a light-shielding region, a translucent region, and a transmissive region.

  The light shielding region in the present invention is a region where a light shielding film is provided on a transparent substrate, and is determined by the pattern of the light shielding film. As illustrated in FIG. 2, in the light shielding region 11, it is sufficient that at least the light shielding film 3 is formed on the transparent substrate 2. For example, only the light shielding film 3 may be formed on the transparent substrate 2. The light shielding film 3 and the semitransparent film 4 may be formed on the substrate 2.

  The translucent region in the present invention is a region in which only a translucent film is provided on a transparent substrate, and is defined by the pattern of the translucent film and the pattern of the light shielding film. In the semi-transparent region, only the semi-transparent film is formed on the transparent substrate, and no light shielding film is formed.

  Further, the transmission region in the present invention is a region where neither the light shielding film nor the semitransparent film is provided on the transparent substrate, and is defined by the pattern of the semitransparent film and the pattern of the light shielding film.

  The shapes of the light shielding region, the semitransparent region, and the transmissive region are not particularly limited, and are appropriately adjusted according to the use of the gradation mask of the present invention. Examples of the shape of the light-shielding region and the translucent region include various shapes such as a rectangle, a circle, an L shape, a convex shape, and a concave shape.

  The gradation mask of the present invention has a boundary portion where the light shielding region and the translucent region are in contact with each other at least on one side. Here, the light-shielding region and the semi-transparent region are in contact with each other at least on one side only when one side of the rectangular light-shielding region 11 and one side of the rectangular semi-transparent region 12 are in contact with each other as illustrated in FIG. Instead, the case where the inner periphery of the O-shaped light-shielding region 11 and the outer periphery of the circular translucent region 12 are in contact with each other as illustrated in FIG. 9B is also included.

  In the case where the light shielding region and the semitransparent region have a shape having a plurality of corners, it is preferable that the light shielding region and the semitransparent region are in contact with each other at two or more sides. Also, one type of light-shielding region is in contact with multiple types of semi-transparent regions, one type of semi-transparent region is in contact with multiple types of light-shielding regions, or multiple types of semi-transparent regions are multiple types of light-shielding regions It is preferable that it touches. In such a case, in the conventional gradation mask manufacturing method, the shape of the light-shielding region often changes when the alignment is shifted during the second patterning. However, in the present invention, the dimensional accuracy of the light-shielding region is guaranteed. This is advantageous.

  The gradation mask only needs to have a boundary portion where the light shielding region and the semi-transparent region are in contact with each other at least on one side, and there may be a light shielding region that is not in contact with the semi-transparent region.

  Further, at least one side of the pattern of the semitransparent film is disposed on the pattern of the light shielding film in the vicinity of the boundary portion where the light shielding area and the semitransparent area are in contact with each other. Here, in the vicinity of the boundary portion where the light-shielding region and the semi-transparent region are in contact, at least one side of the pattern of the semi-transparent film is disposed on the pattern of the light-shielding film. In other words, it is formed in a wider range and narrower than a region where the semi-transparent region and the light-shielding region in contact with the semi-transparent region are combined. For example, in FIG. 1 and FIG. 9, the pattern of the semitransparent film 4 is wider than the semitransparent region 12 in the vicinity of the boundary portion b where the light shielding region 11 and the semitransparent region 12 are in contact, and the semitransparent region 12 and two light-shielding regions 11 in contact with the semi-transparent region 12 are formed in a narrower range than the combined region.

  Further, that at least one side of the pattern of the semitransparent film is arranged on the pattern of the light shielding film means that one side of the pattern of the rectangular semitransparent film 4 is the pattern of the light shielding film 3 as illustrated in FIG. The case where the outer periphery of the pattern of the circular translucent film 4 is arranged on the pattern of the light shielding film 3 as illustrated in FIG.

  When the light shielding film pattern and the semitransparent film pattern have a shape having a plurality of corners, it is preferable that two or more sides of the semitransparent film pattern are arranged on the light shielding film pattern. Further, each side of one type of semi-transparent film pattern is arranged on a plurality of types of light-shielding film patterns, or each side of a plurality of types of semi-transparent film patterns is arranged on a plurality of types of light-shielding film patterns. Preferably it is. In such a case, in the conventional gradation mask manufacturing method, the shape of the light-shielding region often changes when the alignment is shifted during the second patterning. This is advantageous because dimensional accuracy is guaranteed.

FIG. 3E shows a gradation mask obtained when the alignment is not shifted in the manufacturing process of the gradation mask of the present invention, and FIG. 8 shows a gradation mask obtained when the alignment is shifted. 8A to 8C, a part of the light shielding film is indicated by a broken line. In FIGS. 8D to 8F, the transparent substrate, the light shielding film, and the semitransparent film are omitted, and the light shielding region is omitted. A translucent region and a transmissive region are shown.
For example, as shown in FIGS. 8C and 8F, the shape of the semi-transparent region 12 is obtained even if the exposure region in the second patterning as shown in FIG. Does not change. On the other hand, for example, as shown in FIGS. 8A, 8B, 8D, and 8E, the exposure area at the time of the second patterning as shown in FIG. Then, the shape of the semi-transparent region 12 changes slightly.
Thus, in the present invention, it is possible to guarantee a dimensional change due to misalignment in at least one direction. In particular, a margin can be provided for the alignment of the light shielding film pattern in the line width direction.

2. Translucent film The translucent film used in the present invention has a transmittance adjusting function and contains a different type of metal from the light shielding film described later.

  The translucent film is not particularly limited as long as it has a transmittance adjusting function and contains a different kind of metal from the light shielding film. Especially, it is preferable that a semi-transparent film | membrane has an etching selectivity with respect to a light shielding film. Thereby, as illustrated in FIGS. 4D and 4E, only the semitransparent film 4a can be easily and selectively etched. Also, due to misalignment, particles (such as dust) during semi-transparent film deposition, or peeling, dirt adhesion, patterning unevenness, etc. during patterning of the semi-transparent film, defects in the semi-transparent film pattern Even if the semi-transparent film has etching selectivity with respect to the light-shielding film, only the semi-transparent film can be removed. Therefore, only the semi-transparent film can be removed and recycled. Is possible.

  Examples of such a translucent film include chromium, molybdenum silicide, tantalum, aluminum, titanium, silicon, nickel, nickel alloy, cobalt, cobalt alloy, and oxide, nitride, and carbide films thereof. .

  Among them, as the translucent film, chromium-based films such as chromium, chromium oxide, chromium nitride, chromium oxynitride, chromium oxynitride carbide; Ni—Cu—Ti and Ni—Ta—Cu—Ti mainly composed of nickel, And nickel alloy films such as oxides, nitrides, oxynitrides and oxynitride carbides thereof; Co—Cu—Ti and Co—Ta—Cu—Ti containing cobalt as a main component, and oxides and nitrides thereof Cobalt alloy films such as oxides, oxynitrides, oxynitride carbides, etc .; Ni—Co—Cu—Ti mainly composed of nickel and cobalt, and nickel such as oxides, nitrides, oxynitrides, oxynitride carbides, etc. -A cobalt alloy film is preferred.

  In the nickel alloy film, the cobalt alloy film, and the nickel-cobalt alloy film, the etching rate can be controlled by adjusting the contents of elements other than nickel and cobalt as main components. For example, when the content of elements other than nickel and cobalt increases, the etching rate decreases. In the oxynitride carbide film, the etching rate can be controlled by adjusting the carbon content. Specifically, the etching rate decreases as the carbon content increases.

  As a preferable combination of the semitransparent film and the light shielding film, for example, when a nickel alloy film is used for the semitransparent film and a chromium film is used for the light shielding film, or a chromium film is used for the semitransparent film, For example, a nickel alloy film is used. In the case of this combination, a high etching selectivity can be realized.

  Moreover, it is preferable that the average transmittance | permeability in the wavelength 250nm -600nm of a semi-transparent film | membrane is in the range of 10%-60%, More preferably, it exists in the range of 20%-50%. If the average transmittance is less than the above range, it may be difficult to produce a difference in transmittance between the semi-transparent region and the light shielding region. If the average transmittance exceeds the above range, the transmittance between the semi-transparent region and the transmissive region may be difficult. This is because it may be difficult to produce the difference.

  The average transmittance can be calculated by averaging the values obtained by measuring the transmittance of the semitransparent film with the transmittance of the transparent substrate used for the gradation mask as a reference (100%). As the apparatus, an ultraviolet / visible spectrophotometer (for example, Hitachi U-4000) or an apparatus having a photodiode array as a detector (for example, Otsuka Electronics MCPD) can be used.

  The film thickness of the translucent film may be a film thickness that can exhibit the transmittance adjusting function. Specifically, the film thickness of the translucent film varies depending on the type of the translucent film. For example, in the case of a chromium film, it is preferably about 5 to 50 nm, and in the case of a chromium oxide film, the film thickness is 5 nm to 150 nm. In the case of a nickel alloy film or a cobalt alloy film, it is preferably about 20 nm to 120 nm.

  Since the transmissivity of the translucent film varies depending on the film thickness, the desired transmissivity can be obtained by controlling the film thickness. Further, when the translucent film contains oxygen, nitrogen, carbon or the like, the transmittance varies depending on the composition. Therefore, the desired transmittance can be realized by simultaneously controlling the film thickness and the composition. For example, the transmittance increases as the oxygen content increases, and similarly, the transmittance increases as the nitrogen content increases. Nitrogen has a small effect of increasing the transmittance as compared with oxygen. Therefore, when the transmittance is adjusted more finely, the nitrogen content may be adjusted.

  Further, the shape of the pattern of the semitransparent film is such that at least one side of the pattern of the semitransparent film is arranged on the pattern of the light shielding film in the vicinity of the boundary portion where the light shielding region and the semitransparent region are in contact as described above. It is appropriately selected according to the shape of the adjusted translucent region.

  As a method for forming the translucent film, for example, a physical vapor deposition method (PVD) such as a sputtering method, an ion plating method, or a vacuum vapor deposition method is used. For example, when forming a chromium oxynitride chromium carbide film using a sputtering method, a reactive gas sputtering method using a Cr target by introducing a carrier gas such as Ar gas, oxygen (carbonic acid) gas, or nitrogen gas into the reactor. Thus, a chromium oxynitride carbide carbide film can be formed. At this time, the composition of the chromium oxynitride carbide film can be controlled by controlling the flow rates of Ar gas, oxygen (carbonic acid) gas, and nitrogen gas.

3. Light-shielding film The light-shielding film used in the present invention substantially does not transmit exposure light, and contains a different kind of metal from the semitransparent film.

  As the light shielding film, a light shielding film generally used for a photomask can be used. Examples of the light shielding film include films of chromium, chromium oxide, chromium nitride, chromium oxynitride, molybdenum silicide, tantalum, aluminum, silicon, silicon oxide, silicon oxynitride, titanium, and the like. Further, as the light-shielding film, a nickel alloy, a cobalt alloy, a nickel-cobalt alloy, and films of these oxides, nitrides, oxynitrides, oxynitride carbides, and the like can also be used.

  Among them, examples of the light-shielding film include chromium-based films such as chromium, chromium oxide, chromium nitride, and chromium oxynitride; Ni—Cu—Ti and Ni—Ta—Cu—Ti mainly composed of nickel, and oxides thereof. Nickel alloy films such as nitride, oxynitride, oxynitride carbide, etc .; Co—Cu—Ti and Co—Ta—Cu—Ti mainly composed of cobalt, and oxides, nitrides, oxynitrides thereof, Cobalt alloy films such as oxynitride carbides; Ni—Co—Cu—Ti mainly composed of nickel and cobalt, and nickel-cobalt alloy films such as oxides, nitrides, oxynitrides and oxynitride carbides thereof Preferably used. The chromium film may be a single layer or may be a laminate of two or more layers.

  Moreover, it is preferable that the average transmittance | permeability in the exposure wavelength of a light shielding film is 0.1% or less. In addition, about the measuring method of average transmittance | permeability, it is the same as that of the method described in the term of the said semi-transparent film | membrane.

  The film thickness of the light shielding film is not particularly limited, and varies depending on the type of the light shielding film. For example, in the case of a chromium film, it is preferably about 50 nm to 150 nm.

  The shape of the light shielding film pattern is appropriately selected according to the shape of the target light shielding region.

  As a method for forming the light shielding film, for example, a physical vapor deposition method (PVD) such as a sputtering method, an ion plating method, or a vacuum vapor deposition method is used.

4). Transparent substrate The substrate generally used for a photomask can be used for the transparent substrate used for this invention. As the transparent substrate, for example, optically polished low expansion glass such as borosilicate glass and aluminoborosilicate glass, quartz glass, synthetic quartz glass, Pyrex (registered trademark) glass, soda lime glass, white sapphire and the like are not flexible. A transparent rigid material, or a transparent flexible material having flexibility such as a transparent resin film or an optical resin film can be used. Among them, quartz glass is a material having a small coefficient of thermal expansion, and is excellent in dimensional stability and characteristics in high-temperature heat treatment.

5). Gradation mask The gradation mask of the present invention can be used in the manufacture of various products manufactured through an exposure process, such as a lithography method. Among these, the effects of the present invention can be utilized to the maximum when used for manufacturing a display device such as a liquid crystal display device, an organic EL display device, or a plasma display panel, particularly for manufacturing a large display device.

  Applications of the gradation mask of the present invention include, for example, simultaneous formation of drain electrodes and channels in thin film transistors (TFTs), simultaneous formation of spacers and alignment control protrusions in liquid crystal display devices or color filters for liquid crystal display devices, liquid crystal display devices or Simultaneous formation of spacers and overcoat layers in color filters for liquid crystal display devices, simultaneous formation of spacers of different heights in color filters for liquid crystal display devices or liquid crystal display devices, for transflective liquid crystal display devices or transflective liquid crystal display devices Simultaneous formation of colored layer for transmitting portion and colored layer for reflecting portion in color filter, simultaneous overcoat layer for white pattern and overcoat layer for red / green / blue pattern in color filter for organic EL display device or organic EL display device Cite formation It is possible.

  In addition, the size of the gradation mask is appropriately adjusted according to the application. For example, when used for manufacturing a display device such as a liquid crystal display device or an organic EL display device, the size is 300 mm × 400 mm to 1,600 mm. It can be about x1,800 mm.

B. Next, a method for manufacturing a gradation mask according to the present invention will be described.
The method for producing a gradation mask of the present invention includes a light shielding region in which a light shielding film and a translucent film having a transmittance adjusting function are stacked in random order on a transparent substrate, and the light shielding region in which the light shielding film is provided on the transparent substrate; The light-shielding region and the semi-transparent region in which only the semi-transparent film is provided on the transparent substrate, and the transmission region in which neither the light-shielding film nor the semi-transparent film is provided on the transparent substrate. A method of manufacturing a gradation mask having at least a boundary portion where a semi-transparent region is in contact with at least one side, wherein the light-shielding film and the semi-transparent film contain different types of metals, wherein a resist is coated on the light-shielding film And exposing, etching the light shielding film and patterning the light shielding film, applying a resist on the light shielding film and the translucent film, and at least one side of the exposure region Exposed so as to be disposed on the pattern of the light shielding film, by etching only the semi-transparent film, is characterized in that a second patterning step of patterning only the semi-transparent film.

  The method for manufacturing a gradation mask according to the present invention can be divided into two modes according to the order of lamination of the light shielding film and the semitransparent film. In the first aspect, the light shielding film and the semi-transparent film are laminated in this order on the transparent substrate, and in the second aspect, the semi-transparent film and the light shielding film are laminated in this order on the transparent substrate. Hereinafter, each aspect will be described.

1. 1st aspect The 1st aspect of the manufacturing method of the gradation mask of this invention WHEREIN: The light shielding film and the semi-transparent film | membrane which has a transmittance | permeability adjustment function are laminated | stacked in this order on the transparent substrate, The said light shielding is carried out on the said transparent substrate. A light-shielding region provided with a film, a semi-transparent region in which only the semi-transparent film is provided on the transparent substrate, and a transmission region in which neither the light-shielding film nor the semi-transparent film is provided on the transparent substrate. A shade mask and a semi-transparent region at least having a boundary portion that contacts at least one side, wherein the light-shielding film and the semi-transparent film contain different types of metals. And
A first patterning step of patterning the light-shielding film by applying a resist on the light-shielding film, exposing, etching the light-shielding film, using a mask blank having the light-shielding film formed on the transparent substrate When,
A translucent film forming step of forming the translucent film on the entire surface of the transparent substrate on which the light shielding film pattern is formed;
A resist is applied on the light-shielding film and the semi-transparent film, exposed so that at least one side of an exposure region is arranged on the pattern of the light-shielding film, and only the semi-transparent film is etched, and the semi-transparent film And a second patterning step for patterning only.

  3 and 4 are process diagrams showing an example of the method of manufacturing the gradation mask of this embodiment. 4 is a cross-sectional view taken along line BB in FIG.

  First, a mask blank having a light shielding film 3a formed on the transparent substrate 2 is prepared. Next, a positive resist is applied on the light-shielding film 3a, baked for a predetermined time after the application, the first resist film 21 is formed, and then pattern exposure is performed (FIGS. 3A and 4A). At this time, the first resist film 21 remains in the semi-transparent region and the transmissive region so that the semi-transparent region and the transmissive region in the obtained gradation mask become the exposure region 24 (outside the thick line frame), that is, in the light-shielding region. 1. Exposure is performed so that the resist film 21 is removed. Subsequently, development is performed to form a first resist pattern, the light shielding film 3a exposed from the first resist pattern is etched, the remaining first resist pattern is removed, and a light shielding film pattern 3b is formed. (FIG. 3 (b) and FIG. 4 (b)). 3A and 3B and FIGS. 4A and 4B show the first patterning step.

  Next, a semi-transparent film 4a is formed on the entire surface of the transparent substrate 2 on which the light-shielding film pattern 3b is formed (FIGS. 3C and 4C, a semi-transparent film forming process).

  Next, a positive resist is applied onto the translucent film 4a, baked for a predetermined time after application, a second resist film 25 is formed, and then pattern exposure is performed (FIGS. 3D and 4D). At this time, the exposure is performed so that the six sides of the concave opening in the exposure region 28 (outside the thick frame) are arranged on the light shielding film pattern 3b, that is, a range wider than the translucent region in the obtained gradation mask. Then, exposure is performed so that the second resist film 25 remains. Subsequently, development is performed to form a second resist pattern, the semitransparent film 4a exposed from the second resist pattern is etched, the remaining second resist pattern is removed, and the semitransparent film pattern 4b is formed. It forms (FIG.3 (e) and FIG.4 (e)). 3D, 3E, 4D, and 4E show the second patterning process.

  In this embodiment, only the light shielding film is patterned in the first patterning step, only the semitransparent film is patterned in the second patterning step, and the light shielding film and the semitransparent film are separately etched. For this reason, the light shielding region in the obtained gradation mask is defined by the light shielding film pattern formed in the first patterning step. Therefore, even if the alignment is shifted in the second patterning step, the dimensional accuracy of the pattern of the light shielding film and the light shielding region is guaranteed, so that the gradation mask can be manufactured with high accuracy.

  Moreover, in this aspect, since only the semi-transparent film is patterned in the second patterning step, it can be said that the light-shielding film is not etched when the semi-transparent film is etched. For this reason, it is possible to remove only the translucent film after the second patterning step. Therefore, the alignment is shifted in the second patterning process, the semitransparent film is peeled off, dirt is attached to the semitransparent film, patterning is uneven, or particles are generated in the semitransparent film forming process. Even if it does, only a semi-transparent film | membrane can be removed and a semi-transparent film | membrane film-forming process and a 2nd patterning process can be performed again. That is, in this embodiment, recycling is possible.

Furthermore, in the second mode to be described later, only the light shielding film is patterned in the first patterning step, and only the semitransparent film is patterned in the second patterning step. In addition, it is required that the etching selectivity of the semi-transparent film to the light shielding film be taken. On the other hand, in this embodiment, it is not necessary until the etching selection ratio of the light-shielding film to the semi-transparent film can be obtained, so that it is possible to produce a gradation mask in a simpler process than in the second embodiment. it can.
Hereafter, each process in the manufacturing method of the gradation mask of this aspect is demonstrated.

(1) 1st patterning process The 1st patterning process in this aspect applies a resist on a light shielding film using the mask blank by which the light shielding film was formed on the transparent substrate, exposed, and etched the light shielding film. In this step, the light shielding film is patterned.

  A mask blank in which, for example, a chromium film is formed as a light-shielding film on a transparent substrate is a commonly used mask blank and is easily available.

  As the resist used in this embodiment, either a positive resist (one in which the light irradiation part dissolves) or a negative resist (one in which the light irradiation part hardens) can be used. The positive resist is not particularly limited, and examples thereof include a chemically amplified resist using a novolac resin as a base resin. The negative resist is not particularly limited. For example, a chemically amplified resist based on a crosslinkable resin, specifically, a chemically amplified resist obtained by adding a crosslinking agent to polyvinylphenol and further adding an acid generator. A resist etc. are mentioned.

  In pattern exposure of the light shielding film, exposure is performed so that a light shielding region in the obtained gradation mask is formed, that is, the resist remains in the light shielding region and the resist is removed in the semitransparent region and the transmission region. At this time, when a positive resist is used, the exposure is performed so that the translucent region and the transmissive region become exposure regions. When a negative resist is used, exposure is performed so that the light shielding area becomes the exposure area.

  Examples of the exposure method include a method of controlling the exposure amount of the energy beam, a method of performing exposure with a constant exposure amount, and the like. The drawing method is not particularly limited, and an electron beam drawing method or a laser drawing method used for normal photomask drawing can be used. When the electron beam drawing method is used, the exposure amount can be easily converted. When the laser drawing method is used, since it takes time to convert the exposure amount, the exposure may be repeated without changing the exposure amount. In addition, with the increase in the size of display devices such as liquid crystal display devices and organic EL display devices, and the increase in the number of facets at the time of manufacture, the tone masks are also increasing in size. Laser drawing method is applied.

  At the time of pattern exposure of the light shielding film, a plurality of alignment marks used at the time of pattern exposure in the second patterning step can be drawn on the non-transfer area on the transparent substrate.

  Development after pattern exposure can be performed according to a general development method.

  As a method for etching the light shielding film, for example, wet etching using a ceric ammonium nitrate aqueous solution or the like, or dry etching using a chlorine-based gas or the like can be applied. Among these, wet etching is preferable. Wet etching is advantageous in terms of cost and production efficiency. In addition, since the wet etching is dissolved by a chemical reaction, it is preferable from the viewpoint that the etching rate can be easily controlled by selecting an etchant. When the light shielding film is a chromium film, a cerium nitrate wet etchant is preferably used.

  The method for removing the resist is not particularly limited, and is usually performed by ashing by oxygen plasma treatment or cleaning with an organic alkali solution.

  Moreover, in this aspect, you may perform the inspection process which inspects a light shielding film pattern, and the correction process which corrects a defect as needed after a 1st patterning process. When the light shielding film is a chromium film, a general photomask inspection technique and correction technique can be applied. By performing the inspection process of the dimension of the light-shielding film pattern, the defect inspection of the light-shielding film pattern, and the correction process, it is possible to prevent a substrate having a defect from passing over to the next process, increase the yield of non-defective products, and contribute to reducing the mask cost. .

  Since the transparent substrate and the light shielding film are described in the above “A. gradation mask”, the description is omitted here.

(2) Translucent film forming step The translucent film forming step in this embodiment is a step of forming a translucent film on the entire surface of the transparent substrate on which the pattern of the light shielding film is formed.

  The method for forming the translucent film and other points are described in the above “A. Gradation mask”, and thus the description thereof is omitted here.

(3) Second patterning step In the second patterning step in this embodiment, a resist is applied on the light shielding film and the semitransparent film, and exposure is performed so that at least one side of the exposure region is disposed on the pattern of the light shielding film. In this step, only the transparent film is etched and only the semi-transparent film is patterned.

  In the pattern exposure of the translucent film, the exposure is performed so that at least one side of the exposure region is arranged on the light shielding film pattern. Here, the exposure so that at least one side of the exposure region is arranged on the light shielding film pattern is a range wider than the translucent region in the obtained gradation mask, and the translucent region and the translucent region The exposure is performed so that the resist remains in a narrower range than the area combined with the light shielding area in contact therewith. For example, when a positive resist is used, the unexposed area is wider than the translucent area, and more than the combined area of the translucent area and the light shielding area in contact with the translucent area. Exposure is performed in a narrow range. When a negative resist is used, the exposure area is wider than the semi-transparent area, and is narrower than the area where the semi-transparent area and the light-shielding area in contact with the semi-transparent area are combined. Exposure to be in range.

  Furthermore, the fact that at least one side of the exposure region is arranged on the light shielding film pattern means that the rectangular opening of the exposure region 28 (outside the thick line frame) having a rectangular opening as illustrated in FIG. In addition to the case where one side is arranged on the pattern of the light-shielding film 3, as shown in FIG. 9B, the outer periphery of the circular opening in the exposure region 28 (outside the thick frame) having a circular opening is formed. The case where it arrange | positions on the pattern of the light shielding film 3 is also included.

  When forming a light-shielding film pattern and a semitransparent film pattern having a shape having a plurality of corners, it is preferable to perform exposure so that two or more sides of the exposure region are arranged on the light-shielding film pattern. Further, it is preferable that each side of one type of exposure region is arranged on a plurality of types of light shielding film patterns, or each side of a plurality of types of exposure regions is arranged on a plurality of types of light shielding film patterns. . In such a case, in the conventional gradation mask manufacturing method, the shape of the light-shielding region often changes when the alignment is shifted during the second patterning. However, in the present invention, the dimensional accuracy of the light-shielding region is guaranteed. This is advantageous.

  At the time of pattern exposure of the semitransparent film, the alignment mark drawn in the first patterning step can be detected and alignment can be performed.

  Since the resist, the exposure method, and the development method are the same as those described in the first patterning step, description thereof is omitted here.

  In this embodiment, since the light-shielding film and the semi-transparent film contain different types of metals, the fact that the etching rate varies depending on the type of metal contained in the light-shielding film and the semi-transparent film makes it semi-transparent. The etching rate of the film can be made faster than the etching rate of the light shielding film. Thereby, only the semitransparent film can be selectively etched.

  The etching rates of the translucent film and the light shielding film can be easily controlled by appropriately selecting an etchant. For example, when the translucent film is a nickel alloy film and the light shielding film is a chromium film, the etchant includes an iron (III) chloride solution, a mixed solution of nitric acid / acetic acid / acetone, phosphoric acid / acetic acid / nitric acid. A mixed solution of phosphoric acid / acetic acid / nitric acid / water is preferably used. The volume ratio of each component in the mixed solution of nitric acid, acetic acid and acetone is preferably nitric acid: acetic acid: acetone = 1: 1: 1. The volume ratio of each component in the mixed solution of phosphoric acid / acetic acid / nitric acid is preferably phosphoric acid: acetic acid: nitric acid = 250: 20: 3. The volume ratio of each component in the mixed solution of phosphoric acid / acetic acid / nitric acid / water is preferably phosphoric acid: acetic acid: nitric acid: water = 16: 1: 2: 1. Further, for example, when the translucent film is a cobalt alloy film and the light shielding film is a chromium film, a mixed liquid of sodium hydroxide and hydrogen peroxide, hydrogen peroxide is preferably used as the etchant. In addition, about the liquid mixture of sodium hydroxide and hydrogen peroxide, Unexamined-Japanese-Patent No. 2000-71103 can be referred.

  As a means for improving the etching selectivity, there can be used a method in which fluorine ions are implanted into the light shielding film to further increase the difference in etching rate, or a method of changing an etching technique (etching apparatus, etchant, etc.). Note that JP-A-2005-91855 can be referred to for fluorine ion implantation.

  Note that the other points of etching and the method of removing the resist are the same as those described in the first patterning step, and a description thereof will be omitted here.

  In this aspect, after the second patterning step, an inspection step for inspecting the light shielding film pattern and the translucent film pattern may be performed. In this embodiment, the dimensional accuracy of the pattern of the light shielding film is guaranteed, but the yield rate can be further increased by performing the inspection process.

  In addition, in the inspection process, if there is a defect in the dimension of the semitransparent film pattern or there is a defect in the semitransparent film pattern, a semitransparent film removal process for removing the semitransparent film is performed after this inspection process. You may go. As described above, since this embodiment can be recycled, the gradation mask can be regenerated by performing the semitransparent film forming process and the second patterning process again after the semitransparent film process. it can. As a result, the yield rate can be increased and the mask cost can be reduced.

2. Second Aspect A second aspect of the method for producing a gradation mask according to the present invention is that a translucent film having a transmittance adjusting function and a light shielding film are laminated in this order on a transparent substrate, and the light shielding is performed on the transparent substrate. A light-shielding region provided with a film, a semi-transparent region in which only the semi-transparent film is provided on the transparent substrate, and a transmission region in which neither the light-shielding film nor the semi-transparent film is provided on the transparent substrate. A shade mask and a semi-transparent region at least having a boundary portion that contacts at least one side, wherein the light-shielding film and the semi-transparent film contain different types of metals. And
Using a mask blank in which the translucent film and the light shielding film are formed in this order on the transparent substrate, a resist is applied on the light shielding film, exposed, and only the light shielding film is etched, thereby shielding the light shielding A first patterning step of patterning only the film;
A resist is applied on the semi-transparent film and the light-shielding film, exposed so that at least one side of an exposure region is disposed on the pattern of the light-shielding film, and only the semi-transparent film is etched. And a second patterning step for patterning only.

  10 and 11 are process diagrams showing an example of the method of manufacturing the gradation mask according to this embodiment. 11 is a cross-sectional view taken along the line DD of FIG.

  First, a mask blank in which a translucent film 4a and a light shielding film 3a are formed in this order on a transparent substrate 2 is prepared. Next, a positive resist is applied on the light-shielding film 3a, baked for a predetermined time after the application, the first resist film 21 is formed, and then pattern exposure is performed (FIGS. 10A and 11A). At this time, the first resist film 21 remains in the semi-transparent region and the transmissive region so that the semi-transparent region and the transmissive region in the obtained gradation mask become the exposure region 24 (outside the thick line frame), that is, in the light shielding region. 1. Exposure is performed so that the resist film 21 is removed. Subsequently, development is performed to form a first resist pattern, the light shielding film 3a exposed from the first resist pattern is etched, the remaining first resist pattern is removed, and a light shielding film pattern 3b is formed. (FIG. 10 (b) and FIG. 11 (b)). FIGS. 10A and 10B and FIGS. 11A and 11B show the first patterning step.

  Next, a positive resist is applied on the translucent film 4a and the light-shielding film pattern 3b. After the application, the resist is baked for a predetermined time to form the second resist film 25, and then pattern exposure is performed (FIG. 10C and FIG. (C)). At this time, the exposure is performed so that the six sides of the concave opening in the exposure region 28 (outside the thick frame) are arranged on the light shielding film pattern 3b, that is, a range wider than the translucent region in the obtained gradation mask. Then, exposure is performed so that the second resist film 25 remains. Subsequently, development is performed to form a second resist pattern, the semitransparent film 4a exposed from the second resist pattern is etched, the remaining second resist pattern is removed, and the semitransparent film pattern 4b is formed. They are formed (FIG. 10 (d) and FIG. 11 (d)). In addition, FIG.10 (c), (d) and FIG.11 (c), (d) are 2nd patterning processes.

  In this embodiment, only the light shielding film is patterned in the first patterning step, only the semitransparent film is patterned in the second patterning step, and the light shielding film and the semitransparent film are separately etched. For this reason, the light shielding region in the obtained gradation mask is defined by the light shielding film pattern formed in the first patterning step. Therefore, even if the alignment is shifted in the second patterning step, the dimensional accuracy of the pattern of the light shielding film and the light shielding region is guaranteed, so that the gradation mask can be manufactured with high accuracy.

Further, in this embodiment, it is not necessary to perform a semi-transparent film forming step between the first patterning step and the second patterning step as in the first embodiment, that is, halfway in the process of manufacturing the gradation mask. There is no need to perform a transparent film forming step. For this reason, the risk (defect, dirt, etc.) at the time of film-forming of a translucent film | membrane can be reduced. Further, TAT (Turn Around Time) can be shortened.
Hereafter, each process in the manufacturing method of the gradation mask of this aspect is demonstrated.

(1) 1st patterning process The 1st patterning process in this aspect applies a resist on a light shielding film, and exposes it using the mask blank by which the semi-transparent film and the light shielding film were formed in this order on the transparent substrate. In this step, only the light shielding film is etched and only the light shielding film is patterned.

  The mask blank can be produced using the transparent substrate, the translucent film, and the light shielding film described in the above “A. gradation mask”.

  In pattern exposure of the light shielding film, exposure is performed so that a light shielding region in the obtained gradation mask is formed. At this time, in the case of using a positive resist, the semi-transparent region and the transmissive region become the exposure region, that is, the resist remains in the light shielding region, and the resist is removed in the semi-transparent region and the transmissive region. Exposure. When a negative resist is used, exposure is performed so that the light shielding region becomes an exposure region, that is, the resist remains in the light shielding region, and the resist is removed in the semitransparent region and the transmission region.

  Note that the resist, the exposure method, and the development method are the same as those described in the first embodiment, and thus description thereof is omitted here.

  In this embodiment, since the light-shielding film and the semi-transparent film contain different types of metals, the fact that the etching rate varies depending on the type of metal contained in the light-shielding film and the semi-transparent film makes it semi-transparent. The etching rate of the film can be made faster than the etching rate of the light shielding film. Thereby, only the semitransparent film can be selectively etched.

  The etching rates of the translucent film and the light shielding film can be easily controlled by appropriately selecting an etchant.

  Note that the other points of etching and the method of removing the resist are the same as those described in the first embodiment, and thus the description thereof is omitted here.

  In this aspect, after the first patterning step, an inspection step for inspecting the light-shielding film pattern and a correction step for correcting defects as necessary may be performed.

(2) Second Patterning Step In the second patterning step in this embodiment, a resist is applied on the semitransparent film and the light shielding film, and exposure is performed so that at least one side of the exposure region is disposed on the pattern of the light shielding film. In this step, only the transparent film is etched and only the semi-transparent film is patterned.
Since the second patterning step is the same as that described in the first aspect, description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described using examples and comparative examples.

[Example]
(Production of gradation mask)
On a conventional mask blank in which a Cr film and a CrO _x film are laminated in this order on an optically polished 520 mm × 800 mm synthetic quartz substrate, a commercially available photoresist (ip-3500, manufactured by Tokyo Ohka Kogyo Co., Ltd.) has a thickness of 600 nm. After coating and baking for 15 minutes on a hot plate heated to 120 ° C., a desired light-shielding film pattern was drawn with a photomask laser drawing apparatus (LRS11000-TFT3 manufactured by Micronic Co., Ltd.). Next, development was performed with a dedicated developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) to obtain a resist pattern for a light shielding film. Next, using the resist pattern for light shielding film as an etching mask, the Cr / CrO _x film was etched, and the remaining resist pattern for light shielding film was peeled off to obtain a desired light shielding film pattern. For the etching of the Cr / CrO _x film, a commercially available cerium nitrate-based etchant (MR-ES manufactured by The Inktec) was used. A special developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used to remove the resist pattern for the light shielding film.

  Next, a magnetron sputtering apparatus using argon, oxygen and nitrogen (gas flow ratio argon: oxygen: nitrogen = 2: 1: 1) with Ni, Cu and Ti as targets on the substrate on which the light shielding film pattern is formed. A Ni—Cu—Ti oxide film containing Ni as a main component was formed. The thickness of this Ni—Cu—Ti oxide film was 40 nm. The transmittance spectrum of the Ni—Cu—Ti oxide film is shown in FIG. The transmittance of the Ni—Cu—Ti oxide film at 365 nm was 46%.

  Next, a commercially available photoresist (ip-3500 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on the Ni—Cu—Ti oxide film at a thickness of 600 nm and baked on a hot plate heated to 120 ° C. for 15 minutes. Subsequently, a desired translucent film pattern is drawn with a laser drawing apparatus for photomask (LRS11000-TFT3 manufactured by Micronic Co., Ltd.) and developed with a dedicated developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.). Obtained. Next, the Ni—Cu—Ti oxide film was etched using the semitransparent film resist pattern as an etching mask. Etching of nitric acid / acetic acid / acetone (nitric acid: acetic acid: acetone = 1: 1: 1) was used for etching. Furthermore, the desired semitransparent film pattern was obtained by peeling off the remaining semitransparent film resist pattern. A dedicated developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used to remove the resist pattern for the translucent film.

  In this way, a gradation mask having a light shielding region 11, a semitransparent region 12, and a transmission region 13 as shown in FIG. At this time, the line width design value of the pattern of the light shielding film 3 shown in FIG. Further, the light shielding regions 11 and the semi-transparent regions 12 shown in FIG. 13A are provided at 12 locations around the gradation mask 1 as shown in FIG. In FIG. 13A, the translucent film is omitted.

[Comparative example]
(Production of gradation mask)
On a conventional mask blank in which a Cr film and a CrO _x film are laminated in this order on an optically polished 520 mm × 800 mm synthetic quartz substrate, a commercially available photoresist (ip-3500, manufactured by Tokyo Ohka Kogyo Co., Ltd.) has a thickness of 600 nm. After coating and baking for 15 minutes on a hot plate heated to 120 ° C., a desired light-shielding film pattern was drawn with a photomask laser drawing apparatus (LRS11000-TFT3 manufactured by Micronic Co., Ltd.). Next, development was performed with a dedicated developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) to obtain a resist pattern for a light shielding film. Next, using the resist pattern for light shielding film as an etching mask, the Cr / CrO _x film was etched, and the remaining resist pattern for light shielding film was peeled off to obtain a desired light shielding film intermediate pattern. For the etching of the Cr / CrO _x film, a commercially available cerium nitrate-based etchant (MR-ES manufactured by The Inktec) was used. A special developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used to remove the resist pattern for the light shielding film.

Next, a CrO _x film was formed by sputtering on the substrate on which the light shielding film intermediate pattern was formed. The film thickness of this CrO _x film was 50 nm. The transmittance of the CrO _x film at 365 nm was 45%.

Next, a commercially available photoresist (ip-3500 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on the CrO _x film at a thickness of 600 nm, and baked on a hot plate heated to 120 ° C. for 15 minutes. Subsequently, a desired pattern was drawn with a photomask laser drawing apparatus (Micronic LRS11000-TFT3) and developed with a dedicated developer (Tokyo Ohka NMD3) to obtain a resist pattern. Next, the CrO _x film was etched using the resist pattern as an etching mask, and the underlying Cr / CrO _x film was further etched. For the etching, a commercially available cerium nitrate-based etchant (MR-ES manufactured by The Ink Tech Co.) was used. Furthermore, the desired resist pattern and light-shielding film pattern were obtained by peeling off the remaining resist pattern. A dedicated developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used for stripping the resist pattern.

  In this way, a gradation mask having a light shielding region 11, a semitransparent region 12, and a transmission region 13 as shown in FIG. At this time, the line width design value of the pattern of the light shielding film 3 shown in FIG. Further, the light shielding regions 11 and the semi-transparent regions 12 shown in FIG. 13A are provided at 12 locations around the gradation mask 1 as shown in FIG. In FIG. 13A, the translucent film is omitted.

[Evaluation]
For the gradation masks of the example and the comparative example, the line widths x1, x2, y1, and y2 of the pattern of the light shielding film 3 shown in FIG. At this time, the line widths x1, x2, y1, and y2 of the pattern of the light shielding film were measured at each of the twelve locations shown in FIG. For the measurement, Mercury 5000 (manufactured by V Technology) was used. The results are shown in Table 1 below. Further, photographs of the gradation masks of the example and the comparative example are shown in FIGS. 14 (a) and 14 (b), respectively.

  In Table 1, in the comparative example, the average value of (x1−x2) / 2 was 0.69 μm and the average value of (y1−y2) / 2 was 0.34 μm in FIG. As shown, it means that the center position p1 of the first drawing and the center position p2 of the second drawing are shifted by 0.69 μm in the x direction and 0.34 μm in the y direction. In FIG. 15, the translucent film is omitted.

From Table 1 and FIG. 14 (b), the alignment in the comparative example was shifted, and the line width of the pattern of the finished light-shielding film was changed from the line width design value (10 μm). On the other hand, from Table 1 and FIG. 14A, in the example, the same degree of misalignment as in the comparative example (about 0.7 μm in the x direction and about 0.35 μm in the y direction) occurred. The dimension of the light-shielding film pattern was not affected by misalignment, and a gradation mask with good dimensional accuracy was obtained.
In the embodiment, the line width of the finished light-shielding film pattern does not completely match the line width design value because of the accuracy of the drawing apparatus itself.

It is a top view which shows an example of the gradation mask of this invention. It is the sectional view on the AA line of FIG. It is process drawing which shows an example of the manufacturing method of the gradation mask of this invention. FIG. 4 is a sectional view taken along line BB in FIG. 3. It is process drawing which shows an example of the manufacturing method of the conventional gradation mask. It is CC sectional view taken on the line of FIG. It is a top view which shows an example of the conventional gradation mask. It is a top view which shows the other example of the gradation mask of this invention. It is a top view which shows the other example of the gradation mask of this invention. It is process drawing which shows the other example of the manufacturing method of the gradation mask of this invention. It is the DD sectional view taken on the line of FIG. It is a graph which shows the transmittance | permeability spectrum of the semi-transparent film | membrane in an Example. It is a figure for demonstrating the gradation mask of an Example and a comparative example. It is a photograph of the gradation mask of an Example and a comparative example. It is a figure for demonstrating the gradation mask of a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Tone mask 2 ... Transparent substrate 3, 3a ... Light-shielding film 3b ... Light-shielding film pattern 4, 4a ... Semi-transparent film 4b ... Semi-transparent film pattern 11 ... Light-shielding region 12 ... Semi-transparent region 13 ... Transmission region b ... Light-shielding region And the border where the translucent area touches

Claims (4)

A light shielding film and a translucent film having a transmittance adjusting function are laminated in this order on a transparent substrate, and a light shielding region in which the light shielding film is provided on the transparent substrate, and only the semitransparent film on the transparent substrate. A gradation mask having a translucent area provided and a transmission area in which neither the light-shielding film nor the translucent film is provided on the transparent substrate;
The light-shielding region and the semi-transparent region have at least a boundary part that contacts at least one side, and at least one side of the pattern of the semi-transparent film is disposed on the pattern of the light-shielding film in the vicinity of the boundary part,
The light-shielding film is one of a chromium-based film and a nickel alloy-based film, and the semi-transmissive film is the other,
The gray scale mask, wherein an average transmittance of the semi-transmissive film at a wavelength of 250 nm to 600 nm is in a range of 20% to 50% . A light shielding film and a translucent film having a transmittance adjusting function are laminated in random order on a transparent substrate, and a light shielding region in which the light shielding film is provided on the transparent substrate, and only the semitransparent film on the transparent substrate. A boundary portion where the semi-transparent region is provided and a transmission region where neither the light-shielding film nor the semi-transparent film is provided on the transparent substrate, and the light-shielding region and the semi-transparent region contact at least on one side A method for manufacturing a gradation mask, wherein the light shielding film and the translucent film contain different types of metals,
Applying a resist on the light shielding film, exposing, etching the light shielding film, and patterning the light shielding film;
A resist is applied on the light-shielding film and the semi-transparent film, exposed so that at least one side of an exposure region is disposed on the pattern of the light-shielding film, and only the semi-transparent film is etched. have a second patterning step of patterning the only
The light-shielding film is one of a chromium-based film and a nickel alloy-based film, and the semi-transmissive film is the other,
A method for producing a gradation mask, wherein an average transmittance of the semi-transmissive film at a wavelength of 250 nm to 600 nm is in a range of 20% to 50% . The first patterning step is a step of patterning the light shielding film using a mask blank in which the light shielding film is formed on the transparent substrate, and is between the first patterning step and the second patterning step. 3. The method of manufacturing a gradation mask according to claim 2 , further comprising a translucent film forming step of forming the translucent film on the entire surface of the transparent substrate on which the pattern of the light shielding film is formed. . Wherein the first patterning step, the claims wherein the semi-transparent film and the light-shielding film on the transparent substrate by using the mask blank has been formed in this order, characterized in that it is a step of patterning only the light shielding film 2. A method for producing a gradation mask according to 2 .