JP2007199700A - Mask blank and photomask - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a large mask and a mask blank for FPD suitable for multicolor exposure. <P>SOLUTION: The mask blank for the manufacture of an FPD device, having at least a semi-light transparent film for a gray tone mask having the function of regulating transmission amount provided on a light transparent substrate, is characterized in that the semi-light transparent film for the gray tone mask is a film regulated so that, in a wavelength range at least from (i) line to (g) line radiated from an ultrahigh pressure mercury lamp, the transmittance (that is, semitransmittance) range of the semi-light transparent film is within less than 5%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a mask blank and a photomask, and more particularly to a mask blank (a blank for a photomask) for manufacturing an FPD device, a photomask (transfer mask) manufactured using the mask blank, and the like.

In recent years, in the field of large FPD masks, attempts have been made to reduce the number of masks using a gray-tone mask having a semi-transparent film (so-called gray-tone mask half-transparent film) (Non-Patent Document 1). ).
Here, as shown in FIGS. 9A and 10A, the gray tone mask has a light shielding portion 1, a transmission portion 2, and a gray tone portion 3 on a transparent substrate. The gray tone part 3 has a function of adjusting the transmission amount, for example, as shown in FIG. 9 (1), a region where a gray-tone mask semi-transparent film (half translucent film) 3a ′ is formed, Alternatively, as shown in FIG. 10 (1), a gray tone pattern (a fine light shielding pattern 3a and a fine transmission part 3b below the resolution limit of a large LCD exposure machine using a gray tone mask) is formed. For the purpose of reducing the amount of light transmitted through these regions and reducing the amount of irradiation by this region, and controlling the reduced film thickness after development of the photoresist corresponding to the region to a desired value. It is formed.
When a large gray-tone mask is mounted on a large-scale exposure apparatus using a mirror projection system or a lens system using a lens, the exposure light that has passed through the gray tone section 3 becomes insufficient as a whole. The positive photoresist exposed through the portion 3 remains on the substrate only by reducing the film thickness. That is, since the resist can have a difference in solubility in the developer between the portion corresponding to the normal light-shielding portion 1 and the portion corresponding to the gray tone portion 3 due to the difference in exposure amount, the resist shape after development is shown in FIG. ) And FIG. 10B, the portion 1 ′ corresponding to the normal light-shielding portion 1 is, for example, about 1 μm, and the portion 3 ′ corresponding to the gray tone portion 3 is, for example, about 0.4 to 0.5 μm. The portion corresponding to the portion 2 is a portion 2 ′ without resist. Then, the first etching of the substrate to be processed is performed in the portion 2 ′ without the resist, the resist in the thin portion 3 ′ corresponding to the gray tone portion 3 is removed by ashing or the like, and the second etching is performed in this portion. The process for two conventional masks is performed with one mask to reduce the number of masks.
Monthly FPD Intelligence, p.31-35, May 1999

By the way, an LSI mask for manufacturing a semiconductor device such as a microprocessor, a semiconductor memory, or a system LSI is relatively small at a maximum of about 6 inches square, and is reduced projection by a stepper (shot-step exposure) method. Often used in an exposure apparatus. In such an LSI mask, a silicon wafer is used as a transfer substrate, and the final form is cut into a large number of chips. In such LSI masks, the exposure wavelength is shortened in order to overcome the resolution limit determined by the exposure wavelength. Here, in the LSI mask, monochromatic exposure light (single wavelength exposure light) is used from the viewpoint of eliminating chromatic aberration by the lens system and thereby improving resolution. The shortening of the monochromatic exposure wavelength for LSI masks has progressed to g-line (436 nm), i-line (365 nm), KrF excimer laser (248 nm), and ArF excimer laser (193 nm) for ultra-high pressure mercury lamps. Yes. In addition, the minimum line width of the mask pattern formed on the LSI mask is about 0.26 μm (the minimum line width of the pattern formed on the wafer is about 0.07 μm).
On the other hand, when a large mask for FPD (flat panel display) is mounted and used in an exposure apparatus of mirror projection (same-exposure projection exposure by scanning exposure method) method, (1) the mask is formed only by the reflective optical system. Chromatic aberration caused by the intervention of a lens system such as an LSI mask is not a problem, and (2) the influence of multi-color wave exposure (multi-wavelength exposure with multiple wavelengths) at present. Compared to monochromatic wave exposure (single wavelength exposure), it is more advantageous from the overall production aspect than investigating (interference based on transmitted light or reflected light, influence of chromatic aberration, etc.). For this reason, and when mounted on a large-scale exposure apparatus of the lens type, it is described in (2) above, and therefore, a wide wavelength band of i-line to g-line of an ultrahigh pressure mercury lamp is used. It has implemented a wave exposure.

In addition, in the case of a large mask blank for FPD, the reason for the limit surface on the manufacturing principle (the limit surface derived from the manufacturing method and the manufacturing device) and the fluctuation of manufacturing conditions (as compared to the case where the substrate size is small due to the large substrate size) Based on the factors of process variation, various characteristics (film composition, film quality, transmittance, reflectance, optical density, etching characteristics, other optical characteristics, film thickness, etc.) are likely to vary within the plane and between the substrates. There is a feature that it is difficult to make a large quantity of materials with uniform characteristics in the plane and between the substrates. Such a feature tends to be increased as the FPD is further increased in size and definition.
Here, there are the following inconveniences when there are large variations in characteristics in the plane and between the substrates.
(1) A product with large variations in various characteristics cannot be said to be high quality in terms of large variations, and cannot be said to be in terms of performance.
(2) If the variation in various characteristics is large, it is difficult to fit within the standard, and it is difficult to manufacture a large quantity of products that fit within the standard, making it difficult to manufacture.
(3) Due to large variations in various characteristics, non-standard products appear, resulting in poor productivity (yield).
(4) When the variation of various characteristics is large, it is necessary to loosen the standard accordingly. Therefore, high standardization cannot be pursued and it is difficult to meet high standardization.

  Furthermore, the minimum line width of the pattern formed on the large mask for FPD is about 1 μm or less, and the minimum line width of the pattern formed on the large glass substrate for transfer is about 2 to 3 μm. Larger than the line width. However, the FPD is used as one FPD product with a large area, and the final form is large compared to an LSI, and all of a large number of elements need to function. Therefore, defects that prevent all elements from functioning and defects that are considered to have the possibility of inhibiting are not allowed. As described above, in the FPD product, it is necessary to realize that there is no defect with a large area. However, when there are large variations in characteristics within the plane and between the substrates in the FPD large mask blank, There is a feature that it is difficult to achieve high quality and yield improvement for the area FPD product. Such a feature tends to be increased as the FPD is further increased in size and definition.

As described above, the FPD large mask requires characteristics that are not required (that is, need not be considered) for LSI masks based on the difference in the use environment of the mask and the difference in the mask size. It is necessary).
Regarding the required characteristics specific to the large-sized mask for FPD that arises based on such differences in the use environment of the mask, the present inventor has paid attention to multicolor wave exposure.
Now, the advantage of the exposure (multicolor wave exposure) processing with a plurality of wavelengths is that the exposure light intensity can be increased as compared with the exposure with a single wavelength (monochromatic wave exposure). For example, the exposure light intensity is higher when the exposure is performed with light in the wavelength band including the h line and extending from the i line to the g line, as compared with the monochromatic exposure using only the i line or only the g line. For this reason, the productivity of the device can be improved.
For example, large display devices such as FPD devices are often manufactured using the same magnification exposure method. Compared with the reduced exposure method used in the manufacture of LSI devices, etc., in the 1X exposure method, the incident intensity of the exposure light applied to the device surface is small, so the device surface can be irradiated by using multiple wavelengths. The advantage that the incident intensity of the exposure light is compensated can be obtained.
An object of the present application is to find out problems associated with multicolor wave exposure and to devise countermeasures.

The present inventor paid attention to the multicolor wave exposure unique to the large mask for FPD, and studied the required characteristics specific to the large mask for FPD suitable for this multicolor wave exposure.
As a result, the following was found.
(1) The exposure light intensity (relative intensity) of i-line, h-line, and g-line emitted from an ultra-high pressure mercury lamp as an exposure light source is substantially equal. More specifically, the exposure light intensity (relative intensity) of i-line, h-line, and g-line is substantially equal, but the intensity of the central h-line is slightly lower than the intensity of i- and g-line at both ends (see FIG. 1).
In other words, the i-line, h-line, and g-line all need to be regarded as equally important in terms of relative intensity, and the effects expressed according to the relative intensity during exposure through the mask, such as the photosensitive action of the resist, etc. Both of them should be equally important.
Here, considering the transmissivity (semi-transmittance, half-transmittance) in the semi-transparent film (half translucent film) for the gray tone mask, the transmissivity (that is, semi-transmittance) T of the semi-transparent film. Is a function of the wavelength λ and is represented by T = f (λ). The spectral curve of transmittance (ie, semi-transmittance) T of the semi-transparent film is mainly determined by the film material, film composition, film quality, manufacturing conditions, manufacturing apparatus, and the like.
On the other hand, the transmissivity (that is, translucency) T of the translucent film is represented by T = I / I ₀ (1) (in formula (1), T: of the translucent film Transmittance (ie, semi-transmittance), I ₀ incident light intensity, I: transmitted light intensity).
From the above, i-line, h-line, relative intensity of the g-line equivalent, thus i-line, h-line, the incident light intensity I ₀ of the g-line is equivalent, i-line, h-line, to the wavelength of the g-line However, if the transmissivity (that is, semi-transmissivity) T of the semi-transparent film is almost equal, the transmitted light intensity I with respect to the i-line, h-line, and g-line is almost equal from the above equation (1). Such characteristics should be considered preferable from the viewpoint of ease of simulation such as the photosensitive action of the resist.
In other words, the vertical axis represents the transmissivity of the semi-transparent film (that is, the semi-transmissivity), and the T-horizontal axis represents the spectral transmission having a flat spectral characteristic in a wide wavelength band of i-line to g-line. A rate line (that is, a spectral transmittance line having a small inclination with respect to the horizontal axis) is considered preferable. Note that the slope of the transmittance of the semi-transparent film (ie, semi-transmittance) with respect to the horizontal axis of the spectral transmittance line varies (changes) depending on how the vertical axis is taken, but comparison is possible if the vertical scale is the same. It is.
(2) A film having substantially the same transmissivity (that is, semi-transmittance) of a semi-transparent film with respect to i-line, h-line, and g-line can be actually manufactured.
(3) In a large FPD mask used in multicolor wave exposure, the transmissivity of a semi-transparent film (ie, semi-transmission) is substantially the same for i-line, h-line, and g-line, which are substantially equivalent in relative intensity. The film having a large variation width of the transmissivity of the translucent film (i.e., semi-transmissivity) with respect to i-line, h-line, and g-line was applied Compared to the case, it is easy to make a large amount of a translucent film having a uniform transmissivity (that is, semi-transmittance) between the in-plane and between the substrates, so that it can contribute to higher mask blank quality and improved yield, and so on. It has been confirmed that it can contribute to quality improvement and yield improvement for large area FPD products.
(4) In relation to the above (1) and (3), i-line, h-line, and g-line are used rather than a film design that takes into account the effects of multi-color wave exposure (such as the effects of interference of transmitted light). On the other hand, the design of the film having substantially the same translucency (ie, semi-transmissivity) of the semi-transparent film is beneficial for improving the quality of the mask blank and the FPD product itself and improving the yield.
(5) In relation to (1), (3), and (4) above, the translucent film has almost the same transmissivity (ie, semi-transmissivity) for at least i-line, h-line, and g-line. An optically designed and manufactured film with a flat slope of the spectral transmittance line, preferably a film with a flat slope of the spectral transmittance line in a wider wavelength band including i-line to g-line (for example, Variation in manufacturing conditions in a wavelength band ranging from 330 nm to 470 nm is a film that is optically designed so that the fluctuation range of the transmissivity of the translucent film (i.e., semi-transmissivity) is less than 10% or even less than 5%. The variation width H of the transmissivity of the semi-translucent film (that is, semi-transmissivity) is small with respect to (process variation) and the accompanying variation in film composition and film quality (physical properties) (FIG. 7 ( 1)), and therefore more uniform (more stringent mask blanks and masks with higher standards k and k '). (See FIG. 8 (2)), and blanks and masks that fall within the standards k and k ′ can be easily manufactured in high yield (see FIG. 7 (2)).
On the other hand, if the fluctuation range H ′ of the spectral transmittance with a steep inclination in the above wavelength band is large (see FIG. 7 (2)), the spectral transmittance line shifts up, down, left and right with a slight process variation. As a result, the uniformity of various characteristics deteriorates (see FIG. 8 (1)), and the ratio of out of the standard k and k ′ due to the shift of the spectral transmittance line increases, so it is difficult to manufacture and the productivity is not good. (See FIG. 7 (2)). Therefore, in reality, it is impossible to manufacture with high productivity unless the standards k and k ′ are loosened as compared with the flat type.
When the fluctuation width h ′ of the spectral transmittance line in the wavelength band is originally large, the fluctuation width H ′ before and after the shift of the spectral transmittance line also increases (see FIG. 7 (1)). On the other hand, if the fluctuation width of the spectral transmittance line in the wavelength band is originally small, the fluctuation width H before and after the shift is also small (see FIG. 7 (1)). This is because, when the spectral transmittance line shifts up, down, left and right due to process variation, the fluctuation width H ′ composed of the minimum value before the shift and the maximum value after the shift is the case where the slope of the spectral transmittance line is flat. This is because it becomes larger than the fluctuation range H (assuming that the shift amount in the vertical and horizontal directions is the same) (see FIG. 7 (1)).
Further, when the slope of the spectral transmittance line is tight (if the fluctuation range is large), it is difficult to obtain a margin m ′ with respect to the standard values k and k ′, and an attempt is made to obtain a sufficient margin m ′ according to the upper limit of the fluctuation range. The standard value k ′ becomes too bad (see FIG. 7 (2)). On the other hand, when the slope of the spectral transmittance line is flat, it is possible to increase the margin m with respect to the upper limit of the fluctuation range (to allow a margin) (see FIG. 7B).
In the case of a film having a large fluctuation range of the spectral transmittance line in the above wavelength band, the same film is manufactured even if there is a change within the fluctuation range of the spectral transmission line (for example, a change in inclination or a shift of the line). It is not preferable because it will be managed and certified as being present (see FIG. 8 (1)).
(6) In connection with the above (2), a film having substantially the same translucency (ie, semi-transmittance) as that of the i-line, h-line, and g-line can be actually manufactured. In the course of finding something, I found out the following.
(I) A chrome oxide film-based semi-transparent film for gray tone masks (for example, a CrO film) contains O in the film (because there is a lot of O in the film), so the wavelengths of i-line to g-line It has been found that the spectral transmittance line basically has a tight slope (a large slope with respect to the horizontal axis λ) in a wider wavelength band including the wavelength band and the wavelength band, and the fluctuation range of the spectral transmittance increases.
(Ii) Compared to the chromium oxide film-based semi-transparent film, the chromium nitride film-based semi-transparent film (for example, CrN, CrCN, CrON) includes the wavelength band of i-line to g-line and further includes such a wavelength band. Spectral transmittance line slope is basically gentle and flat in a wide wavelength band (small slope with respect to the horizontal axis λ), but the mask blank and FPD itself are of higher quality and more uniform (strict standards) In order to achieve the purpose of facilitating the production of a large amount of), it is not possible to achieve such a purpose with any chromium nitride film semi-transparent film. It has been found that it is necessary to find and use a chromium nitride-based semi-transparent film that satisfies the conditions. That is, even if the film material is the same chromium nitride film system, it does not satisfy the predetermined condition due to differences in film composition adjustment, manufacturing conditions, selection and control of manufacturing equipment, etc., and control of film quality by these. It turns out that there is something.
(Iii) The MoSi-based semi-transparent film for gray tone masks also has a wider wavelength band including the wavelength band of i-line to g-line and the wavelength band than the chromium oxide film-based semi-transparent film. Basically, the slope of the spectral transmittance line is gentle and flat. However, in order to achieve the objectives such as improving the quality of mask blanks and FPDs themselves and making it easier to mass-produce more uniform ones (strict ones with strict specifications), what kind of MoSi-based translucent film is used? However, it has been found that it is not possible to achieve such an object, and it is necessary to find and use a MoSi semi-translucent film capable of achieving such an object. In other words, even if the film material is the same MoSi-based semi-transparent film, the film satisfies the predetermined condition due to differences in film composition adjustment, production conditions, selection and control of production equipment, etc., and film quality control by these. It turned out that there was something that did not satisfy. It has been found that, for example, a semi-transparent film such as MoSi ₄ or MoSi ₂ is suitable as the MoSi-based semi-transparent film that satisfies the predetermined conditions and can achieve the above object. Further, when compared with the MoSi ₄ semi-transparent film, the MoSi ₂ semi-transparent film is wider than the wavelength band of i-line to g-line and further includes such a wavelength band when compared with the same scale of the horizontal axis. It was found that the spectral transmittance line slope is more flat in the wavelength band, which is preferable.

The method of the present invention has the following configuration.
(Configuration 1) A mask blank for manufacturing an FPD device having at least a semi-transparent film for a gray tone mask having a function of adjusting a transmission amount on a translucent substrate,
The translucent film for the gray tone mask has a variation width of the transmissivity of the translucent film (that is, translucency) of at least 5 in the wavelength band from the i-line to the g-line emitted from the ultrahigh pressure mercury lamp. A mask blank for manufacturing an FPD device, characterized in that the film is controlled to be within a range of less than%.
(Configuration 2) A mask blank for manufacturing an FPD device having at least a semi-transparent film for a gray tone mask having a function of adjusting a transmission amount on a translucent substrate,
The semi-transparent film for gray tone mask has a variation range of the transmissivity (that is, semi-transmissivity) of the semi-transparent film within a range of less than 10% in the wavelength band extending from 330 nm to 470 nm. A mask blank for manufacturing an FPD device, characterized by being a controlled film.
(Configuration 3) The gray-tone mask semi-transparent film has a variation range of transmittance (that is, semi-transmissivity) of less than 5% in the wavelength band extending from 330 nm to 470 nm. A mask blank for manufacturing the FPD device according to Configuration 2, which is a film controlled to be
(Structure 4) The gray-tone mask semi-transparent film is a chromium nitride film-based semi-transparent film optically designed and manufactured to satisfy the above requirements. A mask blank for manufacturing the FPD device according to any one of the above.
(Structure 5) Any of Structures 1 to 3, wherein the gray-tone mask semi-transparent film is a MoSi-based semi-transparent film optically designed and manufactured to satisfy the above requirements. A mask blank for manufacturing the FPD device according to claim 1.
(Configuration 6) In a mask blank having at least a semi-transparent film having a function of adjusting a transmission amount on a translucent substrate,
The mask blank is a mask blank for a photomask that is exposed to exposure light including a plurality of wavelengths when a device is manufactured after the semi-transparent film is patterned to form a photomask. And
The translucent film has a variation range of the transmissivity of the translucent film (that is, transmissivity) of less than 5% in a wavelength band extending from at least i-line to g-line emitted from the ultra-high pressure mercury lamp. A mask blank, which is a film controlled to be inside.
(Structure 7) A photomask for manufacturing an FPD device, which is manufactured using the mask blank according to structures 1 to 5 and has at least a semi-transparent film pattern for a gray tone mask.
(Configuration 8) A photomask manufactured using the mask blank according to Configuration 6.

  ADVANTAGE OF THE INVENTION According to this invention, the large sized mask for FPD and mask blank suitable for multicolor wave exposure can be provided.

Hereinafter, the present invention will be described in detail.
In the mask blank and the mask for manufacturing the FPD device according to the present invention, the semi-transparent film (half translucent film) for the gray tone mask is changed from at least i-line to g-line emitted from the ultra-high pressure mercury lamp. The film is controlled so that the fluctuation range of the transmissivity (semi-transmittance, half-transmittance) of the gray-tone mask semi-transparent film is within a range of less than 5% in a wavelength band across. As a result, the transmissivity of the gray-tone mask translucent film for i-line, h-line, and g-line is almost equal regardless of the wavelength (for example, transmissivity of the translucent film (i.e., transmissivity) (Transmissivity) is less than 5%) (Configuration 1).
In the present invention, the gray-tone mask translucent film satisfying the above requirements is considered to have a possibility of satisfying the above requirements (a film suitable for satisfying the above requirements), and further a film. It is obtained by confirming that it is possible to satisfy the above requirements by adjusting the composition, selecting and controlling the production conditions, production equipment, etc., and controlling the film quality by these. Even if the film materials are the same, there are some that satisfy the above requirements and others that do not satisfy the above requirements due to differences in adjustment of the film composition, production conditions, selection and control of the production apparatus, and control of the film quality.
In the present invention, the gray-tone mask semi-transparent film is a semi-transparent film in a wavelength band extending from at least i-line to g-line emitted from an ultrahigh pressure mercury lamp under the above-described circumstances. The fluctuation range of the transmittance (ie, semi-transmittance) is within a range of less than 5%, and the transmittance (ie, semi-transmittance) of the semi-transparent film with respect to i-line, h-line, and g-line is almost independent of the wavelength. The film is optically designed and manufactured so as to be equivalent.

In the mask blank and the mask for manufacturing the FPD device according to the present invention, the translucent film for gray tone mask has a transmittance (that is, a semitransparent film) in a wavelength band ranging from 330 nm to 470 nm. It is preferable that the film be controlled so that the fluctuation range of the transmittance and the half transmittance is within a range of less than 10% (Configuration 2).
Examples of such a film include a MoSi _X (X> 2) film (for example, a MoSi ₃ film or a MoSi ₄ film).
Further, in the mask blank and the mask for manufacturing the FPD device according to the present invention, the gray-tone mask semi-transparent film has a transmissivity of the translucent film in a wavelength band extending from 330 nm to 470 nm ( That is, the film is preferably controlled so that the fluctuation range of the semi-transmittance and the half-transmittance is within a range of less than 5% (Configuration 3).
Examples of such a film include a CrN film and a MoSi ₂ film, a metal film such as Ta, Ti, W, Mo, and Zr, an alloy film of these metals, or these metals and others. Alloy films with other metals (other metals include Cr and Ni) and films containing these metals or alloys and silicon.

The mask blank and the mask for manufacturing the FPD device according to the present invention include a mode in which at least the gray-tone mask semi-transparent film and the light-shielding film are arranged in any order on the translucent substrate. That is, a mode in which a light-shielding film is formed for the purpose of blocking the exposure wavelength separately from the translucent film is included. Specifically, for example, as shown in FIG. 3A, a gray-tone mask semi-transparent film 11 and a light-shielding film 12 are formed in this order on a translucent substrate 10, and these films are formed. As shown in FIG. 3 (2), the translucent film underlaying type formed by forming the semi-transparent film pattern for the gray tone mask and the light-shielding film pattern. A light-shielding film and a gray-tone mask semi-transparent film are formed in this order on the substrate, and these films are patterned to form a light-shielding film pattern and a gray-tone mask semi-transparent film pattern. Examples include a semi-transparent film-mounted type that is formed.
Here, the material of the light semi-transmissive film is not limited to the MoSi material composed of Mo and Si, but metal and silicon (transition metals such as MSi, M: Mo, Ni, W, Zr, Ti, Cr). Oxynitrided metal and silicon (MSSiON), oxycarburized metal and silicon (MSiCO), oxynitridized carbon and silicon (MSiCON), oxidized metal and silicon (MSio), nitrided metal and Silicon (MSiN), etc., and metals such as Ta, Ti, W, Mo, and Zr, alloys of these metals, or alloys of these metals and other metals (as other metals, Cr And Ni), and materials containing these metals or alloys and silicon.
In addition, as the material of the light-shielding film, for example, a material different from the etching characteristics of the light translucent film may be used. When the metal constituting the translucent film is molybdenum, chromium, chromium oxide, chromium nitride Products, chromium carbides, chromium fluorides, and materials containing at least one of them. Similarly, when the translucent film is made of a chromium nitride film-based material, chromium, a chromium oxide, a chromium carbide, a chromium fluoride, or a material containing at least one of them is preferable.

In the mask blank and the mask for manufacturing the FPD device according to the present invention, the semi-transparent film for the gray tone mask is optically designed and manufactured so as to satisfy the above requirements. (Configuration 4).
Further, in the mask blank and the mask for manufacturing the FPD device according to the present invention, the semi-transparent film for gray tone mask is optically designed and manufactured to satisfy the above requirements. (Configuration 5).
These reasons are because these materials easily satisfy the above requirements by adjusting the film composition, selecting and controlling production conditions, production equipment, and the like, and controlling the film quality by these, compared with other materials.
Note that the chromium nitride film-based semi-transparent film for gray-tone masks is suitable for the semi-transparent film-mounted type shown in FIG. The MoSi-based semi-transparent film for gray tone mask is suitable for the semi-transparent film underlay type shown in FIG.

  In the mask blank and the mask for manufacturing the FPD device according to the present invention, the transmissivity (that is, translucency) of the semi-transparent film for gray tone mask is a target value within a range of 15 to 65%. And the transmittance of the semi-transparent film having the target value (that is, semi-transmittance) is obtained by controlling the film thickness.

In the present invention, examples of the ultra-high pressure mercury lamp include those having the characteristics shown in FIG. 1, for example, but the present invention is not limited to this.
Examples of the translucent substrate include synthetic quartz, soda lime glass, and alkali-free glass.

In the present invention, mask blanks and masks for manufacturing FPD devices include mask blanks and masks for manufacturing FPD devices such as LCD (liquid crystal display), plasma display, and organic EL (electroluminescence) display. .
Here, the LCD manufacturing mask includes all masks necessary for LCD manufacturing. For example, TFTs (thin film transistors), particularly TFT channel portions and contact hole portions, low-temperature polysilicon TFTs, color filters, reflectors ( A black matrix), and the like. Other display device manufacturing masks include all masks necessary for manufacturing organic EL (electroluminescence) displays, plasma displays, and the like.

  A photomask for manufacturing the FPD device according to the present invention is manufactured using the mask blank for manufacturing the FPD device according to the present invention, and has at least a semi-transparent film pattern for a gray tone mask. Characteristic (Configuration 6).

The mask blank according to the present invention is a mask blank having at least a semi-transparent film having a function of adjusting a transmission amount on a translucent substrate.
The mask blank is a mask blank for a photomask that is exposed to exposure light including a plurality of wavelengths when a device is manufactured after the semi-transparent film is patterned to form a photomask. And
The translucent film has a variation range of the transmissivity of the translucent film (that is, transmissivity) of less than 5% in a wavelength band extending from at least i-line to g-line emitted from the ultra-high pressure mercury lamp. The film is controlled so as to be inside (Configuration 6).
In the mask blank according to the present invention, the transmissivity of the semi-transparent film (i.e., semi-transmissivity) for i-line, h-line, and g-line is almost equal regardless of the wavelength (e.g., transmissivity of the semi-transparent film (i.e., transmissivity). The difference in the semi-transmissivity) is less than 5%), whereby a mask blank and a photomask suitable for multicolor wave exposure can be provided.
Specifically, with the above configuration, even if the manufacturing conditions (film forming conditions) during the formation of the semi-transparent film change, the spectral transmittance (transmittance at each wavelength) may change due to this. Therefore, it is possible to manufacture a mask blank or a mask that falls within the specifications with a high yield. In addition, the film thus controlled is less likely to have a large variation in spectral transmittance (transmittance at each wavelength) with respect to the vertical and horizontal shifts of the spectral transmittance curve due to process variations. Uniformity of transmittance at wavelength.
Moreover, the mask blank and mask of this invention are suitable as a mask blank and a photomask corresponding to the exposure machine which performs a 1x exposure process.
Further, the mask blank and the mask according to the present invention are suitable as a mask blank and a mask corresponding to an exposure apparatus in which the illumination optical system is configured as a reflection optical system.
Further, the mask blank and the mask according to the present invention are suitable as a large mask of 330 mm × 450 mm rectangle or more and a large mask blank corresponding to this mask. Examples of the use of such a large mask include a mask for manufacturing a display device, for example, a photomask for manufacturing an FPD device.
The present invention is suitable as a mask blank corresponding to a gray tone mask.
A photomask according to the present invention is manufactured using the mask blank according to the present invention, and has at least a semi-transparent film pattern (Configuration 8).
In addition, about the other matter regarding the mask blank and photomask (Configuration 6 and Configuration 8) according to the present invention, the matters described in the mask blank and photomask (Configuration 1 to 5 and Configuration 7) according to the present invention described above. It is the same.

Hereinafter, the present invention will be described in more detail based on examples.
Example 1
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, a Cr target is used, and Ar and N ₂ gases are used as sputtering gases, and a CrN semi-transparent film is formed at 100 angstrom (sample 1), 80 angstrom (sample 2), 50 angstrom (sample 3), 30 angstrom ( Samples 4) were changed stepwise to produce a plurality of samples.
Among these, the spectral transmittance line of sample 2 is shown in FIG. 2A, and the spectral transmittance line of sample 3 is shown in FIG. 2B. D indicates the spectral transmittance of QZ. The spectral transmittance was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-4100).
In the spectral transmittance line A according to the sample 2 and the spectral transmittance line B according to the sample 3 shown in FIG. 2, the translucent film is at least in the wavelength band extending from the i-line to the g-line emitted from the ultrahigh pressure mercury lamp. The fluctuation range of the transmittance (ie, semi-transmittance) was within a range of less than 5%.
Further, in the spectral transmittance line A related to the sample 2 and the spectral transmittance line B related to the sample 3 shown in FIG. 2, the transmittance of the semi-transparent film (that is, the semi-transparent film) also in the wavelength band extending from 330 nm to 470 nm. The fluctuation range of the transmittance was within a range of less than 5%.
When a plurality of sheets (between substrates: 100 sheets) were examined in the same manner for in-plane (equal 9 positions), all of them were within the range of fluctuation width of the transmissivity of the semi-translucent film (that is, semi-transmissivity). confirmed.
Further, any film prepared by setting an arbitrary film thickness within the range of 20 to 250 Å of the CrN semi-transparent film has a transmittance (that is, a semi-transmittance) of the semi-transparent film. ) Was confirmed to be within the range of fluctuation.

(Comparative Example 1)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, a Cr target is used, and Ar and O ₂ gases are used as sputtering gases to form a CrO semi-transparent film of 100 angstrom (sample 1 ′), 250 angstrom (sample 2 ′), 400 angstrom (sample 3 ′), A plurality of samples were prepared by changing in steps of 500 angstrom (sample 4 ′).
Among these, the spectral transmittance line of sample 3 ′ is shown in FIG.
In the spectral transmittance line C relating to the sample 3 ′ shown in FIG. 2, the transmissivity of the semi-transparent film (that is, the semi-transmittance) is at least in the wavelength band extending from the i-line to the g-line emitted from the ultrahigh pressure mercury lamp. The fluctuation range of was 6% or more.
Further, in the spectral transmittance line C relating to the sample 3 ′ shown in FIG. 2, in the wavelength band extending from 330 nm to 470 nm, the fluctuation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film is about 12. % Or more.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), the spectral transmittance line C shifted up and down and left and right with only a slight process variation. It has been found that the fluctuation range of the transmittance (that is, the semi-transmittance) of the conductive film increases by about 2-3%.
In addition, the film | membrane produced by setting arbitrary film thicknesses within the range of the film thickness of 100-500 angstroms of a CrO semi-transparent film | membrane is all the transmittance | permeability (namely, the translucent film | membrane of Example 1). It was confirmed that it was out of the range of the fluctuation range of (semi-transmittance).

(Production of blank and mask)
Using a large in-line sputtering apparatus on a large glass substrate (synthetic quartz (QZ) 10 mm thickness, size 850 mm × 1200 mm), a Cr-based light shielding film was formed (a mask blank was produced). Patterning was performed. Here, the Cr-based light shielding film was formed by using a Cr target and forming a CrC film of 620 to 570 angstroms using Ar and CH ₄ gas as sputtering gases.
Next, a gray-tone mask translucent film was formed in the same manner as in Example 1 and Comparative Example 1 (mask blank was prepared), and this gray-tone mask semi-transparent film was patterned. It was.
As described above, a large-sized mask for FPD of a semi-translucent film placement type as shown in FIG.
As a result, when the film of Example 1 is used as the semi-transparent film for a gray tone mask, it is beneficial for improving the quality of the mask and improving the yield as compared with the case of using the film of Comparative Example 1. It was confirmed.

(Example 2)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a target of Mo: Si = 20: 80 (atomic% ratio), Ar and helium as sputtering gases, a semi-transparent film (MoSi ₄ ) for a gray-tone mask made of molybdenum and silicon is 100. A plurality of samples were prepared by changing stepwise from angstrom (sample 5), 50 angstrom (sample 6), and 30 angstrom (sample 7).
The spectral transmittance line of Sample 5 is shown in FIG. 4, the spectral transmittance line of Sample 6 is shown in FIG. 5, and the spectral transmittance line of Sample 7 is shown in FIG. The spectral transmittance was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-4100).
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is within the range of Sample 5: less than 3.9%, Sample 6: Within the range of less than 4.6%, Sample 7: within the range of less than 3.1%.
Further, in the wavelength band ranging from 330 nm to 470 nm, the fluctuation range of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is within the range of Sample 5: less than 6.0%, and Sample 6: 8.5%. The sample 7 was within the range of less than 5.8%.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, any film produced by setting an arbitrary film thickness within the range of 20 to 250 angstroms of the MoSi ₄ film is a variation width of the transmissivity of the translucent film (that is, semi-transmissivity). Was confirmed to be within the range of sample 6 or less.

(Example 3)
In Example 2 described above, a semi-transparent film for a gray-tone mask having a plurality of transmittances was formed in the same manner as Example 2 except that the target was set to Mo: Si = 1: 2 (atomic% ratio). went.
As a result, the film formed by setting an arbitrary film thickness within the range of 15 to ₂₀₀ Å of the MoSi ₂ film is a semi-transparent film in the wavelength band extending from the i-line to the g-line. It was confirmed that the variation range of the transmittance (that is, the semi-transmittance) was within a range of less than 4%.
From the results of Examples 2 and 3, when compared with the MoSi ₄ semi-transparent film, the MoSi ₂ semi-transparent film has a wavelength scale of i-line to g-line when compared with the same scale on the horizontal axis. Furthermore, it has been found that the spectral transmittance line is more inclined in a wider wavelength band including such a wavelength band, which is preferable.

(Production of blank and mask)
Using a large in-line sputtering device on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm), a MoSi-based semi-transparent film for a gray-tone mask and a Cr-based light-shielding film are sequentially formed. Then, a large mask blank for FPD was produced.
Here, the film formation of the MoSi-based gray-tone mask translucent film was the same as in Example 2 or 3.
The Cr-based light-shielding film is formed by arranging Cr targets in three spaces (sputtering chambers) arranged continuously in a large in-line sputtering apparatus, and first using a CrN film with Ar and N ₂ gases as sputtering gases. 150 Å, Ar and CH ₄ gas as sputtering gases, CrC film as 650 Å, and Ar and NO gas as sputtering gases, and CrON film as 250 Å continuously.
After patterning the Cr-based light-shielding film, patterning is performed on the semi-transparent film for the MoSi-based gray-tone mask, and a semi-transparent film underlay type large-sized FPD mask as shown in FIG. Was made.
As a result, when the films of Examples 2 and 3 are used as the semi-transparent film for the gray tone mask, it is beneficial for improving the quality of the mask and improving the yield as compared with the case of using the film of Comparative Example 1. It was confirmed that.

Example 4
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, a Ta target is used, Ar is used as a sputtering gas, and a gray-tone mask semi-transparent film (Ta) made of tantalum has a wavelength band extending from at least i rays to g rays emitted from an ultrahigh pressure mercury lamp. , The transmissivity (that is, transmissivity) of the semi-transparent film after film formation is about 60% (sample T-4), about 40% (sample T-5), and about 20% (sample T), respectively. A plurality of samples were prepared by forming the film thicknesses such that −6).
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 11 shows spectral transmittance lines of the respective samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, the semi-transmittance) is Sample T-4: 0.4%, Sample T-5: 0.2%, sample T-6: 0.4%, within the ranges of less than, almost flat.
In addition, FIG. 12 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band ranging from 330 nm to 470 nm, the variation width of the transmissivity of the semi-transparent film of each sample (that is, semi-transmissivity) is within a range of less than 2.0%, and is almost flat. It was.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, the film is manufactured by setting an arbitrary film thickness within a range where the transmissivity (that is, semi-transmissivity) of the semi-transparent film (Ta) after film formation is about 20% to about 60%. It was confirmed that all of the obtained films had a variation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film within the range of the sample T-4.

(Example 5)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a Ti target, Ar as a sputtering gas, a gray-tone mask translucent film (Ti) made of titanium, and a wavelength band extending from at least i rays to g rays emitted from an ultrahigh pressure mercury lamp. , The transmissivity of the semi-transparent film after film formation (that is, semi-transmissivity) is about 60% (sample T-8), about 40% (sample T-9), and about 20% (sample T), respectively. −10), and a plurality of samples were prepared.
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 13 shows the spectral transmittance lines of the samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is as follows: Sample T-8: 1.7%, Sample T-9: 1.5%, sample T-10: 0.3%, within the ranges of less than, almost flat.
Further, FIG. 14 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band ranging from 330 nm to 470 nm, the variation width of the transmissivity (that is, semi-transmissivity) of the semi-transparent film of each sample was in the range of less than 5.0%. However, as shown in FIG. 14, there is a place where the transmittance increases on the short wavelength side, and the peak at which the transmittance increases as the transmittance increases (the film thickness decreases) moves to the long wavelength side, i It was found that the fluctuation range of the transmittance of the semi-transparent film (that is, the semi-transmittance) in the wavelength band extending from the line to the g-line tends to increase.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, the film is manufactured by setting an arbitrary film thickness within a range where the transmissivity (that is, semi-transmissivity) of the translucent film (Ti) after film formation is about 20% to about 60%. It was confirmed that all of the obtained films had a variation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film within the range of each sample.

(Example 6)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a W target, Ar as a sputtering gas, a gray-tone mask translucent film (W) made of tungsten, a wavelength band extending from at least i-line to g-line emitted from an ultrahigh pressure mercury lamp. , The transmissivity of the semi-transparent film after film formation (ie, semi-transmittance) is about 60% (sample T-11), about 40% (sample T-12), and about 20% (sample T), respectively. −13), and a plurality of samples were prepared.
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 15 shows spectral transmittance lines of the samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is, respectively, Sample T-11: 1.8%, Sample T-12: 1.5%, sample T-10: 1.1%, within the ranges below, and was almost flat.
In addition, FIG. 16 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band extending from 330 nm to 470 nm, the variation width of the transmittance (that is, the semi-transmittance) of the semi-transparent film of each sample was in the range of less than 4.0%. However, as shown in FIG. 16, it was found that the inclination becomes slightly larger toward the longer wavelength side as compared with Examples 4 and 5.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, the film is manufactured by setting an arbitrary film thickness within a range where the transmittance (that is, the semi-transmittance) of the semi-transparent film (W) after film formation is about 20% to about 60%. It was confirmed that all of the obtained films had a variation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film within the range of each sample.

(Example 7)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a Mo target, Ar as a sputtering gas, a gray-tone mask translucent film (Mo) made of molybdenum, a wavelength band extending from at least i-line to g-line emitted from an ultrahigh pressure mercury lamp. , The transmissivity (that is, transmissivity) of the semi-transparent film after film formation is about 60% (sample T-14), about 40% (sample T-15), and about 20% (sample T), respectively. A plurality of samples were prepared by forming the film thicknesses so as to be -16).
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 17 shows the spectral transmittance lines of the samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, the semi-transmittance) is Sample T-14: 2.1%, Sample T-15: 2.4%, sample T-16: 1.8%, within the range of less than, and was almost flat.
In addition, FIG. 18 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band ranging from 330 nm to 470 nm, the variation width of the transmissivity (that is, semi-transmissivity) of the semi-transparent film of each sample was in the range of less than 5.0%. However, as shown in FIG. 18, it was found that the inclination becomes slightly larger toward the longer wavelength side as compared with Example 6.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, the film is manufactured by setting an arbitrary film thickness within a film thickness range in which the transmissivity (ie, semi-transmissivity) of the semi-transparent film (Mo) after film formation is about 20% to about 60%. It was confirmed that all of the obtained films had a variation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film within the range of each sample.

(Example 8)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a target of Ti: W = 1: 1 (atomic% ratio), Ar as a sputtering gas, a translucent film (TiW) for gray tone mask made of titanium and tungsten is used as an ultrahigh pressure mercury lamp. In at least the wavelength band extending from i-line to g-line emitted from the film, the transmissivity (that is, semi-transmittance) of the semi-transparent film after film formation is about 60% (sample T-23) and about 40, respectively. % (Sample T-24) and about 20% (sample T-25), respectively, to form a plurality of samples.
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 19 shows the spectral transmittance lines of the samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line emitted from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is, respectively, Sample T-23: 0.26%, Sample T-24: 1.47%, sample T-25: 0.66%, within the ranges of less than, almost flat.
In addition, FIG. 20 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band ranging from 330 nm to 470 nm, the variation width of the transmissivity (that is, semi-transmissivity) of the semi-transparent film of each sample was in the range of less than 3.0%. However, as shown in FIG. 20, there is a place where the transmittance increases on the short wavelength side, and the peak at which the transmittance increases as the transmittance increases (the film thickness decreases) moves to the long wavelength side. It was found that the fluctuation range of the transmittance of the semi-transparent film (that is, the semi-transmittance) in the wavelength band extending from the line to the g-line tends to increase.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, the film is manufactured by setting an arbitrary film thickness within a film thickness range in which the transmissivity of the translucent film (TiW) after film formation is about 20% to about 60%. It was confirmed that all of the obtained films had a variation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film within the range of each sample.

Example 9
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a target of W: Si = 1: 2 (atomic% ratio), Ar as a sputtering gas, a translucent film (WSi) for gray tone mask made of tungsten and silicon is used as an ultrahigh pressure mercury lamp. In at least the wavelength band extending from i-line to g-line emitted from the film, the transmissivity of the semi-transparent film after film formation (ie, semi-transmittance) is about 60% (sample T-20) and about 40, respectively. % (Sample T-21) and about 20% (sample T-22), respectively, to form a plurality of samples.
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 21 shows spectral transmittance lines of the samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is, respectively, Sample T-20: 2.6%, Sample T-21: 2.8%, sample T-22: 2.5%, within the range of less than, was almost flat.
In addition, FIG. 22 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band ranging from 330 nm to 470 nm, the variation width of the transmissivity (that is, semi-transmissivity) of the semi-transparent film of each sample was in the range of less than 5.0%. However, as shown in FIG. 22, it has been found that the inclination becomes slightly larger toward the longer wavelength side.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined for in-plane (equal 9 positions), all were within each range of fluctuation width of the transmissivity (that is, semi-transmissivity) of the semi-translucent film. It was confirmed.
Further, it is manufactured by setting an arbitrary film thickness within the range of the film thickness in which the transmissivity of the semi-transparent film (WSi) after film formation is about 20% to about 60%. It was confirmed that all of the obtained films had a variation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film within the range of each sample.

(Comparative Example 2)
A semi-transparent film for a gray tone mask was formed on a large glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm × 1200 mm) using a large in-line sputtering apparatus. Specifically, using a Si target, Ar as a sputtering gas, a semi-transparent film (Si) for gray tone mask made of silicon, and a wavelength band extending from at least i-line to g-line emitted from an ultrahigh pressure mercury lamp. , The transmissivity (that is, transmissivity) of the semi-transparent film after film formation is about 60% (sample T-17), about 40% (sample T-18), and about 20% (sample T), respectively. A plurality of samples were prepared by forming the film thicknesses so as to be -19).
About each said sample, the spectral transmission factor was measured with the spectrophotometer (Hitachi Ltd. make: U-4100).
FIG. 23 shows the spectral transmittance lines of the samples in the wavelength band extending from the i-line to the g-line emitted from the ultra-high pressure mercury lamp.
In at least the wavelength band from the i-line to the g-line radiated from the ultra-high pressure mercury lamp, the variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity) is Sample T-17: 13.0%, Sample T-18: 13.4%, Sample T-19: 9.7%, and even in comparison with Comparative Example 1, the fluctuation range of the transmissivity (that is, semi-transmissivity) of the translucent film was large. It was.
In addition, FIG. 24 shows spectral transmittance lines of the respective samples in a wavelength band ranging from 200 nm to 800 nm.
In the wavelength band ranging from 330 nm to 470 nm, the variation width of the transmissivity of the semi-transparent film of each sample (that is, semi-transmissivity) is about 20%, respectively. The fluctuation range of the transmissivity of the semi-translucent film (that is, semi-transmissivity) was large.
When a plurality of sheets (between substrates: 100 sheets) were similarly examined in the plane (equal 9 positions), the spectral transmittance line shown in FIG. It was found that the fluctuation range of the transmittance (that is, the semi-transmittance) of the semi-transparent film increases by about 3 to 5%.
Further, the film is manufactured by setting an arbitrary film thickness within a film thickness range in which the transmissivity (that is, semi-transmissivity) of the semi-transparent film (Si) after film formation is about 20% to about 60%. Each of the formed films has a variation width of the transmissivity of the semi-transparent film (that is, semi-transmissivity), and a variation width of the transmissivity of the semi-transparent film of Examples 1 to 9 (that is, the semi-transmittance). It was confirmed that it was out of range.

(Production of blank and mask)
Using a large in-line sputtering apparatus on a large glass substrate (synthetic quartz (QZ) 10 mm thickness, size 850 mm × 1200 mm), a semi-transparent film for a gray tone mask and a Cr-based light-shielding film are sequentially formed, and FPD A large mask blank was prepared.
Here, the film formation of the semi-transparent film for the gray tone mask was performed under the same conditions as in the above Examples 4 to 9.
The Cr-based light-shielding film is formed by arranging Cr targets in three spaces (sputtering chambers) arranged continuously in a large in-line sputtering apparatus, and first using a CrN film with Ar and N ₂ gases as sputtering gases. 150 Å, Ar and CH ₄ gas as sputtering gases, CrC film as 650 Å, and Ar and NO gas as sputtering gases, and CrON film as 250 Å continuously.
After patterning the Cr-based light-shielding film, patterning of the gray-tone mask semi-transparent film is carried out to produce a large semi-transparent film type FPD mask as shown in FIG. did.
As a result, when the films of Examples 4 to 9 are used as the semi-transparent film for a gray tone mask, the quality of the mask is improved and the yield is improved as compared with the case of using the films of Comparative Examples 1 and 2. It is confirmed that it is beneficial.

  While the present invention has been described with reference to the preferred embodiments, the present invention is not limited to the above embodiments.

It is a figure which shows the spectral distribution of the ultra high pressure mercury lamp which is an exposure light source. It is a figure which shows the spectral transmission factor of the semi-transparent film | membrane produced in Example 1. FIG. It is a figure for demonstrating the aspect of a mask. It is a figure which shows the spectral transmission factor of the semi-transparent film | membrane produced in Example 2. FIG. It is a figure which shows the spectral transmission factor of the other semi-translucent film | membrane created in Example 2. FIG. It is a figure which shows the spectral transmittance of the further another semi-transparent film | membrane created in Example 2. FIG. It is a figure for demonstrating the behavior of the spectral transmittance line of a semi-translucent film | membrane. It is a figure for demonstrating the behavior of the spectral transmittance line of a semi-translucent film. It is a figure for demonstrating the gray tone mask which has a translucent film | membrane, (1) is a fragmentary top view, (2) is a fragmentary sectional view. It is a figure for demonstrating the gray tone mask which has the fine light-shielding pattern below a resolution limit, (1) is a partial top view, (2) is a fragmentary sectional view. It is a figure which shows the spectral transmission factor in the wavelength range | band extending from i line to g line of the semi-transparent film | membrane created in Example 4. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength of 200 nm-800 nm of the semi-transparent film | membrane produced in Example 4. FIG. It is a figure which shows the spectral transmission factor in the wavelength band ranging from i line to g line of the semi-transparent film | membrane produced in Example 5. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength of 200 nm-800 nm of the semi-transparent film | membrane produced in Example 5. FIG. It is a figure which shows the spectral transmission factor in the wavelength band ranging from i line to g line of the semi-transparent film | membrane produced in Example 6. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength 200nm-800nm of the semi-transparent film | membrane produced in Example 6. FIG. It is a figure which shows the spectral transmittance | permeability in the wavelength range | band extending from i line to g line of the semi-transparent film | membrane produced in Example 7. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength 200nm -800nm of the semi-transparent film | membrane produced in Example 7. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band extending from i line to g line of the semi-transparent film | membrane produced in Example 8. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength of 200 nm-800 nm of the semi-transparent film | membrane created in Example 8. FIG. It is a figure which shows the spectral transmittance | permeability in the wavelength band ranging from i line to g line of the semi-transparent film | membrane created in Example 9. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength of 200 nm-800 nm of the semi-transparent film | membrane produced in Example 9. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band extending from i line to g line of the semi-transparent film | membrane produced in the comparative example 2. FIG. It is a figure which shows the spectral transmission factor in the wavelength range | band over the wavelength 200nm-800nm of the semi-transparent film | membrane produced in the comparative example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light-shielding part 2 Transmission part 3 Gray tone part 3a Fine light-shielding pattern 3b Fine transmission part 3a 'Semi-transmissive film 10 Translucent substrate 11 Semi-transmissive film 12 Light-shielding film

Claims (8)

A mask blank for manufacturing an FPD device having at least a semi-transparent film for a gray tone mask having a function of adjusting a transmission amount on a translucent substrate,
The translucent film for a gray tone mask has a transmissivity fluctuation range of less than 5% in a wavelength band extending from at least i-line to g-line emitted from an ultra-high pressure mercury lamp. A mask blank for manufacturing an FPD device, characterized in that the film is controlled to be a film. A mask blank for manufacturing an FPD device having at least a semi-transparent film for a gray tone mask having a function of adjusting a transmission amount on a translucent substrate,
The semi-transparent film for gray tone mask is a film that is controlled so that the fluctuation range of the transmissivity of the semi-transparent film is within a range of less than 10% in a wavelength band extending from 330 nm to 470 nm. A mask blank for manufacturing an FPD device.   The semi-transparent film for gray tone mask is a film that is controlled so that the fluctuation range of the transmissivity of the semi-transparent film is within a range of less than 5% in the wavelength band extending from 330 nm to 470 nm. A mask blank for manufacturing the FPD device according to claim 2.   4. The gray-tone mask semi-transparent film is a chromium nitride film-based semi-transparent film that is optically designed and manufactured to satisfy the above requirements. A mask blank for manufacturing the FPD device according to item.   The translucent film for gray tone mask is a MoSi-based translucent film that is optically designed and manufactured to satisfy the above requirements. A mask blank for manufacturing the FPD device described in 1. In a mask blank having at least a semi-transparent film having a function of adjusting a transmission amount on a translucent substrate,
The mask blank is a mask blank for a photomask that is exposed to exposure light including a plurality of wavelengths when a device is manufactured after the semi-transparent film is patterned to form a photomask. And
The semi-transparent film is controlled so that the fluctuation range of the transmissivity of the semi-transparent film is within a range of less than 5% in at least a wavelength band from the i-line to the g-line emitted from the ultra-high pressure mercury lamp. A mask blank, characterized by being a coated film.   A photomask for producing an FPD device, which is produced using the mask blank according to claim 1 and has at least a semi-transparent film pattern for a gray tone mask.   A photomask manufactured using the mask blank according to claim 6.

Images