Method for manufacturing a mask blank, method for manufacturing a transfer mask, and method for manufacturing a display device.

Abstract

The present invention provides a mask blank that has high light resistance to exposure light including wavelengths in the ultraviolet region, high chemical resistance, and can form a good transfer pattern. [Solution] A mask blank comprising a translucent substrate and a thin film for pattern formation provided on the main surface of the translucent substrate, wherein the thin film contains titanium, silicon, and nitrogen, and the photoelectron intensity at a binding energy of 455 eV in the Ti2p narrow spectrum obtained by analyzing the internal region of the thin film by X-ray photoelectron spectroscopy is P N The photoelectron intensity at a binding energy of 10² eV in the Si2p narrow spectrum is P S When P N / P S The relationship is greater than 1.18, the internal region is the region excluding the vicinity region on the translucent substrate side of the thin film and the surface region on the opposite side of the translucent substrate, and the nitrogen content in the internal region is 30 atomic percent or more.

Description

[Technical Field]

[0001] The present invention relates to a mask blank, a transfer mask, a method for manufacturing a transfer mask, and a method for manufacturing a display device. [Background technology]

[0002] In recent years, display devices such as FPDs (Flat Panel Displays), exemplified by OLEDs (Organic Light Emitting Diodes), have seen rapid advancements in screen size, viewing angle, resolution, and display speed. One of the elements necessary for this resolution and speed is the fabrication of fine, highly dimensionally accurate electronic circuit patterns, including elements and wiring. Photolithography is often used for patterning these electronic circuits for display devices. Therefore, transfer masks (photomasks) such as phase-shift masks and binary masks for the manufacture of display devices, which have fine and highly accurate patterns, are required.

[0003] For example, Patent Document 1 describes a photomask for exposing a fine pattern. Patent Document 1 describes that the mask pattern formed on the transparent substrate of the photomask is composed of a light-transmitting portion that transmits light of an intensity that substantially contributes to exposure and a light-semitransmitting portion that transmits light of an intensity that substantially does not contribute to exposure. Patent Document 1 also describes that the contrast at the boundary is improved by using a phase shift effect so that the light that passes near the boundary between the light-semitransmitting portion and the light-transmitting portion cancels each other out. Furthermore, Patent Document 1 describes that the photomask is composed of a thin film made of a material mainly composed of nitrogen, metal, and silicon as its light-semitransmitting portion, and that the silicon component of the material constituting the thin film is 34 to 60 atomic percent.

[0004] Patent Document 2 describes a halftone phase-shift mask blank for use in lithography. Patent Document 2 describes that the mask blank comprises a substrate, an etch-stop layer deposited on the substrate, and a phase-shift layer deposited on the etch-stop layer. Furthermore, Patent Document 2 describes that a photomask having a phase shift of approximately 180 degrees at a selected wavelength of less than 500 nm and a light transmittance of at least 0.001% can be manufactured using this mask blank.

[0005] Patent Document 3 describes a photomask blank having a pattern-forming thin film on a transparent substrate. Patent Document 3 describes the photomask blank as a master plate for forming a photomask having a transfer pattern on a transparent substrate by wet etching of the pattern-forming thin film. Furthermore, Patent Document 3 describes that the pattern-forming thin film of the photomask blank contains a transition metal and silicon and has a columnar structure. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 2966369 [Patent Document 2] Special Publication No. 2005-522740 [Patent Document 3] Japanese Patent Publication No. 2020-95248 [Overview of the project] [Problems that the invention aims to solve]

[0007] In recent years, transfer masks used in the fabrication of high-resolution (1000 ppi or higher) panels require transfer masks that enable high-resolution pattern transfer and have a transfer pattern formed on them that includes a thin film pattern for forming fine patterns with a hole diameter of 6 μm or less and a line width of 4 μm or less. Specifically, transfer masks have a transfer pattern formed on them that includes a fine pattern with a diameter or width of 1.5 μm.

[0008] On the other hand, transfer masks obtained by patterning a thin film for pattern formation on a mask blank are used repeatedly for pattern transfer to the object to be transferred. Therefore, it is desirable that they have high light resistance to ultraviolet light (UV light resistance), which is expected in actual pattern transfer. Furthermore, since transfer masks are repeatedly washed during manufacturing and use, it is also desirable that they have high resistance to mask washing (chemical resistance).

[0009] However, conventionally, it has been difficult to manufacture mask blanks with a thin film for pattern formation that satisfies the requirements for transmittance to exposure light including wavelengths in the ultraviolet region, as well as the requirements for ultraviolet light resistance (hereinafter simply referred to as light resistance) and chemical resistance.

[0010] This invention was made to solve the above-mentioned problems. Specifically, the present invention aims to provide a mask blank that has high light resistance to exposure light including wavelengths in the ultraviolet region, high chemical resistance, and can form a good transfer pattern.

[0011] Furthermore, the present invention aims to provide a transfer mask that has high light resistance to exposure light including wavelengths in the ultraviolet region, high chemical resistance, and a good transfer pattern, a method for manufacturing a transfer mask, and a method for manufacturing a display device. [Means for solving the problem]

[0012] The present invention has the following configuration as a means of solving the above problems.

[0013] (Configuration 1) A mask blank comprising a translucent substrate and a thin film for pattern formation provided on the main surface of the translucent substrate, The thin film contains titanium, silicon, and nitrogen. The photoelectron intensity at a binding energy of 455 eV in the Ti2p narrow spectrum obtained by analyzing the internal region of the thin film using X-ray photoelectron spectroscopy was P N The photoelectron intensity at a binding energy of 10² eV in the Si2p narrow spectrum is P S When P N / P S The relationship is greater than 1.18, The aforementioned internal region is the region of the thin film excluding the vicinity of the translucent substrate and the surface region on the opposite side of the translucent substrate. The nitrogen content in the aforementioned internal region is 30 atomic percent or more. A mask blank characterized by the following features.

[0014] (Configuration 2) The photoelectron intensity at which the binding energy in the Ti2p narrow spectrum is 461 eV is P NU When P NU / P S A mask blank according to configuration 1, characterized in that the relationship is greater than 1.05.

[0015] (Configuration 3) The mask blank according to Configuration 1 or 2, characterized in that the ratio of the titanium content to the total titanium and silicon content in the internal region is 0.05 or more.

[0016] (Configuration 4) A mask blank according to any one of Configurations 1 to 3, characterized in that the total content of titanium, silicon, and nitrogen in the internal region is 90 atomic percent or more.

[0017] (Configuration 5) A mask blank according to any one of Configurations 1 to 4, characterized in that the oxygen content of the internal region is 7 atomic percent or less.

[0018] (Configuration 6) The surface layer region on the side opposite to the light-transmissive substrate is a region extending from the surface on the side opposite to the light-transmissive substrate to a depth of 10 nm toward the light-transmissive substrate side, and the mask blank according to any one of Configurations 1 to 5, characterized in that.

[0019] (Configuration 7) The vicinity region on the light-transmissive substrate side is a region extending from the surface on the light-transmissive substrate side to a depth of 10 nm toward the side opposite to the light-transmissive substrate, and the mask blank according to any one of Configurations 1 to 6, characterized in that.

[0020] (Configuration 8) The thin film is a phase shift film, The phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365 nm, and a phase difference with respect to light having a wavelength of 365 nm is 150 degrees or more and 210 degrees or less, and the mask blank according to any one of Configurations 1 to 7, characterized in that.

[0021] (Configuration 9) An etching mask film having different etching selectivity with respect to the thin film is provided on the thin film, and the mask blank according to any one of Configurations 1 to 8, characterized in that.

[0022] (Configuration 10) The etching mask film contains chromium, and the mask blank according to Configuration 9, characterized in that.

[0023] (Configuration 11) A transfer mask including a light-transmissive substrate and a thin film provided on a main surface of the light-transmissive substrate and having a transfer pattern, The thin film contains titanium, silicon, and nitrogen, When the photoelectron intensity at a binding energy of 455 eV in the Ti2p narrow spectrum obtained by analyzing the internal region of the thin film by X-ray photoelectron spectroscopy is P N , and the photoelectron intensity at a binding energy of 102 eV in the Si2p narrow spectrum is P S When, P N / P S satisfies a relationship greater than 1.18, The aforementioned internal region is the region of the thin film excluding the vicinity of the translucent substrate and the surface region on the opposite side of the translucent substrate. The nitrogen content in the aforementioned internal region is 30 atomic percent or more. A transfer mask characterized by the following features.

[0024] (Configuration 12) The photoelectron intensity at which the binding energy in the Ti2p narrow spectrum is 461 eV is P NU When P NU / P S A transfer mask according to configuration 11, characterized in that the relationship is greater than 1.05.

[0025] (Configuration 13) The transfer mask according to Configuration 11 or 12, characterized in that the ratio of the titanium content to the total titanium and silicon content in the internal region is 0.05 or more.

[0026] (Configuration 14) A transfer mask according to any one of Configurations 11 to 13, characterized in that the total content of titanium, silicon, and nitrogen in the internal region is 90 atomic percent or more.

[0027] (Configuration 15) A transfer mask according to any one of Configurations 11 to 14, characterized in that the oxygen content of the internal region is 7 atomic percent or less.

[0028] (Configuration 16) The transfer mask according to any one of Configurations 11 to 15, characterized in that the surface region on the side opposite to the translucent substrate is a region extending from the surface on the side opposite to the translucent substrate to a depth of 10 nm toward the translucent substrate.

[0029] (Configuration 17) The transfer mask according to any one of Configurations 11 to 16, characterized in that the vicinity region on the translucent substrate side is a region extending from the surface of the translucent substrate side to a depth of 10 nm toward the opposite side from the translucent substrate.

[0030] (Configuration 18) The thin film is a phase-shift film, The transfer mask according to any one of configurations 11 to 17, characterized in that the phase-shift film has a transmittance of 1% or more for light with a wavelength of 365 nm, and a phase difference of 150 degrees or more and 210 degrees or less for light with a wavelength of 365 nm.

[0031] (Configuration 19) A step of preparing a mask blank as described in any of Configurations 1 to 8, A step of forming a resist film having a transfer pattern on the thin film, A step of performing wet etching using the resist film as a mask to form a transfer pattern on the thin film, A method for manufacturing a transfer mask, characterized by having the following features.

[0032] (Configuration 20) A step of preparing the mask blank described in Configuration 9 or 10, A step of forming a resist film having a transfer pattern on the etching mask film, A step of performing wet etching using the resist film as a mask to form a transfer pattern on the etching mask film, A step of performing wet etching using the etching mask film on which the transfer pattern is formed as a mask to form the transfer pattern on the thin film, A method for manufacturing a transfer mask, characterized by having the following features.

[0033] (Configuration 21) A step of placing the transfer mask described in any of Configurations 11 to 18 on the mask stage of the exposure apparatus, The process involves irradiating the transfer mask with exposure light to transfer a transfer pattern onto a resist film provided on a substrate for a display device, A method for manufacturing a container, characterized by having the following features. [Effects of the Invention]

[0034] According to the present invention, it is possible to provide a mask blank that has high light resistance to exposure light including wavelengths in the ultraviolet region, high chemical resistance, and can form a good transfer pattern.

[0035] Furthermore, according to the present invention, it is possible to provide a transfer mask that has high light resistance to exposure light including wavelengths in the ultraviolet region, high chemical resistance, and a good transfer pattern, a method for manufacturing a transfer mask, and a method for manufacturing a display device. [Brief explanation of the drawing]

[0036] [Figure 1] This is a schematic cross-sectional view showing the film structure of a mask blank according to an embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing another film configuration of the mask blank according to an embodiment of the present invention. [Figure 3] This is a schematic cross-sectional view showing the manufacturing process of a transfer mask according to an embodiment of the present invention. [Figure 4] This is a schematic cross-sectional view showing another manufacturing process for a transfer mask according to an embodiment of the present invention. [Figure 5] This figure shows the results (Ti2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase-shifted mask blanks according to each embodiment of the present invention. [Figure 6] This figure shows the results (Si2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase-shifted film of the mask blank according to each embodiment of the present invention. [Figure 7] This figure shows the results (Ti2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase-shifted mask blanks according to each comparative example of the present invention. [Figure 8] This figure shows the results (Si2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase-shifted films of the mask blanks according to each comparative example of the present invention. [Modes for carrying out the invention]

[0037] First, we will describe the process leading to the completion of this invention. The inventors diligently studied the configuration of a mask blank that has high light resistance to exposure light including wavelengths in the ultraviolet region (hereinafter sometimes simply referred to as "exposure light"), high chemical resistance, and can form a good transfer pattern. The inventors were considering using titanium silicide-based materials as the material for the thin film pattern of a transfer mask used to manufacture display devices such as FPDs (Flat Panel Displays). Thin films of titanium silicide-based materials had excellent optical properties and chemical resistance. On the other hand, thin films of titanium silicide-based materials were thought to have excellent resistance to irradiation with exposure light (exposure light including wavelengths in the ultraviolet region), but it was found that the light resistance to exposure light could decrease significantly in some cases. For this reason, the inventors conducted a multifaceted investigation into the differences between thin films of titanium silicide-based materials with high light resistance to exposure light and thin films of titanium silicide-based materials with low light resistance to exposure light. First, the inventors investigated the relationship between the composition of the thin film and its lightfastness to exposure light using analysis methods such as X-ray photoelectron spectroscopy (XPS), but no clear correlation was found between the composition of the thin film and its lightfastness. Furthermore, observations of cross-sectional SEM images, planar STEM images, and electron diffraction patterns were performed, but no clear correlation was found with lightfastness in any of these cases.

[0038] As a result of further intensive research, the inventors observed Ti2p narrow spectra and Si2p narrow spectra obtained by analyzing the internal region of a thin film used for pattern formation using X-ray photoelectron spectroscopy (XPS). They found that even when the overall behavior of the Ti2p narrow spectra and Si2p narrow spectra was similar, there were differences in light resistance (see the narrow spectra of Examples 3 and 4 shown in Figures 5 and 6, and Comparative Example 1 shown in Figures 7 and 8). Further investigation revealed that thin films of titanium silicide-based materials with a nitrogen content of 30 atomic percent or more exhibited the following photoelectron intensity in their internal regions: P, which corresponds to the TiN bond of Ti2p 3 / 2 in the Ti2p narrow spectrum (photoelectron intensity at a bond energy of 455 eV). N This corresponds to the photoelectron intensity of the Si3N4 bond in the Si2p narrow spectrum (photoelectron intensity at a bond energy of 102 eV) P S We concluded that if the ratio obtained by dividing by is greater than 1.18, then the material has high light resistance to exposure light.

[0039] The mask blank of the present invention was derived as a result of the above-mentioned diligent research. Specifically, the mask blank of the present invention is a mask blank comprising a translucent substrate and a thin film for pattern formation provided on the main surface of the translucent substrate, wherein the thin film contains titanium, silicon, and nitrogen, and the photoelectron intensity at a binding energy of 455 eV in the Ti2p narrow spectrum obtained by analyzing the internal region of the thin film by X-ray photoelectron spectroscopy is P N The photoelectron intensity at a binding energy of 10² eV in the Si2p narrow spectrum is P S When P N / P S The relationship is that the ratio is greater than 1.18, the internal region is the region excluding the vicinity region on the translucent substrate side of the thin film and the surface region on the opposite side of the translucent substrate, and the nitrogen content in the internal region is 30 atomic percent or more. The embodiments of the present invention will be described in detail below with reference to the drawings. Note that the following embodiments are examples of how the present invention can be implemented, and do not limit the present invention to their scope.

[0040] Figure 1 is a schematic diagram showing the film structure of the mask blank 10 of this embodiment. The mask blank 10 shown in Figure 1 comprises a light-transmitting substrate 20, a thin film 30 for pattern formation (e.g., a phase-shift film) formed on the light-transmitting substrate 20, and an etching mask film (e.g., a light-shielding film) 40 formed on the thin film 30 for pattern formation.

[0041] Figure 2 is a schematic diagram showing the film structure of a mask blank 10 in another embodiment. The mask blank 10 shown in Figure 2 comprises a translucent substrate 20 and a thin film 30 for pattern formation (e.g., a phase-shift film) formed on the translucent substrate 20.

[0042] In this specification, "thin film 30 for pattern formation" refers to a thin film on which a predetermined fine pattern is formed on the transfer mask 100, such as a light-shielding film and a phase-shift film (hereinafter sometimes simply referred to as "thin film 30"). In the description of this embodiment, a phase-shift film may be used as a specific example of the thin film 30 for pattern formation, and a phase-shift film pattern may be used as a specific example of the thin film pattern 30a for pattern formation (hereinafter sometimes simply referred to as "thin film pattern 30a"). The same applies to other thin films 30 for pattern formation and thin film patterns 30a for pattern formation, such as light-shielding films and light-shielding film patterns, transmittance-adjusting films and transmittance-adjusting film patterns.

[0043] The following describes in detail the translucent substrate 20, the thin film 30 for pattern formation (e.g., a phase-shift film), and the etching mask film 40 that constitute the mask blank 10 for manufacturing a display device in this embodiment.

[0044] <Transparent substrate 20> The translucent substrate 20 is transparent to exposure light. The translucent substrate 20 has a transmittance of 85% or more, preferably 90% or more, to exposure light, assuming no surface reflection loss. The translucent substrate 20 is made of a material containing silicon and oxygen, and can be composed of glass materials such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, and low thermal expansion glass (SiO2-TiO2 glass, etc.). When the translucent substrate 20 is made of low thermal expansion glass, positional changes of the thin film pattern 30a due to thermal deformation of the translucent substrate 20 can be suppressed. Furthermore, translucent substrates 20 used in display device applications are generally rectangular. Specifically, a translucent substrate 20 with a main surface (the surface on which the thin film 30 for pattern formation is formed) of 300 mm or more in length on the shorter side can be used. In the mask blank 10 of this embodiment, a large translucent substrate 20 with a main surface of 300 mm or more in length on the shorter side can be used. Using the mask blank 10 of this embodiment, a transfer mask 100 can be manufactured on a translucent substrate 20 having a transfer pattern including a thin film pattern 30a for forming a fine pattern, for example, with a width and / or diameter of less than 2.0 μm. By using such a transfer mask 100 of this embodiment, it is possible to stably transfer a transfer pattern including a predetermined fine pattern to a transfer target.

[0045] <Thin film 30 for pattern formation> The thin film 30 for pattern formation of the mask blank 10 for manufacturing a display device in this embodiment (hereinafter sometimes simply referred to as "the mask blank 10 of this embodiment") is made of a material containing titanium (Ti), silicon (Si), and nitrogen (N). This thin film 30 for pattern formation can be a phase-shift film having a phase-shift function.

[0046] The thin film 30 for pattern formation contains nitrogen. In the above-mentioned titanium silicide, nitrogen, a light element component, has the effect of not lowering the refractive index compared to oxygen, which is also a light element component. Therefore, by including nitrogen in the thin film 30 for pattern formation, the film thickness required to obtain the desired phase difference (also called the phase shift amount) can be reduced. Furthermore, the nitrogen content in the thin film 30 for pattern formation is preferably 30 atomic% or more, and more preferably 40 atomic% or more. On the other hand, the nitrogen content is preferably 60 atomic% or less, and more preferably 55 atomic% or less. A high nitrogen content in the thin film 30 can suppress the transmittance to exposure light from becoming excessively high.

[0047] The interior of the pattern-forming thin film 30 is divided into three regions, in the order of the nearby region, the internal region, and the surface region, from the side of the translucent substrate 20. The nearby region is the area extending from the interface between the pattern-forming thin film 30 and the translucent substrate 20 to a depth of 10 nm (more preferably 5 nm, and even more preferably 4 nm) toward the surface side opposite to the translucent substrate 20 (i.e., the surface region side). When X-ray photoelectron spectroscopy analysis is performed on this nearby region, it is easily affected by the translucent substrate 20 located beneath it, resulting in low accuracy of the maximum peak of photoelectron intensity in the acquired Ti2p narrow spectrum and Si2p narrow spectrum of the nearby region.

[0048] The surface region is an area extending from the surface opposite to the translucent substrate 20 toward the translucent substrate 20 to a depth of 10 nm (more preferably 5 nm, and even more preferably 4 nm). The surface region is susceptible to the influence of other films, such as the etching mask film 40, if they are present on it. Furthermore, if no other films are present on it, the surface region contains oxygen incorporated from the surface of the pattern-forming thin film 30. For this reason, when X-ray photoelectron spectroscopy analysis is performed on this surface region, the accuracy of the maximum peak of photoelectron intensity in the acquired Ti2p narrow spectrum and Si2p narrow spectrum of the surface region is low.

[0049] The internal region is the area of ​​the thin film 30 used for pattern formation, excluding the neighboring region and the surface region. The Ti2p narrow spectrum and Si2p narrow spectrum obtained by analyzing this internal region using X-ray photoelectron spectroscopy show that the photoelectron intensity at a binding energy of 455 eV is P N , the photoelectron intensity at a binding energy of 10² eV is P S When P N / P S This satisfies the relationship greater than 1.18. Here, the bond energy of 455 eV corresponds to the bond energy of the TiN bond at the Ti2p 3 / 2 peak, and the bond energy of 102 eV corresponds to the bond energy of the Si3N4 bond at the Si2p peak (see Figures 5-8).

[0050] The inventors of the present invention, P N / P S Regarding the relationship between lightfastness and other properties, the following is my hypothesis: When the thin film 30 for pattern formation is composed of a titanium silicide material containing titanium and silicon, the titanium (Ti) in the thin film 30 mainly exists as elemental Ti and in a TiN bonded state (see Figures 5 and 7). As shown in Figures 5 and 7, at the Ti2p3 / 2 peak, the bond energy of Ti in a TiN bonded state is higher than that of elemental Ti. Therefore, Ti in a TiN bonded state is more resistant to changes in the state of Ti due to irradiation with exposure light including ultraviolet light than Ti in a elemental state, and is less likely to cause fluctuations in transmittance due to changes in the state of Ti. On the other hand, nitrogen in the thin film 30 also bonds with silicon (Si) in addition to titanium (Ti), so if the nitrogen content is low, the amount of nitrogen that bonds with titanium will be relatively small, and it is thought that the amount of elemental Ti will increase. When the nitrogen content is 30 atomic percent or more, it is thought that a certain amount of Si exists in a stoichiometrically stable Si3N4 bonded state. Under these circumstances, P N / P SIf the relationship is greater than 1.18, it is considered that in the thin film 30, Si is bonded to nitrogen to a certain extent, and Ti is in a TiN bonded state with a certain proportion or more, and therefore it is inferred that it has high light resistance to exposure light including ultraviolet light. However, this inference is based on current knowledge and does not limit the scope of the rights of the present invention in any way.

[0051] Even when performing compositional analysis such as X-ray photoelectron spectroscopy (XPS) on the region near the interface with the translucent substrate 20, it is inevitably affected by the composition of the translucent substrate 20, making it difficult to determine numerical values ​​regarding the composition and the number of bonds present. However, it is presumed to be composed in a similar manner to the internal region described above.

[0052] P N / P S It is more preferably 1.19 or higher, and even more preferably 1.20 or higher. Also, P N / P S It is preferably 3.00 or less, more preferably 2.50 or less, and even more preferably 2.00 or less.

[0053] Furthermore, the Ti2p narrow spectrum obtained by analyzing the internal region using X-ray photoelectron spectroscopy showed that the photoelectron intensity at a binding energy of 461 eV was P NU When P NU / P S It is preferable that the relationship is greater than 1.05, more preferably 1.10 or greater, and even more preferably 1.15 or greater. Here, the bond energy of 461 eV corresponds to the bond energy of the TiN bond at the Ti2p 1 / 2 peak (see Figures 5 and 7).

[0054] As shown above, even at the Ti2p 1 / 2 peak, the bond energy of Ti existing in the TiN bond state is higher than that of Ti existing as elemental Ti. Therefore, when the nitrogen content is 30 atomic percent or more,NU / P S If the relationship is greater than 1.10, it is considered that Si is bonded to nitrogen to a certain extent, and a certain proportion or more of Ti is in a TiN bonded state, and therefore it is presumed to have high light resistance to exposure light, including ultraviolet light. However, this presumption is based on current knowledge and does not limit the scope of the rights of the present invention in any way. Also, P NU / P S It is preferably 2.50 or less, and more preferably 2.00 or less.

[0055] Furthermore, the Ti2p narrow spectra and Si2p narrow spectra obtained by analyzing the internal region using X-ray photoelectron spectroscopy were (P N +P NU ) / P S It is preferable that the relationship is greater than 2.22.

[0056] As shown above, in both the Ti2p 3 / 2 peak and the Ti2p 1 / 2 peak, the bond energy of Ti in the TiN bond state and Ti in the TiO bond state is higher than that of Ti in elemental form. Therefore, when the nitrogen content is 30 atomic percent or more, P NU / P S If the relationship is greater than 1.10, it is considered that Si is bonded to nitrogen to a certain extent, and a certain proportion or more of Ti is in a TiN bonded state, and therefore it is presumed to have high light resistance to exposure light, including ultraviolet light. However, this presumption is based on current knowledge and does not limit the scope of the rights of the present invention in any way. (P N +P NU ) / P S It is more preferably 2.25 or higher, and even more preferably 2.30 or higher. Also, (P N +P NU ) / P SIt is preferably 5.00 or less, and more preferably 4.50 or less.

[0057] Furthermore, the Ti2p narrow spectra and Si2p narrow spectra obtained by analyzing the internal region using X-ray photoelectron spectroscopy showed that the photoelectron intensity at a binding energy of 453 eV was P TS When P N / P TS It is preferable that the relationship is greater than 2.13. Here, the bond energy of 453 eV corresponds to the bond energy of the TiSi2 bond at the Ti2p 3 / 2 peak (see Figures 5 and 7). P N / P TS It is more preferable that the value be 2.20 or higher, and even more preferable that it be 2.50 or higher. P N / P TS It is preferably 4.00 or less, and more preferably 3.50 or less.

[0058] Furthermore, the Ti2p narrow spectra and Si2p narrow spectra obtained by analyzing the internal region using X-ray photoelectron spectroscopy showed that the photoelectron intensity at a binding energy of 454 eV was P T When that happens, (P N +P T ) / P TS It is preferable that the relationship is greater than 3.53. Here, the bond energy of 454 eV corresponds to the bond energy of elemental Ti at the Ti2p 3 / 2 peak (see Figures 5 and 7). (P N +P T ) / P TS It is more preferable that the value be 3.60 or higher, and even more preferable that it be 3.90 or higher. (P N +P T ) / P TS It is preferably 5.50 or less, and more preferably 5.00 or less.

[0059] The ratio of titanium content to the total titanium and silicon content in the internal region (hereinafter sometimes referred to as the Ti / [Ti+Si] ratio) is preferably 0.05 or higher, and more preferably 0.10 or higher. If the Ti / [Ti+Si] ratio in the internal region is too low, it becomes difficult to obtain the benefits of optical identification and chemical resistance by using a titanium silicide-based material for the thin film 30 used for pattern formation. On the other hand, the Ti / [Ti+Si] ratio in the internal region is preferably 0.50 or lower, and more preferably 0.45 or lower. The total content of titanium, silicon, and nitrogen in the internal region is preferably 90 atomic percent or more, and more preferably 95 atomic percent or more. If the content of elements other than titanium, silicon, and nitrogen in the internal region is high, various properties such as optical properties, chemical resistance, and light resistance to ultraviolet rays may deteriorate.

[0060] The pattern-forming thin film 30 can contain oxygen as long as its performance does not deteriorate. Oxygen, a light element component, has the effect of lowering the extinction coefficient compared to nitrogen, which is also a light element component. However, if the oxygen content of the pattern-forming thin film 30 is high, it may adversely affect the ability to obtain a cross-section of a nearly vertical fine pattern and high mask cleaning resistance. Therefore, the oxygen content of the pattern-forming thin film 30 is preferably 7 atomic percent or less, and more preferably 5 atomic percent or less. The pattern-forming thin film 30 may not contain oxygen.

[0061] As shown in Figures 5 and 7, the photoelectron intensity at a binding energy of 453 eV corresponds to the binding energy of the TiSi2 bond at the Ti2p 3 / 2 peak, the photoelectron intensity at a binding energy of 454 eV corresponds to the binding energy of elemental Ti at the Ti2p 3 / 2 peak, the binding energy at 455 eV corresponds to the binding energy of the TiN bond at the Ti2p 3 / 2 peak, the binding energy at 456.9 eV corresponds to the binding energy of the TiO bond at the Ti2p 3 / 2 peak, the binding energy at 458.5 eV corresponds to the binding energy of the TiO2 bond at the Ti2p 3 / 2 peak, the binding energy at 460 eV corresponds to the binding energy of elemental Ti at the Ti2p 1 / 2 peak, and the binding energy at 461 eV corresponds to the binding energy of the TiN bond at the Ti2p 1 / 2 peak.

[0062] Furthermore, in addition to the oxygen and nitrogen mentioned above, the thin film 30 for pattern formation may also contain other light element components such as carbon and helium for the purpose of reducing film stress and / or controlling the wet etching rate.

[0063] The atomic ratio of titanium to silicon in the pattern-forming thin film 30 is preferably in the range of titanium:silicon = 1:1 to 1:19. Within this range, the effect of suppressing the decrease in wet etching rate during pattern formation of the pattern-forming thin film 30 can be greatly enhanced. Furthermore, the cleaning resistance of the pattern-forming thin film 30 can be improved, and the transmittance can be easily increased. From the viewpoint of improving the cleaning resistance of the pattern-forming thin film 30, the atomic ratio of titanium to silicon (titanium:silicon) in the pattern-forming thin film 30 is preferably in the range of 1:1 to 1:19, more preferably in the range of 1:1 to 1:11, and even more preferably in the range of 1:1 to 1:9.

[0064] The pattern-forming thin film 30 may consist of multiple layers or a single layer. A pattern-forming thin film 30 consisting of a single layer is preferable because it is difficult for interfaces to form within the pattern-forming thin film 30 and the cross-sectional shape is easy to control. On the other hand, a pattern-forming thin film 30 consisting of multiple layers is preferable in terms of ease of film formation, etc. The thickness of the thin film 30 for pattern formation is preferably 200 nm or less, more preferably 180 nm or less, and even more preferably 150 nm or less, in order to ensure optical performance. Furthermore, the thickness of the thin film 30 for pattern formation is preferably 80 nm or more, and more preferably 90 nm or more, in order to ensure the function of generating the desired phase difference.

[0065] <<Transmittance and phase difference of the thin film 30 for pattern formation>> In this embodiment, the mask blank 10 for manufacturing a display device preferably has a thin film 30 for pattern formation that is a phase-shift film having optical properties such as a transmittance of 1% or more and 80% or less with respect to a representative wavelength of exposure light (light with a wavelength of 365 nm), and a phase difference of 150 degrees or more and 210 degrees or less. Unless otherwise specified, transmittance in this specification refers to the transmittance of a translucent substrate converted to a standard (100%).

[0066] When the thin film 30 for pattern formation is a phase-shift film, the thin film 30 for pattern formation has the function of adjusting the reflectance to light incident from the translucent substrate 20 side (hereinafter sometimes referred to as back surface reflectance) and the function of adjusting the transmittance to exposure light and the phase difference.

[0067] The transmittance of the pattern-forming thin film 30 to the exposure light satisfies the required value for a pattern-forming thin film 30. The transmittance of the pattern-forming thin film 30 is preferably 1% to 80%, more preferably 3% to 65%, and even more preferably 5% to 60%, with respect to a predetermined wavelength of light (hereinafter referred to as the representative wavelength) included in the exposure light. That is, when the exposure light is composite light including light in the wavelength range of 313 nm to 436 nm, the pattern-forming thin film 30 has the above-mentioned transmittance with respect to the representative wavelength included in that wavelength range. For example, when the exposure light is composite light including i-lines, h-lines, and g-lines, the pattern-forming thin film 30 can have the above-mentioned transmittance with respect to any of the i-lines, h-lines, and g-lines. The representative wavelength can be, for example, the i-line with a wavelength of 365 nm. By having such characteristics with respect to the i-line, a similar effect can be expected with respect to the transmittance at the wavelengths of the h-lines and g-lines when composite light including i-lines, h-lines, and g-lines is used as the exposure light.

[0068] Furthermore, when the exposure light is selected monochromatic light obtained by filtering out a certain wavelength range from the wavelength range of 313 nm to 436 nm, or monochromatic light selected from the wavelength range of 313 nm to 436 nm, the thin film 30 for pattern formation has the above-mentioned transmittance for that single wavelength monochromatic light.

[0069] Transmittance can be measured using a phase shift measurement device or the like.

[0070] The phase difference of the pattern-forming thin film 30 with respect to the exposure light satisfies the required value for the pattern-forming thin film 30. The phase difference of the pattern-forming thin film 30 with respect to the representative wavelength light included in the exposure light is preferably 150 degrees to 210 degrees, more preferably 160 degrees to 200 degrees, and even more preferably 170 degrees to 190 degrees. This property allows the phase of the representative wavelength light included in the exposure light to be changed to 150 degrees to 210 degrees. As a result, a phase difference of 150 degrees to 210 degrees occurs between the representative wavelength light transmitted through the pattern-forming thin film 30 and the representative wavelength light transmitted only through the translucent substrate 20. That is, if the exposure light is composite light including light in the wavelength range of 313 nm to 436 nm, the pattern-forming thin film 30 has the above-mentioned phase difference with respect to the representative wavelength light included in that wavelength range. For example, if the exposure light is composite light including i-lines, h-lines, and g-lines, the pattern-forming thin film 30 can have the above-mentioned phase difference with respect to any of the i-lines, h-lines, and g-lines. The representative wavelength can be, for example, the h-line at a wavelength of 405 nm. Having such characteristics with respect to the h-line allows for similar effects on the phase difference between the i-line and g-line wavelengths when composite light containing the i-line, h-line, and g-line is used as exposure light.

[0071] The phase difference can be measured using a phase shift amount measuring device or the like.

[0072] The back surface reflectance of the pattern-forming thin film 30 is preferably 15% or less, and more preferably 10% or less, in the wavelength range of 365 nm to 436 nm. Furthermore, when the exposure light includes the j-line (wavelength 313 nm), the back surface reflectance of the pattern-forming thin film 30 is preferably 20% or less, and more preferably 17% or less, for light in the wavelength range of 313 nm to 436 nm. Even more preferably, it is desirable to have a back surface reflectance of 15% or less. In addition, the back surface reflectance of the pattern-forming thin film 30 is preferably 0.2% or more, and more preferably 0.2% or more, in the wavelength range of 365 nm to 436 nm.

[0073] The back surface reflectance can be measured using a spectrophotometer or similar instrument.

[0074] The thin film 30 for pattern formation can be formed by known film deposition methods such as sputtering.

[0075] <Etching mask film 40> In this embodiment, the mask blank 10 for manufacturing a display device preferably comprises an etching mask film 40 on top of a thin film 30 for pattern formation, with etching selectivity different from that of the thin film 30 for pattern formation.

[0076] The etching mask film 40 is placed above the pattern-forming thin film 30 and is made of a material that has etching resistance to the etching solution used to etch the pattern-forming thin film 30 (its etching selectivity differs from that of the pattern-forming thin film 30). The etching mask film 40 may also have the function of blocking the transmission of exposure light. Furthermore, the etching mask film 40 may have the function of reducing the surface reflectivity of the pattern-forming thin film 30 so that the surface reflectivity of the pattern-forming thin film 30 with respect to light incident from the pattern-forming thin film 30 side is 15% or less in the wavelength range of 350 nm to 436 nm.

[0077] The etching mask film 40 is preferably composed of a chromium-based material containing chromium (Cr). More preferably, the etching mask film 40 is composed of a material that contains chromium and is substantially silicon-free. Substantially silicon-free means that the silicon content is less than 2% (except for the compositional gradient region at the interface between the pattern-forming thin film 30 and the etching mask film 40). More specifically, chromium-based materials include chromium (Cr), or materials containing chromium (Cr) and at least one of oxygen (O), nitrogen (N), and carbon (C). Also, chromium-based materials include materials containing chromium (Cr), at least one of oxygen (O), nitrogen (N), and carbon (C), and further containing fluorine (F). For example, materials that constitute the etching mask film 40 include Cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, and CrCONF.

[0078] The etching mask film 40 can be formed by known film deposition methods such as sputtering.

[0079] When the etching mask film 40 has the function of blocking the transmission of exposure light, the optical density with respect to exposure light in the portion where the pattern-forming thin film 30 and the etching mask film 40 are stacked is preferably 3 or higher, more preferably 3.5 or higher, and even more preferably 4 or higher. The optical density can be measured using a spectrophotometer or OD meter, etc.

[0080] The etching mask film 40 can be a single film with a uniform composition depending on its function. Alternatively, the etching mask film 40 can be made up of multiple films with different compositions. Furthermore, the etching mask film 40 can be a single film with a composition that continuously changes in the thickness direction.

[0081] The mask blank 10 of this embodiment shown in Figure 1 includes an etching mask film 40 on a thin film 30 for pattern formation. The mask blank 10 of this embodiment includes a mask blank 10 having a structure in which an etching mask film 40 is provided on a thin film 30 for pattern formation, and a resist film is provided on the etching mask film 40.

[0082] <Method for manufacturing mask blank 10> Next, the manufacturing method of the mask blank 10 of the embodiment shown in Figure 1 will be described. The mask blank 10 shown in Figure 1 is manufactured by performing the following thin film formation step for pattern formation and etching mask film formation step. The mask blank 10 shown in Figure 2 is manufactured by the thin film formation step for pattern formation.

[0083] The following describes each step in detail.

[0084] <<Thin film formation process for pattern formation>> First, a translucent substrate 20 is prepared. The translucent substrate 20 can be made of a glass material selected from synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, and low thermal expansion glass (such as SiO2-TiO2 glass), as long as it is transparent to exposure light.

[0085] Next, a thin film 30 for pattern formation is formed on the translucent substrate 20 by sputtering.

[0086] The thin film 30 for pattern formation can be deposited using a predetermined sputtering target in a predetermined sputtering gas atmosphere. The predetermined sputtering target is, for example, a titanium silicide target containing titanium and silicon, which are the main components of the material constituting the thin film 30 for pattern formation, or a titanium silicide target containing titanium, silicon, and nitrogen. The predetermined sputtering gas atmosphere is, for example, a sputtering gas atmosphere consisting of an inert gas containing at least one selected from the group consisting of helium, neon, argon, krypton, and xenon, or a sputtering gas atmosphere consisting of the above inert gas, nitrogen gas, and optionally a mixed gas selected from the group consisting of oxygen, carbon dioxide, nitric oxide, and nitrogen dioxide. The thin film 30 for pattern formation can be formed when the gas pressure in the deposition chamber during sputtering is 0.3 Pa or more and 2.0 Pa or less, preferably 0.43 Pa or more and 0.9 Pa or less. This suppresses side etching during pattern formation and enables a high etching rate. The atomic ratio of titanium to silicon in a titanium silicide target is preferably in the range of titanium:silicon = 1:1 to 1:19, from the viewpoint of improving light resistance and chemical resistance, as well as adjusting transmittance.

[0087] The composition and thickness of the pattern-forming thin film 30 are adjusted so that the pattern-forming thin film 30 has the above-mentioned phase difference and transmittance. The composition of the pattern-forming thin film 30 can be controlled by the content ratio of the elements constituting the sputter target (for example, the ratio of titanium content to silicon content), the composition and flow rate of the sputter gas, etc. The thickness of the pattern-forming thin film 30 can be controlled by the sputtering power and sputtering time, etc. Furthermore, it is preferable to form the pattern-forming thin film 30 using an in-line sputtering apparatus. When the sputtering apparatus is an in-line sputtering apparatus, the thickness of the pattern-forming thin film 30 can also be controlled by the substrate transport speed. Thus, the pattern-forming thin film 30 contains titanium, silicon, and nitrogen, and in the internal region of the thin film 30, the nitrogen content is 30 atomic percent or more, and the Ti2p narrow spectrum and Si2p narrow spectrum are in the desired relationship (P N / P T The control is performed so that the relationship (such as the relationship being greater than 1.52) is satisfied.

[0088] If the thin film 30 for pattern formation consists of a single film, the above-described film deposition process is performed only once, with appropriate adjustments to the composition and flow rate of the sputtering gas. If the thin film 30 for pattern formation consists of multiple films with different compositions, the above-described film deposition process is performed multiple times, with appropriate adjustments to the composition and flow rate of the sputtering gas. The thin film 30 for pattern formation may also be deposited using targets with different elemental content ratios. If the film deposition process is performed multiple times, the sputtering power applied to the sputtering target may be changed for each film deposition process.

[0089] <<Surface treatment process>> The thin film 30 for pattern formation can be made of a titanium silicide material (titanium silicide nitride) that contains oxygen in addition to titanium, silicon, and nitrogen. However, the oxygen content is greater than 0 atomic percent and 7 atomic percent or less. When the thin film 30 for pattern formation contains oxygen in this way, a surface treatment step may be performed on the surface of the thin film 30 to adjust the surface oxidation state of the thin film 30 in order to suppress penetration by the etching solution due to the presence of titanium oxide. Note that when the thin film 30 for pattern formation is made of titanium silicide nitride containing titanium, silicon, and nitrogen, the titanium oxide content is smaller compared to the titanium silicide material containing oxygen as described above. Therefore, when the material of the thin film 30 for pattern formation is titanium silicide nitride, the above surface treatment step may or may not be performed.

[0090] Surface treatment steps to adjust the surface oxidation state of the thin film 30 for pattern formation include methods of surface treatment with an acidic aqueous solution, methods of surface treatment with an alkaline aqueous solution, and methods of surface treatment with dry treatment such as ashing.

[0091] In this way, the mask blank 10 of this embodiment can be obtained.

[0092] <<Etching Mask Film Formation Process>> The mask blank 10 of this embodiment may further have an etching mask film 40. The following etching mask film formation steps are then carried out. Preferably, the etching mask film 40 is made of a material that contains chromium and is substantially silicon-free.

[0093] After the thin film formation process for pattern formation, surface treatment is performed as needed to adjust the surface oxidation state of the thin film 30 for pattern formation, and then an etching mask film 40 is formed on the thin film 30 for pattern formation by sputtering. It is preferable to form the etching mask film 40 using an in-line sputtering apparatus. When the sputtering apparatus is an in-line sputtering apparatus, the thickness of the etching mask film 40 can also be controlled by the transport speed of the translucent substrate 20.

[0094] The etching mask film 40 can be deposited using a sputtering target containing chromium or a chromium compound (such as chromium oxide, chromium nitride, chromium carbide, chromium oxidiznitride, chromium carbide nitride, and chromium oxidiznitride carbide) in a sputtering gas atmosphere consisting of an inert gas, or a sputtering gas atmosphere consisting of a mixture of an inert gas and an active gas. The inert gas may include, for example, at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas. The active gas may include at least one selected from the group consisting of oxygen gas, nitrogen gas, nitric oxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon gases, and fluorine gases. Examples of hydrocarbon gases include methane gas, butane gas, propane gas, and styrene gas. By adjusting the gas pressure in the deposition chamber during sputtering, the etching mask film 40 can be made into a columnar structure, similar to the thin film 30 for pattern formation. This suppresses side etching during pattern formation, as described later, and enables the achievement of a high etching rate.

[0095] If the etching mask film 40 consists of a single film with a uniform composition, the above-described film deposition process is performed only once without changing the composition and flow rate of the sputtering gas. If the etching mask film 40 consists of multiple films with different compositions, the above-described film deposition process is performed multiple times, changing the composition and flow rate of the sputtering gas for each deposition process. If the etching mask film 40 consists of a single film whose composition continuously changes in the thickness direction, the above-described film deposition process is performed only once, changing the composition and flow rate of the sputtering gas with the elapsed time of the deposition process.

[0096] In this way, the mask blank 10 of this embodiment having the etching mask film 40 can be obtained.

[0097] In Figure 1, the mask blank 10 has an etching mask film 40 on a thin film 30 for pattern formation; therefore, an etching mask film formation step is performed when manufacturing the mask blank 10. Furthermore, when manufacturing a mask blank 10 that has an etching mask film 40 on a thin film 30 for pattern formation and a resist film on the etching mask film 40, the resist film is formed on the etching mask film 40 after the etching mask film formation step. Also, in the case of the mask blank 10 shown in Figure 2, when manufacturing a mask blank 10 that has a resist film on a thin film 30 for pattern formation, the resist film is formed after the thin film formation step for pattern formation.

[0098] In the embodiment shown in Figure 1, the mask blank 10 has an etching mask film 40 formed on a thin film 30 for pattern formation. In the embodiment shown in Figure 2, the mask blank 10 has a thin film 30 for pattern formation formed on it. In both cases, the thin film 30 for pattern formation contains titanium, silicon, and nitrogen, and the nitrogen content in the internal region of the thin film 30 is 30 atomic percent or more, and the Ti2p narrow spectrum and Si2p narrow spectrum are in a desired relationship (P N / P S The relationship (that is greater than 1.18, etc.) is satisfied.

[0099] The mask blank 10 of the embodiment shown in Figures 1 and 2 has high light resistance to exposure light including wavelengths in the ultraviolet region, as well as high chemical resistance. Furthermore, when patterning the thin film 30 for pattern formation by wet etching, etching in the film thickness direction is promoted while side etching is suppressed. As a result, the cross-sectional shape of the thin film pattern 30a obtained by patterning is good and has the desired transmittance (e.g., high transmittance). By using the mask blank 10 of the embodiment, the thin film pattern 30a for pattern formation can be formed in a short etching time. Moreover, even after being subjected to integrated exposure light including wavelengths in the ultraviolet region, it is possible to form a thin film pattern 30a for pattern formation that maintains exposure transfer characteristics within a desired range. Therefore, by using the mask blank 10 of this embodiment, it is possible to manufacture a transfer mask 100 that has high light resistance to exposure light including wavelengths in the ultraviolet region, high chemical resistance, and can accurately transfer a thin film pattern 30a for high-resolution pattern formation.

[0100] <Method for manufacturing transfer mask 100> Next, the manufacturing method of the transfer mask 100 of this embodiment will be described. This transfer mask 100 has the same technical features as the mask blank 10. The matters concerning the light-transmitting substrate 20, the thin film 30 for pattern formation, and the etching mask film 40 in the transfer mask 100 are the same as those of the mask blank 10.

[0101] Figure 3 is a schematic diagram showing a method for manufacturing the transfer mask 100 of this embodiment. Figure 4 is a schematic diagram showing an alternative method for manufacturing the transfer mask 100 of this embodiment.

[0102] <<Manufacturing method for the transfer mask 100 shown in Figure 3>> The method for manufacturing the transfer mask 100 shown in Figure 3 is a method for manufacturing the transfer mask 100 using the mask blank 10 shown in Figure 1. The method for manufacturing the transfer mask 100 shown in Figure 3 includes the steps of: preparing the mask blank shown in Figure 1; forming a resist film on the etching mask film 40; wet etching the etching mask film 40 using the resist film pattern formed from the resist film as a mask to form an etching mask film pattern (first etching mask film pattern 40a) on the pattern formation thin film 30; and wet etching the pattern formation thin film 30 using the etching mask film pattern (first etching mask film pattern 40a) as a mask to form a transfer pattern on the translucent substrate 20. In this specification, the transfer pattern is obtained by patterning at least one optical film formed on the translucent substrate 20. The optical film can be the pattern formation thin film 30 and / or the etching mask film 40, and may further include other films (such as light-shielding films, reflection-suppressing films, and conductive films). In other words, the transfer pattern may include a patterned thin film and / or etching mask film for pattern formation, and may further include other patterned films.

[0103] The manufacturing method for the transfer mask 100 shown in Figure 3 specifically involves forming a resist film on the etching mask film 40 of the mask blank 10 shown in Figure 1. Next, a resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (see Figure 3(a), the step of forming the first resist film pattern 50). Next, the etching mask film 40 is wet-etched using the resist film pattern 50 as a mask to form an etching mask film pattern 40a on the pattern-forming thin film 30 (see Figure 3(b), the step of forming the first etching mask film pattern 40a). Next, the pattern-forming thin film 30 is wet-etched using the etching mask film pattern 40a as a mask to form a pattern-forming thin film pattern 30a on the translucent substrate 20 (see Figure 3(c), the step of forming the pattern-forming thin film pattern 30a). Subsequently, the process may further include the steps of forming a second resist film pattern 60 and forming a second etching mask film pattern 40b (see Figures 3(d) and (e)).

[0104] More specifically, in the process of forming the first resist film pattern 50, a resist film is first formed on the etching mask film 40 of the mask blank 10 of this embodiment shown in Figure 1. The resist film material used is not particularly limited. The resist film can be, for example, sensitive to laser light having any wavelength selected from the wavelength range of 350 nm to 436 nm, as described later. The resist film can also be either positive or negative.

[0105] Subsequently, a desired pattern is drawn on the resist film using laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm. The pattern drawn on the resist film is a pattern to be formed on the thin film 30 for pattern formation. Examples of patterns drawn on the resist film include line-and-space patterns and hole patterns.

[0106] Subsequently, the resist film is developed with a predetermined developer to form a first resist film pattern 50 on the etching mask film 40, as shown in Figure 3(a).

[0107] <<<Formation step of the first etching mask film pattern 40a>>> In the step of forming the first etching mask film pattern 40a, the etching mask film 40 is first etched using the first resist film pattern 50 as a mask to form the first etching mask film pattern 40a. The etching mask film 40 can be formed from a chromium-based material containing chromium (Cr). If the etching mask film 40 has a columnar structure, it is preferable in that the etching rate is fast and side etching can be suppressed. The etching solution used to etch the etching mask film 40 is not particularly limited as long as it can selectively etch the etching mask film 40. Specifically, an etching solution containing ceric ammonium nitrate and perchloric acid can be used.

[0108] Subsequently, the first resist film pattern 50 is removed using a resist stripping solution or by ashing, as shown in Figure 3(b). In some cases, the process of forming the next thin film pattern 30a for pattern formation may be carried out without removing the first resist film pattern 50.

[0109] <<<Process for forming the thin film pattern 30a for pattern formation>>> In the first step of forming the thin film pattern 30a for pattern formation, the thin film 30 for pattern formation is wet-etched using the first etching mask film pattern 40a as a mask to form the thin film pattern 30a for pattern formation as shown in Figure 3(c). Examples of the thin film pattern 30a for pattern formation include line-and-space patterns and hole patterns. The etching solution used to etch the thin film 30 for pattern formation is not particularly limited as long as it can selectively etch the thin film 30 for pattern formation. Examples include the etching solution A (such as an etching solution containing ammonium hydrogen fluoride and hydrogen peroxide) and etching solution B (such as an etching solution containing ammonium fluoride, phosphoric acid and hydrogen peroxide).

[0110] In order to improve the cross-sectional shape of the thin film pattern 30a for pattern formation, it is preferable to perform wet etching for a longer time (over-etching time) than the time until the translucent substrate 20 is exposed in the thin film pattern 30a for pattern formation (just etching time). Considering the effect on the translucent substrate 20, the over-etching time is preferably within the time obtained by adding 20% ​​of the just etching time to the just etching time, and more preferably within the time obtained by adding 10% of the just etching time.

[0111] <<<Process for forming the second resist film pattern 60>>> In the process of forming the second resist film pattern 60, first, a resist film is formed to cover the first etching mask film pattern 40a. The resist film material used is not particularly limited. For example, any material that is sensitive to laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm, as described later, is acceptable. The resist film may be either positive or negative type.

[0112] Subsequently, a desired pattern is drawn on the resist film using laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm. The pattern drawn on the resist film includes a light-shielding band pattern that shields the outer region of the area where the thin film pattern 30a for pattern formation is formed, and a light-shielding band pattern that shields the central part of the thin film pattern 30a for pattern formation. Depending on the transmittance of the thin film 30 for pattern formation to the exposure light, the pattern drawn on the resist film may not have a light-shielding band pattern that shields the central part of the thin film pattern 30a for pattern formation.

[0113] Subsequently, the resist film is developed with a predetermined developer to form a second resist film pattern 60 on the first etching mask film pattern 40a, as shown in Figure 3(d).

[0114] <<<Formation process of the second etching mask film pattern 40b>>> In the step of forming the second etching mask film pattern 40b, the first etching mask film pattern 40a is etched using the second resist film pattern 60 as a mask to form the second etching mask film pattern 40b as shown in Figure 3(e). The first etching mask film pattern 40a can be formed from a chromium-based material containing chromium (Cr). The etching solution used to etch the first etching mask film pattern 40a is not particularly limited as long as it can selectively etch the first etching mask film pattern 40a. For example, an etching solution containing cerium ammonium nitrate and perchloric acid can be used.

[0115] Subsequently, the second resist film pattern 60 is removed using a resist stripping solution or by ashing.

[0116] In this way, a transfer mask 100 can be obtained. That is, the transfer pattern of the transfer mask 100 according to this embodiment may include a thin film pattern 30a for pattern formation and a second etching mask film pattern 40b.

[0117] In the above description, we have described the case where the etching mask film 40 has the function of blocking the transmission of exposure light. If the etching mask film 40 simply has the function of a hard mask when etching the thin film 30 for pattern formation, the steps of forming the second resist film pattern 60 and the second etching mask film pattern 40b are not performed in the above description. In this case, after the step of forming the thin film pattern 30a for pattern formation, the first etching mask film pattern 40a is peeled off to prepare the transfer mask 100. That is, the transfer pattern on the transfer mask 100 may consist only of the thin film pattern 30a for pattern formation.

[0118] According to the manufacturing method of the transfer mask 100 of this embodiment, since the mask blank 10 shown in Figure 1 is used, the etching time can be shortened and a thin film pattern 30a for pattern formation with a good cross-sectional shape can be formed. Therefore, a transfer mask 100 that can accurately transfer a transfer pattern including a thin film pattern 30a for pattern formation can be manufactured. The transfer mask 100 manufactured in this way can accommodate the miniaturization of line-and-space patterns and / or contact holes.

[0119] <<Manufacturing method for the transfer mask 100 shown in Figure 4>> The method for manufacturing the transfer mask 100 shown in Figure 4 is a method for manufacturing the transfer mask 100 using the mask blank 10 shown in Figure 2. The method for manufacturing the transfer mask 100 shown in Figure 4 includes the steps of preparing the mask blank 10 shown in Figure 2, forming a resist film on a thin film 30 for pattern formation, and wet etching the thin film 30 for pattern formation using the resist film pattern formed from the resist film as a mask to form a transfer pattern on a translucent substrate 20.

[0120] Specifically, in the manufacturing method of the transfer mask 100 shown in Figure 4, a resist film is formed on the mask blank 10. Next, a resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (Figure 4(a), process of forming the first resist film pattern 50). Next, a thin film 30 for pattern formation is wet-etched using the resist film pattern 50 as a mask to form a thin film pattern 30a for pattern formation on the translucent substrate 20 (Figures 4(b) and (c), process of forming the thin film pattern 30a for pattern formation).

[0121] More specifically, in the resist film pattern formation process, first, a resist film is formed on the pattern-forming thin film 30 of the mask blank 10 of this embodiment shown in Figure 2. The resist film material used is the same as described above. If necessary, the pattern-forming thin film 30 can be surface-modified before forming the resist film to improve adhesion between the pattern-forming thin film 30 and the resist film. As described above, after forming the resist film, a desired pattern is drawn on the resist film using laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm. Then, the resist film is developed with a predetermined developer to form a resist film pattern 50 on the pattern-forming thin film 30 as shown in Figure 4(a).

[0122] <<<Process for forming the thin film pattern 30a for pattern formation>>> In the process of forming the thin film pattern 30a for pattern formation, the thin film 30 for pattern formation is etched using the resist film pattern as a mask to form the thin film pattern 30a for pattern formation, as shown in Figure 4(b). The etching solution and over-etching time for etching the thin film pattern 30a and the thin film 30 for pattern formation are the same as those described in the embodiment shown in Figure 3 above.

[0123] Subsequently, the resist film pattern 50 is removed using a resist stripping solution or by ashing (Figure 4(c)).

[0124] In this way, a transfer mask 100 can be obtained. Although the transfer pattern of the transfer mask 100 according to this embodiment consists only of a thin film pattern 30a for pattern formation, it may also include other film patterns. Examples of other films include films that suppress reflection and films that conduct electricity.

[0125] According to the manufacturing method of the transfer mask 100 of this embodiment, since the mask blank 10 shown in Figure 2 is used, there is no decrease in the transmittance of the translucent substrate 20 due to damage to the translucent substrate by the wet etching solution, the etching time can be shortened, and a thin film pattern 30a for pattern formation with a good cross-sectional shape can be formed. Therefore, a transfer mask 100 that can accurately transfer a transfer pattern including a thin film pattern 30a for pattern formation can be manufactured. The transfer mask 100 manufactured in this way can accommodate the miniaturization of line-and-space patterns and / or contact holes.

[0126] <Method for manufacturing a display device> A method for manufacturing the display device of this embodiment will now be described. The method for manufacturing the display device of this embodiment includes an exposure step in which the transfer mask 100 of this embodiment described above is placed on the mask stage of an exposure apparatus, and the transfer pattern formed on the transfer mask 100 for manufacturing the display device is exposed and transferred onto a resist formed on a substrate for the display device.

[0127] Specifically, the method for manufacturing the display device according to this embodiment includes the steps of placing the transfer mask 100 manufactured using the mask blank 10 described above onto the mask stage of an exposure apparatus (mask placement step) and exposing and transferring the transfer pattern onto the resist film on the substrate for the display device (exposure step). Each step will be described in detail below.

[0128] <<Placement Process>> In the placement process, the transfer mask 100 of this embodiment is placed on the mask stage of the exposure apparatus. Here, the transfer mask 100 is positioned to face the resist film formed on the substrate for the display device via the projection optical system of the exposure apparatus.

[0129] <<Pattern Transfer Process>> In the pattern transfer process, exposure light is irradiated onto the transfer mask 100 to transfer a transfer pattern, including a thin-film pattern 30a for pattern formation, onto the resist film formed on the substrate for the display device. The exposure light is composite light containing multiple wavelengths selected from the wavelength range of 313 nm to 436 nm, monochromatic light selected by filtering out a certain wavelength range from the 313 nm to 436 nm wavelength range, or monochromatic light emitted from a light source having the wavelength range of 313 nm to 436 nm. For example, the exposure light is composite light containing at least one of the i-line, h-line, and g-line, or monochromatic light of the i-line. By using composite light as the exposure light, the exposure light intensity can be increased and throughput can be improved. Therefore, the manufacturing cost of the display device can be reduced.

[0130] According to the method for manufacturing a display device of this embodiment, a high-resolution display device having high resolution, fine line-and-space patterns and / or contact holes can be manufactured.

[0131] In the embodiments described above, the case in which a mask blank 10 having a thin film 30 for pattern formation and a transfer mask 100 having a thin film pattern 30a for pattern formation are used has been explained. The thin film 30 for pattern formation can be, for example, a phase shift film having a phase shift effect or a light-shielding film. Therefore, the transfer mask 100 of this embodiment includes a phase shift mask having a phase shift film pattern and a binary mask having a light-shielding film pattern. Furthermore, the mask blank 10 of this embodiment includes a phase shift mask blank and a binary mask blank that serve as raw materials for the phase shift mask and the binary mask. [Examples]

[0132] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0133] (Example 1) To manufacture the mask blank 10 of Example 1, a 1214 size (1220 mm x 1400 mm) synthetic quartz glass substrate was first prepared as the translucent substrate 20.

[0134] Subsequently, the synthetic quartz glass substrate was placed on a tray (not shown) with its main surface facing downwards and transported into the chamber of the in-line sputtering apparatus.

[0135] To form a pattern-forming thin film 30 on the main surface of the translucent substrate 20, a mixed gas consisting of argon (Ar) gas and nitrogen (N2) gas was first introduced into the first chamber. Then, using a first sputtering target containing titanium and silicon (titanium:silicon = 5:7), a titanium silicide nitride containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a pattern-forming thin film 30 with a thickness of 115 nm (Ti:Si:N:O = 20.4:26.7:51.3:1.6 atomic % ratio) made of titanium silicide nitride was deposited. The composition of the pattern-forming thin film 30 was obtained by measurement using X-ray photoelectron spectroscopy (XPS). The method for measuring the film composition of other films is the same (the same applies to Examples 2-4 and Comparative Examples 1 and 2). This pattern-forming thin film 30 is a phase-shift film that exhibits a phase-shift effect.

[0136] Next, a translucent substrate 20 with a thin film 30 for pattern formation attached was brought into the second chamber, and a mixed gas of argon (Ar) gas and nitrogen (N2) gas was introduced into the second chamber. Then, using a second sputtering target made of chromium, a chromium nitride (CrN) containing chromium and nitrogen was formed on the thin film 30 for pattern formation by reactive sputtering. Next, with the third chamber under a predetermined vacuum, a mixed gas of argon (Ar) gas and methane (CH4) gas was introduced, and using a third sputtering target made of chromium, a chromium carbide (CrC) containing chromium and carbon was formed on the CrN by reactive sputtering. Finally, with the fourth chamber under a predetermined vacuum, a mixed gas of argon (Ar) gas and methane (CH4) gas and a mixed gas of nitrogen (N2) gas and oxygen (O2) gas were introduced, and using a fourth sputtering target made of chromium, a chromium carbide oxide nitride (CrCON) containing chromium, carbon, oxygen, and nitrogen was formed on the CrC by reactive sputtering. As described above, an etching mask film 40 having a laminated structure of a CrN layer, a CrC layer, and a CrCON layer was formed on the thin film 30 for pattern formation.

[0137] In this way, a mask blank 10 was obtained on a translucent substrate 20, on which a thin film 30 for pattern formation and an etching mask film 40 were formed.

[0138] A thin film for pattern formation according to Example 1 was deposited on the main surface of another synthetic quartz substrate (approximately 152 mm x 152 mm), and another thin film for pattern formation was formed under the same deposition conditions as in Example 1. Next, X-ray photoelectron spectroscopy analysis was performed on the thin film for pattern formation on this other synthetic quartz substrate. In this X-ray photoelectron spectroscopy analysis, the internal region of the thin film for pattern formation was irradiated with X-rays (AlKα rays: 1486 eV), and the intensity of photoelectrons emitted from the thin film was measured. The internal region of the thin film for pattern formation was then excavated using Ar gas sputtering at a voltage of 2.0 kV and a sputtering rate of approximately 5 nm / min (SiO2 equivalent), and the internal region of the excavated area was irradiated with X-rays, and the intensity of photoelectrons emitted from that region was measured. This step was repeated to obtain Ti2p narrow spectra at each depth of the internal region of the thin film for pattern formation. (The same procedure was followed for Examples 2-4 and Comparative Examples 1 and 2.)

[0139] Figure 5 shows the results (Ti2p narrow spectra) of X-ray photoelectron spectroscopy analysis performed on thin films for pattern formation on different synthetic quartz substrates according to each embodiment of the present invention. Figure 6 shows the results (Si2p narrow spectra) of X-ray photoelectron spectroscopy analysis performed on phase-shifted mask blank films according to each embodiment of the present invention. The narrow spectra shown in Figures 5 and 6 were obtained at a predetermined depth position (a depth position approximately in the center of the film thickness direction in the internal region) of the thin film for pattern formation on different synthetic quartz substrates according to each embodiment. As can be determined from the values ​​shown in Figures 5 and 6, in the Ti2p narrow spectrum and Si2p narrow spectrum of Example 1, P N / P S The value was 1.84, which was greater than 1.18 (as mentioned above, the photoelectron intensity at a binding energy of 455 eV is P N , the photoelectron intensity at a binding energy of 10² eV is P S This is the case. The same applies below. Furthermore, in the narrow spectra of Ti2p and Si2p in Example 1, P NU / P SThe value was 1.60, which satisfies the relationship greater than 1.05 (as mentioned above, the photoelectron intensity at a binding energy of 461 eV is P NU This is the case. The same applies below. Furthermore, in the narrow spectra of Ti2p and Si2p in Example 1, (P N +P NU ) / P S The value was 3.44, which satisfies the relationship greater than 2.22. Furthermore, in the narrow spectrum of Ti2p in Example 1, P N / P TS The value was 3.06, which was greater than 2.13 (as mentioned above, the photoelectron intensity at a binding energy of 453 eV is P TS This is the case. The same applies below. Furthermore, in the narrow spectrum of Ti2p in Example 1, (P N +P T ) / P TS The value was 4.62, which satisfies the relationship greater than 3.53. In Example 1, the Ti2p narrow spectra and Si2p narrow spectra at other depth positions within the internal region also satisfied all of the above-mentioned ratios.

[0140] <Measurement of transmittance and phase difference> The transmittance (wavelength: 365 nm) and phase difference (wavelength: 365 nm) of the thin film 30 for pattern formation on the mask blank 10 of Example 1 were measured using an MPM-100 manufactured by Lasertec. For measuring the transmittance and phase difference of the thin film 30 for pattern formation, a substrate with a thin film deposited on the main surface of another synthetic silica glass substrate was used (the same method was used in Examples 2, 3, 4, and Comparative Examples 1 and 2). As a result, the transmittance of the thin film 30 for pattern formation in Example 1 was 6%, and the phase difference was 180 degrees.

[0141] <Transfer mask 100 and method for manufacturing the same> A transfer mask 100 was manufactured using the mask blank 10 of Example 1, which was produced as described above. First, a photoresist film was applied to the etching mask film 40 of the mask blank 10 using a resist coating apparatus.

[0142] Subsequently, a photoresist film was formed through a heating and cooling process.

[0143] Subsequently, a photoresist film was drawn using a laser lithography device, and after development and rinsing steps, a resist film pattern with a hole diameter of 1.5 μm was formed on the etching mask film 40.

[0144] Subsequently, using the resist film pattern as a mask, the etching mask film 40 was wet-etched with a chromium etching solution containing cerium ammonium nitrate and perchloric acid to form the first etching mask film pattern 40a.

[0145] Subsequently, using the first etching mask film pattern 40a as a mask, the thin film 30 for pattern formation was wet-etched with a titanium silicide etching solution, which was a mixture of ammonium hydrogen fluoride and hydrogen peroxide diluted with pure water, to form the thin film pattern 30a for pattern formation.

[0146] After that, the resist film pattern was peeled off.

[0147] Subsequently, a photoresist film was applied using a resist coating apparatus to cover the first etching mask film pattern 40a.

[0148] Subsequently, a photoresist film was formed through a heating and cooling process.

[0149] Subsequently, a photoresist film was drawn using a laser drawing device, and after a development and rinsing process, a second resist film pattern 60 for forming a light-shielding band was formed on the first etching mask film pattern 40a.

[0150] Subsequently, using the second resist film pattern 60 as a mask, the first etching mask film pattern 40a formed in the transfer pattern formation region was wet-etched with a chromium etching solution containing cerium ammonium nitrate and perchloric acid.

[0151] Subsequently, the second resist film pattern 60 was peeled off.

[0152] In this way, a transfer mask 100 of Example 1 was obtained, on a translucent substrate 20, having a thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm in the transfer pattern formation region, and a light-shielding band consisting of a laminated structure of the thin film pattern 30a and an etching mask film pattern 40b.

[0153] <Cross-sectional shape of transfer mask 100> The cross-section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation on the transfer mask 100 of Example 1 had a cross-sectional shape that was nearly vertical. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Example 1 had a cross-sectional shape that could fully exhibit the phase shift effect.

[0154] From the above, it can be said that when the transfer mask 100 of Example 1 is set on the mask stage of an exposure apparatus and exposed to a resist film on a substrate for a display device, a transfer pattern including fine patterns of less than 2.0 μm can be transferred with high precision.

[0155] <Light resistance and chemical resistance> A sample was prepared by forming a thin film 30 for pattern formation on a translucent substrate 20, the same thin film used in the mask blank 10 of Example 1. The thin film 30 for pattern formation of this sample from Example 1 was irradiated with light from a metal halide light source containing ultraviolet light with a wavelength of 365 nm at a total dose of 10 kJ / cm². 2The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation with a predetermined amount of ultraviolet light and calculating the change in transmittance [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)]. Transmittance was measured using a spectrophotometer.

[0156] In Example 1, the change in transmittance before and after UV irradiation was a good 0.09% (0.09 points). From the above, it was found that the thin film used for pattern formation in Example 1 is a film with sufficiently high light resistance for practical use.

[0157] A sample was prepared by forming a thin film 30 for pattern formation on a translucent substrate 20, the same thin film used in the mask blank 10 of Example 1. The thin film 30 for pattern formation of this sample from Example 1 was subjected to a cleaning test consisting of five cycles: SPM cleaning with a mixture of sulfuric acid and hydrogen peroxide (cleaning time: 5 minutes), followed by SC-1 cleaning with a mixture of ammonia, hydrogen peroxide, and water (cleaning time: 5 minutes), with each cycle comprising one cycle. The chemical resistance of the thin film 30 for pattern formation was evaluated.

[0158] The chemical resistance of the thin film 30 used for pattern formation was evaluated by measuring the reflectance spectrum in the wavelength range of 200 nm to 500 nm before and after a cleaning test, and measuring the change in the wavelength corresponding to the lowest reflectance (bottom peak wavelength) where the reflectance is convex downwards.

[0159] The results of the chemical resistance evaluation showed that in Example 1, which had a titanium silicide-based thin film for pattern formation, the change in the bottom peak wavelength per washing cycle was small, less than 1.0 nm towards the shorter wavelength side, indicating good chemical resistance.

[0160] Based on the above, it has become clear that the thin film for pattern formation in Example 1 is an unprecedented and superior product that satisfies the desired optical properties (transmittance, phase difference) while also possessing high light resistance (chemical resistance), a high etching rate, and a good cross-sectional shape.

[0161] (Example 2) The mask blank 10 of Example 2 was manufactured in the same procedure as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was made as follows. The method for forming the thin film 30 for pattern formation in Example 2 is as follows. In order to form the thin film 30 for pattern formation on the main surface of the light-transmissive substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N2) gas was introduced into the first chamber. Then, using a first sputtering target containing titanium and silicon (titanium:silicon = 1:2), by reactive sputtering, a nitride of titanium silicide containing titanium, silicon, and nitrogen was deposited on the main surface of the light-transmissive substrate 20. In this way, a thin film 30 for pattern formation with a thickness of 130 nm made of a nitride of titanium silicide (Ti:Si:N:O = 15.4:31.6:50.9:2.1 atomic% ratio) was formed. Thereafter, an etching mask film 40 was formed in the same manner as in Example 1.

[0162] Then, on the main surface of another synthetic quartz substrate, another thin film for pattern formation was formed under the same film formation conditions as in Example 2 above. Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on this another synthetic quartz substrate in the same manner as in Example 1. As determined from the values shown in FIGS. 5 and 6, in the narrow spectra of Ti2p and Si2p of Example 2, P N / P S was 1.36, satisfying a relationship greater than 1.18. Also, in the narrow spectra of Ti2p and Si2p of Example 2, P NU / P S was 1.23, satisfying a relationship greater than 1.05. Also, in the narrow spectra of Ti2p and Si2p of Example 2, (P N +P [[ID=I7]] NU ) / P S was 2.59, satisfying a relationship greater than 2.22. Also, in the narrow spectrum of Ti2p of Example 2, PN / P TS was 2.53 and satisfied the relationship of being greater than 2.13. Also, in the narrow spectrum of Ti2p in Example 2, (P N +P T ) / P TS was 3.96 and satisfied the relationship of being greater than 3.53. In Example 2, each Ti2p narrow spectrum and each Si2p narrow spectrum at other depth positions in the internal region also satisfied all the above ratios.

[0163] <Measurement of Transmittance and Phase Difference> For the surface of the thin film 30 for pattern formation of the mask blank 10 in Example 2, the transmittance (wavelength: 365 nm) and the phase difference (wavelength: 365 nm) were measured by MPM - 100 manufactured by Lasertec Corporation. As a result, the transmittance of the thin film 30 for pattern formation in Example 2 was 14%, and the phase difference was 180 degrees.

[0164] <Transfer Mask 100 and Its Manufacturing Method> Using the mask blank 10 of Example 2 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as in Example 1. On the light - transmissive substrate 20, a thin - film pattern 30a for pattern formation with a hole diameter of 1.5 μm in the transfer - pattern formation region and a light - shielding band composed of a laminated structure of the thin - film pattern 30a for pattern formation and an etching - mask film pattern 40b were formed, and the transfer mask 100 of Example 2 was obtained.

[0165] <Cross - Sectional Shape of Transfer Mask 100> The cross - section of the obtained transfer mask 100 was observed with a scanning electron microscope. The thin - film pattern 30a for pattern formation of the transfer mask 100 in Example 2 had a cross - sectional shape close to vertical. Therefore, the thin - film pattern 30a for pattern formation formed on the transfer mask 100 in Example 2 had a cross - sectional shape that could sufficiently exhibit the phase - shift effect.

[0166] From the above, it can be said that when the transfer mask 100 of Example 2 is set on the mask stage of the exposure apparatus and exposed to a resist film on a substrate for a display device, a transfer pattern including fine patterns of less than 2.0 μm can be transferred with high precision.

[0167] <Light resistance and chemical resistance> A sample was prepared by forming a thin film 30 for pattern formation on a translucent substrate 20, the same thin film used in the mask blank 10 of Example 2. The thin film 30 for pattern formation of this sample from Example 2 was irradiated with light from a metal halide light source containing ultraviolet light with a wavelength of 365 nm at a total dose of 10 kJ / cm². 2 The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation with a predetermined amount of ultraviolet light and calculating the change in transmittance [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)]. Transmittance was measured using a spectrophotometer.

[0168] In Example 2, the change in transmittance before and after UV irradiation was a good 0.34% (0.34 points). From the above, it was found that the thin film used for pattern formation in Example 2 is a film with sufficiently high light resistance for practical use.

[0169] Furthermore, a sample was prepared in which a thin film 30 for pattern formation, used in the mask blank 10 of Example 2, was formed on a translucent substrate 20, and the chemical resistance of the thin film 30 for pattern formation was evaluated in the same manner as in Example 1. The results of the chemical resistance evaluation showed that in Example 2, which had a titanium silicide-based thin film for pattern formation, the change in the bottom peak wavelength per washing cycle was small, less than 1.0 nm towards the shorter wavelength side, indicating good chemical resistance.

[0170] Based on the above, it has become clear that the thin film for pattern formation in Example 2 is an unprecedented and superior product that satisfies the desired optical properties (transmittance, phase difference) while also possessing high light resistance (chemical resistance), a high etching rate, and a good cross-sectional shape.

[0171] (Example 3) The mask blank 10 of Example 3 was manufactured using the same procedure as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was made as described below. The method for forming the thin film 30 for pattern formation in Example 3 is as follows. To form a thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N2) gas was introduced into the first chamber. Then, using a first sputtering target containing titanium and silicon (titanium:silicon = 1:3), a titanium silicide nitride containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a thickness of 131 nm (Ti:Si:N:O = 11.4:35.4:52.4:0.8 atomic % ratio) made of titanium silicide nitride was deposited. Subsequently, the etching mask film 40 was deposited in the same manner as in Example 1.

[0172] Next, a thin film for pattern formation was formed on the main surface of another synthetic quartz substrate under the same deposition conditions as in Example 3. Then, X-ray photoelectron spectroscopy analysis was performed on this thin film for pattern formation on the other synthetic quartz substrate, in the same manner as in Example 1. As can be determined from the values ​​shown in Figures 5 and 6, in the narrow spectra of Ti2p and Si2p in Example 3, P N / P S The value was 1.25, which satisfies the relationship greater than 1.18. Furthermore, in the narrow spectra of Ti2p and Si2p in Example 3, P NU / P S The value was 1.18, which satisfies the relationship greater than 1.05. Furthermore, in the narrow spectra of Ti2p and Si2p in Example 3, (P N +P NU ) / P S The value was 2.43, which satisfies the relationship greater than 2.22. In Example 3, the Ti2p narrow spectra and Si2p narrow spectra at other depth positions within the internal region also satisfied all of the above-mentioned ratios.

[0173] <Measurement of transmittance and phase difference> The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) of the thin film 30 used for pattern formation on the mask blank 10 of Example 3 were measured using an MPM-100 manufactured by Lasertec. As a result, the transmittance of the thin film 30 used for pattern formation in Example 3 was 18%, and the phase difference was 180 degrees.

[0174] <Transfer mask 100 and method for manufacturing the same> Using the mask blank 10 of Example 3 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as in Example 1 to obtain the transfer mask 100 of Example 3, in which a thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm and a light-shielding band consisting of a laminated structure of the thin film pattern 30a and the etching mask film pattern 40b were formed on the translucent substrate 20.

[0175] <Cross-sectional shape of transfer mask 100> The cross-section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation on the transfer mask 100 of Example 3 had a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a formed on the transfer mask 100 of Example 3 had a cross-sectional shape that could fully exhibit the phase shift effect.

[0176] From the above, it can be said that when the transfer mask 100 of Example 3 is set on the mask stage of an exposure apparatus and exposed to a resist film on a substrate for a display device, a transfer pattern including fine patterns of less than 2.0 μm can be transferred with high precision.

[0177] <Light resistance and chemical resistance> A sample was prepared by forming a thin film 30 for pattern formation, which was used in the mask blank 10 of Example 3, on a translucent substrate 20. The thin film 30 for pattern formation of this sample from Example 3 was irradiated with a total light dose of 10 kJ / cm² from a metal halide light source containing ultraviolet light with a wavelength of 365 nm. 2 The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation with a predetermined amount of ultraviolet light and calculating the change in transmittance [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)]. Transmittance was measured using a spectrophotometer.

[0178] In Example 3, the change in transmittance before and after UV irradiation was a good 0.45% (0.45 points). From the above, it was found that the thin film used for pattern formation in Example 3 is a film with sufficiently high light resistance for practical use.

[0179] Furthermore, a sample was prepared in which a thin film 30 for pattern formation, used in the mask blank 10 of Example 3, was formed on a translucent substrate 20, and the chemical resistance of the thin film 30 for pattern formation was evaluated in the same manner as in Example 1. The results of the chemical resistance evaluation showed that in Example 3, which had a titanium silicide-based thin film for pattern formation, the change in the bottom peak wavelength per washing cycle was small, less than 1.0 nm towards the shorter wavelength side, indicating good chemical resistance.

[0180] Based on the above, it has become clear that the thin film for pattern formation in Example 3 is an unprecedented and superior product that satisfies the desired optical properties (transmittance, phase difference) while also possessing high light resistance (chemical resistance), a high etching rate, and a good cross-sectional shape.

[0181] (Example 4) The mask blank 10 of Example 4 was manufactured using the same procedure as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was made as described below. The method for forming the thin film 30 for pattern formation in Example 4 is as follows. To form a thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N2) gas was introduced into the first chamber. Then, using a first sputtering target containing titanium and silicon (titanium:silicon = 1:3), a titanium silicide nitride containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a thickness of 134 nm (Ti:Si:N:O = 11.7:35.0:52.0:1.3 atomic % ratio) made of titanium silicide nitride was deposited. Subsequently, the etching mask film 40 was deposited in the same manner as in Example 1.

[0182] Then, on the main surface of another translucent substrate, a thin film for pattern formation and an etching mask film were formed under the same deposition conditions as in Example 4. Next, X-ray photoelectron spectroscopy analysis was performed on the thin film for pattern formation on this other translucent substrate, in the same manner as in Example 1. As can be determined from the values ​​shown in Figures 5 and 6, in the narrow spectra of Ti2p and Si2p in Example 4, P N / P S The value was 1.19, which satisfies the relationship that it is greater than 1.18. Furthermore, in the narrow spectra of Ti2p and Si2p in Example 4, P NU / P S The value was 1.11, which satisfies the relationship greater than 1.05. Furthermore, in the narrow spectra of Ti2p and Si2p in Example 4, (P N +P NU ) / P S The value was 2.30, which satisfies the relationship greater than 2.22. In Example 4, the Ti2p narrow spectra and Si2p narrow spectra at other depth positions within the internal region also satisfied all of the above-mentioned ratios.

[0183] <Measurement of transmittance and phase difference> The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) of the thin film 30 used for pattern formation on the mask blank 10 of Example 4 were measured using an MPM-100 manufactured by Lasertec. As a result, the transmittance of the thin film 30 used for pattern formation in Example 4 was 22%, and the phase difference was 180 degrees.

[0184] <Transfer mask 100 and method for manufacturing the same> Using the mask blank 10 of Example 4 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as in Example 1 to obtain the transfer mask 100 of Example 4, in which a thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm and a light-shielding band consisting of a laminated structure of the thin film pattern 30a and the etching mask film pattern 40b were formed on the translucent substrate 20.

[0185] <Cross-sectional shape of transfer mask 100> The cross-section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation on the transfer mask 100 of Example 4 had a cross-sectional shape that was nearly vertical. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Example 4 had a cross-sectional shape that could fully exhibit the phase shift effect.

[0186] From the above, it can be said that when the transfer mask 100 of Example 4 is set on the mask stage of the exposure apparatus and exposed to a resist film on a substrate for a display device, a transfer pattern including fine patterns of less than 2.0 μm can be transferred with high precision.

[0187] <Light resistance and chemical resistance> A sample was prepared by forming a thin film 30 for pattern formation on a translucent substrate 20, the same thin film used in the mask blank 10 of Example 4. The thin film 30 for pattern formation of this sample from Example 4 was irradiated with light from a metal halide light source containing ultraviolet light with a wavelength of 365 nm at a total dose of 10 kJ / cm². 2The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation with a predetermined amount of ultraviolet light and calculating the change in transmittance [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)]. Transmittance was measured using a spectrophotometer.

[0188] In Example 4, the change in transmittance before and after UV irradiation was a good 1.48% (0.34 points). From the above, it was found that the thin film used for pattern formation in Example 4 is a film with sufficiently high light resistance for practical use.

[0189] Furthermore, a sample was prepared in which a thin film 30 for pattern formation, used in the mask blank 10 of Example 4, was formed on a translucent substrate 20, and the chemical resistance of the thin film 30 for pattern formation was evaluated in the same manner as in Example 1. The results of the chemical resistance evaluation showed that in Example 4, which had a titanium silicide-based thin film for pattern formation, the change in the bottom peak wavelength per washing cycle was small, less than 1.0 nm towards the shorter wavelength side, indicating good chemical resistance.

[0190] In summary, the thin film for pattern formation in Example 4 is an unprecedented and superior product that satisfies the desired optical properties (transmittance, phase difference) while also possessing high light resistance (chemical resistance), a high etching rate, and a good cross-sectional shape.

[0191] (Comparative Example 1) The mask blank 10 of Comparative Example 1 was manufactured using the same procedure as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was made as described below. The method for forming the thin film 30 for pattern formation in Comparative Example 1 is as follows. To form a thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N2) gas was introduced into the first chamber. Then, using a first sputtering target containing titanium and silicon (titanium:silicon = 1:3), a titanium silicide nitride containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a thickness of 130 nm (Ti:Si:N:O = 11.7:35.5:51.0:1.8 atomic % ratio) made of titanium silicide nitride was deposited. Subsequently, the etching mask film 40 was deposited in the same manner as in Example 1.

[0192] Then, another thin film for pattern formation was formed on the main surface of a different synthetic quartz substrate under the same deposition conditions as in Comparative Example 1. Next, X-ray photoelectron spectroscopy analysis was performed on this thin film for pattern formation on the other synthetic quartz substrate, in the same manner as in Example 1. Figure 7 shows the results of X-ray photoelectron spectroscopy analysis (Ti2p narrow spectrum) performed on the phase-shifted mask blanks according to each comparative example of the present invention. Figure 8 shows the results of X-ray photoelectron spectroscopy analysis (Si2p narrow spectrum) performed on the phase-shifted mask blanks according to each comparative example of the present invention. The narrow spectra shown in Figures 7 and 8 were obtained at a predetermined depth position (approximately the center in the film thickness direction of the internal region) of the thin film used for pattern formation on another synthetic quartz substrate according to each comparative example. As can be determined from the values ​​shown in Figures 7 and 8, in the Ti2p narrow spectrum and Si2p narrow spectrum of Comparative Example 1, P N / P S The value was 1.18, and it did not satisfy the relationship greater than 1.18. Furthermore, in the narrow spectra of Ti2p and Si2p in Comparative Example 1, P NU / P S The value was 1.05, and it did not satisfy the relationship greater than 1.05. Furthermore, in the narrow spectra of Ti2p and Si2p in Comparative Example 1, (PN +P NU ) / P S The value was 2.22, and it did not satisfy the relationship greater than 2.22. Furthermore, in the narrow spectrum of Ti2p in Comparative Example 1, P N / P TS The value was 2.13, and it did not satisfy the relationship greater than 2.13. Furthermore, in the narrow spectrum of Ti2p in Comparative Example 1, (P N +P T ) / P TS The result was 3.53, which did not satisfy the relationship greater than 3.53.

[0193] <Measurement of transmittance and phase difference> The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) of the thin film 30 used for pattern formation on the mask blank 10 of Comparative Example 1 were measured using an MPM-100 manufactured by Lasertec Corporation. As a result, the transmittance of the thin film 30 used for pattern formation in Comparative Example 1 was 23%, and the phase difference was 180 degrees.

[0194] <Transfer mask 100 and method for manufacturing the same> Using the mask blank 10 of Comparative Example 1 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as in Example 1 to obtain the transfer mask 100 of Comparative Example 1, in which a thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm and a light-shielding band consisting of a laminated structure of the thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20.

[0195] <Cross-sectional shape of transfer mask 100> The cross-section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation on the transfer mask 100 of Comparative Example 1 had a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a formed on the transfer mask 100 of Comparative Example 1 had a cross-sectional shape that could fully exhibit the phase shift effect.

[0196] From the above, when the transfer mask 100 of Comparative Example 1 is set on the mask stage of the exposure apparatus and exposed and transferred onto the resist film on the substrate for the display device, it can be said that the transfer pattern including fine patterns less than 2.0 μm can be transferred with high precision.

[0197] <Light resistance and chemical resistance> A sample was prepared by forming the thin film 30 for pattern formation used in the mask blank 10 of Comparative Example 1 on the light-transmissive substrate 20. With respect to the thin film 30 for pattern formation of this sample of Comparative Example 1, light from a metal halide light source containing ultraviolet light with a wavelength of 365 nm was irradiated so that the total irradiation amount was 10 kJ / cm 2 The transmittance was measured before and after the irradiation of the predetermined ultraviolet light, and the change in transmittance [(transmittance after ultraviolet light irradiation) - (transmittance before ultraviolet light irradiation)] was calculated to evaluate the light resistance of the thin film 30 for pattern formation. The transmittance was measured using a spectrophotometer.

[0198] In Comparative Example 1, the change in transmittance before and after ultraviolet light irradiation was 2.00% (2.00 points), which was outside the allowable range. From the above, it was found that the thin film for pattern formation of Comparative Example 1 did not have sufficient light resistance for practical use.

[0199] Also, a sample was prepared by forming the thin film 30 for pattern formation used in the mask blank 10 of Comparative Example 1 on the light-transmissive substrate 20, and the chemical resistance of the thin film 30 for pattern formation was evaluated in the same manner as in Example 1. As a result of the chemical resistance evaluation, in Comparative Example 1 having a titanium silicide-based thin film for pattern formation, the amount of change in the bottom peak wavelength per cleaning cycle was as small as 1.0 nm or less on the short wavelength side, and the chemical resistance was sufficient.

[0200] Thus, the thin film for pattern formation of Comparative Example 1 did not have sufficient performance in terms of light resistance. (Comparative Example 2) The mask blank 10 of Comparative Example 2 was manufactured using the same procedure as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was made as described below. The method for forming the thin film 30 for pattern formation in Comparative Example 2 is as follows. To form a thin film 30 for pattern formation on the main surface of the translucent substrate 20, a mixed gas consisting of argon (Ar) gas and nitrogen (N2) gas was first introduced into the first chamber. Then, using a first sputtering target containing titanium and silicon (titanium:silicon = 1:4), a titanium silicide nitride containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a thickness of 186 nm (Ti:Si:N:O = 7.6:33.6:40.6:18.2 atomic % ratio) made of titanium silicide nitride was deposited. The high oxygen content of the thin film 30 is not due to intentionally introduced oxygen components, but rather to residual moisture in the deposition apparatus and adsorbed moisture introduced into the environment. Subsequently, the etching mask film 40 was deposited in the same manner as in Example 1.

[0201] Then, another thin film for pattern formation was formed on the main surface of a different synthetic quartz substrate under the same deposition conditions as in Comparative Example 2. Next, X-ray photoelectron spectroscopy analysis was performed on this thin film for pattern formation on the other synthetic quartz substrate, in the same manner as in Example 1. As can be determined from the values ​​shown in Figures 7 and 8, in the narrow spectra of Ti2p and Si2p in Comparative Example 2, P N / P S The value was 0.31, which did not satisfy the relationship greater than 1.18. Furthermore, in the narrow spectra of Ti2p and Si2p in Comparative Example 2, P NU / P S The value was 0.33, which did not satisfy the relationship greater than 1.05. Furthermore, in the narrow spectra of Ti2p and Si2p in Comparative Example 2, (P N +P NU ) / P SThe value was 0.64, which did not satisfy the relationship greater than 2.22. Furthermore, in the narrow spectrum of Ti2p in Comparative Example 2, P N / P TS The value was 1.53, which did not satisfy the relationship greater than 2.13. Furthermore, in the narrow spectrum of Ti2p in Comparative Example 2, (P N +P T ) / P TS The value was 2.64, which did not satisfy the relationship greater than 3.53.

[0202] <Measurement of transmittance and phase difference> The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) of the thin film 30 used for pattern formation on the mask blank 10 of Comparative Example 2 were measured using an MPM-100 manufactured by Lasertec Corporation. As a result, the transmittance of the thin film 30 used for pattern formation in Comparative Example 2 was 57%, and the phase difference was 180 degrees.

[0203] <Transfer mask 100 and method for manufacturing the same> Using the mask blank 10 of Comparative Example 2 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as in Example 1 to obtain a transfer mask 100 of Comparative Example 2, in which a thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm and a light-shielding band consisting of a laminated structure of the thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20.

[0204] <Cross-sectional shape of transfer mask 100> The cross-section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation on the transfer mask 100 of Comparative Example 2 had a cross-sectional shape in which the boundary portion with the translucent substrate 20 was excessively etched. Therefore, the thin film pattern 30a formed on the transfer mask 100 of Comparative Example 2 did not have a cross-sectional shape that could fully exhibit the phase shift effect.

[0205] Based on the above, when the transfer mask 100 of Comparative Example 2 is set on the mask stage of the exposure apparatus and exposed to transfer to the resist film on the substrate for the display device, it is difficult to transfer the transfer pattern containing fine patterns of less than 2.0 μm with high precision.

[0206] <Light resistance and chemical resistance> A sample was prepared by forming a thin film 30 for pattern formation on a translucent substrate 20, the same thin film used in the mask blank 10 of Comparative Example 2. The thin film 30 for pattern formation of this Comparative Example 2 sample was irradiated with light from a metal halide light source containing ultraviolet light with a wavelength of 365 nm at a total dose of 10 kJ / cm². 2 The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation with a predetermined amount of ultraviolet light and calculating the change in transmittance [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)]. Transmittance was measured using a spectrophotometer.

[0207] In Comparative Example 2, the change in transmittance before and after UV irradiation was 2.55% (2.55 points), which was outside the acceptable range. From the above, it was found that the thin film used for pattern formation in Comparative Example 2 does not have sufficient light resistance for practical purposes.

[0208] Furthermore, a sample was prepared in which a thin film 30 for pattern formation, which was used in the mask blank 10 of Comparative Example 2, was formed on a translucent substrate 20, and the chemical resistance of the thin film 30 for pattern formation was evaluated in the same manner as in Example 1. The results of the chemical resistance evaluation showed that in Comparative Example 2, which had a titanium silicide-based pattern formation thin film containing 8 atomic percent or more of oxygen, the change in the bottom peak wavelength per washing cycle was large, at 1.0 nm or more towards the shorter wavelength side, indicating insufficient chemical resistance.

[0209] Thus, the thin film used for pattern formation in Comparative Example 2 did not have sufficient performance in terms of light resistance and chemical resistance.

[0210] In the above embodiments, examples of the transfer mask 100 for manufacturing a display device and the mask blank 10 for manufacturing the transfer mask 100 for manufacturing a display device have been described, but the present invention is not limited thereto. The mask blank 10 and / or the transfer mask 100 of the present invention can also be applied to semiconductor device manufacturing, MEMS manufacturing, printed circuit board manufacturing, and the like. Further, the present invention can also be applied to a binary mask blank having a light-shielding film as the thin film 30 for pattern formation and a binary mask having a light-shielding film pattern.

[0211] In the above embodiments, an example of the size of the light-transmissive substrate 20 being the 1214 size (1220 mm × 1400 mm × 13 mm) has been described, but the present invention is not limited thereto. In the case of the mask blank 10 for manufacturing a display device, a large-sized light-transmissive substrate 20 is used, and the size of the light-transmissive substrate 20 is such that the length of one side of the main surface is 300 mm or more. The size of the light-transmissive substrate 20 used for the mask blank 10 for manufacturing a display device is, for example, 330 mm × 450 mm or more and 2280 mm × 3130 mm or less.

[0212] In the case of the mask blank 10 for semiconductor device manufacturing, MEMS manufacturing, or printed circuit board manufacturing, a small-sized light-transmissive substrate 20 is used, and the size of the light-transmissive substrate 20 is such that the length of one side is 9 inches or less. The size of the light-transmissive substrate 20 used for the mask blank 10 for the above applications is, for example, 63.1 mm × 63.1 mm or more and 228.6 mm × 228.6 mm or less. Usually, for the light-transmissive substrate 20 for the transfer mask 100 for semiconductor device manufacturing and MEMS manufacturing, the 6025 size (152 mm ×  152 mm) or the 5009 size (126.6 mm × 126.6 mm) is used. Further, usually, for the light-transmissive substrate 20 for the transfer mask 100 for printed circuit board manufacturing, the 7012 size (177.4 mm × 177.4 mm) or the 9012 size (228.6 mm × 228.6 mm) is used.

Explanation of Reference Numerals

[0213] 10 Mask blank 20 Translucent substrate 30 Thin films for pattern formation 30a Thin Film Pattern 40 Etching mask film 40a First etching mask film pattern 40b Second etching mask film pattern 50 First resist film pattern 60 Second resist film pattern 100 Transfer Masks

Claims

1. The process of preparing a translucent substrate, The process involves forming a thin film containing titanium, silicon, and nitrogen on the translucent substrate by sputtering, It has, The composition of the thin film is controlled by the ratio of elements constituting the sputtering target, as well as the composition and flow rate of the sputtering gas, and the thickness of the thin film is controlled by the sputtering power and sputtering time. In the internal region of the thin film, the photoelectron intensity at a binding energy of 455 eV in the Ti2p narrow spectrum obtained by analyzing the internal region using X-ray photoelectron spectroscopy is P Ｎ The photoelectron intensity at a bond energy of 10² eV in the Si²p narrow spectrum is P Ｓ In that case, P Ｎ / P Ｓ A method for manufacturing a mask blank, characterized in that the thin film is formed such that the relationship is 1.19 or greater.

2. In the internal region of the thin film, the photoelectron intensity at which the binding energy in the Ti2p narrow spectrum is 461 eV is P ＮＵ In that case, P ＮＵ / P Ｓ A method for manufacturing a mask blank according to claim 1, characterized in that the thin film is formed such that the relationship is 1.11 or higher.

3. In the internal region of the thin film, (P Ｎ + P ＮＵ ) / P Ｓ is 2.30 or more, and the method for manufacturing a mask blank according to claim 2, characterized in that the thin film is formed.

4. The method for manufacturing a mask blank according to any one of claims 1 to 3, characterized in that the sputtering gas consists of a mixed gas containing an inert gas and nitrogen gas.

5. The method for manufacturing a mask blank according to claim 4, characterized in that the inert gas includes at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas.

6. A method for manufacturing a mask blank according to any one of 1 to 5, characterized in that the thin film is formed in the surface region opposite to the translucent substrate side, such that the region extends from the surface opposite to the translucent substrate toward a depth of 10 nm toward the translucent substrate side.

7. A method for manufacturing a mask blank according to any one of 1 to 6, characterized in that the thin film is formed in a region near the translucent substrate side, such that the region extends from the surface of the translucent substrate side to a depth of 10 nm toward the opposite side from the translucent substrate.

8. The thin film is a phase-shift film, The method for manufacturing a mask blank according to any one of claims 1 to 7, characterized in that the phase-shift film is formed such that the transmittance to light with a wavelength of 365 nm is 1% or more, and the phase difference with respect to light with a wavelength of 365 nm is 150 degrees or more and 210 degrees or less.

9. A method for manufacturing a mask blank according to any one of 1 to 8, characterized in that an etching mask film having different etching selectivity from the thin film is formed on the thin film.

10. The method for manufacturing a mask blank according to claim 9, characterized in that the etching mask film is formed such that it contains chromium.

11. A step of preparing a mask blank manufactured in a method for manufacturing a mask blank according to any one of claims 1 to 8, A step of forming a resist film having a transfer pattern on the thin film, A step of performing wet etching using the resist film as a mask to form a transfer pattern on the thin film, A method for manufacturing a transfer mask, characterized by having the following features.

12. A step of preparing a mask blank manufactured in the method for manufacturing a mask blank according to claim 9 or 10, A step of forming a resist film having a transfer pattern on the etching mask film, A step of performing wet etching using the resist film as a mask to form a transfer pattern on the etching mask film, A step of performing wet etching using the etching mask film on which the transfer pattern is formed as a mask to form the transfer pattern on the thin film, A method for manufacturing a transfer mask, characterized by having the following features.

13. A method for manufacturing a transfer mask according to claim 11 or 12, comprising the step of placing the manufactured transfer mask on the mask stage of an exposure apparatus, The process involves irradiating the transfer mask with exposure light to transfer a transfer pattern onto a resist film provided on a substrate for a display device, A method for manufacturing a container, characterized by having the following features.

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