TW544549B - Half-tone type phase shift mask blank, process for prodncing half-tone type phase shift mask, pattern transfer method, laminate and method of forming pattern - Google Patents

Abstract

The present invention relates to a half-tone type phase shift mask blank useful in the production of a half-tone type phase shift mask, comprising on a transparent substrate, a light transmittable portion for transmitting an exposure light, a phase shift portion for shifting the phase of transmitted light to a given extent when a part of the exposure light transmits, and a phase shift film for forming the phase shift portion. It has good optical property that in the vicinity of the margin of the light transmittable portion and phase shift portion, the transmitted lights deny each other, and the contrast of the margin portion of the exposure pattern transferred on the surface of exposed body maintained at good condition. The phase shift film uses silicon, oxygen and nitrogen as the main components and consists of an etching stop film formed between the above film and the transparent substrate.

Description

544549

544549 V. Description of the invention (1) TECHNICAL FIELD The present invention relates to a half-tone phase-shift mask blank plate, a half-tone phase-shift mask, and a method for manufacturing the same, especially the ArF standard suitable for a short-wavelength exposure light source in the next generation. A half-tone phase shift mask blank used for molecular laser (19311111) and F2 excimer laser (157nm). Previous technology Currently, DRAM (Dynamic Random Access Memory) has established a mass production system of 256Mbit. In the future, it is expected to enter another high-integration integration from Mbit to Gbit. As the design rules of this collective circuit become more and more refined, the time required for a fine pattern with a line width (half pitch) of 10 μm is a problem. It is one of the methods corresponding to the miniaturization of the pattern. Until now, the high-resolution of the pattern has been achieved by shortening the wavelength of the exposure light source. As a result, KrF excimer laser (248nm) and ArF excimer laser (193nm) are mainly used as the light sources for lithography. However, shortening the exposure wavelength has an inverse relationship with improving the resolution and reducing the depth of focus. Therefore, there is an adverse effect of increasing the burden on the design of the optical system starting from the lens or reducing the stability of the steps. To solve this problem, a phase shift method is used. The phase shift method uses a phase shift mask as a mask to reproduce fine patterns. The phase shift mask is formed of, for example, a phase shift portion in which a pattern portion is formed on the mask and a non-pattern portion in which no phase shift portion is present. This structure is to make the two transparent. 544549 V. Description of the invention (2) The phase shift of light is 180. In order to improve the contrast of the reproduced image, light interference is caused at the border portion of the pattern. The amount of phase shift (cKrad) of the light passing through the phase shift section is known in relation to the real refractive index part η of the phase shift section and the film thickness d, and the following formula (1) is established. φ-2 7L d (n- Xs) / λ (Expression 1) (where 'λ is the wavelength of the exposure light source, and the film thickness d can be expressed by (2) ), D- λ / {2 (nl)} ...... (Equation 2) With this phase shift mask, the focal depth can be increased to obtain the necessary resolution, without changing the exposure wavelength. It can improve the resolution and the applicability of the step. At the same time, phase-shift masks are actually divided into full-transmission type (Rebenso type) phase-shift masks with light transmission characteristics of the phase-shifting portion forming the mask pattern, and halftones. Type phase shift mask. The former is a mask that has the same light transmittance as the non-patterned part (light-transmitting part) of the phase shift part, and is generally transparent to the exposure wavelength. Generally, it can effectively copy lines and space. 'The light transmittance of the halftone type phase shifting part (translucent part) of the latter is a few% to several tens% of the non-pattern part (light transmitting part), which can effectively make a contact hole or an isolated pattern. The phase shift mask is a two-layer halftone phase shift mask consisting of a layer mainly for adjusting the transmittance and a layer mainly for adjusting the phase, or a simple structure Single-layer half-tone phase-shifted light manufactured by Zakuya 544549 5. Description of the invention (3) Mask. Because the single-layer type is easy to process, it is currently the mainstream. Half-tone phase-shifted masks are almost all made of MoSiN or A single-layer film made of MoSiON. In addition, the two-layer type is a combination of the half-tone phase shifting unit and the layer that mainly controls the transmittance, and the layer that controls the amount of phase shift. It can independently control the typical spectral characteristics of transmittance. And phase shift amount (phase angle). In addition, with the miniaturization of LSI patterns, the wavelength of the exposure light source (exposure wavelength) is predicted to be from the current KrF excimer laser (248nm) to ArF excimer laser (193nm), And the future F2 excimer laser (157nm) will be shortened. In addition, the current half-tone phase shift mask is designed with a half-tone phase-shifted part where the light source transmittance is around 6%. 'When a high resolution is preferred and a high transmittance is required, it means that the transmittance must be 15% or more in the future. With the short wavelength or high transmittance of the exposure light source to meet the predetermined transmittance and phase shift Quantity part The material selection of the hue-type phase shifting part tends to have a narrow width. In addition, as the transmittance is increased with high transmittance, it is necessary to use a material with high light transmittance. In addition, as the wavelength of the exposure light source is shortened, it is known When viewing wavelengths, it is necessary to use a material with high light transmittance. For this requirement, there is a problem that the etching selectivity of the quartz substrate becomes smaller during pattern processing. Two or more layers of a halftone phase shifting unit are used to combine multiple layers. Membrane or 2

544549 V. Description of the invention (4) The layer film and materials that can control the phase difference and transmittance are easy to choose. In addition, a material that achieves the effect of the upper etch block can be selected as the lower layer. In addition, the phase shift mask must be made to reduce the reflectance of the exposure to a certain degree. In addition, the step of inspecting the appearance of a pattern usually uses light having a longer wavelength than the exposure wavelength as the inspection light source wavelength, and generally uses a transmission-type defect inspection device (such as the KLA300 system) for inspection. Therefore, the inspection wavelength (for example, the exposure wavelength is KrF excimer laser (248im), the inspection wavelength is 488nm or 364nm) is too difficult to inspect when the transmittance is too high (for example, 40% or more). In particular, with the shortening of the exposure wavelength, it is necessary to shift the above-mentioned half-tone type phase having high light permeability. In addition, a material with high light transmittance means that the increase rate of the transmittance tends to be large with respect to the change on the longer wavelength side. Therefore, it is more difficult for a half-tone phase shift of a single layer to reduce the transmittance for the wavelength of the inspection light source to a predetermined range. In addition, a newly developed inspection method for transmitted light and reflected light is used in defect inspection devices. The transmittance of the inspection wavelength when inspected in this way can be slightly higher (for example, 50 to 60%) than when inspected using only transmitted light. In addition, the reflectance of the inspection wavelength must be controlled to a certain extent (for example, 3% or more) from the transparent substrate. This condition is a multilayer type in which a partial halftone phase shift is two or more layers, and the reflection characteristics and transmission characteristics of the exposure light source and the inspection light source can be easily controlled. For example, a two-layer halftone type phase shift mask is disclosed in Japanese Patent Application Laid-Open No. 4-544549. V. Invention Description (5) 140635 describes a halftone type phase shifter having a two-layer structure with thin Cr and coating and peeling. (Knowledge Example 1). In addition, a multi-layered structure that can be formed in the same device and etched with the same etching gas is a half-tone type phase shifter located in Japanese Unexamined Patent Publication No. 6-83034 and having a multi-layered structure containing the same element (such as a Si layer and A half-tone phase shifter formed by a two-layer structure of a SiN layer (conventional example 2). In addition, the technique for reducing the transmittance with respect to the wavelength of the light source (conventional example 3) is a single-layer halftone phase shift described in Japanese Patent Application Laid-Open No. 7-168343. The film and the combination with a single-layer film contain a two-layer structure of a transmission film with a small wavelength dependence of transmittance. The desired transmittance can be obtained for both the exposure light source (KrF excimer laser) and the inspection light source (488 nm). (Known example 3). In addition, the phase shifting section focusing on the multilayer structure of the silylated macro-system material is described in Japanese Patent Application Laid-Open No. 200 1 74973. The phase-shifting section includes a macrolayer, a silicon oxide compound, and an oxygen-based upper layer and a molybdenum-based component. A half-tone phase shifter composed of a two-layer structure including a lower layer that does not include Shi Xi (Knowledge Example 4). In addition, Japanese Patent Application Laid-Open No. 200 1-337436 describes that a macrotone, a siloxane, and an oxygen Halftone type phase shifter composed of a two-layer structure consisting of an upper layer as a main component and a lower layer containing chrome or a giant alloy as a main component (conventional example 5). 544549 5. Description of the invention (6) Conventional examples have the following problems. Generally, when an etching mask layer is used as a halftone type phase shift film on a halftone type phase shift film, and then a light-shielding portion is formed at a desired position on the mask. Form a light-shielding Cr layer. For example, in the coating peeling / thin Cr layer / glass substrate of the conventional example 1, a light-shielding Cr layer is formed on the coated glass. At this time, during the pattern processing, a light-shielding pattern that replicates a photoresist pattern is generally used 3 layers of Cr layer / coating peeling / thin Cr layer to construct a mask pattern The selective etching removes the light-shielding Cr layer. Moreover, as far as the light-shielding Cr layer and the thin Cr layer are made of the same material, the effect of the selective removal step of the light-shielding Cr layer on the thin Cr layer is a problem. Specifically, the The thin Cr layer is etched and the pattern is removed by the same principle as the peeling method. When the thin Cr layer is etched on the side, the transmittance in the vicinity of the pattern etch will change. Second, in the conventional example 2, the Si layer and the The SiN layer can be continuously formed by using the same sputtering device and the same silicon as the target. The SiN layer is formed by reactive sputtering using a sputtering atmosphere containing a Si target and nitrogen. The target pores cannot be reproduced, and productivity is problematic. In addition, when SiN is used, the transmittance may decrease excessively with the reduction of the exposure wavelength in recent years. Secondly, MoSiO or Conventional Example 3 is used. MoSiON is used as the material of the single-layer film (upper layer). Here, the inclusion of a metal causes the transmittance to be 544549. 5. Description of the invention (7) becomes smaller and is not suitable for shortening the exposure wavelength in recent years. When the amount becomes smaller, the refractive index becomes smaller, and the film thickness of the halftone phase shift becomes thicker, which is disadvantageous for microfabrication. In addition, in Conventional Example 4 and Conventional Example 5, TaSi.〇 was used as the material of the upper layer. Here, borrow The inclusion of metal reduces the transmittance and is not suitable for short wavelengths of exposure wavelengths in recent years. In addition, as the metal content becomes smaller, the refractive index becomes smaller, and the film thickness of the halftone phase shift becomes thicker, which is disadvantageous for microfabrication. In conventional examples, the lower layer can achieve an etching blocking effect for dry etching by using an upper fluorine-based gas, and then the lower layer is etched by dry etching using a chlorine-based gas. Here, in the conventional example 4, the lower layer system formed by the giant is insufficient in the etching selectivity ratio for the upper layer fluorine-based dry etching. The chrome giant alloy of the conventional example 5 has a slow etching rate with a chlorine-based gas, and a high-precision pattern cannot be obtained. ^ The purpose of the present invention is to provide a half-tone phase shift portion in view of the above background, and provide fineness during etching. The purpose of the halftone type phase shift mask blank plate and the halftone type phase shift mask which are excellent in processability is < The present invention is provided especially when the exposure light source is shortened1, and it can be particularly used for an exposure wavelength of 140 nm to 200 nm Specifically, the half-tone type phase shift mask blank plate and half at high transmittance (transmittance 8 丨 ~ 30%) near 157 nm of F2 excimer laser wavelength and 193 nm of ArF excimer laser wavelength. The purpose is toned-type phase shift mask. -9- 544549 V. Explanation of the invention (8) The invention shows the blank plate of the halftone phase shift mask of the present invention, which is characterized in that the phase shift film is a film mainly composed of silicon, oxygen, and nitrogen, And an etching stopper film formed between the film and the transparent substrate. In the present invention, the half-tone phase shift layer formed on the transparent substrate has a film on the transparent substrate side as the lower layer and a film formed on the lower layer as the upper layer. The inventors of the present invention made the film matrix dense due to SiNx or Si-N bonds, which made it possible to have high resistance to irradiation for exposure, chemical resistance to cleaning liquids, and the like, and that SiOx was high even on the short wavelength side The fact that the transmission rate is based on, therefore, focuses on SiOxNy which can produce the advantages of two materials. In addition, when the composition was controlled in SiOxNy, it was found that a phase shift film suitable for use with a short-wavelength exposure light source was obtained. Furthermore, by using a half-tone phase shift film as a two-layer structure of a SiOxNy film (upper layer) and an etching retardation film (lower layer), it was found that a phase with good exposure light source irradiation resistance, chemical resistance, and pattern processability can be realized Transfer film. Here, the 'etching retardation film' is a film made of a material having a function of preventing the SiOxNy film from being etched, or a film having a function of easily detecting the end point of the phase shift film, or a material having both functions. The upper material is essentially made of silicon, oxygen, and nitrogen. In other words, the upper layer is made of a film mainly composed of silicon, oxygen, and nitrogen. Even when the exposure light source is short-wavelength, it can control the desired transmittance and phase difference in combination with the lower layer of -10- 544549 V. Description of Invention (9), and can improve the resistance to exposure to the exposure light source or wash Chemical resistance of detergent. In addition, since the refractive index can be made large, the film thickness of the entire halftone type phase shift film can be controlled to obtain a phase difference, and the fine processability of the halftone type phase shift film is excellent. The upper layer material is preferably adjusted so that the real part of the complex refractive index η is in the range of n2 1.7, and the imaginary part of the complex refractive index k is preferably adjusted to kS 0.450. This is extremely advantageous for satisfying the optical characteristics of a halftone-type phase shift mask with the single wavelength of the exposure light source. In addition, a range of kS 0.40 is preferred for ρ2 excimer lasers, and a range of 0.07 ′ 0.35 is more preferred. A range of 0.1F kS 0.45 for ArF excimer lasers is preferred. In the case of the 'F2 excimer laser, a range of η ^ 2 · 0 is preferable, and a range of η "2 · 2 is more preferable. The ArF excimer is preferably in the range of η22.0 and more preferably in the range of η22.5. In order to obtain the above-mentioned optical characteristics, the composition range of the above-mentioned constituent elements is 35 to 45 atom% for silicon, 1 to 60 atom% for oxygen, and 5 to 60% for nitrogen. In other words, if the silicon is more than 45% or the nitrogen is more than 60%, the light transmittance of the film is insufficient. Conversely, if the nitrogen is less than 5%, or the oxygen is more than 60%, the function of the half-tone phase shift film will be lost because the transmittance is too high. In addition, if the silicon content is less than 35% or the nitrogen content is more than 60%, the physical and chemical properties of the film structure are unstable. In addition, from the above point of view when using 52 excimer lasers, the above-mentioned -11-544549 V. Description of the invention (1) The composition range of the constituent elements is 35 to 40 atomic% for silicon, 25 to 60 atomic% for oxygen, Nitrogen is preferably 5 to 35 atomic%. Similarly, when ArF excimer is used, the composition range of the above constituent elements is preferably 38 to 45 atomic% for silicon, 1 to 40 atomic% for oxygen, and 30 to 60 atomic% for nitrogen. In addition to the above-mentioned composition, trace impurities (metal, carbon, fluorine, etc.) may be contained. The upper layer of the present invention is formed by reactive sputtering using a target made of substantially silicon, and reactive sputtering using a sputtering atmosphere containing a rare gas and a reactive gas containing nitrogen and oxygen. When a target substance substantially composed of silicon and a mixed target substance such as a metal silicide are used, a stable target substance having a high number density or purity can be obtained. Therefore, it refers to the advantage that the particle generation rate of the obtained film is small. In addition, the etching retardation layer is a film made of a material having a function of preventing the SiOxNy film from being etched, a film having a function of easily detecting the end point of the phase shift film, or a material having both functions. The above-mentioned film system with the function of preventing the SiOxNy film from being etched is a material with a lower ratio for the etching of the phase shift layer, in other words, the etching speed of the SiOxNy film is slower than that of the SiOxN xy film. Materials, specifically, a film made of a material having an etching selection ratio of a phase shift film of 0 or less, preferably 0.5 or less. In addition, the latter has an etch-blocking film that can easily detect the end point of the phase-shift film etching. Its material is that the reflectance difference between the detection of the transparent substrate (such as a synthetic quartz substrate) and the etch-terminated etch terminal (such as 680nm) is relatively low. A film having a large difference between the transparent substrate and the SiOxNy film. -12- 544549 V. Description of the invention (11) Preferably, the material is a material having a higher refractive index (the real part of the complex refractive index) than the SiOxNy film and the transparent substrate. Specifically, a film made of a material having a refractive index difference between the SiOxNy film and the wavelength of the light source for detecting the end of the etching is 0.5 or more, more preferably 1 or more, and the refractive index difference from the transparent substrate is 0.5 or more. A film made of a material of 1 or more is preferred. The uranium etching selection ratio of the etching retardation layer to the substrate is 1.5 or more, and preferably 2.0 or more. In other words, when it is necessary to remove the etching retardation layer, the light transmittance of the light-transmitting portion decreases, and the contrast at the time of pattern reproduction is not good. Even if it can be removed and the etching speed must be larger than the substrate, the substrate may be etched near the end of the etching, resulting in poor processing accuracy. Considering the materials suitable for the above, for example, one or two or more materials selected from the group consisting of magnesium, aluminum, titanium, vanadium, chromium, indium, chromium, niobium, molybdenum, tin, lanthanum, molybdenum, tungsten, sand, materials, or the like Compounds (oxides, nitrides, oxynitrides), etc. The thickness of the etching retardation film is preferably 10 to 200 angstroms. In other words, if it is less than 10 angstroms, the etching cannot be completely prevented and the change in the intended reflectance cannot be detected, so that the pattern processing accuracy may be poor. In addition, depending on the etching step, the pattern enlargement by isotropic etching is performed to a maximum of twice the thickness of fe. Therefore, when the pattern line width is 0.1 μm = 1000 Angstrom or less and the film thickness is greater than 200 Angstrom, a dimensional error of more than 40% will occur, which will have a profound impact on the quality of the photomask. -13- 544549 5. Explanation of the invention (12) Moreover, it is better to etch the retardation layer to have the function of adjusting the transmittance. For the exposure wavelength of the etching retardation layer itself (wavelength 140 ~ 200nm, or near l57nm, or near 193nm), the transmittance is 3 ~ 40%. In this way, the transmittance of the phase-shifted portion can be maintained, and the transmittance of the inspection wavelength longer than the exposure wavelength can be reduced by the etching retardation layer (depending on the stack of different materials) formed under the phase-shifted portion. In other words, the mask inspection in the manufacturing step is a conventional method of measuring the transmitted light intensity by using light having a longer wavelength than the exposure wavelength. In the current inspection wavelength range of 200 to 300 nm, the light transmittance of the light semi-transmitting portion (phase shift portion) is preferably 40% or less. That is, when it is 40% or more, the contrast with the light transmitting part is detached, and the inspection accuracy is not good. When the etching retardation film is a material having a high light-shielding function, the material is, for example, one or two or more materials selected from the group consisting of aluminum, titanium, vanadium, chromium, zirconium, niobium, molybdenum, lanthanum, giant, tungsten, silicon, and bell. Film or such nitride. In addition, the film thickness of the etching retardation layer is preferably introduced with a film thickness sufficiently thinner than the phase shift portion, and a film thickness of 200 angstroms or less is preferable. In other words, if it is more than 200 angstroms, the possibility of reducing the light transmittance at the exposure wavelength to 3% is extremely high. At this time, the phase angle and transmittance can be adjusted by 2 餍 between the SiOxNy film and the etching retardation film. Specifically, the transmittance for the exposure wavelength (wavelength 140 ~ 200nm, or near 157nm, or near 193nm) of the etching block itself is 3 ~ 40%, and the transmittance when laminated with SiOxNy film is adjusted to 3 ~ 40 % Is better. When an etching retardation film is provided, the etching retardation layer exposed on the surface of part (13) corresponding to the light-transmitting part -14-544549 must be removed. This type of etch-blocking layer covers the light-transmitting portion, causing the transmittance of the light-transmitting portion to decrease. The removal method of the etching retardation film is a method in which the etching retardation film is a film made of a material having a function of preventing the SiOxNy film from being etched, which must be different from the etching method of the SiOxNy film. In addition, when the etching retardation film is a film made of a material having the function of easily detecting the end point of the phase shift film etching, the etching method of the SiOxNy film and the etching retardation film may be the same or different. The etching of the phase shift film made of the SiOxNy film is performed by, for example, (11: 3 or fluorine-based gas such as CF4, SF6, C2F6, and a mixed gas thereof (RIE: Reactive Ion Etching). In addition, by making the etching resist When the etching is performed by a different method from the retardation film and the phase shift film, dry etching using a fluorine-based gas different from the user of the phase-shift film is used, or dry etching using a chlorine-based gas such as (Cl2, Cl2 + 02), or By wet etching with acid, alkali, etc. Etching retardation film that can be removed with the same fluorine-based dry etching as the phase shift film made of SiOxNy film, such as silicon, MoSix, TaSix, WSX, CrSix , Zi.Six, HfSix, etc. are better materials. When the etching stopper film which is continuous with the SiOxNy film and can be etched in this way, the step has great advantages. Moreover, it is different from the etching of the phase shift film formed by the SiOxNy film. Method can be used to etch an etching retardation film, such as Ta or containing films that can be etched with dry uranium etched with C12, such as TaNx, TaCrx, butaZrx, TaHfx, etc., or Zi *, Hf, or Cl2 + 〇2

-15- 544549 V. Description of the invention (14) The dry etching such as Cr which can be etched is a better material. When the etching stopper film which is continuous with the Si 0 x N y film and can be etched in this way is provided, the step has a great advantage. Moreover, the etching retardation film can be etched by a method different from the etching of the phase shift film formed by the S10xNy film, such as T a or a film containing τ a that can be etched with a dry uranium etch of C12, such as

TaCrx, TaZrx, TaHfx, etc., or Zr, Hf, or Ch +, etc., which can be etched by dry etching are preferred materials. In addition, when the etching retardation film is a film made of a material having a function of preventing the SiOxNy film from being etched and has a high transmittance, it may be transparent to the halftone type phase shift mask of the single-layer structure described above A structure in which a uranium-etched retardation film is provided between the substrate and the light semi-transmissive film without removing the etching retardation film exposed at the light-transmitting portion. This is particularly effective when the oxygen in the Si 0 x N y film in the etching retardation layer is 40 atomic% or more, or the refractive index difference with the transparent substrate is 0.5 or less, and preferably 0.3 or less. In addition, when the present inventors discovered that the upper layer is a layer of dry-type engraving using a fluorine-based gas, the lower layer is a gas that is resistant to the fluorine-based gas and is different from the fluorine-based gas (for example, a chlorine-based gas). ) Dry etching, can etch any given material. The first of the predetermined material is, for example, selected from the group A metal monomers of Ga, Hf, Ti, V, and Zr, or a material containing two or more of these metals (other alloys containing alloys, etc.) ( Hereinafter referred to as the first material). These are selected from the first group of metal monomers or materials, in order to make -16-544549 V. Description of the invention (15) Use a gas that has resistance to fluorine-based gases and is different from fluorine-based gases (such as chlorine-based gases) Gas) dry etching, etchable materials. These are selected from the first group of metal monomers or materials that are highly resistant to etching in dry etching using system gases and use gases different from fluorine-based gases (such as chlorine-based gases, bromine-based gases, iodine-based gases, etc.) Materials that can be easily etched in dry etching. The lower layer must have resistance to dry etching using a fluorine-based gas to obtain the effect of the etching retardation layer on the upper layer. The speed of the lower layer material depends on the thickness of the lower layer and the etching speed of the upper layer (hereinafter referred to as Operational selection ratio) is different, with 0 ~ tens of angstroms / min being better. In addition, in the dry etching using the lower chlorine-based gas, the degree of etching allowed in the required etching step can be removed, and it is better to have a high etching rate of 5 or more than the selection of the substrate material, and it is better to have 1 〇 A material with an etching speed more than doubled. Among the metal monomers selected from the first group, Hf, Zr and the like are preferred in terms of high chemical resistance. Al, Ti, V, and the like are preferable because the target for sputtering can be easily produced. The second predetermined material is, for example, a second group of metals selected from the group consisting of Ci ·, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, Po, Mo, and w. Materials of group i (Al, Ga, Hf, Ti, V, and Zr) (including other mixtures of alloys, etc.). These materials are made by adding a metal selected from the first group to a metal selected from the second group, 'having sufficient resistance to fluorine-based gases, and using -17-544549. V. Description of the invention (16) and Dry etching and materials that can be etched for different gases (such as chlorine-based gas, bromine-based gas, and grade-level gas). In short, a material that achieves the same effect as the first material can be obtained. Here, the metal (except c r) exemplified in the second group is less resistant to the fluorine-based gas than the metal exemplified in the first group. When a metal selected from the first group is added, it has a higher resistance to the fluorine-based gas than when it is not added, and when the metal selected from the first group is added, it has a sufficient requirement for the fluorine-based gas. patience. In addition, Cr has the same resistance to fluorine-based gases as the metal exemplified in the first group. In addition, the etching level of the metal of the second group with respect to the chlorine-based gas is the same as that of the metal of the first group, or a material that is slightly inferior by adding the first group. The metals exemplified in the first group are materials that can be easily etched with respect to a chlorine-based gas, as described above, and the materials exemplified by adding the metals exemplified in the first group to the metals exemplified in the second group are, for example, capable of retaining or improving Chlorine gas is a uranium-etched material. In this way, the present inventors have found that by adding a small amount of a metal selected from the first group to a metal selected from the second group, the etching property against a chlorine-based gas can be maintained, and the resistance to a fluorine-based gas can be significantly improved. The addition amount of the metal selected from the first group is 2% or more for the metal selected from the second group. The addition amount of less than this amount cannot have sufficient additive material characteristics, and thus the above-mentioned sufficient effects such as improvement of resistance to a fluorine-based gas cannot be obtained. The third of the predetermined materials is, for example, a material containing nitrogen and / or carbon in the first material or the second material. Without prejudice to the required range, -18- 544549 V. Description of the invention (17) It is preferable to contain nitrogen and / or carbon. Here, the fluorine-based gas is, for example, CxFy (e.g., CF4, C2F6), CHF3, a mixed gas thereof, or a gas (02), a rare gas (He, Ai, Xe), or the like is added thereto. Further, as the gas other than the fluorine-based gas, a halogen-based gas other than fluorine (a gas-based, bromine-based, iodine-based or a mixed gas thereof) can be used. Chlorine-based gas such as Cl2, BC13, HC1, a mixed gas thereof, or a rare gas (He, Ar, Xe) to which a gas is added. The bromine-based gas is, for example, Br2, HBr, a mixed gas thereof, or a rare gas (He, Ar, Xe) to which a gas is added. Iodine-based gas such as I2, HI, a mixed gas thereof, or a rare gas (He, Ar, Xe) to which a gas is added. Here, a chlorine-based gas can be used as a gas different from a fluorine-based gas, and it is preferable that the etching level is faster than that of a bromine-based gas or an iodine-based gas. Alternatively, a gas containing both fluorine and a gas other than fluorine can be used. At this time, the more active species in the plasma, the better the incentive species. When there are many kinds of fluorine-based excitations, the fluorine-based gas is specified. When there are many kinds of gas-excited species other than fluorine-based gas (such as chlorine), it is specified as the gas outside of the fluorine-based gas. Further, when the monomer gas composition contains fluorine and other halogens (for example, C1F3, etc.), it is a fluorine-based gas. The gas other than the fluorine-based gas is preferably one in which oxygen is not added. This reason is that when oxygen is added, etching is reduced due to surface oxidation. In addition, for example, an etching gas commonly used in the etching of Cr

-19- 544549 V. Description of the invention (18). Cl2 + 02. It is easy to remove the etching distribution due to the complex reaction. For example, when dry etching is performed with a separate gas of Cl2, a high-precision pattern can be obtained. Next, the functions of the layers that satisfy the above requirements will be described. The lower layer has resistance to a fluorine-based gas, so that the upper layer is dry-etched using a fluorine-based gas, and even if the surface of the lower layer is exposed, the film of the lower layer decreases slowly. Therefore, it is possible to set a sufficient upper-layer overetching time which takes into account the removal of the etching distribution due to the pattern density difference and the like to generate the upper-layer residual film. As a result, the mask pattern can form a faithful pattern, and the dimensional accuracy can be improved. The lower layer uses a gas different from fluorine-based gas (such as chlorine-based gas). Dry etching can be etched (with a certain degree of etching level for chlorine-based gases). Perform dry etching. Even if the surface of the transparent substrate is exposed, it hardly penetrates into the surface of the transparent laminate. In addition, it is possible to avoid in-plane phase difference due to penetration into the surface of the transparent substrate, variation in phase difference, and uneven etching, and high phase difference controllability can be obtained. This type of quartz substrate, which is mostly used as a substrate for a phase shift mask, has a lower etching level than the underlying material for dry etching to remove the underlying layer. For the lower chlorine-based gas, the higher the etching level is, the better it is, depending on the CD size accuracy requirements or the etching conditions, but it is preferably 2500 Angstroms / min or more, 3000 Angstroms / min or more, and 4000 Angstroms / min or more. Specifically, the lower layer in the phase shift mask is usually 100 angstroms or less. Lower layer -20- 544549 V. Description of the invention (19) Due to the high etching level, the etching of the lower layer is completed in a few seconds. The excessive etching time is short, the etching level is 3 60 angstroms / mm or more, and the amount of etching (deep penetration) at 6 angstroms / sec or more in 1 second is extremely small. In addition, the structure of the light-shielding Cr layer / upper layer / lower layer / transparent substrate of the present invention is different from the structure of the light-shielding Cr layer / coating and peeling / thin Ci: layer / transparent substrate explained by the conventional technology. The material is made of different materials, so it can be selected in the step of removing the light-shielding Cr layer. This removing step is not limited to the wet step in which the second ammonium cerium nitrate solution is generally used, and dry etching can be used correspondingly. In short, wet etching does not require dry etching, which can prevent the adverse effect of the lower layer being etched during the selective removal step of the light-shielding Cr layer. In short, it is suitable for the corresponding steps. In addition, in the case of forming a film on the lower layer and the upper layer, patterning these films into an amorphous structure or a structure with a very small grain boundary can increase the pattern accuracy. When the film structure is a columnar structure or a crystalline structure, unevenness (shine) occurs on the pattern side during the etching process, and when the film structure is an amorphous structure or a structure with a very small grain boundary, the pattern is during the etching process. The side wall is formed by a slightly flat (slightly straight). In addition, when such a structure is a columnar structure or a crystalline structure, a problem of film stress occurs. However, when these film structures have an amorphous structure or a structure with extremely small grain boundaries, it is easy to control the film stress. Moreover, the upper layer of the phase shift film is composed of SiOx'SiNx'SiOxNy, SiCx, SiCxNy, SiCxOyNz or better among them-21-544549 5. Description of the invention (2) M / (Si + H) When X100 is made of 10 atomic% or less metal (for example, one or two or more types of M: Mo, Ta, W, Cr, Zr, Hf), it can be easily processed by dry etching using a fluorine-based gas. Gas dry etching is preferred because it has high resistance. In addition, when the upper layer is made of such materials, the short wavelength of the exposure wavelength of ArF excimer laser (193 nm) or F 2 excimer laser (15 7 nm) can satisfy the predetermined transmittance. And the amount of phase shift can correspond to a shorter wavelength. The phase shift mask blank plate has a structure made of, for example, a SiOx & SiOxNy layer / a lower layer (a layer having the above-mentioned etching characteristics) made of the above-mentioned predetermined material / a transparent substrate. With this structure, the SiOx & SiOxNy layer is pattern-processed by dry etching using a fluorine-based gas, and the portion corresponding to the lower layer is processed by dry-etching using a chlorine-based gas to reduce the damage rate of the bottom layer. By using the blank of this structure, the optical characteristics can be controlled in the generation where the wavelength is shortened, and a phase shift effect can be obtained. Specifically, the transmittance is mainly controlled by the upper layer of 310 and the thickness or composition of the SiOxNy layer. This makes it possible to control the optical characteristics. In addition, the lower layer can be processed by dry etching using a chlorine-based gas to avoid damage to the transparent substrate on the bottom layer. Since the change in the amount of phase shift can be avoided and the optical properties can be controlled by penetrating the transparent substrate, a predetermined phase shift effect can be obtained. Moreover, in the present invention, a light-shielding Cr layer is formed on a blank plate of a phase shift mask, and a photoresist pattern is formed on the light-shielding Cr layer to form a light-shielding Cr layer-22- 544549 V. Description of the Invention (21) The pattern and the photoresist The pattern and the light-shielding Cr pattern, or only using the light-shielding Cr pattern as a photomask make the phase shift film etching better. After the phase shift film is etched, the light-shielding Ci • pattern remains with a portion of the light-shielding band in the non-replication range of the phase shift mask. In addition, the directional mark forming portion inside or outside the reproduction range or the vicinity of the boundary of the pattern is removed to remove the required range. The light-shielding Cr layer may be Cr, or a single layer or a multilayer film containing oxygen, carbon, nitrogen, or the like in the Ci · layer. In the present invention, by making the refractive index of the upper layer film smaller than that of the lower layer, the reflectance to the inspection light source can be adjusted. In addition, in the exposure wavelength, the refractive index of the upper layer film is smaller than that of the lower layer film, so that the reflectance of the exposure light source can be adjusted to be less than or equal to 値. Specifically, a pattern reproduction of the exposure light source having a transmittance of 3 to 20%, preferably 6 to 20%, a reflectance of the exposure light source of 30%, and preferably 20% is desirable. In addition, when the transmittance of the inspection light source is 40% or less, it is preferable to perform defect inspection using the transmitted light of the mask. Since the inspection light source transmittance is 60% or less and the inspection light source reflectance is 12% or more, it is preferable to use the transmitted light and reflected light of the photomask for defect inspection. The exposure light source ' when using the halftone type phase shift mask of the present invention is particularly around 157 nm of F2 excimer laser wavelength and around 193 nm of ArF excimer wavelength. It is possible to obtain a high transmittance quality in which the halftone phase shift portion is set to a high transmittance (transmittance of 8 to 30%). -23-544549 V. Explanation of the invention (22) In addition, in the present invention, the upper layer is the layer mainly having the function of adjusting the phase shift amount (phase adjustment layer), and the lower layer is the layer mainly having the function of adjusting transmittance (transmittance adjustment). Layer). In other words, when the phase shift amount (Kdeg) of the exposure light source with the wavelength λ of the upper layer is φ, the film thickness d of the phase adjustment layer is expressed by the following formula, φ = (φ / 360) X λ / (η-1) ... (Expression 3) Here, η represents the refractive index of the phase adjustment layer for light having a wavelength of λ. When the phase shift amount φ of the halftone type phase shift section is the phase shift amount of the lower layer (transmittance adjustment layer) is Φ ', it must be designed as follows. ρ = φ + 180. The range of Φ 'is approximately -20 ° $ φ' $ 20 °. In other words, when the thickness is outside the range, the film thickness of the lower layer is too thick, and the transmittance of the exposure light source cannot be increased. Therefore, the film thickness d of the upper layer can be designed within the range of the following formula (4). 0.44 × λ / (n-1) SdS0.56xλ / (n-1) ... (Equation 4) Specifically, the film thickness of the lower layer is 1 to 20 nm, and more preferably 1 to 15 nm. As a result, the layer thickness of the halftone type phase shift film can be controlled to 120 nm or less, and more preferably 100 nm or less. Moreover, the ideal phase shift amount of the halftone type phase shift film is 180. , Practically 180. ± 5. . In addition, as the transparent substrate of the present invention, a synthetic quartz substrate or the like can be used. In particular, when an F 2 excimer laser is used as an exposure light source, an F 2 painted quartz substrate, a calcium fluoride substrate, or the like can be used. -24- 544549 V. Description of the invention (23) The materials of the lower layer, especially the materials made of giant and plutonium, or the materials made of silicon and silicon are preferred. This lower layer material has resistance to fluorine-based dry etching and can be removed by a chlorine-based dry etching gas. With this method of processing the halftone phase shift film (uranium etching method), the upper layer can be etched by dry etching using a fluorine-based gas, and the lower layer can be etched by dry etching using a chlorine-based gas. Specifically, giant or silicon is a material that is etched by dry etching using a chlorine-based gas that is not harmful to a transparent substrate, even if it is a single body. However, the resistance to dry etching using a fluorine-based gas in the upper layer is not so excellent. In addition, the single-feed system is a material that is excellent in resistance to dry etching using a fluorine-based gas in the upper layer and can be etched using dry etching using a chlorine-based gas. By adding gadolinium to giant or silicon, it is a material that has higher resistance to dry etching using a fluorine-based gas than the prerequisite for addition, and can maintain or improve the etching characteristics of a chlorine-based gas. The addition amount of rhenium to giant or silicon is 2 atomic% or more, and the resistance to fluorine-based dry etching can be obtained. When the lower layer is a material substantially made of molybdenum and feed, or sand and feed, the added amount contained in the lower layer is preferably 50 atomic% or less. The reason is that the transmittance of the light semi-transmitting film made of giant and silicon at the exposure wavelength and the transmittance of the inspection wavelength are not significantly different. Or because the transmittance of the inspection wavelength is larger than that of the exposure wavelength, and it is suitable for the design of optical characteristics (transmittance and / or reflectance of the exposure light source and the inspection light source), -25-544549 V. Description of the invention (24) Contains sufficient molybdenum or silicon, making it easy to design optical characteristics. In the blank plate of the halftone type phase shift mask and the halftone type phase shift mask of the present invention, the halftone phase shift film can be subjected to heat treatment or laser annealing after film formation. By performing heat treatment, effects such as reducing film stress, improving chemical resistance and irradiation resistance, and fine adjustment of transmittance can be achieved. The heat treatment temperature is 200 ° C or higher, preferably 38CTC or higher. In the present invention, a light-shielding film containing chromium as a main component can be formed on the half-tone phase shift film. This light-shielding film uses an etching mask layer as a half-tone phase-shifting film, and can be selectively removed to form a light-shielding portion at a desired place or range on the half-tone type phase-shifting mask. A light-shielding film containing chromium as a main component includes, for example, a film having a structure of one or more layers including chromium, oxygen other than chromium, nitrogen, carbon, and fluorine (including a film having a continuous composition tilt), and is designed to contain oxygen in the surface layer An anti-reflection film (preventing reflection at an exposure wavelength) is preferred. When a light-shielding film containing chromium as a main component is formed on a half-tone phase-shifting film of a half-tone type phase-shifting mask, a light-shielding film serving as a light-shielding belt can be formed on the periphery of the reproduction range. In addition, it is possible to form a light-shielding film which is formed at the mark formation position when the mark comparison for adjustment and the like is performed. Alternatively, in the case where the phase shift effect is obtained to reduce the side-line light, a light-shielding film formed in a range other than the vicinity of the boundary of the light semi-transmitting portion may be formed. In addition, the present invention includes a form that can activate the dry etching characteristics of the upper layer and the lower layer, and excluding the limitation of the upper and lower relationship and the limitation of use. -26- 544549 V. State of the Invention (25). This makes it suitable for a wide range of etchable lamination materials (laminated materials before dry-etching processing) that can be used in areas such as etching mask materials and activating the use as etch blocking materials. The requirements for materials with excellent dry etching characteristics are not limited to the use of the above-mentioned phase-shifted photomasks, including an etch stop layer (etch stop layer) suitable for the purpose of protecting the underlying layer, and a thin layer of metal that requires high selectivity or pattern refinement Widely used range of melting materials. The second layer of the above-mentioned morphology system is a material which has high resistance to etching in a dry barn engraving using a fluorine-based gas, and can be easily uranium-etched under conditions using a chlorine-based gas (hereinafter, a material having a predetermined effect). The second layer material is a film containing any one of these elements, including Al, Ga, Hf, Ti, V, and Z, and the above elements are obtained by adding these elements to other metals. The intended function of the membrane. Addition to other metals is more than 2%. When the amount is less than this amount, the above-mentioned effect cannot be obtained in etching that does not have sufficient characteristics of the added material. The other metals shown here are materials which can be etched with respect to a chlorine-based gas. Other metals include, for example, Ci., Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, Po, Mo, W, and the like. By using these materials, it is possible to etch with a high selection ratio depending on the type of dry contact characteristics depending on the type of gas. This effect is capable of imparting a thin film to a constituent layer (for example, a thin film of an etching mask layer), and can improve the accuracy of a fine pattern. In addition, the film formation of the first layer material and the second layer material is -27-544549 V. Description of the invention (26) The film is formed with an amorphous structure or a structure with a very small grain boundary. Improves pattern accuracy. When these film structures have a columnar structure or a crystalline structure, unevenness (shine) is generated on the pattern wall side during the etching process, but when the film structure is an irregular structure or a structure with a very small grain boundary, the pattern is formed during the etching process. The side wall is made of a slightly flat (slightly straight). In addition, when these films have a columnar structure or a crystalline structure, a problem of film stress occurs. However, when these films are structured as an amorphous structure or a structure with extremely small grain boundaries, it is easy to control the film stress. The first layer of the above-mentioned aspect includes the phase above the substrate when the phase is at the first layer. In short, when the second layer is used as an etching mask layer, it includes forming a pattern of the surface layer portion (carved portion) of the deep substrate. The laminated body of the above-mentioned form includes a laminated body of the second layer and the substrate (the upper layer corresponds to the first layer). Brief Description of the Drawings Fig. 1 is a sectional view of a blank plate of a halftone type phase shift mask and a halftone type phase shift mask according to an embodiment of the present invention. Fig. 2 is a transmission spectrum diagram of a semi-transmissive portion (phase shift portion) of the sample prepared in Example 2. Figure 3 is a graph showing the relationship between the etching time and the reflected light intensity of the sample produced in Example 7. Fig. 4 is a typical diagram illustrating the processing sequence of each layer in Example 10. Figure 5 is a typical illustration of the processing sequence of each layer in Example 11. 28-544549 V. Description of the invention (27). Fig. 6 is a typical diagram illustrating the processing sequence of each layer in Reference Example 2. FIG. 7 is a manufacturing step diagram of the blank plate of the halftone type phase shift mask and the halftone type phase shift mask of the embodiment. FIG. 8 is a manufacturing step diagram of the half-tone type phase shift mask blank plate and the half-tone type phase shift mask of the embodiment (continued). Fig. 9 is a spectral diagram of the optical characteristics of the blank plate of the halftone-type phase shift mask of Example 13; Fig. 10 is a spectral diagram of the optical characteristics of the blank plate of the halftone type phase shift mask of Example 14. Fig. 11 is a diagram showing a modification of the half-tone type phase shift mask empty whiteboard and the half-tone type phase shift mask according to the embodiment of the present invention. The best-shaped bears for carrying out the invention are examples and reference examples in the following, and specifically describe the present invention, but the present invention is not limited by the following examples. Fig. 1 (1) is a blank plate of a halftone type phase shift mask by the above embodiments and reference examples, and Fig. 1 (2) is a halftone type phase shift light by the above embodiments and reference examples Section of the hood. In Fig. 1 (1), the halftone type phase shift mask blank plate 1 is composed of a transparent substrate 2 and a halftone type phase shift film 5 formed thereon by a lower layer 3 and an upper layer 4 formed on the lower layer. In Figure 1 (2), the half-tone phase shift mask Γ is on the transparent substrate 2 -29- 544549 V. Description of the invention (28) The upper layer portion formed by the lower layer portion 3 'and the lower layer portion 3' 4 'is a halftone type phase shift portion 5'. In this configuration, a mask pattern 8 formed by a semi-transmissive portion 6 forming a half-tone phase shift portion and a translucent portion 7 without forming a half-tone phase shift portion is formed. The half-tone phase shift film 5 and the half-tone phase shift portion 5 'have a required transmittance for the exposure light source, and the phase shift angle is approximately 180 degrees. In addition, the transmittance of the inspection wavelength, or the transmittance and reflectance, are designed within the desired range. (Examples 1 to 8) Examples 1 to 8 are specific examples of halftone phase shift masks corresponding to F2 excimer laser exposure. All of them use a synthetic quartz substrate on the substrate, and the substrate and the SixNy layer An etching retardation layer is provided in between. (Film formation) First, a layer A of an etching retardation layer and a layer B made of SixNy were sequentially laminated on a synthetic quartz substrate. This embodiment is made by a sputtering method. The basic composition of the layers A and B of the two-layer film, the conditions of the target object or the type of the sputtering gas, and the layer thickness of each layer are shown in Table 丨 for each example. When the film thickness of each of the layers A and B and the total phase shift amount of each layer are 180 ° with a wavelength of 157 nm, the above equation (1) is used for adjustment. (Optical characteristics) When the transmittance of the produced two-layer film is measured using a vacuum ultraviolet spectrophotometer, the transmittance of the F2 excimer laser at a wavelength of 157 nm is shown in Table 2. When the etching retardation layer is provided, it can be used as a halftone phase. It is necessary to have a light transmittance of 3 to 40%. -30- 544549 V. Description of the invention (29) Table 1 _ Proportion of substrate gas (%) film thickness hydrogen. Nitrogen oxygen (nm) Example 1 layer A AI2O3 synthetic quartz 100.0 0.00 0.00 15 layer B Si 40.0 59.00 1.00 75 Example 2 layer A Ta synthetic quartz 40.0 60.00 0.00 10 layer B Si 40.0 59.00 1.00 72 example 3 layer A Ta-Zr synthetic quartz 100.0 0.00 0.00 8 layer B Si 40.0 59.00 1.00 78 example 4 layer A Ta-Hf Synthetic quartz 100.0 0.00 0.00 8 layers B Si, 40.0 59.00 1.00 78 Example 5 layer A Zr synthetic stone center 100.0 0.00 0.00 5 layer B Si 40.0 .59.00 1.00 80 Example 6 layer A Hf synthetic stone center 100.0 0.00 0.00 5 layer B Si 40.0 59.00 1.00 80 Example 7 layer A Si synthetic stone center 100.0 0.00 0.00 4 layer B Si .40.0 59.00 1.00 80 Example 8 layer A MoSix □ formed stone center 100.0 0.00 0.00 8 layer B Si 10.0 60.00 30.00 86 Table 2 Light Transmission (%) (l57nm) Example 1 13.1 Example 2 7.6 Example 3 6.6 Binshi Example 4 5.8 Example 5 15.7 Example 6 14.2: Example 7 '9.8 Example 8 10.1 -31- 544549 V. Invention Explanation (30) In addition, Example 2 As shown in Table 2 through the spectrum. The inspection wavelength of the half-tone phase shift mask for h excimer laser exposure is approximately 250 nm. Since the transmittance in this range is 40% or less', sufficient inspection accuracy can be obtained. In addition, in Examples 1, 3 to 7, the transmittance before and after 250 nm was 40% or less. A photoresist was applied to the two layers of films prepared in Examples 1 to 6, and a photoresist pattern was formed through the steps of exposure and development. Then, using this photoresist pattern as a photomask, the upper layer B (SixNy film) of the two films was etched by a dry etching method. In this embodiment, CF4 gas is used, and the etching time is set to be 30% longer than the time that can fully etch the film thickness of the SixNy layer. As a result, the SixNy film is patterned on the basis of the photoresist pattern, and the progress of the etching is stopped by the underlying etching stopper film. Table 3 shows the uranium engraving velocities of the synthetic quartz substrate, layer A, and layer B (SixNy) of this example obtained through other experiments. -Table 3 CF4, I cut rate (A / xnin) selection ratio (A7B) selection ratio (opposite substrate) quartz substrate 118.83 layer B (Si〇xNy) 148.7 ^-1.25 layer A (A1〇J ND η ^ < 01 «0.1 A (TaNx) 15 0.101 0:13 Layer A (Ta-Zr) 10 0.067 0.08 Layer A (Ta-Hf) 20 Γ 0134 0.17 Layer A (Zr) ND« 0.1 Layer A (Hf) 8 l —_〇 ^ 〇54 0.07 [* 1 · N · D · (η 〇tdetected) 'It is a small size that cannot be measured] -32- 544549 V. Description of the invention (μ) For layer B, the etching of layer A The speed is reduced to less than 1/5, and the layer a in Examples 1 and 2 can be confirmed as an "etch stop film having a function of preventing the sixNy film from being etched." Then, the layer A exposed on the surface is removed by etching. Etching gas The good pattern shape was obtained when using perhydrosulfuric acid in Example 1 and Cl2 gas in Examples 2 to 6. The etching rates of the synthetic quartz substrate and layer A obtained by other experiments are shown in Table 4. For synthetic quartz substrates, the etching speed of layer A is 5 times or more, and the layer A of Examples 1 and 2 can be confirmed as a "removable" layer. Table 4

Cl2 etching rate. (A / min) selection ratio (for substrate) persulfuric acid: etching rate (A7min) selection ratio (for substrate) Shiyang substrate 269.8 0 layer B (SiOxNv) 415.9 1.54 0 layer A (Α1〇χ) 101 0.37- Instantaneous dissolution_, »10 layer A (TaNx) 2039.6 7.56 layer A (Ta-Zr) 4020 14.90 1 A (Ta-Hf) 3000 11.12 layer A (Zr) 3300 12.23 layer A (Ηΰ 2800 10.38 [* 1 : ND (not detected); indicates that it cannot be measured.] Examples 7 and 8 were coated with a photoresist on the two-layer film produced, and a photoresist pattern was formed through the exposure and development steps. The photoresist pattern is used as a photomask; the upper layer B (SixNy) and the lower layer A of the two layers are etched by CF4 gas. At this time, the relationship between the etching time and the reflected light intensity of the etched portion for light with a wavelength of 67 8nm There are 33.544549 V. Description of the invention (32) Example 7 shows that the intensity of the reflected light decreases sharply at a certain time as shown in Fig. 3. At this time, when the etching stops, the layers A and B are both The photoresist pattern is used as a reference, and a good pattern shape can be obtained. In other words, the layer A of Example 7 is "easy to detect erosion with SixNy film The "etching end function" etching retardation film is a "removable" film. In addition, the refractive index (the real part of the complex refractive index) of the synthetic quartz substrate, layer A, and layer B with a wavelength of 678 nm is 1.47, 4.70, and 1.67, respectively. When the refractive index of the layer B is larger than that of the synthetic quartz substrate and the layer A by 1 or more, the intensity of the reflected light before and after the etching of the layer B can be drastically changed as shown in FIG. It can also be obtained in Example 8. In addition, the plan view of the relationship between the etching time and the intensity of the reflected light in the example of the single layer of the SiON layer is shown in Figure 3. The end point can be detected when the single layer of Si 0 N layer is used. The end point of 7 is clear. (Example 9) This example reviews the underlying materials. Table 5 shows TaZrx when dry etching is performed using fluorine-based and chlorine-based gases (represents materials containing Ta and Zr, and Ta and Z are not shown). · The composition ratio is the same below.) The results of Zr etching characteristics can be confirmed. Table 6 shows the results of TaAl and TaHf characteristics when dry etching is performed using fluorine-based and chlorine-based gases. Ta is the main material, and When considering the effect of the present invention, the dry etching characteristics of the film of the added material (Al, Hf, Z ··). -34- 544549 V. Description of the invention (π) Table 5 Zr content rate (%) Etching gas etching rate (A / inin ) Selection ratio, L, QZ) TaZrx Cl2 4020 ^ ^ _U.2 Zr 100 Cl2 3370 ^ QZ 0 Cl2 360, TaZrx 1.8 C2F6 40 TaZrx 2.6 C2F6 40 ^ TaZrx 4.3 1 c2f6 10 ^ ___ 0.1 Zr 100 c2f6 7, QZ 0 c2f6 120 ^ ^ Each film material is formed by a sputtering method. Material 3ff4 ^ 0 $ Ta The target material is loaded with the metal sheet of the target material and filmed. The presence or absence of addition in the film can be confirmed by X-ray photoelectron spectroscopy (XPS). For dry etching, the gases shown in Table 6 were used. Moreover, in this embodiment, etching is performed by using a high-density plasma using a derivative-bonded plasma source. Table 6 Etching gas. Etching rate (A / min) Selection ratio (/ QZ) TaAI Cl2 2880 11.5 TaHf Cl2 2980 11.0 QZ Cl2 260 —— TaAI C2F6 70 0.6 TaHf C2F6 20 0.2 QZ C2F6 110 An experimental result shows that Adding a small amount of the material (A1, Hf, Zr) of the present invention can maintain chlorine-based characteristics and improve fluorine-based gas resistance. Moreover, the Zr monomer metal film of the present invention is applied to a dry type 1 insect using a fluorine-based gas.

-35- 544549 V. Description of the invention (34) Materials with high etching resistance during etching (low etching speed) and materials that can be easily etched (high etching speed) during dry etching using chlorine-based gas. (Reference Example 1) In order to confirm the addition effect of Example 9, it was confirmed that the dry etching characteristics of the Ta single metal film in which the above material was not added in the reference example. As shown in Table 7, the selectivity of the fluorine-based gas and the quartz substrate for the Ta single metal film is insufficient. In addition, the etching conditions of this comparative example were implemented based on Example 9. Table 7 Etching Gas Etching Rate (A / min) Selection Ratio (/ QZ) Ta Cl2 2900 8.1 QZ Cl2 360 Ta c2F6 110 0.9 QZ c2f6 120 D (Example 10) This example is a trial test using a film: a film as an etching mask The SiON layer is processed. The photoresist / Zi: / SiON was used as the film structure (Fig. 4 (a)), and each layer formed on the Si substrate was processed to confirm its effect as an etching mask material. The film thickness of each layer in this embodiment is 200 angstroms of Zr layer and 800 angstroms of SiON layer. The photoresist pattern was used as a photomask, and the Zr layer was processed with a chlorine-based gas (Fig. 4 (b)). Result of measuring the residual film of the Zr layer after the SiON layer is processed 'OK -36- 544549 V. Description of the invention (35) It is confirmed that more than 60% of the residual film has sufficient dry etching resistance as an etching mask material. (Embodiment 11) In the embodiment of the present invention, a photomask having a phase shift effect is produced on a trial basis. Here, considering the selection ratio between materials, the microfabrication of the blank formed by the structure of the SiON / TaZr / QZ substrate is performed. Two layers of the QZ substrate were sputtered using RF magnetrons to form a SiON layer of about 800 angstroms and a TaZr layer of about 60 angstroms. For pattern processing (or formation of a light-shielding Cr layer), a Cr film of about 500 angstroms was formed on the SiON layer, and then a ZEP photoresist for electron wires was applied. The electron wire was drawn and developed to form a 0.5 μm width test. Pattern (Figure 5 (a)). Here, the film thickness of each layer is set in consideration of the phase difference of the light transmitted by the mask. This photoresist pattern was simultaneously implemented with Ci · processing using a mixed gas of chlorine + oxygen (oxygen ratio of about 20%) (Fig. 5 (b)). Then, the SiON layer was processed using a C2F6 gas (Fig. 5 (c)). Then, the TaZr layer is etched with chlorine gas (Fig. 5 (d)), and the Ci: layer (containing a photoresist film) is removed by a wet step consisting mainly of erbium nitrate second ammonium solution (or the light-shielding belt portion (Selective removal) (Figure 5 (e)), forming the desired test pattern. The pattern processing is a high-density plasma etching device using a derivative bonding plasma source. The cross-section of the pattern shape after processing was observed using a SEM (scanning electron microscope), and it was confirmed that the formation of the pattern was almost completely incomplete -37- 544549 V. Description of the invention (36) A good pattern in the case of a QZ substrate. In addition, as a result of observing the same pattern in the sample whose processing was stopped during the processing of the SION layer, it was confirmed that there was almost no film reduction of the TaZi. Layer. By setting the excess etching time taking into account the distribution of the dry etching time, the formation of a residual film pattern without a SiON layer can be achieved. In addition, it was confirmed that the TaZr layer was not sub-uranium-etched by removing the Cr layer. (Reference Example 2) In this reference example, the TaZr layer of Example 11 was made of TaN having a contact resistance close to that of the SiON layer by a fluorine-based gas. The same processing as in Example 3 was performed except that the material on the QZ substrate was changed. The TaN film is formed by reactive sputtering using a mixed gas of argon gas and nitrogen gas. Specifically, the photoresist pattern and Cr processing are implemented (Figure 6, (a) (b)), and then the SiON layer is processed using C2F6 gas (Figure 6 (c)). Then, the TaN layer was etched with chlorine gas (Figure 6 (d)), and the Ci • layer (including the photoresist film) was removed in a wet step mainly composed of rhenium nitrate second ammonium solution (Section 6 (e) Figure) to form a predetermined test pattern. As a result of forming a 0.5 μm test pattern in the same manner as in Example 11, it was confirmed that the pattern shape can be processed with a good shape in the same manner as described above to penetrate into the underlying QZ substrate. The etching rate of the TaN film by a fluorine-based gas is about the same as that of QZ. (Example 12) In this example, except that the TaZr layer described in Example 11 was changed to Hf-38-544549. 5. Description of the Invention (37) The same process was performed except for the layer (37) and the Zr layer. As a result of forming a fine pattern by the same process and observing the shape of the pattern by sEM, it was confirmed that the same pattern as that of Example 11 was formed. There is almost no damage to the QZ substrate, and it can be confirmed that a good pattern is formed. (Examples 13 to 18, Reference Examples 3 to 5) Examples 1 to 3, 15, 18, and Reference Examples 3 to 5 were made by using F2 excimer laser (wavelength 157nm) as an exposure light source and using light with a wavelength of 257nm. Phase shift mask blank plate and phase shift mask. In Examples 16 and 17, an ArF excimer laser (having a wavelength of 193 nm) was used as an exposure light source, and a phase shift mask, a blank plate, and a phase shift mask were produced using light having a wavelength of 364 nm as an inspection light source. Next, the manufacturing steps of the present invention will be described with reference to FIGS. 7 and 8. First, on a transparent substrate 2 made of a synthetic quartz type, a target having the composition shown in Table 1 (except that the reference examples 3 and 5 are giant and silicon monomers), and a rare gas (argon) is used as a sputtering agent. The lower layer 3 was formed by spraying a gas and using a DC magnetron sputtering device. Then, the upper layer 4 was formed into a film by using a reactive sputtering method using Ar, 〇2, and N2 as a sputtering gas on the lower layer 3 using a DC magnetron sputtering device (Seventh (1) Figure). Then, the obtained blank halftone-type phase shift mask blank was heat-treated at 400 ° C for 1 hour. Then, a light-shielding film containing chromium as a main component is sequentially laminated on the above two layers of films -39- 544549 V. Description of the invention (38) 9, Electron line scanning photoresistor 10 (Figure 7 (2)). Therefore, after pattern drawing is performed on the photoresist film by an electron beam, development and baking are performed by a dipping method to form a photoresist pattern 10 '(Fig. 7 (3)). Then, the photoresist pattern is used as a photomask, and dry-etching with Cl 2 + 0 2 gas is performed to form a light-shielding tape film pattern 9 ′. In addition, the gas is changed to form a halftone phase shift portion. At this time, the etching of the upper layer 4 uses CH4 + 02, and the etching of the lower layer 3 uses Cl2 gas (Fig. 7 (4)). However, in Comparative Example 3, since the lower layer was etched with 0114 + 02, it was impossible to etch using Cl2 gas. Next, the photoresist on the formed pattern is peeled off (Fig. 8 (1)), and the photoresist pattern is applied on the whole surface again (Fig. 8 (2)), and then formed by laser drawing and developing steps. Photoresist pattern 11, (Fig. 8 (3.)). Therefore, by the wet etching, a light-shielding band 12 is formed on the non-replication range in addition to the reproduction range I. Then, the photoresist pattern was peeled to obtain a half-tone phase shift mask (Fig. 8 (4)). Tables 8 to 11 show the materials of the transparent substrate, the composition of the upper layer, the film thickness, the optical characteristics of the exposure light source and the inspection light source, and the etching characteristics. The composition of the lower layer is substantially the same as that of the object. -40- 544549 V. Description of the invention (39) 5 ί 4! 3 M real _ 16 ί ma L = 1 real surface! 13 nmv 12 F paint F paint F paint CaF2 IF paint CaF2 F paint 11 SiON④ SiON③ SiON④ SiON③ SiON® SiON② SiON®; 1 SiON① j SiON① 1 Upper Tear CO • ο g O CD g CD g 1- 00 ggo 5 oa Zn β TaCr Hf-Si ^ Hf-Si Ta-Hf ① Ta-Hf®. I Ta-Hf①! 1 Ta-Hf ① Lower tear ο oo 〇CO o \ cn cn go ^ iai »—» h- * cn l ·-»3 cn s. 00 h-1 CO CO h- * Hundred's thin Luo • E depends on CD Oi CO o < 1 DJ CO 11.35 15.83 b CD c ^ > g exposure wavelength face rate (%) 11.95 18.20 14.37 1_ QD k) 00 I 18.58 17.00 12.00 13.55 15.60 exposure wavelength | reflectance (% ) 'to α \ ο to cn < 3 to cn < 1 to Ol CO A CO a bo cn < ϊ bo cn < 1 to 3 i Jean Lu 1 43.4 i 29.40 35.4 1 46.58 h-1 CD CD 30.40 49.30 32.39 s 1 19.91 Check wavelength pass rate (%) 25.13 1 24.06 17.83 38.89 21.50 16.80 24.78 32-79 Check wavelength reflectance (%) -41-544549 V. Description of the invention (40) Table 9 Composition of 157nm 193nm (atomic%) Si〇N① η knk Si 〇N 2.0 0 0.20 — — 36 48 16 SiON © — — 2.22 0.18 40 27 33 Si〇N③ 2.05 0.22-36 46 18 Si〇N④ 2.17 0.30 2.05 0.10 38 38 24 Table 10. Ta Hf Si Cr Zr Ta-Hf® 90 10 Ta-Hf® 80 20. Hf-Si 17 83 Ta-Cr 96 4 Table 11 Etch selection ratio (SF6 + He) for the upper layer / etched ρρ ratio (Cl2) for the lower layer for the substrate Example 12 0.25 > Chapter Example 13 0.25 > 5i Example 14 0.08 > 5 Example 15 0.25 > 5 Example 16 0.17 > 5 Example 17 0.17 > 5 Reference Example 3 0.67 > 5 Reference example 4 0.25 2.50. • Reference example 5 8.08-42- 544549 5. Explanation of the invention (41) Figures 9 and 10 are graphs of the transmittance of g for the wavelengths of Examples 1 and 14 respectively. And reflectance curve. The transmittances to the exposure light source (F2 excimer laser) in Examples 1 and 14 were near each of the achieved standard (6%) and the high transmittance (9%). The reflectivity of the exposure light source is low and can meet the required range (less than 20%). In addition, the transmittance of the inspection light source is lower than the required upper limit (40% or less), which can correspond to a sufficient inspection. In addition, in Example 15, a person having a high transmittance (15%) with respect to the exposure light source (excimer laser) can be realized. The reflectance of the exposure wavelength is low, which can meet the required range (less than 20%). In addition, the transmittance of the inspection wavelength is slightly higher. However, in order to satisfy the requirements for inspection using transmitted light and reflected light (transmission of 60% or less, and reflectance of 10% or more), inspections using transmitted light and reflected light are suitable for a sufficient inspector. In addition, in Example 16, an exposure rate (near 15%) can be achieved. Those with low reflectance at the exposure wavelength can meet the required range (less than 20%). In addition, the transmittance of the 'inspection light source' is lower than the required upper limit (less than 40%), and can be used for a sufficient inspector. In addition, the materials of the lower layer in Examples 17 and 18 are those without TaHf of Examples 13 to 16 and HfS :. Example 17 achieved high transmittance for the exposure light source (ArF excimer laser), and Example 18 achieved high transmittance (around 11%) for the exposure light source (F2 excimer laser). Those with low reflectance at the exposure wavelength can meet the required range (less than 30%). In addition, the transmittance of the inspection light source is lower than the upper limit of the required 値 -43- 544549 V. Description of the invention (42) (less than 40%) 'can correspond to a sufficient inspector. In addition, in any of the above embodiments 1 to 18, the lower layer has a smaller etching selection ratio to the upper layer than to the SF6 + He dry etching gas. In addition, the lower layer has sufficient resistance to the etching of the upper layer, and the etching selectivity ratio of the lower layer to the Cl2 dry etching gas is large for the transparent substrate. Thereby, since the damage to the transparent substrate is small when the lower layer is removed, a very good cross-sectional shape can be formed, and the change in optical characteristics can be controlled as much as possible by excessive etching of the transparent substrate to form a halftone type phase shift mask. In addition, Reference Example 3 and Reference Example 5 are examples in which the lower layer material does not contain molybdenum monomer and silicon monomer. These reference examples have a large etching selectivity ratio between the lower layer and the upper layer for the CH4 + 02 dry etching gas. In addition, if the upper layer is dry-etched by using a fluorine-based gas, even if the surface of the lower layer is exposed, the number of films on the lower layer decreases. As a result, it is difficult to set a sufficient excessive etching time that takes into consideration the removal of the upper residual film by the etching distribution produced by the pattern density and the like. In other words, a pattern with a good cross-sectional shape cannot be formed when sufficient over-etching is not performed. When sufficient over-etching is performed, the underlying transparent layer is penetrated into the etched transparent substrate, which changes the optical characteristics. As a result of Reference Example 3, the upper layer was not sufficiently etched. As a result, a pattern with a good cross-sectional shape could not be obtained. In Reference Example 5, the etching selection ratio of the lower layer to the upper layer for the CH4 + 0 2 dry etching gas is very large. As a result of sufficient over-etching of the upper layer, the transparent substrate was deep. -44- 544549 V. Description of the Invention (43) The amount of phase shift has changed. In addition, since Reference Example 4 has a small etching selectivity ratio for Cl2 dry etching gas, the substrate is more harmful and the optical characteristics are changed when the lower layer is removed. Other examples of forming a light-shielding film on the half-tone phase-shifting portion of the half-tone phase-shifting mask are shown in FIG. 11 and formed in a desired range except for the vicinity of the boundary between the light-transmitting portion 6 and the light-transmitting portion 7. Light-shielding layer 丨 3. By forming the light-shielding film 13 in this way, it is possible to reduce the sub-line light in terms of obtaining a phase shift effect. The transmissivity of the half-color g-phase phase shifting section is affected by gij line light. Therefore, this structure is effective especially for high-transmittance products (the transmissivity of the half-tone phase shifting section is 8 to 30%). Industrial application 僭 値 'The present invention can produce a halftone type phase shift mask blank plate and a halftone type phase shift mask which are excellent in fine processability during etching for forming a halftone phase shift portion. In addition, it is excellent in fine workability especially in etching for forming a halftone phase shift portion. In addition, especially when the exposure light source is short-wavelength, a local transmittance product (transmittance near 157 nm of the excimer laser wavelength and 193 nm near the ArF excimer laser wavelength) can be used in the exposure range of 140 nm to 200 nm. 8 ~ 30%). As a result, with the halftone type phase shift mask of the present invention, a high-precision copy pattern can be reproduced. -45-

Claims (1)

544549 2/10 000000000001 0987654321 ... I, 眚 one-one / consistent ‘5 also 1 eve J 2 0 ^ (time) gill buccal gill 40 160 160 200 220 240 260 280 300 wavelength (nm) Figure 2 544549 Etching time (a "b.unit) Country 3 544549 4/10 (a) Photoresist. Zr · SiON Si substrate Dry etching 丨 α2) (c)! 77Ί 71 ΡΊ Dry etching (C2F6 :) Figure 4 544549 5/10 (a) ⑹ (c) (d) (e) Photoresist Cr SiON TaZr QZ substrate dry etching (CI2 + 〇2) __ dry f insect engraving (c2 f6) :::::::响 / 人 ry // y V ////, 々 ////, V //// A r / J b / // 5th dry etching (CI2) Cr film peeling 544549 6/10 (a) Photoresist Cr Si〇N TaNx 〇Z substrate dry etching (C! 2 + 〇2) % W // person 〆 / / 7 >} / 丁 / 7 ⑸ (c). (D) Dry etching (C2 F6) ·: ·: ·: · Ψ /// Α ^ / λ / Dry etching (Cl2) Cr 'film peeling 544549 7/10 (2) 10 9 Check »^ \ SS ^ S ^ sS ^ \\ SS ^ \\ S \\ SSS > ^ 1〇, 9 (3) 丨 丨 I 丨 丨 丨 丨 丨 丨 chuanII 丨 IIIIIIIH 丨 丨 I 丨 丨丨 丨 丨 丨 丨 丨 I 丨 丨 丨 chuan 丨 丨 丨 丨 丨 (4) 544549 8/10 Figure S 12 (4) 544549 9/10 50 40 {SIS 3 544549 10/10 (%) ioe5y Wavelength, (nm) 110 circle 13 6 6