TW200944936A - Substrate for use in a photomask, a photomask, and its manufacturing method - Google Patents

Abstract

The present invention provides a gray tone photomask substrate, gray tone photomask, and the method of manufacturing the same, by which micro patterns can be formed with high precision by using wet etching of high productivity while the etching solution and manufacturing steps such as film-forming step and a photo-process are reduced as much as possible, The gray tone photo mask substrate of the present invention comprises a transparent substrate (10); a semi-transmissive layer (20) formed on the transparent substrate (10) and having a controllable incidence light transmittance; a light shield layer (43) which substantially blocks the irradiation light, where the substances forming the light shield layer (43) and the semi-transmissive layer (20) are composed of the same metal or compound thereof; and a stopper layer (30) which is formed of a substance having an etching resistance different from those of the light shield layer (43) and the semi-transmissive layer (20) and is provided between the light shield layer 43 and the semi-transmissive layer (20), where the stopper layer (30) is laminated on the semi-transmissive layer (20).

Description

200944936 VI. Description of the Invention: [Technical Field] The present invention relates to a substrate for a photomask, a photomask, and a method of manufacturing the same, and more particularly to an LCD (Liquid Crystal Display), PDP (Plasma Display Panel) In the production of display elements such as a display unit pattern, a wiring pattern, a black matrix, and a color filter such as a display panel, such as an EL panel, a black matrix or a color filter, fine-grained bumps are used. A substrate for a pattern forming mask, a mask, and a method for producing the same, which are used for surface modification such as an antireflection sheet or a microparticle array or a microlens array. [Prior Art] A variety of photomasks have been used in connection with the demand for flat panel display elements such as liquid crystal display elements, plasma display elements, organic EL display elements, and other display elements. For example, in the formation of the liquid crystal display element, in order to improve the pattern edge of the display electrode pattern formation and the wiring guide pattern formation (for example, taper formation, etc.), on the side opposite to the color filter side, The formation of a black matrix pattern requiring a semi-penetrating portion, the formation of a % color filter requiring chromaticity adjustment, the formation of a gap material having a different height, or the formation of irregularities such as a partition wall in a plasma display element, and A reticle for each purpose and function. Masks that are used in response to the needs of multiple uses and functions are increasing, and methods for reducing the number of exposures or photons are known: forming a pattern having two or more functions by one exposure, or using the available The same light 200944936 The method of masking the gray scale reticle with different patterns of exposure. The gray scale mask has a plurality of types, and the irradiation light can be changed stepwise by changing the surface shape of the mask or forming a semi-transmissive layer having an intermediate transmittance. For example, in the technique of the patent document 1, in the technique described in Patent Document 1, the characteristics of the photosensitive resin or the photosensitive resin having thermosetting property are utilized by adjusting the surface shape. The gray scale exposure is combined to change the surface unevenness caused by the formation of the unevenness or the residual of the substrate (arbitrarily forming a layer having an antireflection effect or a scattering effect). Further, in the technique described in Patent Document 2, the photoresist is decomposed stepwise or obliquely to an arbitrary depth to form a stepped or tapered edge. In the techniques described in Patent Documents 3 and 4, a method of modifying or upgrading to a certain depth in the vicinity of the surface of a photosensitive resin or a film is disclosed, or the photosensitive resin itself is treated in the same manner to have The new feature method. On the other hand, in the case of a gray scale mask having a semi-transmissive layer (having an intermediate transmittance), a constituent having three layers having different optical characteristics is known: a transparent substrate is substantially illuminated 4 The shaded area of the shadow, the semi-transparent area $ that controls the transmittance of the light, and the area of the transparent substrate through which only the enamel-illuminated light penetrates. The semi-transmissive region of the f gray scale mask can appropriately control the area of the exposure amount to be irradiated, and the photoresist can be hardened or decomposed according to the exposure amount to be developed, thereby making it an afterimage. Therefore, it is possible to ensure a photoresist region different from the light-shielding region and the total penetration region. 200944936 There is also a gray scale mask composed of a substance of the same system as a semi-transmissive layer and a light-shielding layer (for example, refer to Patent Documents 5, 6, 7, 10), and a gray matter layer composed of a heterogeneous substance and a light-shielding layer. The mask (for example, refer to Patent Documents 8, 9, 11), in any case, the number of layers of the semi-transmissive layer and the light-shielding layer, the shape of the pattern, and the number or order of layers formed by the lithography method are various, and there is no Specially limited. In the case where the semi-transmissive layer and the light-shielding layer are formed of the same material, for example, according to the technique described in Patent Document 10, the following method is disclosed: preparing a substrate for a photomask having a semi-transmissive layer or a light-shielding layer After one of the semi-transmissive layer or the light-shielding layer is patterned once, the photoresist is removed and washed. A light-shielding layer or a semi-transmissive layer is formed again on the patterned layer by means of a vacuum device or the like, and thereafter the layer formed later is patterned by a photolithography step. On the other hand, in the case where the semi-transmissive layer and the light-shielding layer are composed of a heterogeneous substance, for example, according to the techniques described in Patent Documents 8, 9, and 11, there is a method of preparing a semi-transparent layer continuously. And the mask substrate for the light-shielding layer' is patterned by dry etching or chemical etching to form each layer. Further, in the techniques described in Patent Documents 6 and 9, the following methods are disclosed: The light shielding layer, the semi-transmissive layer, and the anti-reflection layer are composed of the same metal or a compound thereof, and a light-shielding pattern is formed, and a semi-transparent layer is formed again. The pattern of only the semi-transmissive layer and the laminated portion of the light-shielding layer and the semi-transmissive layer are etched together to form a light-shielding pattern and a semi-transmissive pattern. At this time, patterning can be performed by etching, so that the simplification of the patterning step can be achieved. Further, in the techniques described in Patent Documents 8 and 12, the following method is disclosed: 5, 2009, 449, 364, a method for sequentially forming a substrate having a semi-transmissive layer and a light-shielding layer formed of a material resistant to etching with respect to each other, respectively Each layer corresponds to an etchant, thereby fabricating a gray scale mask. Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-24041 No. JP-A No. 2004-24041 No. 2 Patent Publication No. 2 〇〇 〇 3 3 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 : : : : : : : : : 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 147 147 147 147 147 147 147 147 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 When you are unable to separate from each other, the layers are clearly separated from each other.

琨仃 etch, but must form I β Η ^ of any of the 4 light-shielding layer or semi-transmissive layer, the substrate is patterned once and the agent is removed, and the light-shielding layer or the tooth is again formed. In the absence of J, the second patterning is carried out, so that there is a disadvantage in terms of cost, and when there is a layer composed of a heterogeneous layer, it is used for each other; It constitutes a light-shielding layer and a semi-transmissive layer, so it can be formed for a long time. However, in the step, a plurality of (four) engraving liquids must be prepared, and acid or alkali is used in the substrate cleaning or photoresist removal step. Oxygen, etc., therefore, the selective etchability of the light-shielding layer and the semi-transmissive layer is important, and it is also necessary to ensure sufficient resistance to the chemical liquids. In either of the dry rhyme and the wet remnant, the combination of substances that can be selectively etched by the heterogeneous material is small, and the adhesion at the contact interface of each layer or the residue near the interface causes subtlety. The mask effect or the edge of the pattern is unclear, the damage caused by the etching solution or the etching gas, or the film thickness is reduced by excessive etching, resulting in an increase in the transmittance, etc., so that it is difficult to ensure sufficient accuracy in the patterning step. . In view of the above problems, the present invention provides a method for producing a substrate for a photomask for producing a gray scale mask by wet etching with high productivity, a photomask, and a method for producing a photomask using the substrate. According to the reticle substrate of claim 1, the above problem can be solved by the following method: The reticle substrate of claim 1 is a gray scale reticle substrate having a transparent substrate and a transparent substrate. a first layer having a semi-transmissive property to the irradiation light, a third layer formed on the U-th and substantially shielding the irradiation light, and being formed between the second layer and the third layer and having an illumination light a second layer having a semi-transparent property, wherein the i-th layer and the third layer are insoluble or poorly soluble to the second etching liquid and are more soluble in the first etching liquid than the second layer, and the second layer The layer is more soluble in the second etching solution than the i-th layer and the third layer, and is insoluble or poorly soluble in the i-th etching solution, and the i-th layer and the third layer are respectively selected from chromium. , oxidized complex, 7 200944936 a layer composed of one or more of the group consisting of chromium nitride and chromium oxynitride as a main component, the good layer 71 is selected from the group consisting of titanium, titanium oxide, titanium nitride and titanium. One or two layers in the group formed, the above components are used as the main component The first remaining liquid is a mixture of cerium nitrate, a mixture of a acid and water. The second liquid is a mixture of potassium hydroxide, hydrogen peroxide and water. According to the above configuration, the first portion has a semi-penetration property. The second layer is formed by the same layer or a compound thereof, which is formed of the same metal or a compound thereof, and is formed between the third layer and having semi-transparency to the irradiation light. The third layer is inferior to the first one, and the first Li and the third layer are selectively engraved with the engraving liquid. Further, the second layer 1 and the third layer are inferior to the second etching solution and are insoluble or poorly soluble in the etching liquid, so that the second layer is described. "Use the first surname engraving to select, that is, the stone osmium reduction, titanium nitride and I titanium oxide to 帛1 刻刻液 (4), the mixture of peroxyacid and water is insoluble or the second engraving, ie chlorine. The mixture of unloading, peroxidizing gas and water is easy to dissolve. ®35 chromium oxide, chromium nitride and chromium oxychloride are the mixed etching solution of ammonium cerium nitrate, peroxy acid and water. Mixing with water: It is insoluble or difficult for the second sputum sputum. Therefore, the first layer and the third layer are respectively selected from the group consisting of chromium oxychromium and chromium oxynitride. Or two or more components 200944936 = component, such that the second layer is selected from the group consisting of: chin, oxidized chin, nitriding, and oxynitride; or two or more components as the main component: The selectivity of the etching solution is increased to form a finer pattern. The second layer and the first layer and the third layer are resistant to different surnames, and by utilizing the difference in tolerance, the layer 2 is hardly It will be affected by the modification or damage of the first and third layers of the etchant, and the first layer and the third layer will hardly be affected. The second etching liquid in which the second layer is dissolved is modified or damaged. Therefore, it is possible to produce a mask having a high precision in forming a layer formed by the low film forming step by a continuous photolithography step. Further, by changing the composition ratio of the second layer, it is possible to finely adjust the optical characteristics and the scribe speed of the semi-transmissive layer, thereby ensuring higher cost. Further, the second layer is The material which is heterogeneous with the i-th and the second layer is f: another aspect is semi-transparent, so that the pattern of the i-th layer and the second layer can be formed by using an etching step 以 to form a The semi-transparent layer having a different transmittance of the U. Further, since the titanium compound has high resistance to chemicals such as acid or alkali, it is less susceptible to damage by the agent used in the etching process such as the photoresist removal liquid. The selection process can be carried out smoothly, and the high-precision and fine-grained can be formed. Even if the etching is performed with high precision by wet etching, the productivity of the large-sized photomask can be improved, and the gray-scale light can be inexpensively manufactured 200944936. Specifically, as described in claim 2 The first layer is preferably formed directly on the transparent substrate. According to the above configuration, the transmittance of the irradiation light can be easily maintained at a desired value. More specifically, as described in claim 3, the second The layer preferably has a transmittance of 5% or more and 70% or less to the irradiation light. Further, as described in the claim 4, the second layer preferably has a film thickness of 1 〇 nm or more and 70 nm or less. The second layer has the function of completely protecting the first layer in the step of etching the third layer' and can form a semi-transmissive layer having an appropriate transmittance in the region with the first layer of the layer. The photomask substrate is preferably formed by sequentially laminating the first layer, the second layer, and the third layer on the transparent substrate, as described in claim 5 and claim 6, wherein the third layer is substantially a light shielding layer that shields the illumination light and an antireflection layer that is formed on the more surface side than the light shielding layer, wherein the antireflection layer is selected from the group consisting of chromium oxide, chromium nitride, and chromium oxynitride. Or two or more components as a main component. According to the above configuration, since the third layer is provided with the antireflection layer, an antireflection effect can be obtained, and by preventing the moire or halation caused by the diffusion of the illuminating light at the time of exposure. Produced, and the accuracy of the pattern can be improved. Further, the antireflection layer is formed of a layer selected from one or more components selected from the group consisting of chromium oxide, chromium nitride, and chromium oxynitride having a low reflectance as a main component of 200944936. A higher anti-reflection effect is obtained, and an increase in pattern accuracy can be achieved by preventing generation of moiré or blooming caused by diffusion of the illuminating light by the reticle during exposure. At this time, by forming the antireflection layer with a substance which is homogenous to the light shielding layer, the light shielding layer can be simultaneously etched by the same etching liquid. Further, as described in claim 7, the first layer, the second layer, and the third layer are preferably formed by a sputtering method, an ion plating method, or a vapor deposition method. As described above, the first layer, the second layer, and the third layer can be formed by a vacuum film formation method such as a sputtering method, an ion plating method, or a vapor deposition method, whereby the film thickness can be appropriately adjusted and the like. A substrate for a photomask that requires optical characteristics. Further, it can be produced by a thin film forming technique such as sputtering, and physical properties such as chemical resistance and firmness of the substrate for a photomask can be appropriately adjusted. According to the reticle of claim 8, the above problem can be solved by the reticle obtained by using the reticle substrate: the reticle substrate is provided with a transparent substrate, is formed on the transparent substrate, and is semi-transparent to the illuminating light. An i-th layer, a third layer formed on the upper side of the first layer and substantially shielding the irradiation light, and a first layer formed between the second layer and the third layer and having semi-transparency to the irradiation light The first layer and the third layer are superior to the upper nectar, and the upper layer is insoluble or poorly soluble to the second liquid J and more soluble in the second etching liquid than the second layer. The second layer is easily soluble in the i-th layer and the sweet etching solution, and is insoluble or poorly soluble in the first can. The first layer and the third layer are respectively selected from the group consisting of chromium, chromium oxide, and 11 200944936. One or two or more of the components consisting of chromium nitride and chromium oxynitride; a layer composed of paper, rattan, milk, 41 titanium or two or more components as a main layer,

The first etching liquid is a mixture of nitric acid and a mixture of a acid and water, and the second engraving liquid is a mixture of hydrogen peroxide, peroxygen gas and water. The light according to the present invention, in particular, The glare of a large reticle is enhanced, and a multi-gray reticle can be obtained inexpensively. The above problem can be solved by the method for manufacturing a photomask according to the method of manufacturing a photomask according to claim 9, which is a method for manufacturing a photomask using a substrate for a photomask, which is transparent. a third surface on the substrate, the transparent substrate, and having a semi-transparent property for irradiation, a third surface formed on the upper side of the ith layer and shielding the illuminating light, and a third layer formed on the U and the third layer a second layer that is semi-permeable to the illuminating light, and

The first layer and the third layer are insoluble or poorly soluble in the second etching solution as compared with the second layer. The etching solution is easily soluble, and the second layer and the above-mentioned first! The layer is more soluble in the second etching liquid than the third layer, and is insoluble or poorly soluble in the second etching liquid, and the first layer and the third layer are respectively composed of gasification complex and chromium oxynitride. a layer as a main component in the group, selected from the group consisting of chromium, chromium oxide, species or two or more components, wherein the second layer is selected from the group consisting of titanium, titanium oxide, titanium nitride, and nitrogen oxide 12 200944936 titanium. The first etching liquid having a component of one or two or more layers as a main component is ammonium cerium nitrate. The second etching liquid is potassium hydroxide, and a mixture of perchloric acid and water, hydrogen peroxide and water. The method for producing the reticle is as follows: a first photoresist coating step of coating a # 踯 I pre-reagent on the surface of the third layer; and a first exposure step, forming a first 1 mask pattern mask will be on top! The photoresist coated in the photoresist coating step is exposed; the first photoresist removing step removes the exposed portion or the unexposed portion of the photoresist after the first exposure step; 1 money engraved steps, use the above mentioned! The money engraving liquid etches the third layer exposed by removing the photoresist region to form a case; Ο the second etching step, using the second etching liquid, removing the above by the first etching step The second layer exposed in the third layer region is etched to form a light-shielding pattern; and the first photoresist stripping step peels off the photoresist remaining in the second photoresist removal step; a resist coating step of re-coating the photoresist on the surface; and a second exposure step of transmitting the photoresist coated in the second photoresist coating step through the mask having the second mask pattern formed thereon Exposure; a second photoresist removing step of removing the exposed portion or the unexposed portion of the light 13 200944936 resist after the second exposure step; and the third remaining step, using the first surname And removing the layer of the third .. x < 罘1 layer exposed in the region of the photoresist, and the second layer and the transparent substrate are exposed by the knife; and the second photoresist is stripped Step of removing the second photoresist from the step Above the remaining photoresist is stripped. Thus, according to the method of manufacturing the reticle of claim 9, by using the difference in the resistance of the etchant to the ι layer and the third layer and the 帛2 layer, the etchant used for etching the other layer is hardly modified. Or damage, it is possible to obtain a high-precision four-gray reticle having a region in which the opaque layer is exposed on the surface, and the first layer is exposed on the surface by the second etching step. The through region, the second step by the second etching step! The second semi-transmissive region exposed on the surface and the fully penetrating region in which the transparent substrate is exposed on the surface by the step 3 (4). According to the method of manufacturing a reticle of claim 10, the above problem can be solved by a reticle manufacturing method, which is a method of manufacturing a reticle using a substrate for a reticle, wherein the reticle substrate includes a transparent substrate a second layer formed on the transparent substrate and having semi-transparency to the irradiation light, a third layer formed on the upper side of the second layer and substantially shielding the irradiation light, and the second layer and the first layer a second layer having a semi-transparent property between the three layers and the first layer and the third layer being insoluble or poorly soluble to the second #刻液 and being the first layer The etching liquid is easily soluble, and the second layer is more soluble in the second 200944936 recording liquid than the second layer and the third layer, and is insoluble or poorly soluble in the first etching solution 1 The first layer and the third layer of the third layer of the A./L 3 layer are one or more selected from the group consisting of chromium, chromium oxide, chromium nitride 'chromium oxynitride ^ ^ + The layer containing the component as the main component, and the second layer is the free titanium, In the group consisting of titanium, titanium nitride, and nitrogen oxide, the group of 4 # Τ # or two or more components is added as a main component, ❹ ^1(四)液为德钸录,过气酸和水a mixture of the second (four) liquid oxygen cut, a mixture of hydrogen peroxide and water, and the method for manufacturing the mask described above performs the following steps: a first photoresist coating step, a RB β W photoresist Breaking over the surface of the third layer; and exposing the photoresist coated in the first photoresist coating step through the mask having the first mask pattern; ©1st photoresist removal step, where is the portion of the photoresist exposed to the exposed portion and the second unexposed portion after the first exposure step; the first surname step, the use of the first fan The etching solution removes the upper third layer exposed in the region of the resist to be etched to form a light shielding group; the i-th photoresist stripping step, which remains in the above-mentioned third photoresist removal step The photoresist is peeled off; the second photoresist is broken, and the photoresist is again coated a second exposure step of exposing the photoresist coated in the second photoresist coating step of the above 15 200944936 through a mask having a second mask pattern; and a second photoresist removing step; After exposing the second exposure step, the exposed portion or the unexposed portion of the photoresist is removed; and the second etching step exposes the region in which the photoresist is removed by using the second button engraving The second layer is etched to make the above-mentioned first! a third silver etching step of exposing the third layer exposed in the region of the photoresist and the second layer removed by the step 2 (4) using the i-th engraving liquid The ith layer is etched to expose the transparent substrate, and the second photoresist detachment step detaches the photoresist remaining in the second photoresist removing step. As described above, according to the method of manufacturing the reticle of claim 10, the etchant used for the etching of the other layer is hardly modified by utilizing the difference in resistance between the first layer and the third layer and the second layer to the etching solution. Or damage, it is possible to form a high-precision three-gray reticle having a region in which the 帛3 layer is exposed to the light-shielding region on the surface, and the first layer is exposed to the first half-penetration on the surface by the first etching step. The region and the total penetration region of the transparent substrate exposed on the surface by the second etching step and the third etching step. According to the substrate for a photomask of claim 1, the second layer, the second layer, and the third layer are resistant to the different etching liquids, and by utilizing the difference in the resistance, the second layer is hardly affected by the first layer. The layer and the third layer dissolve the i-th etching solution to be modified or damaged. Conversely, the second layer and the third layer are hardly modified or damaged by the second etching solution capable of dissolving the second layer. Therefore, it is possible to manufacture a light army in which a layer formed by a single film forming step is formed into a fine pattern with high precision by a continuous photolithography step. Further, by changing the composition ratio of the second layer, the optical characteristics and the etching rate of the semi-transmissive layer can be finely adjusted to ensure higher etching properties, and the second layer is composed of the first layer and The third layer is composed of a heterogeneous substance, and on the other hand, because of the semi-transparency, the pattern of the first layer and the second layer can be formed by an etching step, thereby forming a layer different from the ith layer. The transmittance of the semi-turn-through layer X' can be etched with high precision even by wet etching, so that the productivity of a large-sized photomask can be improved, and the light of a multi-gray mask can be inexpensively manufactured. A cover substrate. According to the substrate for a photomask of claim 2, it is possible to provide a substrate for a photomask which can easily maintain the transmittance of the irradiation light to a desired value. According to the substrate for a photomask of claim 3 and claim 4, a substrate for a photomask can be provided: the second layer has a function of completely protecting the first layer in the step of etching the third layer, and can be applied to the second layer A semi-transmissive layer having a suitable S penetration rate is formed in the laminate region. According to the substrate for a photomask of claim 5 and claim 6, the substrate for a photomask can be provided. The antireflection layer is selected from the group consisting of chromium oxide, chromium nitride, and chromium oxynitride having a low reflectance. A layer formed by using one or two or more components as a main component in the group, so that a high anti-reflection effect can be obtained by preventing the reticle from being shattered due to diffusion of the illuminating light during exposure or The generation of blooming is achieved, and the accuracy of the pattern is improved. According to the substrate for a photomask of claim 7, the first layer, the second layer, and 17 200944936 are formed by a vacuum film formation method such as a chain eliminator method, an ion ore removal method, or a vapor deposition method, and are appropriately adjusted. A cover substrate having a film thickness or the like and having desired optical characteristics. By using Ik as a thin film forming technique such as a money method, it is possible to provide a substrate for a photomask which can appropriately adjust physical properties such as chemical resistance or firmness of the substrate for a mask. According to the reticle of the item 8 of the invention, in particular, the productivity of the large reticle is improved, and the multi-gray reticle can be provided at low cost. According to the manufacturing method of the reticle of the claim 9 and the claim 10, the etchant used for the etching of the other layer is hardly affected by the difference in the resistance of the etching liquid to the first layer and the third layer and the second layer. Modification or damage provides a gray scale reticle that forms a highly precise and fine pattern. [Embodiment] Hereinafter, an embodiment of the present invention will be described with reference to Fig. 4 . Further, the present invention is not limited to the members, structures, configurations, sequences, and the like described below, and various modifications can be made without departing from the spirit and scope of the invention. 1 is a longitudinal cross-sectional view of a substrate for a gray scale mask according to an embodiment of the present invention. FIG. 2 is a longitudinal cross-sectional view of a gray scale mask according to an embodiment of the present invention, and FIG. 3 to FIG. An explanatory diagram of a patterning step of a gray scale mask, FIG. 6 to FIG. 8 are explanatory diagrams showing a patterning step of a three-gray mask, and FIG. 9 is an electron microscope (scanning electron microscope) for taking a test pattern from an upper surface. Bell (SEM)) photo. In addition, in FIGS. 1 to 8 , the thickness of each layer is thicker than the actual thickness for the purpose of explanation, thereby schematically showing the substrate for the gray scale mask, the gray scale mask, and the gray scale mask. Manufacturing method. Further, various test results of the examples and comparative examples are shown in Table 1. 18 200944936 FIG. 1 is a cross-sectional view of a substrate 1 for a gray scale mask according to the present invention. The substrate 1 for a gray scale mask is a transparent substrate 1 , a semi-transmissive layer 20 formed on a transparent substrate 1 , and a composite layer. 40. And a smear preventing layer (blocking layer 3 形成) formed between the semi-transmissive layer 2 〇 and the composite layer 4 。. Further, the stopper layer 30 corresponds to the second layer of the present invention, and the semi-transmissive layer 2〇 and the composite layer 40 correspond to the i-th layer and the third layer, respectively. Further, the composite layer 40 is formed of a light shielding layer 43, which is substantially shielded by irradiation light, and an antireflection layer 45 laminated on the surface thereof. The substrate 1 for the gray scale mask is used to manufacture the substrate of the gray scale mask 2, and the semi-transparent layer 20, the light shielding layer 43, and the blocking layer are formed by using different etching liquid pairs in the etching step and the photolithography step which will be described later. The gray scale mask substrate 30 of 30 is sequentially etched and patterned, whereby the gray scale mask 2 can be manufactured. The semi-transmissive layer 20 is a layer formed on the substrate 1 for the gray scale mask, and has a semi-transparent contrast light. It is possible to adjust the layer including the transmittance of the i-line (wavelength 365 nm) or the g-line (wavelength 436 nm) at a wavelength of 300 φ nm to 450 nm by changing the film thickness. The semi-penetrating layer composed only of the semi-transmissive layer 2 is set as the first semi-transmissive layer (region). The stopper layer 30 is formed on the semi-transmissive layer 2, has a blocking function for restricting the etching range when the composite layer 40 is etched, and has a function of protecting the semi-transmissive layer. Further, since it is a layer which is semi-transparent to the irradiation light, the second semi-transmissive layer (region) can be formed by maintaining a layer with the semi-transmissive layer in the photolithography step described later. Therefore, the transmittance of the second semi-transmissive layer (region) can be made different from that of the semi-transmissive layer (region) composed only of the semi-transmissive layer 2〇. 19 200944936 The composite layer 40 composed of the light shielding layer 43 and the antireflection layer 45 functions as a layer which functions as a light shielding layer which substantially shields the irradiation light of the present invention. 2 is a longitudinal cross-sectional view of the gray scale mask 2 of the present invention, which is formed by the transparent substrate 10, the first semi-transmissive pattern 20a formed on the transparent substrate 10, and formed on the first semi-transmissive pattern 20a. The pattern 30a, the light-shielding pattern 43a formed on the stopper pattern 30a, and the anti-reflection pattern 45a formed on the surface of the light-shielding pattern 43a are comprised. The semi-transmissive pattern 2〇a is a pattern formed by etching the semi-transmissive layer 20 of the substrate 1 for a gray scale mask of the present invention, and the pattern 30a is a pattern formed by blocking the layer 30, and a light-shielding pattern is formed. 43a is a pattern in which the light-shielding layer 43 is formed by etching, and the anti-reflection pattern 45a is a pattern formed by etching the anti-reflection layer 45. The light shielding layer pattern 40a is formed by the light shielding pattern 43a and the anti-reflection pattern 45a. When the gray scale mask 2 is viewed from the upper surface, a light-shielding region u (light-shielding region 1a) formed by partially exposing one of the anti-reflection patterns 45a (ie, the light-shielding pattern 40a) to the surface prevents a portion of the pattern 3〇a from being exposed on the surface. The area lb (the second semi-transmissive area lb), the area lc (the first semi-transmissive area lc) partially exposed on the surface, and the area ld of only the transparent substrate (the full penetration area) Id). Hereinafter, each member constituting the substrate 1 for the gray scale mask will be described. (Transparent Substrate 10) The transparent substrate 10 is a transparent substrate to be a base when a substrate for a gray scale mask is formed. As the transparent substrate 10, a natural quartz glass, a synthetic quartz glass, a glass substrate such as 20 200944936 borosilicate glass or soda glass, and a material such as a low-expansion transparent resin can be used. In addition, the term "transparent" as used herein refers to the transmittance of exposure light (Air Reference) for the i-line (wavelength 365 nm) or g-line (wavelength 436 nm) in the photolithography step included in 80-95. Within the range of %. (semi-penetrating layer 20)

❹ The semi-transmissive layer 20 (first semi-transmissive layer) is formed on the surface of the transparent substrate. The transflective layer 20 of the present embodiment has a transmittance of 5 to 70% for exposure light of a ridge line (wavelength 365 nm) or a g line (wavelength 436 nm) in the photolithography step, and is made of chromium (Cr). ) formed with a compound of nitrogen (N2) and oxygen (〇2). The film thickness is changed depending on the application to determine the transmittance. Regarding the semi-transmissive layer 20, depending on the exposure wavelength to be used and the characteristics of the photoresist, the wavelength of use is intentionally increased by the respective wavelengths, and the transmittance is stabilized in a plurality of wavelength ranges. . These penetration adjustments can be carried out by forming a compound of chromium (9) with any of oxygen (?2), nitrogen (N2) or a combination of such gases. For example, by increasing the ratio of oxygen in the film (the ratio of chromium, oxygen, and nitrogen in the film is "Η. Lai, 43.5~50.5 a_15.0~19.5, which is obtained by AX ray photoelectron spectroscopy manufactured by Sakamoto Electronics". The quantitative analysis value, based on the ESCA quantitative analysis value, can be referred to as the difference between the transmittance of the 1 line and the g line, which is 8.5% to 9.0%, and by increasing the ratio of τ heart to milk in the film (in the film) The ratios of chromium, gas and gas are 44.0~50.5 a ^ + 〇 / ^ Ζ 5 · ϋ ~ 29.0 atm% and 25.5 ~ 28.0 blood %, and the difference between the octet and the rate is m. 6%. When the etching layer of the contact layer is contacted with 20, the etching resistance of the semi-transmissive layer 21 200944936 3 and the etching rate of the composite layer 40 are considered, and any of metal, gas, nitrogen and carbon is used. In the present embodiment, since the matrix metal is chromium (Cr), the etching liquid (the etching liquid) is a mixture of pervaporic acid, ammonium cerium nitrate and water (( NH4)2Ce(N03)6. HCIO4. H2〇=15 : 3 : 82 normal temperature) (blocking layer 30) A barrier layer 3 is formed on the semi-transmissive layer 20. 3〇 layer system having a composite layer in which the etching of the upper end of the etching reliably function 40, and

a layer that prevents the semi-transmissive layer 20 from being subjected to etching, and is a layer that is resistant to the composite layer 4. Further, when the semi-transmissive layer 20 is etched, the blocking layer 3 is also used as a mask. Since the function of the cover is required to be a layer having resistance to the etching liquid of the semi-transparent layer 2, it is necessary to form a substance having high chemical resistance and good etching characteristics.

For the barrier layer 3 of the present embodiment, titanium (butadiene), and titanium and oxygen, t compounds (the ratio of titanium, oxygen, and nitrogen in the film are = 5 36.5 atm%, 32.0 to 39.5 atm, respectively). % and 29.5 to 41.0 atm%, ESC4 刀 knife analysis value) to adjust to meet the above characteristics. Further, as the etching liquid (second etching liquid) of the blocking layer 30, a mixed solution of hydrogen peroxide, potassium hydroxide and water ((H2〇2 (35%): Κ〇Η(3()%)) can be used. · H2〇= 1 : 16 : 32 (volume t匕) room temperature. In this month, use chromium oxynitride (chromium, oxygen and nitrogen compounds) with chromium and oxidized network to form semi-transparent layer 20 and shading The layer 43 and the anti-reflection layer 45 can be etched by the same-synchronized > a etching solution, but the light-shielding layer 43 and the reading tray 20 are provided as long as the blocking layer 3 has a property f of 22 200944936 (4). ^丄 "w ~ f is a substance composed of different components and the corresponding etching liquid is different" is also not particularly limited. Moreover, the blocking layer 30 is semi-penetrating due to the semi-penetrating substance. Layer 2 is stratified and has a second gray-scale function (2nd semi-penetrating region lb)e, for example, when the film thickness of the compound of chromium and oxygen, nitrogen is 100 A and the transmittance is 54.11%. When the barrier layer (film thickness % 200 A) is formed on the $ 2 (), the transmittance of the g line of the second semi-penetrating region lb is 26.08%. The film thickness of the barrier layer 30 is as follows. More It is to 1〇~7〇 nmU〇〇~7〇〇 into) the configured range. (Composite layer 40) The composite layer 40 of the present embodiment is formed on a layer in which the semi-transmissive layer 2〇 and the stopper layer 30 are laminated, and is composed of a light-shielding layer 43 and an anti-reflection layer on the surface side thereof. The light shielding layer 43 is composed of a chrome metal which absorbs a large amount, and the 0 antireflection layer 45 is a compound which absorbs less chromium than oxygen and nitrogen than the light shielding layer 43 (the ratio of chromium metal, oxygen and nitrogen in the film is 37.5 respectively). ~44.5 atm%, 39·5~46.0 3 plus % and 13·5~17 〇atm%, ESca quantitative analysis value). That is, between the light shielding layer 43 and the antireflection layer 45 formed thereabove, an antireflection effect by multiple interference of light is generated. In the present embodiment, the principle is used to form an optical film thickness λ/4 in accordance with the exposure wavelength to be used: η is a refractive index, and d is a substantial film thickness. Therefore, the light shielding layer 43 and the antireflection layer 45 may be composed of a compound of nickel, molybdenum, aluminum, copper, or the like, by changing the surface etching liquid. 23 200944936 Further, the composite layer of the irradiation light, that is, the light for exposure, is substantially the optical density of 3.0 (the transmittance is 〇·1% or less) or more, and is laminated on the stopper layer 30 in the present embodiment. Since it is formed, the light-shielding effect can be reliably exhibited, and the reflectance of the film surface can be reduced to less than 10 hours in the range of 350 nm to 450 nm, and the reflectance of the glass surface side can be reduced to less than %, thereby preventing exposure. No reflection or scattering is required. Next, a method of manufacturing the gray scale mask of the present invention will be described. The gray scale mask 2 of the present invention is manufactured by sequentially laminating a semi-transparent layer 2, a barrier layer 30, a light shielding layer 43 on the surface of the transparent substrate 1 by film formation. The mask substrate ι of the anti-reflection layer 45 is formed into a specific pattern by wet etching for each layer. The film formation method may be a physical vapor deposition (pVD) using a vacuum method such as a sputtering method, an ion electricity method, or a steam recording method.

Gas phase vapor deposition (CVD) such as CVD (Chemical Vapor Deposition) or thermal cvD. Further, when a film is formed by sputtering, reactive sputtering can be used in addition to sputtering. In the present embodiment, film formation is performed by reactive sputtering. (Thin film forming step) 中 In the film formation (film formation) of the present embodiment, a chromium target is used to deposit the semi-transmissive layer 20 on the transparent substrate 10. In a thin film forming apparatus adjusted to a vacuum of about 1χ1〇·4 Pa(pascai), a reaction of argon (Af) and nitrogen (NO and/or oxygen (02)' at about 2 to 3x1 G·1 Pa is introduced. Sputtering is performed in a gas atmosphere to form a thin film of a compound composed of chromium, gas, and oxygen. The transparent substrate 10 is disposed in the device opposite to the dry material, and is sprayed from the target by applying a negative voltage to the target. The chrome plated in a nitrogen and oxygen environment 24 200944936 by: plasma to promote the reaction, and reach the substrate, thereby forming a film. The proportion of nitrogen in the right film is less 'the etching rate is faster, while etching the light shielding layer It is easy to have excessive residuals, so it is necessary to properly control the amount of gas introduced during the money plating. ❹ ❹ ' · ', the multiple exposure wavelengths (350 nm to 500 nm) used in the field should be smooth, or When a certain difference in transmittance is required, not only the above-mentioned nitrogen gas and oxygen gas can be used, but also a reaction gas such as oxygen, carbon dioxide (c〇2) or hydrocarbon (CH4) can be used in combination. Then, a titanium target is used in half. The blocking layer 30 is sputtered on the penetrating layer 20. The film formation is the same as that of the semi-transmissive layer 20, and oxygen (〇2) and nitrogen (NO are introduced in a reaction gas atmosphere of about 2 to 3 χ1 〇 ^ Pa in a thin film forming apparatus adjusted to a vacuum of about lxio·4 Pa. Into the (four) ore, thereby forming a nitrogen oxide film. The transparent substrate 1 () formed with the semi-transmissive layer 20 is disposed opposite to (4). By applying a negative electric magic to the coarse material, the mineralization is reduced from (4) In the oxygen and nitrogen environment, the reaction is promoted by the plasma and reaches the substrate to form a thin film. At this time, the ratio of the titanium, oxygen and nitrogen compounds in the film is preferably such that the ratios of titanium, oxygen and nitrogen in the film are respectively The range of 26·5~36 5 _%, 32 〇~39 $ atm% and 29.5~41. 〇atm% (ESCA quantitative analysis value). In the case of the barrier layer 30, if incorporated in the film formation process When the ratio of nitrogen is increased, the function is prevented from exhibiting a tendency to decrease and the etching rate is slowed. On the other hand, if the ratio of nitrogen is low and the ratio of oxygen is increased, the cut of the pattern is deteriorated, and the alkali resistance also shows a tendency to deteriorate. Alternatively, only argon (Ar)' may be introduced into the thin film forming apparatus and k 25 200944936

Sputtering is carried out in an inert gas atmosphere around Pa, whereby a titanium (Ti) film is formed by applying a negative voltage to the material. The titanium is deplated from the starting material and reaches the substrate, thereby forming a stopper layer 3?. Next, on the stopper layer 3 formed in the above manner, a chromium target money mask layer 43 is used. Similarly to the above, only a argon gas (Ar) is introduced into the thin film forming apparatus adjusted to a vacuum of about lxl〇-4pa, and sputtering is performed in an inert gas atmosphere of about 1χ1 to form a chromium thin film. The transparent substrate 1 having the semi-transmissive layer 20 is disposed in the device opposite to the target. By applying a negative charge to the target, the chromium sputtered from the target reaches the substrate, thereby forming a light-shielding Further, an anti-reflection layer 45 is formed on the light shielding layer 43. The anti-reflection layer 45 can also be formed into a thin film by sputtering. In order to make the anti-reflection layer (4) exhibit an anti-reflection effect, it is necessary to form less absorption of the illumination light. In the film of the light shielding layer, a reaction gas such as oxygen or nitrogen is used. Further, the reaction rate or the edge shape of the pattern can be subtly controlled by the reaction with any one of carbon dioxide and hydrocarbons or a mixed gas. 3 to 5 and 6 to 8, the procedure for patterning the substrate 1 for the gray scale mask formed as described above will be described. First, the pattern shown in Figs. 3(a) to 5(1) The formation steps are explained. As shown in Figure 3(a) A substrate 1 for a gray scale mask which is formed into a film (film formation) by sputtering. Fig. 3(b) shows a first photoresist coating step. The photoresist is rubbed by spin coating or roll coating. The photoresist is coated on the surface of the substrate 1 for the gray scale mask, and the coated photoresist 5 is cured (prebaked) by an oven or the like. 26 200944936 Fig. 3(c) shows the first exposure step. 6G 'writes the mask pattern on the photoresist 5G. The mask is pre-formed with the desired pattern, and the pattern can be transferred to the photoresist 50 h through the original to irradiate the photoresist 5 () with ultraviolet light. The exposure is performed. Thereby, the photoresist 50 is exposed. Fig. 3(d) shows the first photoresist removal step. The exposed photoresist 50 is immersed in the developer 10, and the photoresist 5 is removed. The photoresist which has been exposed to light by ultraviolet rays is dissolved and removed, and the surface of the antireflection layer 45 is exposed along the photoresist pattern. After removing one portion of the photoresist 5, the remaining photoresist is removed by an oven or the like. The pattern 5 is heated and subjected to main hardening (post-baking p forms a pattern similar to the mask pattern i by the photoresist 5). 4(e) shows the first etching step. The antireflection layer 45 and the light shielding layer 43 are etched using the first etching liquid (a mixture of ammonium cerium nitrate, peroxy acid and water). Any method can be used as a method in which the substrate of the state is immersed in a thermostatic bath filled with an etching solution and controlled at a constant temperature, and a method of spraying an etching liquid by a shower such as an etchant controlled at a constant temperature. 45 and the light shielding layer 43 are formed of a material having physical properties that can be collectively etched in the film formation step, and are formed in the anti-reflection layer 45 and the light shielding layer 43 corresponding to the mask pattern 1 by the first etching step. The anti-reflection pattern 45a and the light-shielding pattern 43a. At this time, the stopper layer 30 has sufficient resistance to the first etching liquid (mixed liquid of ammonium cerium nitrate, peroxy acid and water), so that the composite layer 4 can be reliably etched and completely It does not cause damage to the semi-transparent layer 2〇. 27 200944936 Figure 4(f) shows the second etching step. After the etching liquid used in the first etching step is washed away, the etching liquid is replaced in this state, and the stopper layer 3 is etched. The etching system is the same as the remaining step 1, and has a method of immersing the substrate in a thermostatic bath filled with a second etching liquid (a mixture of hydrogen peroxide, potassium hydroxide, and water) and controlling it at a constant temperature. Any method may be used, such as a method of spraying an etchant such as a shower of a certain temperature etchant. Thus, the blocking layer 30 is etched to form the blocking pattern 3〇a. At this time, the semi-transmissive layer 20 and the anti-reflection pattern 45a and the light-shielding pattern 43a have sufficient resistance to the etching of the layer of the blocking layer © 3〇, and thus are not damaged by etching. Further, according to the configuration of the etching line, even if the photoresist pattern is removed and then etched, the light-shielding pattern 43a and the anti-reflection pattern 45a have sufficient resistance to the second etching liquid without any problem. Fig. 4(g) shows the first photoresist stripping step. The photoresist remaining on the surface is dissolved and removed by a photoresist stripping solution to clean the surface. Thereby, the same pattern as the i-th mask pattern can be formed on the transparent substrate 1A. 4(h) shows a second photoresist coating step in the semi-transmissive layer 20 and the stopper layer 30 (blocking pattern 3〇a), the light shielding layer 43 (light-shielding pattern 43a), and the anti-reflection layer 45 (anti-reflection pattern) 45a) The pattern of the deposited layer is exposed on the surface of the substrate by spin coating of the photoresist, and then the photoresist is resisted (prebaked) by an oven or the like. Fig. 5(i) shows a second exposure step. 28 200944936 Using the 2nd mask original 7 〇, the mask pattern is written for the light p and the state 丨 A $ nine resist 50. When the mask is pre-formed with the desired pattern, the reverse film is transferred to the photoresist 50. The second mask is irradiated with ultraviolet rays by the second mask 7 and the exposure is exposed. Thereby, the photoresist 5 is made photosensitive. Fig. 5(j) shows a second photoresist removing step. The exposed photoresist 5〇 is immersed in the developing solution. The photoresist of the photoresist 50 which has been exposed to ultraviolet light is dissolved and removed, so that the surface of the antireflection layer 45 and the semi-transmissive layer 20 are removed. The pattern of the photoresist along the buddhist κη μ φ is exposed. After a part of the photoresist 50 is removed, the remaining photoresist pattern 5 is heated by the drying of the photoresist to form a hardening (post-baking). Thereby, the same pattern of the pattern 2 is masked by light. Fig. 5(k) shows a third etching step. The anti-reflection pattern 45a, the light-shielding pattern 43a, and the semi-transmissive layer 2 are etched using an i-th etching liquid (a mixture of ammonium cerium nitrate, a mixture of peroxy acid and water). The etching is performed by the same method as the first etching step. The anti-reflection pattern 45a and the light-shielding pattern are formed of a material having physical properties that can be etched and etched in the film forming step. At this time, the semi-transmissive layer 20 is also collectively engraved with a mixture of nitric acid, peroxyacid and water to form a semi-transparent pattern 20a. The pattern is prevented from being sufficiently resistant to the i-th silver engraving liquid (mixture of nitrate, perchloric acid, and water), so that it can be reliably described without any damage or the like. Fig. 5 (1) shows a second photoresist stripping step. The photoresist remaining on the surface is dissolved and removed by a photoresist stripping solution to further clean the surface. Thereby, the same pattern as the second 29 200944936 mask pattern can be formed on the transparent substrate 1A. In this manner, a pattern in which the first mask pattern and the second mask pattern are combined is produced. As a result, a four-gray-order pattern (four-gray-order mask) of the cross-sectional view shown in Fig. 2 can be manufactured. Next, the pattern forming steps shown in Figs. 6(a) to 8(1) will be described. First, as shown in Fig. 6 (a), the substrate 1 for a gray scale mask formed by sputtering is prepared. Fig. 6(b) shows a first photoresist coating step. The photoresist 50 is coated on the surface of the substrate for the gray scale mask by spin coating or roll coating or the like. Further, the coated photoresist 5 is cured (pre-baked) by an oven or the like. Fig. 6(c) shows the first exposure step. The mask pattern was written on the photoresist 5 () using the first mask original 6 。. The mask is pre-formed with the desired pattern that can be transferred to the photoresist. The material is exposed to the green material 5G by the original material. Thereby, the photoresist 5 is exposed to light. ❹ Figure 6(d) shows the ith photoresist removal step. The exposed photoresist 5 is impregnated. The area which has been sensitized by ultraviolet light = the photoresist 5. The surface of the shot layer 45 is "removed by the first resist" to remove the anti-reverse, and the oven or the like remains as one of the resist 5G. Hardening (post-baking). Thereby, the agent pattern 50 is heated to form the same pattern. ,! 1 and the agent 50 is made to be in a circle 7 (e) with the mask pattern 1 to represent the step of engraving. 30 200944936 The antireflection layer 45 and the light shielding layer 43 are etched using a first etching solution (a mixture of ammonium cerium nitrate, perchloric acid and water). In the case of the surname, there is a method of immersing the substrate in the above state in a thermostatic bath filled with an etching solution and controlling it at a constant temperature, and a method of spraying the etching liquid by a shower such as an etching liquid controlled at a constant temperature, and the like. Any method can be used. The antireflection layer 45 and the light shielding layer 43 are formed of a material having physical properties that can be collectively etched in the film formation step. At this time, the stopper layer 30 has sufficient resistance to the first etching liquid (mixed liquid of ammonium cerium nitrate, peroxy acid, and water), so that the composite layer 4 can be reliably etched without causing the semi-transmissive layer 20 at all. Damage and other effects. Fig. 7 (0) shows the first photoresist stripping step. The photoresist remaining on the surface is dissolved and removed by the photoresist stripping solution, and the surface is further cleaned. Thus, the first mask is formed on the transparent substrate 1〇. The pattern of the mask pattern is the same, and the second semi-transmissive layer 20 and the blocking layer 30 are laminated on the transparent substrate 1 , and a pattern 40a of the light-shielding layer and the anti-reflective layer 45a is formed thereon. FIG. 7(g) shows The second photoresist coating step is applied to the surface of the substrate on which the pattern of the blocking layer 30, the light shielding layer 43 and the antireflection layer 45 is formed, and the photoresist 50 is coated by spin coating or roll coating. Further, the coated photoresist 5 is cured (prebaked) by an oven or the like. Fig. 7(h) shows a second exposure step. Using the second mask master 70, the photoresist 5 is masked. The mask is pre-formed with the desired pattern, and the pattern can be transferred to the photoresist 31 200944936 to expose the ultraviolet light to the exposure 50. The mask is passed through the mask to the photoresist $ light. The photoresist 50 is sensitized. Fig. 8(1) shows the second photoresist removal step. ^ = Bizhi photoresist 5G (4) for development The liquid towel dissolves the photoresist of the photoresist which has been exposed by the U-ray to remove the surface of the shot layer 45 and the blocking layer 30 along the light pattern. After removing the portion of the agent 50 , using the baking material to retain the remaining photoresist pattern ^

Heated and officially hardened (post-baking). Thereby, the same pattern as the mask pattern 2 is formed by the photoresist 50. Fig. 8 (1) shows the second money engraving step. The stopper layer 30 was subjected to _ using the second meal liquid (a mixture of hydrogen peroxide, potassium hydroxide and water). (4) "There is a method of immersing a substrate in a thermostatic bath filled with a second etching solution (a mixture of hydrogen peroxide, potassium hydroxide, and water) and controlling it at a temperature, and etching using a controlled temperature. Any method can be used. Anti-liquid shower, etc.

The shot layer 45 and the light shielding layer 43 and the semi-transmissive layer 2 have sufficient resistance to the second etching liquid (mixture of hydrogen peroxide, potassium hydroxide and water), so that the layer 30 can be reliably prevented from being completely prevented. It will cause damage and other effects. Fig. 8(k) shows the third surname step. After the second etching liquid is rinsed, the etching solution is replaced while remaining in the state, and the light shielding layer 43 and the antireflection layer 45 and the semitransparent layer 20 are etched. The last name is the same as the etching step 1, and a method of immersing the substrate in a thermostatic chamber filled with the first etching liquid and controlled to a constant temperature, and a shower capable of controlling the etching liquid at a constant temperature can be used. Thus, the shading 32 200944936 / anti-reflective layer 45 and the semi-transmissive layer 2 can be surnamed. At this time, the barrier layer 3 has sufficient resistance to the etching liquid (first etching liquid) of the semi-transmissive layer 20, the anti-reflection layer 45, and the light-shielding layer 43, and is not damaged by etching. Fig. 8 (1) shows a second photoresist stripping step. The photoresist remaining on the surface is dissolved and removed by a photoresist stripping solution to further clean the surface. Thereby, the same pattern as the second mask pattern is formed on the transparent substrate 1A. e

This pattern is a combination of the first mask pattern and the second mask pattern. As a result, a three-gray-order pattern (three-gray reticle) in which the i-th semi-transmissive layer lc is not present in the cross-sectional view shown in Fig. 2 can be manufactured. According to the manufacturing method of the gray scale mask of the present invention, the i-th film forming step and the second-order photolithography step can be used to produce the existence only by the manufacturing method of FIGS. 3(a) to 5(1). a transparent substrate 1 穿透 penetration region ld, an i-th semi-transmissive region lc, a semi-transmissive layer 2 〇 and a barrier layer 3 〇 layered second semi-transmission region lb, and a light-shielding region having a low reflection layer u's four grayscale reticle (see Figure 2). Further, by the manufacturing method shown in Figs. 6(a) to 8(1), it is possible to manufacture the full penetration region ld having only the transparent substrate 10 by the primary film forming step and the secondary photolithography step. a semi-transmissive layer 2 〇 and a second semi-transmissive region lb formed by stacking the barrier layer 3, and a three-gray reticle having a light-shielding region & [Examples] Hereinafter, specific examples of the invention will be described. (Example 1) 33 200944936 The method for forming each layer of the present invention is a vacuum method, in which the substrate temperature, the film formation pressure, and the like can be basically controlled by the ore reduction method, the ion plating method, the vapor deposition method, or the like. The membrane rate is 'reactive gas' to obtain the desired film. In the first embodiment, a semi-transmissive layer, that is, a film of a compound of chromium and nitrogen and oxygen, a film of titanium, a film of a compound of titanium and nitrogen, a light-shielding layer 43, that is, a chromium film, and an anti-reflection layer 45 are formed on the transparent substrate 1A. That is, an example of a film of a compound of chromium, oxygen, and nitrogen. In the first embodiment, a structure is formed in which a semi-transmissive layer 20, a stopper layer 30, a light shielding layer 43, and an anti-reflection layer 45 are laminated by sputtering. In the first embodiment, a quartz substrate (transparent substrate 10) which was flattened and sufficiently cleaned by polishing was first placed on a holder in a sputtering apparatus, and a commercially available metal chromium teaching material (purity: 99.99% or more) was used. Reactive splashing. As for the demineralization, once it is vented to lxl0·4 Pa, it is introduced into the vacuum apparatus of 25χ1〇-ι while introducing argon, oxygen and nitrogen at a ratio of 35:15:50, and 15〇. . (: at the substrate temperature, the gas is reacted with chromium while performing sputtering, thereby forming a chromium compound as a semi-transmissive layer 2 (the ratio of chromium, oxygen, and nitrogen in the film is 34 5 to 38 5 "111, respectively. %, 43.5~50.5 atm% and 15.0~19.5 atm%, ESCA quantitative analysis value). At this time, the semi-transmissive layer 20 directly forms a film so that the transmittance of the i-line (wavelength 365 nm) reaches 50%. On the substrate, the target material in the case of forming the semi-transmissive layer 20 may be a mixed sintered body of chromium oxide and chromium metal in addition to the metal chromium target. The metal chromium target is replaced by a metal. The titanium target film is formed on the surface of the semi-transmissive layer 2 by a film thickness of 1 〇〇A (1 〇 nm). As for 34 200944936 sputtering, one side is 98: 2 The ratio of nitrogen, oxygen, and oxygen is maintained in a vacuum apparatus at 1x101 Pa, and the compound 30 is formed at a substrate temperature of 150 ° C (the ratio of titanium, oxygen, and nitrogen in the film is 26·5 to 36.5 3 plus %, 32.0~39.5 3 plus% and 29.5~41.0& plus %13€ quantitative analysis value). In addition to the target, it may be a sintered body of titanium nitride powder. Also, it is the same as the semi-transmissive layer 2〇, and the degree of reaction varies depending on the device. Therefore, the film formation conditions are combined and adjusted in a timely manner. Then, 'the other metal is replaced. In the chromium target, a chromium film as the light shielding layer 43 is formed so as to have a film thickness of 7 〇〇A (70 nm). At this time, the mirror is held at lxl〇-i Pa while introducing only argon gas. It is formed in the environment of the vacuum apparatus and at a substrate temperature of 150 C. The chromium film formed here has a thickness of 700, and its optical density is about 3.1, and it has a function of sufficiently shielding light for exposure light (365 nm, 436 nm). 'The reflectance of the chrome film of the light-shielding layer at this time is usually about 55%, and the φ reflectance will have an adverse effect upon exposure. Therefore, it is necessary to reduce the reflection as much as possible. Then 'change the chrome-free material into a semi-penetration The metal chromium target used for film formation of layer 2 is placed in a vacuum apparatus of 2.5×10·1 Pa while introducing argon gas, oxygen gas and nitrogen gas at a ratio of 30:1〇:60, and i5〇〇 Sputtering while reacting the gas with chromium at the substrate temperature of c A chromium compound is formed as the antireflection layer 45 (the ratio of chromium metal, oxygen, and nitrogen in the film is 37.5 to 44.5 atm%, 39.5 to 46.0 atm%, and 13.5 to 17.0 atm%, respectively, ESCA quantitative analysis value). 35 200944936 When the anti-reflection layer 45 is a film which absorbs less light than the chrome of the light-shielding layer 43 with a thickness of about 300 A, the anti-reflection layer 45 is formed between the light-shielding layer 43 and the anti-reflection layer 45 formed thereon. The anti-reflection effect (reflectance at 365 nm to 436 nm is 15% or less) obtained by multiple interference of light, thereby reducing reflection or scattering of light during exposure. The film-forming reticle substrate 1 is ultrasonically cleaned in each of a plurality of tanks of a base lotion, a neutral lotion, and pure water, and then coated with a photoresist on the surface (AZ Electronic AZRFP-230K2 manufactured by Materials and pre-hardened. Further, in the photoresist application step, the surface of the mask substrate 1 is subjected to surface treatment without using chemicals, plasma, or ultraviolet rays. Hereinafter, the same is true for the same processing. After curing of the photoresist, 'exposure of the first test pattern (Jet Printer 'Light source CHM-2000 manufactured by OCR Co., Ltd., exposure under ultra-high pressure mercury lamp for 20 seconds), development (Pmer, manufactured by Tokyo Yinghua Co., Ltd.) , the temperature is 30 ° C '1 minute) and the formal hardening (Yamat 〇 Scientific DX4 〇 2 strange temperature dryer '120 ° C, 1 〇 minutes). Next, the substrate is immersed in a first etching solution, that is, a mixture of peroxyacid, ammonium cerium nitrate, and water (pervaporic acid: ammonium cerium nitrate: water = 3: 15: 82, reaction temperature: 3 〇〇 c, etching) The time is 60 seconds, whereby a portion of the layer 30 is prevented from being exposed, and a pattern in which the light shielding layer 43 and the anti-reflection layer 45 are laminated is formed. After the i-th etching liquid was washed with pure water and dried in this state, the substrate (the substrate 1 for processing the photomask 1) was taken out and the surface was observed, and as a result, no damage occurred on the surface, and it was confirmed that the etching stopper layer was prevented. Layer 3 〇 effect. 36 200944936 Next, the substrate is immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide and water (hydrogen peroxide (35%) aqueous solution: potassium hydroxide aqueous solution (3〇%) ): water = 16: 1: 32, the reaction temperature is 3 (TC, etching time is 85 seconds), and the layer 30 is prevented from being left, thereby forming a laminate having the barrier layer 30, the light shielding layer 43, and anti-reflection. The pattern of layer 45. The photoresist is removed by using a special photoresist stripping solution, and the surface of the pattern is confirmed. As a result, the pattern of the semi-transmissive layer 2 is the same as the time of etching. The damage caused by the semi-transparent layer 2〇 is not seen, and the surface of the anti-reflection layer 45 is also the same, and no damage is observed at all. Then, 'the full cleaning is formed by the blocking layer 3, the light shielding layer 43 and the anti-reflection. After the substrate of the pattern formed by the layer 45, the substrate is The surface of the surface is coated with a photoresist (AZRFP-230K2 manufactured by AZ Electronic Materials) and pre-cured. After the photoresist is cured, exposure of the second test pattern is performed (Jet Printer manufactured by 〇RC Manufacturing Co., Ltd.) Light source CHM-2000, exposure under ultra-high pressure mercury lamp for 20 seconds), development (pMER manufactured by Tokyo Chemical Co., Ltd., developer, temperature 30 ° C, 1 minute) and formal hardening (DX402 constant temperature drying by Yamato Scientific) Then, the substrate is immersed in the first etching solution, that is, a mixture of peroxyacid, ammonium cerium nitrate and water (per-acid acid · ammonium cerium nitrate: water = 3: 15: 82, the reaction temperature is 3 (rc, etching time is 60 seconds), and a part of the laminated pattern of the light shielding layer 43 and the antireflection layer 45 and a portion of the semitransparent layer 2 are etched. The resist stripping solution removes the photoresist to form a second semi-transmissive region lb having a light-shielding region la having an anti-reflective layer 45, a resist layer 3 and a semi-penetrating layer 20, and a semi-transparent layer. The first half of 20 wears 37 200944936 through the area lc, and only the transparent substrate The four-gray reticle of the full penetration area ld of 10. The edge of the pattern is confirmed by the reticle formed. As a result, it is confirmed that the pattern edge shape or the cone shape and the appearance defect of each layer are in a very good state. Using one part of the test pattern, The transmittance of the first semi-transmissive region 1 c, the transmittance of the semi-transmissive layer 20 and the second semi-transmissive region lb of the blocking layer 30, the optical density and film thickness of the light-shielding region la, and the final pattern formation The result of the surface observation, the surface observation result when the mask substrate was immersed in the Cr etching solution (5 minutes, 10 minutes, 20 minutes), and the state in which the barrier layer 30 was exposed after the etching of the composite layer 40 was immersed. The surface observation results after the lye were shown in Table 1. (Example 2) Example 2 is a design example in which the film thickness of the stopper layer 30 was changed. In Example 2, the film thickness of the stopper layer 30 was set to 200 by simply adjusting the sputtering time of the stopper layer 30. The film thickness and film formation conditions of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 45 are the same as in the first embodiment. In the same manner as in the first embodiment, the substrate was immersed in a first etching solution, that is, a mixture of peroxyacid, tartaric acid, and water (peracid acid: acid-depleted: water = 3:15:82, reaction temperature) In the case of 30 ° C and an etching time of 60 seconds, a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated is formed by partially exposing a portion of the barrier layer 30. While maintaining the state in which the first etching liquid was washed away with pure water and dried, the substrate was taken out and the surface was observed. As a result, damage to the semi-transmissive layer 2 was not observed, and the effect of the layer 30 was reliably expressed. . 38 200944936 Then, the substrate is immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide and water (aqueous solution of hydrogen peroxide (35%): aqueous potassium hydroxide solution (30%): water = 16: 1 : 32, the reaction temperature was 30 ° C, and the etching time was 17 sec.), and the stopper layer 30 was etched, thereby forming a pattern in which the resist layer 30, the light shielding layer 43, and the anti-reflection layer 45 were laminated. Then, the photoresist is removed by using a specific photoresist stripping solution, and the surface of the pattern is confirmed. As a result, the pattern surface of the semi-transmissive layer 3 is the same as that at the time of etching, and the surface of the anti-reflection layer 45 is Very good stomach state. Then, after the substrate having the pattern formed by the stopper layer 3, the light-shielding layer 43, and the anti-reflection layer 45 is sufficiently cleaned, the first etching liquid, that is, the pervaporic acid, ammonium cerium nitrate, and the like are immersed in the same manner as in the first embodiment. The mixture of water (pervaporic acid / cerium nitrate bond: water = 3 : 15 : 82 'reaction temperature is (4), etching time is 6 〇 second), and the light-shielding layer 43 and the anti-reflection layer are judged to be a laminated pattern A portion, and a portion of the semi-transmissive layer 2, are etched. Then, the photoresist is removed by a specific photoresist stripping solution to form a light-shielding region 1a having the anti-reflective layer 45, a second semi-transmissive region lb in which the barrier layer and the semi-transmissive layer 20 are laminated, There is only a semi-transmissive region of the semi-transmissive layer lc, and a four-gray reticle of the full penetration region Id. The edge of the pattern was confirmed for the formed mask, and as a result, it was confirmed that the edge shape, the tapered shape, and the appearance defect of the pattern of each layer were not in good condition. Using the test pattern material, the transmittance of the first semi-transmissive region le, the semi-transmissive layer 20 and the second semi-transmissive region of the barrier layer 3 are compared to the transmittance, and the optical transmittance of the light-shielding region la Concentration, film thickness, and final pattern formation 39 Surface observation results after 200944936, surface observation results when the mask substrate was immersed in a Cr etching solution (5 minutes, 10 minutes, 20 minutes), and in the composite layer 40 # The surface observation results after the immersion in the state in which the stopper layer 30 was exposed after the engraving was shown in Table 1. (Example 3) Example 3 is a design example in which the film thickness of the stopper layer 3 was changed. In the third embodiment, the film thickness of the stopper layer 30 is set to 300 A by simply adjusting the splattering time of the stopper layer 3 。. The film thickness and film formation conditions of the semi-transmissive layer 2, the light-shielding layer 43, and the anti-reflection layer 45 were the same as in the first embodiment. In the same manner as in the first embodiment, the substrate was immersed in the first etching solution, that is, a mixture of peroxyacid, ammonium cerium nitrate and water (pervaporic acid: ammonium cerium nitrate: water = L 15 : 82, reaction temperature: 3 CTC, etching) In a period of 6 sec., a portion of the stopper layer 30 is exposed by etching to form a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated. While maintaining the state, the third etching liquid was washed away with pure water and dried, the substrate was taken out and the surface was observed, and as a result, damage to the semi-transmissive layer 2 was not observed, and it was confirmed that the blocking layer 30 was prevented from being etched. The effect of the layer. Next, the substrate is immersed in a mixture of peroxide gas, gas oxidizing and water, which is a second residual liquid (hydrogen peroxide (35%) aqueous solution: potassium hydroxide aqueous solution (30%): water = 丨6: i: 32, the reaction temperature is 3 generations, and the etching time is sec.), and the layer 3G is prevented from being subjected to (4), thereby forming a pattern in which the barrier layer 3, the light shielding layer 43, and the antireflection layer 45 are laminated. Tttj p m team cloud, on the map

The surface was confirmed, and as a result, the pattern surface of the semi-transparent layer 2G was not observed. (IV) I 200944936 The surface of the anti-reflection layer 45 was not problematic. Then, after the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the antireflection layer 45 is sufficiently cleaned, the same as in the first embodiment, the immersion in the first surname liquid, that is, perchloric acid, acid deposition, and A mixture of water (peracid acid. _ ammonium citrate: water = 3: 15 : 82, reaction temperature of 30 ° C, etching time of 60 seconds), and a layer of the light shielding layer 43 and the antireflection layer 45 A portion of the pattern, and a portion of the semi-transmissive layer 20 are etched.继 In turn, the photoresist is removed by a specific photoresist stripping solution to form a second semi-transmissive region lb in which the light-shielding region la having the anti-reflective layer 45 is present, and the barrier layer 3 and the semi-transmissive layer 20 are laminated. There is only a first semi-transmissive region lc of the semi-transparent layer, and a four-gray reticle with a full penetration region id. The edge of the pattern was confirmed for the formed mask, and as a result, it was confirmed that the edge shape, the tapered shape, and the appearance defect of the pattern of each layer were not in good condition. Using one of the test patterns, the transmittance of the first semi-transmissive region 丨c, the semi-transparent layer 2〇 of the laminate, and the penetration rate of the second semi-transparent region of the barrier layer 3〇, the light-shielding region la The optical density and the film thickness, the surface observation result after the formation of the final pattern, the surface observation result when the mask substrate was immersed in the etching liquid (5 minutes, 10 minutes, 2 minutes), and the etching in the composite layer 40 The surface observation results after immersion in the lye in a state in which the stopper layer 3 was exposed later is shown in Table 1. (Example 4) Example 4 is a design example in which the film thickness of the stopper layer 30 was changed. In Example 4, the film thickness of the stopper layer was set to 400 A by simply adjusting the killing time of the stopper layer 30. The film thickness and film formation conditions of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 45 200944936 are the same as those in the first embodiment.

In the mixture of citrate and water (permantic acid · cerium ammonium nitrate: water = 3: i 5 : 82, reaction temperature is 30X:, #刻时间为60秒), the barrier layer is etched One of the portions 30 is exposed, and a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated is formed. When β was kept in this state, the first etching liquid was washed away with pure water and dried, and then the substrate was taken out and the surface was observed. As a result, damage to the semi-transmissive layer 20 was not observed, and it was confirmed that the stopper layer 30 was prevented from being etched. The effect of the layer. Then, the substrate is immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide, and water (aqueous solution of hydrogen peroxide (35%): aqueous potassium hydroxide solution (%%): water = 16:1 32, the reaction temperature is 3 Å, and the etching time is "Ο 矜 clock", and the blocking layer 30 is etched, thereby forming a pattern in which the blocking layer 30, the light shielding layer 43, and the anti-reflection layer 45 are laminated. The photoresist is removed by a specific photoresist stripping solution, and the surface of the pattern is confirmed. As a result, no damage is observed on the pattern surface of the semi-transmissive layer 20, and the surface of the anti-reflective layer 45 is not problematic. In the case of =3 60 seconds), and then the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the antireflection layer 45 is sufficiently cleaned, the first etching liquid is immersed in the same manner as in the example i. Mixture of peroxyacid, ammonium cerium nitrate and water (pergas acid: nitrate

In the middle portion, a portion of the laminated pattern of the light shielding layer 43 and the antireflection layer 45 and a portion of the semi-transmissive layer 20 are engraved. Partially, then 'removing the photoresist with a specific photoresist stripper to form 42 200944936. There is a light-shielding region la having an anti-reflective layer 45, a second layer of the barrier layer 3 and a semi-penetrating layer 20 penetrated. A region lb, a first semi-transmissive region 1c having only a semi-transmissive layer, and a four-gray reticle having a full penetration region Id. The edge of the pattern was confirmed for the formed mask, and as a result, it was confirmed that the edge shape, the tapered shape, and the appearance defect of the pattern of each layer were not in good condition. Using a portion of the test pattern, the transmittance of the first semi-transmissive region lc, the transmittance of the semi-transmissive layer 20 and the second semi-transmissive region lb of the blocking layer 30, the optical density of the light-shielding region la, and The film thickness and the surface observation result after the formation of the final pattern, the surface observation result when the mask substrate was immersed in the Cr etching solution (5 minutes, 10 minutes, 20 minutes), and the blocking layer was exposed after the etching of the composite layer 40. The surface observation results after immersion in lye in the state of 30 are shown in Table 1. (Example 5) Example 5 is a design example in which the film thickness of the stopper layer 30 was changed. In Example 5, the film thickness of the stopper layer 30 was set to 500 A by simply adjusting the sputtering time of the stopper layer 30. The film thickness and film formation conditions of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 45 were the same as in the first embodiment. In the same manner as in the first embodiment, the substrate was immersed in a mixture of peroxyacid, ammonium cerium nitrate and water as the first surname (perchloric acid: ammonium cerium nitrate: water = 3: 丨 5: 82, and the reaction temperature was At 30 ° C for 60 seconds, a portion of the stopper layer 30 is exposed by the surname to form a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated. Keeping in this state, 'after washing the first remaining solution with pure water and drying it, taking out the substrate and observing the surface', the damage to the semi-transmissive layer 2〇43 200944936 is not observed, and the blocking layer 30 can be confirmed. The effect as an etch stop layer. Next, the substrate was immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide, and water (hydrogen peroxide (35%) aqueous solution: potassium hydroxide aqueous solution (30%): water = 16: 丨: 32 The reaction temperature is 3 〇t, the etching time is "ο sec", and the blocking layer 3 〇 is etched, thereby forming a pattern in which the blocking layer 3 〇, the light shielding layer 43 and the anti-reflection layer 45 are laminated. The photoresist is removed by using a specific photoresist stripping solution, and the surface of the pattern is confirmed. As a result, the pattern surface of the semi-transmissive layer 20 is not damaged.

Further, the surface of the anti-reflection layer 45 has no problem. D. After the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the anti-reflection layer 45 is sufficiently cleaned, the same etching liquid as the first etching liquid, that is, the pervaporic acid and the ammonium cerium nitrate, and the like are immersed in the same manner as in the example i. A mixture of water (peracid acid: nitric acid: water = 3:15:82, reaction temperature of 3 (TC, 60 seconds remaining), and a layer of the light-shielding layer 43 and the anti-reflection layer 45 A portion of the pattern, and a portion of the semi-transmissive layer 20, is etched. Then the photoresist is removed by a specific photoresist stripper to form a light-shielding region la having an anti-reflective layer, a barrier layer and a half-through layer.第 the second semi-penetrating region lb of the permeable layer 20, the ith semi-transmissive region lc having only the semi-transmissive layer, and the four-gray reticle of the full-penetration region id. Confirming the pattern edge of the formed reticle As a result, it was confirmed that there was no pattern edge shape or a taper shape and appearance defects of each layer, and the state was very good. Using one of the test patterns, the transmittance of the ? semi-penetrating region lc, the semi-penetrating layer 20 and the barrier layer were laminated. 3第 The second half of the penetrating area “The penetration rate, the optics of the shading area la Degree and film thickness, final pattern formation 44 Surface observation results after 200944936, surface observation results when the mask substrate was immersed in a Cr etching solution (5 minutes, 10 minutes, 20 minutes), and etching in the composite layer 40 The surface observation result after the immersion in the state in which the stopper layer 30 was exposed was not shown in Table 1. (Example 6) Example 6 was different from the above Examples 1 to 5 in that the chemical composition of the stopper layer 30 was composed of a titanium compound. The film (titanium and nitrogen, oxygen compound) is replaced by a titanium film, wherein 'the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflective layer 45 are the same as those of the embodiments 1 to 5w. In the embodiment 6, the first method is to be ground. The flattened and sufficiently cleaned quartz substrate (transparent substrate 10) is placed on a holder in the sputtering apparatus, and a commercially available metallic chromium target (99.99% or more) is used for reactive sputtering. Once exhausted to 1x10-4 Pa, argon, nitrogen and oxygen are introduced at a ratio of 35:15:5〇 while maintaining at 2.5χ1 (ΓΐPa in the environment of the two devices, and at a substrate temperature of 150C) Sputtering while gas and chromium are reversed Thereby, a chromium compound is formed as the semi-transmissive layer 20. At this time, the semi-transmissive layer 20 is formed in the same manner as in the first embodiment, so that the transmittance of the earth line (wavelength 365 nm) is 50%. On the substrate, the metal chromium target is replaced with a metal titanium target, and the barrier layer is formed on the surface of the semi-transmissive layer 2 by a film thickness of A (l 〇 nm). The plating is performed while the argon gas is introduced while being held at 1 χ 1 (the titanium film is formed in the environment of the vacuum device. Then, another metal chromium target is replaced to make the film thickness 7 〇〇A (7 〇 nm). In this manner, a chromium film as the light shielding layer 43 is formed. The sputtering at this time is formed in the environment of a vacuum apparatus in which only argon gas is introduced while being held in a vacuum apparatus of about 1 χ10-ι?3. The chrome layer formed here has a thickness of 700 A and an optical density of about 3.1, and has a light-shielding function for exposure light (365 nm, 436 nm). Then, the chromium target material is replaced with a metal chromium dry material for film formation of the semi-transmissive layer 20, and argon gas, oxygen gas, and nitrogen gas are introduced at a ratio of 30:1 〇:60 while maintaining at 2·5χ1〇-ι In the environment of the vacuum apparatus of the pa, sputtering is performed while reacting the gas with chromium, thereby forming a chromium compound as the antireflection layer 45. The substrate formed by the film is ultrasonically cleaned in each of the baths of the lotion, the neutral detergent, and the pure water, and then the photoresist is coated on the entire surface of the substrate 1 for the mask ( AZRFP-230K2 manufactured by AZ Electronic Materials and pre-hardened. After the photoresist is cured, exposure of the first test pattern (Jet Printer manufactured by 〇RC, light source CHM-2000, exposure under ultrahigh pressure mercury lamp for 20 seconds), development (PMEr manufactured by Tokyo Yinghua Co., Ltd.), development Liquid, temperature 3 ° ° C, 1 minute) and formal hardening (Yamat〇scientific manufacturing Βχ 4 〇 2 strange temperature dryer, 12 ° ° C, 10 minutes). Then, the substrate is immersed in a mixture of peroxyacid, ammonium cerium nitrate and water (perchloric acid: acid: ammonium = 3:15:82, reaction temperature is 30 ° C, In an etching time of 60 seconds, a portion of the stopper layer 30 is exposed to form a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated. While the first etching liquid was washed with pure water and dried, the substrate was taken out and the surface was observed. As a result, damage to the semi-transmissive layer 2 was not observed, and it was confirmed that the stopper layer 30 was used as an etching stopper layer. Effect. 46 200944936 Next, the substrate is immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide and water (aqueous solution of hydrogen peroxide (35%): aqueous potassium hydroxide solution (30/〇). Water-16 . . . 32, the reaction temperature is 3〇〇c, the last time is 65 seconds), and the blocking layer 30 is etched, thereby forming a pattern of the laminated layer 30, the light shielding layer 43 and the anti-reflection layer 45. . Then, the photoresist was removed by a specific photoresist stripping solution, and the surface of the pattern was confirmed. As a result, no damage was observed on the pattern surface of the semi-transmissive layer 20, and the effect of the layer 30 was exhibited. The surface of the anti-reflection layer 45 has no problem. After the substrate is sufficiently cleaned to form a substrate having a pattern of the barrier layer 3, the light shielding layer 43 and the anti-reflection layer 45, a photoresist is coated on the surface of the substrate (made by AZ Electronic Materials). AZRFP-230K2) and pre-hardened. After the photoresist is cured, exposure of the second test pattern is performed (jet printer manufactured by ORC, light source CHm_2〇〇〇, exposure under ultrahigh pressure mercury lamp for 20 seconds), development (pMER manufactured by Tokyo Yinghua Co., Ltd.), development Liquid, temperature 30 ° C '1 min) and formal hardening (Yamat〇 Scientific DX402 constant temperature dryer, 12 〇. (:, 1 〇 minutes). Next, the substrate is immersed in the first etching solution, that is, peroxy acid , a mixture of ammonium cerium nitrate and water (per-acid acid: ammonium citrate: water = 3: 15: 82, reaction temperature is 30 〇 C, etching time is 60 seconds), and the light-shielding layer 43 is resistant A portion of the buildup pattern of the reflective layer 45 and a portion of the semi-transmissive layer 20 are etched. Then, the photoresist is removed by a specific photoresist stripper to form a light-shielding region ia having the anti-reflective layer 45, and the laminate is The barrier layer 30 and the second semi-transmission region lb of the penetrating layer 20, the first semi-transmissive region lc having only the semi-transmissive layer, and the four-gray mask of the fully penetrating region Id. 47 200944936 The formed mask confirms the edge of the pattern, and as a result, it is confirmed that there is no pattern side of each layer. The edge shape or the cone shape and the appearance defect are very good. The transmittance of the i-th half-transmissive region 1 c, the semi-transmissive layer 20 and the second half of the barrier layer 30 are penetrated by using one of the test patterns. The transmittance of the region lb, the optical density and film thickness of the light-shielding region la, and the surface observation result after the formation of the final pattern, and when the mask substrate is immersed in the Cr etching solution (5 minutes, 10 minutes, 20 minutes) The results of the surface observation and the surface observation after the impregnation of the lye in the state in which the barrier layer 30 was exposed after the composite layer 40 was not shown in Table 1 (Example 7) Example 7 was changed to the barrier layer of Example 6. A design example of film thickness of 3 Å. In Example 7, the film thickness of the stopper layer 30 is set to 200 Αβ semi-transmissive layer 2 〇, light shielding layer 43 by simply adjusting the sputtering time of the stopper layer 3 〇. The film thickness and film formation conditions of the antireflection layer 45 were the same as in Example 1. In the same manner as in Example 6, the substrate was immersed in a second etching solution, that is, a mixture of peroxyacid, ammonium cerium nitrate and water (peracid acid). : ammonium cerium nitrate: water = 3: ΐ 5: Μ, the reaction temperature is 3 (TC, the last time is 6 〇 In the case where a portion of the stopper layer 30 is exposed by #, a pattern in which the light-shielding layer 43 and the anti-reflection layer 45 are laminated is formed. In this state, after the first etching solution is washed with pure water and dried, When the substrate was taken out and the damage caused by the surface of the sheet was observed, the effect of the stopper layer 3 as the residual stopper layer was confirmed. Next, the substrate was immersed in the second remaining liquid. A mixture of nitrogen oxides, nitrogen oxides and water (hydrogen peroxide (35%) aqueous solution: aqueous hydroxide solution 48 200944936 (30%): water =: 1 : 32, reaction temperature 30 ° C, etching time 13 In the second), the layer 3 is prevented from being silver-engraved, thereby forming a pattern in which the barrier layer 30, the light shielding layer 43, and the anti-reflection layer 45 are laminated. Then, the photoresist is removed by a specific photoresist stripping solution to confirm the surface of the pattern. As a result, no damage is observed on the pattern surface of the semi-transmissive layer 20, and the surface of the anti-reflective layer 45 has no problem. Then, after the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the anti-reflection layer 45 is sufficiently cleaned, the substrate is immersed in the first etching liquid, that is, perchloric acid or ammonium cerium nitrate, in the same manner as in the sixth embodiment. And the mixture of water (pervaporic acid: ammonium cerium nitrate: water = 3: 15: 82, reaction temperature is 30. (:, the remaining time is 60 seconds) in the 'light shielding layer 43 and anti-reflection layer 45 A portion of the buildup pattern and a portion of the semi-transmissive layer 20 are etched. Then, the photoresist is removed by a specific photoresist stripper to form a light-shielding region la having the anti-reflective layer 45, and a resist layer 3 is laminated. The second semi-transmissive region lb of the tantalum and semi-transmissive layer 20, the first semi-transmissive region lc of the semi-transmissive layer 20, and the four-gray-order mask of the full-penetration region id. The cover confirmed the edge of the pattern, and as a result, it was confirmed that the pattern edge shape or the taper shape and the appearance defect of each layer were not in good condition. The transmittance of the first semi-transmissive region lc and the semi-penetrating layer 20 were laminated by using one of the test patterns. And the transmittance of the second semi-penetrating region lb of the blocking layer 30, the light shielding region The optical density and film thickness of a, the surface observation result after the formation of the final pattern, the surface observation result when the mask substrate was immersed in the Cr etching solution (5 minutes, 10 minutes, 20 minutes), and in the composite layer 40 Surface observation after immersion in lye in the state in which the stopper layer 30 was exposed after exposure 49 200944936 The results are shown in Table 1. (Example 8) Example 8 is a design example in which the film thickness of the stopper layer 30 of Example 6 was changed. In the eighth embodiment, the film thickness of the stopper layer 30 is set to 300 A by simply adjusting the sputtering time of the stopper layer 30. The film thickness of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 45 is The film formation conditions were the same as in Example 1. In the same manner as in Example 6, 'the substrate was immersed in a first etching liquid, that is, a mixture of peroxy acid, ammonium cerium nitrate and water (pervaporic acid: ammonium cerium nitrate: water = 3: 15: 82, a reaction temperature of 30 ° C, and an etching time of 60 seconds), a portion of the resist layer 30 is exposed by etching to form a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated. In this state, after the third etching solution is washed away with pure water and dried, the substrate is taken out and When the surface was observed, the damage to the semi-transmissive layer 2 was not observed. The effect of the blocking layer 30 as an etching stopper layer was confirmed. Next, the substrate was immersed in the second etching liquid, that is, hydrogen peroxide or hydrogen peroxide. Mixture of potassium and water (aqueous solution of hydrogen peroxide (35%): aqueous solution of potassium hydroxide (3〇%): water = 16: 1 : 32 'The reaction temperature is 30 ° C, the etching time is 2 〇〇〇 seconds In the middle, the blocking layer 30 is etched, thereby forming a pattern in which the blocking layer 30, the light shielding layer 43, and the anti-reflection layer 45 are laminated. Then, the photoresist is removed by using a specific photoresist stripping solution, and the surface of the pattern is removed. As a result, it was confirmed that the pattern surface of the semi-transparent layer 2 was the same as that at the time of the t-etching, and no damage was observed, and the surface of the anti-reflection layer 45 was not problematic. Then, after sufficiently cleaning the substrate on which the pattern formed by the stopper layer 3, the light shielding layer 43, and the anti-reflection 50 200944936 radiation layer 45 is formed, the substrate is bonded to the embodiment 6, and the first surname is inflated. A mixture of acid, lanthanum nitrate and water (per-gas acid acid): water = 3: 15: 82, reaction temperature is 3 『c, _ seconds, and the light-shielding layer 43 and the anti-reflection layer 45 The laminate pattern = portion, and a portion of the semi-transmissive layer 20 is etched.

Then, the photoresist is removed by using a specific photoresist stripping solution to form a second semi-transmissive region lb in which the light-shielding region la having the anti-reflective layer 45 is present, and the layer-cutting layer and the semi-penetrating layer 20 are laminated. The fourth semi-transmissive region lc of the semi-transmissive layer and the four-gray reticle of the fully penetrating region Id. The edge of the pattern was confirmed for the formed mask, and as a result, it was confirmed that the edge shape, the tapered shape, and the appearance defect of the pattern of each layer were not in good condition. Using a portion of the test pattern, the transmittance of the ith semi-transmissive region lc, the transmittance of the semi-transmissive layer 20 and the second semi-transmissive region lb of the blocking layer 30, the optical density of the light-shielding region la, and The film thickness and the surface observation result after the formation of the final pattern, the surface observation result when the mask substrate was immersed in the Cr money engraving liquid (5 minutes, 10 minutes, 20 minutes), and exposed after the composite layer 40 was burned. The surface observation result after the layer of the barrier layer 30 was immersed in the test liquid was not in Table 1. Further, even in the state in which the chromium compound film of the semi-transmissive layer 20 is nitrogen, the ratios of chromium, oxygen, and nitrogen in the film are 44.0 to 50.5 atm%, respectively, in the states of Examples 1 to 5 and Examples 6 to 8. In the case of 25.0 to 29.0 atm% and 25.5-28.0 atm%, ESCA quantitative analysis value, the same results as in Examples 1 to 5 and Examples 6 to 8 were obtained. In the above Examples 1 to 8, the semi-transmissive layer 20 was formed of a compound of chromium, nitrogen, and oxygen 51 200944936. In the following Comparative Examples 1 to 8, an example in which the semi-transmissive layer 20 is replaced with a chrome metal will be described. Further, the blocking layer 30' light shielding layer 43 and the antireflection layer 45 are the same as those of the first to eighth embodiments. (Comparative Example 1) In Comparative Example 1, first, it was polished and planarized and sufficiently washed.

The quartz substrate 10 was placed on a holder in a sputtering apparatus, and reactive sputtering was carried out using a commercially available metal chromium target (99.99% or more). As for the sputtering, after exhausting to lxlO4 pa, it is kept at 1χ1〇-1 while introducing argon gas.

Metal chromium is sputtered in the environment of the vacuum apparatus of Pa, thereby forming a film as the semi-transmissive layer 20. At this time, the semi-transmissive layer 2 was directly formed on the substrate so that the transmittance of the i-line (wavelength 365 nm) was 50%. Next, the metal chromium material was replaced with a titanium metal dry material, and the stopper layer 30 was formed on the surface of the semi-transmissive layer 20 in such a manner that the film thickness reached 1 〇〇 A (10 nm).

At this time, the yttrium bond is formed into a titanium compound 30 while being introduced into the vacuum apparatus while introducing nitrogen gas and oxygen gas (the ratio of titanium, oxygen, and nitrogen in the film is 26.5 to 36.5 atm%, 32.0 to 39.5). Atm% and 29.5~41.0 atm%, ESr δ β quantitative analysis value). At this time, the sputtering system formed a titanium compound while introducing nitrogen gas and oxygen at a rate of 98:: while maintaining the inside of a vacuum apparatus of 1 x 10 -1 Pa. The metal foil target was replaced by a metal chromium target, and the film thickness was 700 (70 nm) to form a chromium film as the light shielding layer 43. The sputtering at this time was formed in the environment of the vacuum apparatus in which only one side of the gas was kept at lx10-丨Pa. 52 200944936 Its optical density is about 3. ,, for exposure

In the environment of the vacuum device, the gas is formed into a thickness of 700 A with the complex film formed here, and is irradiated with light (3 65 nm, 43 6 nm) with 4 chrome reaction, thereby achieving a film thickness of 3 〇〇 In this manner, a chromium oxynitride film which is a chromium compound as the antireflection layer 45 is formed.

After the substrate of the film-formed substrate was ultrasonically cleaned, a photoresist (AZRFP-230K2 manufactured by AZ Electronic Matedals) was coated on the surface of the substrate for the mask, and pre-hardened. Further, in the photoresist application step, the surface of the substrate for the mask is rubbed without using chemicals, electricity, or ultraviolet rays. Hereinafter, the same is true for the same processing. After the photoresist is hardened, exposure of the i-th test pattern (Jet Printer manufactured by 〇RC, light source CHM-2000, exposure under ultra-high pressure mercury lamp for 20 seconds) and development (PMER manufactured by Tokyo Yinghua Co., Ltd.) are performed. Developer, temperature 30C, 1 minute) and formal hardening (Yamat〇Scientific thermostat dryer, 120 ° C, 10 minutes). Then, the substrate is immersed in the i-th etching liquid, that is, a mixture of peroxy acid, ammonium cerium nitrate and water (per-acid acid: ammonium cerium nitrate. water - 3.15:82, reaction temperature is 3〇»c, etching The time is 6 sec., whereby a portion of the stopper layer 30 is exposed, and a pattern in which the light shielding layer 43 and the anti-reflection layer 45 are laminated is formed. ^ ^ 丄 列 状 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The damage caused by the film can confirm the effect of the barrier layer. Next, the substrate was immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium oxyhydroxide, and water (aqueous solution of hydrogen peroxide (35%): aqueous potassium hydroxide solution (30%): water = 16:1: 32, the reaction temperature is 3 (rc, etching time is 85 seconds), and the blocking layer 30 is etched. Then, the photoresist is removed by using a specific photoresist stripping solution, and the surface of the pattern is confirmed, and the result is half worn. The surface of the transmissive layer 20 is not damaged, and the surface of the anti-reflective layer 45 is not problematic. Next, the semi-penetrating layer 20 (semi-transmission pattern 2〇a) and the blocking layer 30 (blocking pattern) are sufficiently cleaned. After 30a) and the pattern substrate of the composite layer 40 (composite pattern 4〇a), a photoresist (AZRFP_23〇k2) manufactured by AZ Eieetrc nic Materials is coated on the surface of the substrate and pre-hardened. . After the photoresist is cured, exposure of the second test pattern is performed (Jet Printer manufactured by 〇rc Manufacturing Co., Ltd., light source CHM-2000, exposure under an ultrahigh pressure mercury lamp for 2 sec seconds), and development (PMER, manufactured by Tokyo Yinghua Co., Ltd.) Developer, temperature 3 (rc, j minutes) and formal hardening (DX402 tempering dryer manufactured by Yamato Scientific, 120 ° C, 10 minutes). Then, the substrate is immersed in the first etching solution, ie, sulphuric acid, a mixture of ammonium cerium nitrate and water (pervaporic acid: ammonium cerium nitrate: water = 3: 15 : 82, reaction temperature is 30 ° C, the remaining time is 60 seconds), and the light shielding layer 43 and anti-reflection A portion of the buildup pattern of the layer 45 and a portion of the semi-transmissive layer 20 are etched. Then the photoresist is removed by a specific photoresist stripper to form a light-shielding region having an anti-reflective layer. 3 〇 and the second semi-transmissive region lb of the semi-transmissive layer 20, only the semi-transmission layer of the i-th half penetrating 54 200944936 region lc, and the full-transmission region id of the four gray-scale mask. The reticle confirms the edge of the pattern, and as a result, it is confirmed that there is no pattern edge shape of each layer. Cone shape and appearance defects, the state is very good. Using one of the test patterns, the transmittance of the second semi-transparent region lc, the semi-transmissive layer 20 and the second semi-penetrating region lb of the barrier layer 30 are worn. The transmittance, the optical density and film thickness of the light-shielding region la, the surface observation result after the formation of the final pattern, and the surface observation result when the substrate for the mask is immersed in the engraving solution of the cr (5 minutes, 10 minutes, 20 minutes) The surface observation result after immersing in the lye in the state in which the blocking layer 30 was exposed after the etching of the composite layer 40 was shown in Table 1. (Comparative Example 2) Comparative Example 2 was a film in which the blocking layer 3 of Comparative Example 1 was changed. A thick design example. In Comparative Example 2, the film thickness of the stopper layer 30 was set to 200 by simply adjusting the sputtering time of the stopper layer 3, the semi-transmissive layer 2, the light-shielding layer 43, and the anti-reflection. The film thickness and film formation conditions of the layer 45 were the same as those of the comparative example. In the same manner as in the comparative example 1, the substrate was immersed in a mixture of peroxylic acid, ammonium cerium nitrate and water as the first etching liquid (pervaporic acid: cerium nitrate) Ammonium: water = 3 : ^ 82, reaction temperature is 3 (TC, etching time is 60 seconds), borrowed Etching exposes a portion of the stopper layer 30 to form a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated. While maintaining the state, the first etching liquid is washed with pure water and dried, and then the substrate is taken out and the surface is observed. The damage to the chromium thin film as the semi-transmissive layer 20 was not observed, and the effect of the blocking layer 3 was confirmed. Then, the substrate was immersed in the second etching liquid, that is, hydrogen peroxide, hydrogen and oxygen 55 200944936, and potassium. Water mixture (hydrogen peroxide (35%) aqueous solution: potassium hydroxide aqueous solution (3〇 ° / 〇): water = 16: 1: 32, reaction temperature is 3 (TC, etching time is 17 〇 seconds) The blocking layer 30 is etched, thereby forming a pattern in which the blocking layer 3, the light shielding layer 43, and the anti-reflection layer 45 are laminated. Then, the photoresist was removed by using a specific photoresist stripping solution, and the surface of the pattern was confirmed. As a result, the pattern surface of the semi-transparent layer 2 was not damaged, and the surface of the anti-reflective layer 45 was not problematic.

Then, the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the antireflection layer 45 was sufficiently cleaned, and then the same as the comparative example, the pervaporic acid, ammonium cerium nitrate and water, were immersed in the same etching solution. The mixed solution (pervaporic acid: ammonium cerium nitrate: water = 3: 15 : 82, reaction temperature of 3 Torr. (:, etching time: 60 seconds), and the laminated pattern of the light shielding layer 43 and the antireflection layer 45 A portion of the portion and a portion of the semi-transmissive layer 20 are etched.

Then, the photoresist is removed by a specific photoresist stripping solution to form a second semi-transmissive region lb in which the light-shielding region la having the anti-reflective layer 45 is present, and the barrier layer 3 and the semi-transmissive layer 20 are laminated. The first semi-transmissive region lc having a semi-transmissive layer and a four-gray reticle having a full penetration region id. The edge of the pattern was confirmed for the formed mask, and as a result, it was confirmed that the edge shape, the tapered shape, and the appearance defect of the pattern of each layer were not in good condition. Using a portion of the test pattern, the transmittance of the ith semi-transmissive region u, the transmittance of the semi-transmissive layer 20 and the second semi-transmissive region lb of the blocking layer 30, the optical density of the light-shielding region la, and The film thickness and the surface observation result after the formation of the final pattern, the surface observation result when the photomask substrate was immersed in the Cr etching liquid (5, 8, 10 minutes, 20 minutes), and the etching was performed at Fu Ren ^ 56 200944936 40 The surface observation results after immersion in the lye state in the state where the stopper layer 30 was exposed later are shown in Table 1. (Comparative Example 3) Comparative Example 3 is a design example in which the film thickness of the stopper layer 30 was changed. In Comparative Example 3, the film thickness of the stopper layer 30 was set to 300 A by simply adjusting the sputtering time of the stopper layer 30. The film thickness and film formation conditions of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 45 were the same as in Comparative Example 1.

In the same manner as in Comparative Example 1, the substrate was immersed in a first etching solution, that is, a mixture of peroxylic acid, cerium nitrate, and water (perchloric acid: ammonium nitrate: water = 3:1 5:82, reaction temperature: 30) In the case where °C 'etching time is 60 seconds, a part of the stopper layer 30 is exposed by etching, and a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated is formed. While the first etching liquid was washed with pure water and dried, the substrate was taken out and the surface was observed. As a result, damage to the chromium thin film as the semi-transmissive layer 20 was not observed, and the blocking layer 3 was confirmed. effect. Next, the substrate was immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide, and water (aqueous solution of hydrogen peroxide (35%): aqueous potassium hydroxide solution (30%): water = 16: 丨: 32, the reaction temperature is 3 〇β (:, etching time is _ seconds), and the blocking layer 30 is etched, thereby forming a pattern in which the blocking layer 30, the light shielding layer 43, and the anti-reflection layer 45 are laminated. No damage was caused to the pattern, and then the surface of the photoresist was confirmed by a specific photoresist stripping solution, and as a result, the surface of the semi-transmissive layer 2 was further free of the surface of the anti-reflective layer 45. After the substrate of the pattern composed of the stopper layer 3G, the light-shielding layer Μ, and the anti-reflection layer 57 200944936, the same layer as the first etching solution was mixed with a mixture of peroxy acid, ammonium cerium nitrate and water. (per-acid acid: nitric acid: water = 3: 15: 82, reaction temperature is 301, etching time is 6 sec), and the _ part of the laminated pattern of the light-shielding layer 43 and the anti-reflection layer 45 and One portion of the semi-transmissive layer 20 is etched. Then 'using a specific photoresist stripper to illuminate the light The resist is removed to form a second semi-transparent region lb having a light-shielding region la having an anti-reflection layer 45, a barrier layer 3 and a semi-penetrating layer 20, and a semi-transparent layer The area 1c and the four-gray mask of the full-penetration area Id. ® confirms the edge of the pattern on the formed mask, and as a result, it is confirmed that there is no pattern edge shape or cone shape and appearance defects of each layer, and the state is very good. In part, the transmittance of the second semi-transmissive region lc, the semi-transmissive layer 20 and the second semi-transmissive region of the blocking layer 30 are compared to the transmittance, the optical density and film thickness of the light-shielding region la, and finally The surface observation result after pattern formation, the surface observation result when the mask substrate was immersed in the core etching liquid (5 minutes, 10 minutes, 20 minutes), and the state in which the stopper layer 30 was exposed after the composite layer 40 was etched The surface was observed after immersion in lye. The result 7F is shown in Table 1. (Comparative Example 4) Comparative Example 4 is a design example in which the film thickness of the stopper layer 3 is changed. In Comparative Example *, the stopper layer 30 is simply adjusted. Sputtering time, which will prevent the film thickness setting of layer 3 The thickness of the semi-transmissive layer 2, the light-shielding layer 43, and the anti-reflection layer 45 and the film formation conditions were the same as in Comparative Example 1. In Comparative Example 4, the substrate was immersed in the 帛i (four) solution. Gas acid, 58 200944936 lanthanum nitrate and water mixture (perchloric acid: ammonium nitrate ammonium: water = • 13.82, reaction temperature 30 ° C, etching time is 6 〇 seconds), by etching to prevent the layer One of the portions 30 is exposed, and a pattern of the light-shielding layer 43 and the anti-reflection layer 45 is formed. In this state, after cleaning the i-th etching liquid with pure water and drying it, the substrate is taken out and the surface is observed, and the result is not visible. As a damage caused by the chromium thin film of the semi-transmissive layer 20, the effect of the blocking layer can be confirmed.

Next, the substrate is immersed in a mixture of peroxidation gas, potassium oxychloride, and water, which is a second-order engraving liquid (hydrogen peroxide (35%) aqueous solution: potassium hydroxide aqueous solution (3 〇〇/〇): water = 16 : 丨: 32, the reaction temperature is 3 generations, and the etching time is

In the second, the blocking layer 30 is etched, thereby forming a pattern in which the blocking layer 3, the light shielding layer 43, and the anti-reflection layer 45 are laminated. Then, the photoresist is removed by using a specific photoresist stripping solution, and the surface of the pattern is confirmed. As a result, the surface of the pattern of the semi-transmissive layer 2G is not produced without the surface of the other anti-reflective layer 45. After the substrate was formed by a pattern of ...H...3 and anti-reverse 5, it was the same as the comparative example, and it was impregnated with a mixture of peric acid, acid (4) and water (15). : 82 ' The reaction temperature is 30 ° C, and the time of the engraving is (4)), and a part of the pattern of the light-shielding layer 43 and the anti-reflection layer 45 and a part of the semi-transmissive layer 20 are engraved. The specific photoresist stripping solution removes the photoresist to form a light-shielding region 1a that is half-pierced as the anti-reflective layer 45, a second semi-transmissive region lb in which the barrier layers 30 and 20 are laminated, and only a semi-transmissive layer. The second half 59 200944936 penetrates the area lc, and the four-gray mask of the full penetration area Id. The edge of the pattern was confirmed for the formed mask, and as a result, it was confirmed that the edge shape, the tapered shape, and the appearance defect of the pattern of each layer were not in good condition. Using one of the test patterns, the transmittance of the first semi-transmissive region lc, the transmittance of the semi-transmissive layer 20 and the second semi-transmissive region lb of the blocking layer 30, the optical density of the light-shielding region la, and The film thickness and the surface observation result after the formation of the final pattern, the surface observation result when the mask substrate was immersed in the Cr contact liquid (5 > clock, 10 minutes, 20 minutes), and after the composite layer 40 was etched The surface observation results after the immersion in the state in which the stopper layer 30 was exposed were shown in Table 1. (Comparative Example 5) Comparative Example 5 is a design example in which the film thickness of the stopper layer 30 was changed. In Comparative Example 5, the film thickness of the stopper layer was set to 500 A by simply adjusting the antimony time of the stopper layer 30. The film thickness and film formation conditions of the semi-transmissive layer 20, the light shielding layer 43, and the anti-reflection layer 45 were the same as in Comparative Example 1. In the same manner as in Comparative Example 1, the substrate was immersed in a first etching solution, that is, a mixture of peroxyacid, nitric acid, and water (pervaporic acid: cerium nitrate: water = 3: 丨 5 : 82, reaction temperature: 30 t) In the case where the etching time is 60 seconds, a portion of the stopper layer 30 is exposed by etching to form a pattern in which the light shielding layer 43 and the antireflection layer 45 are laminated. While the second etching liquid was washed with pure water and dried, the substrate was taken out and the surface was observed. As a result, damage to the semi-transmissive layer 2 was not observed, and the effect of the blocking layer 30 was confirmed. Next, the substrate is immersed in a second etching liquid, that is, hydrogen peroxide, hydrogen oxygen 200944936 _, and water iota solution (hydrogen peroxide (35%) aqueous solution: aqueous solution of hydrogen oxyhydroxide (30%)·water = 16: I:], w, the reaction temperature is 3 (TC, etching time is 420 seconds), and the layer 30 is prevented from being engraved, thereby forming a laminate having the barrier layer 3, the light shielding layer 43 and the anti-reflection layer 45. The pattern is then removed. The resist remover removes the photoresist to confirm the surface of the pattern. As a result, the surface of the semi-transmissive layer 20 is not scratched, and the surface of the anti-reflective layer 45 has no problem. ❹ Next, the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the anti-reflection layer 45 is sufficiently cleaned, and then, in the same manner as in the comparative example, the first surname liquid is impregnated with pervaporic acid and nitric acid. A mixture of water (perchloric acid: acid, ammonium, water = 3:15:82, reaction temperature of 3 (TC's time is a private clock), and the light-shielding layer 43 and the anti-reflection layer 45 are laminated. A portion of the pattern and a portion of the semi-transmissive layer 20 are etched. Then, the photoresist is removed using a specific photoresist stripper, and the shape is removed. There is a light-shielding region la having an anti-reflection layer, a second semi-transmission region lb having a barrier layer 3〇 and a semi-through T layer 20, an ith semi-transparent region lc having only a semi-transmissive layer, and a full wear The four-gray mask of the area id is confirmed. The edge of the pattern is confirmed on the formed mask, and as a result, it is confirmed that the pattern edge shape or the cone shape and the appearance defect of each layer are not in a good state. Using one of the test patterns, the third half is worn. The transmittance of the transmissive region lc, the transmittance of the semi-transmissive layer 20 and the second semi-penetrating region ib of the blocking layer 30, the optical density and film thickness of the light-shielding region la, and the surface observation result after the formation of the final pattern When the mask substrate is immersed in the Cr etching solution (5 minutes, minutes, 20 minutes), the surface observation result, and after the composite layer 200944936 40 is exposed, the barrier layer 30 is exposed and the lye is impregnated. The surface observation results are shown in Table 1. (Comparative Example 6) Comparative Example 6 differs from the comparative example id in that the chemical composition of the blocking layer 3 is replaced by a titanium compound film (a compound of titanium and nitrogen, oxygen) into titanium (Ti). An example of the case of a film. The layer 20, the light shielding layer 43, and the antireflection layer 45 were the same as those of Comparative Examples 1 to 5. In Comparative Example 6, 'a quartz substrate (transparent substrate 1) which was planarized and sufficiently cleaned by polishing was first placed in a sputtering apparatus. On the holder, ◎ is sprayed with a commercially available metal chromium target (99. 99% or more). As for sputtering, once it is exhausted to lxlO·4 Pa, it is kept while only introducing argon. Chromium is sputtered in the environment of the vacuum apparatus of lxlO·1 Pa, thereby forming a chromium thin film as the semi-transmissive layer 20. At this time, the transflective layer 2 is made to have a transmittance of i-line (wavelength 365 nm). The film is directly formed on the substrate by 50%. Next, the metal chrome material was replaced with a titanium metal dry material, and a stopper layer 3 was formed on the surface of the semi-transmissive layer 20 in such a manner that the film thickness reached 丨〇〇 A (10 nm). At this time, the sputtering was performed while the argon gas was introduced while being held at 1 χ1 (the titanium thin film was formed in the environment of the vacuum device), and then replaced with another metal chromium target to have a film thickness of 7 〇〇 ( A chromium film as the light shielding layer 43 is formed in a manner of 7 〇 nm). At this time, sputtering is formed in an atmosphere of a vacuum apparatus which is held in a lxl 〇-i Pa while introducing only argon gas. 700 A, its optical density is about 31, and it has a light-shielding function for exposure light (365 nm, 436 nm). Then it replaces the metal-chromium 62 used for film formation of the semi-transparent layer 2 2009 200944936 Target 'When argon gas, oxygen gas, and nitrogen gas are introduced while being held in a vacuum apparatus of IxlO·1 pa, the gas is reacted with chromium while performing sputtering, thereby forming a chromium compound as the antireflection layer 45. After the ultrasonically cleaned the substrate on which the film is formed in each of the tanks, the neutral detergent, and the pure water, the photoresist is coated on the surface of the substrate for the mask (AZ Electronic) AZRFP-230K2 manufactured by Materials After curing the photoresist, 'exposure of the first test pattern (Jet Printer manufactured by ORC, light source CHM-2000, exposure under ultra-high pressure mercury lamp for 20 seconds), and development (PMER made by Tokyo Yinghua Co., Ltd.) Developer, temperature 30C '1 minute) and formal hardening (DXA geek dryer manufactured by Yainato Scientific, 120 C, 10 minutes). Then, immersed in the ith remaining liquid, ie, sulphuric acid, ammonium cerium nitrate and water a mixture (pervaporic acid: ammonium cerium nitrate: water = 3:15:82, reaction temperature of 3 (rc, etching time: 6 sec), thereby partially exposing one of the blocking layers 30 to form a laminate There is a pattern of the light-shielding layer 43 φ and the anti-reflection layer 45. After this state, the i-th etching liquid is washed with pure water and dried, the substrate is taken out and the surface is observed, and as a result, the chromium film as a semi-transmissive layer is not observed. The damage caused by the layer 3 can be confirmed. Next, the substrate is immersed in a second etching solution, that is, a mixture of hydrogen peroxide, potassium hydroxide and water (hydrogen peroxide (35%) aqueous solution: hydroxide Potassium aqueous solution (3〇%): water=16 : 1 : 32 The reaction temperature is 3 CTC, the etching time is 65 seconds, and the layer 3 is prevented from being added, thereby forming a pattern in which the barrier layer 30, the light shielding layer 43 and the anti-reflection layer 45 are laminated. 63 200944936 The photoresist stripping solution removes the photoresist and confirms the surface of the pattern. As a result, the pattern surface of the semi-transmissive layer 20 is not damaged, and the surface of the anti-reflective layer 45 has no problem. Then, the 'cleaning layer is formed by the sufficient layer. After the substrate of the pattern formed by the light-shielding layer 43 and the anti-reflection layer 45, a photoresist (AZRFP_23〇K2 manufactured by AZ Electronic Materials) was applied to the surface of the substrate and pre-cured. After the photoresist is cured, exposure of the second test pattern is performed (Jet Printer manufactured by 〇RC, light source CHM-2000, exposure under ultrahigh pressure mercury lamp for 2 sec.), and development (pMER manufactured by Tokyo Yinghua Co., Ltd.).显® liquid solution 'temperature 30eC, 1 minute' and formal hardening (Yamat〇Scientific DX402 constant temperature dryer, 12 (rc, 1 〇 minutes). Then, immersed in the first etching solution, ie, peroxyacid, lanthanum nitrate A mixture of ammonium and water (pervaporic acid: ammonium cerium nitrate: water = 3: 15 : 82, reaction temperature of 3 Torr. 〇, etching time of 60 seconds), and the light shielding layer 43 and the antireflection layer 45 The portion of the laminate pattern and a portion of the semi-transmissive layer 20 are etched. Then, the photoresist is removed by using a specific photoresist stripper to form a light-shielding region la having the anti-reflection layer 45, and a barrier layer is laminated. 3〇 and the second semi-penetrating region lb of the semi-transmissive layer 20, the fourth transmissive region lc having only the semi-transmissive layer, and the full-transparent region 1 (the four-gray-order mask of 1). The reticle confirms the edge of the pattern, and as a result, it is confirmed that there is no pattern edge shape or cone shape of each layer and Observing the defect, the state is very good. Using one of the test patterns, the transmittance of the i-th semi-transparent region u, the semi-penetrating layer 20 of the laminate, and the penetration rate of the second semi-penetrating region of the blocking layer 3〇 The optical density and film thickness of the light-shielding area la, the final pattern formation 64, the surface observation result after 200944936, and the surface observation result when the mask substrate was immersed in the Cr recording liquid (5 minutes, 10 minutes, 20 minutes) The surface observation result after impregnation of the alkali layer in the state in which the barrier layer 30 was exposed after the etching of the composite layer 40 is shown in Table 1. (Comparative Example 7) Comparative Example 7 is a design example in which the film thickness of the stopper layer 3 is changed. In Comparative Example 7, the film thickness of the stopper layer was set to 200 A by simply adjusting the sputtering time of the stopper layer 3, and the film thickness of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 45. The film formation conditions were the same as in Comparative Example 1. In the same manner as in Comparative Example 1, the substrate was immersed in a j-th etching liquid, that is, a mixture of peroxy acid, ammonium cerium nitrate and water (perchloric acid: ammonium cerium nitrate: water = 3) : Η: 82, the reaction temperature is 30〇C, the last time is 60 seconds), and it is blocked by the residual One of the layers 3 is partially exposed, and a pattern of the light-shielding layer 43 and the anti-reflection layer 45 is formed. / In this state, the i-th liquid is washed with pure water and dried, and then the substrate is taken out and the surface is observed. The damage to the chromium thin film as the semi-transmissive layer 20 was not observed, and the effect of the blocking layer 3 was confirmed. Next, the substrate was immersed in the second residual liquid, that is, a mixture of peroxidizing gas and nitrogen-oxygen water. Liquid (iv) hydrogen (35%) aqueous solution: aqueous hydroxide solution aqueous solution 16.1 .32 'reaction temperature is 3 ° C, etching time is 13 〇 3 乂 0, and 'will prevent layer 3G from (4), thereby A pattern in which a barrier layer, a light shielding layer 43, and an antireflection layer 45 are laminated is formed. Then, the photoresist was removed by using a specific photoresist stripper, and as a result, the pattern surface of the semi-transparent layer 2 () was not damaged. 65 200944936 Further, the surface of the anti-reflection layer 45 was free from problems. Then, after the substrate having the pattern formed by the stopper layer 30, the light shielding layer 43, and the antireflection layer 45 was sufficiently cleaned, the substrate was immersed in the first surname liquid, that is, the peroxy acid and the nitric acid were the same as in the comparative example 6. And a mixture of water (pervaporic acid: ammonium cerium nitrate: water = 3: 15 : 82, reaction temperature of 30. (:, the remaining time is 60 seconds), and the light shielding layer 43 and the anti-reflection layer 45 A portion of the buildup pattern and a portion of the semi-transmissive layer 20 are etched. Then, the photoresist is removed by a specific photoresist stripper to form a light-shielding region la having the anti-reflective layer 45, and a barrier layer 3 is laminated. The second semi-transmissive region lb of the tantalum and semi-transmissive layer 20, the first semi-transmissive region lc having only the semi-transmissive layer, and the four-gray-order mask of the full-penetration region id. The edge of the pattern was confirmed, and it was confirmed that the pattern edge shape or the taper shape and the appearance defect of each layer were not in good condition. The transmittance of the first semi-transmissive region lc, the semi-penetrating layer 20 and the laminated layer were laminated with one of the test patterns. The penetration rate of the second half-penetrating region lb of the blocking layer 30, the light-shielding region la The surface observation result after the concentration and the film thickness and the final pattern formation, the surface observation result when the mask substrate was immersed in the Cr etching solution (5 minutes, 10 minutes, 20 minutes), and the surface of the composite layer 40 The surface observation result after the immersion in the state in which the stopper layer 30 was exposed was shown in Table 1. (Comparative Example 8) Comparative Example 8 is a design example in which the film thickness of the stopper layer 30 was changed. The film thickness of the stopper layer 30 was set to 300 by simply adjusting the sputtering time of the stopper layer 30. The film thickness and film formation conditions of the semi-transmissive layer 20, the light-shielding layer 43, and the anti-reflection layer 200944936 45 and comparative examples 1 is the same as in Comparative Example 1. 'The substrate is immersed in a first etching solution, that is, a mixture of peroxyacid, ammonium cerium nitrate and water (pervaporic acid: ammonium cerium nitrate: water ^ 1 4 3 · 15 · 82, In the case where the reaction temperature was 30 ° C and the etching time was 60 seconds, a part of the stopper layer 30 was partially exposed by the remainder, and a pattern in which the light shielding layer 43 and the antireflection layer 45 were laminated was formed.

While maintaining the state in which the second etching solution was washed with pure water and dried, the substrate was taken out and the surface was observed. As a result, damage to the chromium film as the semi-transparent layer was not observed, and the blocking layer 3 was confirmed. The effect of 〇. Next, the substrate was immersed in a second etching liquid, that is, a mixture of nitrogen peroxide, potassium oxychloride, and water (aqueous solution of hydrogen peroxide (35%): aqueous potassium hydroxide solution (30%): water = 16: 1: 32, the reaction temperature is 3 (rc, etching time is seconds), and the blocking layer is etched, thereby forming a pattern in which the blocking layer 30, the light shielding layer 43, and the anti-reflection layer 45 are laminated. Then, using a specific photoresist The agent stripping solution removes the photoresist and confirms the surface of the pattern. As a result, no damage is observed on the surface of the semi-transmissive layer 2, and the surface of the anti-reflective layer 45 is not problematic. Then, the layer is sufficiently cleaned to form a barrier layer. After the substrate of the pattern formed by the three layers of the light-shielding layer and the anti-reflection layer 45, in the same manner as in the comparative example 6, the first etching liquid, that is, a mixture of perchloric acid, ammonium cerium nitrate and water (peracid acid) :: Ammonium citrate: water = 3:15.8, Cl* Shaw 82, reaction temperature 3 〇t, etching time 60 seconds), and 1 is the layered diagram of the Shiyou layer 43 and the anti-reflection layer 45 Part of the knife, and + penetration | 20 part of the button engraved. Then, using a specific photoresist stripping solution to remove the photoresist ' Formation 67 200944936 There is a light-shielding region la having an anti-reflection layer 45, a second semi-penetration region ib in which the barrier layer 3〇 and the semi-transmissive layer 20 are laminated, and a first semi-penetration region lc having only a semi-transparent layer, And the four-gray reticle of the full penetration area id. The pattern edge of the reticle is confirmed. As a result, it is confirmed that the pattern edge shape or the cone shape and the appearance defect of each layer are in a very good state. Using one of the test patterns, the first The transmittance of the semi-transmissive region lc, the transmittance of the semi-transmissive layer 20 and the second semi-transmissive region lb of the blocking layer 3, the optical density and film thickness of the light-shielding region la, and the final pattern formation The surface observation result, the surface observation result in which the mask substrate was immersed in the Cr etching solution (5 minutes, 10 minutes, 20 minutes), and the state in which the barrier layer 3 was exposed after the bonding of the composite layer 40 was performed. The surface observation after the lye is not shown in Table 1. 68 200944936

G [I ϊ Blocking layer 30 1 KOH 4% -40 ° C impregnation damage 120 minutes later 〇〇〇〇〇〇〇Ο 〇〇〇〇〇〇〇〇 60 minutes later 〇〇〇〇〇〇〇〇〇〇 Cr 〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 之 蚀刻 蚀刻 Cr 〇〇〇〇〇〇〇〇 〇 〇 〇 〇 〇 〇 〇 〇 10 minutes after 〇 〇〇〇〇〇〇〇XX 0 〇〇X < 〇5 minutes later 〇〇〇〇〇〇〇〇XX 〇〇X 〇〇After the formation of the injury Helium penetration rate (436 nm) 〇[58.20 57.96 57.61 59.98 丨58.54 159.66 58.34 46.44 47.36 45.51 45.94 46.87 46.52 47.32 46.89 31.65 23.17 17.91 14.94 12.94 21.53 12.41 7.22 40.21 28.25 22.53 19.4 16.68 26.39 15.25 8.78 Permeability (365 Nm) 〇49.69 50.68 49.41 49.19 51.13 49.54 50.5 49.51 50.11 51.11 49.57 50.58 50.19 51.07 50.6 -〇27.55 20.05 15.77 13.15 00 23.95 13.77 7.97 27.78 19.2 15.76 13.74 11.6 7 23.46 13.51 7.76 Λ 3.27 3.51 3.77 4.01 4.12 3.41 4.05 4.29 3.54 3.76 3.96 4.18 4.34 3.81 4.29 4.41 ei: cd 1245 1353 1450 1541 1649 1250 1345 1447 1170 1274 1381 1475 1575 1176 1275 1372 Multilayer (combination) Λ» Is 5 to CrON (300)/Cr(700)/TiON(100)/CrOx(145)/Sub CrON(300)/Cr(700)/TiON(200)/CrOx(145)/Sub CrON(300)/Cr(700) /TiON(300)/CrOx(145)/Sub CrON(300)/Cr(700)/TiON(400)/CrOx(145)/Sub CK)N(300)/Cr(700)/TiON(500)/ CrOx(145)/Sub CrON(300)/Cr(700)/Ti(100)/CrOx(145)/Sub CrON(300)/Cr(700)/Ti(200)/CrOx(145)/Sub CrON( 300)/Cr(700)/Ti(300)/CrOx(145)/Sub CrON(300)/Cr(700)/TiON(100)/Cr(75)/Sub CrON(300)/Cr(700)/ TiON(200)/Cr(75)/Sub CrON(300)/Cr(700)/TiON(300)/Cr(75)/Sub CrON(300)/Cr(700)/TiON(400)/Cr(75 ) /Sub CrON(300)/Cr(700)/TiON(500)/Cr(75)/Sub CrON(300)/Cr(700)/Ti(100)/Cr(75)/Sub a〇N(300 /Cr(700)/Ti(200)/Cr(75)/Sub CrON(300)/Cr(700)/Ti(300)/Cr(75)/Sub Embodiment __1 Embodiment 1 1 Example 2 Example 3 I Example 4 I Example 5 Example 6 Example 7 Example 8 1 Comparative Example 1 1 Comparative Example 2 1 Comparative Example 3 Comparative Example 4 1 Comparative Example 5 1 Comparative Example 6 | 1 Comparative Example 7 Comparative Example 8 $ 200944936 In the present invention, semi-penetrating properties are formed by using titanium or a compound containing titanium as a main component. The layer 30 can be etched using an etching solution different from the composite layer 40 and the semi-transmissive layer 20, so that patterns can be formed with high precision without causing etching damage to each other by wet etching. Further, since the film formation of the photomask substrate can be completed by one film formation, the mask substrate can be manufactured at low cost, and the gray scale mask can be easily manufactured using the substrate. [Simple description of the map]

Fig. 1 is a longitudinal cross-sectional view showing a substrate for a gray scale mask according to an embodiment of the present invention. Fig. 2 is a longitudinal sectional view showing a gray scale mask according to an embodiment of the present invention. Fig. 3 is an explanatory view (丨) showing a patterning step of a four-gray mask. Fig. 4 is an explanatory diagram (2) showing a patterning step of a four-gray mask. Fig. 5 is an explanatory diagram (3) showing a patterning step of a four-gray mask. Fig. 6 is an explanatory view (丨) showing a patterning step of a three-gray mask. Fig. 7 is an explanatory view (2) showing a patterning step of a three-gray reticle. Ο Fig. 8 is an explanatory view (3) showing a patterning step of the three-gray mask. An electron microscope (SEm) photograph of a test pattern taken from the upper surface. [Description of main component symbols] 1 Substrate for photomask 2 Photomask 1 a Shading area lb 2nd semi-transparent area 1 c 1st semi-transparent area 70 200944936

Id 10 20 20a 30 30a 40 40a 43 43a 45 45a 50 60 '70 Full penetration area transparent substrate translucent layer semi-transmissive pattern blocking layer blocking pattern composite layer composite pattern light shielding layer light shielding pattern anti-reflection layer anti-reflection pattern light resistance Agent mask

Claims (1)

200944936 VII. Patent application scope: 1. A substrate for a photomask, which is formed on the first substrate and is formed on the transparent substrate, and is formed on the transparent substrate and has a semi-transparency to the illumination light. a third layer on the upper side of the layer and substantially shielding the illumination light, and a second layer forming the (four)th layer and the third layer and having semi-transparency to the illumination light, and the first layer and the third layer The layer is insoluble or poorly soluble to the second etching liquid and is more soluble in the second etching liquid than the second layer, and the second layer and the first layer! The layer is more soluble in the second remaining liquid than the third layer, and is insoluble or poorly soluble in the first etching liquid, and the first layer and the third layer are selected from chromium, chromium oxide, and the like. a layer containing one or more components of a group consisting of chromium nitride and chromium oxynitride as a main component, the second layer being selected from the group consisting of titanium, titanium oxide, titanium nitride, and titanium oxynitride. a layer in which one or two or more components are used as a main component, and the first etching liquid is a mixture of ammonium cerium nitrate, peroxy acid and water, and the second cooking liquid is potassium hydroxide, hydrogen peroxide and water. Mixture. 2. The substrate for a photomask according to claim 1, wherein the first layer is directly formed on the transparent substrate. The substrate for a photomask according to the first aspect of the invention, wherein the second layer has a transmittance of 5% or more and 70% or less. 4. The substrate for a photomask according to the first aspect of the invention, wherein the thickness of the second layer is 10 nm or more and 70 nm or less. 5. The substrate for a photomask according to claim 1, wherein the photomask 72 is formed on the transparent substrate, and the first layer, the second layer, and the third layer are sequentially formed on the transparent substrate. The third layer is composed of a light shielding layer that substantially shields the irradiation light and an antireflection layer that is formed on the more surface side than the light shielding layer. 6. The substrate for a photomask according to claim 5, wherein the antireflection layer contains, as a main component, one or more components selected from the group consisting of chromium oxide, chromium nitride, and chromium oxynitride. 7. The substrate for a photomask according to claim 1, wherein the first layer, the second layer, and the third layer are formed by a ship method, an ionization method, or an evaporation method. 8. A type of photomask for manufacturing a photomask substrate, wherein the photomask substrate includes a transparent substrate, a first layer formed on the transparent substrate and having semi-transparency to the irradiation light, and is formed on a third layer on the upper side of the first layer and substantially shielding the illumination light, and a second layer formed between the first layer and the third layer and having semi-transparency to the illumination light, and Φ the first layer The layer and the third layer are insoluble or poorly soluble in the second etching liquid and are more soluble in the first etching liquid than the second layer. The second layer is compared with the second layer and the third layer. It is soluble in the second etching liquid and insoluble or poorly soluble in the first etching liquid, and the first layer and the third layer are each selected from the group consisting of chromium, chromium oxide, chromium carbide, and chromium oxynitride. a layer having one or two or more components as a main component in the group, the second layer being selected from the group consisting of titanium, titanium oxide, nitride, and titanium oxynitride, or two or more components As a main component layer, 73 200944936 The first etching liquid is a mixture of ammonium cerium nitrate, peroxy acid and water, and the second Unloading engraved hydroxide solution, chlorine peroxide and water mixture. A method of manufacturing a reticle, which is a method of manufacturing a reticle using a mask substrate having a transparent substrate and formed on a transparent substrate and having a semi-transparent effect on irradiation light! And a first portion formed on the upper side of the ith layer and substantially shielding the illuminating light, and a portion formed between the ith layer 盥 the third layer and having semi-transparency to the illuminating light, and the first The first layer and the third layer are inferior to the second layer, and the second etching layer is insoluble or poorly soluble compared to the second layer, and is soluble in the first etching liquid. Compared with the third layer, the second layer is more soluble in the engraving liquid and is insoluble or poorly soluble in the first etching solution, and the first layer and the third layer are respectively selected from the group consisting of a complex, an oxidizing agent, and a nitrogen. a layer in which one or two or more components of the group consisting of chromium and oxynitride are used as a main component, and the second layer is a group selected from the group consisting of titanium, oxidized chin, nitriding, and gas oxidized a layer in which one or two or more components are used as a main component, and the first etching liquid is a mixed liquid of ammonium cerium nitrate, peroxy acid and water, and the second etching liquid is a gas oxidation clock, hydrogen peroxide, and The method of manufacturing the photomask is characterized in that the first photoresist coating step is performed to coat the photoresist On the surface of the third layer; in the first exposing step, the bonding agent coated in the U-resist coating step is exposed through the mask formed with the second mask pattern; 74 200944936 The first photoresist is removed Step, after the ith exposure step, the exposed portion of the photoresist or the unexposed portion is removed; the first step is to use the first! The engraving liquid etches the third layer exposed by the area of the photoresist sword to form a light shielding pattern; the second engraving step, using the second engraving liquid, is removed by the i-th engraving step The second layer exposed in the region of the 帛3 layer is etched to form a light shielding pattern; The first photoresist stripping step 'This is the first! The photoresist remaining in the photoresist removing step is peeled off; the second photoresist coating step is performed to cover the photoresist again; the second exposure step 'passes through the mask formed with the second mask pattern The photoresist coated in the second photoresist coating step is exposed; the second photoresist removing step removes the exposed portion or the unexposed portion of the photoresist after the second exposure step a third surname step of etching the third layer and the first layer exposed by the region from which the photoresist is removed using the first etching solution to expose the second layer and the transparent substrate; μ The second photoresist removing step, the photoresist remaining in the second photoresist removing step is peeled off. A method for producing a reticle, wherein the photomask is produced by using a photomask, and is formed on a transparent substrate, formed on the upper side of the first layer, and formed on the first layer The photomask substrate includes a first layer having a semi-transmissive property for transparent substrate irradiation, a third layer substantially shielding the illumination light, and a third layer between the layers of 75, 2009,449 and 36, and having semi-transparency to the illumination light. In the second layer, the first layer and the third layer are insoluble or poorly soluble to the second etching solution and are more soluble in the first etching solution than the second layer of the second layer. The second layer is more soluble in the second etching liquid than the first layer and the third layer ^ ^ ^ ^ third layer, and is insoluble or poorly soluble in the first etching liquid. The layer and the third layer are respectively helmets, and a is listed as a layer selected from a group consisting of chromium, oxidized complex, chromium nitride and chromium oxynitride as a main component, or two or more components. © The second layer is one or two selected from the group consisting of titanium, ^ _ titanium hydride, titanium nitride, and titanium oxynitride. a layer as a main component, wherein the first etching liquid is a mixture of ammonium cerium nitrate and a mixture of water and water, and the second etching liquid is a mixture of potassium hydroxide, hydrogen peroxide and water; and the light The manufacturing method of the cover is characterized in that: the first photoresist is coated, and the well is coated on the surface of the third layer; the first exposure step is transmitted through the shape of the right ^ And forming a mask having a first mask pattern to expose the photoresist which is covered by the frost in the first photoresist coating step; the first photoresist removing step is to form a mask After the exposure step, the exposed portion or the unexposed portion of the photoresist is removed, and in the first etching step, the third exposed portion of the photoresist is removed by using the first etchant (4). a layer is added to form a light-shielding pattern by etching; a first photoresist stripping step is performed to peel off the photoresist remaining in the first photoresist removing step; 76 200944936 2 photoresist #丨 coating step, light is applied The resist is again coated on the surface; 2 exposure step 'transformed through The second mask pattern 该 the photoresist coated in the T-coating step is exposed to a wide exposure by exposure 2::: except = 'the portion of the photoresist that remains or is not exposed after the second exposure step ; €1 The area:: step: using the second engraving liquid to remove the photoresist, the fourth layer of the fourth layer is etched, and the lf is exposed; the area of the agent = step 'use the first The engraving removes the third layer of the photoresist: the third layer, and the etching process is removed: the first layer exposed in the product layer is etched to expose the transparent substrate And the catalyzed phoenix second photoresist repellent step, and the second remaining photoresist is separated. In the exhaustion of the steps VIII, the pattern: (such as the next page) 77