TW200921264A - Substrate for photomask, photomask, and method for manufacturing the same - Google Patents

Abstract

To provide a substrate for a photomask, which can form a fine pattern by wet etching with high accuracy, a photomask, and a method for manufacturing the same. A substrate (2) for a photomask, comprising a transparent substrate (10), a semitransparent layer (20), and a light shielding layer (33) for substantially shielding irradiated light provided on the semitransparent layer (20). The semitransparent layer (20) is formed of titanium nitride (TiNX wherein 0 < X < 1.33) of which the insolubility or sparing solubility in an etching solution (A) is higher than that in the light shielding layer (33) and which is easily soluble in an etching solution (B). On the other hand, the light shielding layer (33) is formed of metallic chromium (Cr) which is more easily soluble in the etching solution (A) than the semitransparent layer (20) and is insoluble or sparingly soluble in the etching solution (B). Since the individual layers are different from each other in resistance to the etching solution, the semitransparent layer (20) and the light shielding layer (33) can be selectively etching without damage to other layers.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate for a photomask having a semi-transmissive layer, a photomask, and a method of manufacturing the same. The present invention relates in particular to an LSI (Large Scale)

Fine patterning such as integration, large integrated circuit, and flat display devices such as LCD (Liquid Crystal Display), PDP (plasma display panel), and el (electroluminescence) A mask substrate, a mask, and a mask for pattern formation used for surface modification such as a display element, an antireflection plate which is finely scattered and uneven, a diffuse reflection plate for microparticles, a microlens array, and other array-like unevenness formation Its manufacturing method. [Prior Art] With the development of liquid crystal display elements (reflective, transmissive, and semi-transmissive), electro-polymer display elements, organic EL (electroluminescence), and other flat-panel display elements, - One of the various production masks, such as size and pattern, used in the production site of πhai. ❹H day display component formation in the t TFT (Thin Fiim TransistGr' thin transistor) process, the use of the light army depends on the method of fabrication: usually must be 3 to 5 pieces of different patterning In the case of the color chopper side in which the night crystal display elements are arranged to face each other, the photomask to be used must also be a photomask for forming the liquid-day display elements for forming the colored matrix and for forming the colored layer. For the reticle used to form the fine pattern of τ ς 黎 黎 SI SI 4 200921264, a halftone (half_t〇ne) mask is used to improve the pattern accuracy (for example, 'Patent Documents 1 to 9'). The halftone mask is a photomask that forms a semi-transmissive layer (halftone layer) between the transmissive portion and the light shielding portion. The film thickness of the semi-transmissive layer is designed to reverse the phase λ/2 or offset ± human/4 in accordance with the exposure wavelength used. Thereby, the diffraction of light generated between the adjacent patterns is prevented, so that the difference in light intensity between the edge portion of the light shielding portion of the mask and the transmission portion becomes clear. Moreover, since it is difficult to generate m叠ire or hamion, the resolution can be improved. In addition to this, there is a method of obtaining the same effect as a halftone by using a fine continuous stripe pattern (graytone mask) as a method of manufacturing the above-described photomask with a halftone layer. There is a method in which a photoresist substrate (a substrate for a mask) on which a first layer (semi-transmissive layer or light-shielding layer) is formed is coated with a photoresist and exposed to perform patterning once, and then the light is removed and washed. Resisting, and again using a vacuum device or the like to form a second layer (light shielding layer or semi-transmissive layer), and then patterning the second layer formed in the second time in the photolithography step (for example, 'refer to Patent Documents 3 and 9). Further, as another manufacturing method, a method is also known in which a film having a multilayer structure having a homogenous or heterogeneous structure is first formed. Each pattern is formed by a dry type (IV) (for example, Patent Documents 2 and 5). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 9-127677.曰 专利 专利 〇〇 〇〇 — — — — 29 29 29 29 29 29 29 29 29 2009 2009 2009 2009 2009 2009 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 7: 曰太直士丨4士H Patent Publication No. 2003-322949, Japanese Patent Laid-Open No. 2004-29746, Patent Document 9: Japanese Patent Winning + Searching Special 2006- 18001 SUMMARY OF THE INVENTION In the above-described conventional method, it is necessary to form a film into a second layer by using a vacuum apparatus or the like after patterning the first layer of the film formed by using a vacuum apparatus or the like. Therefore, it is necessary to use the vacuum enamel film step at least twice. Because of this, the need to manufacture a photomask (4) has increased, resulting in a bad manufacturing cost. In addition, in order to form a pattern of a reticle, there are two methods of dry etching and thirst Μ-), and the above-mentioned dry type method uses plasma or laser light of reactive gas to the substrate for the reticle. The layer of the radiant ion is used to carry out (4) 'the above-mentioned wet type (four) method uses the chemical name to mark (chemical) to chemically etch the layer. Among them, in general, a dry etching method is used in order to form a pattern of a photomask. However, in the dry type, there is a problem in various techniques (4) corresponding to the enlargement of the mask and mass production. For example, in the direct drawing step of the dry type (four), as the size of the mask is increased, the drawing time is increased, and the drawing time of the (4) beam or laser is increased, and it is difficult to improve the working time of the mask manufacturing (plus Uime). In addition, as the size of the mask is increased, equipment such as vacuum chambers and switching devices for gas types must be large-sized. Therefore, the following defects are also present. 200921264 The burden on the equipment is increased. - Sub-processable substrate production. The cost of manufacturing the mask is increased. The number of sheets is limited. Therefore, it is not suitable for a large number of dry and dry, in wet (four), usually equipment or cheap, and = type In contrast, the button engraving can form a pattern in a shorter time, so the wet etching is more suitable for the manufacture of a large mask, the mass production of the mask, and the production in a short period of time. Any one of the layers of the layer is layered...the other layer is dissolved, or at the interface of the other layer with the interface of the surname, the material forming the other layer reacts with the surname Metamorphic to a chemically heterogeneous structure to other layers The damage is caused, so it is difficult to advance the precision of the m. Especially when manufacturing a photomask in which a layer of a different layer of a halftone mask having a phase shift layer and a light shielding layer is laminated, In view of the above problems, it is an object of the present invention to provide a substrate for a photomask which is difficult to use for wet etching in conventional mask manufacturing techniques. The method can form two kinds of fine patterns on the surface of the transparent substrate in a short time and at low cost. Further, another object of the present invention is to provide a photomask and a method for manufacturing the same, the mask is wet-etched to the mask The substrate is sequentially etched to have two kinds of fine patterns which are formed in a short time and at low cost. The above problem can be solved by the substrate of the reticle according to the present invention having a transparent substrate formed on the transparent substrate. And a first layer having a semi-transmissive property to the illuminating light, and a concealer formed on the first layer and forming a pre-pattern of the second enamel layer which shields the illuminating light 200921264 a shape: a surface: a semi-transmissive portion that is formed by the second semi-transmissive pattern, and a transparent portion that is formed by the side of the first layer: the transparent layer is insoluble or difficult to be exposed on the surface of the surface The solubility is the same as the ratio of the first layer to the first etching liquid, and the second layer is easily soluble to the first etching liquid; the first layer is insoluble or poorly soluble. The % liquid is easily soluble and As described above, according to the second etching liquid of the present invention, the first layer of the light to the i-th etching liquid substrate is more soluble than the second layer, and the other is too "exciting or poorly soluble" and 2 The etching solution is 'comparable to the first layer, the second layer is the first; the last name is y is easy to be soluble, and the second etched first etched liquid is selectively difficult to use with the η worm liquid. The liquid is selectively engraved to the layer of the second layer, and the second layer and the second layer can be selectively etched using the second etching layer, which can be patterned on the transparent substrate. And the etched liquid and the light-shielding pattern can be used to form two portions of the light-shielding pattern exposed plate, the semi-transmissive portion of the semi-transmissive pattern exposed on the surface, and The transparent substrate is in three areas of the transparent portion exposed on the surface. As described above, the substrate for the photomask of the present invention is the first! Layer and layer 2: do not have different tolerance to #刻液, (4) the difference of this tolerance, the second; almost no modification due to the engraving of the first layer... or the injury of the shell 'opposite' The first layer is hardly damaged by the first surname (four) which can dissolve the second layer. Therefore, it is possible to manufacture a photomask which is formed with a high precision and a ''field pattern'. Further, it is preferable that the second layer is directly formed on the transparent substrate. In general, between the transparent substrate and the first layer, in order to improve the adhesion between the two, the metal compound layer or the like is interposed therebetween, but since the second layer is directly formed on the transparent substrate, it is not necessary to The metal compound layer is somewhere in between. Thus, the number of steps and materials for forming a metal compound layer on the surface of the transparent substrate can be reduced, thereby improving the yield of the substrate for the photomask.

Further, the bauxite layer is formed on the transparent substrate by a metal compound layer having a transmittance of 70% or more and less than 100/0. As described above, the 帛i layer is formed on the transparent substrate through the metal compound layer having a transmittance of 70% or more and less than 100%, whereby the transmission is transparent.

The light of the panel is hardly reflected, so that the transparent substrate and the U-thickness can be improved, and the surface of the transparent substrate can be protected from the residual liquid during the manufacture of the mask.

More preferably, the refractive index of the metal compound layer at this time is the same as or lower than the refractive index of the substrate. Further, it is preferable that the first etching liquid is ammonium cerium nitrate, perchloric acid, and water, and more preferably a mixture of water and water. The second liquid is mainly composed of potassium hydroxide, titanium oxynitride and titanium, and the first layer is one selected from the group consisting of nitrogen oxides. Or the two points are 0 and 'preferably, the third and the decoration M are selected from the group consisting of chromium, chromium vapor, '. τ< species or more of nitride and chromium oxynitride

C υ 200921264 Ingredients are the main components. :: In the above, the fourth engraving liquid, the second engraving liquid, and the first layer are appropriately selected, whereby the selectivity to the etching liquid of each layer can be improved, thereby forming a more precise and fine pattern. And 疋l one or more of the group T consisting of titanium, titanium nitride and titanium oxynitride, and the mixture of cerium ammonium nitrate, bismuth and water of the first etching solution is insoluble or It is poorly soluble, and it is easily soluble in the mixture of potassium oxide, hydrogen peroxide and water in the second money. On the other hand, one or more components selected from the group consisting of chromium, chromium oxide, complex nitride, and nitrogen oxynitride are used as the first etching solution of cerium ammonium nitrate, perlactic acid, and water. The mixed solution is easily soluble, and the mixture of nitrogen oxidizing, hydrogen peroxide and water in the 帛2 (four) liquid is impure or poorly soluble. Therefore, 'Titanium or titanium compound is used as the ith layer, chromium or chromium compound as the second layer, and the selectivity of the etching solution is determined by the individual ur 4S. / ' ^ h, thereby forming a more accurate and fine pattern. . In particular, since titanium nitride has high acidity for acid or chemical treatment, it is difficult to damage the chemical used in the step of etching the yak by the photoresist removal liquid. Therefore, it is possible to smoothly advance the rod, select the etching, and form a highly precise and fine pattern. Further, preferably, the s layer is provided with a light shielding layer and an antireflection layer formed on the surface side of the light shielding layer. As described above, since the flute 9 a and the Le 2 layer are provided with the antireflection layer, the antireflection effect can be obtained, and it is preferable to prevent the flicking or the like caused by the reflection of the illumination light before the exposure. 200921264 Further, since the second layer is formed by the light shielding layer and the antireflection layer, the light shielding layer and the antireflection layer can be collectively etched, whereby the light shielding pattern having the antireflection layer pattern on the surface can be easily formed. Furthermore, in this case, the antireflection layer is preferably a layer containing one or more components selected from the group consisting of chromium oxide, chromium nitride and chromium oxynitride as a main component. As described above, the antireflection layer is formed of a layer mainly composed of one or two or more components selected from the group consisting of chromium oxide, chromium nitride, and chromium oxynitride having a low reflectance. Therefore, a higher anti-reflection=fruit can be obtained, so that it is possible to prevent blooming or the like caused by reflection of the light when the mask is exposed, and thus it is preferable. Even in the case where the first layer is a component selected from the group consisting of chromium, chromium oxide, chromium nitride, and chromium oxynitride, or two or more components. The second layer is a layer selected from the group consisting of titanium, titanium nitride, and titanium oxynitride, or a component containing a component as a main component; The etching solution is a mixture of potassium hydroxide, peroxidizing wind and water; the 帛2 button engraving liquid is a mixture of oxalic acid, perchloric acid and 2, and the material is improved by the same effect as above. The selectivity of ~ to form a more precise and fine pattern. Further, it is preferable that the (iv) i layer and the second layer are formed by a sputtering method, a thousand plating method, or a vapor deposition method. As described above, the first layer and the second layer are in the form of Μ Μ Μ 1 . . . L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L Since Liang Cheng has the substrate for the first cover of the desired optical structure, it is possible to form a chemical resistant bite which has a substrate for use in the film formation technique such as the sputtering method, and the photomask can be appropriately adjusted. Physical properties such as solidity. The above problem can be solved by forming a reticle according to the present invention by the reticle substrate, and forming the reticle on the transparent substrate, and the slab and the ribbon 具有1 have a high transmittance. The second layer and the second layer are substantially shielded from light by the second light, and the second layer is

It is poorly soluble and is easily soluble in the first liquid. It is == insoluble or the second layer is easily soluble in the i-th etching liquid. Dimensional ratio, Heidi or poorly soluble, and the mask shape &amp; The second etching liquid is insoluble—the light-shielding portion, the semi-transmissive portion, and the transparent mail·the h-light portion are exposed on the surface by the eclipse, °, and the light-shielding pattern. The passage, the abundance transmission portion, is formed by sculpt the first layer to expose the semi-transmissive pattern on the surface; and the transparent portion is etched by the second BBy&lt;2 sound and m And the second etching liquid of the second brother etches the first layer and exposes the transparent substrate to the surface. As described above, according to the photomask of the present invention, compared with the second layer, the first layer is insoluble or poorly soluble in the liquid, and is soluble in the second surrogate, on the other hand, compared with the first layer. The 帛2 layer is easy to combine with the "insect liquid and is insoluble or poorly soluble to the second etching liquid. Therefore, the second liquid can be selectively used to name the second layer, and the second money can be used. The liquid selectively etches the layer. Further, the first layer and the second layer are selectively etched by using different etching liquids, and the two patterns of the light shielding pattern and the semi-transmission pattern are formed on the transparent substrate to be used. The etchant is wet etched on the surface of the transparent substrate 13 200921264. The light-shielding portion, the semi-transmission-transmissive portion, and the transparent substrate are exposed in three regions, the surface of which is exposed, and the transparent portion of the surface 16 is exposed on the surface. As described above, according to the present invention, the difference in the alignment of the liquid I _ 2 layer is different from that of the first layer, and therefore the second layer is almost unconformed, and the layer is modified by rhyme or Damaged: Modified or damaged due to the 1st W! solution, it will not be finely patterned due to precision Cover. It can be provided that the method of manufacturing the mask according to the above-mentioned reticle is solved: the first φ @J error is applied by the following #first resist coating step, on the surface of the second layer, "帛1 exposure step, transmission formation The photomask of the first mask pattern is exposed to the photoresist covered in the first photoresist coating step; the first #resistance removal step, after the first exposure step, the photoresist is warmed: removed; 1 I insect engraving step d is the removed U (four) 1 button engraving to etch the second layer out of the G-domain removed by the photoresist, to form a photoresist stripping step, which will be # M , L 茱, The photoresist stripping step remaining in the first detachment/photoresist removal step and the coating step 're-coating the photoresist again on the surface; the second exposure step is performed by the step of forming the second photo-pattern 2 The light-blocking light is 5 Hz, the second photoresist, the second exposure step (four), the photoresist removal step, the step, the (4) 2:=light portion is removed, the second button is etched, and the photoresist is already (4) a region exposed to form the semi-transmissive pattern; and a second photoresist stripping step 'the photoresist remaining in the second photoresist removing step According to the manufacturing method of the photomask according to the present invention, the photoresist is exposed by using a patterned mask to remove the exposed portion of the photoresist in the photoresist 14 200921264, and the first money is used. The button is engraved on the second layer, and then the photoresist is exposed by using the photomask formed with the second mask pattern, and the exposed portion of the photoresist is removed, and the second engraving liquid is used to name the second, thereby A plurality of pattern forming regions are formed on the surface of the transparent substrate. That is, the difference in resistance between the first layer and the second layer (four) liquid is not modified or affected by the money engraving used in the other layer of rhyme. The damage can be accurately formed into a fine pattern. According to the substrate for a photomask of the present invention, the first layer can be selectively etched by the second etching liquid by using the second etching solution. The first layer and the second layer are hardly modified by the etching liquid of each other or are damaged. Thus, it is possible to manufacture the fine pattern with a south precision by using a difficult wet etching method in the conventional mask manufacturing technique. a reticle according to the present invention, and a method of manufacturing the same Shang name by the first liquid 7 to selectively engraved name second layer, and by the second liquid selectively engraved name ...] of / layers', the first layer and the second layer is hardly affected by another moment surname

L Difficulty or "too" can use the difficult wet silking method in the conventional mask manufacturing technique to form a photomask having a fine pattern with high precision. Therefore, according to the present invention, it can be adapted to a large mask. The wet pattern of the mass production and the large amount of production of the mask is patterned, so that the mask can be manufactured in a shorter time and at lower cost than the patterning of the conventional dry type. [Embodiment] The present invention will be described with reference to the accompanying drawings. The components, arrangements, steps, and the like described below are not intended to limit the invention, and may be variously modified in accordance with the spirit of the invention.

1 is a longitudinal cross-sectional view of a reticle substrate according to an embodiment of the present invention, FIG. 2 is a longitudinal cross-sectional view of a reticle according to an embodiment of the present invention, and FIG. 3 is a view showing a reticle from a photomask substrate. 4 is an explanatory view showing a step of patterning a mask, FIG. 5 is a longitudinal sectional view of a substrate for a mask according to another embodiment of the present invention, and FIG. 6 is a light after forming a light-shielding pattern. The electron micrograph of the longitudinal section of the mask and the plane photographed is shown in Fig. 7 as an optical microscope photograph of the plane image after the formation of the cross pattern (handsome (10)). The longitudinal section of the mask after the formation of the semi-transmissive pattern is shown. And electron micrographs obtained by plane shooting. Further, in Fig. 1 to Fig. 5, in order to facilitate the understanding of the present invention, the film thickness of each layer is drawn to be larger than the actual thickness, thereby schematically showing the substrate for the mask and the manufacturing steps of the mask. The substrate for a photomask (also referred to as a substrate for a photomask) 2' of the present embodiment is a transparent substrate 10, a semi-transmissive layer 2 formed on the surface of the transparent substrate 1, and a surface of the semi-transmissive layer 2 The light shielding layer 33 is formed. Further, an anti-reflection layer 35 is formed on the surface of the = light layer 33. The reticle substrate 2 is used to manufacture the initial substrate of the reticle 1, and is lightly etched (4) and purely shadowed, and the reticle substrate 2 is sequentially etched using I with an etching solution to perform patterning. Photomask 1. The semi-transmissive layer 2G corresponds to the i-th aspect of the present invention

The layer '% of the composite layer composed of the light shielding layer 33 and the antireflection layer 35 is the second layer of the present invention. W, as shown in FIG. 2, the photomask 1 of the present embodiment is formed by a transparent substrate process, a semi-transmissive pattern formed on the surface of the transparent substrate 1G, and a light shielding layer pattern 33a formed on the surface of the semi-transmissive pattern 16 200921264 2〇a, And formed in the anti-reflection layer pattern formed on the surface of the light shielding layer pattern. The semi-transmissive pattern 20 is a pattern formed by etching the semi-transmissive layer 20 of the mask substrate, and the light-shielding layer pattern is formed by patterning the light-shielding layer 33, and the anti-reflection layer pattern is formed by the anti-reflection layer 35 (four). The light-shielding pattern 30a ° 35 of the present invention is formed by the light-shielding layer pattern 33a and the anti-reflection layer pattern Γ. When the dielectric mask 1 is formed from above, the surface is exposed with an anti-reflection layer pattern/semi-transparent pattern: pattern The light-shielding portion 1a of one of 3°a), the semi-transmissive portion 1b of a part of the surface exposed ==, and the transparent portion 1c of a portion of the surface of the moon-transmissive substrate 355. (Transparent substrate 1 0 ) Each member of the cover substrate 2 will be described. The substrate plate is used to form a transparent cover plate as a bottom layer for the pattern for the photomask as: a fine shape, the transparent substrate 10 is a fully ground quartz: a transparent substrate 10' Natural quartz glass, synthetic quartz glass, transparent resin film, etc. can be used. Here, the term refers to a wavelength of 35 to 5. The wave of nm is transparent, specifically P. &amp; Transmittance (Air

Reference) is in the range of 80 to 95%. (Semi-transmissive layer 20) A semi-transmissive layer 2 is formed on the surface of the transparent substrate 10. The energy + transmission layer 20 is a layer having a phase shifting function in the range of 5 to 70% of the transmittance in the range of 5 to 70% in the wavelength range of 350 to 5 Å. Titanium (TiNx, here, ^, ) is formed as a material of the main component 17 200921264. According to the wave optics, a film having an upper optical property can be formed by thinning a dielectric material in a plurality of layers, but considering the selectivity of the patterning agent from the etching solution and the adhesion to the photoresist material, the operation is performed. The above method is not necessarily good from the viewpoints of time, pattern accuracy, and the like. Therefore, the material transmission layer 20 is preferably formed as a single layer as long as it is not a laminated structure. Moreover, it is also necessary to use a material that is easy to pattern to ensure optical characteristics. Further, from the viewpoint of 2 photolithography, it is necessary to suppress the reflectance as low as possible, and from this viewpoint, a film having appropriate light absorptivity is suitable. Examples of the substance having the above properties include metal oxides, nitrogen: nitrogen oxides, and the like. Further, as for the light-shielding layer 33 described below, an oxygen (tetra)' nitride or an oxynitride of 2 (d) may be used as a constituent material. In the material A constituting the semi-transmissive layer 20 and the light-shielding layer 33, the basic element is homogenous, and can also be clarified, 〇^, and stand up, "Ma 贝 、, should be appropriately selected and used in the conventional mask system.

Make the steps and manufacture the materials that can be used in the injury. The first cover I, that is, the semi-transmissive layer (10), the light-shielding layer 33 is characterized in that the same etching liquid exhibits resistance (insoluble or poorly soluble) and exhibits solubility. ^ u worm 2), compared with the calender layer 33, the semi-transmissive layer 20 is insoluble or poorly soluble in the engraved liquid VIII (d liquid), and the liquid is soluble. On the other hand, the button engraving liquid β (the second (four) is opposite to the etching liquid A Α , , the 'transmissive layer 20, the light-shielding layer 33 is further, and the (four) liquid helium is insoluble or poorly soluble. Liquid action nitric acid decoration clock, perchloric acid τρ horse instrument engraving liquid A, you use calcium preparation for potassium oxyhydroxide, hydrogen peroxide and 18 200921264 water mixture as etchant B d as described above, semi-transmissive layer 2G and The light shielding layer % is different from each other (4) liquid A is insoluble or poorly soluble, and the solubility of the money engraving liquid B is different. The etching liquid B is used to selectively describe the semi-transmissive layer 2〇, and the last name A is used to selectively etch. The light-shielding layer 33. x In this case, the so-called semi-transmissive layer is insoluble or poorly soluble compared to the light-shielding layer 33, meaning that the solubility of the semi-transmissive layer 2〇 to the engraving liquid a is substantially zero. 'or the dissolution of the light-shielding layer 33 is extremely lower than that of the light-shielding layer 33. The semi-transmissive layer 2 is more soluble than the light-shielding layer 33, and the semi-transmissive layer 20 is dissolved in the light-shielding layer 33 for the surname B. The solubility of the etching solution B. It is also known that, in contrast to the semi-transmissive layer 2M, the light-shielding layer 33 pairs (four) sputum The property of It open V also means that the solution of the opaque layer 33 to the etchant B is substantially zero, or is extremely lower than the solubility of the semi-transmissive layer.

On the contrary, the light-shielding layer 33 is opposite to the semi-transmissive layer 2G.

Cj: Easily soluble&apos; means that the solubility of the light-shielding layer 33 to (iv) liquid A is extremely higher than that of &quot;transmission layer 2〇 to money engraving liquid A. Specifically, in the present embodiment, in the etching liquid A, the transmittance of the semi-transmissive layer 2G at a wavelength of 436 _ is about 70 seconds (that is, the time at which the light shielding layer 33 can be completely etched). The grounding rate before the (four) liquid A is 5% or less. It is shown that even in the case where the light-shielding layer 33 can be completely engraved with the residual liquid A, the semi-transmissive layer 20 hardly changes (not etched) by the etching liquid A. Also, in the surname B, it is at 30. 〇, has been immersed for 120 seconds (that is, 19 200921264 can be completely (four) semi-transmissive layer 2G time), the optical density of the light-shielding layer 33 UPucaldensity) ^ 0_3 or less. In the table *, even under the condition that the semi-transmissive layer 2 can be completely etched with the residual liquid B, the light-shielding layer 33 hardly changes (not etched) by the etching liquid B. As described above, since the solubility of the semi-transmissive layer 2 and the light-shielding layer 33 to the etching liquid is not 13 Å, the solubility characteristics can be utilized to selectively etch the semi-transmissive layer 20 and the light-shielding layer 33. The inventors investigated the etching solution A (mixture of ammonium cerium nitrate, perchloric acid and water) and etching solution B (potassium hydroxide, hydrogen peroxide) for several kinds of metal oxides, nitrides and nitrogen oxides. Soluble of the mixture of water and water). The metals used are recorded, titanium, group, sulphur, indium and copper.

As a result, in nickel, molybdenum, and copper, any of an oxide, a nitride, and an oxynitride is soluble in the etching liquid A, and is insoluble to the etching liquid B. Therefore, it is understood that it is not suitable for selective etching with the light shielding layer 33. In addition, after investigating the oxides, nitrides, and nitrogen oxides of Ming, Group, and Titanium, it can be seen that 'any of them are insoluble to the money engraving liquid A, but the engraving liquid B, titanium nitride and titanium The nitrogen oxides are soluble. Further, the compounds are etched to form a pattern, and the pattern precision is separately inspected. As a result, it has been found that oxides, nitrides, oxynitrides, oxides of yttrium, and oxides of yttrium cannot be formed into patterns or patterns, and are not suitable for wet etching. According to the results of the investigation, it was investigated whether or not the titanium oxide (TiNx) film having the rice-resistance and optical properties of the etching liquid A can be used to determine the etching property. After the first discussion is repeated, the solubility and the surname of various chemicals are engraved in the photolithography step. It is known that the titanium nitride (TiNx) film has and is soluble in: = for example, potassium oxychloride (KOH) Sex, combined with liquid, and then visible, potassium hydroxide (K0H) and water in addition to V 丨, the field pattern 0 can also be known, titanium nitride (TiNx) in addition to having the ability to form the desired optics to shading In addition to the characteristics of the nine characteristics of the layer, the layer 33 has the resistance to the inclusion of the engraving liquid A, and has resistance to the photoresist. Therefore, from the steep angle of selection between the light-shielding layer 33, Lu's selection of titanium nitride with Μ, μ., # ώ 6 ΓΐΝχ ) is used as the material of the semi-transmissive layer 20, and thus has its own good characteristics. . Next, the adhesion of the semi-transmissive layer 2 ^ ^ /, the transparent substrate 10 and the compatibility with the precursor 33 are investigated. ± J for the + transmission layer 20 must be performed under the following conditions The etching also ensures that the opaqueness with the transparent substrate 10 does not occur between the patterning step &quot;the masking layer 33. Further, the semi-transmissive layer 20 is required to be a layer having both optical specific characteristics and chemical resistance. It is said that the adhesion of the semi-transmissive layer 20 is tested and the adhesion of the semi-transmissive layer 2's "transparent substrate H" is evaluated. Specifically, it is transparent. Titanium nitride (TiNJ film was formed on the surface of the substrate H), and a plurality of lattices were formed by using a cutter in a lattice shape of an imm knife, and a plurality of lattices were adhered thereto, and a peeling (four) test was performed thereon. As a result, it was found that "all the lattices were not peeled off. Therefore, the adhesion to the transparent substrate 1 is good. Therefore, the adhesion between the titanium nitride (wind) film and the transparent substrate is high, and it is suitable as a material for the semi-transmissive layer 2 2009 21264. Further, even if it is transparent Since the substrate 1 is directly formed into a film and has good adhesion to the transparent substrate 10, the surface of the transparent substrate 1 () which is not adhered to the metal compound layer or the like is directly formed. As described above, the nitridation is performed. Titanium (Dings) has optical properties, resistance to rhyme A (insoluble or poorly soluble), and etchant: (especially): further, adhesion to transparent groups is good, and most I δ is used as a semi-transmissive layer. Material of 20. (Light-shielding layer 33) It-person, the light-shielding layer 33 is added The light-shielding layer 33 has a property of shielding light to almost completely (approximately ΙΟΟ%), and is formed on the surface of the semi-transmissive layer 20. In the present embodiment, the transmittance is below (the optical density is 3.0 Å). The metal chromium (Cr) is formed into a film. As the material of the light shielding layer 33, in addition to chromium, metals such as titanium, molybdenum, aluminum, nickel, and copper, or oxides, nitrides, and oxynitrides of the metals may be mentioned. Further, an alloy composed of two or more kinds of these metals or metal compounds, etc. may be mentioned. The light shielding layer 33 has a property of being easily soluble to the etching liquid A as compared with the semi-transmissive layer 2〇. It is insoluble or poorly soluble for the etching solution B. Therefore, the semi-transmissive layer 2〇 can be used without using the residual liquid A, and only the light-shielding layer 3 3 can be selectively engraved. (Anti-reflection layer 3 5 ) Secondly, the anti-reflection layer 35. The anti-reflection layer 35 is a layer formed on the surface of the light shielding layer 33 and used to reduce the reflectance of the light shielding layer 33. In the present embodiment, chromium oxide (Cr〇x) of chromium oxide is used as the anti-anti-22. 200921264 The main component of the material of the shot layer 35' but anti-reverse The material of the layer 35 is not limited thereto. In the present invention, the anti-reflection layer 35 is of an arbitrary configuration, and it is not necessary to provide the reflection layer 35. However, the mask i obtained by centrifuging the substrate 2 for the mask is used. When a fine pattern such as LSI is formed, the anti-reflection layer 35 can be used to prevent reflection of the irradiation light, thereby reducing the occurrence of moiré or blooming due to interference of the reflected light. Anti-reflection I 35 is an interference of light using wave optics And obtaining an anti-reflective film. Forming the anti-reflective layer 35 &lt;substance' by the refractive index (η) and absorption (1) of the incident light (here, the so-called refractive index and absorption, the speed in the vacuum first The phase of the substance (in the film), that is, the complex refractive index, generally means a combination of a and N (n) expressed by N = n - ik, and has the following table, rate (n), and characteristic. "The left barrier (refractive index) of the table indicates the relative anti-reflection refractive index: the ratio of the ratio to the shading ("lower", 7 = degree", or "more"). ^ ^ r- „ 〒 拦 ( 吸收 吸收 吸收 吸收 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表Happening. h degree", "more right column (reflectance) means that the reflectivity of the reflectivity is low, ", indicating that the reflectance is in the middle, and the raw PL is high. Further, the block φ ^ ^ I" is not reflected." △", ". From low to high, with "X", price. The evaluation of A-low is also the same. 23 200921264 [Table 1]

According to the table, the following matters can be known: In the sound 35, the light 曰 33 is smaller than the absorption of the illuminating light and the anti-reflection = less absorption (for example, the k value is .2 to .5): The radiation rate is low, so the anti-reflection effect is high. Compared with the light-shielding layer 3 3, the material which has a lower absorption of the light, and which absorbs less light in the anti-reflection layer 35 and has a medium-range ϋ K value of 〇.5 to 1.0), 〃; medium ' degree', so the anti-reflection effect is moderate. ^ Aspects satisfying the following necessary conditions f, ^ low reflection effect or no anti-reflection effect. • Compared with the light-shielding layer 33, the absorption of the irradiation light is small and the anti-reflection layer 35/absorbs a large amount (for example, the k value is iG to 2Q), since the reflectance is high, the anti-reflection effect is low. According to the above, the anti-reflection layer 35 is a substance which absorbs less light to the wavelength used than the light-shielding layer 33, and is formed to satisfy the optical film thickness Μ=ρχλ/4 (here, λ is the design wavelength, p For i, n is the refractive index, and d 24 200921264 is the substantial film thickness). = Upper] Since the light shielding layer 33 and the antireflection layer 35 respectively have wavelength dispersion characteristics of refractive index, p is formed within a range of less than 5 to 1 。. Further, if the absorption of the anti-reflection layer 35 is further reduced (for example, k _ 〇 1 1), the reflectance shifts toward the direction of the liter and the anti-reflection effect is lower than when the thickness is 0.2 to 0.5, for example, it is necessary to match the shading. The optical characteristics of the layer U are appropriately adjusted. ▲ The anti-reflection layer 35 has the same etch characteristics as the light shielding layer 33. That is, the antireflection layer 35 has a property f which is more soluble to the etching liquid a than the semi-transmissive layer 2, and which is insoluble or poorly soluble to the (IV) liquid B. Therefore, only the anti-reflection layer 35 can be etched without etching the semi-transmissive layer 20 using the residual Ά. Moreover, since the antireflection layer 35 and the light shielding layer 33 are laminated, the antireflection layer 35 and the light shielding layer 33 can be collectively etched using the etching liquid A. The material of the anti-reflection layer 35 is preferably made of a material which is homogenous to the light-shielding I 33 in consideration of the etching property and the convenience of film formation, as long as the etching liquid A is easily soluble η + + &amp; ρ i C Note that if the money engraving liquid B is insoluble or poorly soluble, it may be other materials. Next, a method of manufacturing the photomask 1 of the present invention will be described. The photomask 1 of the present invention is manufactured by sequentially laminating a semi-transmission I 20, a light-shielding layer 33 on the surface of the moon-permeable substrate 10 by film formation.

The light star of the anti-reflection layer 35 is formed into a predetermined pattern by wet etching for each of the 1 AI substrate 2 for each layer. Examples of the gland-forming, soil, and wind film methods include physical deposition by vacuum (pvD, V叩machi D-), or plasma c VD, heat (4) by sputtering, vapor deposition, or ion plating. Equal vapor deposition (C vd, 25 200921264

Chemical Vapor Deposition). f

In the case of film formation by a sputtering method, reactive sputtering can be utilized in addition to the usual money bonds. The reactive sputtering apparatus is a device having a film formation region for sputtering a target material and a reaction region for plasma-treating a film formed by using a plasma of a reactive gas; Second, it is a device in which a reactive gas is introduced into a film in a usual sputtering device, and a plasma generated in the old bond is used to promote the reaction. Hereinafter, film formation is performed by the second reactive storage bell device to form titanium nitride (transferred) as a semi-transmissive layer 2, a metal via (Cr) as a light-shielding layer 33, and an anti-reflective layer 35. The film of chromium oxide (〇Οχ) is described as an example. (Film Forming Step) First, film formation of the semi-transmissive layer 20 is performed. The semi-transmissive layer 2 was formed into a film, and titanium metal was used as a target. Before the film formation starts, the transparent substrate is mounted on the substrate holder of the sputtering apparatus. The inside of the sputtering apparatus is made into a high vacuum, and an inert gas (Ar) and a reactive gas (n2) are introduced into the target, and a voltage is applied to the sputtering electrode, whereby titanium (Ti) and reactivity fly out from the target. The gas (N2) reacts in the plasma to form a titanium nitride (TiNx) film on the surface of the transparent substrate. Thereby, the semi-transmissive layer 20 is formed on the surface of the transparent substrate ι (the semi-transmissive layer film-forming step). Next, film formation of the light shielding layer 33 is performed. Before the light shielding layer 33 is formed into a film, the dry material is replaced with titanium metal to metal I ( &amp; In this state, the inside of the ageing apparatus is again in a high vacuum state, and the material is sputtered, whereby a metal layer is formed on the surface of the semi-transmissive layer 20 (filming step of the light shielding layer). ^ to 26 200921264, followed by 'anti-reverse (four) 35 film formation. Since the antireflection layer 35 is mainly composed of chromium as the light shielding layer 33, it is possible to continue film formation after the light shielding layer 33 is formed, without replacing the target. A metal matrix is used as a dry material from the same viewpoint as when forming titanium nitride. After the light shielding layer 33 is formed, an inert gas (Ar) and a reactive gas (〇2) are introduced into the dry material, and a voltage is applied to the sputtering electrode, whereby the chromium (~) and the reactive gas fly out from the target ( 〇 2) A reaction is formed in the plasma to form a chromium oxide (10) film on the surface of the light shielding layer 33. Thereby, an antireflection layer 35 is formed on the surface of the light shielding layer 33 (antireflection layer film formation step). The anti-reflective layer 35 is formed of a metal material different from the light-shielding layer 33, and is formed into a film by the light-shielding layer 33, and then the target is replaced and the anti-reflection layer 35 is formed. — 'Secondly, by ultrasonic cleaning or the like The mask 2 after the film formation is cleaned to remove foreign matter on the surface. (Patterning step) The photomask system 2' having the laminated structure formed as described above is formed using photolithography technology and (4) technique. The pattern forming step (patterning step) will be described with reference to Fig. 3 and Fig. 4. "First, the mask substrate 2 before patterning is prepared (Fig. 3 (a)). It is manufactured by a film forming technique such as the above sputtering method. Secondly, the mask is used. The surface of the substrate 2 is coated with a photoresist such as a spin coating or the like. The photosensitive polymer material is cured by ultraviolet rays or the like. The photoresist coating method is not limited to spin coating. For example, a known method such as a coating, a roll coating, or the like can be used. Next, the photoresist 50 coated by 27 200921264 is heated to a high temperature by a heater or the like to perform pre-bake (temporary hardening) by the above method. The surface of the cover substrate 2 is coated with a photoresist 5 (resistance coating step). Next, the mask original mask 60 is used to form a mask pattern on the photoresist 5, and the mask 60 is pre-written (4) (the case) It is a member for transferring the pattern onto the photoresist 5. The ultraviolet light is irradiated to the photoresist 5G through the plate 6 to expose (Fig. 3(e)). The step of making the light )). The surface of the photoresist 50 is sensitized (the first exposure is followed by the exposure of the light M, , *, 矣 & 5 溃 in the developer. The region where τ is exposed to the outer line of the photoresist is removed, so that the anti-reflection layer 35 under the region is exposed to the surface light. 5. After one part is removed, as shown in Fig. 3(d)), the remaining photoresist is turned into a temperature by using a heater or the like to perform post-baking (^50 one part eight, * It is said that the photoresist is removed and the residual photoresist 50 is used to form the same pattern of the second mask pattern (the i-th photoresist removal step), the cover layer 35 and the over: The etchant A (i.e., the first etchant) is used to counteract the reflective acid "layer 33". (4) Liquid A is a mixture of ammonium sulphate and sulphuric acid. Fill the bath with Mansaki A, so that the anti-reflective layer 35 from the photoresist is removed, and the main anti-reflective layer 35 is in the etchant. In this state, the light layer 33 &amp; etching temperature is etched. Since the antireflection layer 35 and the liquid opaque layer A - n are all easily soluble for the remaining liquid ’, it is possible to use a etch: a pattern to form the same pattern as the residual pattern of the photoresist 5 。. Since the semi-transmissive layer 20 is insoluble to the etching liquid a or insoluble in 28 200921264, it has an effect of an etching stop layer. Therefore, even if the light-shielding layer 33 is etched using the etching liquid A, the semi-transmissive layer 2〇 remains in the original state without being etched by the etching liquid A (Fig. 3 (e. Thus, the semi-transmissive layer 20) The light-shielding pattern 3〇a composed of the light-shielding layer pattern 33a and the anti-reflection layer pattern 35a is formed on the surface (first etching step). Next, the photoresist 5 残留 remaining on the surface is dissolved by a release agent, and washed with pure water or the like. The net surface (Fig. 3 (7)). The pattern similar to the first mask pattern remains on the surface of the transparent substrate 1G (the i-th photoresist stripping step). Next, the surface is coated with a photoresist to be temporarily hardened (Fig. 4(b)). The photoresist 70 can be made of the same material as the singularity of the singularity of the singularity of the singularity of the singularity of the singularity, and the use of different materials such as hardening properties. The photoresist 70 is coated on the surface (the second photoresist coating step). Next, the photomask 7 is formed on the photoresist 7 by using the mask original 80 to form a mask. The original mask 80 is attached to the mask original 6 and the gentleman is pre-written. Into the established 2 mask pattern). Through the eight. ^ Zhuo original version 8 〇 on the photoresist 70 Zhao shooting external line to expose (Fig. 4 (〇). Thus, as in the second mask, the surface of the photoresist 70 is exposed (the second exposure step). %, &quot;Τ! After exposure, the photoresist 70 is immersed in the developer. To remove the area where the light is applied to the outer line of I (the part of the photoresist 70, and make =(d)) 1 , remove I and use the residual photoresist 7 to etch the same pattern of the mask pattern (2nd light) Step 2) Next, use the etching solution B (that is, the layer 20 to perform rhyme. The rhyme B-based gas X liquid) to the semi-transmissive mixture. In the sputum, potassium, hydrogen peroxide, water The groove is filled with the etching solution B 々 so that the first resistance is removed. 29 200921264: The transmission layer 20 is completely immersed in the engraving liquid B. In this state, the temperature is maintained (4). Due to the semi-transmissive layer 2q The (four) liquid B is gluten-based, so that the working liquid B is subjected to _ to form a pattern corresponding to the residual pattern of the photoresist 。. On the other hand, since the light shielding layer 33 and the anti-reflection layer are either etchant B All of them are insoluble or poorly soluble, so the pattern 30a formed by the layers is not etched by the etching solution B (圊*"). 1 〇 矣 矣 花 士 士 士 士 士 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... f)), the same as the second light army pattern: the case remains on the surface of the transparent substrate 1 (second photoresist peeling step). i-light: Figure = method after (4), as shown in Figure 2 The portion of the semi-transmissive layer 20, the light-shielding layer 33, and the anti-reflection layer 35 is not etched to form an anti-reflection portion, which is not exposed by the first portion.

When V = the second layer 35 is "the light-shielding layer 33", the area exposed on the surface: the portion which is exposed by the first mask pattern and which is not exposed by the second mask pattern, only the light-shielding layer 33 and anti-reverse; 1 layer is formed by the side of the side to form a half of the surface exposed area (semi-transmissive part (6). Further 'the part exposed by the i-th reticle pattern and the second reticle pattern' half Any of the transmissive layer 20, the light-shielding layer 33, and the anti-reflection layer '" is formed by a long-formed transparent base &amp; Μ 表 ( ( 透明 透明 透明 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 1 can be used to manufacture a multi-gray mask used in the TFT panel, etc. 30 200921264, etc. On the surface side of the tft surface (four) ϋι-order reticle (the anti-reflection layer is diametrically opposed to the substrate, and the transparent substrate The shank]n is transferred to the transfer substrate by the transfer substrate 10. When the light is irradiated from the transparent substrate H) to the side of the anti-reflection layer 35, the illuminating light is shielded from light, and the amount of light is transmitted to the semi-transmissive portion η (transmittance) 5~; the second is transmitted through 'and the light is transmitted through the sun, and the light is transmitted at a transmittance of approximately (10)%. Therefore, in the relative shovel

The light-shielding portion i a is t: different three exposure positions: the unexposed portion, the semi-transmissive portion of the semi-transmissive portion 1b, and the fully exposed portion of the transparent portion 1c are transferred. As described above, the photomask 1 of the present invention is used as a pattern: P mask by photolithography, and this can easily form an exposure intensity non-transfer pattern. Further, by changing the wavelength and intensity of the irradiated light, the variation of the exposure can be further increased. Further, since the semi-transmission@20 system of the present embodiment is directly covered with transparency, it is not necessary to be on the transparent substrate 1. The surface of the surface is formed in advance with a special layer for increasing the adhesion of 20, and it is possible to reduce the film formation 7 and the semi-transmissive layer 20- and to reduce the reflectance from the surface side of the light-shielding layer 33 at the time of exposure. effect. As a result, it is possible to reduce the patterning phenomenon such as the irradiation of the light or the continuous fine stripe pattern portion, thereby improving the pattern accuracy. On the other hand, as shown in Fig. 5, the metal compound layer 9 can be formed on the surface of the transparent substrate 1 to improve the adhesion to the semi-transmissive layer 20. At this time, it is attributed. The material layer 90 preferably has a transmittance of illuminating light of 7 〇% or more and less than 100% 〇 31 200921264 The metal compound layer 90 protects the surface of the transparent substrate 1 不受 from the rhyme, and the semi-transmissive layer A substance with a higher adhesion is formed. Examples of such a substance are as follows: oxidized oxide, oxidized, titanium oxide, and other metal oxides. The base metal compound layer 9G is formed on the surface of the transparent substrate W before the film formation of the semi-transmissive layer 2 () by a well-known film formation technique such as 贱钱. Further, in the description of the above embodiment, the following cases are described: &quot;1 etching liquid etching solution A (mixed liquid of ammonium cerium nitrate, perchloric acid and water), and etching of the second etching liquid (four) B ( a first layer of semi-transmissive layer of potassium hydroxide, hydrogen peroxide, and water (a layer containing titanium nitride as a main component), a second layer (light-emitting layer) that is substantially light-shielded by light, and an anti-reflection layer Oxide layer), the same effect and effect can be obtained in the case where the material of the i-th layer and the material of the second layer are mutually entangled, and the first engraving liquid and the second engraving liquid are interchanged. (4) Further, the first layer is made of one or more of a group selected from the group consisting of chromium, chromium oxide, chromium nitride, and chrome-mouse: A layer selected from the group consisting of titanium, titanium nitride, and arsenic oxide as a main component. On the other hand, a mixture of potassium hydroxide, hydrogen peroxide and water is used as the second &quot;insert liquid&quot;, and a mixture of ammonium sulphate, peroxyacid and water is used as the second surname. The same effect and effect as those of the above embodiment can be obtained by this = shape. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific embodiment will be described with reference to the manufacture of the photomask substrate 2 of the present invention and the photomask k using the optical (four) substrate 2. 32 200921264 (Example 1) In the present embodiment, each layer on the surface of the transparent substrate 10 was produced by a vacuum film formation method. Specifically, a reactive sputtering device (measured by shln_株式会社) is used. The reactive scoop device uses a reactive gas such as nitrogen or oxygen. f 本 In this example, the quartz substrate (transparent substrate 10) was first mounted on a sputtering apparatus, and a commercially available metal titanium target (purity of 99.99% or more) was used for reactive sputtering. In the sputtering step, sputtering is performed while introducing nitrogen gas, and titanium is nitrided to form a thin film of titanium nitride (TiNX, here, 0 &lt; X &lt; 1D), whereby the semi-transmissive layer 20 is formed. At this time, the semi-transmissive layer 20 was formed to have a transmittance of 15% at a wavelength of 436 nm. Further, the target material at this time is not limited to the use of the metal titanium target as in the present example, and the sintered body of titanium nitride may be bonded (bQnding). Further, since the degree of nitriding differs depending on the device, it is only necessary to appropriately combine the film forming conditions and adjust them. The human titanium metal tantalum material was changed to a metal chromium target, and the light shielding layer 33 was formed on the surface of the semi-transmissive layer 2G in a manner of a film thickness of 7 〇〇A I. Table: Two reactive gases, only metal chromium (Cr) in the semi-transmissive layer '. The light-shielding layer 33 functioning as a light-shielding layer has an optical density (〇D) &amp; 3, which is preferably as hot as possible, and is characterized by a high-speed splash. plating. However, when the film thickness is increased rapidly, the film is formed with a mask (four) film = the force of the film is strengthened. The car is carried out in a proper range. Get splashed. The material was changed to another new metal chromium target, and the anti-reflector sputtering layer 35 was formed in such a manner that the film thickness was 33 200921264 300A (30.0 nm). In the sputtering step, sputtering is performed while introducing oxygen to convert gold chrome to chromium oxide (CrOx ' here, 0 &lt;x&lt;. The reflectance of the chrome layer of the concealer layer is usually about 60%, in order to By reducing the reflectance, the anti-reflection layer 35 has an appropriate refractive index and absorption film formation. - The general reflectance at this time is 65 〇 nm when the anti-reflection layer 35 is formed. The reflectivity is 25~30%, and the reflectivity near the wavelength of 43〇nm is the lowest.

It is 6 to 8%. The antireflection layer 35 is laminated 2 to 3f, whereby the reflectance can be suppressed to an average percentage. Next, the mask substrate 2 formed in the above-described sputtering step is taken out from the sputtering apparatus, and the crucible is placed in the warehouse. Then, the photomask substrate 2 taken out from the warehouse is ultrasonically washed in each of the alkali lotion, the neutral detergent, and the pure water which are formed by a plurality of grooves, and then the entire surface of the photomask substrate 2 is applied. A photoresist (AZ RFP-230K2 manufactured by AZ Electronic Materials Co., Ltd.) was applied and temporarily hardened. Further, in the photoresist coating step, the surface of the mask substrate 2 is not surface-treated by chemical chemicals, plasma, ultraviolet rays or the like. Hereinafter, the same processing is also the same. After the photoresist is temporarily hardened, exposure of the second stripe pattern is performed (Jet Printer manufactured by 〇RC Co., Ltd., light source CHM-2000, exposure under ultrahigh pressure mercury lamp for 16 seconds), and development (PMEr developer made by Tokyo Yinghua Co., Ltd.: temperature) 3 (TC '1 minute), and formal hardening (Yamat〇Scientific DX4〇2 drying furnace: not:, 10 minutes). The stripe pattern uses line widths of 5 μπι and 2 μιη. A mixture of perchloric acid, ammonium cerium nitrate, and water in the first | insect liquid (per-acid acid: ammonium cerium nitrate: 34 200921264 17.70, reaction temperature · 30 C, etching time: 1 sec) In the same manner, the light-shielding layer 33 and the anti-reflection layer 35 are patterned together to form a stripe pattern formed by the light-shielding pattern t 30a in which the light-shielding layer pattern 仏 and the anti-reflection layer pattern 35a are laminated. Secondly, the chemical is removed by a predetermined chemical or the like. The over-etching size of the light pattern 30a after the light-shielding layer pattern 33a and the anti-reflection layer pattern 35a are combined cannot be measured by an optical microscope, so that the pattern is formed in the longitudinal direction (photoresist removal) Substrate for reticle 2 (hereinafter simply referred to as "substrate"), and observe the cross section and plane with an electron microscope. The photographed electron micrograph is shown in Fig. 6"): Fig. 6(c). Fig. 6(a) shows a straight line pattern. A cross-sectional photograph of a cross-sectional shape taken in an electron microscope photograph taken before the photoresist is removed/Fig. 6 (b) is a cross-sectional photograph showing a cross-sectional shape of the straight line pattern, and the state after the photoresist is removed The electron micrograph obtained by photographing is shown in Fig. 2 (a front photograph taken by enlarging the edge portion of the straight line pattern, which is an electron micrograph taken after the photoresist is removed.) [Based on Fig. 6 (a) and As a result of the cross-sectional observation of Fig. 6 (1), it is understood that the semi-transmissive layer 2 () and the light-shielding pattern 30a are provided on the surface layer of the transparent substrate 1G. Further, it can be seen from the end of the photoresist toward the inner side according to the cross-sectional observation of Fig. 6 'The light-shielding pattern 3〇a is over-etched. According to the 6(1) photo, the size of the money is 〇.38μηι. Also, according to the result of the surface observation, it is known that the unevenness is generated at the edge of the straight line pattern. Big and The width of the small is 0] _ or less. At this time, there is no significant change in the titanium nitride (TiNx) film of the semi-transmissive layer, and it is known that it remains on the surface of the transparent slab. 35 200921264 面面::纟After the photoresist was removed, the substrate was rotated by 90 degrees, and the photoresist was applied to the entire surface again to perform the gentleman HR ^ ^ 仃 temporary hardening. Thereafter, the Jet Printer of the 1st pattern was produced by the RC manufacturer: the light source CHM-2000 , super = pressure mercury lamp exposure for 16 seconds), development (Tokyo Yinghua (stock), the current developer, temperature 3 ° ° Γ, 1 person, _ drying furnace 12. And formal hardening (Dahe Scientific' 20 C, 10 minutes). Next, a mixture of hydrogen peroxide, hydrogen (IV) and water impregnated in the second (four) liquid (35 hydrogen peroxide (35% water solution): potassium hydroxide (3 (%) aqueous solution): water = 16:1 : 32, the reaction 'dishness · % C ' (four) time: 15 G seconds) to the semi-transmissive layer 20 in 4 'by forming a stripe pattern of the semi-transmissive pattern (10). Thereby, the light-shielding portion 1a in which the semi-transmissive pattern is applied to the light-shielding pattern 30a and the semi-transmissive portion 1b formed only by the semi-transmissive pattern (10) are obtained on the surface of the transparent substrate 1G (refer to FIG. 7). ). The photograph on the left side of Fig. 7 shows an example in which the pattern has a line width of $, and the photograph on the right side of Fig. 7 shows an example in which the line width is 2. The straight line pattern (the straight line in the longitudinal direction) of each of the photographs is the light-shielding pattern 30a, and the straight line pattern (the straight line in the lateral direction) formed under the light-shielding pattern 3a is the semi-transmitting pattern 2〇a. The lattice-like region located below the semi-transmissive pattern 20a is above the transparent substrate 1''. According to the photograph of Fig. 7, even when the line width is as short as 2 μη, the patterns have good linearity. Therefore, according to the method of manufacturing a photomask of the present invention, it is understood that a fine pattern can be formed with high precision. Next, the substrate was cut in the longitudinal direction in the same manner as when the etching size was measured after the formation of the light-shielding pattern 30a, and the cross section 36 200921264 and the plane were observed by an electron microscope. The photographed electronic display # 镜片片 is shown in Figure 8 (a) ~ Figure 8 (a) Select a ping-pong from the straight line selected from the line pattern of the cross-sectional shape of the photo, with the line removed On the eve of Zhuang r,,. The electron micrograph taken under the heart, Figure 8 (b) shows the cross-sectional photograph of the cross-sectional shape of the straight line image, which is taken after the photoresist is removed. Photo ' ® 8 (0 is the edge of the liver straight green pattern post 丄 τ , ' 正面 邛 邛 拍摄 拍摄 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面 正面As a result of the cross-sectional observation of Fig. 8), a semi-transmissive pattern core can be formed on the surface of the crucible. Further, as a result of cross-sectional observation of the root map (), it is known that the semi-transmissive pattern 2Ga has been subjected to the inner side from the end of the photoresist. (4) According to the photograph of Fig. 8 (a), the size of the surname is 0.37 _. Further, according to Fig. 8 (the result of the front view of the crucible, it is known that the unevenness of the edge portion relative to the straight line pattern is small, and is 0.05 or less. Linearity is fully maintained, so for the linearity of the pattern, It is not a problem. Using another substrate that is not patterned, the optical density (〇D) is measured using a Macbeth densitometer manufactured by Xiao Xi Liu Photo Industry Co., Ltd., and is composed of a mixture of perchloric acid, ammonium cerium nitrate, and water. The opaque layer A was used to etch the light-shielding layer 33 and the anti-reflection layer 35, and then sufficiently washed, and the optical transmittance of the optical characteristic was measured using an automatic spectrophotometer u-4000 manufactured by Hhachi High-Techn Co., Ltd.. The resulting optical density was 3.38, the transmittance was 6.91% at a wavelength of 350 nm, 14.73° at a wavelength of 436 nm, and 18.29% at 500 nm. Using one of the cross patterns, and using a stylus made by Ulvac The surface shape measuring device Dectak measures the semi-transmitting pattern 2〇a and the light-shielding pattern 30a. As a result, the film thickness of the semi-transmitting pattern 20a is 319 A (31.9 nm), and the film thickness of the light-shielding pattern 30a is 1020 A. (102.0 nm), the film thickness is set to 700 A according to the light shielding layer pattern 33a, and the film thickness of the antireflection layer pattern 35a is 300 A (30.0 nm). The film thickness of the light shielding pattern 3〇a is 1〇2〇A (102.0). Nm ) within the error range of the measuring device, from It can be confirmed that it is approximately the same as the target value. The results are shown in Table 2. [Table 2] \ 1st layer (semi-transmissive layer) 2nd layer (摭 layer + anti-beam, optical density \ film thickness '&quot ;a&quot; 350 nm Transmittance 365 nm _(_%) 436 nm 500 nm Pattern -------------- 0/Ε (μπι) 'ϋ Film thickness&quot;(A)&quot; ........ Round case 0/Ε (μιη) Degree (OD) Example 1 319 6.91 8.54 14.73 18.29 0.37 ◎ 1020 0.38 〇3.38 Example 2 260 12.85 14.81 2L14 25.53 0.39 ◎ 1015 0.37 〇3 29 Example 3 231 18.79 20.74 29.67 32.78 0.35 ◎ 1005 0.39 〇3 22 Example 4 209 28.05 29.94 39.93 48.18 0.38 (δ) 1000 0.38 〇3 17 Example 5 153 40.01 39.56 52.03 59.59 0.40 ◎ 980 0.35 Ο 3.03 Example 6 118 48.06 50.98 60.52 68.30 0.39 ◎ 1010 0.40 〇3.13 Example / 487 7.65 9.55 18.97 27.66 0.38 ◎ 1000 0.39 ο 3 07 Real 8 287 29.03 30.95 37.66 43.48 0.37 ίδ) 1020 0 39 〇3 〇5 Example 9 "124 48.21 51.00 59.06 64.98 0.36 ◎ 1010 ο 3.03 Comparative Example 1 esssaaBssBKsaae 0.38 — — — — 1280 0 40 〇 3 18 Comparative Example 2 — — — — — — 980 0 38 〇 3 04 Comparative Example 3 — One One - - _ 290 f) 38 〇 0 39 Comparative Example 4 —-_ 720 0.35 ◎ 3.02

(Example 2) Example 2 is different from Example 1 in that the semi-transmissive layer 20 was designed such that the transmittance of light having a wavelength of 436 nm was 20%. In this example, the film thickness of the semi-transmissive layer 20 is adjusted so that the transmissive layer 2 is designed to have a transmittance of about 20% at a wavelength of 436 nm. The other conditions are the same as in the first embodiment. 38 200921264 ... In the same procedure as in the first embodiment, the light shielding layer 33 and the antireflection layer 35 are etched to form a stripe pattern composed of the light shielding patterns 3A. The substrate was cut in the longitudinal direction, and the same electron microscope photograph as in Fig. 6 of Example i was taken, and the viewing tube and the surface were not provided with the cross section and the plane. According to the results of the cross-sectional observation, the size of the surname is 4 〇·37. Further, according to the result of the front observation, it can be seen that 'the edge of the straight line pattern is slow--u is not &lt; the edge of the apron 4 is uneven, and the maximum and minimum widths are 0.1 μηι or less. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The semi-transmissive layer 20 is opened to form a stripe pattern composed of the semi-transmissive pattern 2Ga. The substrate was cut in the longitudinal direction and the disk was taken. 1 The film was observed and the cross section and plane were observed with the same electron micrograph I of "". In the basin, the result of the long-term unloading, the over-etching size is 0 39 _ °, and it is known that the edge portion has a sufficiently small concave-convex dimension relative to the straight line pattern, which is 〇.〇5 μηι or less. horse

Further, the transmittance and the like were measured in the same manner as in Example i. As a result, the optical densities t and 3.29 were (10) at a wavelength of 35 〇 nm. /. At a wavelength of 436 nm, 21 '14%' is 25_53% at a wavelength of 5 〇〇 nm. Further, as a result of the film thickness measurement, the film thickness of the semi-transmission figure ostrich was 26 〇, and the film thickness of the light-shielding pattern was (8)^^^). The specific results are shown in Table 2. (Example 3) Example 3 and Example The transmittance of light was 30%. The difference between 1, 2 and 2 was that the semi-transmissive layer 20 was designed to have a wavelength of 436 nm. In this example, 39 200921264 The film thickness of the transmission layer 2G is adjusted to design the semi-transmissive layer to be ',, and emit light at a wavelength of 436 nm a temple transmittance of about &amp; 0.3%, in addition to The conditions were the same as in Examples 1 and 2. In the same procedure as in the first embodiment, the light-shielding layer 33 and the anti-reflective (tetra) 35 &amp; (d) are opened to form a stripe pattern composed of the light-shielding pattern 3〇a. The formed substrate was cut in the longitudinal direction 2, and the same two micrographs as in Fig. 6 of Example i were taken to observe the cross section and plane. According to the cross section, the size of the money is G.39 _. Further, according to the front view, the unevenness is generated at the edge portion of the straight line pattern, and the maximum and minimum ίτ.Μ, when the titanium nitride surface of the transflective layer 20 is not observed, the film changes significantly, and it is known that it remains in the transparent Substrate 1. The formation 2 was carried out in the same order as in Example 1 to transmit the layer 2. Taking the substrate formed by the + transmission pattern 2〇a槿, and taking the disk embodiment 〃. The mirror image was cut in the longitudinal direction, and the same electron microscope _ of Fig. 8 was observed. Again... and plane. As a result, the over-etching size was 0·35 〇〇5 _, and it was found that the edge portion had a sufficiently small unevenness with respect to the straight line pattern, and was υ; &gt; μΐϊΐ or less ❶ was 3: '= V/sample, and the transmittance was measured. As a result, the optical density was 1% in the skin: 35°_time (10) and 32 78% at the wavelength of 500 nm. Further, the film thickness measurement of the gentleman, the main Thai &amp; Λ (23), + transmission pattern 2〇a film thickness of 231, the film thickness of the case is (10) to (10) · 5 ·). The results of Zhong, , and ° are not shown in Table 2. 200921264 (Embodiment 4) Example 4 is different from Embodiments 1 to 3 in that the semi-transmissive layer 2q is designed such that the transmittance of light having a wavelength of 436 nm is applied. In this example, the film thickness of the semi-transmissive layer 20 is adjusted so that the semi-transmissive layer 20 is designed to have a transmittance of about 4 4% at a wavelength of 436 (10), and other conditions. The same as Examples 1 to 3. In the same procedure as in the first embodiment, the light-shielding layer 33 and the anti-reflection layer 35 are formed in a stripe pattern composed of a light-shielding pattern core. Cut the formed substrate in the vertical direction and shoot with the example! Figure 6 is the same electron microscope image [observing its cross section and plane. According to the observation of the cross section, the size of (4) is G.38 _. Further, according to the result of the front view, irregularities are generated at the edge portion of the straight line pattern, and the maximum and the center of the heart are = 〇. At this time, the titanium nitride 1 J film in which the semi-transmissive layer was not observed was significantly changed, and it was found that it remained on the surface of the transparent substrate. Next, the semi-transmissive layer 2 is named in the same order as in the embodiment i to form a stripe pattern composed of a semi-transmissive pattern. The formed substrate was cut in the longitudinal direction, and the same electron micrograph as in the eighth example of Example i was taken, and the cross section and plane were observed. As a result, the excess size is Ο.% μπι. Further, it is understood that the unevenness of the edge portion with respect to the straight line pattern is sufficiently smaller than 〇·〇5 μιη or less. Further, the transmittance and the like were measured in the same manner as in the examples, and as a result, the optical density was 3"7, the transmittance was 28 at a wavelength of 35 Qnm, 39.93% at a wavelength of two, and 48.18% at a wavelength of 500 nm. . 41 200921264 Further, as a result of the film thickness measurement, the film thickness of the semi-transmissive pattern was 2 〇 9 A (20.9 nm), and the film thickness of the light-shielding pattern 30a was l 〇〇〇 A (i〇〇〇). The specific results are shown in Table 2. (Example 5) Example 5 is different from Examples 1 to 4 in that the semi-transmissive layer 2 was designed such that the transmittance of light of the wavelength 436 - was as follows. An example. In this example, the film thickness of the semi-transmissive layer 20 is adjusted so that the semi-transmissive layer 2 () is designed to have a transmittance of about 5% by the transmittance of light at a wavelength of 436 nm, and the other conditions are the same as in the first embodiment. ~4 the same. The light-shielding layer 33 and the anti-reflection #35 are left in the same order as in the first embodiment, and the stripe_ is formed by the light-shielding pattern 3Ga. The formed substrate was cut in the vertical direction, and the same micromirror photograph as in Fig. 6 of Example i was taken, and the cross section and plane were observed. According to the results of wearing the face observation, the size of the (four) is 〇.35 _. Further, according to the front view surname =' is generated at the edge portion of the straight line pattern... the maximum and minimum: the visibility is 0.1 μm or less. At this time, the m "the titanium nitride surface of the transmissive layer 20" was significantly changed, and it was found that it remained on the transparent substrate. The table was followed by the same order as in the first embodiment. Layer 2〇, a stripe pattern composed of the semi-transmissive pattern 20a is formed. On the formed substrate, the same electronic material as in Fig. 8 of the embodiment is shown: the photograph 'observes its cross section and plane. 'Over (four) size is (4) = again, the edge portion is relatively small in size with respect to the straight line pattern, which is 〇〇5_ 42 200921264 is 3 03 : The transmittance is measured in the same manner, and the optical density is 4 at a wavelength of 350 nm. 〇〇1% is 52 peaches, 59.59% at 5GGnm. At the wavelength of 436 nm and then the film thickness is measured by the gentleman black, the main α ^ + A (15 ., , , , , , fruit + transmission pattern 2, such as a film thickness of 153. _) 'film thickness of the light-shielding pattern 3〇a, the results are shown in Table 2. 8-〇nm) (Example 6) Example 6 and Examples 1 to 5 5 is not limited, so that the transmittance of the wavelength 436 nm2 is 6〇%. The main example is the method of calculating the transmission layer 20. In this example, the film thickness of the +-transmissive layer 20 is adjusted, α ά ά, to design the semi-transmissive layer 20 to illuminate at a wavelength of 436 nm. #叹^条社- 夺 之 transmittance is about 60% ' The other conditions are the same as those of the first to fifth embodiments. In the same manner as in the first embodiment, the yoke (4) is inserted into the rod (4), and the anti-reflection layer 35 is etched to form a stripe pattern composed of the shading pattern 30a. Cut off the substrate of the money, and destroy p (4) in the square +, and take the same microscopic photo of the bun as shown in Figure 1, and observe the cross section and plane of the Gong 31. According to the results of the cross-sectional observation, the over-etched size is 〇 4 ^ · μΐΏ. Further, according to the result of the front observation, it is known that the width of the side of the straight line pattern 1 is uneven, and the maximum and minimum visibility is 0.1 μηι or less. At this time, r Τ·χτ , ^ ^ did not see + the transmission layer 20 of the titanium nitride C ΤιΝχ ) film produced a significant change, surface. It is known that it remains on the surface of the transparent substrate 10, and the semi-transmissive layer 20 is etched in the order of the first embodiment in the same manner as in the first embodiment, and is formed by the semi-transmissive pattern 20a槿忐, y. Stripe pattern. The substrate after the opening was cut in the longitudinal direction, and the same electron microscope 43 as that of FIG. 8 of Example 1 was taken. The photo of the mirror was observed and the cross section and the plane were observed. The overetched size was 〇39. Ηηι. Further, it is understood that the edge portion has a sufficiently small unevenness with respect to the straight line pattern and is 0.05 μm or less. Further, the transmittance and the like were measured in the same manner as in Example 1. As a result, the optical density was 3.13, the transmittance was 48 〇 6% at a wavelength of 350 nm, and 60.52% at a wavelength of 436 nm was 68.30% at a wavelength of 500 nm. Further, the result of the film thickness measurement is a semi-transmission pattern, and the film thickness of the pattern 20a is π8 A (ii. 8 nm), and the film thickness of the light-shielding pattern 30a is 1〇l〇A (i). 〇i. The results are shown in Table 2.

According to the observation results of the optical microscope and the electron microscope, the patterning characteristic of the light-shielding pattern t 3Ga of the embodiment ～6 is that the (four) size is 〇35 〇.4〇pm, and the concave-convex size of the edge portion of the straight line pattern is 〇ΐμιη. the following. Further, the over-etching pattern 20a has an over-etching size of 〇 35 to 〇 4 〇 , and for the linearity of the pattern edge, the concave-convex size of the straight-line pattern is . One or less. The unevenness was small with respect to the pattern width of 2_, which was (10) (〇.〇5 μηι), and thus it was confirmed that there was no problem in terms of linearity. Furthermore, (4), the reason for hindering the linearity of the pattern money is that the reaction between the film and the photoresist interface due to the reaction of the liquid crystal grain interface with the (four) liquid or the surface treatment without the surface treatment is performed. Insufficient fit. The reason for the lack of the snapping is considered to be the oxidation and contamination of the surface of the film due to the base film 2 after the film is formed, and other reasons. (Example 7) The present embodiment differs from Examples i to 6 in that 2 &amp; ^ I burdock layer) H 2 layer C light-shielding layer) materials are interchanged, and the first medullary engraving is recorded (recorded at 44 200921264) An example of a case where the liquid A) is interchanged with the second rhyme (button engraving liquid B). Further, the order of the film forming step and the patterning step is the same as that of the embodiment 丨~6. In the same manner as in Example ,, first, a quartz substrate (transparent substrate 1) was attached to the apparatus (4), and a commercially available chromium metal (purity of 99 99% or more) was used for reactive sputtering. In the splashing step, a set of powders is introduced while introducing oxygen and nitrogen gas to form a film of a compound (Cr〇N) composed of chromium, oxygen, and nitrogen, thereby forming the semi-transmissive layer 20. At this time, the semi-transmissive layer 2 was formed into a film so that the transmittance at a wavelength of 436 nm was 20%. Next, the metal chromium target is replaced with a metal titanium target to form a light-shielding layer on the surface of the semi-transmissive layer 2G so that the thickness is 7 (eight) A (7 〇 nm). The metal is formed into a film on the surface of the semi-transmissive layer 20.

Next, the target was replaced with a new titanium target, and the antireflection layer 35 was formed to have a film thickness of 3 〇〇 A (W nm). In the sputtering step, while the oxygen and nitrogen are introduced, the plating is performed to form titanium, oxygen and nitrogen (TiON). . When the reflectance at this time is formed in the antireflection layer 35, the reflectance at a wavelength of 650 nm is 35 to 38%, and the reflectance at the vicinity of the wavelength 43 is 10%. The person-to-person, remove the substrate 2 for the photomask formed in the above-mentioned sputtering step from the sputtering apparatus: after being placed in the warehouse-week, use the engraving liquid B (potassium hydroxide, :: first 匕: two mixed illusion 'In the same order as the implementation...', the pattern of the light-shielding pattern 3〇a laminated with the anti-reflection layer 35 is formed into a stripe pattern. The substrate is cut in the longitudinal direction, and the image is taken. 6 The same electron micrograph, the observation result of the observation, it can be seen that the over-etched size is = face and thousand faces. According to the cross-sectional view, the body is 娄τα. From 111. Also, according to the front, it is known, in the straight line pattern The width of the edge portion is large and the smallest is (Μ μηι or less. The nitrogen oxide complex (10) Ν) film changes significantly, but the surface of the transmission layer (9) substrate 10 is not visible. ^ In the same procedure as in Example 1, the semi-transmissive layer 2 was engraved by using _Liquid A (a mixture of succinic acid and translucent 20 water) to form a stripe pattern of the slab and photographed by 1 in the longitudinal direction. The same electron micrograph of Fig. 8 of Example 1 of Example 1 is formed after the formation of the fracture, As a result, the cross-section of the over-etched edge portion with respect to the straight line pattern, μη1, and '77 J are 〇.1 μπι or less. In the same manner, the transmittance was measured in the same manner as in Example 1, and the optical density was measured.

V., the transmittance is 7 65 at a wavelength of 350 nm. / , when the time is 18 97. / Lu Hao 7.65/. At a wavelength of 436 nm . 'at 27 66% at a wavelength of 500 nm. A (4^7 and the thickness of the film is measured. The semi-transmission pattern is 487. The film thickness of the light-shielding pattern is l〇〇〇A (i〇0nm). The results are shown in the table. 2. The embodiment 8 is different from the embodiment 7, and the semi-transmissive layer 20 is designed such that the light of the wavelength 436 is half-read, '', and 4%%. In this example, The film thickness of the layer 2 was adjusted to design the semi-transmissive layer 2G to be 46 200921264, and the transmittance of light at a wavelength of 436 nm B is about &amp; 0.4%, and the other conditions are the same as in the seventh embodiment. In the same procedure as in the seventh embodiment, a stripe pattern formed by the light-shielding layer t 3Ga in which the light-shielding layer 33 and the anti-reflection layer 35 are laminated is formed. The formed substrate is cut in the longitudinal direction, and the image is taken as an example. (I) The same electron micrograph is used to observe the cross section and the plane. According to the results of the cross-section observation, the over-etching size is 〇·39_. Further, according to the result of the front observation, it is known that the unevenness is generated at the edge portion of the straight line pattern. With the smallest width below, at this time 'no semi-transmissive layer 2... chromium oxide (CK) N) film produced significantly Of 'clear transparent substrate which remains on the surface of ι〇. Next, the semi-transmissive layer 20 is described in the same order as in the embodiment 7, and a stripe pattern composed of semi-transmissive (tetra) 2Ga is formed. The formed substrate was cut in the longitudinal direction, and an electron micrograph of the same example as that of Fig. 8 of Example 1 was taken, and the cross section and plane were observed. As a result, the overcut size was 0.37, and it was found that the edge portion has a sufficiently small unevenness with respect to the straight line pattern and is 0.1 μηι or less. Further, in Example 1, the transmittance and the like were measured in the same manner, and as a result, the light was 3.05, and the transmittance was 29.3% at 37 (four) when the oil was again at a wavelength of 43 - *'. / 〇 at a wavelength of 500. At nm, it is 43.480/. . As a result of the measurement of the film thickness of (::], the film thickness of the semi-transmissive pattern core was set to be equal to two g, and the film thickness of the light-shielding pattern was (10) to (5) (10). The results of Cai 5 Hai Temple are shown in Table 2. (Example 9) 47 200921264 Example 9 differs from Examples 7 and 8 in that the semi-transmissive layer 2 is designed such that the transmittance of the wavelength is 60%. In this example, the film thickness of the material transmission layer 2G is adjusted to design the semi-transmissive (four) 20 to be: first: the transmittance at a wavelength of 436 nm is about A 6 〇%, and the other examples are the same. 7 '8 is the same. In the same manner as in the seventh and eighth embodiments, the light-shielding layer 33 and the anti-reflective layer were formed into a stripe pattern of the light-shielding pattern 3Qa. The formed substrate was cut in the longitudinal direction and photographed in the same manner as in Fig. 6 of Example i = microscope photograph 'observed its cross section and plane. According to the cross-section observation, the (4) engraved size is . · 38 μιη. Further, according to the front view, the shape of the straight line pattern is uneven, and the maximum and minimum final arrays are generated. At this time, no significant change was observed in the semi-transparent (four) 2 氮 oxynitride film, which was found to remain on the surface of the transparent substrate 10. Next, the (four) semi-transmissive layer is opened in the same order as in the embodiments 7 and 8, and the stripe pattern composed of the semi-transmission pattern 2〇a椹ώ-政 is formed. Cut the formed substrate in the longitudinal direction, and take a picture of the section and plane of the electron microscopy of the same figure as in Fig. 8 of the shovel. As a result, the (four) size is Ο·% _ and it is also known that the edge portion has a sufficiently small unevenness with respect to the straight line pattern, and is 〇. 1 μηι or less. Further, in the same manner as in the example i, the transmittance and the like, ', , and . It is 64.98% at a wavelength of 500 nm. Furthermore, the result of the film thickness measurement, the main reading "η, heart-fruit + transmission pattern 20a film thickness is 124 48 200921264 A (12.4nm) 'The light-shielding pattern 30 &amp; film thickness is 1〇1〇A (1〇inm The results are shown in Table 2. As shown in the above Examples 7 to 9, even if the material of the semi-transmissive layer of the second layer is exchanged with the material of the second layer of the light-shielding layer, f (etching liquid) When the etchant A was exchanged with the etchant B of the second etchant, the same results as in the first to sixth embodiments were obtained. As a result, it was confirmed that the current liquid crystal display element or color filter substrate was used. Needless to say, the use of the black matrix is also possible as a mask. The evaluation results of the examples 丨 to 9 are shown in Table 2. Hereinafter, a comparative example will be described. (Comparative Example 1) Comparative Example 1 and Implementation In the case of the example 丨9, the following three layers are sequentially laminated on the surface of the transparent substrate: a first anti-reflection layer composed of chromium oxide (Cr〇x) and a light shielding layer composed of a metal complex (Cr). And a second anti-reflective layer made of chromium oxide (CrOx). The laminated structure and general use of this example The structure of the photomask is the same, that is, the photomask is generally formed of oxide, nitride, oxynitride or the like according to the absorption degree of the light shielding layer or is disposed under the light shielding layer. In either or both of the layers, the substrate for forming the above-described general photomask is used as a comparison object for comparison with the above embodiments. In the case of the parent example 1, the same as in the first embodiment is used. The sputtering apparatus is replaced with a metal wire (purity of 99. 99% or more) to replace the metal chain dry material of the embodiment i, using oxygen as a reactive gas, and # is reactive deplating as the first antireflection layer. Chromium oxide (Cr〇x) is directly formed on the surface of the transparent substrate 1〇49 200921264. In addition, since the degree of oxidation differs depending on the sputtering apparatus, it is only necessary to combine the film formation conditions and adjust them appropriately. The metal chromium target is replaced with a new metal chromium target, and a light-shielding layer made of metallic chromium (Cr) is formed by sputtering on the surface of the "reflective reflection layer". The film thickness of the w-light layer is almost Complete (big 纟 i 〇 遮蔽 照射 照射 ( (OD &gt; 3 In the film of .0), 隹 and , 戌 M ^ further, a second anti-reflective layer composed of chromium oxide (Cr〇x) is formed continuously on the surface of the light-shielding layer.

Next, the laminated substrate which was formed into the film by the above-described sputtering step was taken out from the deplating device and placed in the warehouse for one week. Next, the substrate taken out from the warehouse is ultrasonically washed in each of a plurality of tanks of a lotion, a neutral lotion, and pure water, and the entire surface of the substrate is coated with the embodiment &quot; The photoresist is temporarily hardened. Thereafter, the pattern used in the embodiment is used for exposure, development, and main hardening, and a mixture of ammonium perchlorate and water of the first-order engraving liquid is used - and (iv) anti-reflection layer, shading The layer and the second anti-reflective layer form a stripe pattern. The cross section and the flat surface were observed using an electron microscope in the same manner as in Example 1, and the over-etching of the stripe pattern composed of three layers at this time was evaluated. As a result, the Aα and the over silver cut size A 0.4() _ were observed from the cross section, and it was found from the results of the front observation that the width of the unevenness at the edge portion of the straight line pattern was 0.1 μη or less. The optical reflectance (〇D) and the spectral reflectance of the optical characteristics were measured using an automatic spectrophotometer H-4〇〇〇 manufactured by Hitachi High-Technologies in the same manner as in Example 1 using another substrate which was not patterned. As a result, the obtained optical density was 3.18, and the reflectance from the surface side of the substrate was 7.1 1% at a wavelength of 436 50 200921264 nm. Further, the film thickness of the pattern composed of the second anti-reflection layer, the light-shielding layer, and the second anti-reflection layer is measured by using one of the etched stripe patterns, and the total film thickness is 1280 cents (nm). The results are shown in Table 2. (Comparative Example 2)

Comparative Example 2 and Example Example 9 and Comparative Example! Differently, the surface of the transparent substrate 1 is sequentially laminated with two layers: a chromium oxide (Cr〇x) layer as an antireflection layer, and a metallic chromium (cr) layer as a light shielding layer. In this example, a film for a black matrix provided on the outer periphery of each pixel (for example, a periphery of a pixel such as red, green, or blue of a color filter) for improving the display quality of a liquid crystal display element or the like, or a micrometer to several tens of micrometers. The layered reticle used by the grading mask has the same structure. In the case of the I color matrix, in order to reduce the reflectance from the visual side opposite to the mask, a structure of chromium oxide (Cr?x) as an antireflection layer is disposed on the substrate side. In this example, chromium oxide (Cr〇x) was laminated in the same order as in Example i so that the film thickness was A (·0 nm), and then the film thickness was 700 A (70.0 nm). The way to laminate metal chromium (heart,). Next, exposure, development, and formalization were carried out in the same manner as in Example ,, and chromium oxide (Cr〇x) was collectively etched using a mixed solution of perchloric acid, ammonium cerium nitrate, and water in the first etching solution. The layer and the metal chromium (cr) layer 'form a stripe pattern. In the same manner as in the first embodiment, an electron microscope was used to observe the cross section and the plane by which the sulphur oxide (CrOx) layer of the antireflection layer and the metal layer (cr) layer of the mask of the 200921264 layer were used. Over-etching of the formed stripe pattern. According to the cross-section observation, it can be seen that the size of the money is 〇. According to the results of the observation on the front side, the initial w &amp; μ is less than or equal to μηι. The width of the unevenness at the edge of the case is 〇·】 Η::·Other substrates that have not been smashed, and the actual measurement of the light wind=Trhnologies automatic spectrophotometer 4000

The resulting light::;) and the spectral reflectance of the optical properties. As a result, the optical density of the corpse V was 3 〇 4, and that of the Ling A was 7.53%. The reflectivity from the side of the substrate at the wavelength 436 is measured by the portion of the stripe pattern of the surname to measure the film thickness of the pattern composed of the light-shielding layer and the anti-reflection layer. As a result, the total film thickness of the temple was 980 (98.〇nm). The results are shown in Table 2. (Comparative Example 3) ^Comparative Example 3 and Example (1) and Comparative Example 2 W are examples in which only an oxidized (loud) layer is formed on the surface of the (c). Chromium oxide: x “The use of a layer of the same etchant as the metal chrome (the (7) layer, so that a halftone mask is produced by a conventional method, a light-shielding metal chromium, Cr) layer and a semi-transmissive chromium oxide (Cf〇) x) The layers are respectively (that is, divided into 2 times) into a crucible. Therefore, in Comparative Example 3, an example in which only an oxide circuit (Cr〇X) layer having only a semi-transmissive layer function b is formed is used as the above Comparative Example of the Example In this example, a chromium oxide (Cr〇x) layer was formed in the same manner as in Example 1 so that the film thickness was 300 A (30.0 nm). Exposure and development were carried out in the same order as in Example 1 and the use of perchloric acid, ammonium cerium nitrate, and water in the etching solution was carried out. A chromium (Cr〇x) layer is formed to form a striped pattern. :: Besch: i Similarly, an electron microscope is used to observe the cross-section and the pattern of the pattern formed by the chromium oxide (Cr0x) layer at this time. The result is 'based on the cross-sectional observation, the size of the (four) is 3—, according to the result of front observation, the width of the unevenness at the edge portion of the straight line pattern is 0·1 μmη or less.

The optical transmittance (0D) and the spectral transmittance of the optical characteristics were measured by using an automatic spectrophotometer manufactured by Hitacn Hlgh-Techn〇l〇gies in the same manner as in Example 1 using another substrate which was not patterned. The optical density obtained was 0.39, and the transmittance was 40.64% ° at a wavelength of 436 nm. Further, the film thickness of the pattern was measured by using one of the etched stripe patterns, and the film thickness was 290 A (29.0 nm). The results are shown in Table 2. (Comparative Example 4) Comparative Example 4 is different from Examples 丨 to 9 and Comparative Examples 1 to 3 in that only a metal chromium (Cr) layer was formed on the surface of the transparent substrate 1 . Since the metal chromium () has a high reflectance, it is used for an electrode or a mirror including wiring, and thus is referred to in comparison with the patterning characteristics of the examples. In the present example, a metal chromium (Cr) layer was formed in the same manner as in Example 1 so that the film thickness was 7 Å (70.0 nm). Next, exposure, development, and main hardening were carried out in the same manner as in Example 1, and a metal chromium (Cr) layer was named by using a mixed liquid of perchloric acid, ammonium cerium nitrate, and water in the first etching liquid. To form a stripe pattern. 53 200921264 In the same manner as in the first embodiment, the cross section and the flat surface were observed using an electron microscope, whereby the pattern of the pattern composed of the metal chromium (Cr) layer at this time was evaluated. As a result, it can be seen from the cross-sectional observation that the over-etching size is 〇 3 $ , and as a result of the front observation, the width of the unevenness at the edge portion of the linear pattern is 0.05 μm or less. An automatic spectrophotometer side manufactured by Hitachi High-Technologies was used in the same manner as in Example 1 using another substrate which was not subjected to (iv)

The optical reflectance and transmittance of optical density (OD) and optical characteristics were measured. The resulting optical density was 3·〇2' transmittance at a wavelength "" at η of 0.092% and a reflectance of 59.71%. Further, the film thickness of the pattern was measured by using one of the cross-cut pattern of the money. The total film thickness of the pattern was 72 G a (72 g fruit - shown in Table 2. The result of the 【 [ FIG. 1 is a simple illustration of the present invention Fig. 2 is an explanatory view of the present invention, Fig. 3 (a) to (f), and Fig. 3 (a) to (f) are longitudinal cross-sectional views of the reticle of the embodiment of the reticle substrate of the embodiment. Description of the procedure for patterning the mask from the mask substrate Fig. 4 (a) to (f) show the mask. Figure. Fig. 5 is a longitudinal cross-sectional view of a longitudinal section of a substrate for a photomask according to another embodiment of the present invention, and an electron micrograph of a mask 54 after the formation of a mask 54 after the formation of a light-shielding pattern is shown in Figs. 6(a) to 6(c). Optical microscopy obtained from the plane of the 7-series and the posterior mirror image

[Description of main component symbols] 1 Photomask 2 Photomask substrate 1 a Light-shielding portion lb Semi-transmissive portion 1 c Transparent portion 10 Transparent substrate 20 Semi-transmissive layer (1st layer 20a Semi-transmissive pattern 30 Composite layer (2nd layer) 3 〇a shading pattern 33 light shielding layer 33a light shielding layer pattern 35 antireflection layer 35a antireflection layer pattern 50 photoresist 60 photomask original 70 photoresist 55 200921264

56

Claims (1)

200921264 X. Patent application scope: The substrate for the reticle cover has a transparent substrate, is formed on the transparent substrate: and is semi-transmissive to the illuminating light... and is formed on the ith!:: contrast: the light is substantially shielded from light The second layer can be formed on the surface of the semi-transmissive portion of the semi-transmissive pattern formed by the light-shielding portion of the light-shielding pattern formed by the two layers of the Haidi, and the surface exposed by the (four) one layer. And a transparent portion of the transparent substrate on the surface, wherein the second layer is insoluble or difficult to bathe, and the second layer is insoluble to the first etching solution. Easily soluble; and Dong + 2 ^ 3 compared to 'the second layer of the 帛 1 surname is easy to dissolve the second etchant is insoluble or poorly soluble. 2 · For example, if you apply for a patented whistle X m, ^ a film for a mask for a brother, where the first layer is directly formed on the (four) transparent substrate. The substrate for a photomask according to the first aspect of the invention, wherein the second compound having a second transmittance of 7 % by mass or less and less than 100% is formed on the transparent substrate. Among them, the t/specific~11 first to third items are used as the substrate for the m cover, and the ^1 is a mixture of ammonium cerium nitrate, perchloric acid and water. I. The substrate for the photomask according to any one of the items (1) to (1) to (1), (6), as claimed in the patent range: a mixture of hydrogen peroxide and water. 1A substrate for a photomask according to any one of items 1 to 3, consisting of: The first layer is mainly composed of a component selected from the group consisting of titanium, titanium nitride, and titanium oxynitride, or two or more components. A substrate for a photomask according to any one of the items i to 3 of the patent track, 57 200921264 wherein 'the second layer' is a group selected from the group consisting of chromium, chromium oxide, chromium nitride and chromium oxynitride One or more of the components are the main components. The substrate for a photomask according to any one of claims 1 to 3, wherein the crucible 2 is provided with an antireflection layer which is shielded from light and formed on a surface side of the light shielding layer. 9. The substrate for a reticle of the ninth aspect of the invention, wherein the antireflection layer is one or more selected from the group consisting of chromium oxide, chromium nitride, and nitrogen oxynitride. The ingredients are the main ingredients. 1 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a layer of one or more components of the group towel as a main component; the second layer is one or more components selected from the group consisting of titanium, titanium nitride, and titanium oxynitride. The layer of the main component; the first etching liquid is a mixture of potassium hydroxide, hydrogen peroxide and water; and the second etching liquid is a mixture of ammonium cerium nitrate, perchloric acid and water. &quot;&gt; The substrate for a photomask according to any one of claims 1 to 3 wherein the &lt;6&gt; first layer and the second layer are formed by a clock-breaking method, an ion-money method or a steaming method. 12. A reticle, wherein the reticle substrate is formed with a transparent substrate, a first layer formed on the transparent substrate and having semi-transmissive light to the illuminating light, and being formed on the fi layer The second layer that substantially blocks the illumination light is characterized by: 58 200921264 &quot; Compared with the second layer, the flute, a. is insoluble and is easy to dissolve on the second button engraving. The liquid is insoluble or inferior to the first layer, and the second etching liquid is +^10. The etching liquid is insoluble or insoluble, and the light shielding portion is formed in the mask. The light shielding pattern is exposed on the surface by the i-th silver engraving; ^ the first layer is etched and r (four): the transmissive portion is formed by the second engraving liquid on the first layer n (: the semi-transmission pattern is The surface is exposed; and the layer is etched and etched, and the second layer and the second etchant are respectively separated by the fourth layer and the second etchant. The layer is etched to make the transparent substrate The surface exposed item: the manufacturing method of the cover type if is the first cover of the 12th member of the patent application scope, and its characteristics Therefore, the following steps are performed: "The photoresist coating step" is applied to the surface of the second layer to cover the photoresist; the first exposure step of the first embodiment is performed by the mask of the first photoresist in the pattern of the f... Particularly, the exposure of the photoresist covered in the coating step is performed; the first photoresist removing step removes the exposed portion; and after the exposing step, the photoresist is subjected to an etching step, and the first etching solution is used to etch the The photoresist has removed the second layer exposed in the germanium region to form the light-shielding pattern; the resist 1 stripping step has been performed, and the photoresist remaining in the first photoresist removing step is peeled off; the second photoresist of W In the coating step, the photoresist is again coated on the surface; 59 200921264 The second exposure step is performed by removing the portion exposed by the second photoresist removal step in the second photoresist coating step; and transmitting the light through the second mask pattern formed by the second mask pattern Exposure of the resist, the photomask is performed, and after the second exposure step, the second etching step of the photoresist is removed, and the removed etching region is etched to etch the photoresist at the second photoresist; Step: to the semi-transmission . Text; and will resist peeling the remaining second resist removal step of eleven, FIG formula: such as hypophosphorous Page 60