TW200830363A - Method of producing a photo mask - Google Patents

Abstract

In a method of producing a photo mask including the steps of preparing a mask blank in which a light semi-transmitting film and a light-shielding film are successively formed on a light transmitting substrate and patterning the light-shielding film and the light semi-transmitting film, to prevent pattern defects in the light semi-transmitting film and/or the light shielding film resulting from a gas generated by wet etching of the light semi-transparent film. In a method of producing a photo mask including the steps of preparing a mask blank in which a light semi-transparent film and a light-shielding film are successively formed on a light transmitting substrate and patterning the light shielding film and the light semi-transparent film, the light semi-transparent film is made of a material having a function of adjusting the amount of transmission with respect to exposure light and containing metal and silicon. The light-shielding film has a function of shielding the exposure light. The light semi-transparent film is patterned by wet etching using an etching liquid containing at least one fluorine compound selected from hydrofluoric acid, fluorosilicic (hydrofluorosilicic) acid, and ammonium hydrogen fluoride and at least one oxidizing agent selected from hydrogen peroxide, nitric acid and sulfuric acid. In the etching liquid, a molar ratio of the fluorine compound and the oxidizing agent is selected so that the tabove-mentioned pattern defects can be prevented.

Description

200830363 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method of manufacturing a photomask, and more particularly to a method of manufacturing a photomask used in the manufacture of an fpd device. [Prior Art] In recent years, in the field of large-scale FPD reticle, an attempt to reduce the number of hoods using a gray-scale mask having a semi-translucent field (so-called gray-scale portion) (Monday FPD Intelligence p.31_35) May 999 (Non-patent literature)). Here, as shown in Figs. 3(1) and 4(1), the gray scale mask has a light-shielding 胄1 and a light-shielding portion 2 and a gray-scale portion 3 in a semi-transmissive field on the transparent substrate. The gray scale portion 3 has a medium for adjusting the amount of transmission to the exposure light, for example, 'as shown in the third ® (1)' in forming a semi-transmissive film (semi-transmissive film) 3a' of the gray scale mask, or Is forming the ash as shown in Fig. 4 (1)

The field of the I5 white pattern (the resolution of the large M FPD using the gray scale mask is: the fine shading pattern 3a and the fine transmissive portion 3b), so that the transmission amount of the exposure light transmitted through the k-field is reduced. The reduction in the amount of irradiation in this field is formed by controlling the film thickness corresponding to the development of the photoresist in the relevant field to the value of the target. Dali gray-scale reticle, in the lens mounted on the mirror ~ eight π4 K with the S sie lens only when the shadow of the way is mostly warm φ boat ice waves set to use, due to the exposure of the light through the gray 13⁄4 part 3 + 曰兀 篮 而 而 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

2130-9184-PF 6 200830363 on the board. That is, since the photoresist corresponds to a portion of the corresponding gray scale portion 3 and corresponds to a portion of the corresponding gray scale portion 3, the resistivity of the photoresist pattern after development is shown for the solubility of the developer. The portion of the light-shielding portion i, 3, (1) and 4 (2) is a portion 3 of the gray-scale portion 3, for example, a trowel is, for example, about 1 (four), and a portion 2 is a portion 2 having no photoresist. "Heart", corresponding to the portion 2 of the transmissive portion 2, the second portion of the substrate to be reinforced: in the thin portion 3 where there is no photoresist, the photoresist is corresponding to the gray scale portion 3 by ash (2) etching, and it is possible to remove the film, and to reduce the number of masks, and to carry out the mask of the conventional W. [Explanation] [The problem to be solved by the invention] However, in the manufacture of micro processing The UI ', ', and the side used for the 7G device, the semiconductor memory, and the system semiconductor are relatively small, so they are mounted on the projection exposure device by the method of 2). A precision of the small mask for manufacturing the LSI reticle is necessary, so that a pattern of the film is formed on the second high. Dry-type in the reticle base relative to this, FPD (flat-panel display) with large light grass _W 220mx1400_, relatively large, and more than 7 mirror projection (by scanning exposure, D; lens projection with lens Exposure device to use. ~Exposure first) way or make

2130-9184-PF 7 200830363 f: Nu: FPD is used in the manufacture of large masks. Because of the large dry money engraving: ^! Difficult, even if it is made, it is very high 15 and it is difficult to technically engrave it. Because of this

In the case of the large-scale reticle base for the manufacture of the FPD cover, it is better to use the etch-like precision of the stencil, and it is better to pay attention to the cost surface and the swallowing. Wet etching is performed on the base film of the reticle. One

The inventors of the present invention have a large-sized photomask base for FPD and a large-sized photomask for the use of a wet-type remnant for forming a semi-transparent film of a total bismuth-based semi-transparent film from a material containing metal and bismuth (Si). Careful research and development have been carried out. As a result, the following can be known. In the case of a film, a mixed solution of metal halide and nitric acid such as a molybdenum compound film is usually used. However, the problem of the gas in the above-mentioned money reaction (the first problem). It is known that there are a large number of occurrences of N02, etc.

The present inventors have inferred the reason from the viewpoint of the reaction formula. Hereinafter, the reaction mechanism after the investigation is shown. (1) (2) (3)

Si + 4HN〇3-> S1O2+2H2O+4 NO2 S1O2+ 4HF^ S1F4+ 2H2O From (1), (2)

Si+ 4HN〇3+4HF->SiF4 + 4H2O+ 4NO2 or

Mo+ 6HF-^MoFe+ 3H by (3) and (4) 2130-9184-PF 8 (4) 200830363

MoSi2+ 8HNO3+ 14HF->2SiF4+ MoFb+ 8H2O + 8NO2 f + 3H2 f (5) In the above reaction formulas (1) to (5), it is important that the hydrofluoric acid reaches the function of the acid which dissolves cerium and molybdenum (the above (2) In the formula (4), nitric acid is not effective for dissolving the acid of cerium and molybdenum, and is only necessary for oxidizing cerium, and is used as a reaction of the oxidizing agent (formula (1) above). As described above, the above-mentioned formulas (1) to (5) are etched by the use of the hydrofluoric acid + nitric acid molybdenum telluride, and the use of highly toxic hydrofluoric acid (poison) and nitric acid (extremely toxic) occurs again. The problem of toxic and corrosive nitrogen dioxide (N〇2). In addition, in the above reaction by fluoric acid + nitric acid, there is a problem that a large amount of harmful gas such as N(1) is generated (the first problem). Therefore, the present inventors have reviewed the use of hydrogen peroxide (10) 2) in place of the above-mentioned nitric acid as an oxidizing agent, and replaced the hydrofluoric acid with a vaporized nitrogen bond (NW·HF) based on past research results (Patent Document No.: Japanese Patent Special) Kai-zhao 62-218585). By this, it is possible to dissolve seconds and enthalpy without using toxic, nitrous acid, which does not emit toxicity and is highly corrosive, thief I, 〇 虱 (N〇2). In the above-mentioned geese and 夂 夂 夂 , , , , , 由于 由于 由于 由于 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟happened. However, in the above-mentioned reaction caused by the field, it is known that there is still a generation of gas due to the occurrence of gas and the sighing of the bubble (a relatively large-sized bubble can be visually confirmed). The inventors of the present invention have inferred the reason from the viewpoint of the reaction formula. Hereinafter, the mechanism for detecting the reaction is shown.

2130-9184-PF 9 200830363

Si + H2〇2^ S1O2+H2 (1)' S1O2+4NH4F · HF S1F4+4NH4F+2H2O (2)' From (1), (7),

Si + H2O2+ 4NH4F · HF^SiF4+ 4NH4F+ 2H2O (3), or

Mo+ 6NH4F · HF^MoFe+ 6NH4F+ 3H2 (4), therefore, by (3)’ and (4)’

MoSi2 + 2H2O2 + 14NH4F · HF->2SiF4 + 14NH4F + M0F6 + 4H2O+ 3H2 t (5), and '' can also oxidize hydrogen of formula (5) with retinoic acid, as shown in the following formula, it can be turned into water. However, the occurrence of relative nitrogen dioxide (N〇2) gas will increase. 3H2+6HN〇3-> 6H2〇+6N〇2f As described above, the above-mentioned formula (1)'~(5) is obtained by the above-mentioned i by the ammonium fluoride fluoride + hydrogen peroxide to make the molybdenum telluride Compared with the reaction of acid + nitric acid (1M5), it was found that the generation of bubbles in the gas can be greatly suppressed. 'However, in the above (four) by #化^+ (4), you are smashed by the chaotic hydrazine + hydrogen peroxide to make the money of the lithological compound (1), ~ (. C5) know the gas Occurrence and bubble with Ik (HO still occurs. Then the inventors, explained that 7 ^ + explained as in the above, in the reaction of ammonium bifluoride + compound, the gas is generated and the formation is long (2nd) H)2 Since the bubble starts to grow from the surface of the film (Fig. 2), it is not necessary to attach the bubble, and the film defect such as the film residue is left. Semipermeable

2130-9184-PF 10 200830363 The problem of the pattern of the semi-transparent mirror film is 2, as in the case of the gray scale of 1 〇 to 100 angstroms: the gas generated by the etching (") causes the trapping ( The first △ < Lesson 4). The semi-transparent film in the first mask is firstly coated, and if the film thickness is as thin, the effect is large. The inventors of the present invention -4 / t peroxidation heart palpitations found that the gasification of ammonium hydroxide +, sheep L phlegm money engraving, hydrogen peroxide molar ratio x. γ ... 'etched hydrogen fluoride in solution With

Gas generated by 亀: = In order to prevent the pattern defect of the semi-transmissive film caused by the wet type of the semi-transmissive film, -2, the countermeasure of the second problem is effective, and Further, the molar ratio L_y which minimizes the amount of gas generated by the silver engraving suppresses the generation of gas, and the second problem is that the side enthalpy is very effective. However, it is known that even if the etching liquid to ear ratio is set in this way, hydrogen peroxide is easily decomposed. This oxygen gas (〇2) has a problem of being easily generated, and it is difficult to completely suppress the occurrence of gas (the third problem). The main thing is 'such as a gray-scale mask, forming a light-shielding film on the metal halide film 1 'According to the material of the light-shielding film, the oxygen gas generated by the metal-lithium film in the wet residual state (〇〇 When the light-shielding film is viewed in a cross section, the upper surface or the side surface of the light-shielding pattern is prevented from being infiltrated, and therefore, the profile of the light-shielding film is changed by changing the degree of etching of the light-shielding film. The shape changes, or the optical characteristics (reflectance or optical density) of the light-shielding film changes, and the light-shielding film pattern defect of the gas (02, etc.) occurs due to the wet etching of the semi-transmissive film (No. Problem 4) The object of the present invention is to provide a solution to the above problems and to prevent

2130-9184-PF 11 200830363 A method of manufacturing a reticle of the above-described transflective film and/or pattern defect of the above-mentioned premature film by a gas generated by a wet pattern of a film of 14 first. [Means for Solving the Problem] The method of the present invention has the following constitution. (Configuration 1) The method for producing a cover is a semi-transmissive film formed of a material containing an ancient eve from a light-transmissive substrate and having a function of transmitting light for exposure light for 5 weeks. And a mask base for shading the exposure light, wherein the light-shielding film and the front-precursive film are patterned to produce a mask for the photomask, and the pattern of the pre-transparent film By using a wet line comprising at least one fluoride selected from the group consisting of hydrogen fluoride acid, shixi η, ammonium hydrogen fluoride, and the like, and at least one oxidizing agent selected from the sulfuric acid; the aforementioned money engraving liquid, The molar ratio of the aforementioned vapor = emulsifying agent in the engraving liquid is an etching liquid which is set to prevent the pattern of the defect caused by the gas which is generated by the etching. (Configuration 2) - A method of manufacturing a reticle is to form a semi-transmissive film formed of a material containing Meng and Shi Xi from the light transmission = having a function of adjusting the amount of transmission to the exposure light, and A method of manufacturing a mask for producing a photomask by masking a film having exposure light = a cover base, and patterning the light-shielding film and the semi-transmissive film, wherein the semi-transmissive film is patterned. It’s made by people, but it’s servant’s temperament’

At least one oxidant selected from the group consisting of 虱化, pure money, etc., I nitrogen, (iv), sulfuric acid, and at least one oxidizing agent, and defoaming agent i

2130-9184-PF 12 200830363 The wet type of liquid (4) is carried out. Structure 3) constituting or 2: before the etchant, f~ "method, which is characterized by wet etching; the molar ratio of the substance to the oxidant is: The method for preparing a semi-transparent hood, the film thickness of the bovine transparent film is 1 〇 1 〇〇 。. (Constituent 5) constituting!

It is based on the above-mentioned reticle, ‘ /, special [invention effect]. According to the present invention, the uranium is said to be a translucent film translucent film and/or method. It is possible to solve the above problems, and it is possible to prevent the manufacture of a mask having the pattern defect of the above-mentioned light-shielding film caused by a gas generated by wet etching. [Embodiment] Hereinafter, the present invention will be described in detail. According to a first aspect of the invention, there is provided a method for producing a reticle, wherein the light-transmissive group is formed of a reverse enthalpy, and has a function of adjusting a transmittance for exposure light: "3 Meng and Shi Xi materials a method for producing a reticle of a reticle, wherein the semi-transmissive film and the reticle base of the light-shielding film that exposes the exposure light are patterned, and the semi-transmissive film is patterned The photo film is formed by using at least one fluoride selected from the group consisting of hydrogen fluoride fluoric acid, ammonium fluorinate, and the like, and at least one oxidizing agent selected from the peroxide gas and sulfuric acid. Money engraved wet type II

2130-9184-PF 13 200830363 is characterized in that: the molar ratio of the fluoride to the oxidizing agent, U = the etching of the above-mentioned formula in the engraving, and the occurrence of the Wet (the composition of the 造成 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体In order to solve the above problems 1 to 2, the gas generated by the above-mentioned car, #, /", or etching causes a pattern defect of the j-transparent film, and a method of manufacturing the photomask. The moiré ratio of the oxidizing agent described in the etching, the m/liquid command of the mouse compound and the front deafness 5 are further reduced to prevent the oxidizing agent of the pattern which is caused by the wet etching. Moerby, the disk accompanying ^ 'will be the relationship between the defects of the trace gas before the gas, so that the gas produced by the above-mentioned Mo Er Ersheng is determined by the change of the Mobi ratio, according to this, : The aforementioned molar ratio is set to prevent the occurrence of a pattern of gas accompanying the wet rhyme The ear is more than expected. And 'the above-mentioned silver etched liquid ten and the oxidant Mo 〃 X are set to prevent the pattern caused by the gas generated by the heart-shaped wet pattern, trapped in the Mo Erbi The liquid, in simple terms, the molar ratio of the fluoride to the weathering agent and the occurrence of bubbles, and the molar ratio is changed to obtain 'based on this, by setting the aforementioned molar ratio to It is possible to obtain a molar ratio in which bubbles do not occur. However, in this case, it is practical to set a pattern in which the bubble ratio does not occur, whether or not the pattern defect caused by the gas generated by the wet type is prevented. Confirmation is necessary.

2130-9184-PF 14 200830363 In addition, the ratio of the fluoride of the above-mentioned I insect sputum φ 乂 f fch, i Α β to the above oxidant is usually not your peptide ^ 4 < The idea of creating a gas-like defect in the engraving and setting the image caused by the rolling of the raw material ^, but from other viewpoints (such as maintaining the adhesive performance), the rhyme and the 乂4 are quasi-etched sharp and 疋The aforementioned Moerby. Therefore, the fluorides, _p ^ y j, the gas that was engraved before the engraving of the money, and the J-Ten are the same as the prevention of the wet type. There is a considerable difference in the molar ratio of the pattern defects caused by the ritual body. In the first invention, the moiré ratio of the gasification oxidant in the money engraving liquid is abundance... It is preferable that the gas generated by the wet etching is set to be a small molar ratio (constitution 3). = is believed to be caused by the fact that the amount of gas generated by the wet-type surname is the minimum I-to-ear ratio (minimum value), which can be minimized by Ik wet etching. The pattern is defective. ^ The amount of gas generated by wet etching in the middle of the month is the molar ratio of the fluoride to the oxidant, which can be obtained from the above-mentioned reaction formula. This is as explained below. For example, in the above (5)', the generated hydrogen peroxide can be turned into water by adding 5 moles of peroxygen peroxide. If it is represented by a reaction formula, it is the following formula (5),. M0S12+ 7H2O2+ 14NH4F · HF->2SiF4+ 14 NH4F+ MoFb + 12H2O (5),, ^ Here, the molybdenum telluride does not necessarily exist in a stoichiometrically equivalent ratio to MoSi2, but mostly in the case of M〇SL . The reaction formula in this case is the following formula (5),,,.

2130-9184-PF 15 200830363 M〇Slx+aH2〇2+2aNH4F xSiF4+u + 2aH2〇(5),,,〇F6 [But in (5),,, where 'a=2x+3> (5),,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, , is the ratio of the minimum (minimum value) (in the above (5),,, 〇). Li: that is, the material of the semi-translucent film is M〇Slx' and the etching solution makes the gas (10)0 and ammonium hydrogen fluoride (10)4F. In the case of HF), if the molar ratio of hydrogen to ammonium hydrogen fluoride = 1:2 is used, the gas generation (quantity) is the smallest (minimum value), so it is preferable. Moreover, the material of the semi-transmissive film is MoSix, and the etchant uses peroxidation: (in the case of pottery and fluorinated citric acid (HF), if cerium peroxide is set: fluorinated decanoic acid = 1 K molar ratio , the occurrence of gas (quantity) is the best. 彳世 j, again, the semi-translucent film material is MoSix, and the etched liquid (on the hydrogen fluoride tank), or the _ _ and fluorine 2 (4) If the tank acid is set: gasified nitrogen acid, jing acid: gas: chlorine: .1 molar ratio, the gas generation (quantity) is the smallest (very good is good. resistance ^ and 'for example, if The film material containing the metal ruthenium and the sho (Sl) is K, which is a transition metal such as "1, 讦, 〇, etc.", according to the above (5) ' ' ', the aforementioned fluoride and The molar ratio of the aforementioned oxidizing agent (for example, the molar ratio of ammonium hydrogen fluoride to hydrogen peroxide) is such that the amount of gas generated as a result of wet characterization is the minimum or minimum molar ratio.

2130-9184-PF 16 200830363, and if it is MSixZ (but, Z4n, c, h, 〇, f#^, m two Nl W, Zr, Τι, Ta, Cr, etc.), although according to Z Combining the morphology or the type of Z 'not necessarily the addition of Z - the fixed tooth) occurs in the body 'but the addition of Z is related to the gas generation; the brother also wants to consider the content ratio of z to make hydrogen fluoride The molar ratio of ammonium to cerium peroxide is the molar ratio of the minimum or minimum value of the gas generation. In the first invention, the fluorine compound in the etching liquid and the front molar and the molar ratio of the cerium oxide X. γ are such that the amount of gas generated by the wet type is minimized. The molar ratio of fluoride to the aforementioned oxidizing agent X: y may be X ± 1% by weight: y ± 1. For this reason, it is considered that as long as it is within the above range, the amount of gas generated by the wet etching can be reduced as much as possible. Further, it is considered that the above-mentioned consumption is substantially preventable from pattern defects caused by the gas generated by the wet type. According to a second aspect of the present invention, in a method of manufacturing a photomask, a half of a material including a metal and a stone material is formed on a light-transmissive Φ substrate in such a manner as to have a function of adjusting a transmittance for exposure light. a method for producing a reticle of a reticle, wherein the light-shielding film and the reticle base of the light-shielding film that shields the exposure light are patterned by patterning the light-shielding film and the semi-transmissive film, and the method is as follows The semi-transmissive film is patterned by using at least one selected from the group consisting of vaporized citric acid, shixi hydrogen hydride, ammonium hydrogen fluoride, and the like, and at least one oxidant selected from the group consisting of ammonia peroxide, acid, and sulfuric acid. It is carried out with a wet remnant of a defoaming agent or a defoaming agent (solution 2). According to the second invention, the above problem can be solved, and the provision can be prevented.

2130-9184-PF 17 200830363 : The semi-translucent film and the pupil of the light-shielding film are formed in accordance with the wet-type rice engraving of the semi-translucent film. In the case of the manufacturer, it is also possible to use a fluorinated foaming agent or a defoaming agent, a fish 汾rt, a female, a hydrogen peroxide, a gas, a gas, or a bubble. 'Body: Defoaming or defoaming to remove... "Oxygen or gas wet type _ should occur gas: etc. =^^ Problem of pattern defect (2nd problem). Again:= The wet film of the film of the film _ occurs when the τ solves in the semi-transparent problem), and the problem caused by t (the third class (the fourth subject). The problem of the pattern defect occurs this second is In combination with the first invention of the present invention, it is preferable to suppress the occurrence of gas by the sputum, and it is preferable. In particular, in the second invention, dry etching is described. In the liquid, the ratio of the gas to the gas is better than that of the wet oxidizer (the composition 3). Thus, ^ Shengli Taking the small mobs from the above-mentioned residual liquid, the squirrel compound and the oxidizing agent are described, the table ear is compared to suppress the gas generation, and the defoaming agent or the defoaming agent is used in the second liquid. The multiplying action bubble containing the effect on the _sheng:: It is only necessary to contain a trace amount. In the second invention, the defoaming agent can also defoam the bubble by a bubble ^ The agent has an infiltration in the attached to the defoaming of the production, the bubble between the surface of the soil plate and the substrate.

2130-9184-PF 18 200830363 The bubble of the surface is preferably used from the substrate I® to have a function of detaching from the surface of the substrate. "::" is a defoaming agent having such a function, and examples thereof include lauryl alcohol, sodium lauryl sulfate (sodium lauryl sulfate), etc. The content of the defoaming agent is, for example, 1 〇mt % of the aqueous solution of lauryl sulfate vinegar, the average of (4) liquid per 1 liter (M~2ffil is preferred. As a defoaming agent, to have small bubbles dissolved (absorbed) in the liquid

It is preferred to use or to cause the bubble to rupture. Further, the antifoaming agent preferably has a function of a surfactant such that the gas/package and the film on the substrate are reduced in suction, and the bubbles are removed from the surface of the film. Specific defoamers are as follows: low-grade, high-grade aliphatic alcohols, low-grade, high-grade fatty acids, low-grade, high-grade aliphatic amides, low-grade, high-grade fats, and polyepoxyethylene H-epoxy glycerol fatty acids. : Defoamers such as polyepylene oxides and polyoxyalkylenes. In the present invention, both a defoaming agent and an antifoaming agent may be added. In the first invention or the second invention, the temperature of the etching liquid is preferably in the range of 10 C or more and 61 or less. In the case where it is not full, it is not preferable because the etching rate of the semi-transmissive film is slow and the productivity is deteriorated. Further, when the temperature exceeds 60 °C, the etching speed of the semi-translucent film is increased, and the dimensional accuracy of the pattern of the semi-transmissive film formed is changed, which is not preferable. The temperature of the preferred etching solution is preferably in the range of 2 ° C or more and 45 ° C or less. In the above-described first invention or the second invention, molybdenum (M〇), nickel (Ni), tungsten (W), and the metal of the semi-transmissive film formed of the material containing the metal and the ruthenium, Niobium (Zr), titanium (Ti), tantalum (Ta), chromium (Cr) or gold containing 2130-9I84-PF 19 200830363, or a material containing the above element or the above alloy. And the body and σ, for example, metal ruthenium and iridium (MSi, M: M〇, Ni, W Zr Τι, Ta, Cr, etc.), zirconia metal and lanthanum (MSl〇N), Emulsified carbonized metal and Shixi (MSiCO), oxidized and nitrided carbonized genus and lanthanum (MSiCON), oxidized metal and lanthanum (MSi〇), nitriding and cerium (MSiN). The semi-translucent film is described in such a manner that it has a function of adjusting the amount of exposure light to set its composition and film thickness. In the first invention or the second invention of the present invention, the material of the light-shielding film which is used as the light-shielding exposure light can be combined with +" mountain corpse, + chrome precursor or chromium, and contains oxygen, nitrogen, and I. 'Yuzhizhi') (one material containing Cr), etc. Specifically, examples thereof include a material containing at least a nitride of chromium or chromium, an oxide of chromium, a carbide of chromium, and a fluoride of chromium, or a hydrogen or ruthenium as a light-shielding film. The film structure can be formed by a single layer or a plurality of layers of the above-mentioned film material. Further, in a different combination, the formation of a plurality of layers in a two-stage manner or a combination of continuous changes in the film, as a method of wet remnant, may be immersed, blown, and The above-mentioned method or the method of spraying the soup type is engraved, and in the (4) dry g-bubbles, there may be a 1 〃 on the surface of the substrate. The second invention, the 发明 舱 舱 舱 舱 舱 舱 舱 舱 舱 舱But according to the effect of such as defoaming is the defoamer (four) ^ so the left of the lactation. A method of manufacturing a photomask of the present invention. In the semi-translucent film

2130-9184-PF 20 200830363 It is particularly effective when the thickness is 00 angstroms (construction 4). For this reason, as described above, in the above-described second problem, a semi-transmissive film in a gray scale mask in which a photomask for FPD τ is used is exemplified, and if the film thickness is as thin as 1 〇 1 〇 The effect of the 〇$ degree is very large. The manufacturing method of the mask of the present invention is particularly effective as a method of manufacturing a mask for producing a rigid member (structure 5). In the method of manufacturing a photomask according to the first aspect of the invention or the second aspect of the invention, the translucent substrate is sequentially formed on the translucent substrate from the semi-transmissive film and the mask film. The light-shielding film and the semi-film are patterned to produce a photomask.

Regarding the manufacturing method of such a photomask, an example of a manufacturing process of manufacturing a gray scale mask which is an example of a photomask for producing an FPD 70 is shown in the following. 17 ΙΪ, a semi-transmissive film is sequentially formed on the surface of the light-transmitting substrate 16 (=: a film forming process of the green film 18 to form the mask substrate 2), and preparation (the eighth light) The film 17 is formed by using, for example, a metal and a stone (Si) ::: sulphate to reduce the ore film formation, and can form a semi-transmissive film comprising a metal and a transparent/formed film. The transmittance of the semi-transmissive film is appropriately selected. Next, the lightness of the first light is 8, for example, ❹(4), (4) a reactive gas of a reactive gas such as nitrogen, oxygen, or emulsified carbon, which can form a layer or a film of a layer structure (for example, a light-shielding film with a reflection preventing film). These semi-transmissive films 17 and a light-shielding film are in the gray scale mask 10.

2130-9184-PF 21 200830363 In manufacturing engineering, it is resistant to etching. Also, the Thousand Light Acting Film 17 is resistant to an etching solution for chromium. Further, the light-shielding film 1 & is resistant to the etching liquid for metal halides. And then, a photoresist film (a positive-type photoresist film and a negative-type photoresist film) is formed on the light-shielding film 18 of the mask substrate 20, and the photoresist film is exposed by using an electron neon laser drawing device. The first resist pattern 21 is formed by development with a developing solution (Fig. 1(B)). y The first photoresist pattern 21 is formed by forming the light transmitting portion 14 into a shape of an opening region on the manufactured gray scale mask. Further, as the photoresist for forming the photoresist pattern 21, a novolak-based photoresist can be used. Give this number! The reticle substrate 2 formed by the photoresist pattern 21 is immersed in the chrome for the etched liquid, and the chrome is used as the occlusion liquid, and the j-th photoresist pattern 21 is used as the occlusion, and the opaque film 18 of the hood substrate 20 is wet. The syllabary (the ι ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Further, the photoresist constituting the first photoresist pattern 21 generally has a good two-dimensionality with the light-shielding film, so that it does not peel off due to the chrome-consuming etching solution. 22 ==: After the pattern 22 is formed, The light-shielding film pattern 槐"1 first resistance pattern 21 peeling off (Fig. 1 (8)). This ith photoresist pattern '(4) becomes the mask base of the light-shielding film 22, which is impregnated with the bismuth compound. Using this metal lithology compound, the film pattern 22 is used as the material, and the semi-transparent film 17 is wet-type, and the semi-transmissive film „23 (the first item (10).

Sample 22 and semi-transmissive film „23 to form a light-transmissive portion 2 2130-9184-PF 22 200830363 The above-mentioned etching solution for metal telluride includes at least one selected from hydrogen fluoride acid, hydrazine hydrogen fluoride acid, and ammonium arsenide fluoride— a fluoride, and at least one oxide selected from the group consisting of chlorine peroxide, wall acid, and sulfuric acid. In the present invention, the molar ratio of the foregoing compound in the etching solution for the metal halide to the oxidizing agent may be The moiré ratio is set to prevent pattern defects caused by gas generated by wet silver engraving, or the second ratio is set to a molar ratio that minimizes the amount of gas generated as the wet type is engraved. X, it is also possible to include a defoaming agent or a defoaming agent in the secret engraving liquid. Further, the 'shading film 18' is inclined to be etched with the etching liquid for the above metal halide, so it is not to be (4) The mask film 22 formed of the light-shielding film 18 is made of the (four) material, and the pure film 17 (four) is used for the metal, so that the foreign matter formed by the light of the first photoresist pattern 21 is formed. Producing a two-formed film of 既 :: semi-transmissive film After the sample 23, the desired light-shielding film is formed on the film 22 of the desired light-shielding film 18 and the light-shielding film is formed on the light-transmitting substrate 16, and the photoresist film is formed in the same manner as described above. Exposure, display 24 (Fig. 1 (F)). This 2nd 7th brother 2 photoresist pattern resist pattern 2 4 system makes the gray scale neighboring p; the shape of the gentleman, & mouth area to form. Then, The 9th 成为15 becomes open # ^ „ m The brother 2 photoresist pattern 24 is used as a mask, and the chrome is used to make the etched liquid (the cover 臈 18 and then the remaining (the ^ (6)). W film I After the shading of 22, 'the remaining 2nd pattern of the second brother's second pattern is peeled off'.

2130-9184-PF 23 200830363 Photorefractive film 1 7 hard, + > Membrane" layered step i5, pre-emptive one and semi-transparent 00). 'Concealing cut» 3 to ® gray scale light The cover is called the above-mentioned composition, and according to the above manufacturing example, the following effects can be achieved.

In the manufacturing process of the first illuminator 10, as shown in Fig. 1(D), the whole genus is used: after the sample 21 is peeled off, it is used as a mask for the light-shielding film pattern 22, and the liquid _ liquid: two light ::? The photoresist is chemically reacted with the above-mentioned metal-chemical reaction to form a foreign matter. Therefore, the light-shielding film 13 can be surely formed. In the light-shielding substrate 16 or the light-shielding film pattern 22, examples of the light-transmitting substrate include a substrate such as synthetic quartz, lime-lime glass, barium borate glass, and alkali-free glass. In the present invention, as a mask base and a photomask for manufacturing an FPD element, there is a light for manufacturing an FpD element such as an LCD (Liquid Crystal Display), a plasma display, or an organic £L (electroluminescence) display. Cover base and reticle. Here, the reticle for LCD manufacturing includes all of the photomasks required for manufacturing an LCD, for example, TFTs (thin film transistors), particularly for forming m-channel portions or contact holes, low-temperature polysilicon TFTs, and color filters. A light mask such as a light sheet or a reflection plate (black matrix). The photomask for manufacturing other display elements includes all of the photomasks necessary for manufacturing an organic EL (electroluminescence) display, a plasma display, and the like.

[Embodiment] 2130-9184-PF 24 200830363 Hereinafter, the present invention will be described in more detail based on examples. (Example 1) (Preparation of etching liquid) An etching liquid for a semi-translucent film was prepared and prepared as follows. - The water/hydrogen ratio of hydrogen peroxide:ammonium hydrogen fluoride is n2 to combine these water/exciting liquids, and further, this is diluted with pure water to prepare an etching liquid. At this time, the amount of fluorinated #hydrogen ammonium is reduced to 〗 〖wt% (for the entire volume (100 wt%) of the etching solution) with respect to the total amount (1 (10% 纣%) of the etching liquid diluted with pure water, so that hydrogen fluoride is used. The ratio of ammonium is from 0. iwt% to 20 wt%). Further, a 10% lauryl sulfate solution 〇. 〇lwt% was added to the whole. As the etching liquid for the light-shielding film, a jjy liquid (manufactured by Wako Pure Chemical Industries, Ltd.) of an etching solution for chromium (containing a second etching solution of nitric acid and a peroxyacid) was prepared. (Manufacturing of reticle base) On a large glass substrate (synthetic quartz (10) 10 _ thick, size 85 〇 dragon X 1 200 mm), a large-scale in-line sputtering device is used to perform half-transmission of a gray scale mask. Film formation. Specifically, a target of M〇:= 8 〇 (atomic % ratio) is used, and Ar is used as a sputtering gas to form a semi-transmissive film for a gray scale mask formed of molybdenum and niobium (MoSi4; M〇: 20 atom%, Si: 8〇^ sub%) (refer to Fig. 1 (A)). At this time, the film thickness was adjusted in the range of the i-line to the line of the wavelength of the exposure light source so that the transmittance was 6〇%. The film thickness of the bovine translucent film is in the range of 10 to 100 angstroms. Next, a large-scale in-line sputtering apparatus was used on the semi-transmissive film for the gray scale mask to form a film of the light-shielding film. Specifically, as the light-shielding film 18, Q is continuously formed by sputtering from the side of the substrate side in a vaporized manner.

2130-9184-PF 25 200830363 Membrane, chromium carbide nitride film, chromium oxynitride film (reflection prevention layer) (refer to Fig. (A)). At this time, the film thickness is adjusted by setting the optical density of the range of the i-line to the g-line of the wavelength of the exposure light source to 3 or more. Next, a novolac-based resist film was applied to the light-shielding film by a spin coating method to have a film thickness of 100,000 angstroms. As described above, the photomask base 20 with the photoresist film according to the embodiment is obtained (see Fig. 1(A)).

(Production of Photomask) Next, a photomask was produced in accordance with the manufacturing process of the gray scale mask manufactured by the semi-transmissive film described in Fig. 1 described above. At this time, the above-mentioned prepared (four) liquid was used as the sap of the semi-translucent film. x, as the money engraving liquid of the light-shielding film, the etching liquid of the above prepared chromium was used. In the above-mentioned reticle manufacturing process, no hydrogen (HO, oxygen (〇2) bubbles were observed in the light transmissive film. (Evaluation) • #在该光的光光After the semi-transmissive film pattern formed on the cover and the light-shielding film pattern were examined, it was not confirmed that the bubble was caused by the bubble generated when the semi-translucent film was wet. The cross-sectional shape of the pattern is good. The reflectance of the anti-reflection film in the light-shielding film pattern is unchanged after the etching process of the semi-transmissive film (refer to (D), (E) of Fig. 1). (Comparative Example 1) The same procedure as in Example 1 was carried out except that an etching solution in which the molar ratio of the molar ratio of lauryl lauryl sulfate was not added as in Example 1 was used.

2130-9184-PF 26 200830363 Specifically, as an etching solution, the conditions of the patent document 〗 〖$ # & ιp u 1圯 (fluorination (10) + hydrogen peroxide reduction 44 wt% (hydrogen peroxide: ammonium hydrogen fluoride) Moerby is about 4 ·· 1)). Further, in the mask manufacturing process, when a semi-transmissive film is engraved, it is confirmed that bubbles such as helium (H2) are generated. As a result of the evaluation, the pattern "short-circuit" caused by the bubble generated by the wet silver engraving of the semi-transmissive film is generated in two places at all, in the light-transmitting portion (the surface of the surface should be completely There are 10 film residues (the thickness is the same as the film thickness) in the portion where the surface of the substrate is removed after the ink is removed. (Comparative Example 2) Except that in Example 1, the use of hydrofluoric acid (hydrofluoric acid lanthanum nitrate (gas acid 1Wt% 'gas acid: the molar ratio of tartaric acid is 4:7) is the same as Example 1. In the manufacturing process of the mask, it was confirmed that a large amount of bubbles such as nitrogen dioxide (N02) occurred during the engraving of the semi-transmissive film. The result of the evaluation was considered to be caused by the bubble. The pattern short-circuited P曰 occurred at 33 places in total, and the film residue was 21. (Example 2) Except that in Example 1, the residual solution without adding lauryl sulfate was used (hydrogen peroxide: ammonium hydrogen fluoride) In the Xe project of the reticle, the ear ratio is 1:2, which is set so that the amount of gas (H2) generated by the wet type Μ@ occurrence is the smallest molar ratio). In the case of the semi-transmissive film, the occurrence of bubbles such as minute and small amounts of oxygen was confirmed.

2130-9184-PF 27 200830363 ", for the semi-translucent film pattern, defects caused by the recognition of ", bubbles generated during the wet residual of the semi-transmissive film, etc." were not confirmed. "The surface of the light-shielding film is originally covered with sufficient oxygen reflection." After the etching process of the semi-transmissive film (refer to Fig. 1 (D), )), the surface reflection of the light-shielding film is almost Change in rate. Moreover, in the etching process of the light-shielding film (especially in the processes (7) and (8) of the first drawing), since the gas is contained in the masking film, the influence of oxygen is small, and the moisture level of the light-shielding film is + What effect is caused, and there is no deterioration in the cross-sectional shape of the pattern of the light-shielding film. (Examples 3 to 4) Except that in Example 2, in the money engraving liquid, the acid (vaporized nitrogen acid) was used as the gas substance, and the molar ratio of hydrogen peroxide:fluoric acid was i:2. The rest was the same as in Example 2 to make a photomask (Example 3). Further, in Example 2, a mask was prepared in the same manner as in Example 2 except that the hearing agent in the surname was 4 acids, and the molar ratio of the diaphoric acid: ll ammonium hydride was used. 4). , /,, "Fruit, in the example 3, 4, in the manufacturing process of the mask, in the case of the semi-translucent film, the hair b ^ mussel half of the tiny and trace oxygen is confirmed As a result of the light transmissive film pattern, no defects were found to be caused by the bubbles which occurred when the semi-transparent film was wet (four). Adding, the etching solution of Examples 3 and 4 is the same as that of Example 1, adding de- and Λ h conditions; and it is confirmed that it is considered to be caused by the wet-type button of the semi-transparent film. The defects caused by the bubbles.

2130-9184-PF 28 200830363 (Example 5) *In addition to the molar ratio of ammonium hydrogen fluoride:peroxide in the liquid in Example 2, "the amount of gas generated by the wet type (four) is minimized. A mask was produced in the same manner as in Example 2 except that the molar ratio of the oxide was changed from 2 to 2, and the ratio of y+mu was changed to 2.4:1. As a result, in the case of the photomask manufacturing method, the occurrence of bubbles such as minute and small amounts of oxygen was observed during the etching of the semi-transmissive film, but the result of evaluating the semi-transmissive film pattern was evaluated. There was no confirmed defect caused by bubbles which were caused by wet etching of the semi-transmissive film. (Reference Example) The same as Example 2 except that the light-shielding film was a chromium single layer film in Example 2. As a result of the evaluation, the change in the surface reflectance of the light-shielding film was larger than that of Example 2 due to the generation of a trace amount of oxygen, and the pattern cross-sectional shape of the light-shielding film was also deteriorated compared with Example 1 or 2. The present invention has been described above by way of preferred embodiments, but the invention is not limited to the embodiments described above. [Simple description of the drawing] The UAMIO drawing shows the manufacturing process of the gray scale mask for manufacturing the underlying semi-transmissive film. Fig. 2 is a schematic view for explaining the state of occurrence of bubbles. 3 is a view for explaining a gray scale mask having a semi-translucent film, (1) is a partial plan view, and (2) is a partial cross-sectional view.

2130-9184-PF 29 200830363 Fig. 4 is a view showing a gray scale mask having a fine shading pattern having a resolution limit or less, (1) being a partial plan view, and (2) being a partial cross-sectional view. [Description of main components] 1 light-shielding portion 2 light-transmitting portion 3 gray-scale portion 3a fine light-shielding pattern 3b fine light-transmitting portion 3a' semi-transmissive film 10 light-transmitting substrate 11 semi-transmissive film 12 light-shielding film 13 light-shielding portion 14 Light transmitting portion 15 Gray scale portion 16 Translucent substrate 17 Semi-transmissive film, 18 Light-shielding film 21 First light resist pattern 22 Light-shielding pattern 23 Semi-transmissive film pattern 24 Second light resist, pattern 2130- 9184-PF 30

Claims (1)

200830363 X. Patent application scope: 丨. A method for manufacturing a photomask, which is formed of a material containing metal and T in order to form a function for adjusting the amount of transmission of exposure light on a light-transmitting substrate. The semi-transmissive film is formed by patterning the light-shielding film and the semi-transmissive film on the base of the light-shielding film which is shielded from light by exposure light, and is characterized in that: The patterning of the semi-transmissive film is performed by using at least one fluoride selected from hydrogen fluoride acid, hydrazine hydrogen fluoride, ammonium hydrogen fluoride or the like: at least one oxidizing agent selected from hydrogen peroxide, nitric acid, sulfuric acid Wet etching is performed to etch the etching solution, and the molar ratio of the fluoride to the oxidized J in the etching solution is set to prevent pattern defects caused by gas generated by wet etching. The ear is compared to the etching solution. A method for producing a varnish and a reticle, wherein a semi-transmissive film formed of a material containing metal and pulverized material is formed on the light-transmitting substrate in order to adjust the function of the amount of light transmitted to the exposure light. And the mask base of the light-shielding film which is exposed to light (four) is formed by dicing the light-shielding film and the semi-transmissive film to produce a photomask, and is characterized in that the semi-transmissive film is patterned. By using at least one vapor selected from the group consisting of fluorinated acid, sulphuric acid hydrogen fluoride, ammonium hydrogen hydride, etc., at least one oxidizing agent selected from hydrogen peroxide, nitric acid, sulfuric acid, and a defoaming agent. Or wet etching of an etchant of an antifoaming agent. The method for manufacturing a photomask according to claim 1 or 2, wherein the molar ratio of the fluoride to the oxidizing agent in the etching solution is such that the wet etching is performed. The amount of gas generated is the smallest molar ratio. The method of manufacturing a photomask according to any one of the first to third aspects of the present invention, wherein the semi-transmissive film has a film thickness of 1 Å to 1 Å. Manufacture of the reticle of any of the patent ranges 1 to 4 • The fascia of the eighth is a reticle for the manufacture of FPD components. 2130-9184-PF 32