TW201001055A - Blank mask, photomask and method for manufacturing the same - Google Patents

Abstract

Disclosed are a photomask, a blank mask and a method for manufacturing the same, to reduce loading effects causing size differences between single patterns and dense patterns of a photomask. The method comprises depositing an etching prevention film or a light-shielding film allowing at least wet-drying on a transparent substrate, depositing a hard mask film having the same etching characteristics as the etching prevention film or the light-shielding film thereon, coating a photoresist thereon to a low thickness, followed by exposing and developing, and etching the hardmask film to remove the photoresist pattern and the hardmask film used as an etching mask for forming at least the light-shielding film.

Description

201001055 VI. Description of the invention: [Technical field of invention] Blank blank mask and the use of the circuit, the person crying ΐ 曰 中 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该Twilight mirror, etc. Type 様, the circuit integration circuit involved in the high integration trend of the circuit 'the circuit line has become miniaturized, so that the technology of the connection and the connection of the adjacent layer is gradually increased. . Thus, in the reticle of the lithography application (where the recording is electrically Κ 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 摅 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积 沉积Development '#Engraving and Peeling ϊϊΐΐΐIn the traditional blank reticle and reticle, although the photoresist is specific and delicate, it has a macroscopic/microscopic loading effect due to its thickness, resulting in a six-integrated type and a low-integration type. Between the two; and the size difference between the first type and the dense type. The ϊ / ΐΐΓ = =, shadow and etching and use the photoresist as a mask to etch the shadow solution, _ solution or _ gas amount The condition of the whole = ρ ancient = early reaction area has a low reaction/removal rate of the reactants, so that it is not etched and causes the critical scale domain performance _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Chen Yu,: When the type ί is formed, the set is toward the bottom of the metal film. The difference between the top CD and the bottom CD of the metal type is reduced. 201001055 f. The isolated pattern area is thinned by the base surface due to its etched surface. (4) In the case of a larger feed problem, you can change the load effect, linearity and fidelity of the sample. _ = dry reticle ice, because the miscellaneous turns enough, so the lower layer is etched Damage to the photoresist at the time of the damage = making it difficult to perfection; Sii loading to reduce the size of the mask used as a mask, the miniaturization of the mask type also results in the fF of the photoresist pattern 'When only the anti-surface is miniaturized and the small light _ thickness and photoresist = the accuracy of the pattern is lowered. In the serious situation, the sorrow is 遗 ϊ 而 而 and is omitted. From * 'based on the miniaturization of the fresh type, borrow = , the ratio of the light to the width of the pattern used to form the mask of the light-shielding film is adjusted to the required level. Μ Μ The thickness of the pattern, 2 meet all the requirements of the photoresist mask, the traditional type , (four) degree 'has technical difficulties, and as long as the use of the t-axis process" will be reduced in addition to reducing the thickness of the photoresist, reduce the hard cover, =. Hard cover as a side cover, dry this / 'considering macro/micro load", also requires the best thickness of the hard cover It can also be used to guide the 'and the light', it must be fully tested. In order to solve these problems, in order to reduce the load of the photoresist and thus form a high 201001055, in order to improve the resolution, it is coated with chemical amplification. The anti-butterfly* white enamel cover is used for the silk cover. The touch is amplified and the fine paste (H+), which is generated by the magnifying exposure, is used in the blank mask of the y, y, y, y, y, Chemically amplified two" "two nitrogen-containing materials are controlled such as reflection "scaled phase. However, due to the nitrogen contained in the metal film, the strong acid derived from the anti-surname agent binds to nitrogen and is then neutralized. The strong acid cannot be released. The development failure makes it difficult to achieve an inter-resolution, and it is difficult to manufacture a high-quality photomask. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and the present invention is a kt, a blank mask. And the type of reticle and its manufacturing method, ^ load effect, improved linearity and selectivity: straight root =! ===: £ 'the reticle in the transparent base' sublayer according to the invention another secret Providing a method of viewing the empty cover of the present invention, the party The method includes: a) preparing a substrate; bl) forming an H-anti-side film as needed; and C1 forming a hard cover film on the side metal film on the substrate or the anti-film; El) selectively treating the hard film with an organic material; fl) forming an anti-rice film on the hard mask film of the test table to make a blank mask. In the step 31), the substrate refers to a transparent earth plate of 6025 size which is usually used and a synthetic quartz substrate, a domain lime glass material, is used as the material. In step a), when the substrate needs to be applied to the immersion lithography, it has a birefringence of 5 nm/6.35 mm with 201001055.抗 t ‘if ^ necessary' can form the anti-etch film as needed. Effect / When you are less than 3 nm thick, it is resistant to truncation. It is expected that when the anti-film is thicker due to blasting, the undercut of the anti-grain film increases, so that == long time affects the CD or f to be treated for a long time, and the production (four) _, the main component of the anti-reduction It is a metal. The anti-magnet is a nitride, which is selected from a genus oxide, a metal dish, a metal oxycarbon wire, a ferrite, a metal carbonitride, and gold. All the time, when the meal is difficult, the gas-based gas can only be named after the anti-membrane H. The metal is difficult to pick up. The metal is too hard to be placed on the metal film. The film in the step (4) includes a film selected from the group consisting of CU, Zn, Ga, Ge, Zr, Nb, M, Ru, Rh, Pd, Ag, and metal. In one or more of 2 Sn Hf Ta, W 〇 s, IrHAu, when the anti-side film contains (d) as a main component, one of :=t, Crc, crcN, crN, and crc〇N Or a plurality of structures are also selected from one or more selected from the group consisting of cr, crc, crcN and crN, in step bl), the anti-scratch contains as a main component, which is composed of ia, Tac, TacN, TaN& One or more of Tac〇N, preferably, consists of one or more selected from the group consisting of Ta, TaC, TaCN, and TaN. Eight in step bi) The anti-side film may contain TM〇Cr as the main component. For example, the anti-etching film may be composed of a compound such as TaCr, TaCrN, TaCr or TaCr〇N. 201001055 The main anti-etching pancreas is made of Cr and/or Ta as a 30-90 at%, preferably 5〇_8〇田Λ卜f into a Cr and/or Ta carbon engraved r is lost and the bipolar membrane has a low engraving rate, more particles ft'b: l〇at%^5 and a high transmissivity, which adversely affects the optical density and Anti-skin membrane. When the nitrogen content exceeds 60 a, the anti-fine film can be degraded, and too high = making it difficult to control the etching time. In the case of step c), the metal film is a single layer multilayer film. The wealth includes two layers or in step cl). When the metal film is a single film, the single sound k is used as a light shielding film for shielding light and an anti-reflection film for reducing incidence. And cl), when the metal film is a multilayer film, the multilayer film comprises a light-shielding light-shielding film and an anti-reflection film for reducing light reflection. In step cl), the metal film is composed of a compound mainly containing & and further containing or a plurality of metals. In the step cl), the metal film contains a metal, and is specifically selected from the group consisting of a compound of an oxide, a nitride, a carbide, an oxynitride, a carbide and a carbonitride. In the step cl), the metal film mainly contains the metal-stone, and the genus includes: selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and ^e:

Zr, Nb, Mo, RU, Rh, Pd, Ag, Cd, In, Sn, Hf, Ta, W,

One or more of Os, Ir, Pt, and AU orders. In step cl), when the metal film is a single layer film, the metal film is selected from the group consisting of MoSi, MoSiC, MoSiN, MoSiO, MoSiON, MoSiCN,

It is composed of one compound of MoSiCO and MoSiCON. 201001055 In step cl), when the metal film is a single layer film, the metal film is selected from the group consisting of MoTaSi, MoTaSiC, MoTaSiN, MoTaSiO, MoTaSiON,

It is composed of one of MoTaSiCN, MoTaSiCO and MoTaSiCON. In the step cl), when the metal film is a two-layer film, the two-layer film includes an anti-reflection film disposed on the substrate as a lower layer of the light-shielding film and an optical shielding film. When the light-shielding film and the anti-reflection film contain MoSi as a main component, the light-shielding film is composed of a compound selected from the group consisting of M〇si, MoSiC, MoSiN, and MoSiCN, and the anti-reflection film is selected from the group consisting of

It is composed of one of MoSiN, MoSiO, MoSiON, MoSiCN, MoSiCO and MoSiCON. In addition, when the light-shielding film and the anti-reflection film contain MoTaSi as a main component, the light-shielding film is composed of a compound selected from the group consisting of: Si Ding, MoTaSiN, MoTaSiC, and MoTaSiCN, and the film is selected from the group consisting of MoTaSiN, MoTaSiO, MoTaSiON, MoTaSiCN,

It is composed of one of MoTaSiCO and MoTaSiCON. Further, the light-shielding film may contain MoSi as a main component, and the anti-reflection film may contain M〇TaSi as a main component. Alternatively, the light-shielding film may contain M〇TaSi as a main component, and the anti-reflection film may contain MoSi as a main component. In step cl), when the metal film is a two-layer film and the light shielding film is composed only of MoSi, the MoSi is composed of Mo 20-70 at%, preferably 30-60 at%, and Si 30-70 at %, preferably 40-60 at%. In step cl), when the metal film is a two-layer film and the light-shielding film is composed of a MoSi compound, the MoSi compound is composed of Mo 1_20 at0/. 3-15 at%, Si 40-80 at%, preferably 50-70 at%, nitrogen 10-50 at%, preferably 20-40 at%, and carbon 0-10 at%, Preferably 〇 _5 at% composition. In step cl), when the metal film is a two-layer film and the anti-reflection film is composed of a]VioSi compound, the MoSi compound is composed of Mo 1-20 at%, preferably 3-15 at%, Si 40 -80 at%, preferably 50-70 at%, oxygen (MO at 〇 / 〇, preferably 0-5 at%, nitrogen 10-50 at%, preferably 20-40 at%, and carbon Μ 〇 at%, preferably 0-5 at%. In step cl), when the metal film is a two-layer film and the light-shielding film 201001055 is composed only of MoTaSi, the MoTaSi is composed of Mo 10-60 at% Preferably, 20-50 at%, Ta 2-30 at%, preferably 5-20 at%, and Si 30-70 at%, preferably 40-60 at%. In step cl) 'When the metal film is a two-layer film and the light-shielding film is composed of a MoTaSi compound, the MoTaSi compound is composed of Mo 1-15 at%, preferably 3-12 at%, Ta 1- 15 at%, preferably 3-12 at%, Si 40-80 at%, preferably 50-70 at%, nitrogen ΐ〇·5〇at%, preferably 20-40 at%, and carbon 0 -10 at%, preferably 0-5 at%. In step cl), when the metal film is a two-layer film and the anti-reflection film is composed of a MoTaSi compound, the M〇TaSi compound is composed of M〇丨7 at%, preferably 3-12 at% 'Ta 1-15 at%, preferably 3-12 at%, Si 40-80 at%, preferably 50-70 at%, oxygen 0_10 at%, preferably 〇_5 at%, gas 1〇·5 〇 at%, preferably 20-40 at%, and carbon 0_10 at%, preferably 〇_5, % composition. In the second step cl), the 3H metal film is engraved by a fluorine-based gas, and it is not engraved with a chlorine-based gas. At this time, the anti-scratch film and the hard cover film are not inscribed by the fluorine-based gas. x has an exposure wavelength of 193 Nai, the metal film

(10), when steps ai) to ci) are formed on the substrate, the optical density of the metal film is 5.2 m or higher at 931 m/s. Buckle: to cl) when the anti-etching film is sequentially formed on the substrate is a bismuth film, the thickness of the film and the optical film of the metal film is 5 (K) at 193 nm. When the metal film is formed on the miscellaneous sheet, the reverse film is the main component of the hard cover film containing the metal as the main component.亥海硬容罩-metal, or composed of metal compound selected from metal oxide 9 201001055 carbide metal nitride, metal carbon oxide, metal oxynitride, metal carbonitride and metal oxycarbonitride . In step dl), the metal of the hard cover film is selected from the group consisting of τί, V, Cr, Μη, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ru, Rh,

One or more of Pd, Ag, Cd, In, Sn, Hf, Ta, W, Os, ir, pt, and au. The hard cover film may contain both Ta and Cr as main components. For example, the hard cover film may be composed of a compound such as TaCr, TaCrN, TaCrO or Tacr〇N. In the step di), the hard cover film contains Cr and/or Ta as a main component: and is composed of one material selected from the group consisting of Cr and Ta, and nitrides, carbides, oxides, carbon nitrogen of Cr and Ta. It is composed of a compound, an oxynitride, a carbon oxide, and an oxycarbonitride. In the step di), the composition of the hard cover film is: transition metal 3〇_7〇at%, preferably 40_60 at%, carbon〇_3〇at%, preferably 〇_2〇%, oxidation For example, at%, preferably 〇15 at%, and 〇_4〇at%, preferably 〇_3〇. . In step dl), the hard cover film is not etched by a fluorine-based gas, but is etched by one moment. The chlorine-based gas can only engrave the hard cover film and cannot silver engrave the metal film underneath. Alternatively, the anti-etching film disposed on the substrate may be etched by the hard etching gas. In the gas step dl), the hard cover film preferably forms H: 2, the thickness of the (four) cover film is more than 3, and the cover layer is formed, so that the metal film is caused by the dry film. The time for the remnant of the moment is also prolonged, and the production efficiency is degraded, and the load effect caused by # degrees makes it difficult to achieve a good quality CD. 6 The membrane and the hard mask are formed on the substrate in a stepwise manner. Under the barrier of the metal apricot film, the anti-cursive film is thicker than the hard mask film. Shovel "The film is thin" when the bottom of the anti-model: 201001055 On the borrowing and hard cover film, the formation of anti-money film, metal film engraving speed, the paste rate of the film is higher than the rate of the hard cover film The low 11 film rate is lower than the quality of the hard cover film. The D-Hai anti-money film undercut makes it difficult to achieve a high recovery: Step 4) 'One true pass table: room, one furnace in the son uses 2teL The main lord' usually performs surface treatment by heat treatment, and when ugly is used for surface treatment heat treatment, ^ ^ (10)) lamps, hot line lamps, ultraviolet lamps, letters/lights, etc. The mail is (10). C to the circle. C. It is better to lie down - vacuum level ❹ Newton, 5 to ^ 261) ― surface treatment period is 1 to 6Q minutes, preferably

Xe, etc. In the step el), the gas for surface treatment is Ν2, ΑΓϋ Ψ ° ' and the cooling treatment is performed under cooling, in which the liquid is a liquid or a gas surface treatment step e). In step el), for surface treatment In step el), the medium for surface treatment mainly contains Shi Xi. In the step e), the medium mainly containing bismuth includes a group selected from the group consisting of hexamethylene bismuth, bismuth sulfonate, diethylamine, 〇_三甲芙石, ^trimethyMlylPn) Pri〇nate ' 〇4rimethy^ylbi ^rate f Trimethyltrifluoroacetic acid 'dimethyl oxoacetate, N•methyl_N_trimethylheteroyl triethylene acetamide, DTMMA, di-f-cylinder, trimethylsulfide trifluoro One or more of acetamide, dimethylthiononylenediamine, and tridecylethoxylate. 201001055 In step fi), a positive or negative chemical film is used.孜 Large resist production resistance is applied in step fl), using one selected from the group consisting of rotary varnish, and Λ and 1 rpm coating, the thickness of one of the s-resistant anti-noise films is two, in the step fl) After forming the anti-money agent film, at a temperature, A. . Soft bake on a hot plate for 5 to 3 minutes. X 170〇c

In step fl), an anti-surname film was formed and the soft-baked-cold plate was cooled for 5 minutes. MM 'in the maintenance of 23V in the step ^ " 0 towel, # the hard fresh company to contain 妓, need to face the chemical amplification of the anti-Happy - metal film nitrogen binding and then neutralized . By using the roadside combination as a strong acid for Lewis acid, it leads to the strong acid neutralization and the second = because it is recorded in the chemical amplification type and the hard cover film. The strong acid is neutralized and == = ; ί: 7 ΐ, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The substrate relies on the difficulty of achieving - the CD and the manufacture of a high quality hard cover that must be surface treated. 3 In the picking step, the hard cover containing no nitrogen may be dependent on the substrate of the chemically amplified anti-surplus agent which is neutralized by the strong acid as needed, but when the hard cover film does not contain nitrogen, The hard cover film is preferably surface treated to increase the resist adhesion and reduce the stress on the film. In steps Μ) to e, the formation of the anti-etching film, the metal film and the hard mask film is performed by reactive sputtering or vacuum deposition of G columns such as PVD, CVD or ALD, and vacuum deposition is performed by The inert gas and the reaction gas are introduced into a vacuum chamber for execution. The reaction gas is selected from the group consisting of decane (Ch4), acetylene (C2h2), ethylene (3⁄4⁄4), propane (3⁄4⁄4), vinyl acetylene (C4h4 divinyl acetylene (C6^I6), butadiene ((: 4111()) ), butene (c4H8), ethyl bromide (C2H6), nitrogen (N2), oxygen (〇2), = carbon oxide (co), carbon dioxide (c〇2), fluorocarbon (CF4), nitrous oxide (N20), nitric oxide (NO), nitrogen dioxide (7) (6), ammonia (leg 3), and fluorine (F) 12 201001055. The reaction gas preferably includes carbon to reduce the reflectance. The vacuum level is 0.1 to 30 mTorr and the applied power is 〇} to 6 〇 kW. The reaction gas is inert gas: nitrogen (A): 氡 (〇2): 曱 (CH4) = 1 〇 _100% : 〇 _ 95% : 0_95% : 〇 _95% of one of the mixing ratios present. $ to use selected from - nitrous oxide (N2 〇), nitric oxide (NO), nitrogen dioxide, ammonia (NH3) and fluorine At least one of (F) in place of nitrogen or oxygen, or nitrogen in steps M) to el), in forming the anti-etching film, the metal tantalum, the hard cover film, the carbon content is preferably 0 to 3 〇at%. The reason is that when the carbon content is increased with respect to the total weight of the film material composition, the surface of the film is low, and more specifically, when the content of the carbonaceous material is 1% or more, the sheet resistance and chemical reliability are deteriorated. In the above steps (4) to (1), preferably, the surface resistance of the anti-side film, the metal film and the hard cover film is 1,000 Ω ohm or less. During electron beam exposure during reticle fabrication, a charging phenomenon may occur when the surface impedance is high. Charge, resulting in a type defect or a type position defect resulting from the movement of the pattern. More preferably, the surface impedance can be entangled to 丨, 0 ohms or less by controlling the carbon content of the smear. In the second step bl) s el), when the anti-side film, the metal film and the hard t-cover are subjected to SPM and SC1 treatment in a sub-sulphuric acid or ammonia water for two hours, the metal film is etched. And the hard cover film must have a reflectivity of i = (193 nm). The process of making a reticle with a blank reticle is usually repeated three to one times. Thus, when ρ has high chemical stability, the transmittance and reflectance change from the step bl) s el) the anti-scratch film, the film, or higher. When the density of the film is less than 2^, the ruthenium film and the anti-reflective film are shielded from exposure, and the surface of the same thickness is used, and the material may be fully utilized to reduce the load-carrying effect. Or smog defects in growth defects. The low density of _ appears as ί二=疋 forms a residue on the film. The composition of the semiconductor work is rs :== the composition of the film. Various factors such as the control film are determined; ΜΠ' } ^ is used to form the shape, and the subtractive film can be in the steps bl) to el), the anti-etching film and the cover film are amorphous. It can be made by processing in the Wei shot ^ = or lower. When the films are: body open == ί Ϊ 3 Ϊ roughness ' adversely affects CD performance ' and makes it difficult to Μ ) to el), preferably at a temperature of 10 (rc to 50 (rc under i. film) , metal film and hard cover film can be selected for heat = ^ ^ 1 = change = = engraving ratio "heat treatment can be improved at gamma - the underlying silk film and an it stability. This heat treatment is not only in Blank light binding. That is, after forming a pattern on the hard shell cover by a photoresist button in the mask manufacturing process, heat treatment can be performed on the hard mask. The above-mentioned secret operation Wei touches The hard cover film resists the chain, thereby realizing a thinner hard cover film of 14 201001055. Since the hard cover is thin, the hard cover film with improved corrosion resistance can be used for the dog side under the film, and the gas is changed. Or the reactivity of the solution. Thus, the hard cover film can increase the resistance to money and reduce the thickness of the hard cover, thereby advantageously improving the etching selectivity to the underlying film, increasing cd = energy (eg linearity or fidelity)' and Reducing the exposure required to manufacture the mask ° [Embodiment] λ below L will be attached Body embodiments of the invention described in more detail. This

The present invention is provided by way of example only and is not to be construed as limiting the scope and spirit of the invention.第一 (First Embodiment 1) In a specific embodiment, in order to determine a linear, dense pattern, a single pattern, a pattern property (for example, line edge roughness, ler) and fidelity according to the thickness of the photoresist For the difference, two blank masks were fabricated using photoresists having different thicknesses. 1A through 1F are cross-sectional views illustrating a method of fabricating a blank reticle and a reticle in accordance with an embodiment of the present invention. As shown in Fig. 1A, in this embodiment, a blank, a cover is formed in the following manner. An anti-scratch film 2, a light-shielding film 3, an anti-reflection film 4, and a hard cover film 5 are sequentially formed on a substrate 1. Next, the obtained structure was coated with a chemically amplified anti-surname agent 6 to make a blank mask. The figure shows the blank mask thus obtained. A detailed explanation of forming the blank mask will be given below. First, according to a reactive sputtering method, an anti-etching film 2 composed of chromium carbonitride (CrCN) is deposited on a transparent substrate by applying a DC power to a transparent substrate, wherein the reactive sputtering method uses a chromium target. And a gas mixture comprising argon, nitrogen and decane in a ratio of 40 sccm: 15 sccm: 5 sccm. It is possible to use a CR7-S wet etching chromium carbon nitrogen (CrCN) as a chromium etching solution, and it is possible to use chlorine ((3⁄4) and oxygen (〇2) gas dry side chromium carbon nitrogen). Hold up to 470. (: until the hard cover film is formed. In addition, a sputtering pressure of 1 to 15 201001055 5 mtorr is applied to all the anti-imprinting film 2, the light-shielding film 3, the anti-reflection film 4, and the hard cover film 5, and 1 〇〇 to the sputtering power of 2〇〇〇w. 15 : 5 : 8〇^%/a^ > |θ

Mat c. L, thin and gamma 2 deposited with a thickness of 30 nm, according to the sputtering method, by applying a direct current work iN 'where the sputtering method uses a ratio of argon (A0 and nitrogen (10)) - a gas mixture and the same dry material as the ruthenium film 3 . In the case of a single example, a MoTaSi-based material is applied to the metal film, i.e., mii:reflecting film 4. Alternatively, the -M〇si substrate = t ? and _ her, the test has a high extinction coefficient of 00, thereby achieving a desired optical density under a small thick member. Therefore, it is more preferable to use MoTaSi as the material of & In addition to consolation, a transition metal with a higher extinction coefficient can be used. When the anti-removal film 2 is deposited at the 193 nm ArF exposure wavelength after the light-shielding film 3 and the anti-reflection film 4, the optical density of the anti-scratch film 2 is included. It was 2.98, and the surface reflectance of the anti-reflection film 4 was 18.2% at this wavelength. These measurements indicate that both the optical density and the reflectance are normal. According to the reaction method, a hard cover film composed of chromium oxynitride (Cr〇NC) having a thickness of 10 nm is deposited on the obtained structure by applying a direct current power, wherein the reactive sputtering method uses chromium ( Cr) target and includes a gas mixture of argon, oxygen, nitrogen and methane in a ratio of 4 〇 SCCm: 5 SCCm: 1 〇 sccm: 3 sccm. In order to achieve a charging problem, the surface impedance is measured when the hard cover film is exposed to an electron beam (E-beam). The surface impedance thus obtained is normal, specifically 200 Ω ω / port. At this time, after the CrCN etching resist film, the M〇TaSi light shielding film, the MoTaSiN antireflection film, and CrCON were formed on the transparent substrate, the density of the film was measured by X-ray reflectivity (XRR). The density of the anti-marking film 2, the light-shielding film 3, the anti-reflection film 4, and the hard cover film 5 are respectively 2 7 , 16 201001055 3.25 g/cnf λ 2.95 g/cnf - Λ ^ must be at least 2 g / shirt (four) gland. That is, the density of the film, the light-shielding film, and the filming resistance are not used for clearing the blank energy. In addition, chemical reactions occur when chemical stability is degraded, resulting in inclusion to control optical density. In addition, there may be a defect of ===. "The low-density film causes a surface power difference between the ammonia water" or "mechanical bonding; = the formation of a residue on the / film. In the use of semi-conductive / residue by exposure to continue the reaction, from the ' Self-borrowing: i-average; grain-making materials can be selected for analysis. By using the results, it can be determined that all films are of a type with excellent line edge slash (LER): at 15〇 The surface of such a hard cover film is surface treated. The residual film 'forms a good profile profile and thus obtains a high quality subsequent 'for-electron beam exposure device' as a positive corrosion inhibitor (CAR) FEP_171 was spin coated to 2 = thickness: and then soft baked to make two blank masks. In order to find out whether the difference in photoresist thickness affects CD, the rice resistance is different, and the photoresist of the present invention is coated. Covered to 17 201001055, the dryness is set to 2 nanometers. The purpose is to create a uniform D-mask by reducing the aspect ratio (the aspect ratio is defined as the ratio of resist thickness to CD size). Other than the difference, the impact of reading CD is minimized, The photoresist is uniformly applied according to a conventional method under controlled conditions (for example, photoresist viscosity, photoresist coating amount, rotation of each coating, dry squash and soft baking temperature). '1 to 1G will be referred to. A method of fabricating a reticle by using a blank reticle made according to the present invention, in particular, is shown in Fig. 1C, which exposes the blank reticle in an electron beam exposure apparatus. The acceleration of the 奈奈(四)光财%Nymi To the first anti-blank reticle for post-exposure bake (ρΕβ) and development treatment to form the gas ί ΐ ΐ 1D 'in the ratio of gas (Cl2) to oxygen (〇2) is 8〇-m 4〇W, pressure Under the condition of 1 _, by _ into the hard melt _ chrome oxycarbon carbon ((10) 戦 type with 1 ^ in the photoresist pattern as a cover to the hard cover film formation # -, by using oxygen (〇 2) Ashing cleaning removes residual photoresist. Γ* i <者> Makeup Figure 1F, in CF4 including 80sccm, power 40W 0 Use this hard mask type 赖 = connect t to remove the screen _ and the anti- Reflection ^ After using the c^s film and the anti-reflection film, engrave, perform the most anti-contact and oxygen reading mixture or the dry film anti-synthesis film 2 and ^ hard film 5 In the dry side towel, at the same time, the money is engraved with the 2 〇〇. In the use of - sweeping the body to clean the structure obtained to complete the light sheet to determine the etched eve W", 'micromirror observation of the two reticle section view By the fact that the cross-sectional shape (LER) is good, the step between the optical film 18 201001055 and the anti-f film is not observed, and by using the light-shielding film and the anti-reflection film The specific ratio of the formed contact hole (measured CD area / design degree is indeed connected: the difference between the CD of the molded sample is evaluated by the sample = sample ί «;; ί, ^ in I Yixing early type The difference between them becomes smaller. ^ Coating a thin layer of photoresist to achieve an excellent CD, thereby solving the increase in reactivity by the two-reaction gas, and compared with the thick photoresist, thin = having a low aspect ratio, so the actual CD The difference is reduced. As apparent from the above, when the anti-surname film formed according to the present invention is deposited to a small thickness, there is a CD difference and fidelity between the early-type and the dense pattern. . The solid cover towel, the air mask has a structure, a towel, a transparent, an anti-removal film, a light shielding film, an anti-reverse film, a hard cover film and a photoresist film in the sequential layer. product. Alternatively, the blank mask can be applied to a halftone phase offset cover of the same construction as described above. That is, the blank mask can be applied to a halftone phase shift including a transparent substrate, a phase offset film, an anti-etching film, a light shielding film, an anti-reflection film, a hard cover film, and a photoresist film. Move the cover. The phase offset film includes MoSiN, MoSiO, MoSiC, MoSiON, MoSiCN, MoSiCO, and MoSiCON or includes MoTaSiN, MoTaSiO, MoTaSiON,

A single layer film or a multilayer film of MoTaSiCN, MoTaSiCO, and MoTaSiCON. Further, when the phase shifting film is a multilayer film comprising two or more layers, the multilayer film includes at least one underlayer of a substrate serving as a transport control film, which first controls transmission and secondly controls phase shift and is caused by, for example, TaHf a material such as Ta or Hf; and at least one layer used as a phase shifting film, which first controls the phase shift and secondly controls the transmission 'and is composed of, for example, SiO, SiN, SiON, MoSiO, MoSiN, MoSiCN,

A material such as MoSiCO, MoSiCON, MoTaSiO, MoTaSiN, MoTaSiCN, MoTaSiCO or MoTaSiCON. In addition, it is possible to offset from the halftone phase 19 201001055 blank mask to omit the anti-silver engraved film. (Specific embodiment 2) In the specific embodiment, in order to determine the linearity and density according to the thickness of the photoresist: a single type, a cross-sectional view of the money engraving (line edge roughness), and a difference in the direct production, the use has Two blank masks are fabricated with different thicknesses of photoresist. In order to influence the difference in thickness of the self-hard cover film, the film was formed in the same structure, and the same chemically amplified resist was coated thereon. First, 'the same thickness as the specific thin 1 is deposited on the transparent substrate, the thickness is 15 nm - the anti-side film, and a 5 nm deposited on the anti-cursor film is composed of moSi. The light shielding film and the antireflection film composed of molybdenum tantalum (MoSiN) of one% of nanometer. Thus, in order to determine the difference in thickness according to the thickness of the hard cover film, a 15 nm and 35 nm hard cover film was formed and the receiver was heated at 300 ° C for one hour. #Next' was coated with a FNP-171 having a thickness of 150 nm as a positive chemically amplified anti-money agent (CAR) to produce a blank mask. The resulting structure was exposed, pEB and developed using the blank reticle. The hard cover film, the anti-reflection film, and the light-shielding film were sequentially removed by dry surname, and the result obtained as such was obtained by wet etching with CR-7S to remove the lowermost resistance. The results obtained by the second embodiment were compared with those obtained by the first specific example, the aspect ratio of the hard mask photoresist was reduced, and the level of the singularity was lowered. According to the same principle, by the result, it can be confirmed that the aspect ratio can be reduced by reducing the thickness of the hard film and the cover film during the etching of the underlying film, that is, the antireflection film and the light shielding film, and the The reactivity of the gas is engraved, and thus the level of CD difference can be significantly reduced. (Third Embodiment) In a far specific embodiment, the anti-side was evaluated after the fact that the heat treatment was performed, after the blank mask was deposited. After depositing the hard cover film, a blank mask and a blank mask which was not subjected to heat treatment were subjected to heat treatment for 4 minutes at 35 〇t:. 20 201001055 In order to determine only the heat treatment of the hard f mask

The structure forms a film, and is coated with the same chemical type. The electron beam exposure is performed on the hard cover film, and the film is used as a _ coherent gamma hard mask: The residue. Let = l ==== and the light shielding film 'and the back of the hard cover type dry _ the light shielding film and = fixed 'the blank reticle type is seriously deteriorated, and the heat is good, the view. The results show that the hard-screened and miscellaneous reflective linings that have not been heat-treated can not meet the requirements of anti-recording. ^The moon b retains its shape, resulting in damage to such defects. w As can be seen from the results, in the formation of the hard cover film, the hard cover film can be formed into a low-thickness type due to the improvement of the thickness of the film, thereby achieving a vertical plate ratio and a denser cd. (Fourth embodiment) Body fJ; Example relates to surface treatment in blank mask processing. Forming the screen on the transparent substrate in the same way as the disk-: body, the same way =

; film = film: the metal f body is formed on the f, the S ί: "夂: light ^ white first cover. At the same time 'for comparison' manufacturing is not carried out at the surface of the electron: = and $ ^ ^ empty t-mask The TM accelerating voltage is _ _ ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Carrying out the jin ^ 21 2101001055 as shown in Fig. 4B 'Because the interface between the anti-surname film and the hard cover film is smuggled, i and then being developed', therefore, due to the area on the anti-side side of the wire: = _ And forming - residual film 7. In addition, the pattern profile is not vertical but the precision of the face is reduced. It can also be seen that this reduction results in a reduction of the final reticle CD. In this particular embodiment, A heat-treated nitrogen-containing hard J film is applied to the chemical amplification ship _ obtaining - bribe anti-L. However, the fine nitrogen-free hard cover film is also subjected to surface treatment. Although it does not cause the substrate in the hard cover film Dependent on nitrogen' but strong acid can diffuse into the hard mask or be lost. For this reason, the chemistry The accuracy of the large anti-residue pattern may be deteriorated. In addition, the surface treatment operation can increase the adhesion. Thus, a nitrogen-free hard cover film is preferably subjected to surface treatment. (Fifth Embodiment) This embodiment relates to A blank mask that does not include an anti-etching film.

. First, 'by using a DC magnetron sputtering comprising a single target of Mo and Si in a ratio of i〇: 9〇 (at%/at%), a thickness of about 30 nm is formed on a substrate by MoSiN. A light shielding film is formed. The thickness can range from 1 奈 nanometer to 40 nanometers. In addition to MoSiN, M〇si, MoSiC or MoSiCN can be used as one of the materials for the light-shielding film. Thus, a primary electrode having a thickness of 15 nm was formed on the light-shielding film by DC magnetron sputtering using a single target including Mo and Si in a ratio of 10:90 (at%/at °/〇). Reflective film. The antireflection film may be composed of a material selected from the group consisting of M〇SiN, MoSiCN, MoSiO, and MoSiCO. Then, after the MoSiN light-shielding film and the MoSiCON anti-reflection film were formed on the transparent substrate, a hard cover film made of Cr and having a thickness of 10 nm was formed. The hard cover film was formed by sputtering with a DC magnetron of a chromium dry material. The hard cover film may be composed of a material selected from the group consisting of Cr alone, a Cr compound including CrC, CrO, CrN, CrCN, CrCO, and CrCON, Ta alone, and a Ta compound including TaC, TaO, TaN, TaCO, TaCN, and TaCON. . 22 201001055 X-ray photoelectron spectroscopy (XPS) analysis of the composition of this _. The analysis determines that the light-shielding film includes M〇, Si, and N in a ratio of 11.8 at%: 59.2 at%: 29 at=, and the anti-reflection film includes a ratio of 1〇4 stations%: %3=:1 ^% : 1,6 stations % : 28.5 M, Si, C, 0 and N. The hard cover film is composed of 100 atm/〇 of chromium. Gallery]:: A " oxime (HMDS) on the 15G °C hot plate to treat the surface 'and coated with a thickness of 150 nm - chemically amplified etchant photoresist to create a blank light cover. It is exposed that the blank mask is fabricated in a -5 GKV electron beam exposure apparatus, and PEB and development processing are performed to form a resist pattern. The resist pattern is used as an etching mask to dry-etch the Cr hard mask film. At 4, the dry mask of the hard mask film is dried by induction ICP (ICP), and the unnecessary resist pattern is removed by washing with ozone water. According to Icp etching using SF6 and oxygen as a monofluoro-based gas, it is used as a mask-dry side of the anti-reflection film and the light-shielding film. = SF6, CF4 "The light-shielding gas from the iso-fluorine-based gas causes the light-shielding film and the cloth screen (4) T-square of the plate (broken substrate) damage detector (EPD) to detect the end point of the light-shielding film, to cover Forming the anti-film between the film and the transparent substrate prevents the hybrid film from containing a transition metal such as Cr or Ta as a main knife, which is not slowed by a fluorine-based gas or a slow rate. Thus, ICp etching is performed using a gas mixture of I and oxygen to form a mask. The fluorine-based gas does not cause damage to the MoSiCON anti-reflection film and the transparent substrate. μ, CD is measured by CD. Measure the circuit in a circuit of 50 nm (line and space) ^) = mean of the material (剌 is 3 nm or less, c;;;: 2.4 is not meters or smaller, the density deviation is 21 nm, and LEj u 23 201001055 Worry CD. It can be seen that a high-precision mask can be manufactured, which forms a 22 nm optical proximity correction (〇pc), and the ancient film density is 2g/Gnf and the fact that the crystallinity of the film is J. The specific implementation is achieved by forming the μ〇_photowell film, the VIOS1CON anti-reflection film, and the q·hard cover on the flip substrate. Oh and /

Into the film, to make the blank mask. Each of the specific embodiments = f is possible. This specific embodiment can be modified into various forms such as an anti-etching film composed of a transition metal such as Cr or Ta, a MoSi-based light shielding film, an M〇TaSi-based anti-reflection MoTaSi-based light shielding film, and an M〇si-based anti-reflection film. Further, the correction of the hard cover film can be realized by using various transition metals such as Ta, W, Hf, Zr, Ti, etc. As apparent from the above description, the blank mask and the photomask of the present invention have the following advantages: /, First, high-precision photoresist, pattern, and pattern transcription can be realized by eliminating the substrate dependency of the chemically amplified resist film. It can provide a blank mask of good CD. By combining the heat treatment during the formation of the hard cover film, the corrosion resistance of the hard cover can be improved without affecting the reflectivity and the etching ratio, and the dry and wet sculpt can be reduced. The following anti-reflection film and light shielding film are damaged. Thus, a blank mask which realizes transcription of a high-precision type and exhibits high selectivity and excellent CD due to low thickness is provided. Third, the reticle can be fabricated using the inventive blank reticle, which exhibits good fidelity, mechanical linearity, equal twist deviation, and good quality of LER in a 50-100 nm pattern. Although the preferred embodiment of the present invention has been disclosed for the purpose of illustration, those skilled in the art will recognize that various modifications, and modifications may be made without departing from the scope and spirit of the invention disclosed in the appended claims. Adding and replacing are possible. [Simplified illustration of the drawings] 24 201001055 Detailed description of the dry materials by the drawings 'The above and other target features and other advantages of the present invention will be more easily understood, wherein: W ί i Α to Figure 1G are diagrams according to the present invention - specific BRIEF DESCRIPTION OF THE DRAWINGS FIG. 3 is a cross-sectional view showing a method of fabricating a reticle and a reticle; FIG. 3 is a diagram illustrating a blank according to an embodiment of the present invention. FIG. A table of the performance of the reticle and the reticle; and Figures 4A and 4B are schematic cross-sectional views illustrating the outline of the photoresist pattern according to the surface treatment. [Description of main component symbols] 1. Substrate 2. Anti-etching film 3. Light-shielding film 4. Anti-reflection film 5. Hard cover film 6. Chemically amplified anti-surname agent

7. Remnant film 100. Photomask 200. Photomask 25

Claims (1)

201001055 VII. The scope of application for patents: 1. - A kind of empty self-mask" which consists of a sequential film, a metal film, a hard cover film and a photoresist film on the plate, which is resistant to the residual, = The crystallinity of the engraved film, the metal film and the hard cover film is amorphous, and the density of the anti-caries film, the metal film and the hard f cover film is a film, and the medium-rubber cover film mainly contains a metal and Nitrogen, and a coating-chemically amplified anti-(four) shaped anti-money agent film, wherein in forming the resist film, the gamma agent film is surface-treated before coating the hard cover film to reduce the The substrate of the chemically amplified type anti-film is a blank mask according to item 1 or 2, wherein the metal of the hard mask comprises Τι, V, Cr, Mn, Fe, Co, Ni, and 7r , Ge^Zr^Nb^M〇.Ru>Rh>Pd.Ag^Cd>In.Sn>Hnf>Ta' W, 〇s, lr, pt, Au, and combinations thereof. d 4 2, as described in claim 3 of the patent scope, the towel is composed of a metal as a main component, and is selected from the group consisting of metal compounds, metal nitrides, metal halides, metal oxynitrides. It is composed of a metal or a metal compound of carbon and metal oxycarbonitride. A blank mask made of I, such as 4^Λ, wherein when the hard mask field 3 has Cr and/or Ta as a main component, the compound consists of Cr and/or Ta 30-70 at% , carbon 0-30 at%, oxo 2〇at〇 / and nitrogen 10-40 at% composition. A blank reticle according to claim 1 or 2, wherein the wide film is composed of a metal including Ti, v, Cr, Mn, Fe, c'o, Zn. Ga, Ge, Zr, Nb, Mo, RU, Rh, Pd, Ag, cd, In, Hf, Ta, W, Os, lr, Pt, Au, and combinations thereof. n 7· The blank mask according to item 6 of the patent application scope, wherein the anti-surname film is patented by the first or second item of the patent patent range 26 201001055 lltml 〇 nitrogen TMat%, carbon 0 drive, oxygen oxime film The blank reticle, wherein the anti-slip stencil 10. The blank reticle according to claim 1 or 2, wherein the thickness of the anti-scratch film and the hard cover film is 3 nm. To 3 〇 capture rice. The blank mask according to Item 1 or 2, wherein the blank mask according to the invention of claim i or 2, wherein the rate of the scratch-resistant I film is thirsty or dry Higher than the hard f cover film. The film θ13, the blank mask of item 1 or 2, wherein the metal film is an early film or a multilayer film comprising two or more layers. Xingru, the scope of patents! Or the blank mask described in 2, wherein when the gold film is a blessing, the single layer is used for the purpose of anti-rejection. _ A blank reticle as described in the chest ί1 or 2, wherein the refractory includes a light-shielding film to shield the light' and a film: a blank reticle of the two SiTS, wherein the metal is formed. Wang wants to have a blank reticle as described in claim 1 or 2, wherein the metal ί! Li is composed of an oxide selected from the group consisting of It is composed of one of carbide, nitride, milk compound, carbon oxide and carbonitride. 18. The blank reticle of claim i or claim 2, wherein the metal 27 201001055 film mainly contains the metal ruthenium and the metal comprises a material selected from the group consisting of ruthenium, V, Cr, Mn, Fe, Co, Ni, One or more of Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ru, Rh, pd, Ag, Cd, In, Sn, Hf, Ta, W, Os, lr, pt, and AU. 19. The blank reticle of claim 2 or 2, wherein the film is a two-layer film, and the two-layer film comprises a layer disposed on the substrate for use as a light-shielding layer and a layer Arranged on the lower layer as an upper layer of an anti-reflection film, the light-shielding film is composed only of MoSi, and the MoSi is composed of Mo 20-70 at% and Si 30-70 at °/〇. 20. The blank mask of claim i or 2, wherein the metal film is a two-layer film composed of a MoSi compound, and the metal film comprises a light shielding film disposed on the substrate. a lower layer and an upper layer disposed on the light shielding film as an anti-reflection film, wherein the light shielding film is composed of Μο 1·20 at%, Si 4G_8〇at%, nitrogen 丨 (four), and 0-10 at% . 21. The blank mask of claim 1 or 2, wherein the A film is a two-layer film composed of a MoSi compound, and the metal film comprises - disposed on the substrate for use as a light shielding And an upper layer disposed on the light shielding film as an anti-reflection film, wherein the anti-reflection film is composed of M. 1-20 at%, Si 4 please at%, oxygen _ Qin at% and carbon 0-10 at%. The blank reticle of the first or second aspect of the invention, wherein the metal film comprises a film of two or more, the metal film comprising - disposed on the substrate for use as a light shielding film sound and an arrangement of the light shielding The film is used as an upper layer of an anti-reflection film, and the light shielding film is composed only of MoTaSi, and θ the light shielding film is composed of Mo 10-60 at%, Ta 2_3 () at%, and & 3 (4) a blank reticle, wherein the film is a two-layer film composed of a MoTaSi compound, the metal film comprising - disposed on the substrate as a light-shielding film underlying layer 28 201001055 and a light shielding layer disposed thereon The film is used as an upper layer of an anti-reflection film composed of Mo 1-15 at%, Ta 1-15 at%, Si 40-80 at 〇/0, producing 10-50 at%, and carbon O-io At% composition. A blank mask according to claim 1 or 2, wherein the gold film is a two-layer film composed of a MoSi compound, and the metal film comprises a substrate disposed on the substrate for use as a film. a lower layer of the light shielding film and a layer disposed on the light shielding film as an anti-reflection film, wherein the anti-reflection film is composed of: Μ〇1-15 at%; Ta 1-15 at%; Si 4〇 _8() at%; oxygen 0-10 at%, preferably 0·5 at%; nitrogen 1〇_5〇at%; and carbon at〇/. 25. as claimed in item i or 2 The blank mask, and the 0 film is a two-layer film, and the two films include: a lower layer disposed on the substrate, which serves as a light and mainly contains MoSi; and an The upper layer of the light-shielding film, which is an anti-reflection film and mainly contains MoTaSi. 26. A blank mask as described in claim 2 or 2, wherein the gold film is a two-layer film, and &quot The two-layer film comprises: - a lower layer disposed on the substrate, which serves as a photon and mainly contains MoTaSi; and an upper layer disposed on the light shielding film, It is used as an anti-reflection film and mainly contains M〇Si. Please use the blank mask described in Item 1 or 2, wherein the anti-etching film is not dried by the mouse-based gas, but is a gas-based gas. All the time, and, without the substrate side, there is no substrate or the ΐΐϊΐ ϊ, and the auxiliary time paste is arranged on the metal film; the blank reticle according to Item 1 or 2, wherein the metal is fine, the dry side of the base is Instead of being a gas-based gas butterfly, and engraving. Grasp the age m and the money cover film; ^ is the fluorine-based gas touched by the side of the gold gamma. 29. When the metal film is formed on the ninth substrate of the patent application, The blank mask of the item, wherein the blank mask 29 201001055 has an optical density of 2.5 or higher when the transparent exposure wavelength is 193 nm. 30. The blank as described in claim 9 a reticle, wherein when the bismuth metal film is formed on the transparent substrate, the metal film has a thickness of A or less. 31. The blank reticle of claim 9, wherein the transparent reticle When the metal film is formed on the substrate, the gold is exposed at an exposure wavelength of 193 nm. The film is a 25% or less reflective film. The blank mask of claim 1 or 2, wherein the anti-etching film and the metal film are formed on the transparent substrate. The blank reticle has an optical density of -2.5 or higher at an exposure wavelength of ^ nanometer. Snapshot 193 33. A blank reticle as described in claim 1 or 2, wherein When the ruthenium-etching film and the metal film are formed, the total thickness of one of the films is not more than 34. The blank reticle of claim 1 or 2, wherein the anti-film is formed on the transparent substrate and In the case of the metal film, the metal film has a reflectance of 25% or less under the exposure. ^5·If you apply for a patent scope! Or a blank reticle as described in 2, wherein the film is not 疋-gas-based gas dry etched' but is a chlorine-based gas side, and The job is hard and fresh, and the metal film placed under the 5 hai hard shell mask is not etched. A blank mask as claimed in claim i or 2, wherein the mask and the anti-etching film are simultaneously etched by the chlorine-based gas. The heat treatment is carried out by means of a device selected from the group consisting of - a hot plate, a vacuum hot plate, a straight air baking phase, a vacuum chamber and a furnace. - 障碍 38. = the blank reticle of the second application of the patent scope, wherein the reticle of the relay speed (RTP) lamp, the scale lamp, the purple ray range, the second ray cover, in addition to the The heat is used to carry out the surface treatment with a liquid or gas containing ruthenium, and the medium mainly containing ruthenium includes a group selected from the group consisting of hexamethylene diwei, triterpenoid Wei 30 201001055 bis diethylamine, 0-trimethyl shi Acetic acid, 〇-trimethylsilylproprionate, O-trimethylsilylbutyrate, tridecyltrifluoroacetic acid, trimethyl methoxy acetam, N-methyl-N-trimethyl decyl trifluoroacetamide, DTMMA, tridecyl decane, One or more of tridecylsulfonyltrifluoroacetamide, dimethylthiononphenyldiamine, and trimethylethoxysilane. 40. A method of manufacturing a blank reticle according to any one of claims 1-3. 41. A reticle manufactured using the ventilating cover according to any one of claims 1 to π. 42. A method of manufacturing a reticle by using a blank reticle according to any one of claims 1 to 39. 31