TWI380127B - Half-tone phase shift blankmask, half-tone phase shift photomask and its manufacturing method - Google Patents

Description

1380127 26792pif IX. Description of the Invention: [Technical Field] The present invention relates to a method for semi-tone phase shifting blank masks used in the production of semiconductor direct components, in particular for stabilizing the transmittance and chemical resistance, and relieving stress a semi-tone phase shifting blank mask having a phase shifting film containing at least a molybdenum (?), a button (Ta), a ytterbium (Si) and a transition metal. [Prior Art] The high integration of direct components uses a half-tone phase shift blank mask that reflects high definition. The half-tone phase shift blank mask consists of a phase shift film, hood, and anti-reflection film over the transparent substrate (antireflecti〇n film). ), the light resistance is formed; due to the phase shift film, the optical path difference of the exposure light is phase-shifted. Due to the 180-degree phase shift function, a pattern smaller than the original binary blank mask can be formed. There are schemes for MoSi series, such as MoSiN, MoSiCN, MoSiO, MoSiON, etc. containing molybdenum (Mo) and Shi Xi (Si), but because of the above phase shifting film, when washing blank mask and mask engineering Alkaline chemical series

The ammonia of the drug has the characteristics that the characteristics are easily changed, so it has the disadvantage that it is difficult to carry out sufficient washing work. D. Because it is difficult to carry out sufficient washing work, the particles on the surface of the phase shift film cannot be completely removed, eventually leading to defects; It is difficult to sufficiently remove the disadvantages of chemical residues such as ammonia and sulfuric acid. These chemical residues, which are chemically reacted with lasers having a wavelength of 193 nm or 248 nm used in semiconductor lithography engineering, cause the chemical residue to grow into a defect of 1380127 26792 pif; it is called Growth Defect. It in turn leads to fatal flaws in shortening the life of the mask. At the same time, the phase shifting cover composed of the original MoSi has a problem of high residual stress due to its unstable state. Due to these problems, when the phase shift mask patterning process is performed, problems such as falling off of the pattern occur due to high residual stress. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and the object thereof is to improve molybdenum, optical phase shift, chemical resistance, and exposure resistance by using molybdenum button and bismuth as essential components, including adding transition metal. , residual stress, growth defects, provide a half-tone phase transfer blank mask with excellent quality. In order to achieve the above object, the half-tone phase shift blank mask of the present invention is characterized in that a phase shifting 貘, a hood, and an anti-reflection film are sequentially formed on a transparent substrate, and then a photoresist is formed to constitute a half-tone phase shift. Blank mask. In particular, in accordance with the present invention, the fabrication of a half-tone phase shift blank mask is performed in a time-sharing process. The most advanced processes can be divided into: 0) the stage of preparing a transparent substrate. (8) In order to ensure excellent uniformity and repeatability of the product in mass production, a transition metal is included on the transparent substrate using an earlier 贱_ comprising a plurality of compositions on a surface larger than 1/3 of the surface of the transparent substrate. Shi Xi and Nitrogen; the density of the formed film is 3g / cm; above the phase shift film (4) above the phase shift film, formed in the hood, anti-reflective film and hard mask (Hard mask) order, more than one selected The stage of the membrane.曰 1380127 26792pif (d) One or more films are selected from the above-mentioned hood, antireflection film and hard mask, and at least one of the phase shift films is subjected to reforming.

(e) The stage of forming a light and a resist. The transparent substrate prepared in the above a) stage is characterized by having a KrF of 248 nm exposure wavelength and ArF lithography of 193 nm exposure wavelength, and having a transmittance of 85%.

The transparent base 4 prepared in the above stage a) has the feature of being able to make (4) on the ArF immersion lithography; and at this time, the birefringence of the transparent substrate is characterized by 'in order for the (10) immersion lithography project to occur. The Portion phenomenon is minimized and is characterized by w6.35 inm. The phase shift film of Shif f is characterized by the necessity of including molybdenum, button and yttrium, for the purpose of improving chemical resistance, controlling growth loss, reducing the residual stress of the film, and regulating the transmittance.

The phase shift film of the above bl) stage is characterized by ruthenium, 2-20 at% of molybdenum, and 2-20 at% of transition metal. L〇-5〇at% of nitrogen; must include 30-80at%. The addition of molybdenum in addition to molybdenum is characterized by the fact that the formation of the optical phase shift film includes the turning, dreaming and transition metals. The above b]) stage is characterized in that it comprises l-30 at% of molybdenum and 50-95 at% of stone and dryness when forming the optical phase shifting film: the same as -30 at% of the transition metal. 1,380127 26792pif in addition to molybdenum The above-mentioned bl) phase is characterized by the formation of a phase-shifting film. The phase-shifting film conforms to the KrF lithography of the 248 nm exposure wavelength, and includes 5_3〇at% of the turn, 50- 90at% of niobium and 5_3〇at% transition metal other than molybdenum. The above bl) stage is characterized in that the ruthenium plating of the phase shift film is characterized in that the phase shift film conforms to KrF lithography having an exposure wavelength of 193 nm, and includes 1 -20 at% of molybdenum, 70-95 at% of yttrium and molybdenum except molybdenum.丨-2〇at% transition metal.

The phase shift film of the above bl) phase, when conforming to the KrF lithography having an exposure wavelength of 248 nm, must include both molybdenum of Moru, % of niobium at 2〇_7〇, and transition of l-20at% other than molybdenum. Metal and 2〇_7〇at% of nitrogen. The phase shift film of the above M) phase conforms to the KrF lithography day temple with 丨93·exposure wavelength, and must include M〇at% molybdenum, 2〇_8〇%% of Shizhan, and M〇 other than molybdenum. At% of the transition metal and 2% 〇8% of the nitrogen. The phase shift film of the above bl) stage is characterized by a single layer of film.

The phase shift film of the above bi) stage is characterized by a film of a plurality of layers of two or more layers. The phase shift film of the above M) is formed by DC magnetron frequency dc magnetron tive sputtering, and there is ot heating, including 10·50ν〇1% of inert gas nitrogen, and the phase shift of the white phase The film is specially made to prevent the residual stress of the film from being reduced, and the film is followed by a long defect. The phase shift film is subjected to heat treatment by the heat treatment device. The phase shift film heat treatment of the above-mentioned stage is: from the electric furnace, 1380127 26792pif is selected from the methods of air-capacity f, hollow oven, etc.; the temperature is 200-500 ° C, the time is 5-60 min, and the pressure is 76 Gmton·. The phase shift film of the above bl) has a characteristic of 3 g/cm 3 or less when a density of a film is measured by x-ray reflectivity by adding a transition metal other than molybdenum. The phase shift film of the above bl stage is characterized by being lightly formed by reactive sputtering: the inert gas is selected from the group consisting of argon, helium (He), neon (Ne), and xenon (Xe); reactive gas is used. From oxygen (〇2), nitrogen (n2), nitrous oxide (N2〇), ammonia (NH3), carbon monoxide (c〇), carbon dioxide (C02), nitric oxide (NO), nitrogen dioxide (n〇 2) One or more gases selected from decane (CH4). After the formation of the phase shift film in the above bl) stage, in order to prevent the occurrence of growth defects, there is a feature of washing using a washing process. The above bl) stage is to improve the stability of the phase shift film and reduce the occurrence of growth defects. After the phase shift film is washed, it has a method such as a hot-plate, a rapid thermal process, an oven, and the like. One or more methods are selected to perform the heat treatment feature. In the above step bl), the phase shift film is sequentially washed and heat-treated, and then analyzed by ion chromatography (Ion chromatography, 1C), which is characterized in that the total amount of ions generated is 5 ppmv or less. After the phase shift film is sequentially washed and heat-treated in the above bl) stage, it is characterized by gas chromatography/mass septroscopy (GC/MS), and is characterized by including Butylated Hydrotoluene (BHT). The total amount of volatile organic compounds (v〇latile core compound) such as aromatic hydrocarbons (Aromatic 1380127 26792pif hydrocarbon) is 5 ppmv or less. The phase shift film of the above bl) stage is characterized in that no growth defects occur when exposed by an energy of 3Q or more by i93 nm Arp > laser. The hood and the anti-reflection film of the above-mentioned cl) and dl) are characterized in that a selected one of a transition metal, a ruthenium and a ruthenium compound is a main component; in these nitrides, oxides, carbides, oxynitrides, A form in which one of nitrogen carbides, oxycarbides, and nitrogen oxides is selected. The hood and anti-reflection film of the above cl) and dl) stages, considering the selection ratio of the phase shift film in the case of the remaining engineering, the hood and the anti-reflection screen having direct contact with the phase shift film, and the phase shift film and Other etching media are etched. After forming the hood and the antireflection film at the above-mentioned stages c1 and dl), the reflectance at all wavelengths of 193, 248, and 365 nm is 30% or less. The above-mentioned cl) and dl) stage hoods and anti-reflection films have a thickness of 1100 A or less. After forming the hood and the anti-reflection film at the stages of cl) and dl) described above, after forming the substrate, the phase shift film, the hood, and the anti-reflection film, it has a light transmittance of p/ at an exposure wavelength of 248 nm at 193 nm. The following features. After forming the hood and the anti-reflection film in the above steps c1 and dl), the low selectivity ratio of the photoresist is improved by adding a hard mask to the anti-reflection film. After forming the hood and the anti-reflection film in the above cl) and dl) stages, the hard cover 11 丄湖丄27 26?92pif layer is characterized by: among the transition elements, bismuth and telluride, the selected species are the main components; One of the compounds, oxides, carbides, nitrogen oxides, nitrogen carbides, oxycarbides, and nitrogen oxides is selected.

After the above cl) and the stage form a hood or an anti-reflection film or a hard cover layer, the feature is that the heat treatment process is selectively performed.

The above-mentioned cl) and dl) stages form a hood or an anti-reflection film or a hard cover layer, and the selective heat treatment process is characterized in that: one of the methods of electric furnace, hollow space=, and empty baking is selected; The temperature is 2〇〇_5〇〇. 〇, ^ between 5-60min, the pressure is below 760mtorr. The photoresist of the above el) stage has a feature formed by a positive or negative type of photoresist. The photoresist of the above el) stage of Putian is characterized by: selected by spin coating method, = (four) method, capillary coating method; at this time light = two degrees A 5GG-5_, soft baked (SGft The temperature of bakhlg) is

When the photoresist is not formed, it becomes a photoresist substrate or a phase frequency or a hood or an organic substance containing antimony above the hard layer or the hard cap layer to perform surface reforming. _The above-mentioned 61) stage does not form a surface rework between the photoresists = levy is: using cut organic matter, above the substrate by rotating ^ vapor or vapor priming - a method Before the photoresist is formed, the surface is reformed, and the central substrate or the phase or the mask or the anti-reflective film or the hardened film has the characteristic of no substantial change in characteristics. Cover 12 1380127 26792pif After the surface reforming process in the above el) stage, the waiting time is two hours or less until the sputum is applied. [Remedy] By the above process, a half-tone phase shift mask was fabricated in accordance with the present invention. The present invention will be specifically described by the following examples, which are used for the purpose of illustration and description of the invention, the meaning of the invention, In terms of technology, people with #遍知识 can reason. From the beginning of the example, it is possible to edit all kinds of deformed and equal sands. Therefore, this technique (4) is the technical matter of the scope.实施 刊 实施 <Example 1 and Comparative Example> Fig. 1 is a cross-sectional view of a half-tone phase shift* white mask manufactured in accordance with an embodiment of the present invention. In this case, in the following description, the same reference numerals are used: the same reference numerals are attached, and the description thereof is omitted. °

The embodiment performed is an embodiment of a KfF lithography that performs a halftone phase shift blank mask. Referring to the figure, a transparent substrate (1〇) having a surface area of 231.04 cm 2 and a size of 6 x 6 x 0.25 inches was prepared, and a phase shift film (20) was deposited using a DC magnetron sputtering apparatus. In the transparent substrate at this time, in consideration of the formation of the immersion lithography of the phase shift film conforming to the ArF lithography, the use of a transparent substrate having a birefringence of 5 nm / 6.35 mm can minimize the occurrence of the polarization phenomenon. The target size used when vapor-depositing the phase shift film, taking into account the uniform thickness of the phase shift film

(S 13 1380127 26792 pif, using a splashing age of 3 〇〇 cm 2 larger than the surface area of the substrate. Also, in order to form a half-tone phase shifting blank mask (four) f, in order to have its excellent repeat / renaturation 'use only a target. At this time, the target contains I5at%

(M〇), 5%%|Dan (ding a), 80at% Shi Xi (Si). If a phase shift film conforming to ArF··- lithography is produced, a suitable dry is 5 at% of molybdenum _), 5 at% of idan (Ta), and 90 at% lanthanum (Si). There is also the sputtering used in the evaporation phase shifting film. The sputtering condition is argon gas and nitrogen gas for 5_i〇〇s_, the power is ^1_4KW, and the pressure is (u_1〇mt〇rr, formed with A phase-shifting film of a single film consisting of a sinking layer. Also, for comparison, a step of forming a M〇SiN phase shifting film was carried out using a target of molybdenum (Mo) and shixi (si) composed of 20:80 at%. At this time, the target surface area used was a circular target smaller than the surface area of the substrate by 4 inches; the sputtering condition was the same as the condition of forming the phase shift film of the Μ S Ta S iN. The MoTaSiN and MoSiN formed by the above conditions were used. The phase shift film thickness was measured using the n&amp;k Analyzer 1512RT' from N&k Analyzer, USA, and the result was 5〇〇_9〇〇A. In terms of thickness uniformity, MoTaSiN used a larger surface area than the substrate. The sputtering target exhibits excellent uniformity of 20 A or less in the effective field (142 mm &gt;&lt; 142 mm) in the substrate. However, MoSiN uses a dry ore than the substrate area to measure 50 A in the effective field. The following bad thickness. Also, the date of use Lasertec's MPM-193, which measures both the transmittance and the optical phase shift, determined that MoTaSiN and MoSiN have a fluoroscopy and a phase shift of 180 degrees at 248 nm. However, both the transmittance and the optical phase shift (S) 14 1380127 26792pif Uniformity view 'MoTaSiN in the effective field of the substrate (I42mmxl42mm field), each measured 0.18% and 1.9 degrees uniformity; while MoSiN measured 0.42% and 3.9 degrees poor uniformity. Also, through X-ray reflection analysis showed that the phase shift film density was 4.3 g/cm 3 for MoTaSiN and 2.5 g/cm 3 for MoSiN. It can be known that the phase shift film density of MoTaSiN is high. The following is to eliminate particles and pollutants on the surface of the phase shift film. To prevent the occurrence of growth defects, a washing process was used. [Table 1] Phase shift film thickness 248 nm Perspective phase shift 骐 Thickness formation After 1 wash followed by 2 washes After 3 washes Example 1 MoTaSiN 857 A 5.87 5.89 5.90 5.90 Comparative Example 1 MoSiN 874 A 5.78 5.97 6.13 6.35 Example 1 and Comparative Example 1 of Table 1 are the results of measuring the amount of change in the see-through rate after performing multiple washings on the phase-shift film. It can be seen in Example 1. After forming the phase shift film, and after washing 3 times, as compared to an increase of 〇.〇3〇 / q; Comparative Example 1 and washed three times due to a perspective of increase of 0.57%. Therefore, compared with the MoSiN phase shift film, the MoTaSiN phase shift film is excellent in chemical (Chemical) by adding a button (Ta), sulfuric acid, sci (ammonia/hydrogen peroxide/aqueous solution) used in the washing process. Chemical resistance. The following is an ionic impurity and an organic substance for improving the stability of the phase shift film and reducing the cause of growth defects, and heat treatment is performed at 35 (TC for 1 minute using a hot plate. As described above, after heat treatment, in order to confirm the thinness Stability, (S) 15 1380127 26792pif. At this time, the amount of change in the transmittance was measured for comparison with the passage of time compared to various projects.

[Table 2.] After phase shift film formation Example 1 MoTaSiN 5.76 % Comparative Example 1 MoSiN 5.84 % ------

Table 2 shows the results of the change in the transmittance of the film after the phase shift film was washed and heat-treated. In the case of the MQTaSiN phase shift film, the see-through rate of the sky is 5.79%, which is only 0.03% higher than the perspective rate of $76%. However, in the case of the phase shift film of M〇SiN, the see-through rate after 2 days was 5.97%, which was found to be 0.13% higher than that after the formation. Therefore, it can be strengthened, and the stability of the phase shift film is improved as the material is added.

At the same time, in order to reduce the degree of blurring caused by the addition of the Ta (New Zealand) (Ta), the pretreatment of the ion impurity and the organic chemical impurity generated in the phase shift film was measured. A container (70) capable of containing a blank mask formed by a phase shifting film, placed therein in a blank mask, filled with deionized water (80), and then heat treated at 120 C for 20 minutes using an autoclave (am〇clave) . Next, deionized water from which ions were extracted by heat treatment was analyzed for ion impurity using 1C'. In the case of determining the concentration of the organic compound, the same as the ion analysis, referring to Figure 16 1380127 26792pif 3, placing a blank mask in a blank-filled container (71), and after cleaning with nitrogen or dry air, the container is at 85. The oven was heated in a °c oven (〇VEN) for 6 minutes; then the gas was withdrawn through the vent (90) and the organic compounds were analyzed using GC and MS with an aotomatic thermal desorption. The results of the ion analysis are the same as those in Table 3. The analysis results of volatile organic compounds are the same as in Table 4. [Table 3] Unit: ppmv Phase shift film NH/cr S042·F no2-Ν03· Total ion temperature Example 1 MoTaSiN 0.3 0.2 0.4 0.2 0.2 0.2 23 Comparative Example 1 MoSiN 0.7 0.8 1.2 0.5 0.4 0.7 6.4 [Table 4] Unit : ppmv phase shift film BH butane aromatic total VOC concentration Example 1 MoTaSiN 0.75 2.31 3 24 Comparative Example 1 MoSiN 1.86 4.12 6.14

Table 3 above shows the results of ion analysis for Example 3 and Comparative Example 3, and Table 4 shows the results of analysis of volatile organic chemicals for Example 3 and Comparative Example 3. First, referring to Table 3, it can be seen that the total ion concentration of the MoTaSiCN phase shift film is only 2.3 ppmv, and the ion intensity of MoSiN is 6.4 ppmv. Thus, it can be known that with the addition of Syria (Ta), the ions of the film 17 丄 :) δ υΐ: Ζ / 26792pif

== Difficulty will improve. Next, referring to Table 4, Example 3 ^ Chen degree is only 3.24 ppmv, and the concentration lower than _ 3 is ppmv. This is the same as the ion analysis result. With the addition of (10), the surface of the f film is transferred to the chemical level (10). and also_. Therefore, it is possible to analyze the results of the sinking of the scales and the volatile organic compound, and the addition of a small amount of Ta (Ta) can reduce the adsorption of ions and volatile organic chemicals on the surface of the phase shifting film, and ultimately reduce the occurrence of growth defects. At the same time, the result of measuring the phase shift film contact angle by the contact angle measuring instrument was that the contact angle of the lake was 15 degrees and the contact angle of the MoSiN was 36 degrees. This indicates that the surface energy of M〇TaSiN is relatively lower than that of M〇SiN, and it can be said that the surface is in a stable state. Referring to Fig. 4, a hood (30) having a TaN composition is formed by a reactive sputtering method using a button (Ta) target and nitrogen gas above the phase shift film. Next, referring to Fig. 5, an antireflection film (4 Å) having a Ta 〇 N composition is formed by a reactive sputtering method using a button (3⁄4) target and nitrogen and oxygen. Referring also to Fig. 6, a positive-type chemically amplified photoresist fep-171 was used to form a photoresist (6 Å) having a thickness of 3000 A to fabricate a half-tone phase shifting blank mask. As described above, according to the invention of the present embodiment, in manufacturing a half-tone phase-shifting blank mask, at least a region containing a ruthenium (Mo), a ruthenium (Ta), a ruthenium (Si) is used at a larger area than the substrate area. The target is sputtered to form a phase shifting film. Thus, it is possible to produce a bell-dried film having excellent uniformity. In the case of mass production, a phase shift film excellent in uniformity can also be produced. At the same time, due to the addition of the button (Ta), it is possible to produce a phase shift film which ensures excellent chemical resistance, thermodynamic stability, high density of 18 1380127 26792pif, and high dimensional stability of the film due to thermodynamic stability. According to the residual stress of the material, the lower residual stress can produce a half-tone phase-changing blank without a defect and excellent quality, and the cover; at the same time, the X can reduce the phase shift film due to the addition of Ta (Ta). The energy of the surface, improving the adsorption characteristics of ions and volatile organic chemicals, can produce a half-tone phase transfer blank mask without growth defects. <Embodiment 2> This embodiment is an embodiment in which a half-tone phase shift blank mask is performed in accordance with ArF lithography. Figure 7 is a cross-sectional view of the fabrication of a half-tone phase transfer blank mask in accordance with an embodiment of the present invention. In the following description, the same reference numerals are given to the same or substantially the same parts, and the description thereof is omitted. A 6x6x0.25 inch quartz substrate (1 inch) was prepared with reference to Fig. 7'. At this time, the measured transmittance of the quartz substrate was 9% or more at 193 mm, the TIR (total indicated reading) value of the flatness was 0.32 焖; the surface roughness was 〇.2 nm Ra; and the double light at 193 nm. The birefringence was 2 nm/mm. Then, the formation of the phase shift film (20) was carried out by DC magnetron sputtering on a quartz substrate. The bismuth ore is a single dry ‘this time includes 9 〇 along the % Shi Xi (Si), 5 at% (Mo) and 5 at% of the boat (Ta); at the same time, a target larger than the surface area of the substrate is applied. At this time, the sputtering target conditions for forming the phase shift film were 5 Torr argon, 5 〇 Sccm ammonia, 2 W/cm 2 power density, 〇 2 Pa pressure, and 19 1380127 26792 pif. The MoTaSiN phase shift film formed by the above process was subjected to measurement results 疋' thickness of 600-700A, 6% of the wavelength at the I93nm wavelength, and the phase shift film at the wavelength of 193nm was 180 degrees 6 :· For comparison, a composition having a ratio of 10:90 at% was used, and a μ〇&amp;ν phase shift film formation test was carried out using an M〇Si material having a diameter of 4 inches smaller than the surface area of the substrate. At this time, the remaining conditions were the same as those of the M〇TaSiN minus the clock strip; the fluoroscopy at a thickness of 67 〇A was measured to be 6%, and the phase shift was 1 to 80 degrees. Then, in order to increase the density of the phase shift film, a hollow chamber (-) was used, and heat treatment was performed for each of the wars for 20 minutes. The film density was then measured by X-ray reflection for each phase shift film. As a result of the measurement, the density of MGTaSiN was 4 25 g/cm 3 , and the density of SiN was (4) of melon 3. It can be concluded that the density of the phase shift film increases with (4) Qiu. Because of the ionization energy of the button (Ta), when the phase shift is added, the button and the M〇, si, and N atoms are combined, and the combination of the soil is difficult to interrupt. Therefore, as the addition of New Zealand (4) is more rigid, the hardness of the film is increased, and the density is also high, so that the stability of the high film and the characteristics of the phase shift film are also improved. After the apricot/heat treatment, the chemical resistance of each phase shift film was carried out. - Bayer = 85 degree sulfuric acid and normal temperature sen, and 2 hours of soaking was observed. J. The phase shift of the phase shift film was observed. First, the MoTaSiN's phase Ϊ i exhibits a 11% change in the transmittance and a MoSiN phase shift film. The change is 〇_4%. From this, you can see &amp;, with the addition of a button (Ta) with an ionization energy of 20 1380127 26792pif, the phase shift film density can be increased, and the bonding force is stronger to improve the chemical resistance. Then, in order to grasp the degree of occurrence of blurring defects of the phase shift film, an energy of 193 nm was used to accelerate the energy of 3 kJ, and an inspection experiment was performed using KLA § LF77 device '2. As a result of the experiment, a fuzzy defect of 个3/cm occurred in M〇TaSiN, and a defect of 22/cm2 was detected by M〇SiN. From

It can be concluded that with the addition of the button (Ta), there is less blurring defects. This is because, as the button is added, the surface-adsorbed ion impurities and the exhaust gas impurities are strongly combined, and it is difficult to move, so that it is difficult to combine the impurities, so that blurring defects rarely occur. Then, above the phase shift film, a hood (3 〇) containing Cr as a main component and an anti-reflection film (40) were tested by sputtering targets with a thickness of 450 Å. Then, a step of forming a hard cap layer (5 Å) having a composition of M 〇 SiN was carried out by DC sputtering using a target formed of 1 Å: 90 at% M 〇 Si over the antireflection film. Then, at this time, a phase shift film and a shading are sequentially formed over the quartz substrate.

After the cover, the antireflection film, and the hard coat layer, the optical density at 193 nm was found to be 2.9. Then, on the hard coat layer, the surface was reformed by a cerium-containing organic substance. The surface reforming at this time is carried out by a vacuum chamber in which a hot plate is mounted. Then, on the hard coat layer which had been subjected to surface reforming, a step of forming a photoresist having a thickness of 2 Å was carried out using a negative-type chemically amplified photoresist. At this time, in order to prevent the photoresist from adsorbing moisture in the atmosphere and reduce the surface reforming effect, after the surface is refinished within 30 minutes, the photoresist is coated with a 21 1380127 26792 pif coating step. Through the above process, a step of manufacturing a half-tone phase shifting blank mask (1 〇〇) was carried out. Then, through the above process, a half-tone phase shift mask is used to fabricate a half-tone phase shift mask. Referring first to Fig. 8, an electron beam exposure apparatus using an acceleration voltage of 50 Kv is used to perform exposure of a photoresist, and after performing a PEB-p〇st exposure bake process, then 2.38 is used. / developer of tetramethyl hydride (tmAH) developer (developer solution), the step of developing to form a photoresist pattern (pattern 60a). Then, referring to FIG. 9, the photoresist pattern is used as a mask, and a hard mask layer pattern (5〇a) is formed by dry etching, and the photoresist pattern is stripped by a hydroxyl radical (〇H Radical); In order to form a hard cap layer pattern, a step of forming a hard cap layer pattern is performed by dry etching of fluorine-containing SF6 gas and inductively coupled plasma (ICP); at this time, chromium having a high selectivity to fluorinated gas is formed. The chrome-based hood and anti-reflection film are not dry etched. Previously, a photoresist pattern was used to form a chrome layer pattern, and recently a CD (critical dimension, minimum critical dimension) of 65 nm, 45 nm, etc., was required with an increase in the degree of accumulation. Therefore, the thickness of the photoresist is originally used at about 3000A, and currently, in order to reflect high definition, it is required to use a thinner photoresist having a thickness of 2500A and 2000A; at the same time, the chrome layer is the same, and the thickness is originally required to be about 1000A. Recently, the thickness of 500 people and 450 people is as thin as possible. Then, using a photoresist pattern such as a thin film of 2000A, and forming a chrome layer pattern by dryness, the chlorine gas of the chrome layer can be burned. 22 1380127 26792pif At this time, when etching the chrome layer, the photoresist pattern is also etched at the same time; because the thickness of the photoresist is thin, the selection ratio of the chrome layer is also lowered, and it is difficult to form a high-definition pattern; Thick thickness, negative wear during dry etching 'should be 0〇adillg also 1), resulting in unbalanced CD size, causing CD size error when manufacturing photomasks for ·-, 65nm, 45nm . So the hard cover layer is used. When the hard mask is dry etched on the hood and the anti-reflection film, the etching gas used has a high selectivity. Therefore, the hard layer can be formed with a thin thickness of several hundred A to greatly reduce the load effect; and has a high selection ratio for the hood, the anti-reflection film, and the etching medium, and is easy to form an optical like an auxiliary pattern. A subsidized pattern of 30 nm or 20 nm which is close to the correction (optical pr〇ximity correction; OPC) effect. Referring to Fig. 10, a step of forming a hood pattern (3〇a) and an anti-reflection film pattern (40a) is carried out by dry etching using chlorination with the hard mask layer pattern as a mask. Then, referring to Fig. 11, a step of forming a phase shift film pattern (20a) is performed. The formation of the phase shift film pattern was carried out by dry etching, using fluorinated gas 'SF6 rolling, and dry etching by ICP. At this time, the hard coat layer is etched when the phase shift film pattern is formed. There is also a hood with a chromium-based composition and an anti-reflection film pattern, which has a high selectivity to the fluorinated gas, so that the hard mask pattern is removed without being dry etched. Referring to Fig. 12, in order to form the pattern of the secondary mask and the anti-reflection film, the step of forming the photoresist (60) is performed. Then, referring to FIG. 13 'Using a pattern forming period having a 365 nm exposure wavelength', after performing exposure in the field to be used, a genus containing 2.38% ΤΜΑΗ 23 (S ) 26792 pif is used; a photoresist pattern is formed by liquid immersion ( Steps of 60a). Then, referring to Figure 14 as a mask with a photoresist pattern, the pattern of the (3Gb) and anti-reflective film (40b) is formed by using the vaporization %. @。 &gt;... Figure 15, using OHRadical to eliminate the photoresist pattern, to make a half-tone phase transfer mask (2〇〇). As described above, in accordance with the invention of the present embodiment, in the manufacture of half-tone white cover For the cover and the half-tone phase transfer reticle, a sputtering target having a surface area of 1/3 Å 6 φ η Λ can be used to produce an excellent thickness in the effective field (= 142 mm area) in the substrate. Through the sale of L: with the sentence phase shift film. At the same time, due to the phase shift film addition group (Ta), Tao = hard, can achieve film stability, improve the film's dense chemical resistance Low-quality, high-quality phase film with a =2 phase shift blank mask On the hood, f anti-reflective cap layer, may be manufactured in Manufacturing 45 toward the thief, nm "Wu ❾ left foot, to make a paste qPC case butterfly halftone shift mask. &lt;Embodiment 3&gt; This embodiment is a mask having a mask and a half-tone type. W-mesh transfer two white First, the stone base 4c, 1Λ, and the specifications are the same as those of the solid surface 2 with reference to FIG. ^ 石英 的 quartz substrate = after the implementation of the 32GA phase shift film on the quartz substrate using MoSi by 10, the composition of the single 1 = 24 1380127 26792pif argon and gas DC reactive respiration Phase shift film formation of MoSiN. The detailed engineering conditions were the same as those in the second embodiment. Then, using a single 5:5:90 at% of the phase shift film on the surface of the MoTaSi dry, the composition of the MoTaSi was converted by a DC reaction (reactive printing (4)%), argon and nitrogen with a composition of MoTaSi. The formation of the second phase shift film (21) was subjected to a heat treatment process. % Through the above process, the phase shift film formed has a total thickness of 670 A, and the wavelength of 193 nm has a fluoroscopy of 6% and a phase shift of 18 〇. Further, by forming the phase shift film of the above two-layer film structure, the residual stress of the phase shift film can be minimized; and the film is stabilized by using a phase shift film having a composition of MoTaSi including ruthenium (Ta) formed on the upper portion. 'Improve the binding force; By increasing the density, it is possible to use a phase shift film with high chemical resistance and less occurrence of blur defects. Then, on the second phase shift film, a visor (3 〇) having a thickness of 3 〇〇A and a TaON consisting of a Ta (Ta) as a main component and having a thickness of 200 A were formed. The step of reflecting the film (4 〇). At this time, the main substance of the hood and the anti-reflection film is not limited to only Ta, but can be used.

Among the tellurides such as Si, Ge, transition elements, and MoSi, one or two or more kinds of alloy materials are selected; oxides, carbides, nitrides, oxycarbides, oxynitrides, and oxygenated carbons may be used. The form of the nitride is not limited to a two-layer film such as a hood or an anti-reflection film, and may be composed of a plurality of films such as a single film, a two-layer film, or a three-layer film. Then, the step of forming a hard mask layer (50) is carried out on the anti-reflection film of TaON, and 25 丄 127 26792pif composed of M 〇 SiN. The hard coat layer was carried out under the same conditions as in Example 2. In this case, the hard cap layer is not limited to M 〇 SiN, and one or two or more alloy materials selected from Si, Ge, transition elements ' Μ〇 &amp; Oxides, sulphides, nitrides, oxycarbides, oxynitrides,

At the same time, it is not only a hood, an anti-reflection film, etc., H = formation, and is composed of a plurality of films such as a single film, a two-layer film, and a three-layer film. Further, after the phase shift film, the second phase shift film, the hood, and the anti-reflection film were formed on the quartz substrate, the optical density was measured at a wavelength of 193 nm, and as a result, the density was 3.0, and then, The process of forming a phase shift film (6〇) was carried out above the hard cap layer with the real two 2, and the square go to 'bee &amp; surface reforming'. A halftone phase shift blank mask was fabricated.

The above-mentioned procedure was carried out to produce a semi-phase-shifting fresh step. = Fig. 17 'In the same manner as in Example 2, the half-tone phase shift of the quartz substrate anti-reflection film pattern _ is made ==== hair: manufacturing half-tone phase transformation greatly reduces the residual stress of the phase shift film Helps strength and stability. At the same time, the film on the _ shift film (10) makes the film bond harder, can achieve the stability of the film, and increase the density of the CS 1 26127 26792pif film; thereby producing a high-quality product with excellent chemical resistance and less occurrence of blur defects (4) By using a half-tone net phase shift blank mask with a high selectivity ratio of the hard mask layer, it is possible to manufacture a phase shift mask suitable for manufacturing a 45mn, 65 nm component suitable for the auxiliary pattern of the 〇pc. &amp; The half-tone phase shifting blank mask and the half-tone phase shifting reticle of the present invention have an area larger than 1/3 of the substrate area when forming the phase shifting film, and the single-twisted filament of the plural structure is subjected to real-time phase shifting film The formation of the phase shift film is excellent in stability, and the thickness, the transparency, and the uniformity of the phase shift film in the effective field (142 ΠΠ Χΐ _ 42_ field) in the substrate can be produced. At the same time, the membrane is composed of a single layer or a plurality of membranes, and the maximum thickness of the membrane is _ residual stress, which helps to improve the mystery and stability of the mystery, and at the same time 'the phase shifting membrane is pure (10), so that The combination, addition and hardness of the film can achieve a stable bond and increase the density of the film. It is manufactured by ΐΓχ ΐΓχ 具有 to have excellent _ chemical resistance, less occurrence of ambiguity == more:: at the same time, by forming a half-tone phase transfer blank (four); :: 5nm-class ion fabrication, half-tone phase transfer mask for a 0pc support pattern. [Simple description of the diagram] Figure 1 is the root county (four), in the face of the film. | For the purpose of analyzing ion chromatography, the solution is dissolved in the analytical container. 27 1380127 26792pif

Fig. 3 is a cross-sectional view showing a phase shift film which is concentrated in order to analyze gas chromatography. In the container, Figure 4 is a cross-sectional view of the hood formed over the transparent substrate in accordance with the present invention. Phase shift film of Fig. 5 and Fig. 5 is a cross-sectional view of a square hood and an antireflection film on a transparent substrate according to the present invention. Fig. 6 is a cross-sectional view showing a hood, an antireflection preventing film and a photoresist film formed above the diffusing plate according to the present invention. In the meantime, Fig. 7 is a cross-sectional view of the blank mask removed in accordance with Embodiment 2 of the present invention. The resulting half-tone phase transition is illustrated in Figures 8 through 15 which are schematic views of a process for making a phase shift mask in accordance with the present invention. Example 2, the half-turn type produced by the manufactured half ’ '

Figure 17 is a cross-sectional view showing a mask according to an embodiment of the present invention. [Description of main component symbols] 10: Transparent substrate 2: Phase transfer film 21: Second phase shift film 30 · 'Shield 4: Anti-reflection film 50 · _ Hard cover 60: Photoresist (resistance The half-tone phase transfer made by the membrane 28 1380127 26792pif

70 : Analytical container for ion chromatography analysis 71 : Analytical container for gas chromatography analysis · 80 : Purified water (deionized water) 90 : Vent hole 100 : Half-tone phase shift blank mask 200 : Half-tone phase shift light Cover 29

Claims (1)

1380127 26792pifl is the Chinese patent scope of No. 9615033 No-line correction This revision period: 1〇1 June 13th, the scope of application for patent: 1. A half-tone phase shift blank mask, according to = shift, light a resisting agent; and between the phase shifting film and the photoresist, and having one or more kinds of films selected from the anti-reflective and hard-mask layers, and characterized by The repeatability is greater than the above-described use of a single sputtering target including a plurality of surface areas for ensuring uniformity and surface area of a bright substrate during mass production, the hood, the anti-reflection film, and the hard cover. A film of the above type or more is selected from the layers; and at least one or more films are subjected to surface reforming in the transparent substrate and the phase shift film, wherein the surface reforming is performed using an organic substance including ruthenium. 2. The half-tone phase transfer blank mask of claim 1, wherein the phase shifting film is a single sputtering using a transition metal including molybdenum (M〇), shi (Si), and molybdenum. Formed by the target. 3. The half-tone phase transfer blank mask of claim 1, wherein the phase shift film is used with 5-30 at% of molybdenum when the phase shift film is applied to KrF lithography having a wavelength of 248 nm. It is formed by a sputtering target of 5-30 at% of transition metal other than molybdenum and 50-90 at% of ruthenium. 4. The half-tone phase shift blank mask of claim 1, wherein when the phase shift film is applied to a KrF lithography having a wavelength of 248 nm, the phase shift film is made of l_20 at% of molybdenum ( Mo), 20-70 at% of ruthenium, a transition metal of l_2〇at% other than molybdenum, and 20-70 at% of nitrogen. 30 1380127 26792pifl is Chinese Patent No. 96150331 No underline correction. Amendment date: June 13, 101. 5. Half-tone phase shift blank mask as described in claim 1 of the patent application. When the film is suitable for ArF lithography having a wavelength of 193 nm, the phase shift film is a lanthanum (Mo) containing 1-10 at%, a transition metal of 1-20 at% other than molybdenum, and a ruthenium of 7 〇 _95 at%. It is formed by sputtering a target. 6. The half-tone phase shift blank mask according to claim 1, wherein the phase shift film is suitable for an ArF micro-shirt having a wavelength of 193 nm. The phase shift film is llatat%. Molybdenum (Mo), 20-80 at% of Shixia, and a 10-10 at% transition metal other than indium and 20-80 at% of nitrogen are formed by splashing dry. 7. The half-tone phase transfer blank mask of claim 1, wherein the phase shift film is formed by a single layer or a plurality of layers for reducing stress. 8. The half-tone phase transfer blank mask described in claim 1 of the invention, wherein in the formation of the phase shift film, the residual stress of the film is reduced, To prevent the formation of enamel film characteristics and the formation of growth defects, the phase shift film is subjected to a washing process and a heat treatment process; the heat treatment process is carried out in an electric furnace, a hollow container, or a hollow oven, and is selected to be 2 〇〇 5 〇〇. 〇 Temperature, time of 5-6 〇 min, pressure below 760 mtorr. 9', as described in the first paragraph of the patent application, the half-tone phase shift blank mask, 'where the phase shift film is sequentially subjected to washing and heat treatment, and ion chromatography (Ion chr〇 matography, 1C) is used for analysis. The total ion generation amount is 5 ppmv or less. 31 1380127 26792ρΐΠ Amendment date: June 13th, 2011 - No. 06150331 Chinese patent scope without a slash correction. 'J 10. The half-tone phase shift blank mask described in claim 1 of the patent scope, wherein After the above-mentioned phase shift film is sequentially subjected to washing and heat treatment, and analyzed by gas chromatography and mass spectrometry (Gas chromatography/Mass 'sePctrOSC〇Py, GC/MS), including butylated hydroxytoluene (Butylated 'hydr〇xyt) The total amount of volatile organic compounds (Volatile organic compounds) such as 〇luene, BHT) is 5 ppmv. 11. The semi-adjustable phase-shifting blank hood as described in the scope of the patent application, wherein the hood, the anti-reflection film and the hard cover layer are mainly selected from the group consisting of transition metals, bismuth and telluride. One form is selected among these nitrides, oxides, sulphides, oxynitrides, oxycarbides, and oxycarbonitrides. ' I2. The half-tone phase shift blank mask according to claim 1, wherein the phase shift film, the hood, the anti-reflection film and the hard mask layer are sequentially formed on the transparent substrate, and the optical is 193 nm. The density is between 2.5-3 5 . .. _ 13. The half-tone phase shift blank mask as described in the scope of claim </ RTI> wherein the phase shift film has a density of 3 g/cm 3 or more. M. The half-tone phase transfer blank mask of claim 1, wherein one or more of the above-mentioned hood, anti-reflection film and hard cover layer are selected; and in the transparent substrate and the phase shift film At least for the surface reforming of one film before and after the implementation, the individual films are actually and equivalent. ~ 15 · The half-tone phase transfer blank mask as described in the first paragraph of the patent application, wherein a phase shift film is formed on the transparent substrate, and a hood, 32 1380127 26792pifl. Revision date: June 13, 101 _ No. 96_31 Chinese Patent No. B has no scribe line correction. When the reflective film and the hard mask layer are formed, the phase shift film and the hard mask layer described above are etched by the same etching medium. The above-mentioned phase shift film is formed when the phase shift film, the hood 'reflecting film and the hard cover layer are sequentially formed on the transparent substrate in the above-mentioned transparent substrate. And the hard mask layer is not etched by the same etching medium. Π.-A semi-adjusted phase transfer blank, in which a transparent substrate, a phase shift film, and a photoresist are sequentially formed, and one or more of a hood, an anti-reflection film, and a hard cover layer are selected between the phase frequency and the optical auxiliary. The film is characterized in that the transparent substrate has a birefringence of 5 nm/6 or less in order to minimize the polarization phenomenon of the ArF immersion lithography. A half-tone phase shift mask is produced by using a half-tone phase shifting space as described in any one of the above-mentioned claims. 19. A method of fabricating a half-tone phase transfer blank mask, comprising: ~ (a) a stage of preparing a transparent substrate; (b) greater than said transparency to ensure uniformity and repeatability of the product during mass production a phase of 1/3 of the surface area of the substrate, using a single sputtering target comprising a plurality of components, forming a phase shift film comprising a transition metal, ruthenium and nitrogen on the transparent substrate; (c) on the phase shift film In the hood, anti-reflection film and hard cover layer, the stage of forming more than one film is selected; 曰33 1380127 26792pifl is the Chinese patent range of No. 96150331. No slash correction. Amendment date: January 1st, i3 day (d1) a step of performing surface modification (reforming) on at least one of the light-shielding film, the anti-reflection film, and the hard coat layer, and at least one of the transparent substrate and the phase shift film, wherein the surface reforming It is carried out using an organic substance including ruthenium; and (e) a stage of forming a photoresist. 20. A method of fabricating a half-tone phase shift mask, comprising: - (a) a half-tone phase shift blank mask as recited in any one of claims 1 through 17 a photoresist on the mask, after exposure and development is performed to form a photoresist pattern; (b) using the photoresist pattern as a mask, forming a hard mask pattern by dry etching, and removing the photoresist pattern (c) a stage in which the hood and the anti-reflection film are patterned by a dry etching process using the above-mentioned hard mask pattern as a mask; (d) a stage of forming a phase transfer pattern by dry etching; (4) In order to form a secondary hood and an anti-reverse (four) stencil pattern, a stage of forming a photoresist is formed; the air enthalpy is used to perform the exposure process in the field of the photoresist film formed in the (e) stage using the pattern forming process a step of developing a pattern; (f) removing the step (h) of forming the hood pattern and the anti-reflection film pattern by using the photoresist film pattern formed in the above ((4) as a mask; (The pattern of the photoresist film formed in the 〇 stage. 34