TW200837493A - Half-tone phase shift blankmask, half-tone phase shift photomask and its manufacturing method - Google Patents

Abstract

A sputtering target including Mo, Ta, Si and its area larger than a surface area of a substrate is used for fabricating a half-tone phase shift blank mask. Therefore a phase shift film having excellent uniformity can be fabricated, and a product having excellent uniformity can be fabricated by batch production. A excellent chemical resistance of the phase shift film can be obtain by adding Ta therein, and the phase shift film having excellent thermal stability can be fabricated. Meanwhile, base on those stability, a high quality half-tone phase shift blank mask that the properties of transparency ratio and phase shift will not be changed and the defeat will not be occurred due to the low residual stress can be fabricated. Further the absorption properties of ion and violate organic compound of the phase shift film can be improved by adding Ta therein, therefore a half-tone phase shift blank mask that the growth defect will not be occurred can be fabricated.

Description

200837493 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for producing a semiconductor direct component by using a phase shifting blank mask, in particular, for stability, relaxation, stress, and control. A half-tone phase shifting blank mask having a phase shifting film with growth defects, at least simultaneously containing molybdenum (Mo), button (Ta), and Shi Xi (Si) and capable of adding a transition metal. [Prior Art] Due to the integration of semiconductor direct components, a half-shield phase shift blank mask that exhibits high definition is used. The half-tone phase shift blank mask is composed of a phase shift film, a hood, an antireflective film, and a photoresist above the transparent substrate. Due to the phase shift film, the optical path difference of the exposure light is phase-shifted. Features. Due to the 180 degree phase shift function, a smaller pattern can be formed than the original one-size blank mask. The original scheme is a phase shifting film of MoSi series such as MoSiN, MoSiCN, M0S1O, MoSiON containing molybdenum (Mo) and bismuth (Si). However, because of the above-mentioned phase f film: ammonia, which is an inspective series of chemicals used in the blanking mask and the mask work, has characteristics that the characteristics are easily changed, so that it is difficult to perform sufficient washing work. Because it is difficult to carry out sufficient washing works, the phase shift film - surface particles can not be completely removed, eventually leading to defects; at the same time, it has the disadvantage that it is difficult to sufficiently remove chemical residues such as ammonia and sulfuric acid. These chemical residues are chemically reacted with a laser having a wavelength of i93 nm or 248 nm used in semiconductor lithography engineering to cause chemical residue growth to lead to defects in 200837493; it is called growth defect (Growth Defect) ); it in turn leads to a fatal flaw in shortening the life of the reticle. At the same time, the phase shifting cover composed of the MoSi of the original province has a problem of high residual stress due to its 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 use molybdenum, group, and stone eve as essential components, including adding transition metal, improving transmittance, optical phase shift, chemical resistance, and exposure resistance. Sex, 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 shift film, a mask, and an anti-reflection film are sequentially formed on a transparent substrate, and then a photoresist is formed to form a half-tone phase. White matte. In particular, in accordance with the present invention, the fabrication of a half-tone phase transfer blank mask is time-division, and the most advanced processes can be divided into: (a) the stage of preparing a transparent substrate. - (9) In order to ensure excellent uniformity and repeatability of the product in mass production, on the surface of more than 1/3 of the surface of the transparent substrate, a single-type 贱_ comprising a plurality of compositions is used, and a transition metal is included on the transparent substrate. Shi Xi and milk gas; the stage of forming a phase shift film having a density of 3 g/cm 3 or more. (c) A stage in which one or more types of films are selected in the shape of the remaining hood, the anti-aliasing and the hard mask. 200837493 r - (d) One or more films selected from the above-mentioned hood, anti-reflection film and hard mask, and at least one stage of reforming the surface of the film in the phase shift film. ... (e) the stage of forming a photoresist. _ ........................................ The transparency prepared in the above stage al) The substrate is characterized by a KrF having an exposure wavelength of 248 nm and an ArF lithography having an exposure wavelength of 193 nm, having an 85% transmittance. The transparent substrate prepared in the above a) stage has a feature that can be used on ArF immersion lithography; and at this time, the birefringence of the transparent substrate is characterized by polarization occurring in the ArF immersion lithography process ( Polarization phenomenon is minimized, with a sign of 5nm/6 35in. The phase shift film of the above bl) is characterized by: essential components including molybdenum, button and bismuth; in order to improve chemical properties, control the occurrence of growth defects, minimize the residual stress of the film, and adjust the characteristics of the transmittance. element.

Must include 30-80 at%. In addition to bismuth, the phase shift film added with the above b 1) stage is characterized by a stone eve, 2-20 at% of I mesh, 10-50 at% of nitrogen, and 2-20 at%. Transition metal. The above bl) stage includes molybdenum, ♦, and a transition metal when the sputtering _ of the optical phase shift film is formed. The characteristics are as follows: when the Μ· _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In addition to the above-mentioned 200837493, the above bl)M is also characterized by the formation of a phase shift film. The phase shift film conforms to the KrF lithography of the 248 nm exposure wavelength, and includes 5 tear % of indium, 50-90 at%. Shi Xi and 5, 3〇at% transition metals other than indium. ::In the above, when the film is formed to conform to a lithography having an exposure wavelength of 193 nm, it also includes l-20 at% of yttrium, 70-95 at% of Shi Xi and a transition metal other than yttrium. The phase shifting film mentioned above, which conforms to the (4) lithography with a 248 nm filament wavelength, must include (iv) at% molybdenum, 2 (four) station % Shi Xi and l-20 at % transition metal other than molybdenum and 2 〇 _7 〇% of the nitrogen. The phase shift film of the above mm segment conforms to the KrF lithography with an exposure wavelength of 193 nm, which is included when it is married! The %_, the added % of Shi Xi and the transition metal of Ι-lOat% other than molybdenum and the nitrogen of 2〇_8〇at%. The above phase shift film of bl) P is characterized by a single layer of film. The phase shift film of the above M) is characterized by a film of a plurality of layers of two or more layers. When the above bl) stage _ _ magnetron reactive sputtering is formed, the substrate has the following characteristics; there is i〇〇-5〇 (rc heating, including 10_50v () 1% inert (tetra) nitrogen, 30-10 〇v〇l% of the reactive gas nitrogen, and the pressure is l1W/cm2 or more.

The phase shift film of the above blW section is characterized in that after the phase shift film is formed, the phase shift film is heat-treated by a heat treatment apparatus in order to prevent residual stress reduction of the film, change in thinness characteristics, and prevention of growth defects. X The phase shift film heat treatment of the above bl) stage is characterized by selecting one of the methods of electric furnace, 200837493, and hollowing out oven, and the time is 5, 'pressure, rain, phase shift film, because of adding The transition metal other than ruthenium is reflected by the ruthenium (x-my read eetivi_density density, 3g/cm3 or less.

The phase shifting film in the above-mentioned enthalpy stage has the following characteristics when the reactive bismuth is formed: the inert gas is selected from the group consisting of argon, neon (10), neon (Ne), and xenon (Xe); reactive gas Used by oxygen (Ο:), nitrogen (10), nitrous oxide _), ammonia _3), carbon monoxide (c〇), carbon dioxide (C02), nitrogen oxide (NO), nitrogen dioxide (N〇2 And one or more gases selected from methane (CH4). In the above step bl), after the phase shift film is formed, in order to prevent the occurrence of growth defects, there is a feature of washing using a washing process. In the above M) stage, in order to improve the stability of the phase shift film and reduce the occurrence of growth defects, after the phase shift film is subjected to a washing process, there are methods 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. The above-mentioned M) order|and the phase shifting film are sequentially washed and heat-treated, and then analyzed by gas chromatography/mass sepctroscopy (GC/MS), which is characterized by including Butylated Hydrotoluene (Butylated hydroxytoluene, The total amount of volatile organic compounds (such as Aromatic 10 200837493 hydrocarbon) such as aromatic hydrocarbons (v〇latile) is 5 ppmv or less. The phase shift film of the above bl) step is characterized in that no growth defects occur when exposed by an energy of 3 Kj or more by an i93 nm ArF laser. ... ^ The hood and anti-reflection film of the above 〇1) and dl) are characterized by a selected one of transition metals, bismuth and telluride; in these nitrides, oxides, carbides, nitrogen A form in which one of oxide, nitrogen carbide, oxycarbide, and oxynitride is selected. The hood and anti-reflection film of the above cl) and dl) stages, considering the lion ratio of the etching process, the hood and the anti-reflection screen having direct contact with the phase frequency, and the phase shift film and other etching medium The feature of etching. After forming the hood and the antireflection film at the above stages c1 and dl), the reflectance at all wavelengths of 193, 248, and 365 nm was 3 〇% or less. ▲ The above-mentioned cl) and dl) hoods and anti-reflection films have a thickness of 1100A or less. After the hood and the anti-reflection film are formed in the above steps c) and dl), after forming the substrate, the phase shift film, the hood, and the anti-reflection film, the light transmittance is 1% or less at an exposure wavelength of 193 nm to 248 nm. . Further, after forming the hood and the anti-reflection film at the stages of Cl) and dl), in order to improve the low selection ratio of the photoresist, a feature of adding a hard mask to the anti-reflection film is provided. 9 After forming the hood and anti-reflection film in the above cl) and dl) stages, the hard mask 11 200837493 layer is characterized by: among the transition element H compounds, the selected species are the main components; in these nitrides, oxides, and carbides Among the nitrogen oxides, rabbit carbides, oxycarbides, and nitrogen oxides, one is selected. After the above cl) and dl) PU form a hood or an anti-reflection film or a hard cover layer, it is characterized in that heat treatment is selectively performed. The above cl) and dl) IV&amp; forming a hood or an anti-reflection film or a hard cover layer, and selectively performing the heat-removing process is characterized by selecting one of an electric furnace, a hollow space, and an empty roasting method. The treatment is carried out; the temperature is still trapped, the time is 5_60 min, and the pressure is 760 mtorr or less. The above-mentioned el)PH-derived photoresist has a feature formed by a positive or negative-type chemically amplified photoresist. The photoresist of the above el) stage is characterized by being selected by a spin coating method, a spray coating method, or a capillary coating method; at this time, the thickness of the photoresist is 500-5000 A, and soft baking (s〇) Ft ba temperature 8 (M5 〇 °c 〇 above el) stage when the photoresist is not formed, become a quartz substrate or phase shift film or hood or anti-reflective film or hard cover layer of the light bile substrate, using hair The organic substance is characterized by surface reforming. The above el) stage does not form a feature of the surface reforming process performed between the photoresists. · Using a cerium-containing organic substance, by spin coating or steam above the substrate One of the methods of vapor priming is used for reforming. Before the photoresist is formed in the above el) stage, the quartz substrate or the phase shift film or the hood or the anti-reflection film layer which becomes a substrate by surface reforming has a characteristic of no substantial change in characteristics. ' 12 200837493 After the surface reforming process in the above el) stage, the characteristics of the special waiting time is less than two hours until the formation of the photoresist. [Embodiment] Through the above process, a half-tone phase transfer blank is fabricated in accordance with the present invention. In the following, the present invention is specifically described by the examples, but the examples are merely used for the purpose of illustration and description of the invention, and are not intended to limit the scope of the invention. φ Therefore, those skilled in the art can understand various other embodiments that can be variously modified from the embodiment. Therefore, the technical protection scope of the present invention is determined by the technical matters of the scope of patent application. <Example 1 and Comparative Example> Fig. 1 is a cross-sectional view of a half-tone phase shifting blank mask manufactured in accordance with an embodiment of the present invention. In the following description, the same or corresponding portions will be denoted by the same reference numerals, and their description will be omitted. • The embodiment performed is an embodiment of a KfF lithography that performs a halftone phase shift blank mask. Referring to Fig. 1, a transparent substrate (1 Å) having a surface area of 231.04 cm 2 and a size of 6 x 6 x 0.25 Å was prepared, and a phase shift film (20) was vapor-deposited using a DC magnetron sputtering apparatus. For the transparent substrate at this time, consider the immersion lithography that produces a phase shift film conforming to ArF lithography, and use a birefringence • a transparent substrate of 5 nm/6.35 mm, which minimizes the occurrence of polarization. The target size used when vapor-depositing the phase shift film, taking into account the uniform thickness of the phase shift film 13 200837493

For the purpose, a sputtering target having a surface area larger than 300 cm 2 was used. Also, in order to open the semi-adjusted phase-shifting blank mask, only one target was used in order to have excellent re-folding/refolding. At this time, the target is composed of 15 at% of molybdenum, ... (...), (^), (8), and 8% (Si). If a phase shift film conforming to ArF • lithography is produced, the appropriate target is molybdenum (Mo) containing 5 at/〇, 5 at% of the button (Ta), and 90 at% of shi (Si). The sputtering φ (Sputtering) condition used when the 'evaporation phase shift film is used is argon gas of 5_100 SCcm, nitrogen gas, power of 0.1-4 KW, pressure 〇j_i〇mt〇rr, and formation of M〇TaSiN. A phase shift film composed of a single film. Further, for comparison, a step of forming a MoSiN phase shift film was carried out using a target of molybdenum (Mo) and bismuth (Si) having a composition of 20:80 at%. At this time, the dry surface area 疋 used was 4 inches smaller than the surface area of the substrate; the sputtering conditions were the same as those for forming the MoTaSiN phase shift film. The thickness of the phase shift film of MoTaSiN and MoSiN formed by the above conditions was measured by using n&amp;k Analyzer _ 1512RT' of N&amp;k Analyzer, USA, and the result was 500-900A. In terms of uniformity of thickness,

MoTaSiN uses a sputtering sputter having a larger surface area than the substrate, and exhibits excellent uniformity of 20 A or less in the effective field (142 mm x 14 mm area) in the substrate. However, MoSiN uses a sputtering target having a smaller area than the substrate, and has a poor thickness of 50 A or less in the effective field. Also, • Using the MPC-193 from Lasertec, Japan, the transmittance and optical phase shift were measured, and the MoTaSiN and MoSiN were measured to have a transmittance of 6% at 248 nm and an optical phase shift of 180 degrees. However, in the perspective of the transmittance and optical phase shift, the average depth of the MoTaSiN in the effective field of the substrate (i42mmx142mm field) was 0.18% and 1. 9 degrees, and the MoSiN was determined to be 0.42%. 3.9 degrees poor uniformity. Further, as a result of analyzing the phase shift film density by X-ray reflection, MoTaSiN was 4.3 g/cm3 'MoSiN was 2.5 g/cm3. It can be known that the phase shift film density of M〇TaSiN is high. In the following, in order to eliminate particles and contaminants on the surface of the phase shift film and prevent the occurrence of growth defects, a washing process was used. [Table 1] ---------- Phase shift film thickness 248 nm Perspective transfer film thickness after one wash after formation ----- 1 wash 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 results of measuring the amount of change in the fluoroscopy after washing the phase shift film a plurality of times. As can be seen in the Examples, • 3% was increased after the formation of the phase shift film and after 3 washes; = Comparative Example 1 was increased by 〇·57% due to 3 washes. Therefore, it can be known that, compared with the MoSiN phase shift film, the M〇TaSiN phase shift film is added to the chemical product by the use of sulfuric acid, SC1 (ammonia/hydrogen peroxide/water solution), etc. in the washing process. (Chemical) has excellent chemical resistance. The following are heat treatments of 35 Å and 8 minutes using a hot plate in order to improve the stability of the phase shift film and reduce the ionic impurities and organic substances which are the cause of growth defects. Stapling As described above, in order to confirm the stability of the film after the heat treatment, 15 200837493 -----X-- The amount of change in the transmittance was measured as time passed. At this time, a comparison was made through various projects for comparison. : [Table 2] Example 1 Comparative Example Phase shift film MoTaSiN MoSiN After formation 5 days later After 10 days 5.76 % 5.76 % 5.77% 5.84 % 5.88 % 5.93 % 248 nm perspective

Table 2 shows the results of observing the amount of change in the transmittance of the film after washing and heat treatment of the phase shift film. In the MoTaSiN phase shift film, the see-through rate of ^, and the shifting magnification is 5.79%, which is only 0.03% higher than the 5.76Q/^2() in the formation. However, in the phase shift film of MoSiN, the see-through rate of the grade and the second pass is 5.97%, and the masking power is 0.13% compared with that after the formation. Thus, it can be known that the stability of the phase is improved as the addition of the group (Ta). At the same time, in order to grasp the fuzzy process that occurs with the addition of the button (Ta), = the secret of the ionic impurities and organic chemical impurities that occur in the phase shift film. A white masked container (7) is placed over the substrate, and after placing a blank mask, 120 DC into the water (8 〇), the heat treatment is performed by an autoclave. Next, the ion impurity was analyzed by extracting ions 2 by heat treatment. &quot;, when determining the concentration of organic compounds, the same as the ion analysis, refer to Figure 16 200837493 _____ x 3, put a blank mask in the container (71) that can be installed with a blank mask, after cleaning with nitrogen or dry air, The vessel was heated in an 85 °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 automatic thermal desorber (Auotomatie 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 NH4+ cr SO, Γ νο2· Ν〇3· Total ion temperature Example 1 MoTaSiN 0.3 0.2 0.4 0.2 0.2 0.2 2.3 Comparative Example 1 MoSiN 0.7 0.8 1.2 0.5 0.4 0.7 6.4 [Table 4] _ Unit: ppmv phase shifting film 芳香 total aromatic VOC concentration Example 1 MoTaSiN 0.75 2.31 3.24 Comparative Example 1 --- MoSiN 1.86 4.12 6.14 Table 3 above is the ion analysis results for Example 3 and Comparative Example 3, Table 4 is The analysis results of the volatile organic chemicals were carried out in 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 2·3ρρπιν, and the ion concentration of MoSiN is 6.4 ppmv. Thus, it can be known that as the button (Ta) is added, the degree of adsorption or adsorption of the film ions 17 200837493 is improved. Next, referring to Table 4, the total concentration of Example 3 was only 3.24 ppmv, and the concentration measured in Comparative Example 3 was 6.14 ppmv. This is the same as the ion analysis result. As the button (Ta) is added, the degree of volatile organic chemisorption on the surface of the phase shift film is also reduced. Therefore, it can be said that 'based on ion and volatile organic compound analysis results, a small amount of σ button (Ta) can reduce the adsorption of ions and volatile organic chemicals on the surface of the phase shift film, and ultimately reduce the growth defects. occur. At the same time, as a result of measuring the contact angle of the contact film by the contact φ angle measuring instrument, the contact angle of MoTaSiN was 15 degrees, and the contact angle of MoSiN was 36 degrees. This indicates that the surface energy of M〇TaSm is relatively lower than that of MoSiN. It can be said that the surface is a stable 1 ° below. Figure 4, using a button (Ta) target and nitrogen above the phase shift film, by reactive sputtering method, A hood (3 〇) having a TaN composition was formed. Next, referring to Figure 5, use! An anti-reflective film (4〇) having a Ta〇I^-form is formed by a reactive sputtering method using (Ta) gram and nitrogen and oxygen. On the same day, the reference was made to Fig. 6. Using a positive-type chemically amplified photoresist, _ formed a thickness of 3000 A white photoresist (60), and a half-tone phase shifting blank mask was fabricated. As described above, according to the invention of the present embodiment, in manufacturing a half-turn phase shift blank mask, using a region larger than the substrate area, using at least 锢_), group (Ta), state i) Forming a phase shifting film. In this way, it is possible to manufacture a uniform (4) miscellaneous #, and it is also possible to produce a uniform phase shift film in mass production. At the same time, due to the addition of pure (four), it is possible to produce a phase shift film that ensures excellent chemical resistance, thermodynamic stability, 18 200837493 density south; and stability due to thermodynamics, high density of film, phase The film does not change in characteristics, etc., due to the low residual stress, it is possible to produce a half-tone phase change without leaving defects and excellent quality. At the same time, the cover r can reduce the phase shift due to the addition of a button (Ta). The energy of the membrane surface improves the adsorption characteristics of ions and volatile organic chemicals, and can produce a half-tone phase shift 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. As shown in Figure 7, a 6x6x0.25 inch quartz substrate (1 inch) was prepared. At this time, the measured transmittance of the quartz substrate was 9% or more at 193 mm; the TIR (t〇tal indicated reading) value of the tantalum was a surface roughness of 0.2 nm Ra at 193 nm. The upper birefringence was 2 nm/min. Then, the phase of the film (20) was formed by a DC magnetron sputtering target on a quartz substrate. Sewing reduction - 攸, this time includes the theory of Shi Xi =, 5 at% of 锢 (Mo) and the narration (Ta); at the same time applies a larger than the substrate recorded area. This =, for the formation of the phase shift film, the dry conditions are: 5 〇 sccm of subflight, 5 〇 SCCm of ammonia; 2W / cm 2 of power density, 〇. 2pa of pressure, 19 200837493 厶 implemented phase shift film form. The MoTaSiN phase shift film formed by the above process was measured to have a thickness of 600-700 A, a transmittance of ό〇/ο at a wavelength of I93 nm, and a light shift film of 18 〇 at a wavelength of 193 nm. - Also for comparison, have a composition of 10: 90at%, use ratio

A MoSiN phase shift film formation test was carried out on a MoSi material having a surface area of 4 μm smaller than that of the substrate. At this time, the sputtering target condition was equivalent to that of the M〇TaSiN sputtering target φ piece; the transmittance at a thickness of 670 A was measured to be 6%, and the phase shift was 180 degrees. Then, in order to increase the density of the phase shift film, each phase shift film was heat-treated at 300 C for 20 minutes using a vacuum chamber. The film twist was then measured by calender reflection for each phase shifting film. As a result of the measurement, the density of MoTaSiN was 4.25 g/cm3, and the degree of MoSiN was 2.84 g/cm3. It can be concluded that the density of the added phase shifting film increases with the addition of the (Ta). Because the ionization energy of the button (Ta) is still added in the phase shift film, the combination of Mo, Si, and N atoms is combined, and it is difficult to combine them once. Therefore, as the button (10) is added, the phase shift film is more rigid, the hardness of the film is increased, and the density is also high, thereby improving the stability of the film, and the characteristics of the phase shift film are also improved. After the heat treatment, the respective phase-shifted films were subjected to chemical resistance. After the immersion of 85 degrees of sulfuric acid and normal temperature SCI for 2 hours', the change in the transmittance of the phase shift film was observed. First, the phase and film of MoTaSiN exhibited a change in the transmittance of 〇·1〇/❻, and the transmittance of the phase shift film was reduced by 0.4%. It can be seen from this that with the addition of the button (Ta) with high ionization energy 20 200837493, the phase shift film density can be increased, the bonding force is stronger, and thus the high and f chemistry. Then, in order to grasp the degree of occurrence of blur defects of the phase shift film, the leg wavelength was used to accelerate the energy of 1 J, and then an inspection experiment was performed using KLA SLF77 equipment. As a result of the experiment, M〇TaSiN occurred 03/cm2 = fuzzy defects, and M〇SiN detected 2·2/cm2 defects. From , you can ^' With the addition of the group (Ta), there is less blurring defects. This is because, with the addition, the surface adsorption of the lungs and the exhaust gas impurities are combined (4), and it is difficult to move, so that the impurities are difficult to combine, so that blurring defects rarely occur. Then, above the phase shift film, the hood and the anti-reflection film (40)' containing Cr as a main component were examined by sputtering to a thickness of 450 persons. Then, above the anti-reflection film, using a ruthenium formed of 1 〇·· 9〇at%M〇Si, a step of forming a hard cap layer (9) having a composition of MQSiN by DC hybridization is performed. Above, after sequentially forming a phase shift film and a light-shielding hard mask layer, τ ϊΐ ' at an optical density of 193 nm on the hard mask layer, through the cut organic matter f, the surface is reformed by I: ° The installation of the hot plate (hGt plate) is carried out to the (Vacuum Chamber). Size:: In: On the hard cover layer of surface reforming, use a negative type chemical to increase the thickness of the photoresist to a thickness of 2000A. After the surface of the shell was reformed within 11 knives, the photoresist was coated with a 21200837493 ZD/yzpn coating step. Through the above process, a step of manufacturing a half-tone phase shifting blank mask (100) is performed. Then, through the above process, a half-tone phase shift blank mask is used, and a step of fabricating a half-circumferential phase shift mask is performed. First, referring to FIG. 8, an electron beam (exposure beam) exposing device 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, and then using 10 2·· 38/ί&gt; A developer solution of TMAH, developed to form a photoresist pattern (pattern 6〇a). 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 fluorine-containing SF6 gas and inductively coupled plasma (ICp); at this time, the fluorine gas has a high selectivity ratio. The chrome-based hood and anti-reflection film are not burned. Previously, a photoresist pattern was used to form a chrome layer pattern, and recently a CD (critical dimensi〇n, minimum critical dimension) of 65 legs, 45 nm, and the like was required as the degree of accumulation 10 was increased. Therefore, the thickness of the photoresist is originally used by about 3 '. However, in order to reflect high definition, it is required to use a photoresist having a thickness of 250 〇a, 2000 A and a relatively thin thickness; at the same time, the chrome layer is also the same. Thickness and original requirements of 1 (10) 0A, and recently required 500A, 450A - thin thickness. Accordingly, by using a photoresist pattern having a thin thickness like 2000A and forming a chrome layer pattern by dry etching, etching can be performed by etching a chrome layer of chlorine (chl〇rine) gas. 22 200837493 zo /yzpii, at this time, when the side chrome layer is used, the photoresist _ case is also on the side; because the thickness of the photoresist is thin, the selection ratio of the secret layer is also lowered, and it is difficult to form a high-definition pattern; If the thickness of the chrome layer is thick, the negative wear is caused by the dry (four) (loading ef (10), resulting in an imbalance of the -CD size, causing the CD size when manufacturing a 65n-day m, 45nm mask (ph〇t〇mask) Error: = is to make _ is the hard cover layer. When the hard cover layer is dry etched on the hood and anti-reflection film, the etching gas used has a high selectivity. Therefore, the hard cover layer can be as thin as several hundred A. The thickness is formed to minimize the negative interception effect; and the hood, the anti-reflection film, and the lang medium have a high selection ratio, and are easily formed into a pattern-like, optically positive (Qptie non (10) (10) _ 〇 n; OTC The auxiliary pattern of the size of 30 nm, 2 〇, etc. of the effect. Referring to Fig. 10, the hard mask layer pattern is used as a mask, and the hood pattern (3〇a) is formed by using the dry side of the chlorination 1 Step of anti-reflection film patterning (40a) M wood Then, referring to Figure η, a phase shift film pattern is formed ( Step of the method. The formation of the multi-film pattern is carried out by the dry side, at which time the gasification film is used, and the hard cover layer is formed in the phase shift = the side of the case I. The main cover of the county cover and the anti-reflection film ^ will not have a high selection ratio, so that the hard cover layer enters the pattern of the 12-time hood and anti-reflection film, and forms a photoresist (60). Then, referring to Fig. 13, using the 1 ancient hi丄 period, after the exposure of the long-formed pattern formation in the field to be used, the exposure was carried out using a smear solution containing 2, 38% ΤΜΑΗ 200837493. A step of forming a photoresist pattern (6〇a). Then, according to Fig. 14, the photoresist pattern is used as a mask, and the hood pattern and the anti-reflection film are formed by dry cleaning using chlorinated gas. (40b)^ '*...' · Then, refer to Figure 15. The photoresist pattern was removed using OH Radical to create a half-tone phase transfer mask (2 inch). As described above, according to the invention related to the embodiment, in the manufacture of the half-tone phase transfer blank mask and the half-phase phase transfer material, a sputtering target having a surface area larger than 1/3 of the surface area of the substrate is used, which is effective in the substrate. In the field (142mm×l42mm field), it is possible to produce a phase shifting genus with excellent thickness, 'perspective, phase shift uniformity. At the same time, because the film is added to the phase shift film (Ta) to make the film harder, the stability of the film can be achieved, and the density of the film can be improved; thereby, it is possible to manufacture a high-quality film with excellent chemical resistance and less blurring; By forming a hard mask layer on the shimu and anti-reflection film in the phase shift blank mask, it is possible to manufacture a half-tone phase-shifted light which is suitable for the manufacture of 45·, 65 nm-level elements and which is an 0PC-assisted pattern. cover. <Embodiment 3> This embodiment is an embodiment of a half-tone phase shift blank mask and a half-tone phase shift mask composed of two thin films. First, a quartz substrate (1 〇) is prepared with reference to FIG. The specification of the quartz substrate at this time is the same as that of the second embodiment. The soil was then subjected to a step of forming a 320A phase shift film on a quartz substrate. The phase shift film uses a single dry composition of MoSi consisting of 10:90 at%;

200837493 JU\J / DC reactive sputtering (reaciive), implemented

MoSW's film formation. The detailed engineering conditions were the same as those in the second embodiment. • He used a single M〇BSl target consisting of %5 on a 4th-second second pancreas; a second phase shift of thickness 3 was achieved by DC sputtering (active sputteringh with the composition of TaSi) The film (the formation of 2, was subjected to a heat treatment process. &gt; Through the above process, the phase shift film formed had a total thickness of 670 A, and the 193 nm wavelength had a phase shift of 6% of the transmittance and degree. Also, by forming the above 2 The layered structure can minimize the residual stress of the phase shift film; by using the upper part, including (4) Qiu,

A phase shifting film composed of MoTaSi realizes the stability of the film and improves the bonding force; and the phase shift film having high chemical property and less occurrence of blur defects can be obtained by the improvement of the density. Then, on the second phase shift film, a mask having a thickness of 200 A consisting of a hood (3 〇) having a thickness of 3 〇〇A and a Ta 〇N having a TaO component as a main component of the button (Ta) was formed. Step of anti-reflection 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 from Si, Ge, transition elements (廿 出 011 鹏 鹏 ) 、), | One or more alloy materials to be mixed; an oxide, an f compound, a nitride, an oxycarbide, an oxynitride, or an oxycarbonitride may be used; and at the same time, it is not only a hood, an antireflection film, etc. 2 The layer film is formed of a single film, a two-layer film, or a three-layer film. Then, on the anti-reflection film of TaON, 25 200837493 composed of MoSiN is formed to form a hard coat layer (50). 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 MoSiN, but an alloy of Si, Ge, transition element (transiti〇n elemenis), M〇Si, etc. can be used. Substance; it can be used in the form of materials, carbides, nitrides, oxycarbides, oxynitrides, oxycarbons and nitrogens; at the same time, it is not just a two-layer film such as a hood or an anti-reflection film. 1 is composed of a plurality of films such as a single film, a two-layer film, and a three-layer film. Further, after φ formed a phase shift film, a second phase shift film, a hood, an antireflection film, and a hard coat layer on a quartz substrate, the optical density was measured at a wavelength of 193 nm, and the optical density of 3.0 was measured by the pot. Then, a step of forming a phase shift film (6 Å) is performed on the upper surface of the hard coat layer and the method of &lt;2&gt;, and the step of producing a half-tone phase (100) is carried out. Drought Through the above-mentioned process, the step of manufacturing a half-tone phase transfer mask was applied. In the same manner as in the second embodiment, in the same manner as in the second embodiment, on the quartz substrate, (m applies phase shift (4), second phase shift (21a), i^: (rb), anti-reflection ( 40b) The step of manufacturing a half-tone phase-shifting reticle. The present invention has 11 inventions for manufacturing a half-tone phase transition and a two-white mask and a paste phase shifting light, and the shape is a plurality of films, thereby minimizing Phase shifting Π Binding force and stability. Time (Ta) makes peach I δ harder, can achieve the stability of the film, improve the density of 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008皙柏梦 γ Shiyisheng 旲 空白 空白 空白 空白 空白 有 有 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : In the case of epe's subsidized pattern, the half-thief ^, = month half-tone phase shift blank mask and half-tone phase shift light for real-time phase shift film formation, = show / energy / create effective area within the substrate, phase shift The membrane consists of a single-layer or a plurality of membranes: the residual stress of the membrane is transferred to help improve the adhesion and stability of the membrane. Add phase to the phase shift film to make the film = plus: hard 'to achieve stability and increase the density of the film., pass: program can (4) county has (four) _ chemical == shift: at the same time, by forming a half-tone Phase-conversion = mask f +-like transfer mask has a high ratio of hard - = ^ = 65 gas-level ion fabrication, suitable for the two-patterned +-modulation phase transfer mask for 〇 pc. [Simple diagram] Figure 1 is a diagram showing the formation of a phase shifting film over a transparent substrate in accordance with the present invention.

Surface map. J Figure 2疋 In order to analyze ion chromatography, the phase shifting membrane is dissolved in a cross-sectional view of the surface. 1 time and 27

200837493 Figure 3 is a cross-sectional view of the phase shift film dissolved in the analytical volume for analysis of gas chromatography. Figure 4 is a cross-sectional view of a phase shifting film and a hood formed over a transparent substrate in accordance with the present invention. Figure 5 is a cross-sectional view showing a phase shift film, a hood, and an anti-reflection film formed over a transparent substrate in accordance with the present invention. Figure 6 is a cross-sectional view showing a phase shift film, a hood, an anti-reflection preventing film, and a photoresist film formed over a transparent substrate in accordance with the present invention. Figure 7 is a cross-sectional view of a half-tone phase shifting blank mask made in accordance with the present invention. 8 to 15 are schematic views showing the fabrication process of the half-tone phase shift mask produced in accordance with Embodiment 2 of the present invention. Figure 16 is a cross-sectional view of a half-tone phase shifting blank mask produced in accordance with an embodiment 3 of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 3 is a cross-sectional view of a half-tone phase mask manufactured in accordance with an embodiment 3 of the present invention. [Description of main component symbols] 10: Transparent substrate 20: Phase transfer film 21 • Younger phase shift film 3: Shield 40: Anti-reflection film 50: Hard cover layer 60 · Photoresist (resistance) film 28 200837493 70 : Analytical container for ion chromatography analysis 71: Analytical container for gas chromatography analysis. 80 : Purified water (deionized water) _.................9ϋ : Vent hole.............. 100 : Half-tone phase shift blank mask 200 : Half-tone phase shift mask

29

Claims (1)

200837493 X. The scope of application for patents: 1.- A half-tone phase shift blank mask, in order to move the film, light _; and in the upper and the level has = anti, anti-reflective film. The choice of the species is _, the characteristic of the film f is, Tongxian plus transition metal, the density of _, &gt; the film of growth defects; in order to ensure excellent = quantitative repeatability, more transparent than the above a surface area of a surface area of the substrate is formed by using a single sputtering target including a plurality of layers, and a film of the above-mentioned hood, anti-reflection film, and hard mask layer is selected; and the transparent substrate and the phase shift are In the film, at least one or more films are subjected to surface reforming. 2. The half-tone phase transfer blank mask of claim 1, wherein the phase shifting film is a single sputtering target comprising a molybdenum (Mo), a Si (Si), and a transition metal other than the key. And formed. 3. The half-tone phase shift blank mask according to claim 1, wherein when the phase shift film is applied to KrF lithography having a wavelength of 248 nm, the above-mentioned tie film is used with 5-30 at% of molybdenum. 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 according to claim 1, wherein when the phase shift film is suitable for KrF lithography having a wavelength of 248 nm, the phase shift film is used to contain l_2〇at%. Molybdenum (Mo), 20-70 at% of lanthanum, a transition metal of l-2 〇 at% other than molybdenum, and 20-70 at% of nitrogen 30 200837493 are formed. 5. The half-tone phase shift blank mask as described in claim 1 wherein the phase shift film is suitable for ArF lithography with a wavelength of Γ93 ηη η. The phase shift film is a molybdenum containing uOat%. (Mo) is formed by a sputtering target of 1-20 at% of a transition metal other than ruthenium and 70-95 at% of ruthenium. 6. The half-tone phase shift blank mask of claim 1, wherein when the phase shift film is applied to an ArF lithography having a wavelength of 193 nm, the phase shift film is ll 〇 at%. Molybdenum (Mo), 20_80 at% of Shi Xi, a transition metal of MOat% other than cerium, and a sputtering paste of 2 to 8 〇 at% of nitrogen are formed. ^ 7. The half-tone phase shift blank mask according to claim 1, wherein the phase shift film uses a monochromatic light laser having a wavelength of 193 nm or 248 nm, and the investigation energy is 3 kJ, and no growth occurs. defect. 8. The half-tone phase shift blank mask according to claim 1, wherein the phase shifting film is a half-tone type as described in claim 1 in a single layer or a plurality of layers for reducing stress. After transferring the blank hairpin to the thinner, the __retention stress washing process and 12=long defect formation are eliminated. The above-mentioned phase shift film solid gray selection process is in electric furnace, hollow container, hollow oven中遇二I 2: 2. Fusing temperature, 5-_-时一^^ 31 200837493 ιο·The half-tone phase shift blank mask as described in the scope of the patent application, in which the phase shift film is After the washing and heat treatment, the total amount of ionization was 5 ppmv- or less when analyzed by ion chromatography (Ion chromatography, 1C). .................... _ • 11 · The half-tone phase transfer blank mask as described in claim 1 of the patent application, wherein in the phase shift film, After washing and heat treatment in sequence, volatility such as aromatic hydrocarbons including butylated hydroxytoluene (BHT) is analyzed by gas chromatography and mass spectrometry (Gas chromatography/Mass φ sepctrosc®, GC/MS). The total amount of organic compound (Volatile organic compound) was 5 ppmv. The semi-adjustable phase transfer blank mask according to claim 1, 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 of these nitrides, oxides, sulphides, oxynitrides, oxycarbides, and oxycarbonitrides is selected. 13. The half-tone phase transfer blank φ mask as described in the patent application scope, wherein an optical density at 193 nm is formed on the transparent substrate sequentially after forming a phase shift film, a light-shielding anti-reflection film and a hard mask layer. It is between 25 1 . </ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> The surface reforming of at least one of the transparent substrate and the phase shift film is carried out using an organic substance including ruthenium. The translucent phase transfer blank 32 200837493, wherein the mask is selected from the hood, the anti-reflection film and the hard cover layer; and the transparent substrate and the phase are as described in the patent application scope. In the film transfer, at least the surface reforming of the film is carried out before and after the implementation, and each film has two characteristics. ............, 丨 具有 具有 具有 具有 具有 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H 在The above-mentioned phase shift film and hard mask are etched in an etching medium. 3 k匕同1 _ 々 々 转移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移 移The etching medium that passes through the mask and is not etched is not etched. 9 heart with 18·-a kind of semi-adjusted phase transfer blank mask, in order _:, phase shift film, photoresist 'in the above phase shift film and photoresist: 乞: soil g in anti-reflective film, hard cover + is selected The above-mentioned transparent substrate of "1" is produced in order to minimize the maximum value of f9, == __==τ. The method of making a half-tone phase shift blank mask is characterized in that (a) the stage of preparing a transparent substrate; 200837493 a (b) to ensure excellent uniformity and repeatability of the product in mass production, on a transparent substrate, including a plurality of sheets, including a plurality of sheets, on a surface larger than 1/3 of the surface of the transparent substrate Transition metal, chopped with nitrogen, forming a film having a density of 3 g/cm3: a stage of a phase shift film of soil; (c) selecting one or more films of the shield, antireflection film and hard cover layer on the phase shift film (d) selecting one or more types of the light shielding film, the antireflection film, and the hard coat layer, and performing surface modification (reforming) on at least one of the transparent substrate and the phase shift film. Stage; and (e) the formation of a photoresist phase. • 21—a method for fabricating a half-tone phase-shifting reticle, characterized by a half-tone phase shift blank, including (a), as in any one of claims 1 to 18 of the patent application. On the photoresist of the mask, after exposure and development is performed to form a photoresist pattern; "(b) using the photoresist pattern as a mask, by dry etching the pattern, and removing the photoresist pattern Stage; Ώ , , (c) with the above-mentioned hard cover layer _ as a mask, · chlorine gas through the dry private hood and anti-reflection film forming pattern; clothing (d) by dry rhyme, forming a phase transfer pattern (e) a stage for forming a second hood and an anti-reflection preventing film; and a light (f) is formed by performing exposure in an optical field of (8) order. a stage of developing a pattern; a item of money 34 200837493 (g) a stage in which a photoresist film pattern formed in the above (1) stage is a mask, and a hood pattern and an anti-reflection film pattern are formed by dry etching using chlorine gas; (h) removing the photoresist film formed in the above (f) stage . 35