TW201035674A - Blank mask and photomask fabricated using it - Google Patents

Abstract

Provided is a blank mask. The blank mask comprises a metal layer, a hard mask layer, and a photoresist, which are sequentially stacked on a transparent substrate. The metal layer may be a silicide having a thickness of less than about 60 nm, and Si content may range about 30 at% to about 80 at% to obtain a superior flatness. When the metal layer is dry-etched, a loading effect occurring by a distance different between the metal layer and etching radical ions may be reduced to obtain a high-quality blank mask.

Description

201035674 VI. Description of the Invention: [Technical Field] The present invention relates to a blank mask, a manufacturing method using the same, and a blank mask, especially a light applied to a line width. Nm 'especially a blank mask of less than 45 nm, a reticle using the blank, and a method of manufacturing the blank mask. Curtain system [prior art] Ο

Q In order to achieve miniaturization of circuit patterns to improve integrated circuit integration, in micro-semiconductor components, the fabrication of micro-compound technology is considered to be one of the most important technologies. In the integrated circuit, the pattern is further miniaturized to achieve low power consumption and high-speed operation. The route description requires that for a reticle that uses a lithography process, a technique that can produce two full and small line patterns is necessary. In the method of generally making a blank mask, a current layer and a photoresist are sequentially formed on a transparent _; 2 screens, development, (4) and cleaning processes to form a pattern; Can ^ cover the first layer. However, in the above conventional manufacturing method, the giant load effect and the micro load effect may occur. == Although the exposure process is performed on the photoresist to form the same size, the size will still differ depending on the density of the film. When the resistance is #刻光光, the lower the amount of the same developer, the same rate and the unit of the product, the removal rate will be I 5 (critical dimension ^ CD), that is, in the pattern density In the high region, the etching radical concentration of the metal layer 3/27 201035674 will gradually decrease toward the lower part of the metal layer; therefore, the upper critical dimension and the lower critical dimension of the metal pattern are There will be differences. Conversely, in a region where the pattern density is low, such as an isolated pattern region, since the etched region is small, the etching radical concentration is relatively large, resulting in an undercut phenomenon 'on the metal pattern'. There is a considerable gap between the critical dimension and the lower critical dimension. When the photoresist has a thin thickness, l〇ading effects, linearity (ijnearity) and accuracy of the fine pattern (the sinking can be improved; however, when the lower layer is patterned, the photoresist The pattern may be destroyed to deform its configuration. More seriously, since the lower layer may be destroyed, it is impossible to accurately convert the pattern of the original photoresist to the lower layer. In addition, when the pattern of the photoresist becomes Miniaturization, but the photoresist is not thinned, which will increase the aspect ratio of individual photoresist patterns; generally, when the aspect ratio of the photoresist pattern increases, the appearance of the photoresist pattern is more easily destroyed. 'When the above-mentioned damaged photoresist is used as a reticle to pattern the lower layer, the accuracy of the pattern conversion may decrease. In an extreme case, the reticle-part collapses or laps each other. This will result in a situation in which the pattern cannot be converted (missingpattem). In summary, as the pattern is miniaturized, it must be thinned into a thin photoresist that does not have a large depth. However, the thickness of the mask layer is like the thickness of the above-mentioned photoresist. It must be reduced. If the thickness of the hard mask layer reaches the ultra-thin level, the hard mask layer and the photoresist may be formed in the patterning. Therefore, it is necessary to consider the hard turn. The thickness of the layer and its material. Chemically amplified photoresist (comically amplifled _) can be used 4/27 201035674 to improve the resolution of the blank mask, and the chemical film can be produced in the exposure system. Exposure bake, ΡΕΒ) 烊ψ 3,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,彳Characteristics and light; fine, 纟光剂 produced by _ will Wei ride private, 峨 峨 峨 峨 ( 四 四 四 纽 纽 纽 纽 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡 彡Especially I and don't...

Photomask. Difficult to achieve, so it is difficult to produce high quality [invention] The main purpose of the present invention is to provide a white mask, which can be applied to line widths less than 90 nm, especially for line widths less than 45 _, and ^The blank mask has the reliability of the lid; the invention further illuminates the mask made of the blank mask and the method of manufacturing the blank mask. In accordance with an embodiment of the present invention, a method of making a blank mask includes the steps of forming a phase shifting layer, a metal layer, a hard mask layer, and a photoresist on a transparent substrate. When comparing the flat lining of the transparent substrate to which the metal layer has not been formed, the flatness of the metal layer varies in a range smaller than lum. When the blank mask is a binary intensity blank mask, the method comprises: al) providing a transparent substrate; bl) forming a metal layer on the transparent substrate provided in step a) ; cl) forming a hard mask layer on the metal layer formed in step bl); and dl) forming a photoresist on the hard mask layer formed in step ci). 5/27 201035674 maskί Ϊ Blank mask is a phase shift blank mask ((10) Shi_ank k) 4, the method includes: providing a transparent substrate; U), forming a phase shift layer in step hl) Provided on the transparent substrate; J1) forming a - stop layer on the phase shift layer formed in step η), forming a metal layer on the etch stop layer formed in step ji); U) forming - hard a mask layer on the metal layer 3 formed in step k1);

Work 1) forming a photoresist on the hard mask layer formed in step U). Following the example of the invention of the “Gen County County”, the production methods and conditions of the township are disclosed as follows:

In step a), the transparent substrate may comprise a material such as Namma glass, synthetic quartz or gasification. The transparent substrate has a transmissivity greater than, and less than 85%, in the range of the I line (I_lme) wavelength (from 365 nm) to the argon ((10)) laser wavelength (193 nm), wherein the above range The main system is the lithographic green wavelength. In addition, under the condition of immersi〇n lithography, the transparent substrate has a birefringence of less than 5 nm/6 35 dirty, in steps a) and hi), of the transparent substrate The absolute value of flatness is less than lum. In the step M) and the k1), the metal layer may be a single layer structure or a two layer structure 'or a multilayer structure. In steps bl) and kl), if the metal layer is a single layer structure, the single layer structure can block light. Furthermore, if the metal layer is a single layer structure, the metal layer has a continuous group from the surface of the single layer structure to the substrate. 6/27 201035674 ί fi fif ΐ 珍 及 — — — — Or compound == jin selected village material: molybdenum (Μ.), (5), crane (W), compound on the PCT, and the oxide of the above metal, the carbon of the above metal, the above metal An oxycarbide, an oxycarbonitride of the above metal. The amount of the material is gradually increased (gmdu·) from the surface of the single layer and the σ structure toward the transparent substrate. 〇 〇 〇 ( (8) and (1), if the metal layer is a two-layer or multi-layer structure, the anti-^ households are used as a shading layer for shielding light The stop layer can additionally be: = compensated for the difference in critical dimensions, and the difference is due to: 2:3 = created _°_etch stop layer has a more reflective layer than the upper layer (ie, a metal having a three-layer structure) The layer may include an anti-, s upper layer), an etch stop layer, and a light shielding layer. When the handle # oblique as =: the load effect of the anti-reflective layer occurs and the load of the critical dimension V can compensate for the difference in the critical dimension. Then, due to the load effect, the layer can be compensated for the second to the second. When the gold core is used for the second time, after the metal layer is formed, the sub-four causes the chemical impedance characteristic to decrease, and then the change: the second content is greater than the stress of the metal layer, and the content of the metal layer increases. plus. Therefore, the germanium in the metal layer contains a density, and the light of the metal layer is in step M) #kl), and the contact between the metal layer and the hard mask layer is more than 5 in selectivity. In steps Μ) and kl), the thickness of the metal layer is between 2 〇 nm and 60 nm. When the thickness of the metal layer is less than 20, the optical density is very poor; when the thickness of the metal layer is larger than 60 nm, the critical dimension of the lithography becomes difficult to control due to the load effect. In steps bl) and kl), the metal layer is a nitride layer, and the nitrogen content is from Oat% to 80 at%. When the nitrogen content is more than 8 〇 at%, the extinction coefficient of the film rises, resulting in deterioration of the optical density characteristics. In steps bl) and kl), the absolute value of the stress of the metal layer after molding is less than 5,000 MPa. The above absolute value of the stress can be obtained by the following formula: The stress value can be obtained from the difference in the radius of curvature of the substrate before and after molding of the metal layer. When the absolute value of the stress of the metal layer is greater than 5, 〇〇〇 MPa, the substrate exhibits a significant curvature, so that the image displacement error occurs when the critical dimension is defined, so that the critical dimension is difficult to control. In steps Μ) and kl), the metal layer may contain a button (Ta) for controlling the stress of the metal layer. When the film is formed, the molding conditions and the composition of the material affect the stress; and the tantalum (Ta) is not easily affected by the external process variation. In steps M) and kl), the metal layer can be fabricated by a DC sputtering process, an RF sputtering process (rf叩働P) or an ion beam enthalpy process (i〇n-beam deposition). 8/27 201035674

Process); and to ensure the uniformity of the metal layer, a long-distance polishing process can be used to make the metal layer. When a long-distance polishing process is used, the uniformity of the metal layer can be easily controlled, and a high-quality blank mask having a good critical dimension can be manufactured. In steps bl) and kl), the surface reflectance of the metal layer is 25% at a wavelength of 193 nm. In steps cl) and il), the hard mask layer has a metal; the hard mask layer

A material selected from the group consisting of a metal, a metal oxide, a metal carbide, a metal nitride, a metal carbon oxide, a metal carbonitride, and a metal carbon oxynitride may be included. In steps cl) and il), the metal of the hard mask layer may be selected from the group consisting of titanium (Ti), ruthenium (V), chromium (Cr), sensitized (Mn), iron (Fe), recorded (c〇), Nickel (Ni), copper (germanium, zinc (Zn), gallium (Ga), mal (Ge), mal (Zr), niobium (Nb), antimony (Mo), antimony (Ru), rhenium (Rh), Lead (pd), silver (Ag), pot (Cd), indium (ln), (Sn), (Hf), group (Ta), tungsten (w), bismuth (0s), iridium (Ir), platinum At least one of the group consisting of (pt) and gold (Au). In steps cl) and il), the hard mask layer is not engraved by the gas containing the gas.

However, it can be smashed by the seam containing body; the etching selectivity of the sound and the hard mask is greater than 5. S In steps cl) and il), the thickness of the hard mask layer is preferably from 3 nm to 30 nm. When the thickness of the hard mask layer is less than 3 _, the hard mask layer may be used as a hard mask layer to form a metal layer. The hard mask layer has a thicker than 3 〇 surface. The silver engraving time is greatly elongated and the productivity is reduced. And in the money engraving = there is a monthly load effect of the moon, so it is possible to make a high-precision critical dimension beyond the above range. 9/27 201035674 ^ el el) and il} After the hard mask layer is formed, the metal layer has an absolute value of less than 5,000 MPa. In the sound or step Cl) (4), heat treatment, flash (age _), laser or 'treatment” can be performed after forming the gold layer, and the absolute value of the low stress is 5,000 MPa =: . The control of the film stress 'surface treatment can be carried out before, during or after the deposition of the film; - such as the cooling process ((4) (four) 1 i to go and - reticle energy source can be used for: The above stress control can be performed after the metal layer is formed or after the hard mask layer is formed. In step cl li), the sheet resistance of the hard mask layer is between ι 〇 ω / □ to 10 kD / □. In steps C1) and η), the hard mask layer is fabricated by a DC ore reduction process, a frequency (RF) 贱 plating process, or an ion beam deposition process; and in order to ensure the uniformity of the hard mask layer and the new bond It can be used for long-distance mining. In the long-distance ore casting process, the distance between the dry material and the substrate is greater than 200 mm to ensure better uniformity. In steps cl) and η), the hard mask layer may preferably contain impurity ions, i.e., two-salt hetero-f ions containing NV, and the concentrated system of _f ions is smaller than! PPnw. The dibasic base is separated from the strong one, and the strong acid in the photoresist; due to the strong acid neutralized, the photoresist may have a substrate dependency which causes a decrease in the photoresist characteristics. In order to control the substrate dependence described above, the concentration of impurity ions (especially the two ions) is preferably less than 1 ppmv. | The mud beach body In steps cl) and Π), in order to control the substrate dependence, the mask layer can be surface treated. The homogenized wire is coated with a pure speed heat treatment 10/27 201035674 (rapidly thermal processing, RTP), hot plate heat treatment (h〇t-piate thermal treatment), plasma treatment or vacuum baking treatment. In steps cl) and il), the surface treatment of the hard mask layer can be operated at a vacuum of less than 5 mtorr. In step cl) and il), the 'non-exposure developable anti-reflective coating layer (DBARC) can be additionally formed between the hard mask layer and the photoresist to improve the substrate dependence controlled by the hard mask layer. The adhesion between the scratch and the photoresist layer. The composition of the antireflective coating layer under development can be similar to the composition of the photoresist to improve adhesion and reduce scum due to substrate dependence. Furthermore, since the anti-reflective coating layer can be developed by the developer without exposure, no additional strip process is required. In steps cl) and il) t, when developable The antireflective coating layer is formed over the hard mask layer, and the thickness of the antireflective coating layer that can be developed is preferably less than 50 nm, specifically 30 nm. If the anti-reflective coating layer is too thick under development, the reflectivity of the anti-reflective coating layer can be developed, resulting in a photoresist ❹ "light drop"; or (4) T anti-touch coating layer in the cleaning process Cannot be completely removed. Therefore, the above residue may cause defects. When the thickness of the antireflection coating layer under development is less than 3 Å, the substrate dependency is not easily controlled. In steps cl) and U), the (four) lower anti-reflective (four) layer may contain a strong acid (such as a developing chemically amplified type of impurities) due to development under the anti-reflective coating layer forming mask layer. Anti-reflection = 1 contains a strong acid, which can compensate for the strong acid that is neutralized and lost in the chemically amplified photoresist, so the substrate dependence can be reduced. In steps cl) and i, when the anti-reflective coating layer can be developed under development 11/27 201035674 When over the hard mask layer, the soft-bake temperature of the anti-reflective coating layer that can be developed is greater than the soft-bake temperature of the photoresist. [Advantageous Effects] The content of germanium in the metal layer of the blank mask of the present invention accounts for 3 〇 at% to 80 at%, and when compared with the flatness of the transparent substrate on which the metal layer has not been formed, the flatness of the metal layer The system is controlled to be less than lum. Therefore, when dry etching is performed on the metal layer, the difference in density of radical ions occurring can be minimized, whereby a high-quality blank mask having a small load effect can be produced. Screen and reticle; therefore, high-precision patterns and better pattern transfer can be achieved to achieve better critical linearity (CD linearity), critical dimension process index (mean 吣, MTT), critical dimension uniformity And the roughness of the edge of the line _ nniglmess, LER) and other features of the blank mask and mask. BRIEF DESCRIPTION OF THE DRAWINGS The detailed description and the accompanying drawings of the present invention are intended to provide a By. (Embodiment 1) Referring to Fig. 1, a blank mask ι〇ι of the first embodiment of the present invention may be composed of a transparent substrate containing a metal layer 7 of indium (iv) material, a hard mask layer 5, and a photoresist 6. The amount of slope in the metal layer 7 is within a predetermined range. The metal layer 7 containing the MoSi material is made of _ material (10) sub-percent (at_1G: 9 ()), which is formed on the transparent substrate 1, and the reactive gas may include argon ( Ar), nitrogen (n), methane (〇ί4), and/or oxygen (0). The metal layer 7 can be Pinshixi (10) (6)) material, Shishi carbon (MoSiC) material, Shishi nitrogen (MQSi clear material, Qing oxygen (μ〇_ 12/27 201035674 material, molybdenum niobium carbonitride (MoSiCN) material, molybdenum niobium) Carbon-oxygen (MoSiCO) material, molybdenum-niobium-oxygen-nitrogen (MoSiON) material or molybdenum-niobium carbonitride (MoSiCON) material. Please refer to Table 1 for the prediction of the optical and chemical resistance of the metal layer 7. The metal layer 7 is subjected to OD cleaning agent, sulfuric acid heated to 90 ° C and a standard cleaning process (SC) -1 for two hours to observe the light transmittance variability. In addition, the metal layer 7 The inclusion system was analyzed using an Auger Electron Spectrometer (AES). The flatness of the enamel layer 7 was analyzed by using a flatness measuring instrument (f|atinaster). 139 nm Example Γ MoSi 3.1 Example 2 MoSiN 2.9 Example 3 MoSiO 2.6 Example 4 H MoSiC 2.9 'Example 5 MoSiON 3.0 - Example 6 1 MoSiCO 2.8 Example 7 MoSiCN —-— 2.7 Example 8 MoSiCON 2.9 'Comparative Example 1 MoSi 3.2 'Comparative Example 2 MoSi 3.2 Chemical Resistance Of (Delta T% @ 193 nm)

Sex and flatness Sister Sheng Guang's chemical resistance characteristics after the acid-based and standard cleaning process are based on the metal layer 7 at 30 峨 to 80 at% of the electricity, which varies; when the chemical resistance characteristics of the shixi content range, For example, the genus layer 7 has a preference of less than 5%; on the other hand, at a wavelength of 〜3, the light transmittance variation is less than 30 at% in summer (as in Comparative Example 2), 】 3/27 201035674 The metal layer 7 of the tantalum material has poor chemical resistance characteristics, for example, the sulfur transmittance variability is 2.34% under sulfuric acid treatment, and the light transmittance variability is 5.59% under standard cleaning process. Similarly, the flatness of the metal layer 7 varies depending on the amount of germanium in the metal layer 7. When the niobium content ranges from 30 at% to 80 at%, the metal layer 7 has a better flatness 'the value is smaller than lum; on the other hand, when the Shi Xi content is more than 80 at% (as in Comparative Example 2), the metal layer 7 has Poor flatness, which is less than 1.23 um. (Embodiment 2) Referring to Fig. 2, the blank mask 102 of the second embodiment of the present invention may be composed of a transparent substrate 1, a metal layer 7 containing a molybdenum crucible material, a hard mask layer 5, and a photoresist 6. The change in Critical Dimension (CD) varies according to the flatness of Example 1. The metal layer 7 may further include a light shielding layer 2 and an antireflection layer 4 laminated on the transparent substrate and not formed on the transparent layer in the metal layer 7. When the material is on the substrate, the transparent substrate tool has a tensile stress and a flatness of um32um; the light-shielding layer 2 containing the molybdenum-bismuth material has a thickness of 28 nm; and the molybdenum-niobium nitrogen (MoSiN) The anti-reflective layer 4 of the material has a thickness of 17 nm, and the two structural layer matrices are laminated on the metal layer 7 of the permeable material. A hard mask layer 5 containing a chromium carbon oxynitride (CrCON) material has a thickness of the second layer and is deposited on the metal layer 7; the hard mask layer 5 has a compressive stress and a surface flatness thereof is 〇i7um. A chemically amplified photoresist 6 of the type FEP-m is applied on the hard mask layer 5 and has a thickness of 15 Gmn; followed by exposure, development, post-exposure exp雠e bake, brain) and engraving process to form A light mask passed away. Relative to 14/27 201035674 at a critical dimension of 70nm, the critical dimension change of the reticle is measured at four points of the central part and the edge part; as a result, the reticle has a (four) critical dimension value 'that is in the middle ^ The portion is below the critical dimension of 2 nm (the critical dimension is 68 nm), while the edge portion is below the critical dimension of 5 nm. (Comparative Example 2) In order to compare with the above-mentioned Example 2, a single metal layer 7 of a molybdenum-containing material having a thickness of 45 Å (A) was formed, and then a chromium-containing carbon oxynitride (CrCON) material was formed. The hard mask layer 5, the surface of the hard mask layer 5 is flat and flat, and the metal layer 7 has a stone content of 81.02 at%. A type of FEP-171 chemically amplified photoresist is applied to a thickness of 150 nm and then subjected to exposure, development, post-exposure bake and etching processes to produce a mask. As in the second embodiment, the critical dimension variation of the reticle is measured at the central portion and the edge portion relative to a critical dimension of 7 〇 nm; as a result, the reticle is lower than the critical dimension lnm at the center portion, and at the edge 4 points below the critical dimension of 12 nm. Therefore, the greater the flatness, the greater the change in the critical dimension. ❹ (Embodiment 3) Referring to the third figure, the blank mask 1〇3 of the third embodiment of the present invention may be composed of a metal layer 7, a hard mask layer 5 and a chemically amplified photoresist 6, and the above structures are all The stack is stacked on the transparent substrate 1. The metal layer 7 is a three-layer structure and may include a light shielding layer 2, an etch stop layer 3, and an anti-reflective layer 4 . During the etching of the anti-reflective layer 4, the etch stop layer 3 is used to reduce the loading effect. The production conditions are as follows: under the condition of a molybdenum-bismuth target (molybdenum: yttrium ratio of 20:80 at%) and a 〇〇scem of argon (Arg〇n), 15/27 201035674 using a DC sputtering process (DC sputtering process) depositing a light-shielding layer 2 containing a molybdenum-rhenium material on the transparent substrate i, and the thickness of the light-shielding layer 2 is 30 nm, and the optical density of the light-shielding layer 2 under the condition of an exposure wavelength of i93 nm The optical density was 2,82, and the reflectance of the light shielding layer 2 was 52%. Deposited by DC sputtering under the condition of turning the target (molybdenum: yttrium ratio: 1〇: 9〇at%) and argon (Argon): nitrogen gas of 95 seem : 5 seem An etch stop layer 3 containing a molybdenum niobium nitride material is on the light shielding layer 2, and the thickness of the etch stop layer 3 is 5 nm. , molybdenum bismuth target (molybdenum: bismuth ratio of 20:80at%), and argon (Arg〇n):

Under the gas condition of nitrogen gas of 80 sccm: 20 sccm, a anti-reflective layer 4 containing a molybdenum and niobium nitrogen material is deposited on the etch stop layer 3 by DC sputtering, and the thickness of the anti-reflective layer 4 is 1 〇. Nm. Thereby, the optical density of the etch-stop layer 3 was 3. 〇, and the reflectance of the etch-stop layer 3 = 19. = % under the condition that the exposure wavelength was 193 nm. After 'in the chromium (Cr) target, and chlorine (Arg〇n): oxygen: nitrogen chaos. The brothel is 4 〇 sccm: 5sccm: 1 〇 sccm: 3 claw-like gas conditions under the spear reaction f Dc SpUttering deposits a hard mask layer 5 containing chromium carbon oxynitride (CrCON) material, and the thickness of the hard mask layer is 15 nm. Using the Auger electron spectrometer (a_eleetn) n speet_et^ AES), the results are as follows: the light-shielding layer 2! The target: (4) the ratio is 32:68 at%; (4) the stop layer 3 of indium: dream: gas The ratio is ΐ2:72:ι6 heart; the anti-reflective layer 4 is sold: Shi Xi: the ratio of nitrogen is 19:49:32 at%. Next, the sheet resistance is measured by a four-point probe method to observe the surface of the light shielding layer 2, the stop layer 3, the anti-reflective layer 4 and the hard mask layer 5 laminated under an electron beam (E-Beam) irradiation. Is there a phenomenon of charge up S (charge up) 16/27 201035674 Ο. The results were as follows: the average sheet resistance was 326 Ω/□, and no charge residue occurred. The model is FEP_m❾ chemically amplified miscellaneous ship coating, its thickness is 15Gnm, __ is used for the electronic light machine, and after 13,. (:, after 15 minutes of soft baking process, it can be a blank mask 1〇3. / 1 blank mask 1G3 is exposed by electron beam exposure machine, and the light resistance pattern is displayed. The photoresist pattern is The side mask is patterned by the dry name of the Spear King (condition C12: 〇 2 = 8 〇 sccm: 5 sccm, power 4 (8) W, pressure 1 Pa) to form a hard mask pattern. In addition to the photoresist pattern 'then, the hard mask pattern is used as a side mask, and it is made by dry money (condition CF4 = 8〇SCCm, power 400 W, pressure! Pa) etching the light shielding layer 2, and the rest is stopped. Layer 3 and anti-reflective layer 4. Next, the etchant of a fine model of chromium removes the hard mask layer 5 to make a photomask. On the other hand, when the blank mask 1〇3 does not include the etch stop layer 3 , the process and jg production described above. _ ❹ Evaluation item 50 I target criticality scale [nm: etch stop layer (present) accuracy (Fidelity) 0.96 0.97 0.99 100 dense pattern (Dense pattern) single pattern ( Single pattern) 0.8 0.4 0.6 0.5 0,3 0.2 0.1 0.4 0.3 0.1 0.1 Etch stop layer (not present) Accuracy (Fidelity) 0.93 0 .95 0.95 0.97 1 Dense pattern 1,6 1.5 1.5 1.3 Single pattern 0.7 0.7 0.6 0.5 0.3 0.5 0.2 <Table 2> Depending on the presence or absence of the etch stop layer, the amount of critical dimension is 17 /27 201035674 The measured data, the second series shows the result of a critical dimension of the measured data based on the presence or absence of the etch stop layer. Among them, when the residual stop layer 3 is present, the accuracy (Mdity) is relatively high' and intensive The linearity between the pattern (d_ Μ—) and the critical dimension change (CD bms) are relatively small; further, when the etch stop layer 3 is present, in the shigle pattern and the dense pattern The CD bias between (such as pattem) also drops significantly. In other words, the accuracy of the side stop layer 3, the accuracy (Qiu Ru 1), the criticality linearity (linearity) And the critical dimension change (CDbias) is improved. (Embodiment 4) Referring to the second figure, the blank mask 1〇2 of the fourth embodiment of the present invention may include a light shielding layer 2, an anti-reflective layer 4 and a hard cover. Curtain layer 5, the structural layers are _ Transparent laminate of Na Yi m dry smoke is evaluated, which is used in the line ,, has the light shielding layer 2 and the antireflection layer 7 made of the metal layer 4 vertically pattern. Depositing a light-shielding layer 2 containing MoMoSi material with a thickness of 25 um by indium group Shi Xibu (flip: group: Shi Xizhi ratio of 15:5:8 〇 at%); and by (4) Danshi Xi dry material (|目: group: Shi Xizhi ratio: smoke at%), deposited anti-reflective layer 4 containing her money (M〇TaSiN) material is formed, its thickness is l4um, the light shielding layer 2 _ The anti-reflective layer 4 constitutes a metal layer 7. A hard mask layer 5 containing chromium carbon oxynitride (CrC〇N) material is deposited by a chromium (〇·) tree, and the thickness of the hard mask layer 5 is the pool m. The optical density (―汐) of the anti-reflective layer 4 is 2.9, and the reflectance of the anti-reflective layer 4 is 2〇2% under the condition of an exposure wavelength of 193 nm, so the optical density of the anti-reflective layer 4 is opposite to the reflectance. Preferably. In addition, the composition ratio of the light-shielding J8/27 201035674 layer 2 and the anti-reflective layer 4 is analyzed by a chemical analysis electronic instrument (ESCA), and the ratio of the molybdenum_ of the optical layer 2 is 15:5:80 at%. The composition ratio of the molybdenum button nitrogen of the anti-reflective layer 4 is 9:4:60:27 at%. Further, the density of the above structure was analyzed by X-ray reflectometry (XRR). The light-shielding layer 2 has a density of 3.2 g/cm 2 and the anti-reflective layer 4 has a density of 3 6 g/cm 2 . A chemically amplified photoresist (CAR) 6 model of the type FEP-171 is applied to the hard mask layer 5, which has a thickness of i5 〇 nm, and is patterned by dry etching ©; it contains a molybdenum button material. The appearance of the pattern on the anti-reflective layer 4 of the light-shielding layer 2 and the molybdenum-containing Nitrogen material was observed by field emission scanning dectron micr〇sc〇pe (FE-SEM): the measurement results showed The angle of the etched pattern was 89 degrees, and the undercut or foot (f〇〇ti) did not appear to be quite good. The sputtering conditions were changed to produce a light-shielding layer 2 containing a molybdenum button material and an anti-reflective layer 4 containing a molybdenum button nitrogen material. The molybdenum button niobium nitrogen has a 组成 composition ratio of & 5:62:27 at%, and the anti-reflective layer 4 has a molybdenum button niobium nitrogen composition ratio of 9:4:60:27 at%; The density of 2 was 380 g/square = knife, and the film density of the anti-reflective layer 4 was 3.6 g/cm 2 . According to the appearance observation of the pattern of the light-shielding layer 2 and the anti-reflection layer 4, the appearance angle of the pattern was measured to be 82 degrees, and the appearance of the pattern having a trapezoidal shape was observed. As a result, the etching rate will change with the density of the film; and the _8 content will be small along the depth of the financial direction, and the number of reactive radicals will increase. Therefore, it can be obtained in the direction of the twist. The appearance of the preferred pattern; conversely, when having the same tantalum content and density along the depth, it is more difficult to obtain a vertical pattern because 19/27 201035674 film and loading effect lead to continuity Destruction of free radical ions. (Embodiment 5) Referring to the fourth figure, the blank mask 4 of the fifth embodiment of the present invention may be composed of a phase shift layer 8, a metal layer 7, a hard mask layer 5, and a developable lower resist. A low-resistance layer of a developable bottom antireflective coating (DBARC) (layer 1) and a photoresist 6 are formed, and the above structures are sequentially stacked on the transparent substrate 1. A phase shifting layer 8 containing a molybdenum crucible material is formed on a transparent substrate. The transmissivity of the phase shifting layer 8 is 2% to 25% at an exposure wavelength of argon fluoride (ArF) or vaporized krypton (KrF), and the phase shift layer 8 has a thickness of 6 Gnm to 1. The phase shifting layer 8 comprises a layer selected from the group consisting of molybdenum (MoSiO), molybdenum (MoSiN), indium ferrocene (M〇sic), fluorite oxygen (M〇Si〇N), molybdenum a material in the group consisting of oxycarbon (MoSi〇c), tumyl carbonitride (Shi (10)), and molybdenum lanthanum carbon oxynitride (MoSiCON), and the phase shifting layer 8 may be a single layer ❹ layer structure, and multiple layers There is a medium in the structure = even if the interface does not exist, the composition difference between the upper layer and the τ layer is greater than 2 core layers: _ to distinguish. The distance between the available deposition methods is greater than two.长 mm long distance: only two = sputter, LTS} process system is applied. , ng throw (uniformity) her ct leg). When the phase shifting layer 8 is a material, 乂 = gas (one (four) (four), and the layer containing chrome or two 201035674 a may be disposed between the phase shifting layer 8 and the transparent substrate 1, the first etch stop layer a1 may be The chlorine-containing gas (Cl-containing) is not etched by the fluorine-containing gas, so that the first etch stop layer a1 can enhance the phase shift layer 8 and the transparent substrate 1 made of synthetic quartz glass. Etching selectivity. In addition, the first etch stop layer a1 can be used as a transparent layer and a phase shift layer.

A metal layer 7 containing a copper stone material is formed on the phase shift layer 8. The metal layer 7 may be a single layer or a multilayer structure, and the metal layer 7 may have at least two or more layers for use as Phase shift layer or anti-reflective layer. At this time, the metal layer 7 is regarded as a phase shifting layer or an anti-reflective layer, and the metal layer 7 has an interface for dividing the phase shifting layer and the anti-reflective layer, or the metal layer 7 has a composition difference of more than 2 at% in the vertical direction. The condition is such that the metal layer 7 can be regarded as an f layer or a = structure. Preferably, the thickness of the metal layer 7 is approximately 6 G nm. Specifically, 5, when an interface exists between the phase shift layer and the anti-reflective layer, the thickness of the phase shift layer is about 4 Gmn, and the thickness of the anti-reflective layer is about 2 〇 nm; at an exposure wavelength, the anti-reflective layer The shirt (post (four) densky) is larger than the ground. Her material and anti-reflective layer may include - consisting of the following two, 'and selected among them: (MoSi) 'molybdenum oxide (MoSiO), indium phase t-MGSlN), carbon (M°SiC), Oxygen nitrogen (MGSi0N), at a wavelength of less than 20 ^, the reflectance of the anti-reflective layer 4 is 80 at. /0, the Shishi content in the genus layer 7 is adjusted to a range of 30 at% to: the metal layer 7 has the smallest stress. Metal layer 7 Jin 2 ==, Cheng Wei when phase shift layer 8 and can be biased by fluorine gas phase shift layer 8 and metal layer 7 3 have chrome or button material second etch stop layer a2 21/27 201035674 Between the (four) layer 8 and the metal layer 7, the second _ stop layer 虱 3 虱 etched ' but not etched by the fluorine gas, the second etch = 2 can enhance the phase shift layer 8 and the metal layer 7 The red-side stop of the heart-phase-shift layer can also be used as a transparent layer and a layer of other layers (a hard mask layer of c- or group (Ta) material is formed on the metal θ 7; The curtain layer 5 is not easily used by the fluorine-containing gas, but the fluorine-containing gas may be used as the metal layer 7; preferably, the thickness of the hard mask layer 5 is less than 20 nm, and the hard mask layer 5 is subjected to a sputtering process. In particular, it is made by a long-distance polishing process; the hard mask layer 5 may be a material containing chromium (9) or button (5) and selected from the group of Machi Shuncheng - (4): oxide layer & layer, nitrogen a chemical layer, an oxycarbonaceous compound layer, an oxygen compound layer, a carbonitride layer, and an oxycarbonitride layer. The main component of the low-resistance layer 9 is a polymer (p〇iymer), low The value layer 9 is formed on the hard mask layer 5. The low resistance layer 9 can be used to reduce the chemical growth rate of the 6 resistance at the time of molding, and also reduce the atomization effect during the electron beam exposure process. (fogging effect), and uranium scatter and back scattering; in addition, the low resistance layer 9 can be used to reduce the thickness of the photoresist 6. The low resistance layer 9 can be rotated The coating (spin _), scan (scan) or spray (spray) process; the thickness of the low-resistance layer 9 is 3 nm to 50 nm. The low-resistance layer 9 can provide a reflection adjustment function Function, and it contains a strong acid. By the action of the above strong acid, the low resistance layer 9 can be used to reduce the substrate dependence of the chemically amplified photoresist; and since the low resistance layer 9 has a reflection adjustment function, the critical dimension can be improved The reason for this is that the decrease in 22/27 201035674 dose reduction and the standing wave effect is reduced when the laser is exposed, but the electron beam exposure is operated. The low-resistance layer 9 can be made of a developer (tetra) of tetramethylammonium hydride (TMAH) without being subjected to reinforcement; the low-resistance layer 9 can also be deionized water (d). The low-layer 9 preferably has a soft baking temperature of the photoresist 6 and a soft baking temperature of the layer 9 is less than the soft baking of the photoresist 6 when the low-resistance layer 9 is photoresist coated. The effect of soft baking process after cloth;

On the other hand, when the soft baking temperature of the resistance layer 9 is lower than the soft baking temperature of the photoresist, the soft baking process is performed on the photoresist, and the soft baking (4) is simultaneously applied to the photoresist 6 and the low resistance layer 9. The chemically amplified photoresist 6 is formed over the low resistance layer 9; due to the low resistance layer 9, the thickness of the photoresist 6 is less than 1 〇〇 nm. Although the white mask applied to the phase shifting layer 8 is in the fifth embodiment, the technique described in the fifth embodiment can also be applied to the double-white mask (the ank mask) and the double without the layer 8 Light hard blank cover (shirts - pure shirt mask). Next, the above blank mask can be applied to make a mask. The photoresist is exposed by using an electron beam device, and the development process is performed on the shirt with I%% TMAH; at this time, the low resistance value f 9 can be removed by the silhouette process without additional The exposure process allows a mask to be fabricated using a typical mask process. In summary, by adjusting the germanium content of the metal layer and the hard mask layer to form a film with lower stress, and better critical dimension characteristics, better registration and better defect characteristics. Photomask. In addition, since a low-resistance layer is applied and the low-resistance layer can be developed without performing an exposure process, the substrate dependence of the chemically amplified photoresist can be reduced by 23/27 201035674, and the thickness of the rail is reduced. Can also be reduced. Therefore, it is possible to make a mask with a line width of less than 45 nm and 32 nm, which can be fabricated with a better critical dimension characteristic and better defect. [Simple description] The first picture is A side view of a blank mask having a single-layer structure metal layer according to Embodiment 1 of the present invention. The second figure is a side view of a blank mask having a two-layer metal layer according to Embodiment 2 and Embodiment 4 of the present invention.

The third figure is a side view of a blank mask having a three-layered metal layer in accordance with a third embodiment of the present invention. The fourth figure is a side view of the blank mask of the fifth embodiment of the present invention. [Main component symbol description] 101, 102, 103, 104 blank mask 1 transparent substrate 2 light shielding layer 3 etching stop layer

4 anti-reflective layer 5 hard mask layer 6 photoresist 7 metal layer 8 phase shift layer 9 low resistance layer al first etch stop layer a2 second residual stop layer 24/27

Claims (1)

201035674 VII. Patent application scope: 1. A blank mask comprising: a transparent substrate; a metal layer disposed on the transparent substrate; a hard mask layer disposed on the metal layer; and a The photoresist on the hard mask layer, the content of the stone in 2 ί is 3〇at% (atomic percent).空白 〇 Μ Μ Μ Μ Μ Μ Μ Μ Μ 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白 空白The blank mask according to the second aspect of the invention, further comprising a system of stopping the threat layer between the transparent substrate and the phase shifting layer, and the damming layer It is disposed between the transfer layer and the metal layer. The blank mask according to any one of claims 1 to 3, wherein the flatness of the metal layer is in a range smaller than lum when compared to the flatness of the transparent substrate on which the metal layer has not been formed. Variety. The blank cover according to any one of claims 1 to 3, wherein the metal layer comprises a stone eve, and the metal layer further comprises a touch (stolen), a button (five), and a tungsten (W). And a blank mask of any one of the group of the above-mentioned materials, wherein the blank mask is any one of the group of the above-mentioned materials. The metal layer, comprising at least one structural layer selected from the group consisting of a light shielding layer, an inscription stop layer and an anti-reflective layer. 7. The blank according to any one of claims 1 to 3. The mask, wherein the 5 ohm metal layer has an optical density, and at the exposure wavelength, the optical density ranges from 2.5 to 3.5. 8. As described in the pp. Blank mask, wherein 25/27 201035674 The metal layer and the hard mask layer have a side selectivity, the value of which is greater than 5. 9. As stated in the patent item ii to item 1-3 a blank mask in which the content of the Meng dynasty layer is gradually increased from the surface of the metal layer to the transparent substrate 1. A blank mask as claimed in any one of clauses 1 to 3, wherein the metal layer has a nitrogen content of 〇at% (atomic percent) to 8 〇. U. The blank cover according to any one of the above-mentioned items, wherein the metal layer has an absolute value of -stress, the value of which is less than 5, 〇〇〇 MPa. 12 · Patent Application Nos. 1 to 3 A blank mask according to any one of the preceding claims, wherein the metal layer has a ruthenium (Ta) element, wherein the blank mask according to any one of claims 1 to 3, wherein The metal layer has a reflectance of less than 25% at a wavelength of 193 nm. The blank mask according to any one of claims 1 to 3, wherein The hard mask layer is selected from the group consisting of metals, metal oxides, metal carbides, metal nitrides, metal oxycarbides, metal carbonitrides, and metal carbon oxynitrides. A blank mask according to any one of claims 1 to 3, wherein the hard mask layer is dry etched by a chlorine-containing gas The blank mask according to any one of claims 1 to 3, wherein the hard mask layer has a thickness of 3 nm. The blank mask according to any one of claims 1 to 3, wherein the impurity layer containing ammonia (νη3) in the hard mask layer is less than i ppmv. The blank leather curtain of any one of claims 1 to 3, further comprising a low resistance layer disposed between the hard mask layer and the photoresist. 26/27 201035674 Scope 18 The blank mask is described as having a thickness of 3 nm to 5 〇 nm. 20. As claimed in the patent scope 1 & a blank mask as described by the staff member, wherein the low resistance layer is dissolved by the alkalinity agent of the alkali. 21. The method of fabricating a blank mask comprises the steps of: providing a transparent substrate; forming a metal layer on the transparent substrate; forming a hard mask layer on the metal layer; and forming a light Blocking the hard mask layer, the metal layer has a content of 30 峨 (4): atomic percentage to 22.2 凊 patent range, the method of making the blank mask described in item 21, which is even more embarrassing. And a phase shifting layer between the transparent substrate and the metal layer. 23. The method for fabricating the blank mask described in claim 22, wherein the method further comprises: χ between the transparent substrate and the phase shifting layer, or between the phase shifting layer and the metal layer. Stop the layer. The method for manufacturing a blank mask as described in the application of the patent, the phase shifting layer, the surname stop layer and the hard mask layer are processed by a long-distance polishing process (1〇) Ng throw sputtering process ). 25. The method of fabricating the blank mask of claim 24, wherein the transfer between the transparent substrate materials is greater than 200 mm. 26. The method of fabricating a blank mask according to any one of clauses 21 to 23 of the fifth aspect of the invention, further comprising forming a low resistance layer disposed between the hard mask layer and the photoresist . 27. A reticle manufactured by performing exposure and development processes using a blank mask as set forth in any one of claims 1 to 3. 27/27