WO2014080840A1 - マスクブランク、転写用マスク、マスクブランクの製造方法、転写用マスクの製造方法および半導体デバイスの製造方法 - Google Patents
マスクブランク、転写用マスク、マスクブランクの製造方法、転写用マスクの製造方法および半導体デバイスの製造方法 Download PDFInfo
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- WO2014080840A1 WO2014080840A1 PCT/JP2013/080874 JP2013080874W WO2014080840A1 WO 2014080840 A1 WO2014080840 A1 WO 2014080840A1 JP 2013080874 W JP2013080874 W JP 2013080874W WO 2014080840 A1 WO2014080840 A1 WO 2014080840A1
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- mask blank
- mask
- thin film
- glass substrate
- transfer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/60—Substrates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/34—Masking
Definitions
- the present invention relates to a mask blank provided with a low-stress thin film, a transfer mask, and a method for manufacturing them.
- the present invention relates to a mask blank, a transfer mask, and a manufacturing method thereof, in which a change in stress of a thin film with time is reduced.
- the present invention also relates to a method for manufacturing a semiconductor device using the transfer mask.
- a fine pattern is formed using a photolithography method. Further, a number of substrates called transfer masks are usually used for forming this fine pattern.
- This transfer mask is generally provided with a fine pattern made of a metal thin film on a translucent glass substrate, and the photolithographic method is also used in the production of this transfer mask.
- a mask blank having a thin film (for example, a light shielding film) for forming a transfer pattern (mask pattern) on a light-transmitting substrate such as a glass substrate is used.
- the transfer mask manufacturing process using the mask blank includes an exposure process for drawing a desired pattern on the resist film formed on the mask blank, and developing the resist film in accordance with the desired pattern drawing to develop a resist pattern.
- a desired pattern is drawn on the resist film formed on the mask blank (exposure).
- a developer is supplied to the resist film, and the resist film soluble in the developer is dissolved. Thereby, a resist pattern is formed on the resist film.
- the portion where the thin film resist pattern is not formed, that is, the portion where the thin film is exposed is dissolved by dry etching or wet etching using the resist pattern as a mask. Thereby, a desired mask pattern is formed on the translucent substrate. Thus, a transfer mask is completed.
- a binary mask having a light-shielding film pattern made of a chromium-based material on a translucent substrate has been known.
- a binary mask for an ArF excimer laser using a material containing a molybdenum silicide compound (MoSi-based material) as a light shielding film has also appeared (Patent Document 1).
- a binary mask for ArF excimer laser using a material containing a tantalum compound (tantalum-based material) as a light shielding film has appeared (Patent Document 2).
- Patent Document 3 when a photomask composed of a light-shielding film using a metal containing at least two of tantalum, niobium, and vanadium is subjected to acid cleaning or hydrogen plasma cleaning, the light-shielding film is hydrogen brittle. It is described that the light shielding film may be deformed. As a solution to this problem, it is described that after a pattern is formed on the light shielding film, a hydrogen blocking film is formed that airtightly covers the upper surface and side surfaces of the light shielding film.
- Patent Document 4 describes a synthetic quartz glass substrate for excimer laser and a manufacturing method thereof.
- excimer laser light particularly ArF excimer laser light
- the Si—O—Si bond inside the glass is cleaved by the strong energy of the laser light
- E ′ center E It has been shown that the generation of paramagnetic defects called “prime centers” causes an absorption region in the wavelength band of 215 nm, resulting in a decrease in transmittance with respect to ArF excimer laser light. It is also disclosed that the occurrence of paramagnetic defects can be reduced by setting the hydrogen molecule concentration in the synthetic quartz glass to a certain level or higher.
- the glass substrate for manufacturing the mask blank is manufactured by manufacturing a glass ingot as described in Patent Document 4 and cutting it into the shape of the glass substrate.
- the glass substrate immediately after being cut out has poor main surface flatness and a rough surface. For this reason, the glass substrate is subjected to a plurality of stages of grinding and polishing, and finished with high flatness and good surface roughness (mirror surface).
- cleaning with a cleaning solution containing a hydrofluoric acid solution or a silicic hydrofluoric acid solution is performed.
- cleaning with a cleaning solution containing an alkaline solution is performed before the step of forming the thin film.
- the present invention has been made under such circumstances, and the object of the present invention is to provide a mask blank using a material containing tantalum as a thin film for pattern formation.
- An object of the present invention is to provide a method for manufacturing a mask blank and a method for manufacturing a transfer mask, which solve the problem that the tendency of compressive stress becomes strong and suppress the deterioration of flatness. It is another object of the present invention to provide a method for manufacturing a semiconductor device using the transfer mask.
- the mask blank of the present invention is a mask blank having a thin film on the main surface of a glass substrate, and the glass substrate has a hydrogen content of less than 7.4 ⁇ 10 18 molecules / cm 3.
- the thin film is characterized by being made of a material containing tantalum and substantially not containing hydrogen and formed in contact with the main surface of the glass substrate.
- the mask blank of this invention can eliminate the subject that the tendency of the compressive stress becomes strong with the passage of time for the film stress of the thin film, and suppress the deterioration of the flatness.
- the glass substrate preferably has a hydrogen content of 2.0 ⁇ 10 17 molecules / cm 3 or more.
- the glass substrate is preferably made of synthetic quartz glass. Furthermore, it is more preferable that it is a mask blank used for production of a transfer mask to which ArF excimer laser is applied as exposure light.
- the hydrogen content of the glass substrate is less than 2.0 ⁇ 10 17 molecules / cm 3 , especially in the case of a synthetic quartz glass substrate, the excimer laser, particularly ArF excimer laser, has low resistance to light (light resistance). This is because problems arise.
- the thin film is made of a material containing tantalum and nitrogen and substantially not containing hydrogen. By including nitrogen in tantalum, oxidation of tantalum can be suppressed.
- this mask blank it is desirable that a high oxide layer containing 60 atomic% or more of oxygen is formed on the surface layer of the thin film. Since the high oxide film of the thin film material has a high binding energy, hydrogen in the gas surrounding the mask blank can be prevented from entering the thin film from the surface layer of the thin film.
- the thin film has a structure in which a lower layer and an upper layer are stacked from the glass substrate side, and the lower layer is made of a material containing tantalum and nitrogen and substantially free of hydrogen.
- the upper layer is preferably made of a material containing tantalum and oxygen.
- this mask blank it is desirable that a high oxide layer containing 60 atomic% or more of oxygen be formed on the upper surface layer. Since the high oxide film of the thin film material has high binding energy, hydrogen can be prevented from entering the thin film from the surface layer of the thin film.
- the transfer mask of the present invention is characterized in that a transfer pattern is formed on the thin film of each mask blank. Since the flatness of the mask blank of the present invention is maintained at the required high level, the transfer mask manufactured using the mask blank having such characteristics can also have the required high flatness. .
- the semiconductor device manufacturing method of the present invention is characterized in that the transfer pattern is exposed and transferred onto a resist film on a semiconductor substrate using the transfer mask.
- the transfer mask of the present invention By using the transfer mask of the present invention and exposing and transferring a transfer pattern onto a resist film on a semiconductor substrate, a semiconductor device having a highly accurate pattern can be manufactured.
- an ArF excimer laser is used as exposure light for the exposure transfer. Even if the transfer mask is continuously irradiated with exposure light of an ArF excimer laser, a decrease in the transmittance of the glass substrate of the transfer mask is suppressed. For this reason, the semiconductor device which has a highly accurate pattern continuously can be manufactured.
- the mask blank manufacturing method of the present invention includes a step of preparing a glass substrate having a hydrogen content of less than 7.4 ⁇ 10 18 molecules / cm 3 , A step of installing in a film formation chamber, using a tantalum-containing target, introducing a sputtering gas not containing hydrogen into the film formation chamber, and forming a thin film on the main surface of the glass substrate by a sputtering method. It is a feature.
- the mask blank manufacturing method of the present invention can solve the problem that the film stress of the thin film tends to increase in compressive stress over time, and can suppress the deterioration of flatness.
- the glass substrate preferably has a hydrogen content of 2.0 ⁇ 10 17 molecules / cm 3 or more.
- the glass substrate is preferably made of synthetic quartz glass.
- the manufactured mask blank is a mask blank used for manufacturing a transfer mask to which an ArF excimer laser is applied as exposure light.
- the hydrogen content of the glass substrate is less than 2.0 ⁇ 10 17 molecules / cm 3 , especially in the case of a synthetic quartz glass substrate, the excimer laser, particularly ArF excimer laser, has low resistance to light (light resistance). This is because problems arise.
- a sputtering gas that contains nitrogen and does not contain hydrogen in the step of forming the thin film.
- a thin film containing tantalum containing nitrogen can be formed, and oxidation of tantalum can be suppressed.
- the thin film has a structure in which a lower layer and an upper layer are laminated from the glass substrate side, and the step of forming the thin film includes sputtering that contains nitrogen and does not contain hydrogen.
- the method includes a step of forming the upper layer on the surface by a sputtering method.
- the transfer mask manufacturing method of the present invention is characterized in that each of the above mask blanks is used to form a transfer pattern on the thin film of the mask blank. Since the flatness of the mask blank of the present invention is maintained at the required high level, the transfer mask manufactured using the mask blank having such characteristics can also have the required high flatness. .
- the semiconductor device manufacturing method of the present invention is characterized in that a transfer pattern is exposed and transferred onto a resist film on a semiconductor substrate using the transfer mask manufactured by the transfer mask manufacturing method.
- an ArF excimer laser is used as exposure light for the exposure transfer. Even if the transfer mask is continuously irradiated with exposure light of an ArF excimer laser, a decrease in the transmittance of the glass substrate of the transfer mask is suppressed. For this reason, the semiconductor device which has a highly accurate pattern continuously can be manufactured.
- the film stress of the thin film has a strong tendency to compressive stress over time. None become. Thereby, after manufacturing a mask blank, it can suppress that the flatness of a mask blank deteriorates with progress of time. Moreover, since the mask blank manufactured by the mask blank of the present invention and the mask blank manufacturing method of the present invention can suppress the film stress of the thin film for pattern formation from increasing over time, the film of the thin film The stress can be maintained at the manufacturing level.
- membrane stress can be suppressed.
- a transfer mask is manufactured from the mask blank of the present invention and the mask blank manufactured by the mask blank manufacturing method of the present invention, it is possible to suppress the occurrence of pattern misalignment as time passes after the manufacturing.
- the transfer pattern is transferred to the resist film on the semiconductor substrate using a transfer mask that suppresses the deterioration of the flatness of the main surface due to the film stress of the thin film and also suppresses the positional deviation of the pattern formed on the thin film. it can. As a result, a semiconductor device having a fine and highly accurate circuit pattern on the semiconductor substrate can be manufactured.
- Embodiments of the present invention will be described below.
- the inventor conducted intensive studies on the cause of the compressive stress of a thin film containing tantalum formed on a glass substrate increasing with time.
- various storage cases and storage methods were verified in order to confirm whether there was a cause in the storage method of the mask blank after film formation.
- the flatness of the main surface of the mask blank was deteriorated, and there was no clear correlation between the increase in compressive stress and the storage method.
- the mask blank whose main surface flatness deteriorated in the convex direction was subjected to heat treatment using a hot plate. The heat treatment was performed at 200 ° C. for about 5 minutes.
- the present inventor examined the possibility that the material containing tantalum is related to the property of easily taking in hydrogen. That is, it was hypothesized that hydrogen was gradually taken into the tantalum-containing thin film over time, and the compressive stress increased.
- the tantalum-containing thin film of the mask blank in which the phenomenon that the compressive stress increases with the passage of time is formed on the lower surface made of a material containing tantalum and nitrogen and on the lower layer on the main surface side of the substrate. It had a structure in which the formed upper layer made of a material containing tantalum and oxygen was laminated.
- the upper layer made of a material containing tantalum and oxygen has an effect of suppressing entry of hydrogen from the outside air. For this reason, it has been considered that hydrogen in the outside air hardly penetrates into a thin film containing tantalum.
- the following verification was performed to confirm whether hydrogen was taken into the tantalum-containing thin film with the passage of time from the end of film formation.
- the film composition of the following two types of mask blanks provided with a thin film made of a material containing tantalum was analyzed.
- the first mask blank is a mask blank that has been stored in a case after film formation for about two weeks, the number of days has not passed so much, and the flatness of the thin film has not deteriorated so much.
- the second mask blank is housed in the case after film formation, and 4 months have passed, the compressive stress of the thin film has increased, and the flatness has deteriorated (based on the center of the main surface of the substrate).
- HFS / RBS analysis hydrogen forward scattering analysis / Rutherford backscattering analysis
- a glass substrate used for a transfer mask in which an excimer laser, especially ArF excimer laser is applied to exposure light is generally formed of a glass material having an increased hydrogen molecule concentration in the material. .
- the hydrogen content was measured by laser Raman scattering spectroscopy on a glass substrate formed of the same glass material as that used in the mask blank provided with the tantalum-containing thin film in which the film stress was changed, 7.
- the number was 4 ⁇ 10 18 molecules / cm 3 .
- the thin film containing a tantalum was formed into a film in the same procedure with respect to each glass substrate formed with the various glass materials from which hydrogen content differs, and the mask blank was manufactured, respectively.
- the flatness of the thin film surface of each mask blank was measured, and each mask blank was hermetically stored in a case and stored for 4 months. Thereafter, each mask blank was taken out from the case, and the flatness of the thin film surface was measured.
- the mask blank of the present invention is a mask blank including a thin film on the main surface of a glass substrate, the glass substrate has a hydrogen content of less than 7.4 ⁇ 10 18 molecules / cm 3 , and the thin film is tantalum. It is characterized by being made of a material containing substantially no hydrogen and in contact with the main surface of the glass substrate. Also, preferably the hydrogen content of the glass substrate is at 4.0 ⁇ 10 18 molecule number / cm 3 or less, more preferable to be 2.0 ⁇ 10 18 molecule number / cm 3 or less, 8.0 ⁇ 10 17 More preferably, the number of molecules / cm 3 or less.
- the transfer mask is used (the exposure light of ArF excimer laser is It is unavoidable that the transmittance of the glass substrate with respect to the ArF excimer laser light is reduced when it is irradiated.
- a glass material having a hydrogen content of at least 2.0 ⁇ 10 17 molecules / cm 3 or more is used as a glass substrate for a mask blank. It turns out that it is necessary to apply to.
- the glass substrate in the mask blank of the present invention is characterized in that the hydrogen content is 2.0 ⁇ 10 17 molecules / cm 3 or more. Further, the hydrogen content of the glass substrate is preferably 3.0 ⁇ 10 17 molecules / cm 3 or more, and more preferably 5.0 ⁇ 10 17 molecules / cm 3 or more.
- the OH group in the glass material has a function of suppressing structural defects inside the glass material.
- the OH group in the glass material is a factor that promotes the induction of NBOHC when irradiated with ArF excimer laser light. From these things, it is preferable that content of OH group in the glass substrate used for the mask blank of this invention shall be 600 ppm or less, and it is more preferable in it being 500 ppm or less.
- Examples of the material of the glass substrate in the mask blank include synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (SiO 2 —TiO 2 glass, etc.), and the like.
- synthetic quartz glass since synthetic quartz glass has high transmittance with respect to ArF excimer laser light (wavelength 193 nm), it is preferable to use synthetic quartz glass as a material for the glass substrate.
- the exposure light applied to the mask blank and transfer mask of the present invention is not particularly limited, such as ArF excimer laser light, KrF excimer laser light, and i-line light.
- Mask blanks and transfer masks that apply ArF excimer laser to exposure light have very high required levels such as flatness of the main surface and positional accuracy of a transfer pattern formed on a thin film.
- a transfer mask in which an ArF excimer laser is applied to exposure light and a mask blank for producing the transfer mask are desired to have high resistance to the ArF excimer laser. Therefore, the present invention can be effectively applied to a mask blank or a transfer mask in which an ArF excimer laser is applied to exposure light.
- the glass substrate used for the mask blank and transfer mask of the present invention has a flatness of 0. 0 in a square inner region (hereinafter referred to as a 142 mm square inner region) with a side of 142 mm with respect to the center of the main surface. It is desirable that the surface roughness in the square inner region of 5 ⁇ m or less and one side of 1 ⁇ m is 0.2 nm or less in terms of Rq (hereinafter simply referred to as “surface roughness Rq”). Further, the flatness in a square inner region (hereinafter referred to as a 132 mm square inner region) having a side of 132 mm with respect to the center of the main surface of the glass substrate is more preferably 0.3 ⁇ m or less.
- a glass substrate in a state of being cut out from a glass ingot cannot satisfy such high flatness and surface roughness conditions.
- the mirror polishing is preferably performed by double-side polishing in which both main surfaces of the glass substrate are simultaneously polished using a polishing liquid containing colloidal silica polishing abrasive grains.
- a polishing liquid containing colloidal silica abrasive grains is used.
- a material containing tantalum has a property of easily taking in hydrogen. Since a material containing tantalum has a characteristic of becoming brittle when hydrogen is taken in, it is desired to suppress the hydrogen content in the thin film even immediately after the thin film is formed. For this reason, in this invention, the material which contains tantalum and does not contain hydrogen substantially is selected for the thin film formed on the main surface of a glass substrate. “Substantially no hydrogen” means that the hydrogen content in the thin film is at least 5 at% or less. The range of the hydrogen content in the thin film is preferably 3 at% or less, and more preferably the detection lower limit value or less.
- a step of preparing a glass substrate having a hydrogen content of less than 7.4 ⁇ 10 18 molecules / cm 3 and the glass substrate in a film formation chamber And using a target containing tantalum, introducing a sputtering gas not containing hydrogen into the deposition chamber, and forming a thin film on the main surface of the glass substrate by a sputtering method.
- Examples of the “material containing tantalum and not substantially containing hydrogen” for forming the thin film provided on the glass substrate include tantalum metal and tantalum selected from nitrogen, oxygen, boron and carbon. Examples thereof include materials containing the above elements and containing substantially no hydrogen.
- a material containing tantalum and substantially free of hydrogen includes Ta, TaN, TaON, TaBN, TaBON, TaCN, TaCON, TaBCN, and TaBOCN. About the said material, you may contain metals other than a tantalum in the range with which the effect of this invention is acquired.
- tantalum there is a metal having a property of easily taking in hydrogen.
- tantalum in the material of the thin film is replaced with another metal having a property of easily taking in hydrogen, the same effect as the present invention can be obtained. It is done.
- other metals having the property of easily incorporating hydrogen include niobium, vanadium, titanium, magnesium, lanthanum, zirconium, scandium, yttrium, lithium, and praseodymium.
- an alloy composed of tantalum and one or more metals selected from the group of metals having the property of easily taking in hydrogen, and one or more elements selected from nitrogen, oxygen, boron, and carbon of this alloy The same effect can be obtained for a compound containing.
- the thin film of the mask blank is preferably formed of a material containing tantalum and nitrogen and substantially free of hydrogen. Tantalum is a material that easily oxidizes naturally. As tantalum progresses, the light shielding performance (optical density) against exposure light decreases.
- a material in which oxidation of tantalum has not progressed is an etching gas containing fluorine (fluorine-based etching gas) and an etching gas containing chlorine and not containing oxygen (oxygen-free) It can be said that dry etching is possible with any of these chlorine-based etching gases.
- tantalum that has been oxidized is a material that is difficult to dry-etch with an oxygen-free chlorine-based etching gas from the viewpoint of forming a thin film pattern, and can be said to be a material that can be dry-etched only with a fluorine-based etching gas.
- nitrogen in tantalum By including nitrogen in tantalum, oxidation of tantalum can be suppressed.
- a thin film made of a material containing tantalum is formed in contact with the main surface of the glass substrate, oxygen is contained while reducing the back surface reflectance with respect to exposure light by containing nitrogen in tantalum. Compared to the above, it is preferable because a decrease in optical density can be suppressed.
- the nitrogen content in the thin film is preferably 30 at% or less, more preferably 25 at% or less, and further preferably 20 at% or less from the viewpoint of optical density.
- the nitrogen content in the thin film is desirably 7 at% or more when the back surface reflectance needs to be less than 40%.
- the thin film of the mask blank preferably has a highly oxidized layer containing 60 atomic% or more of oxygen on the surface layer (the surface layer of the thin film opposite to the main surface of the substrate).
- hydrogen not only enters the thin film from the substrate, but also enters the thin film from the gas surrounding the mask blank.
- a high oxide film of a thin film material has a high binding energy and a property of preventing hydrogen from entering the thin film.
- the high oxidation layer (tantalum high oxidation layer) of the material containing tantalum has excellent chemical resistance, warm water resistance, and light resistance against ArF exposure light.
- the thin film in the mask blank or transfer mask is desired to have a crystal structure of microcrystals, preferably amorphous. For this reason, the crystal structure in the thin film is unlikely to be a single structure, and a plurality of crystal structures are likely to be mixed. That is, in the case of a high tantalum oxide layer, TaO bonds, Ta 2 O 3 bonds, TaO 2 bonds, and Ta 2 O 5 bonds tend to be mixed. As the abundance ratio of Ta 2 O 5 bonds in the surface layer of the thin film increases, the properties to prevent hydrogen intrusion, chemical resistance, warm water resistance, and ArF light resistance increase. On the other hand, these properties tend to decrease as the abundance ratio of TaO bonds in the surface layer of the thin film increases.
- the bonding state between tantalum and oxygen in the layer tends to be mainly composed of Ta 2 O 3 bonds. It is done.
- TaO bonds which are the most unstable bonds, are considered to be much less than when the oxygen content in the layer is less than 60 at%.
- the bonding state between tantalum and oxygen in the layer tends to be mainly composed of TaO 2 bonds.
- both the TaO bond which is the most unstable bond and the Ta 2 O 3 bond which is the next unstable bond are very few.
- the oxygen content in the tantalum highly oxidized layer is 68 at% or more, it is considered that not only TaO 2 bonds are the main component but also the ratio of Ta 2 O 5 bonding state is increased. At such an oxygen content, the “Ta 2 O 3 ” and “TaO 2 ” bonding states rarely exist, and the “TaO” bonding state cannot exist.
- the oxygen content in the high tantalum oxide layer is 71.4 at%, it is considered that the tantalum high oxide layer is formed substantially only in a bonded state of Ta 2 O 5 .
- the oxygen content in the high tantalum oxide layer is 60 at% or more, not only the most stable bonding state “Ta 2 O 5 ” but also bonding states of “Ta 2 O 3 ” and “TaO 2 ” Will also be included.
- TaO bond which is at least the most unstable bond, has the effect of preventing hydrogen entry, chemical resistance, and ArF light resistance. The amount is very small so as not to give. Therefore, it is considered that the lower limit value of the oxygen content in the layer is 60 at%.
- the abundance ratio of Ta 2 O 5 bonds in the high tantalum oxide layer is preferably higher than the abundance ratio of Ta 2 O 5 bonds in the thin film excluding the high oxidation layer.
- the Ta 2 O 5 bond is a bonded state having very high stability, and by increasing the abundance ratio of the Ta 2 O 5 bond in the high oxide layer, the characteristics of preventing hydrogen intrusion, chemical resistance, Mask cleaning resistance such as warm water and ArF light resistance are greatly increased.
- the high tantalum oxide layer is formed only by a bonded state of Ta 2 O 5 .
- the content of nitrogen and other elements in the high tantalum oxide layer is preferably in a range that does not affect the operational effects such as the property of preventing hydrogen intrusion, and is preferably not substantially contained.
- the thickness of the high tantalum oxide layer is preferably 1.5 nm or more and 4 nm or less. If it is less than 1.5 nm, it is too thin to prevent the effect of blocking hydrogen penetration, and if it exceeds 4 nm, the influence on the surface reflectance increases, and a predetermined surface reflectance (reflectance for exposure light or light of each wavelength) Control for obtaining a reflectance spectrum becomes difficult. Moreover, since the optical density with respect to ArF exposure light is very low, the high tantalum oxide layer reduces the optical density that can be secured by the surface antireflection layer, and acts negatively from the viewpoint of reducing the thickness of the thin film. In consideration of the balance between securing the optical density of the entire thin film and the characteristics of preventing hydrogen intrusion, chemical resistance and ArF light resistance, the thickness of the highly oxidized layer is 1.5 nm or more and 3 nm. The following is more desirable.
- the high tantalum oxide layer is a mask blank after a thin film has been formed, with hot water treatment, ozone-containing water treatment, heat treatment in a gas containing oxygen, and ultraviolet rays in a gas containing oxygen. It can be formed by performing irradiation treatment and / or O 2 plasma treatment or the like.
- the high oxide layer is not limited to the metal high oxide film forming the thin film. Any metal high oxide film may be used as long as it has the property of preventing hydrogen intrusion, and a structure in which the high oxide film is laminated on the surface of the thin film may be used. Further, as long as the material has a property of preventing hydrogen from entering the thin film, the material may not be a high oxide, and the material film may be stacked on the surface of the thin film.
- the thin film of the mask blank has a structure in which a lower layer and an upper layer are laminated from the glass substrate side.
- the lower layer is preferably made of a material containing tantalum and nitrogen and substantially not containing hydrogen
- the upper layer is preferably made of a material containing tantalum and oxygen.
- the oxygen content in the upper layer excluding the surface layer portion may be less than 60 at%. preferable.
- the upper layer is formed of a material containing oxygen in tantalum. From the viewpoint of forming a thin film pattern, dry etching of the upper layer (a material containing oxygen in tantalum) is difficult with a chlorine-based etching gas not containing oxygen, and can be dry-etched only with a fluorine-based etching gas.
- the lower layer is formed of a material containing tantalum and nitrogen. From the viewpoint of forming a thin film pattern, dry etching of a lower layer (a material containing tantalum and nitrogen) can be performed using either a fluorine-based etching gas or an oxygen-free chlorine-based etching gas.
- a pattern is formed by dry etching a thin film using a resist pattern (resist film on which a transfer pattern is formed) as a mask
- the pattern is formed by performing dry etching with a fluorine-based etching gas on the upper layer
- a process of forming a pattern by performing dry etching with a chlorine-based etching gas containing no oxygen on the lower layer using the upper layer pattern as a mask can be used. By applying such an etching process, the resist film can be thinned.
- the ratio of the oxygen content (number of atoms) to the tantalum content (number of atoms) of the upper layer is preferably 1 or more.
- the oxygen content in the upper layer is preferably 50 at% or more.
- the material forming the lower layer of the thin film is the same as the material containing tantalum listed above and substantially not containing hydrogen.
- the material for forming the upper layer is preferably a material containing tantalum and oxygen, and further containing nitrogen, boron, carbon and the like. Examples of the material for forming the upper layer include TaO, TaON, TaBO, TaBON, TaCO, TaCON, TaBCO, and TaBOCN.
- the thin film of the mask blank is not limited to the above laminated structure.
- a three-layer structure may be employed, a single-layer composition gradient film may be employed, or a film structure having a composition gradient between the upper layer and the lower layer may be employed.
- the thin film of the mask blank is desirably used as a light-shielding film that functions as a light-shielding pattern when a transfer mask is produced, but is not limited thereto.
- the mask blank thin film can also be used as an etching stopper film or an etching mask film (hard mask film). If it is within the constraints required for the thin film, a halftone phase shift film or an optical half film can be used. It can also be applied to a permeable membrane.
- the mask blank can suppress the time-dependent change of the compressive stress of the thin film, a double patterning technology (double patterning technology (DP technology) in a narrow sense, double technology) that requires high positional accuracy is required for the pattern formed on the thin film.
- double patterning technology double patterning technology (DP technology) in a narrow sense, double technology) that requires high positional accuracy is required for the pattern formed on the thin film. This is particularly suitable when a transfer mask set to which an exposure technique (DE technique, etc.) is applied is produced.
- the thin film has a structure in which a lower layer and an upper layer are laminated from the glass substrate side, and the step of forming the thin film contains nitrogen and does not contain hydrogen.
- the transfer mask of the present invention is preferably one in which a transfer pattern is formed on the mask blank thin film.
- the transfer mask manufactured by the manufacturing method of the present invention is manufactured by forming a transfer pattern on the thin film of the mask blank using the mask blank manufactured by the above manufacturing method.
- the increase in the compressive stress of the thin film over time is suppressed, so the flatness of the mask blank is maintained at the required high level. ing. If a mask blank having such characteristics is used, a transfer mask having a required high level of flatness can be manufactured.
- the compressive stress of the thin film is suppressed, the amount of displacement on the main surface caused by each pattern of the thin film released from the surrounding compressive stress after the etching process for producing the transfer mask can also be suppressed. it can.
- a transfer mask (conventional transfer mask) manufactured by a conventional manufacturing method has a required high flatness if time has not passed since it was manufactured.
- a conventional transfer mask is stored and stored in a mask case without being used after it is manufactured, or when it is continuously used after being set in an exposure apparatus, the compressive stress of the thin film increases, resulting in flatness. Since the degree of deterioration deteriorates, each pattern of the thin film may be greatly displaced.
- the transfer mask can be used as a binary mask, and is particularly suitable when ArF excimer laser light is applied to exposure light.
- the transfer mask can also be applied to a digging Levenson type phase shift mask, a halftone type phase shift mask, an enhancer type phase shift mask, and a chromeless phase shift mask (CPL mask).
- the transfer mask is excellent in pattern position accuracy, and is particularly suitable for a transfer mask set to which a double patterning technique (DP technique, DE technique, etc.) is applied.
- dry etching effective for forming a fine pattern is preferably used.
- fluorine-based gas such as SF 6 , CF 4 , C 2 F 6, and CHF 3 can be used.
- a chlorine-based gas such as Cl 2 and CH 2 Cl 2 , or at least one of these chlorine-based gases, A mixed gas with He, H 2 , N 2 , Ar and / or C 2 H 4 or the like can be used.
- the transfer mask of the present invention and the transfer mask manufactured by the manufacturing method of the present invention to manufacture a semiconductor device having a highly accurate pattern by exposing and transferring the transfer pattern to a resist film on a semiconductor substrate. Can do. This is because the transfer mask has high flatness and pattern position accuracy required during production.
- the transfer mask is not used after production and is stored in a mask case and stored for a certain period of time, then set in an exposure apparatus and used for exposure transfer, or after the mask is produced. Even when it is set in an exposure apparatus and used for exposure transfer, the required high flatness can be maintained, and the displacement of each pattern of the thin film can be suppressed.
- the light shielding film 30 is constituted by the lower layer 2 and the upper layer 3 including the tantalum high oxide layer 4.
- the transfer mask causes the light shielding film 30 to remain on the glass substrate 1 by patterning the light shielding film 30 of the mask blank shown in FIG.
- a high tantalum oxide layer 4a is formed on the surface layer of the light shielding film pattern (thin film pattern) 30a.
- a tantalum high oxide layer 4b is formed on the surface layer of the pattern 3a of the upper layer 3
- a tantalum high oxide layer 4c is formed on the surface layer of the pattern 2a of the lower layer 2.
- the method for forming the high tantalum oxide layers 4b and 4c on the side walls of the patterns 2a and 3a of the lower layer 2 and the upper layer 3 is the same as the method for forming the high tantalum oxide layer in the mask blank.
- Example 1 A glass substrate made of synthetic quartz glass having a main surface dimension of about 152 mm ⁇ about 152 mm and a thickness of about 6.35 mm was prepared. This glass substrate had a main surface polished to a predetermined flatness and surface roughness, and then subjected to a predetermined cleaning process and a drying process. This glass substrate had a flatness in the inner region of 142 mm square on the main surface of 0.3 ⁇ m or less, and the surface shape was a convex shape.
- the surface roughness of the main surface was 0.2 nm or less in terms of the root-mean-square roughness Rq in the measurement region within a square having a side of 1 ⁇ m.
- This glass substrate was a sufficient level as a glass substrate used in a 22 nm node mask blank.
- the hydrogen concentration in the glass substrate was measured by laser Raman spectrophotometry and found to be 3.0 ⁇ 10 17 molecules / cm 3 .
- one main surface shape of this glass substrate was measured using the surface shape analyzer (UltraFLAT 200M (made by Corning TROPEL)). (The measurement area of the surface shape measured by the surface shape analyzer is the same.)
- the cleaned glass substrate was introduced into a DC magnetron sputtering apparatus.
- a mixed gas of Xe and N 2 was introduced into the sputtering apparatus, and a TaN layer (lower layer) 2 having a thickness of 42.5 nm was formed in contact with the main surface of the glass substrate 1 by a sputtering method using a tantalum target. (See FIG. 3 (a)).
- the gas in the sputtering apparatus was replaced with a mixed gas of Ar and O 2, and a TaO layer (upper layer) 3 having a thickness of 5.5 nm was formed by sputtering using a tantalum target (FIG. 3A )reference).
- this mask blank was placed on a hot plate and heat-treated at 300 ° C. in the atmosphere to form a highly oxidized tantalum layer 4 on the surface layer of the TaO layer 3 (see FIG. 3B).
- the surface shape of the light shielding film 30 on the main surface of the substrate was measured with a flatness measuring device UltraFLAT 200M (Corning TOROPEL).
- the hydrogen content in the TaN layer 2 is below the detection lower limit, and the oxygen content is from the surface of the TaO layer 3 to a depth of 2 nm.
- this mask blank had a reflectance (surface reflectance) at the film surface of the light shielding film 30 of 30.5% in ArF exposure light (wavelength 193 nm).
- the reflectance (back surface reflectance) of the surface of the glass substrate 1 on which the light-shielding film was not formed was 38.8% in ArF exposure light.
- the optical density in ArF exposure light was 3.02.
- the mask blank of Example 1 including the light-shielding film 30 having the stacked structure of the TaN layer 2 and the TaO layer 3 including the tantalum high oxide layer 4 on the surface layer is formed on the main surface of the glass substrate 1. Obtained.
- the mask blank of Example 1 was stored in a sealed state in a storage case and stored in a clean room until 150 days had passed. Then, the mask blank of Example 1 stored for a long time was taken out, and the surface shape of the light-shielding film 30 on the main surface of the substrate was measured with a flatness measuring device UltraFLAT 200M (Corning TOROPEL). Next, the surface shape (difference shape) which took the difference of the surface shape of the light shielding film 30 of the mask blank measured before long-term storage and the surface shape of the light shielding film 30 of the mask blank measured after long-term storage was computed. .
- FIG. 4 shows the result of HFS / RBS analysis performed on the mask blank provided with the light-shielding film 30 after long-term storage.
- the horizontal axis represents the depth (nm) from the surface of the light shielding film
- the vertical axis represents the composition of the light shielding film in atomic concentration (at%). From the results of FIG. 4, it can be said that the TaN layer contains about 1.6 at% hydrogen. From this result, it can be said that the supply source of hydrogen taken into the TaN layer is a glass substrate. It can also be seen from the flatness difference value before and after long-term storage that the flatness of the main surface is hardly affected as long as about 1.6 at% hydrogen is taken into the TaN layer.
- a 100 nm-thickness chemically amplified resist 5 for electron beam drawing was applied by spin coating (see FIG. 3C). After applying the resist 5, the resist 5 was subjected to electron beam drawing and development to form a resist pattern 5a (see FIG. 3D).
- the pattern which performed electron beam drawing used one of what divided
- the transfer mask is placed at 90 ° C. It was immersed in deionized water (DI water) for 120 minutes to carry out warm water treatment (surface treatment). Thereby, the transfer mask of Example 1 was obtained.
- DI water deionized water
- the produced transfer mask of Example 1 was sealed in a mask case (storage case) and stored in a clean room until 150 days passed. Before and after this long-term storage, the pattern width and the space width at a predetermined portion in the surface of the transfer mask were measured. The fluctuation widths of the pattern width and the space width before and after long-term storage were both within the allowable range.
- transfer having the other transfer pattern of the 22 nm node fine pattern divided into two relatively sparse transfer patterns using the double patterning technique A mask was prepared. Through the above procedure, a transfer mask set capable of transferring a fine pattern of 22 nm node to a transfer object was obtained by exposure transfer using a double patterning technique using two transfer masks.
- a glass substrate made of synthetic quartz glass having a main surface dimension of about 152 mm ⁇ about 152 mm and a thickness of about 6.35 mm was prepared.
- This glass substrate had a main surface polished to a predetermined flatness and surface roughness, and then subjected to a predetermined cleaning process and a drying process.
- This glass substrate had a flatness in the inner region of 142 mm square on the main surface of 0.3 ⁇ m or less, and the surface shape was a convex shape.
- the surface roughness of the main surface was 0.2 nm or less in terms of the root-mean-square roughness Rq in the measurement region within a square having a side of 1 ⁇ m.
- This glass substrate was a sufficient level as a glass substrate used in a 22 nm node mask blank.
- the hydrogen concentration in the glass substrate was measured by laser Raman spectrophotometry and found to be 7.4 ⁇ 10 18 molecules / cm 3 .
- one main surface shape of the translucent substrate was measured using a surface shape analyzer (UltraFLAT 200M (Corning TROPEL)).
- a light shielding film 30 was formed in contact with the surface of the glass substrate under the same film forming conditions as in Example 1. Further, the glass substrate on which the light-shielding film 30 was formed was placed on a hot plate, and heat treatment was performed at 300 ° C. in the atmosphere to form the tantalum highly oxidized layer 4 on the surface layer of the TaO layer 3. The surface shape of the light shielding film 30 on the main surface of the substrate was measured with a flatness measuring device UltraFLAT 200M (Corning TOROPEL) on the mask blank after the high oxide layer 4 was formed.
- UltraFLAT 200M Corning TOROPEL
- the mask blank of Comparative Example 1 including the light-shielding film 30 having the laminated structure of the TaN layer 2 and the TaO layer 3 including the highly oxidized tantalum layer 4 on the surface layer is formed on the main surface of the glass substrate 1. Obtained.
- the mask blank of Comparative Example 1 was sealed in a storage case and stored in a clean room until 150 days had passed. Then, the mask blank of Comparative Example 1 stored for a long time was taken out, and the surface shape of the light-shielding film 30 on the main surface of the substrate was measured with a flatness measuring device UltraFLAT 200M (Corning TOROPEL). Next, the surface shape (difference shape) which took the difference of the surface shape of the light shielding film 30 of the mask blank measured before long-term storage and the surface shape of the light shielding film 30 of the mask blank measured after long-term storage was computed.
- UltraFLAT 200M Corning TOROPEL
- FIG. 5 shows the result of HFS / RBS analysis performed on the mask blank provided with the light-shielding film 30 after long-term storage.
- the horizontal axis represents the depth (nm) from the surface of the light shielding film
- the vertical axis represents the composition of the light shielding film in atomic concentration (at%).
- the TaN layer contains about 5.9 at% hydrogen. From this result, it can be said that the supply source of hydrogen taken into the TaN layer is a glass substrate. Further, from the difference in flatness before and after long-term storage, it was found that the flatness of the main surface is greatly deteriorated when about 5.9 at% of hydrogen is taken into the TaN layer.
- a transfer mask of Comparative Example 1 was prepared in the same procedure as Example 1 using the mask blank of Comparative Example 1 that was not stored for a long period of time.
- the produced transfer mask of Comparative Example 1 was sealed in a mask case (storage case) and stored in a clean room until 150 days had passed.
- the pattern width and the space width at a predetermined portion in the surface of the transfer mask were measured. The fluctuation widths of the pattern width and the space width before and after long-term storage are both large, which is clearly outside the allowable range for a transfer mask to which the double patterning technology for at least 22 nm node is applied.
- a transfer mask of Comparative Example 1 was produced in the same procedure as Example 1 using the mask blank after long-term storage.
- the flatness has already deteriorated greatly in the mask blank state, the movement on the main surface of the pattern is remarkable when chucked on the mask stage of the exposure apparatus, and the double patterning technology for at least 22 nm node is applied. It was clearly out of the acceptable range for the transfer mask.
- the compressive stress of the light shielding film was remarkably large, the pattern of the light shielding film after the dry etching was largely deviated from the electron beam drawing pattern.
Abstract
Description
近年では、モリブデンシリサイド化合物を含む材料(MoSi系材料)を遮光膜として用いたArFエキシマレーザー用のバイナリマスクなども出現している(特許文献1)。また、タンタル化合物を含む材料(タンタル系材料)を遮光膜として用いたArFエキシマレーザー用のバイナリマスクなども出現している(特許文献2)。特許文献3には、タンタル、ニオブ、及びバナジウムのうち少なくとも2つを含む金属を用いた遮光膜からなるフォトマスクに対して、酸洗浄や水素プラズマによる洗浄を行った場合、遮光膜が水素脆性化し、遮光膜が変形することがあると記載されている。その解決手段として、遮光膜にパターンを形成後、遮光膜の上面や側面を気密に覆う水素阻止膜を形成することが記載されている。
本発明者は、ガラス基板に成膜されたタンタルを含有する薄膜の圧縮応力が、時間の経過とともに増大する原因について鋭意研究を行った。まず、成膜後のマスクブランクの保管方法に原因がないかを確認するため、種々の保管ケースや保管方法について検証した。しかし、いずれの場合も、マスクブランクの主表面の平坦度が悪化しており、圧縮応力の増大と保管方法との間に明確な相関性はなかった。次に、主表面の平坦度が凸形状の方向に悪化したマスクブランクに対して、ホットプレートを用いて加熱処理を行ってみた。加熱処理の条件は、200℃で5分程度とした。この加熱処理を行うと、一時的には主表面の凸形状が多少良好な方向に変化した。しかし、加熱処理後、時間が経過するとマスクブランクの主表面の平坦度が再び悪化し、根本的な解決には至らないことがわかった。
(実施例1)
[マスクブランクの製造]
主表面の寸法が約152mm×約152mmで、厚さが約6.35mmの合成石英ガラスからなるガラス基板を準備した。このガラス基板は、主表面を所定の平坦度および表面粗さに研磨され、その後、所定の洗浄処理および乾燥処理を施されたものであった。なお、このガラス基板は、主表面における142mm四方の内側領域における平坦度は、0.3μm以下であり、表面形状は凸形状であった。また、主表面の表面粗さは、一辺が1μmの四角形内の測定領域での自乗平方根平均粗さRqで0.2nm以下であった。このガラス基板は、22nmノードのマスクブランクで使用されるガラス基板として十分な水準であった。このガラス基板中の水素濃度をレーザーラマン分光光度法によって測定したところ、3.0×1017分子数/cm3であった。そして、このガラス基板の一方の主表面形状を、表面形状解析装置(UltraFLAT 200M(Corning TROPEL社製))を用いて測定した(測定領域は、ガラス基板の中心を基準とした一辺が148mmの四角形の内側領域。以降、表面形状解析装置で測定している表面形状の測定領域は同じ。)。
長期保管を行っていない実施例1のマスクブランクを用いて、以下の手順で実施例1の転写用マスクを作製した。
長期保管後の転写用マスクセットを用い、ArFエキシマレーザーを露光光とする露光装置を用い、ダブルパターニング技術を適用し、半導体デバイス上のレジスト膜に22nmノードの微細パターンを露光転写した。露光後の半導体デバイス上のレジスト膜に所定の現像処理を行い、レジストパターンを形成し、そのレジストパターンをマスクとして、下層膜をドライエッチングし、回路パターンを形成した。半導体デバイスに形成した回路パターンを確認したところ、重ね合わせ精度不足に起因する回路パターンの配線短絡や断線はなかった。
[マスクブランクの製造]
主表面の寸法が約152mm×約152mmで、厚さが約6.35mmの合成石英ガラスからなるガラス基板を準備した。このガラス基板は、主表面を所定の平坦度および表面粗さに研磨され、その後、所定の洗浄処理および乾燥処理を施されたものであった。なお、このガラス基板は、主表面における142mm四方の内側領域における平坦度は、0.3μm以下であり、表面形状は凸形状であった。また、主表面の表面粗さは、一辺が1μmの四角形内の測定領域での自乗平方根平均粗さRqで0.2nm以下であった。このガラス基板は、22nmノードのマスクブランクで使用するガラス基板として十分な水準であった。このガラス基板中の水素濃度をレーザーラマン分光光度法によって測定したところ、7.4×1018分子数/cm3であった。そして、実施例1の場合と同様に、この透光性基板の一方の主表面形状を、表面形状解析装置(UltraFLAT 200M(Corning TROPEL社製))を用いて測定した。
次に、長期保管を行っていない比較例1のマスクブランクを用いて、実施例1と同様の手順で比較例1の転写用マスクを作製した。作製した比較例1の転写用マスクをマスクケース(保管ケース)に密閉状態で収納し、150日経過するまでクリーンルーム内で保管した。なお、長期保管の前後で、転写用マスクの面内所定部分におけるパターン幅およびスペース幅をそれぞれ測定した。長期保管の前後における、パターン幅やスペース幅の変動幅は、いずれも大きく、少なくとも22nmノード用のダブルパターニング技術が適用される転写用マスクでは明らかに許容範囲外であった。このため、同様の手順で、ダブルパターニング技術を用いて22nmノードの微細なパターンを2つの比較的疎な転写パターンに分割したもののうちのもう一方の転写パターンを有する転写用マスクを作製したとしても、重ね合わせ精度が低く、ダブルパターニング用の転写用マスクセットとしては使用できない。
1 ガラス基板
2 下層(TaN層)
2a 下層パターン
3 上層(TaO層)
3a 上層パターン
4,4a,4b,4c タンタル高酸化層
5 レジスト膜
30 遮光膜
30a 遮光部
30b 透光部
Claims (20)
- ガラス基板の主表面上に薄膜を備えるマスクブランクであって、
前記ガラス基板は、水素含有量が7.4×1018分子数/cm3未満であり、
前記薄膜は、タンタルを含有し、かつ水素を実質的に含有しない材料からなり、前記ガラス基板の主表面に接して形成されている
ことを特徴とするマスクブランク。 - 前記ガラス基板は、水素含有量が2.0×1017分子数/cm3以上であることを特徴とする請求項1記載のマスクブランク。
- 前記ガラス基板は、合成石英ガラスからなることを特徴とする請求項1または2に記載のマスクブランク。
- ArFエキシマレーザーが露光光として適用される転写用マスクの作製に用いられるものであることを特徴とする請求項1から3のいずれかに記載のマスクブランク。
- 前記薄膜は、タンタルと窒素とを含有し、かつ水素を実質的に含有しない材料からなることを特徴とする請求項1から4のいずれかに記載のマスクブランク。
- 前記薄膜の表層に、酸素を60原子%以上含有する高酸化層が形成されていることを特徴とする請求項1から5のいずれかに記載のマスクブランク。
- 前記薄膜は、ガラス基板側から下層と上層とが積層する構造を有し、前記下層は、タンタルと窒素とを含有し、かつ水素を実質的に含有しない材料からなり、前記上層は、タンタルと酸素とを含有する材料からなることを特徴とする請求項1から6のいずれかに記載のマスクブランク。
- 前記上層の表層に、酸素を60原子%以上含有する高酸化層が形成されていることを特徴とする請求項7に記載のマスクブランク。
- 請求項1から8のいずれかに記載のマスクブランクの薄膜に転写パターンが形成されていることを特徴とする転写用マスク。
- 請求項9に記載の転写用マスクを用い、半導体基板上のレジスト膜に転写パターンを露光転写することを特徴とする半導体デバイスの製造方法。
- 前記露光転写は、ArFエキシマレーザーを露光光として適用することを特徴とする請求項10記載の半導体デバイスの製造方法。
- 水素含有量が7.4×1018分子数/cm3未満であるガラス基板を準備する工程と、
前記ガラス基板を成膜室内に設置し、タンタルを含有するターゲットを用い、水素を含有しないスパッタリングガスを成膜室内に導入し、ガラス基板の主表面上にスパッタリング法によって薄膜を形成する工程と、
を備えることを特徴とするマスクブランクの製造方法。 - 前記ガラス基板は、水素含有量が2.0×1017分子数/cm3以上であることを特徴とする請求項12記載のマスクブランクの製造方法。
- 前記ガラス基板は、合成石英ガラスからなることを特徴とする請求項12または13に記載のマスクブランクの製造方法。
- 前記マスクブランクは、ArFエキシマレーザーが露光光として適用される転写用マスクの作製に用いられるものであることを特徴とする請求項12から14のいずれかに記載のマスクブランクの製造方法。
- 前記薄膜を形成する工程は、窒素を含有し、かつ水素を含有しないスパッタリングガスを用いることを特徴とする請求項12から15のいずれかに記載のマスクブランクの製造方法。
- 前記薄膜は、ガラス基板側から下層と上層とが積層する構造を有するものであり、
前記薄膜を形成する工程は、窒素を含有し、かつ水素を含有しないスパッタリングガスを成膜室内に導入し、ガラス基板の主表面上にスパッタリング法によって前記下層を形成する工程と、
酸素を含有し、かつ水素を含有しないスパッタリングガスを成膜室内に導入し、前記下層の表面にスパッタリング法によって前記上層を形成する工程とからなる
ことを特徴とする請求項12から15のいずれかに記載のマスクブランクの製造方法。 - 請求項12から17のいずれかに記載のマスクブランクの製造方法で製造されたマスクブランクを用い、前記マスクブランクの薄膜に転写パターンを形成することを特徴とする転写用マスクの製造方法。
- 請求項18に記載の転写用マスクの製造方法で製造された転写用マスクを用い、半導体基板上のレジスト膜に転写パターンを露光転写することを特徴とする半導体デバイスの製造方法。
- 前記露光転写は、ArFエキシマレーザーを露光光として適用することを特徴とする請求項19記載の半導体デバイスの製造方法。
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