Method for manufacturing a laminate and laminate

Abstract

The present embodiment relates to a manufacturing method of a laminate and the like, and the manufacturing method of the laminate includes: a preparation step of preparing a processing object, the processing object being a laminate before processing provided with a light shielding film, and a carbonic acid water cleaning step of preparing a cleaned laminate by applying a carbonic acid water cleaning process of applying ultraviolet rays and carbonic acid water to the processing object; wherein the light shielding film contains a transition metal, and further contains oxygen, nitrogen, or carbon, the laminate has a residual ion content determined by ion chromatography, the residual ions include a sulfur-based ion and a nitric acid-based ion, the content of the sulfur-based ion is greater than 0 ng / cm 2 and equal to or less than 0.1 ng / cm 2 , the content of the nitric acid-based ion is greater than 0 ng / cm 2 and equal to or less than 0.1 ng / cm 2 . The present embodiment can minimize the performance variation of the laminate, remove particles and the like existing on the outer surface or surface of the laminate, and effectively suppress unexpected haze generated in the exposure process.

Description

TECHNICAL FIELD

[0001] The present embodiment relates to a method for manufacturing an optical laminate and a laminate. BACKGROUND

[0002] In the manufacturing process of a semiconductor, an optical laminate is required to be used. For example, in the case of a semiconductor photomask, a size of about 3 times to about 4 times is enlarged and applied to an exposure step of a semiconductor manufacturing process. As the fine and complex of a semiconductor wiring, the performance of the optical laminate is becoming more demanding, for example, a higher level of line pattern accuracy or complete removal of particles is required.

[0003] A blank mask can include a light-transmitting substrate, a light-shielding film, and the like. The light-transmitting substrate can be manufactured by a polishing process and a cleaning process after a shape processing of a material having a light-transmitting property.

[0004] As a circuit pattern developed on a wafer becomes more and more fine, it is required to more effectively suppress defects that can occur in the manufacturing process of a blank mask. Specific ions remaining on the surface of a blank mask such as a metal-containing thin film can grow into particles when affected by energy such as exposure light or exposed to other chemicals. In addition, when predetermined conditions are satisfied, the above ions can cause a haze to become large and can transfer an unexpected distorted pattern during exposure.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Korean Patent No. 10-0316374

[0008] Patent Document 2: Korean Patent No. 10-0745065 SUMMARY

[0009] Problems to be Solved

[0010] The present embodiment aims to provide a method for manufacturing a laminate and the like, which can remove particles and the like present on the outer surface of a laminate and effectively suppress unexpected haze during exposure.

[0011] Another object of the present embodiment is to provide a blank mask with reduced defects and a method for manufacturing the same.

[0012] Solution to the Problem

[0013] To achieve the above object, the manufacturing method of the laminate of the present embodiment includes: a preparation step of preparing a processing object, which is a laminate before processing provided with a light-shielding film; and a carbonated water cleaning step of preparing a cleaned laminate by applying a first cleaning of applying ultraviolet rays and carbonated water to the processing object.

[0014] The light-shielding film contains a transition metal, and further contains oxygen, nitrogen, or carbon.

[0015] The laminate has a residual ion content measured by ion chromatography, the residual ions including a sulfur-based ion and a nitric acid-based ion, the content of the sulfur-based ion being greater than 0 ng / cm 2 and equal to or less than 0.1 ng / cm 2 , and the content of the nitric acid-based ion being greater than 0 ng / cm 2 and equal to or less than 0.1 ng / cm 2 .

[0016] The light-shielding film can be manufactured by a light-shielding film manufacturing step of applying a sputtering method.

[0017] The sputtering method is a method of performing sputtering in a reactive gas environment after disposing a target material containing a transition metal, the reactive gas including a gas containing an oxygen atom, a gas containing a nitrogen atom, or a gas containing a carbon atom.

[0018] In the carbonated water cleaning step, ultraviolet rays can be irradiated at any one wavelength of 190 nm to 290 nm at a light amount of 1 mW / cm 2 to 11 mW / cm 2 .

[0019] In the carbonated water cleaning step, the conductivity of the carbonated water can be greater than or equal to 1 μS / cm and equal to or less than 10 μS / cm.

[0020] The carbonated water cleaning step can further include a ultraviolet cleaning step before the carbonated water cleaning step.

[0021] The ultraviolet cleaning step is a step of irradiating the processing object with ultraviolet rays having a wavelength of greater than or equal to 120 nm and less than 190 nm.

[0022] In the carbonated water cleaning step, megasonic waves can be applied together with the carbonated water.

[0023] The carbonated water cleaning step can further include a second cleaning step.

[0024] The second cleaning is a process of applying carbonated water and hydrogen water together as a cleaning liquid to the processing object.

[0025] The optical density variation of the laminate before the treatment of the preparation step and the laminate after the carbonated water cleaning step can be greater than or equal to 0% and less than or equal to 0.1%.

[0026] The thickness variation of the laminate before the treatment of the preparation step and the laminate after the carbonated water cleaning step can be greater than or equal to 0 angstrom and less than or equal to 5 angstrom.

[0027] To achieve the above object, a laminate of another embodiment is a laminate provided with a light-shielding film containing a transition metal, further containing at least one of oxygen and nitrogen, and having a reflectance of 35% or less for light having a wavelength of 193 nm, the laminate having a residual ion content determined by ion chromatography, the residual ion including a sulfur-based ion and a nitric acid-based ion, the sulfur-based ion content being greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 , the nitric acid-based ion content being greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 .

[0028] The residual ion can include a halogen ion, the halogen ion content being greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 .

[0029] The transition metal can include chromium, and the halogen ion can include a fluoride ion or a chloride ion.

[0030] The residual ion can include an ammonia ion, the ammonia ion content being greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 .

[0031] The residual ion can include an ionic impurity such as the sulfur-based ion, the nitric acid-based ion, the halogen ion, and the ammonia ion, the ionic impurity content being greater than 0 ng / cm 2 and less than or equal to 1.5 ng / cm 2 .

[0032] The residual ion can include a sodium ion, a phosphate ion, a potassium ion, a magnesium ion, and a calcium ion, the sum of the sodium ion content, the phosphate ion content, the potassium ion content, the magnesium ion content, and the calcium ion content being greater than or equal to 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 .

[0033] The laminate can be a photomask blank or a photomask.

[0034] Effects of the Invention

[0035] The manufacturing method of the laminate of the present embodiment and the laminate and the like can remove particles and the like present on the outer surface or surface of the laminate while minimizing changes in the performance of the laminate, and effectively suppress unexpected haze from occurring during exposure. DETAILED DESCRIPTION

[0036] Hereinafter, the embodiments will be described in detail so that those of ordinary skill in the art to which the present embodiment pertains can easily practice. However, the present embodiment can be implemented in various different forms and is not limited to the embodiments described herein.

[0037] The terms "about", "substantially" and the like degree terms used in the present specification are used in the meaning of equal to or close to the numerical range mentioned in order to prevent unscrupulous infringers from unfairly using the disclosure including accurate numbers or absolute numbers provided to help understand the present embodiment, when providing manufacturing deviations and material allowable deviations inherent in the mentioned meaning.

[0038] Throughout the specification, the term "combination thereof" included in the expression in Markush form means a mixture or combination of one or more selected from the group consisting of components recited in the Markush form, and means to include one or more selected from the group consisting of the above components.

[0039] Throughout the specification, the recitation of "A and / or B" means "A, B, or A and B".

[0040] Throughout the specification, unless otherwise specified, terms such as "first", "second" or "A", "B" are used to distinguish the same terms.

[0041] In the present specification, the meaning that B is on A means that B is directly on A or B is on A and other layers are further provided between B and A, and the explanation is not limited to the meaning that B is in a position in contact with the surface of A.

[0042] In the present specification, unless otherwise specified, the singular form is explained to include the meaning of the singular or plural explained in the context.

[0043] In the present specification, if not specifically indicated, ppm is based on weight.

[0044] In the present specification, room temperature is any one of about 20°C to about 25°C.

[0045] In the present specification, humidity means relative humidity.

[0046] In the present specification, the intensity of light refers to the intensity of a light source.

[0047] Hereinafter, the present embodiment will be described in detail.

[0048] Method for manufacturing a laminate

[0049] To achieve the above object, a method for manufacturing a laminate according to one embodiment of the present embodiment includes a preparation step and a carbonic acid water cleaning step.

[0050] The method for manufacturing a laminate can include a light shielding film manufacturing step, a preparation step, and a carbonic acid water cleaning step.

[0051] The method for manufacturing a laminate can include a preparation step, an ultraviolet cleaning step, and a carbonic acid water cleaning step.

[0052] The method for manufacturing a laminate can include a light shielding film manufacturing step, a preparation step, an ultraviolet cleaning step, and a carbonic acid water cleaning step.

[0053] The method for manufacturing a laminate can include a preparation step, a carbonic acid water cleaning step, and a rinse step.

[0054] The method for manufacturing a laminate can include a light shielding film manufacturing step, a preparation step, a carbonic acid water cleaning step, and a rinse step.

[0055] The method for manufacturing a laminate can include a preparation step, an ultraviolet cleaning step, a carbonic acid water cleaning step, and a rinse step.

[0056] The method for manufacturing a laminate can include a light shielding film manufacturing step, a preparation step, an ultraviolet cleaning step, a carbonic acid water cleaning step, and a rinse step.

[0057] The preparation step is a step of preparing a processing object. The processing object is a laminate before processing, which is provided with a light shielding film to be described later.

[0058] The preparation step can include a process of setting and fixing the processing object in a chamber, or a process of setting a device provided with a plurality of processing objects in a chamber.

[0059] The ultraviolet cleaning step is a step of irradiating the processing object with ultraviolet light having a wavelength of 120 nm or more and less than 190 nm. The wavelength of the ultraviolet light can be 138 nm or more and less than 185 nm, or 154 nm or more and less than 178 nm.

[0060] The ultraviolet irradiation can be performed by a light source, and one or more light sources can be provided. In this case, light of uniform intensity can be irradiated to the entire surface of the substrate to be cleaned.

[0061] The ultraviolet cleaning step can be performed with a light amount of greater than or equal to 20 mW / cm 2 and less than or equal to 55 mW / cm 2 The ultraviolet cleaning step can be performed with a light amount of greater than or equal to 30 mW / cm 2 and less than or equal to 50 mW / cm 2 The ultraviolet cleaning step can be performed with a light amount of greater than or equal to 35 mW / cm 2 and less than or equal to 45 mW / cm 2 The ultraviolet cleaning step can be performed with a light amount of greater than or equal to 35 mW / cm 2 and less than or equal to 45 mW / cm 2 The ultraviolet cleaning step can be performed with a light amount of greater than or equal to 35 mW / cm 2 and less than or equal to 45 mW / cm 2

[0062] By the ultraviolet cleaning step, a compound that strongly absorbs wavelengths in the range of from about 100 nm to about 190 nm can be effectively removed before the next step is performed. Specifically, the ultraviolet cleaning step can transfer light energy to the organic material-containing particles or the like to induce cleavage of chemical bonds in the organic material, and promote decomposition and removal of the organic material-containing particles, thereby further improving the reliability of the entire manufacturing method.

[0063] The carbonic acid water cleaning step is a step of preparing a cleaned laminate by a carbonic acid water cleaning process of applying ultraviolet rays and carbonic acid water to a processing object.

[0064] In the carbonic acid water cleaning step, the following first cleaning, second cleaning, and third cleaning can be selectively applied.

[0065] The first cleaning is a process of simultaneously using ultraviolet rays and carbonic acid water.

[0066] In the carbonic acid water cleaning step, ultraviolet rays belonging to any wavelength in the range of from 190 nm to 290 nm can be applied. The ultraviolet rays can belong to any wavelength in the range of from 230 nm to 280 nm. In the carbonic acid water cleaning step, ultraviolet rays can be irradiated with a light amount of greater than or equal to 1 mW / cm 2 and less than or equal to 11 mW / cm 2 In the carbonic acid water cleaning step, ultraviolet rays can be irradiated with a light amount of greater than or equal to 3 mW / cm 2 and less than or equal to 10 mW / cm 2 In the carbonic acid water cleaning step, ultraviolet rays can be irradiated with a light amount of greater than or equal to 4 mW / cm 2 and less than or equal to 9 mW / cm 2 In this case, by using carbonic acid water together, it is possible to minimize damage to the substrate while effectively performing cleaning.

[0067] In the carbonic acid water cleaning step, carbonic acid water having a conductivity of 1 μS / cm or more and 10 μS / cm or less can be used. The carbonic acid water can have a conductivity of 2 μS / cm or more and 8 μS / cm or less. The carbonic acid water can have a conductivity of 3 μS / cm or more and 7 μS / cm or less. When carbonic acid water having the above conductivity is used, an excellent cleaning effect can be obtained while minimizing damage to the surface of the laminate.

[0068] In the carbonic acid water cleaning step, carbonic acid water can be supplied at a rate of 1500 ml / min to 4000 ml / min per 504 cm 2 of the area of the laminate. Also, the carbonic acid water can be supplied at a rate of 2000 ml / min to 3000 ml / min per 504 cm 2 of the area of the laminate. The carbonic acid water can be supplied through one nozzle, or can be supplied through two or more nozzles.

[0069] When ultraviolet rays and carbonic acid water are used in combination, damage to the surface of the laminate can be reduced while providing an excellent cleaning effect, and the efficiency of the process can also be improved.

[0070] While the carbonic acid water is used as the cleaning liquid, megasonics can also be used. When the cleaning liquid is sprayed through a nozzle, megasonics can be applied by a megasonic generator installed on the nozzle, but are not limited thereto.

[0071] When the front surface (surface exposing the light shielding film) of the laminate is cleaned, the megasonics can be applied at 0.5 MHz to 1.3 MHz and 5 W to 12 W. Also, when the back surface (surface exposing the quartz) of the laminate is cleaned, the megasonics can be applied at 1 MHz to 1.8 MHz and 20 W to 45 W. When megasonics are used in combination, cleaning can be performed more effectively.

[0072] The second cleaning is a process in which carbonic acid water and hydrogen water are used in combination. The second cleaning can be performed after the first cleaning. The second cleaning is a process in which cleaning is performed using carbonic acid water (DICO2) and hydrogen water (DIH2) as cleaning liquids in a volume ratio of 1:0.1 to 10, or 1:0.5 to 2. In this case, the detailed description of the carbonic acid water used is the same as described above, and thus the description thereof will be omitted.

[0073] Hydrogen water having a hydrogen content of 0.7 ppm to 3 ppm can be used, and hydrogen water having a hydrogen content of 0.9 ppm to 2 ppm can also be used.

[0074] The second cleaning step can also apply megasonic waves, and the details are the same as described above.

[0075] The third cleaning is a process of cleaning the surface using hydrogen water. In this case, the concentration of the hydrogen water, whether or not to apply megasonic waves, and the details of the conditions are the same as described above. The third cleaning is preferably performed together with the first cleaning or the second cleaning.

[0076] The rinsing step is a step of rinsing the laminate with carbonic acid water and / or hydrogen water.

[0077] In the rinsing step, carbonic acid water can be supplied to the back surface (the surface on which the quartz is exposed, the surface far from the light-blocking film) of the laminate at a rate of 500 ml / min to 2000 ml / min per 504 cm 2 of the area of the laminate.

[0078] In the rinsing step, carbonic acid water having a conductivity of 1 μS / cm or more and 10 μS / cm or less can be applied. The carbonic acid water can have a conductivity of 2 μS / cm or more and 8 μS / cm or less. The carbonic acid water can have a conductivity of 3 μS / cm or more and 7 μS / cm or less. The carbonic acid water having the same concentration as measured by the conductivity in the carbonic acid water cleaning step can be applied, or carbonic acid water having a different concentration can be applied.

[0079] In the rinsing step, ozone water can be applied. The ozone water is applied only to the treatment of the back surface of the laminate, and is not substantially applied to the treatment of the surface (the surface on which the light-blocking film is exposed). Thus, the change in the optical characteristics of the laminate caused by the cleaning can be more effectively controlled.

[0080] The ozone water can have an ozone concentration of 40 ppm to 120 ppm (weight standard). The ozone water can have an ozone concentration of 50 ppm to 110 ppm (weight standard), and can have an ozone concentration of 80 ppm to 105 ppm (weight standard). The ozone water can be prepared using an ozone generator manufactured by MKS Corporation.

[0081] The ozone water can be supplied to the back surface (the surface on which the quartz is exposed, the bottom surface of the light-blocking film) of the laminate at a rate of 300 ml / min to 1000 ml / min per 504 cm 2 of the area.

[0082] In the manufacturing method of the laminate, the ozone water is not additionally applied to the light-blocking film between the preparation step and the rinsing step. Thus, the chemical change or damage to the surface layer of the light-blocking film can be minimized.

[0083] The carbonated water and the hydrogen water described above are substantially free of ozone. The expression "substantially free of ozone" in the carbonated water and / or the hydrogen water includes a case where a trace amount of ozone is contained, which does not function as ozone water, and the concentration of the ozone can be, for example, 10 ppm or less.

[0084] When the carbonated water is applied or when the carbonated water and the hydrogen water are applied, the damage to the light-shielding film caused by ozone can be substantially suppressed. In addition, the change in the physical properties of the light-shielding film that can occur during cleaning and the like can be minimized.

[0085] This is considered to be due to the shape of the oxide film formed by the combination of the transition metal M and oxygen O. Specifically, this is considered to be because the oxide film is more stable when it exists in the form of M2O3. However, when the M2O3 oxide film encounters ozone, a part thereof can change to the form of MO3. The MO3 can cause damage to the surface of the light-shielding film itself or change the physical properties of the light-shielding film as a whole. This is considered to be because the M2O3 oxide film is less likely to be damaged or peeled off during cleaning, whereas the MO3 oxide film is relatively likely to be damaged or peeled off during cleaning.

[0086] By applying the carbonated water cleaning step and the like of the present embodiment, it is possible to provide a laminate that minimizes the damage to the light-shielding film or the change in the physical properties while reducing the detected trace foreign matter or residual ions as much as possible.

[0087] Detailed explanations regarding the laminate itself, such as the oxide form of the surface, the amount of the residual ions identified from the laminate after cleaning, will be described later in detail, and thus the relevant descriptions are omitted here.

[0088] The laminate includes a light-shielding film provided on a support, and can be manufactured by a light-shielding film manufacturing step using a sputtering method.

[0089] Since the detailed description of the support is repetitive of the description of the laminate described later, the detailed descriptions are omitted here.

[0090] The light-shielding film can be manufactured by a sputtering method.

[0091] The sputtering method is a method in which, after a target containing a transition metal is arranged, sputtering is performed in an atmosphere containing a reactive gas including a gas containing an oxygen atom, a gas containing a nitrogen atom, or a gas containing a carbon atom. The atmosphere can contain both the reactive gas and an inactive gas.

[0092] The target can use one target containing a transition metal.

[0093] The target can use two or more targets, one of which contains a transition metal.

[0094] The target material including a transition metal can include 90 at% or more of the transition metal. The target material including a transition metal can include 95 at% or more of the transition metal. The target material including a transition metal can include 99 at% of the transition metal.

[0095] The target material including a transition metal can be applied to a target material made of a transition metal included in a light shielding film. In this case, "made of a transition metal" means made of one kind of transition metal or mixed of two or more kinds. Among them, "made of a transition metal" includes a case where an unavoidable impurity is contained, and is strictly not interpreted as limited to only made of a transition metal.

[0096] The transition metal can include at least one of Cr, Ta, Ti, and Hf. The transition metal can include Cr.

[0097] The reactive gas reacts with the transition metal to form a sputtered film. As an example, any one selected from the group consisting of an oxide of a transition metal, a nitride of a transition metal, a carbide of a transition metal, and a combination thereof can form a light shielding film. The light shielding film can be an amorphous body as a whole, or an amorphous body partially including a crystal.

[0098] As an example of an oxygen atom-containing gas, oxygen, carbon oxide (CO, CO2, etc.), nitrogen oxide (NO, NO2, N2O, N2O3, etc.) can be cited. As an example of a nitrogen atom-containing gas, nitrogen, nitrogen oxide (NO, NO2, N2O, N2O3, etc.) can be cited. As an example of a carbon atom-containing gas, carbon oxide (CO, CO2, etc.) and methane, etc. can be cited. In order to cause the light shielding film to include an oxygen atom, it is preferable to use an oxygen-containing compound rather than oxygen itself, because it is easier to control the reaction at this time.

[0099] As a non-active gas, helium, argon, etc. can be applied, but are not limited thereto.

[0100] The sputtering is performed by i) placing a target material and a support in a chamber, injecting an atmosphere gas into the inside of the chamber, ii) supplying power to a sputtering device, iii) forming a film on the support with the transition metal particles separated from the target material together with oxygen, nitrogen, or carbon included in the reactive gas.

[0101] The separation of the transition metal particles can be performed by a sputtering gas. The sputtering gas refers to a gas that is ionized in a plasma atmosphere and collides with a target material.

[0102] The sputtering gas can be an Ar gas.

[0103] The power source for sputtering can use a DC power source, or an RF power source.

[0104] The power suitable for sputtering can be greater than or equal to 1.5 kW and less than or equal to 2.5 kW.

[0105] The light shielding film can be a light shielding film that has been subjected to heat treatment. The heat treatment process has the effect of improving physical properties, for example, can eliminate unnecessary stress generated in the film formation process of the light shielding film, and improve the smoothness of the light shielding film, etc.

[0106] When the heat treatment is performed in an atmosphere containing oxygen, a light shielding film surface layer having an increased oxygen content can be formed on the surface of the light shielding film.

[0107] When the heat treatment is performed in an atmosphere containing nitrogen, a light shielding film surface layer having an increased nitrogen content can be formed on the surface of the light shielding film.

[0108] The heat treatment can be performed at a temperature greater than or equal to 150°C and less than or equal to 330°C.

[0109] The heat treatment can be performed for greater than or equal to 5 minutes and less than or equal to 30 minutes.

[0110] The light shielding film manufactured by the above-described method has the properties described in detail in the layered body section.

[0111] The manufacturing method of the layered body can include a preparation step, an ultraviolet cleaning step, a carbonated water cleaning step, and a rinsing step as a cleaning process of the layered body.

[0112] Layered body

[0113] The layered body as a processing target includes a light shielding film.

[0114] The layered body as a processing target has a light shielding film disposed thereon.

[0115] Specifically, the layered body can include a light shielding film disposed on a support.

[0116] The light shielding film can entirely cover one surface of the support, or can cover only a portion thereof.

[0117] The support can be a light-transmissive substrate.

[0118] The support can be manufactured by disposing the light shielding film directly on the light-transmissive substrate.

[0119] The support can be manufactured by disposing a phase shift film on the light-transmissive substrate and disposing the light shielding film thereon.

[0120] The support can be partially provided with the light shielding film. Specifically, the light shielding film can be disposed on the light-transmissive substrate in direct contact with the light-transmissive substrate. Alternatively, the light shielding film can be disposed on a phase shift film disposed on the light-transmissive substrate. In addition, the support can be in a state described above in which the mixed light shielding film and phase shift film exist on one substrate.

[0121] The processing target can be a laminate including a light shielding film. The laminate can have an optical use. The processing target can be a photomask blank or a photomask.

[0122] The light-transmitting substrate can be a quartz substrate or the like. In this case, the light-transmitting substrate refers to a substrate having a transmittance of equal to or greater than 85% and less than or equal to 100% with respect to an exposure light source, which can be ArF light, but is not limited thereto.

[0123] The phase shift film can be any phase shift film applied to the field of photomasks. As an example, the phase shift film can include molybdenum and / or silicon, and can include oxides thereof or nitrides thereof.

[0124] The laminate can include, on a support, a portion (light-transmitting portion) having no phase shift film and a portion (phase shift portion) having a phase shift film at the same time. A phase difference between the light-transmitting portion and the phase shift portion can be about 160 degrees to about 230 degrees, and can be about 168 degrees to about 185 degrees.

[0125] The light shielding film can be a film containing a transition metal, oxygen, nitrogen, or carbon.

[0126] The transition metal can include at least one of Cr, Ta, Ti, and Hf. The transition metal can include Cr.

[0127] Specifically, the light shielding film can include any one element consisting of Cr, oxygen, nitrogen, carbon, and combinations thereof.

[0128] Specifically, the light shielding film can include any one selected from the group consisting of CrO, CrON, CrOCN, and combinations thereof.

[0129] The light shielding film can actually have a double-layer structure. As an example, a light shielding film surface layer in which the content of oxygen or nitrogen is increased can be formed on a side close to the surface of the light shielding film, in order to achieve the purpose of controlling the surface strength of the light shielding film or the like. In order to distinguish from the light shielding film surface layer, the light shielding film other than the light shielding film surface layer is referred to as a light shielding film bottom layer.

[0130] The light shielding film surface layer thickness can be 30 nm to 80 nm, and can be 40 nm to 70 nm. The light shielding film bottom layer and the light shielding film surface layer can have a thickness ratio of 1:0.02 to 0.25, and can have a thickness ratio of 1:0.04 to 0.18. However, it can not be possible to clearly observe the boundary between the light shielding film surface layer and the light shielding film bottom layer. In this case, a region having less than or equal to 25 atomic% can be regarded as the light shielding film surface layer.

[0131] By performing the above-described carbonic acid water cleaning step on the surface layer of the light shielding film, the physical property change before and after the cleaning process can be minimized, and the damage to the surface layer of the light shielding film can be substantially inhibited.

[0132] The thickness change of the laminate before the preparation step and the laminate after the carbonic acid water cleaning step can be equal to or greater than 0 A and equal to or less than 5 A. The thickness change can be equal to or greater than 0 A and equal to or less than 2 A, and can be equal to or greater than 0.1 A and equal to or less than 1.5 A. The thickness change shows a tendency of thickness reduction. This is considered to be caused by the detachment of some metal oxides due to the above-described oxidation reaction. However, the thickness change can also show a tendency of thickness increase, and is not limited to the thickness reduction.

[0133] The transmittance change of the laminate before the preparation step and the laminate after the carbonic acid water cleaning step can be equal to or greater than 0% and equal to or less than 0.05%. The transmittance change can be equal to or greater than 0% and equal to or less than 0.03%, and can be equal to or greater than 0% and equal to or less than 0.008%.

[0134] The optical density change of the laminate before the preparation step and the laminate after the carbonic acid water cleaning step can be equal to or greater than 0% and equal to or less than 0.1%. The optical density change can be equal to or greater than 0% and equal to or less than 0.05%, and can be equal to or greater than 0% and equal to or less than 0.01%. The optical density change shows a tendency of optical density reduction, which is considered to be related to the above-described thickness change. However, the optical density change is not limited to the optical density reduction.

[0135] The reflectance change of the laminate before the preparation step and the laminate after the carbonic acid water cleaning step (after the treatment) can be equal to or greater than 0% and equal to or less than 0.5%. The reflectance can be equal to or greater than 0% and equal to or less than 0.25%.

[0136] The laminate after the treatment (after the cleaning) can be a laminate in which ultrafine particles having a size equal to or greater than 50 nm are substantially not detected. At this time, "substantially not detected" means that, when one laminate is examined, the number of detected ultrafine particles is two or less, one or less, or none.

[0137] The residual ion content of the laminate after the treatment can also be controlled as described below. At this time, "the residual ion content is in trace amounts" means that the residual ion content measured by a specific method is less than the content described below.

[0138] The laminate of the present embodiment is characterized in that the residual ion content measured by ion chromatography is in trace amounts.

[0139] Ultrafine particles adsorbed on the laminate and not completely removed even during the cleaning process or ions remaining on the laminate can adversely affect the quality of the laminate. During the process of applying the laminate, elements that become unstable due to repeated energy irradiation of the laminate can move to the surface, and the remaining ions inside the laminate can unexpectedly react with other ions. At this time, particulate impurities can be formed or haze can be generated in a portion of the laminate.

[0140] When the content of the remaining ions detected during the inspection after cleaning is in trace amounts, the formation of particulate impurities and / or the generation of haze can be reduced. In addition, in recent years, as semiconductor designs have developed in a more fine direction, inhibiting the formation of particulate impurities and inhibiting the generation of haze have been evaluated as more important properties.

[0141] According to the method described in the examples, the remaining ions are measured using ion chromatography. Hereinafter, the measurement process of the remaining ions is briefly described: 1 laminate stored in a product storage box is put into a dust-free bag, 100 ml of deionized water is injected, and the dust-free bag is transferred to a prepared 90°C water tank. Next, it is left for 120 minutes to allow the ions to sufficiently escape from the surface of the laminate. The deionized water recovered from the dust-free bag is detected by ion chromatography and its concentration is quantified. The size standard of the applied laminate is about 5 inches to about 7 inches in length, about 5 inches to about 7 inches in width, and about 0.1 inches to about 0.5 inches in height, and different contents can be applied in proportion to the size (surface area) of the laminate, etc.

[0142] The remaining ions can include sulfur-based ions.

[0143] The sulfur-based ions include SOx, such as sulfate ions (SO4 2- ).

[0144] The remaining ions can include nitric acid-based ions.

[0145] The nitric acid-based ions include NOx, such as nitrite ions (NO2 - ) and nitrate ions (NO3 - ).

[0146] The content of the sulfur-based ions can be about 0.1 ng / cm 2 Hereinafter, it can be about 0.8 ng / cm 2 . The content of the sulfur-based ions can be about greater than 0 ng / cm 2 , about greater than 0.1 ng / cm 2 , about greater than 0.3 ng / cm 2 .

[0147] The content of the nitrate-based ions can be about 0.1 ng / cm 2 The content of the nitrate-based ions can be about 0.05 ng / cm 2 The content of the nitrate-based ions can be about more than 0 ng / cm 2 The content of the nitrate-based ions can be about more than 0.1 ng / cm 2 .

[0148] The content of the sulfur-based ions and the nitrate-based ions as described above is an excellent degree of residual ions suitable for applying the laminate as a photomask, and in particular, haze that can be generated in a process using the photomask can be substantially suppressed.

[0149] The residual ions can include halogen ions.

[0150] The halogen ions can include fluorine ions, chlorine ions, or both.

[0151] The content of the halogen ions can be about 0.1 ng / cm 2 The content of the halogen ions can be about 0.05 ng / cm 2 The content of the halogen ions can be about 0.03 ng / cm 2 The content of the halogen ions can be about more than 0 ng / cm 2 The content of the halogen ions can be about more than 0.01 ng / cm 2 The content of the halogen ions can be about more than 0.03 ng / cm

[0152] When chromium is included as a transition metal, the content of the halogen ions can be high. This is believed to be due to the high affinity of chromium for chlorine ions and the like, and thus chlorine ions and the like in the air or a processing liquid are attracted.

[0153] The residual ions can include ammonium ions.

[0154] The content of the ammonium ions can be about 1.0 ng / cm 2 The content of the ammonium ions can be about 0.7 ng / cm 2 The content of the ammonium ions can be about 0.5 ng / cm 2 The content of the ammonium ions can be about more than 0 ng / cm 2 The content of the ammonium ions can be about more than 0.1 ng / cm 2 The content of the ammonium ions can be about more than 0.3 ng / cm 2 When the content of the ammonium ions is within the above range, generation of particulate impurities or haze can be substantially suppressed.

[0155] The residual ions can include sulfur-based ions, nitrate-based ions, halogen ions, and ammonium ions, and in particular, SO4 2- , NO2 - , NO3 - , Cl -and NH4 + called ion impurities.

[0156] The content of the ion impurities can be about 1.5 ng / cm 2 below, can be about 1.0 ng / cm 2 below, can be about 0.7 ng / cm 2 below. The content of the ion impurities can be about more than 0 ng / cm 2 , can be about more than 0.1 ng / cm 2 , can be about more than 0.3 ng / cm 2 .

[0157] This is considered to be a laminate having these properties extremely well controls the content of ion impurities in a state where a light shielding film has been formed, and when such a laminate is used as a photomask or the like, defects can be more easily controlled.

[0158] The residual ions can include sodium ions.

[0159] The residual ions can include phosphate ions.

[0160] The residual ions can include potassium ions.

[0161] The residual ions can include magnesium ions.

[0162] The residual ions can include calcium ions.

[0163] The sum of the content of the sodium ions, the content of the phosphate ions, the content of the potassium ions, the content of the magnesium ions, and the content of the calcium ions can be about 0 ng / cm 2 above and about 0.01 g / cm 2 below. In this case, the residual ion concentration of the laminate is well controlled, and thus a photomask can be provided which significantly reduces the possibility of occurrence of particle defects and haze.

[0164] The reflectance of the light shielding film with respect to an exposure light source can be about 35% or less, can be about 30% or less. The reflectance can be about 20% or more, can be about 23% or more, can be about 25% or more.

[0165] The exposure light source can be light having a wavelength of about 193 nm.

[0166] The exposure light source can be ArF light.

[0167] The light-shielding film is used to block at least a part of light of a target wavelength. Therefore, the light-shielding film can have a relatively high surface reflectance as compared with a light-transmitting film. However, when the reflectance of the light-shielding film is too high, the accuracy of the inspection result for checking whether the laminate has a defect or the like can be reduced. The inspection process is a process for checking a surface defect of the light-shielding film, the presence or absence of impurities, and the like, and is a process applied to a manufacturing process of a photomask blank. That is, if the surface reflectance of the light-shielding film is too high, the reliability of the laminate can be reduced. Therefore, it is necessary to adjust the surface reflectance of the light-shielding film. The inspection light can be applied similarly to or differently from the exposure light source, but the reflectance is described above on the basis of the exposure light source.

[0168] In order to adjust the surface reflectance of the light-shielding film and obtain an effect of improving durability or the like, different controls can be performed on the properties of the light-shielding film surface layer and the light-shielding film bottom layer. For this purpose, a laminate in which the light-shielding film surface layer has a higher distribution of oxygen or nitrogen than the light-shielding film bottom layer can be used, or a method in which an oxidation treatment or a nitriding treatment is performed on the surface of the light-shielding film that has been formed can be used.

[0169] When the light-shielding film contains a compound in the form of M2O3 (M is a transition metal, and O is oxygen), a part thereof can be changed to the form of MO3 by an oxidation treatment or the like. For example, when chromium is used as the transition metal, a part of Cr2O3 is changed to CrO3 under the influence of an oxidation treatment, cleaning, or the like, and thus the CrO3 content of the light-shielding film surface layer can actually increase. Since Cr2O3 is relatively more resistant to external force or damage, CrO3 is more easily damaged than Cr2O3. Therefore, a light-shielding film containing a large amount of CrO3 is easily damaged in the film itself during cleaning or the like. This can cause changes in various optical properties, such as a change in thickness, a change in optical density, a change in transmittance, and a change in reflectance. In addition, this is considered to be a change that occurs more easily in a light-shielding film containing a large amount of CrO3 when a relatively strong oxidation cleaning treatment is performed. However, if the cleaning is insufficient, the residual ions or impurities can not be sufficiently removed from the laminate.

[0170] The light-shielding film is manufactured by the manufacturing method described above including a cleaning process, and the like, thereby providing a manufacturing method of a laminate that reduces the content of impurities or residual ions while minimizing changes in optical properties such as reflectance of the light-shielding film.

[0171] The light-shielding film contains at least one of a transition metal, oxygen, and nitrogen.

[0172] The light shielding film can include about 35 at% or more of a transition metal, can include about 40 at% or more, can include about 45 at% or more, can include about 50 at% or more. The light shielding film can include about 75 at% or less of a transition metal, can include about 70 at% or less, can include about 65 at% or less, can include about 60 at% or less. In this case, the content of the transition metal of the light shielding film refers to an average value of the content of the transition metal in the entire light shielding film including the bottom layer of the light shielding film and the surface layer of the light shielding film.

[0173] The light shielding film can include about 15 at% or more of oxygen, can include about 20 at% or more of oxygen, can include about 25 at% or more of oxygen. The light shielding film can include about 55 at% or less of oxygen, can include about 50 at% or less of oxygen, can include about 45 at% or less of oxygen. In this case, the content of oxygen of the light shielding film refers to an average value of the content of oxygen in the entire light shielding film including the bottom layer of the light shielding film and the surface layer of the light shielding film.

[0174] The light shielding film can include about 15 at% or more of nitrogen, can include about 20 at% or more of nitrogen, can include about 25 at% or more of nitrogen. The light shielding film can include about 55 at% or less of nitrogen, can include about 50 at% or less of nitrogen, can include about 45 at% or less of nitrogen. In this case, the content of nitrogen of the light shielding film refers to an average value of the content of nitrogen in the entire light shielding film including the bottom layer of the light shielding film and the surface layer of the light shielding film.

[0175] The light shielding film can include about 1 at% or more of carbon, can include about 2 at% or more of carbon, can include about 3 at% or more of carbon. The light shielding film can include about 10 at% or less of carbon, can include about 8 at% or less of carbon. In this case, the content of carbon of the light shielding film refers to an average value of the content of carbon in the entire light shielding film including the bottom layer of the light shielding film and the surface layer of the light shielding film.

[0176] The surface layer of the light shielding film can include about 10 at% or more of a transition metal, can include about 15 at% or more of a transition metal, can include about 20 at% or more of a transition metal. The surface layer of the light shielding film can include about 45 at% or less of a transition metal, can include about 40 at% or less of a transition metal, can include about 35 at% or less of a transition metal, can include about 30 at% or less of a transition metal.

[0177] The surface layer of the light shielding film can include about 35 at% or more of oxygen, can include about 40 at% or more of oxygen, can include about 42 at% or more of oxygen. The surface layer of the light shielding film can include about 65 at% or less of oxygen, can include about 60 at% or less of oxygen, can include about 55 at% or less of oxygen, can include about 50 at% or less of oxygen.

[0178] The surface layer of the light-shielding film may include more than 1 at% nitrogen, more than 3 at% nitrogen, or more than 5 at% nitrogen. The surface layer of the light-shielding film may include less than 25 at% nitrogen, less than 20 at% nitrogen, or less than 15 at% nitrogen.

[0179] The surface layer of the light-shielding film may include more than 3 at% carbon, more than 5 at% carbon, or more than 10 at% carbon. The surface layer of the light-shielding film may include less than 35 at% carbon, less than 30 at% carbon, or less than 25 at% carbon.

[0180] The following will describe the invention in more detail through specific embodiments. These embodiments are merely examples to aid in understanding the invention, and the scope of the invention is not limited thereto.

[0181] Experimental Example: Manufacturing Example

[0182] Manufacturing laminates with light-shielding films

[0183] An identical substrate is fabricated on a synthetic quartz light-transmitting substrate that is 6 inches wide, 6 inches long, and 0.25 inches thick. This identical substrate has a phase-shifting film with a phase difference of about 180° for light with a wavelength of 193 nm, and is applied to the manufacturing process of the light-shielding film described below.

[0184] The phase-shifted film is fabricated by sputtering, during which excess nitrogen gas is introduced to induce the formation of high-concentration NH4, thereby inhibiting No2. x The formation of the film is as follows: Specifically, a phase-shifting film containing molybdenum (Mo) and silicon (Si) is formed by reactive sputtering using a target with a Mo and Si composition ratio of 10.75 at% and 89.25 at%, respectively. The film formation process is carried out by sputtering while applying a power of 2 kW, supplying gas, and rotating the light-transmitting layer. During film formation, gas is injected to maintain a nitrogen (N2) and argon balance of 70 vol%, and the surface ammonium concentration is treated to 50 ng / cm³. 2 Up to 110 ng / cm 2 The phase-shifted film formed through the above process was heat-treated at 400°C for 40 minutes, followed by cooling at 25°C for 40 minutes.

[0185] Similarly, a light-shielding film is prepared by sputtering.

[0186] The substrate with the phase-shifted film formed was placed in the chamber of a DC sputtering apparatus. The T / S distance of the chromium target was set to 255 mm, and the angle between the substrate and the target was set to 25 degrees. Nitrogen (N2) and carbon dioxide (CO2) in a volume ratio of 1:3 to 3.5 were used as the atmosphere gases. The power applied during film formation was approximately 1.5 kW to approximately 1.85 kW.

[0187] Sputtering was performed while rotating the substrate to form a light-shielding film containing chromium. Next, a heat treatment was performed at a temperature of 2000C to 3000C for 15 minutes, and the light-shielding film on which the heat treatment had been completed was cooled with dry air for 5 minutes in an atmosphere of 20°C to 30°C. The light-shielding film was formed to have a total thickness of about 460 A to about 580 A on the phase shift film to prepare a laminate.

[0188] The elemental content of the light-shielding film thus formed was 35.5 atomic % to 41.9 atomic % of chromium, 8.4 atomic % to 10.5 atomic % of nitrogen, 33.0 atomic % to 36.3 atomic % of oxygen, and 14.0 atomic % to 15.4 atomic % of carbon, the content depending on the thickness. A trace amount of Si (0 atomic % to 6.5 atomic %) was detected.

[0189] Cleaning of the light-shielding film: Example

[0190] (1) UV cleaning step

[0191] UV (ultraviolet, wavelength 172 nm) electromagnetic radiation was irradiated by the UV treatment method under uniform radiation exposure conditions of room temperature (23°C) and humidity of 45% ± 5%. The irradiation was performed at a high power of 40 mW / cm 2 using N2, O2, etc. as process gas to prevent recombination of the source of contamination on the mask surface by strong exhaust (0.01 kPa to 1 kPa) or backflow contamination caused by bounce back during the process. By this UV treatment, compounds strongly absorbing wavelengths in the range of about 100 nm to about 190 nm were removed in advance before the subsequent cleaning process.

[0192] (2) Carbonate water cleaning step

[0193] Cleaning was performed (first cleaning) using UV (wavelength 254 nm) and carbonate water (DICO2) as the cleaning liquid at the same time.

[0194] At this time, when cleaning was performed using the carbonate water or the like as the cleaning liquid, megasonics were applied at the same time, and megasonics were also applied when the cleaning liquid was sprayed through a nozzle. When the surface (light-shielding surface) of the laminate was cleaned, megasonics of 1 MHz, 10 W were used, and when the back surface (quartz surface) of the laminate was cleaned, megasonics of 1.5 MHz, 40 W were applied together with the cleaning liquid. At this time, the carbonate water having an electric conductivity of 3 μS / cm to 6 μS / cm was used.

[0195] Next, the surface was cleaned using a cleaning solution containing hydrogen water and carbonic acid water (second cleaning). The hydrogen water was applied with a hydrogen concentration of 1.0 ppm to 2.0 ppm. The concentration of the carbonic acid water, the application of megasonics to the front and back surfaces, and the like were the same as described above. The hydrogen water and the carbonic acid water were applied in a volume ratio of 4:3.

[0196] After that, the surface was cleaned with hydrogen water (DI H2) (third cleaning). The hydrogen ion concentration of the hydrogen water and the application of megasonics were as described above.

[0197] (3) Rinsing Step

[0198] After the cleaning was completed, the surface was rinsed with carbonic acid water (DI CO2) and dried by a ramp-up method.

[0199] Cleaning of Light-Shielding Film: Comparative Example

[0200] Except that carbonic acid water (DI CO2) was not added during the cleaning, all other processes were performed in the same manner as the cleaning method described above.

[0201] The properties of the light-shielding film before and after the cleaning were measured and are shown in Table 3 below.

[0202] Experimental Example: Measurement Example 1

[0203] Sampling and Pretreatment

[0204] Storage / Pretreatment Conditions: The product was stored in a product shipping box, unloaded through a shipping box port, and loaded into a pod. All samples were placed in separate containers and processed individually, and the completed cleaning stack was placed in a separate cleaning product shipping box to be subjected to ion chromatography (IC) inspection. Except for the change in the process conditions (control variable) for evaluation, all other conditions (control variables) were performed in the same manner.

[0205] Ion Chromatography Evaluation

[0206] The evaluation was performed using a Dionex ICS-2100 ion chromatography model from Thermo SCIENTIFIC, Inc. in the following manner. The same method was applied to each sample in Table 1.

[0207] Extraction of Ions: Immediately after opening the product shipping box, the prepared stack sample stored in a dust-free bag was placed and 100 ml of deionized water was injected. The dust-free bag containing the sample was loaded into a prepared water bath at 90°C so that the ions on the surface of the stack sufficiently escaped for 120 minutes.

[0208] Elution: Eluent is obtained to facilitate ion elution, followed by Isocratic to maintain the concentration and composition of the eluent constant during the subsequent process.

[0209] Measurement: The eluent and sample are injected into a measurement device to separate and detect ions.

[0210] Ion exchange column: Dinex ICS-2100 ion chromatography model from Thermo Scientific was used to quantify ion concentration using information obtained from the conductivity of separated ions and the retention time (RT) of ions, the results of which are shown in Tables 1 and 2 below, respectively.

[0211] Experimental Example: Measurement Example 2

[0212] Sampling and Pretreatment

[0213] Storage / Pretreatment Conditions: All stacks were placed in separate wafer boxes and processed individually, and the completed cleaning stacks were placed in separate completed cleaning wafer boxes to be subjected to ellipsometer measurement, all conditions (control variables) were performed in the same way except for the change in process conditions (control variables) for evaluation.

[0214] Ellipsometer Evaluation

[0215] Measurement of 7x7 points (total 49 points) of the sample was performed using the MG-PRO model of Nanoview.

[0216] Measurement Results

[0217] Residual Ion Content

[0218] The ion chromatography (IC) test results are shown in Tables 1 and 2 below. The measurement results of the sample subjected to carbonated water cleaning as an example and the sample not using carbonated water as a comparative example will be shown.

[0219] The calculation of ion content follows the following manner.

[0220] ng / stack = (IC analysis result - Blank) * DIW amount,

[0221] ng / cm 2 = (ng / stack) / 504 (stack area, cm 2 )

[0222] ppb = 100 ml reference.

[0223] Table 1

[0224]

[0225] Table 2

[0226]

[0227] Experimental Examples: Additional Comparative Example and Measurement Example 3

[0228] (Additional Comparative Example)

[0229] A light shielding film was formed and cleaned in the same manner as in the above-described example, but ozone water was used instead of carbonic acid water as the cleaning liquid. The ozone concentration of the ozone water was 80 ppm to 105 ppm.

[0230] In the additional comparative example, the change in the optical characteristics and the like before and after cleaning was evaluated in the same manner as in the above-described example.

[0231] Change in optical characteristics and the like before and after cleaning

[0232] In the present example, the change in the thickness and the optical performance before and after cleaning of the laminate was confirmed through a total of 23 repeated experiments, and the results are shown in Table 3. Also, in the additional comparative example, the change in the thickness and the optical performance before and after cleaning was confirmed through a total of 15 experiments, and the results are shown in Table 4.

[0233] Table 3

[0234]

[0235] Table 4

[0236]

[0237] Referring to Tables 1 and 2, it can be seen that the generation of ions that can cause haze was suppressed when the laminate cleaned using carbonic acid water was used as a photomask. Also, referring to Tables 3 and 4, it can be seen that after cleaning using carbonic acid water, excellent activity in removing impurities and ions was exhibited, and the film changed very little. When compared with the additional comparative example using ozone, the effect was more pronounced, and even when a laminate including a light shielding film manufactured in the same manner was used, differences occurred depending on the cleaning process, for example, the thickness changed by about 2 times, the light transmittance changed by about 10 times, and the optical density changed by about 7 times.

[0238] Although preferred embodiments of the present application have been described in detail above, the scope of the present application is not limited to this, and various modifications and improvements made by those skilled in the art using the basic concept of the present application as defined in the appended claims should also be included in the scope of the claims of the present application.

Claims

1. A method for manufacturing a laminate, wherein comprises: a preparation step of preparing a processing object, the processing object being a laminate before processing provided with a light-shielding film, and a carbonic acid water cleaning step of preparing a cleaned laminate by using a first cleaning of applying ultraviolet rays and carbonic acid water to the processing object; the light-shielding film contains a transition metal, and further contains oxygen, nitrogen, or carbon, the method further comprises, before the carbonic acid water cleaning step, an ultraviolet cleaning step, the ultraviolet cleaning step is a step of irradiating the processing object with ultraviolet rays having a wavelength of 120 nm or more and less than 190 nm, the carbonic acid water cleaning step further comprises a step of using a second cleaning to the laminate that has been subjected to the first cleaning, the second cleaning is a process of applying carbonic acid water and hydrogen water together as a cleaning liquid to the processing object, and in the carbonic acid water cleaning step, the carbonic acid water has a conductivity of 1 μS / cm or more and 10 μS / cm or less, the laminate subjected to the carbonic acid water cleaning step has a residual ion content measured by ion chromatography, the residual ions including a sulfur-based ion, a nitric acid-based ion, and an ammonium ion, The content of the sulfur-based ions is greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 , The content of said nitrate-based ions is greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 , the content of the ammonium ion is greater than 0 ng / cm 2 and less than or equal to 1 ng / cm 2 .

2. The method for manufacturing a laminate according to claim 1, wherein the light-shielding film is manufactured by a light-shielding film manufacturing step using a sputtering method, the sputtering method is a method of performing sputtering in a reactive gas after disposing a target material containing a transition metal, the reactive gas including a gas containing an oxygen atom, a gas containing a nitrogen atom, or a gas containing a carbon atom.

3. The method for manufacturing a laminate according to claim 1, wherein In the first cleaning, ultraviolet light is irradiated at any one wavelength in 190 nm to 290 nm at a light amount of 1 mW / cm 2 to 11 mW / cm 2 .

4. The method for manufacturing a laminate according to claim 1, wherein in the carbonic acid water cleaning step, the carbonic acid water is used together with megasonic waves.

5. A laminate, wherein as a laminate provided with a light-shielding film, the light-shielding film contains a transition metal, and further contains at least one of oxygen and nitrogen, the light-shielding film has a reflectance of 35% or less for light having a wavelength of 193 nm, the laminate is manufactured according to the method for manufacturing a laminate according to claim 1, and the laminate has a residual ion content measured by ion chromatography, the residual ions including a sulfur-based ion, a nitric acid-based ion, and an ammonium ion, the content of the sulfur-based ions is greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 , The content of said nitrate-based ions is greater than 0 ng / cm 2 and less than or equal to 0.1 ng / cm 2 , the content of the ammonium ion is greater than 0 ng / cm 2 and less than or equal to 1 ng / cm 2 .

6. The laminate according to claim 5, wherein the residual ions include ionic impurities, the ionic impurities being the sulfur-based ion, the nitric acid-based ion, a halogen ion, and an ammonium ion, The content of the ion impurities is greater than 0 ng / cm 2 and less than or equal to 1.5 ng / cm 2 .

7. The laminate according to claim 5, wherein the residual ions further include a sodium ion, a phosphate ion, a potassium ion, a magnesium ion, and a calcium ion, the sum of the sodium ion content, the phosphate ion content, the potassium ion content, the magnesium ion content, and the calcium ion content is less than or equal to 0.01 ng / cm 2 .

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