JP2011053013A - Method of inspecting nanoimprint molding laminate - Google Patents

Abstract

To provide an inspection method capable of simply and quickly performing non-destructive defect inspection and film thickness measurement of a nanoimprint molded laminate.
An inspection method of the present invention irradiates a substrate having a film layer made of a resist material molded by a nanoimprint method using a mold mold with light having an excitation wavelength that causes the resist material to emit light. Step (1) for obtaining light emission from a film layer made of a molded resist material as a light emission pattern image, and the light emission pattern image obtained by repeatedly molding the light emission pattern image with a pattern image of a mold mold used for molding or the same mold mold Compare the pattern image with a different light emission pattern image and detect the difference in the image as a defect (2) and / or analyze the light emission pattern image by the light emission intensity and measure the film thickness from the value of the light emission intensity And a film thickness measurement step (3) to be useful for quality control in the manufacture of semiconductors, wiring boards, electronic devices, optical devices and the like.
[Selection] Figure 1

Description

  The present invention relates to a method for inspecting a nanoimprint molding laminate when a resist material on a substrate is molded by a microfabrication method nanoimprint lithography.

In 1995, nanoimprint technology was proposed by Professor Chou and others of Princeton University (Non-patent Document 1). The nanoimprint technology is roughly classified into a thermal nanoimprint lithography method including a heating and cooling process and an optical nanoimprint lithography method including an ultraviolet irradiation process (Non-Patent Document 2).
In the thermal nanoimprint lithography, a thin film of a thermoplastic polymer such as poly (methyl methacrylate), poly (styrene), polycarbonate, polyolefin polymer or the like is formed on a solid substrate, and then heated to increase the thermoplastic property. The molecule is softened, a mold mold having an uneven shape is pressed against the thermoplastic polymer, and the mold is released after cooling. As a result, the concave / convex shape paired with the concave / convex shape of the mold mold is transferred / molded onto the thin film layer made of the thermoplastic polymer on the substrate.
Next, the polymer thin film (hereinafter sometimes referred to as the remaining film) remaining in the concave portion of the thin film layer formed into the uneven shape is removed by reactive ion etching treatment or UV-O ₃ treatment. Thus, only the underlying substrate in the concave portion is exposed, and the underlying substrate in the convex portion is protected by the coating of the thermoplastic polymer thin film.
Hereinafter, the polymer thin film that protects the underlying substrate may be referred to as a resist material or a resist film. In addition, the ability of the polymer thin film to protect the underlying substrate may be referred to as a resist function.
Subsequently, in a dry or wet etching process, the underlying substrate exposed in the recess is shaved to produce an underlying substrate having a fine pattern. A substrate having a fine pattern may be produced by depositing a functional substance such as a metal in an exposed concave portion by a plating process of electroless plating or electrolytic plating, sputtering, or the like instead of the etching process.
In the production of a substrate having such a fine pattern, it is important to ensure and manage the uniformity of the film thickness of the remaining film present in the concave portion of the nanoimprint molding and the polymer thin film of the convex portion.

In general, the film thickness of the remaining film in the recesses is about several nanometers to several hundred nanometers although it varies depending on the nanoimprint molding conditions. If the film thickness of the remaining film in the recesses is uneven, for example, when the remaining film is removed by reactive ion etching or the like to expose the underlying substrate, a thick remaining film can be removed. Since the film may not be removed, the underlying substrate is not exposed, causing defects in subsequent steps. On the other hand, if the thick residual film is removed, the convex polymer thin film is also removed from the surface and thinned, and the resist function of the polymer thin film remaining on the convex part in the subsequent etching process cannot be maintained. Cause.
The uneven film thickness of the residual resist film or the convex resist film of the above-described resist material is caused by a difference in thickness or waviness in a long period derived from the underlying substrate, or a difference in uneven pattern density in the same mold (Non-Patent Document 3). ), Nanoimprint molding conditions (time to reach a constant pressure, holding time at a constant pressure), and differences in kinematic viscosity of resist materials. Further, since the resist material is molded by bringing the mold into contact with the mold, there is a possibility that the resist material may adhere to the mold and foreign matter such as dust may adhere to the mold when the molding is repeatedly performed.

As described above, the uniformity of the initial film thickness of the polymer thin film functioning as a resist material, the film thickness of the concave and convex polymer thin films after nanoimprint molding, the presence or absence of pattern defects, the concave film after the residual film removal step It can be said that simple confirmation and inspection of the presence or absence of the remaining film is an indispensable technique for producing a fine pattern using the nanoimprint method in terms of product management.
For example, the uniformity of the initial film thickness of the polymer thin film on the base substrate can be determined by infrared reflection or transmission absorption device, stylus type surface roughness meter, atomic force microscope (AFM), scanning electron microscope (SEM), optical It can be evaluated by a formula film thickness measuring device.
In addition, the film thickness of the concave film after the nanoimprint molding, the film thickness of the convex polymer thin film, and the film thickness of the concave film after the residual film removal process are measured with a stylus type surface roughness meter, AFM, SEM, optical It can be measured with a film thickness measuring device.
However, since the stylus type surface roughness meter, AFM, and SEM are destructive inspections, the polymer thin film after inspection by these devices cannot be used for nanoimprint molding.
In addition, the stylus type surface roughness meter, AFM, and SEM are not suitable for destructive inspection but also for measurement of a local region, and it takes a long time to measure a film thickness in a wide region. The optical film thickness measuring device is a non-destructive inspection. However, since one measuring area needs to have a diameter of about 5 μm, it cannot be measured unless the film thickness of the measuring area is optically uniform. Is not uniform, it is difficult to evaluate the uneven pattern shape having a horizontal resolution of several tens of μm or less.
Further, the inspection of the non-uniformity of the film thickness over a wide area can be performed by acquiring the reflected light of visible light as an image. However, in order to perform local microscopic examination at the same time, it is necessary to use the above-described other examinations together.
Therefore, in the measurement of the uniformity of the initial film thickness of the polymer thin film, the film thickness of the concave film after nanoimprint molding, the film thickness of the convex film after nanoimprint molding, the film thickness of the concave film after the residual film removal step, It has been difficult to simultaneously perform evaluation in a local area and evaluation in a wide area.

Similar to the nanoimprint technique described above, there are a photolithography method and an inkjet printing method as a method for producing a fine pattern of a resist material on a substrate.
As a method for inspecting a defect of a fine pattern manufactured by these methods, a method of inspecting a pattern defect by using a light emission of the fluorescent material or the like by containing a fluorescent material or the like in a resist material (Patent Documents 1 to 4) Is known.
However, these inspection methods only inspect whether there is a defect, and there is no description about a technique for quantitatively performing film thickness management unique to the nanoimprint technique.
As described above, in thermal nanoimprint lithography, the uniformity of the initial film thickness of the polymer thin film after nanoimprint molding, the film thickness after nanoimprint molding, and the film thickness after the remaining film removal process can be easily and quickly inspected. Development is desired.

JP 2003-243290 A JP 2000-146853 A JP-A-9-257640 JP-A-6-43110

S. Y. Chou, et al., Applied Physics Letters, 67, 3114 (1995) J. Haisma, M. Verheijien and K. Heuvel, J. Vac. Sci. Technol. B, 14, 4124 (1996). N. Chaix, S. Landis, D. Hermelin, T. Leveder, C. Perret, V. Delaye and C. Gourgon, J. Vac. Sci. Technol. B 24, 3011, (2006).

  The subject of this invention is providing the inspection method of the nanoimprint laminated body which can perform the defect inspection and film thickness measurement of a nanoimprint molding laminated body simply and rapidly without destruction.

According to the present invention, a substrate having a film layer made of a resist material molded by a nanoimprint method using a mold mold is irradiated with light having an excitation wavelength that causes the resist material to emit light, and the molded resist material on the substrate A step (1) of acquiring light emission from a film layer comprising:
The light emission pattern image acquired in step (1) is compared with a light emission pattern image that is different from the light emission pattern image that is repeatedly molded with the mold image used in the molding or the same mold, and a difference between the images is detected as a defect. Defect detection process (2) and / or film thickness measurement process (3) for analyzing the light emission pattern image acquired in step (1) based on the light emission intensity and measuring the film thickness from the value of the light emission intensity
And a method for inspecting a nanoimprint molded laminate.
Moreover, according to this invention, the said resist material is a fluorescent resist composition containing a fluorescent substance, The inspection method of the said nanoimprint molding laminated body characterized by the above-mentioned is provided.
Furthermore, according to the present invention, there is provided the method for inspecting a nanoimprint molded laminate, wherein the analysis based on the emission intensity in the step (3) is performed with at least two different detection wavelengths.

  In the method for inspecting a nanoimprint molding laminate of the present invention, a resist material is made to emit light, and the light emission pattern is used for inspection by microscopic observation. In addition, defect inspection and film thickness measurement of the nanoimprint molding laminate can be performed simply and quickly. Such an inspection method is useful for quality control in manufacturing processes of semiconductors, wiring boards, electronic devices, optical devices, and the like.

It is a schematic explanatory drawing for demonstrating one Embodiment of the inspection method of the nanoimprint molding laminated body which concerns on this embodiment. It is the schematic which looked at the casting_mold | template mold 3 shown by FIG. 1 (b) from the downward direction. It is the schematic which looked at the board | substrate A shown by FIG. 2 is a copy of a light emission pattern image of the molded laminate A obtained in Example 1. It is a copy of the optical microscope photograph of the casting_mold | template mold used in order to produce molded laminated body AC. 4 is a copy of a light emission pattern image of the molded laminate B obtained in Example 2. 4 is a copy of a light emission pattern image of a molded laminate C obtained in Example 3. It is a copy of the optical microscope image which observed the shaping | molding laminated body A performed in the comparative example 1 with the optical microscope. It is a copy of the optical microscope image which observed the shaping | molding laminated body B performed in the comparative example 1 with the optical microscope. It is a copy of the optical microscope image which observed the shaping | molding laminated body C performed in the comparative example 1 with the optical microscope. 6 is a schematic diagram for explaining a pattern of a quartz mold used in Production Example 2. FIG. 12 is a chart showing the result of measuring the film thickness of a portion of the molded laminate D that forms a pair with the dotted line a-c shown in FIG. 11 using a reflection spectral film thickness meter in Comparative Example 2. 4 is a copy of a light emission pattern image of a molded laminate D obtained in Example 4. It is a chart which shows the result of having analyzed the emitted light intensity in two detection wavelengths between AB of the light emission pattern image of the molded laminated body D shown in FIG.

Hereinafter, modes for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. And this invention can be deform | transformed suitably and implemented within the range of the summary. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.
An inspection method for a nanoimprint molding laminate according to the present embodiment will be schematically described. FIG. 1 is a schematic explanatory diagram for explaining an embodiment of a method for inspecting a nanoimprint molding laminate according to the present embodiment.

The nanoimprint molding laminate subject to the inspection method of the present invention is a substrate having a film layer made of a resist material molded by a nanoimprinting method using a mold mold. For example, (c) in FIG. The molded laminate shown in FIG. 1 corresponds to the substrate A in FIG.
In the method of manufacturing a molded laminate, for example, first, a resist material is applied on a substrate 1 to produce a substrate having a film layer 2 made of the resist material (see FIG. 1 (A)). Second, a film layer 2 made of a resist material is formed on a substrate having a film layer 2 made of a resist material by a thermal nanoimprint method using a mold 3 to produce a molded laminate (before forming the thermal nanoimprint method: FIG. 1 (b), after thermal nanoimprint method molding: see FIG. 1 (c)).

The substrate 1 may be a substrate having a glass transition temperature higher than that of a thermoplastic polymer molded by a thermal nanoimprint method described later, and examples thereof include inorganic materials such as silicon, glass, quartz, alumina, and barium titanate. Or the board | substrate which consists of inorganic oxide, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, or those laminated bodies, a composite_body | complex is mentioned. When the finally obtained substrate is used as a wiring substrate for electronics, the substrate 1 is made of an inorganic or inorganic oxide material such as silicon, glass or quartz, polyimide, etc. from the viewpoint of smoothness, low expansion coefficient and insulation. A substrate made of a heat resistant organic material is preferred.
Moreover, the board | substrate 1 may have a metal thin film according to the objective, for example, consists of material selected from the group which consists of gold, silver, copper, nickel, aluminum, chromium, zinc, tin, platinum, titanium, and palladium. You may have a metal thin film. Furthermore, in order to ensure adhesion between the substrate and the metal thin film, the metal thin film may be formed after a metal such as chromium or titanium is previously deposited by sputtering or the like.

There is no problem as long as the resist material is a material that emits fluorescence when irradiated with ultraviolet, near-ultraviolet, and visible short-wavelength light, and a thermoplastic polymer having an aromatic ring can be used alone. However, it is preferable to use a material containing a thermoplastic polymer and a fluorescent substance from the viewpoint of emission intensity.
The thermoplastic polymer having an aromatic ring may be, for example, a weight average molecular weight of 2000 to 1000000, a glass transition temperature of room temperature or higher, and soluble in a solvent. From the viewpoint of shortening the molding time, a thermoplastic polymer having a weight average molecular weight of 2,000 to 100,000 is preferable, and specific examples include polystyrene, polyvinyl toluene, and polybenzyl methacrylate.

  The thermoplastic polymer used for the material containing the thermoplastic polymer and the fluorescent material may be, for example, a weight average molecular weight of 2000 to 1000000, a glass transition temperature of room temperature or higher, and soluble in a solvent. . Preferably, a thermoplastic polymer having a weight average molecular weight of 2000 to 100,000 is preferable from the viewpoint of shortening the molding time. Specific examples include polymethyl methacrylate, polystyrene, polyvinyl toluene, polybenzyl methacrylate, polycarbonate, polyethylene, polypropylene, and polyvinyl chloride.

The fluorescent substance is not particularly limited as long as it emits fluorescence, and examples thereof include an acridine fluorescent substance, an anthracene fluorescent substance, a rhodamine fluorescent substance, a pyromethene fluorescent substance, and a perylene fluorescent substance. Preferably, 3,6-dimethylaminoacridine (Acridine Orange), 2,6-di-t-butyl-8-nonyl-1,3,5,7-tetramethylpyromethene-BF ₂ complex (PYRROMETHENE 597-8C9) ), N, N′-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxydiimide, rhodamine 6G (RHODAMINE 590), and the stability of the fluorescent material to heat and ultraviolet light, N, N′-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxydiimide is more preferable from the viewpoints of ultraviolet light permeability and solubility. These fluorescent materials may be used alone or in combination of two or more.
The compounding amount of the fluorescent substance is not a problem if it is dissolved in a solvent, but is preferably 0.0001 to 1 part by mass with respect to 100 parts by mass of the thermoplastic polymer. If the blending amount is less than 0.0001 parts by mass, the fluorescence may not be detected with high sensitivity. If the amount exceeds 1 part by mass, the amount of light emitted may vary depending on whether the fluorescent substance is not dissolved in the solvent or due to the formation of aggregates. May be lacking in sex.

As a method for applying the resist material on the substrate 1, for example, the resist material is dissolved in a solvent, and the solution is formed by spin coating, dipping, spray coating, flow coating, roll coating, die coating, or the like. It can be carried out by forming a film and evaporating the solvent under blowing, heating, and reduced pressure.
As the solvent, there is no problem as long as it can dissolve the fluorescent substance and the thermoplastic polymer, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methoxypropyl acetate, ethyl lactate, tetrahydrofuran, Examples include dioxane, chloroform, butyl chloride, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethylene carbonate, and γ-butyrolactone. Toluene is preferable from the viewpoint of solubility of the fluorescent substance.
The amount of the solvent is such that the concentration of the thermoplastic polymer is usually 0.1 to 20% by mass. When the concentration is lower than 0.1% by mass, the film thickness of the thermoplastic polymer becomes too thin and may not serve as a resist. If the concentration is higher than 20% by mass, the film thickness may not be uniform.
Further, for example, additives such as a surfactant and a leveling agent can be blended in order to improve the coating properties to the substrate. Examples of the surfactant include ionic or nonionic surfactants, and examples of the leveling agent include silicone derivatives and fluorine derivatives. The blending amount of the additive can be appropriately selected according to the purpose.

FIG. 1 (B) used for producing a molded laminate shown in FIG. 1C by molding the film layer 2 on a substrate having a film layer 2 made of a resist material by a thermal nanoimprint method using a mold 3. The mold 3 shown in FIG. 2 is a mold for forming the film layer 2 on the substrate into irregularities by a thermal nanoimprint method. In addition, the schematic which looked at the casting_mold | template mold 3 shown in FIG.1 (b) from the downward direction is shown in FIG.
The material of the mold 3 is mainly surface silicon oxide, synthetic silica, fused silica, quartz, silicon, and nickel. The mold for thermal nanoimprinting can be obtained by forming a desired concavo-convex pattern on the surface of the molding material using a known technique.
Since the chemical composition of the surface silica layer, synthetic silica, fused silica, and quartz of the surface silicon oxide is almost the same SiO ₂ , an uneven pattern is formed by processing the flat plate of the above material using a known semiconductor microfabrication technology can do.

In order to form a concavo-convex pattern in the mold 3, for example, a negative electron beam resist is applied to a flat plate having a smooth surface, and electron drawing is performed on the electronic resist by an electron beam drawing apparatus. Thereafter, when development is performed, the resist in the electron beam non-irradiated portion is removed, and the resist film remains in the electron beam irradiated portion on the flat plate. SiO ₂ is etched by using a negative image of the electron beam resist as an etching mask for dry etching by dry etching such as CHF ₃ / O ₂ plasma. Then, a recess can be produced on the surface of the flat plate by immersing in a stripping solution to remove the negative image of the electron beam resist and washing. In order to accelerate the release of the resist, a treatment with a release agent such as a fluorocarbon-containing silane coupling agent may be performed.

  The mold manufactured in this way can be used as a mold as it is, but after forming a metal film such as nickel on the surface of the mold, the nickel layer is further coated and peeled off using an electroforming process technique. It can also be a mold. Also, after forming a metal film such as nickel on the surface of the flat plate of the above materials and polyimide, polyester resin flat plate by sputtering method, organic image formation is performed using photoresist or electron beam resist, and electroforming process technology Thus, the nickel layer can be further thickened, and can be used as a less expensive nickel mold by surface polishing and resist removal.

An apparatus used for the thermal nanoimprint method includes a heating / cooling section, a pressurizing section, and a decompressing section. The heating / cooling unit is a part that includes a heater and a stage incorporating a water-cooling structure, and is a portion that softens and cools the thermoplastic polymer film by installing a substrate on which a thermoplastic polymer film is formed and heating.
The pressurizing part is a portion that consists of a press that presses the concavo-convex mold onto the substrate on which the thermoplastic polymer film is formed, and that transfers the fine concavo-convex structure of the mold to the substrate on which the thermoplastic polymer film has been softened by pressing. . The decompression unit is a part that keeps the substrate and the mold in a decompressed state when the mold is in a decompressed state with respect to the substrate, and efficiently fills the uneven portion with the thermoplastic polymer.

The method for inspecting a nanoimprint molded laminate according to the present invention irradiates the molded substrate, which is the above-mentioned object, with light having an excitation wavelength that causes the resist material to emit light, and from the film layer made of the molded resist material on the substrate. Step (1) for obtaining light emission as a light emission pattern image, and a light emission pattern different from the light emission pattern image obtained by repeatedly molding the light emission pattern image obtained in step (1) using a mold image or the same mold mold Compared with the image, the defect detection step (2) and / or the light emission pattern image acquired in step (1) for detecting the difference in the image as a defect is analyzed by the emission intensity, and the film thickness is measured from the value of the emission intensity And a film thickness measurement step (3) to be performed, and the nanoimprint molding laminate can be observed by fluorescence observation with a fluorescence microscope apparatus 4 (see FIG. 1 (d)). ).
In short, in the present invention, the step (1) is essential, and at least one of the step (2) and the step (3) is performed using the light emission pattern image acquired in the step (1).

The fluorescence microscope apparatus has a light emitting element that emits fluorescence, and can be used as long as it is an apparatus that can acquire and display and analyze light emission from a film layer made of a molded resist material as a light emission pattern image. A fluorescence microscope apparatus 4 shown in FIG.
The fluorescence microscope apparatus 4 irradiates, for example, light of an excitation wavelength that causes the resist material to emit light by the light emitting element 5, converts the light direction from the horizontal direction to the vertical direction by the half mirror 6, and forms the nanoimprint molding laminate of the substrate A It is possible to emit light, and the emitted light emission pattern image is received by the light receiving element 7 and transferred to the image processing device 8 for display and analysis.

In the step (1) of acquiring the light emission pattern image in the present invention, for example, the substrate A is irradiated with light having an excitation wavelength that causes the resist material to emit light from the light emitting element 5 in the fluorescence microscope apparatus 4 shown in FIG. The light of the light emitting element 5 reflected by the nanoimprint molding laminate formed on the substrate is incident on the light receiving element 7 while the half mirror 6 or the like is used to receive the image of the nanoimprint fluorescent resist that emits fluorescence. The fluorescence resist pattern image observed and obtained by the element 7 can be input to an image processing apparatus 8 composed of a computer and displayed on a monitor.
FIG. 3 shows a schematic view of the substrate A shown in FIG.

The light-emitting element 5 is preferably a light-emitting element having a radiation spectrum in the ultraviolet and visible short wavelength region, and examples of the light source thereof include a gas discharge lamp, a mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, and a xenon lamp. And can be appropriately selected according to the excitation wavelength of the fluorescent substance to be used. In addition, a filter configured to selectively exhibit the maximum transmittance in a specific wavelength region and block in other regions depending on the excitation wavelength of the fluorescent substance to be used can be used.
As a method for avoiding the reflected light of the light emitting element 5 entering the light receiving element 7, it is possible to use a half mirror 6 or a light receiving filter that transmits fluorescence and blocks excitation light. .
An example of the light receiving element 7 is a CCD camera.
The image processing device 8 can display the obtained luminescent image pattern image in color or black and white, and there is no problem as long as the luminescence intensity can be analyzed. However, the viewpoint of performing the shape inspection by analyzing the luminescence intensity at two or more different detection wavelengths. Is preferably an apparatus capable of color display.

In the defect detection step (2) in the present invention, for example, the pattern of the mold mold used in the nanoimprint method is compared with the light emission pattern image of the nanoimprint molding laminate displayed on the image processing apparatus 8, and the difference is regarded as a defect. To detect. In addition, it is possible to detect a difference as a defect by comparing with a light emission pattern image formed repeatedly by the same mold.
In the defect detection step (2), there is no problem in comparison with only the pattern of the mold mold or only with the light emission pattern image produced with the same mold mold, but preferably both are compared from the viewpoint of accuracy of defect detection, It is preferable to detect defects.

  In the present invention, the film thickness measurement step (3) for measuring the film thickness can be obtained by, for example, producing a film layer coated with a resist material to be observed separately from the observation of the light emission pattern image and observing the film layer. The emission intensity of the obtained emission pattern image is analyzed. At the same time, the film thickness of the same film layer is measured with a stylus type surface roughness meter or an optical film thickness measuring device, and a calibration curve with the emission intensity is prepared. Subsequently, the film thickness can be measured by analyzing the light emission intensity of the light emission pattern image and comparing it with the calibration curve.

  In the film thickness measurement step (3), the light emission pattern image is analyzed for light emission intensity at at least two different detection wavelengths, and the nanoimprint molding laminate is inspected by using the light emission pattern image at two or more different detection wavelengths. The light emission intensity can be analyzed by comparing them. Examples of the method of analyzing the emission intensity at two or more different detection wavelengths include a method of performing RGB analysis on the emission pattern image of the nanoimprint molding laminate displayed in color by the image processing apparatus 8. According to this analysis, for example, when a light emission pattern image of a nanoimprint molding laminate having a gentle slope is inspected using only the light emission pattern image or only one detection wavelength, it is more accurate due to interference of emitted fluorescence. However, it is possible to detect the inaccuracy due to fluorescence interference and to estimate the shape by analyzing the emission intensity at two or more detection wavelengths.

The present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.
<Nanoimprint molding>
For nanoimprint molding, a thermal nanoimprinter (NM-400, manufactured by Myeongchang Kiko Co., Ltd.) was used. The mold mold is a nickel mold (lattice pattern, height difference of concave and convex portions 1 μm, concave portion width 5 μm, convex portion width 95 μm) surface-treated with a reactive release agent (Daikin Chemicals Sales, Optool DSX) Was used.

Production Example 1-1 Production of Nanoimprint Molded Laminate A In a 10% by weight toluene solution of polystyrene (Polymer Source Inc., Mw = 300,000), 0.05% by weight of fluorescent substance N, N′-bis (2 , 6-Dimethylphenyl) perylene-3,4,9,10-tetracarboxydiimide was added to obtain a fluorescent resist composition 1. A fluorescent resist composition 1 is spin-coated on the surface of a silicon substrate (film thickness 0.6 mm, 15 mm square) (slope 5 seconds, 3000 rpm: 30 seconds, slope 5 seconds), and a film layer made of a resist material is formed on the silicon substrate. (Hereinafter, the substrate having this resist film may be referred to as a laminate a).
Next, a laminate was obtained using a fluorescence microscope (Olympus, optical microscope BX60 optical microscope equipped with a 100W halogen lamp light source, U-MWIG fluorescent cube (excitation wavelength 530-550 nm, detection wavelength 570 nm or more), FD70 CCD camera). The entire surface of the substrate was observed for light emission from a at a magnification of 50 times. As a result, light emission with the same luminance was observed from the substrate surface excluding the four corners of the silicon substrate, and it was found that the film layer made of the resist material had a uniform film thickness. Further, it was found by a stylus type surface roughness meter (Vekco, DekTak 3ST) that the thickness of the resist film of the layered product a was 1 μm.
Nanoimprint molding was performed on the laminate a under the molding conditions consisting of the heating process, pressurization process, holding process, cooling process, and release process shown in Table 1 to prepare a nanoimprint molding laminate A (abbreviated as molding laminate A). .

Production Example 1-2 Production of Nanoimprint Molded Laminate B The same operation as the production of molded laminate A was performed except that the heating step, the pressurizing step, and the holding step in Table 1 were performed at 120 ° C. instead of 180 ° C. Then, a nanoimprint molded laminate B (abbreviated as molded laminate B) was produced.

Production Example 1-3 Production of Nanoimprint Molded Laminate C The same operation as the production of molded laminate A was performed except that the heating step, the pressurizing step, and the holding step in Table 1 were performed at 80 ° C instead of 180 ° C. Then, a nanoimprint molded laminate C (abbreviated as molded laminate C) was produced.

Example 1 Acquisition Process of Light Emitting Pattern Image of Molded Laminate A (Process (1))
The inspection method of the nanoimprint molding was performed using the following light emission pattern image acquisition device. The light emission pattern image of the molded laminate A was acquired under the image acquisition conditions with an ISO value of 800 and an acquisition time of 2.0 seconds. A copy of the light emission pattern image of the resulting molded laminate A is shown in FIG.
Luminescent pattern image acquisition device includes Olympus BX60 optical microscope, light source 100W halogen lamp, Olympus fluorescent cube U-MWIG (excitation wavelength 530-550nm, detection wavelength 570nm or more), Olympus CCD camera FD70, Mitani A fluorescence microscope equipped with analysis software WinROOF manufactured by Shojisha was used.

Defect detection process of molded laminate A (process (2))
When the obtained FIG. 4 is observed, the convex portions of the thick film resist film generated by nanoimprint molding, the linear bright portions present in the vertical and horizontal directions, and the thin film resist film generated by nanoimprint molding. It can be clearly seen that the concave portion is a horn-shaped dark portion.
FIG. 5 is an optical micrograph of the mold mold used to produce the molded laminates A to C.
Therefore, comparing the pattern image of the mold mold in FIG. 5 with the light emission pattern image in FIG. 4 shows that there is no defect in the convex portions of the linear resist film, and the shape of the mold mold is accurately transferred. Moreover, when the some location of the shaping | molding laminated body A was compared, it turned out that it is a light emission pattern image of the same brightness, and it turned out that the defect does not exist in the shaping | molding laminated body A as a result of the test | inspection.

Film thickness measurement process of molded laminate A (process (3))
2, 4 and 7 mass% toluene solutions of polystyrene (Aldrich, Mw = 35,000 (equal mixture of Mw = 4,000 and Mw = 200,000)) were prepared. 0.05% by mass of N, N′-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxydiimide with respect to polystyrene, and a fluorescent resist composition for calibration curves having different concentrations Was prepared. The calibration curve fluorescent resist composition was spin-coated on a silicon substrate to prepare a silicon substrate having film layers made of resist materials having different film thicknesses.
The film thickness of the obtained film layer was obtained by a stylus type surface roughness meter, and the emission intensity of the film layer was obtained from observation with a fluorescence microscope, and a calibration curve of the film thickness and the emission intensity was prepared.
On the other hand, as a result of comparing the light emission intensity and the calibration curve of the light emission pattern image of the molded laminate A shown in FIG. 4, the height of the portion where the bright resist film is a convex portion is 1.39 μm, and the dark square concave portion is The height was found to be 0.43 μm.

Example 2 Acquisition Process of Light Emitting Pattern Image of Molded Laminate B (Process (1))
Except that the molded laminate B was used instead of the molded laminate A, the same operation as in Example 1 was performed, and a light emission pattern image of the molded laminate B was obtained. In FIG. 6, the copy of the light emission pattern image of the obtained molded laminated body B is shown.

Defect detection process of molded laminate B (process (2))
When the light emission pattern image of the molded laminate B shown in FIG. 6 is observed, it can be seen that the molded laminate B shows no significant difference in emission intensity between the line-shaped convex portions and the angular concave portions. The film thickness of the resist film concave portion corresponding to the convex portion of the mold mold is almost the same as that of the resist film convex portion, indicating that the molding was defective. Further, since the light emission intensity from the boundary between the resist film convex portion and the concave portion is dark, it can be understood that the resist film of the mold mold convex portion cannot be moved due to the edge effect.

Example 3 Acquisition Process of Light Emitting Pattern Image of Molded Laminate C (Process (1))
Except that the molded laminate C was used instead of the molded laminate A, the same operation as in Example 1 was performed, and a light emission pattern image of the molded laminate C was obtained. In FIG. 7, the copy of the light emission pattern image of the molded laminated body C is shown.

Defect detection process of molded laminate C (process (2))
When the light emission pattern image of the molded laminated body C shown in FIG. 7 is observed, it can be seen that the shape of the mold mold shown in FIG. 5 is not transferred. As a result of comparing a plurality of places of the molded laminate C, it was found that there were many differences and defects.

Comparative Example 1 Defect Detection Process Using Optical Microscope Images of Molded Laminates A, B, and C Molded laminates A, B, and C used in Examples 1 to 3 were observed with an optical microscope. A copy of the obtained optical microscope image is shown in FIGS. In FIGS. 8 and 9, linear dark portions that exist vertically and horizontally are confirmed, but it has been found that other analysis methods are necessary to obtain data in the depth direction.

Production Example 2 Production of Nanoimprint Laminate D A 15% by mass toluene solution of polystyrene (Aldrich, Mw = 35,000 (equal mixture of Mw = 4,000 and Mw = 200,000)) was prepared. Further, 0.05% by mass of N, N′-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxydiimide was added to polystyrene to prepare a fluorescent resist composition 2. The fluorescent resist composition 2 was spin-coated on a silicon substrate to prepare a substrate having a film thickness made of a resist material (hereinafter, the substrate having this resist film may be referred to as a laminate d).
As a result of observing the laminate d with a fluorescence microscope, light emission with the same luminance was observed from the substrate surface excluding the corners of the four corners of the silicon substrate, and it was found that the film layer made of the resist material had a uniform film thickness. Further, it was found by a stylus type surface roughness meter that the film thickness of the resist film of the laminate d was 2 μm.
Using the quartz mold having the pattern shown in FIG. 11 having a height difference of 2 μm of the uneven portion subjected to the surface treatment with the reactive release agent for the laminate d under the same conditions shown in Table 1 above. The same operation as the production of the nanoimprint molding laminate A was performed to prepare a nanoimprint molding laminate D (abbreviated as molding laminate D). In FIG. 11, the gray portion indicates the convex portion, the dotted line indicates the portion where the reflection spectral film thickness meter is performed, and the solid line encircled portion indicates the portion where the light emission pattern image is acquired.

Comparative Example 2 Shape Inspection of Molded Laminate D with Reflective Spectral Thickness Meter Using a reflective spectral thickness meter (manufactured by Otsuka Electronics Co., Ltd., FE-3000), a pair is formed between the dotted lines ac shown in FIG. The film thickness at the location of the molded laminate D was measured. The results are shown in FIG.
Since the reflection spectral film thickness meter cannot measure a concavo-convex pattern with a horizontal resolution of several 10 μm or less, the film thickness of the 10 μm convex line at the center between ac cannot be measured. Further, it was found that the shape between bc was poorly formed and the pattern had a gentle slope.

Example 4 Step for Acquiring Light Emission Pattern Image of Molded Laminate D (Step (1))
Using the same method as in Example 1, a light emission pattern image of a portion of the molded laminate D that forms a pair with the solid line encircled portion shown in FIG. 11 was obtained. FIG. 13 shows a copy of the light emission pattern image of the molded laminate D.

Inspection of molded laminate D with two detection wavelengths (process (3))
RGB analysis was carried out between AB of the light emission pattern image of the molded laminated body D shown in FIG. 13, and the light emission intensity of R (thick line) and G (thin line) was acquired. The results are shown in FIG.
In FIG. 14, the unevenness | corrugation of the emitted light intensity of two detection wavelengths did not correspond. From this, it was found that the unevenness of the emission intensity did not originate from the shape of the molded laminate D, but was due to fluorescence interference, and the actual shape was not an uneven shape.

Claims (3)

A substrate having a film layer made of a resist material molded by a nanoimprint method using a mold mold is irradiated with light having an excitation wavelength that causes the resist material to emit light. Acquiring light emission as a light emission pattern image (1);
The light emission pattern image acquired in step (1) is compared with a light emission pattern image that is different from the light emission pattern image that is repeatedly molded with the mold image used in the molding or the same mold, and a difference between the images is detected as a defect. Defect detection step (2) and / or
Film thickness measurement step (3) for analyzing the light emission pattern image obtained in step (1) based on the light emission intensity and measuring the film thickness from the value of the light emission intensity.
And a method for inspecting a nanoimprint molding laminate.   The method for inspecting a nanoimprint molding laminate according to claim 1, wherein the resist material is a fluorescent resist composition containing a fluorescent substance.   3. The method for inspecting a nanoimprint molded laminate according to claim 1, wherein the analysis based on the emission intensity in the step (3) is performed with at least two different detection wavelengths.