JP6768320B2 - A film sample fixing device, an X-ray analyzer and method having the same, a film manufacturing device and method using the same, and a film manufactured by the method. - Google Patents

Description

The present invention comprises a film sample fixing device used for analyzing the characteristics of a film, an X-ray analyzer and an X-ray analysis method having the same, a film manufacturing device and a film manufacturing method using the same, and a film manufacturing method thereof. With respect to the film produced by.

When analyzing the characteristics of a film with a spectroscopic analyzer, X-ray analyzer, etc., the film sample to be analyzed is irradiated with an analysis beam, and the intensity spectrum of the beam light reflected or scattered by the sample is detected. It is possible to specify the physical properties and structure of the film sample such as the refractive index, density, and crystallinity by measuring with. In these analyzers, generally, in order to hold the film sample horizontally and flatly at the analysis beam position, the film sample is placed on a horizontal sample table, or the sample is placed on the back surface of the sample with an adhesive or adhesive tape. The analysis is performed by fixing the sample on the sample table or fixing the end of the sample with tension applied to the sample (for example, Patent Documents 1 and 2).

Further, as a method of measuring information on the structure such as the film thickness, density, and roughness of the surface of the film-like base material and the thin film formed on the surface, for example, even if the film has warpage or waviness, an X-ray beam is used. A method of analyzing the film thickness, density, etc. of a thin film by condensing or narrowing the size to a minute region of 10 μm or less is known (for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2002-107313 JP-A-11-006805 Japanese Unexamined Patent Publication No. 2012-068180

However, if the object to be analyzed is a relatively soft material such as an organic substance or a film, the problem is that the warp of the sample affects the reproducibility of the analysis by simply placing it on the horizontal sample table described above. was there. In addition, even in the method of fixing to the sample table with the adhesive or adhesive tape provided on the back surface of the sample, the surface roughness and waviness of the adhesive and the adhesive tape affect the sample surface, so that the analysis can be repeated repeatedly. There was a problem that it could not be done. Furthermore, in the method of fixing the end of the sample with tension applied to the sample, the wrinkles generated in the sample due to the tension cannot be completely removed, and the analysis beam hits the wrinkles, resulting in poor measurement and tension during analysis. There was a problem that the sample was released from the above and moved.

In addition, with the measurement method of focusing or narrowing down X-rays, it is not possible to collectively analyze a wide area with a side length of 1 mm or more measured by general optical characteristics, electrical characteristics, etc., so the measurement position can be determined. It is necessary to change and concatenate the results of multiple analyzes, which causes problems such as deterioration of measurement accuracy and prolongation of measurement time.

The subject of the present invention is that, in view of the prior art, even if the object to be analyzed is a relatively soft material such as a film or an organic substance provided on the film, it is very easy to achieve high accuracy and excellent repeatability. It is feasible, and even if the analysis area is a wide area with a side length of 1 mm or more, the film sample can be fixed with high accuracy by minimizing warpage, waviness, wrinkles, etc. of the film. An object of the present invention is to provide an apparatus, an X-ray analyzer and an X-ray analysis method having the apparatus, a film production apparatus and a film production method using the apparatus, and a film produced by the film production method.

In order to solve the above problems, the present invention provides the following film sample fixing device, an X-ray analyzer and method having the following device, and a film manufacturing device and method using the same.
(1) A film sample fixing device having a charging mechanism for charging a film sample and a sample stand for holding the charged film sample.
(2) The film sample fixing device according to (1), wherein the charging mechanism and the surface of the sample table face each other.
(3) The film sample fixing device according to (1) or (2), wherein the center line average surface roughness Ra of the surface of the sample table is 50 nm or less and the resistivity is 500 Ω · cm or less.
(4) The film sample fixing device according to any one of (1) to (3), wherein the charging mechanism is either a charging mechanism based on a piezoelectric effect method or a charging mechanism based on a corona discharge method.
(5) The film sample fixing device according to any one of (1) to (4), wherein the charging mechanism is either a gun type charging mechanism or a bar type charging mechanism.
(6) The sample table is provided with a voltage application mechanism, and the voltage application mechanism comprises a mechanism capable of applying a voltage having a polarity opposite to the voltage applied by the charging mechanism (1) to (5). ). The film sample fixing device according to any one of.
(7) The film according to any one of (1) to (6), wherein the charging mechanism, the sample table, or both of them has a movable mechanism capable of changing the distance between the charging mechanism and the sample table. Sample fixing device.

The present invention also provides an X-ray analyzer having the film sample fixing device and an X-ray analysis method using the X-ray analyzer.
(8) An X-ray analyzer having an X-ray irradiation mechanism, an X-ray analysis mechanism, and a film sample fixing device according to any one of (1) to (7).
(9) An X-ray analysis method using the X-ray analyzer according to (8).

Further, the present invention provides a film manufacturing apparatus having the above-mentioned X-ray analyzer, a film manufacturing method using the film manufacturing apparatus, and a film produced by the method.
(10) A film manufacturing apparatus having the X-ray analyzer according to (8).
(11) A film manufacturing method using the film manufacturing apparatus according to (10).
(12) A film produced by the film production method according to (11).

According to the present invention, by using the film sample fixing device according to the present invention, the surface of the film sample can be charged and the film sample can be fixed horizontally and flatly on the sample table. Therefore, the film sample and the sample table can be fixed. It is not necessary to interpose an adhesive or an adhesive tape between the and, and the occurrence of undulations on the surface of the sample to be analyzed is avoided. Further, as described above, the holding of the film sample on the sample table is very easily achieved by charging the film sample, so that it is not necessary to apply tension to the film sample from the outside, which is caused by a large tension. The occurrence of wrinkles and the like is prevented, and the concern about film cracking due to tension is also prevented. As a result, the analysis target portion of the film sample is maintained in a desirable state for analysis using an analysis beam or the like, and the analysis target is a relatively soft material such as a film or an organic thin film provided on the film. However, regardless of whether the film sample to be analyzed is conductive or insulating, it is very easy and highly accurate regardless of the type of film, and under excellent conditions that satisfy repeatability. The desired characteristic analysis can be realized.

The X-ray analyzer and method according to the present invention provided with the film sample fixing device according to the present invention can easily perform X-ray analysis with high accuracy and excellent reproducibility. In the film manufacturing apparatus and method according to the present invention using the film sample fixing apparatus according to the present invention, characteristic analysis of the film being manufactured or manufactured can be easily performed with high accuracy and excellent reproducibility. Becomes possible. By producing a film by this film production method, it becomes possible to stably produce a film with reduced variation in characteristics with excellent productivity.

It is a schematic block diagram which shows an example of the film sample fixing apparatus of this invention. It is a schematic block diagram which shows another example of the film sample fixing apparatus of this invention. It is a schematic block diagram of the state which attached the film sample to the film sample fixing device of FIG. It is a schematic block diagram which shows an example of the X-ray analyzer of this invention. It is a schematic block diagram which shows an example of the gun type charging mechanism. It is a schematic block diagram which shows an example of the bar type charging mechanism. It is a schematic diagram which shows the fixing method of the comparative example 1. FIG. It is a schematic diagram which shows the fixing method of the comparative example 2. It is a schematic diagram which shows the fixing method of the comparative example 3. It is a schematic diagram which shows the fixing method of the comparative example 4.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[Film sample fixing device]
The film sample fixing device of the present invention is a fixing device for holding a film sample, and the fixing device is a film sample fixing device having a sample stand and a charging mechanism. By arranging the charging mechanism toward the film sample placed on the surface of the sample table and applying a voltage from the charging mechanism, the film sample can be fixed horizontally and flatly on the sample table.

The analytical method in which the film sample fixing device of the present invention is used is not particularly limited, and can be used for general spectroscopic analysis and X-ray analysis. Since the film sample can be fixed horizontally and flatly on the sample table, the spectroscopic ellipsometry method, X-ray reflectivity method, small-angle X-ray scattering method, and X-ray diffraction are particularly required for the flatness of the surface of the analysis sample. It can be suitably used for laws and regulations.

FIGS. 1 to 3 show an example of a film sample fixing device. The film sample fixing device 1a shown in FIG. 1 is a voltage application power supply 5 for applying a voltage to the sample table 2, the charging mechanism 3 provided with the movable mechanism 4, the sample table 2 and the charging mechanism 3 by the corona discharge method, respectively. It has. The film sample fixing device 1a is a device for fixing a film sample, and the surfaces of the charging mechanism 3 by the corona discharge method and the sample table 2 face each other. A film sample is placed on the surface of the sample table 2, and a voltage is applied from the charging mechanism 3 by the corona discharge method toward the surface of the film sample to fix the film sample horizontally and flatly on the sample table without waviness. Is possible. As shown in FIG. 3, the film sample 9 is placed so that the analysis surface faces upward, and a positive charge or a negative charge is applied to the film sample from the charging mechanism 3 by the corona discharge method, whereby the film sample 9 is placed. Is fixed to the sample table 2. At that time, a voltage having a polarity opposite to the voltage applied from the charging mechanism 3 by the corona discharge method may be applied to the sample table 2. By applying a voltage having a polarity opposite to the voltage applied from the charging mechanism 3 by the corona discharge method to the sample table 2, the holding force of the film sample 9 on the sample table 2 is further enhanced, and the swell and curl are relatively large. It is possible to easily fix the film sample to the sample table, and it is possible to prevent the film sample 9 from peeling off from the sample table 2 during the analysis.

When the film sample 9 to be analyzed is conductive, a flat and smooth insulating sheet is placed between the film sample 9 and the sample table 2, or an insulating thin film is placed on the surface of the film sample 9 on the sample table side. By forming or the like, the film sample can be fixed horizontally and flatly on the sample table. As the insulating sheet, a known general flat film base material such as polyester, polyimide, polyamide, polycarbonate, and polystyrene can be used. As a method for forming an insulating thin film, a dry coating such as a sputtering method, a CVD method, or a vapor deposition method, or a wet coating for forming an organic compound thin film is mainly used. By positively (or negatively) charging the insulating sheet or insulating thin film on the sample table 2 side, a negative (or positive) charge is naturally induced on the sample table side surface of the conductive film sample 9. It can be fixed horizontally and flatly on the sample table 2. At this time, the adhesion and flatness of the film sample 9 can be adjusted by further applying a negative (or positive) voltage from the charging mechanism 3 toward the analysis surface of the film sample 9.

The surface of the sample table 2 used in the present invention preferably has a centerline average surface roughness Ra of 50 nm or less and a resistivity of 500 Ω · cm or less. If Ra is larger than 50 nm, the film sample is not fixed well to the sample table 2, and even if the film sample is held well on the sample table 2, the flatness of the film sample is impaired, so that the film sample is precise and accurate. Analysis (eg, X-ray analysis) may not be possible. Further, if the resistivity of the sample table 2 is larger than 500 Ω · cm, the film sample may not be well fixed to the sample table 2, and accurate and accurate analysis may not be possible. From the viewpoint that the film sample can be reliably fixed by the sample table 2, it is more preferable that Ra is 30 nm or less and the resistivity is 300 Ω · cm or less. The member constituting the sample table 2 may be any member as long as the above conditions are satisfied, but it is preferable to use a Si wafer from the viewpoint of conductivity, flatness of the sample table surface, and smoothness.

Further, the sample table 2 may have a voltage applying mechanism so that the voltage applying mechanism can apply a voltage having a polarity opposite to the voltage applied by the charging mechanism 3. By applying a voltage having a polarity opposite to the voltage applied by the charging mechanism 3 to the sample table 2, the sample table can be easily used even for film samples that are difficult to fix, such as curved film samples and film samples of various thicknesses. It becomes possible to fix it to.

The charging mechanism used in the present invention is preferably either a charging mechanism based on a piezoelectric effect method or a charging mechanism based on a corona discharge method. The piezoelectric effect method is a method that utilizes the phenomenon that polarization in proportion to the pressure appears by applying pressure to the crystal (piezoelectric body) that generates the piezoelectric effect, and converts the force applied to the piezoelectric body into voltage. It is used as a charging mechanism. The charging mechanism by the corona discharge method is a charging mechanism of a method in which ions are generated by electrically decomposing the air existing in the vicinity by generating a non-uniform electric field around the charging mechanism and irradiating the ions. Is. FIG. 2 illustrates a film sample fixing device 1b using a charging mechanism based on a piezoelectric effect method. In FIG. 2, 6 is a charging mechanism based on the piezoelectric effect method, 7 is a voltage applying portion of the charging mechanism based on the piezoelectric effect method, and 8 is a power supply thereof. The charging mechanism for fixing the film sample is not limited to the charging mechanism based on the piezoelectric effect method or the corona discharge method, and any charging mechanism can be used as long as the film sample can be fixed to the surface of the sample table. It doesn't matter.

The charging mechanism used in the present invention is preferably either a gun-type charging mechanism or a bar-type charging mechanism. The gun type broadly represents a shape as shown in FIG. 5, and is preferably used when charging a relatively narrow range such as fixing a small piece size film sample on a sample table. When holding a film sample whose size exceeds the irradiation range of the gun-type charging mechanism to be used on the sample table, a method in which the gun-type charging mechanisms are arranged at equal intervals is mainly used. Further, the gun type charging mechanism may be either a charging method based on the piezoelectric effect method or a charging mechanism based on the corona discharge method. Further, in FIG. 5, the trigger 23 is integrated with the charging mechanism having the voltage application unit 22, but the trigger may be integrated with the charging mechanism or may be a remote control type. In addition, 24 in FIG. 5 shows an irradiated ion or electron.

Further, the bar type broadly represents a shape as shown in FIG. 6, and is suitable when it is desired to charge a wide range at once, such as fixing a film sample during transport by roll-to-roll to a sample table. Used for. When fixing a film sample that exceeds the irradiation range of the bar-type charging mechanism to be used on the sample table, use a method of arranging the bar-type charging mechanisms at equal intervals or a bar-type charging mechanism having a horizontally movable mechanism. The method is mainly used. As the bar-type charging mechanism, a corona discharge type charging mechanism is preferably used, but other types of charging mechanisms may be used as long as the film sample can be fixed to the sample table. In FIG. 6, 25 is a voltage application unit, 26 is a power cable, and 27 is an irradiated ion or electron.

As described above, the charging mechanism is preferably a gun type or a bar type, but any shape of the charging mechanism may be used as long as the film sample can be fixed horizontally and flatly on the sample table.

The charging mechanism used in the present invention preferably has a movable mechanism. Various forms of the movable mechanism such as a vertical movable mechanism and a horizontal movable mechanism can be considered, but any form of the movable mechanism may be used as long as the film sample can be fixed horizontally and flatly on the sample table. Since the charging mechanism has a movable mechanism in the vertical direction, it is possible to adjust the distance between the sample table and the film sample placed on the sample table and the charging mechanism facing each other. Even a film sample that is relatively difficult to fix, such as a thick film sample, can be easily fixed to the sample table. Further, since the charging mechanism has a movable mechanism in the horizontal direction, even a large-sized film sample can be easily fixed to the sample table.

Further, it is preferable that the sample table used in the present invention also has a movable mechanism. Various forms of the movable mechanism such as a vertical movable mechanism and a horizontal movable mechanism can be considered, but any form of the movable mechanism may be used as long as the film sample can be held. Since the sample table has a movable mechanism, the sample table can be brought closer from the back surface side of the analysis surface of the film sample, so that the film sample such as the film sample during the roll-to-roll transfer can be obtained. Can be easily fixed to the sample table even when it is difficult to place the film on the sample table.

Regarding the above movable mechanism, A. If only the charging mechanism has a movable mechanism, B. If only the sample table has a movable mechanism, C.I. It is conceivable that both the charging mechanism and the sample table have a movable mechanism, but any of A to C may be used.

[Film sample]
The film sample used in the present invention may be a single film base material made of an organic polymer compound, and a single film of an inorganic compound layer or an organic compound layer, a laminated film thereof, or the like is formed on the film base material. It doesn't matter if you do. Moreover, those film samples may be insulating or conductive.

The inorganic compound layer is not particularly limited, and for example, a metal layer composed of one or more elements belonging to Periodic Tables 3A to 4B, oxides, nitrides, oxynitrides, sulfides thereof, and the like. Examples thereof include a thin film layer made of a mixture or the like. The thickness of the inorganic compound layer is not particularly limited, but is preferably in the range of 0.1 nm to 5,000 nm from the viewpoint of ensuring analysis accuracy, and 0.5 nm to 1,000 nm from the viewpoint of analysis accuracy and ease of fixing the sample. The range of is more preferable.

The organic compound layer includes, for example, a heat-curable or active ray-curable polyester resin, a polyvinyl alcohol resin, a polyurethane resin, a phenol resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, and a polyacrylic. Examples thereof include a thin film layer made of a based resin, a polyacrylic nitrile based resin, or the like. The film thickness of the organic compound layer is not particularly limited, but is preferably in the range of 0.1 nm to 5,000 nm from the viewpoint of ensuring analysis accuracy, and 0.5 to 1,000 nm from the viewpoint of analysis accuracy and ease of fixing the sample. The range of is more preferable.

Examples of the film base material used as the film sample include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polystyrenes, polyvinyl alcohols, cycloolefins, and saponified products of ethylene vinyl acetate copolymers. , Polyacrylonitrile, polyacetal and other films made of various polymers can be used. Among these, a film composed of polyethylene terephthalate, polyethylene naphthalate, and cycloolefin is preferable. The polymer constituting the film substrate may be a homopolymer or a copolymer, or may be a single polymer or a blend of a plurality of polymers.

Further, as the film base material, a single-layer film, a film having two or more layers, for example, a film formed by a co-extrusion method, a film stretched in a uniaxial direction or a biaxial direction, or the like may be used. The surface of the base material on the side where the inorganic compound layer is formed is composed of corona treatment, ion bombard treatment, solvent treatment, roughening treatment, and organic or inorganic substances or a mixture thereof in order to improve adhesion. Pretreatment such as formation treatment of an anchor coat layer may be performed.

Further, the film substrate is made of an organic substance or an inorganic substance for the purpose of improving the slipperiness at the time of winding the film and reducing the friction with the inorganic compound layer when the film is wound after forming the inorganic compound layer. Alternatively, a coating layer of a mixture of these may be applied.

The thickness of the film sample used in the present invention is not particularly limited, but the thickness that can be easily fixed to the sample table is preferably 200 μm or less, and more preferably 150 μm or less. From the viewpoint of strength against tension and impact, and ease of handling, 2 μm or more is preferable, and 10 μm or more is more preferable.

The average surface roughness Ra (center line average surface roughness) of the film sample used in the present invention is preferably in the range of 0.05 nm to 25 nm as a range for preventing a decrease in the amount of light due to scattering of the analysis beam light. The range of 1 to 5 nm is more preferable.

[X-ray analyzer]
FIG. 4 shows an X-ray analyzer 10 according to an embodiment of the present invention. The X-ray analyzer 10 includes an X-ray irradiation mechanism 101 for irradiating a sample with X-rays, an X-ray detection mechanism 103 for detecting reflected X-rays, and charging by a charging mechanism 19 on a sample table 15. It is preferable to have a film sample fixing device 102 for X-ray analysis for holding the film sample 20 by utilizing the above. Further, it is preferable that the X-ray irradiation mechanism 101 and the X-ray detection mechanism 103 have a goniometer structure in which the X-ray detection mechanism 103 rotates with respect to the target in synchronization with the center of rotation so as to satisfy Bragg's equation.

The X-ray irradiation mechanism 101 includes an X-ray source 11 for generating X-rays, a parabolic multilayer mirror 12 for monochromaticizing and parallelizing incident X-rays from the X-ray source 11, and a vertical direction. A solar slit 13 for limiting divergence and an emission width limiting slit 14 are provided. As the X-ray source 11, a rotating anti-cathode type X-ray tube or an enclosed tube type X-ray tube can be used. Further, synchrotron radiation can be used as the X-ray source. The parabolic multilayer mirror 12 has a parabolic shape on the reflecting surface, and converts a line-shaped divergent X-ray beam (divergent beam 21a) emitted from the X-ray source 11 into a parallel beam 21b. The X-ray source 11 is arranged at the focal position of the paraboloid. By using a parabolic multilayer mirror, a parallel beam with high X-ray intensity can be produced. As the parabolic multilayer mirror, a mirror having both parallelization and monochromaticization may be used. From the viewpoint of obtaining a large X-ray intensity, it is preferable to use a mirror that parallelizes the incident X-rays, but it is also possible to use a mirror for irradiating the sample with the centralized optical system X-rays. The solar slit 13 for limiting the divergence in the vertical direction limits the divergence of X-rays in the direction perpendicular to the plane including the incident X-ray beam and the diffracted X-ray beam. The emission width limiting slit 14 is a slit for setting the beam width and the beam position of the parallel beam incident on the sample to desired ones.

The X-ray detection mechanism 103 includes a solar slit 16 for limiting lateral divergence, a light receiving width limiting slit 17, and an X-ray detector 18. The solar slit 16 for limiting the divergence in the lateral direction is for limiting the divergence of the diffracted X-rays diffracted from the sample in the diffraction plane. The light receiving width limiting slit 17 is a slit that defines the beam width of the diffracted X-rays incident on the X-ray detector 18, and has a role of cutting scattered light. The X-ray detector 18 is selected so that it can count as high as possible and can realize a low background, and a photon counting type detector such as a scintillation counter or a proportion counter that measures X-ray photons one by one is used.

The film sample fixing device 102 for X-ray analysis is as described in the above-mentioned [Film sample fixing device] section.

[X-ray analysis method]
The present invention also provides an X-ray analysis method for a film sample using an X-ray analyzer having the above-mentioned X-ray irradiation mechanism, X-ray detection mechanism and film sample fixing device. The analytical method in which the X-ray analyzer according to the present invention is used is not particularly limited, and is used for X-ray diffraction method, X-ray reflectivity method, spectroscopic ellipsometry, small angle X-ray scattering method and the like. Among these, it is preferably used in the X-ray reflectivity method (for example, the method described in "Introduction to X-ray Reflectivity" (edited by Kenji Sakurai), pp. 51-78), which requires the flatness of the analysis sample. In the X-ray reflectivity method, an energy dispersion method in which an X-ray having a different wavelength (so-called white X-ray) is used to immediately project the sample while it is fixed, or a monochromatic X-ray angle is greatly dispersed and incident on the sample surface. There is a method of measuring with the sample fixed. In any of these methods, it is preferable to inject X-rays at a total reflection critical angle of X-rays (incident angle of about 0.1 ° to 0.5 °).

As a specific measurement method, first, X-rays are generated from an X-ray source, a parallel beam is formed by a multilayer mirror, the X-ray angle is limited through an incident slit, and the X-rays are incident on a measurement sample. Measuring the angle of incidence of X-rays on the sample By incidenting the X-rays at a shallow angle substantially parallel to the surface of the sample, a reflected beam of X-rays reflected and interfered with each layer of the sample and the interface of the substrate is generated. After passing the generated reflected beam through the light receiving slit and limiting it to the required X-ray angle, the X-ray intensity is measured by incidenting it on the detector. By using this method, the total reflection X-ray intensity profile at each incident angle can be obtained by continuously changing the incident angle of X-rays for measurement.

Here, the incident angle of X-rays is 0.01 to 8 ° in order to accurately measure the structure such as the unevenness of the surface of the base material, the film thickness, the density, and the surface roughness of the thin film formed on the base material. The range is preferred, more preferably 0.01-5 °. In addition, the measurement area is the viewpoint of precisely measuring the structure of the base material surface and the thin film on the base material, the viewpoint of analysis accuracy, or the viewpoint of knowing the average structure for the purpose of clarifying the relationship with other characteristics. ^from the preferred range of 1mm ² ~50mm 2.

As a method for analyzing the number of thin films, the film thickness of each layer, the density of each layer, and the surface roughness, the measured data of the total reflection X-ray intensity profile with respect to the incident angle of the obtained X-rays is applied to the Parratt theoretical formula as a nonlinear least squares. It is obtained by fitting by the method of multiplication.

[Film manufacturing equipment and film manufacturing method using the film manufacturing equipment]
The film manufacturing apparatus including the X-ray analyzer is not particularly limited as long as it is a known film manufacturing apparatus equipped with an X-ray analyzer, and a single film of an inorganic compound layer or an organic compound layer is formed on a film substrate. Alternatively, it can be particularly preferably applied to a film manufacturing apparatus for forming a laminated film thereof. In a film manufacturing apparatus for forming a laminated film, the X-ray analyzer is preferably installed after the film forming step or before the film sample winding step, and the film density, film thickness, and surface roughness of the film are preferably provided. Etc. can be evaluated. At the time of evaluation of X-ray analysis, it is preferable that the film base material of the evaluation unit is stopped, so that the film manufacturing apparatus can adjust the transport of other transport portions when the film base material of the evaluation unit is stopped. It is preferable to provide a mechanism (for example, an accumulator mechanism capable of accumulating a film base material during transportation for a predetermined length of time at a certain portion and temporarily realizing a state in which transport is stopped at the portion after that portion).

According to the film manufacturing method using a film manufacturing apparatus including such an X-ray analyzer, for example, the characteristics of the thin film formed in the film manufacturing process can be detected in real time, so that an abnormality in the product can be immediately detected. Productivity can be improved because it can be detected and product variations can be detected immediately.

[Film obtained by the film manufacturing method]
Since the film obtained by the film manufacturing method is, for example, a film in which the variation in characteristics is reduced, the application in which the variation in characteristics is particularly important (for example, a gas barrier film or an electron that requires extremely high gas barrier properties). It is particularly preferably used for parts, etc.).

Hereinafter, the present invention will be described in more detail based on Examples. However, the present invention is not limited to the following examples.

[Evaluation method]
First, the evaluation method in each Example and Comparative Example will be described.
(1) Method for Measuring Surface Roughness Ra on the Surface Roughness of the Sample Table The surface roughness of the sample table was measured under the following conditions using a stylus type three-dimensional roughness meter ET4000A manufactured by Kosaka Laboratory Co., Ltd. The measurement was performed three times each, and the average value of the three times was adopted as the center line average surface roughness Ra.
Measuring force: 100N, X pitch; 1.00 μm, Y pitch: 5.00 μm, Z measurement magnification: 200,000 times, X feed speed: 0.1 mm / sec, low frequency cut: 0.25 mm, high frequency cut : R + W, Leveling: Unprocessed.

(2) Measuring method of resistivity on the surface of the sample table Using a low resistivity meter Loresta-EP MCP-T360 (manufactured by Mitsubishi Chemical Corporation), the sample table was measured by the 4-probe method (based on JIS0602-1995). The resistivity of the central part was measured. The measurement was performed three times each, and the average value of the three times was adopted as the resistivity.

(3) Density, surface roughness, and film thickness analysis method by X-ray reflectivity Method The density of the measurement sample by the X-ray reflectivity method ("Introduction to X-ray reflectivity" (edited by Kenji Sakurai) p.51-78) The surface roughness and film thickness were measured. That is, the total reflection X-ray intensity profile of the obtained reflected wave is obtained by irradiating the film sample with X-rays from an oblique direction and measuring the incident angle dependence of the total reflection X-ray intensity with respect to the incident X-ray intensity. It was. That is, first, X-rays (CuKα rays) are generated from an enclosed tube type X-ray generator, made into a parallel beam by a multilayer film mirror (CBO unit), and then the X-ray angle is limited through an incident slit (solar slit). Make it incident on the film sample. By incident at a shallow angle substantially parallel to the surface of the film sample for measuring the incident angle of X-rays, a reflected and interfering X-ray reflected beam is generated. The generated reflected beam is passed through a light receiving slit (PSA + solar slit) to limit the required X-ray angle, and then incident on a detector (scintillation counter; SC-70) to measure the X-ray intensity. Using this method, the total reflection X-ray intensity profile at each incident angle was obtained by continuously changing the incident angle of X-rays in the range of 0 to 4.0 ° and performing the measurement.

As a method for analyzing the density, surface roughness, and film thickness, the measured data of the X-ray intensity profile with respect to the incident angle of the obtained X-rays was obtained by fitting to Partrat's theoretical formula by the nonlinear least squares method.
The measurement conditions were as follows.
-Device: "Smart Lab" manufactured by Rigaku
-Measurement range (angle between sample surface): 0-4.0 °, 0.01 ° step-Incident slit size: 0.05 mm x 10.0 mm
-Light receiving slit size: 0.15 mm x 20.0 mm
-Analysis software: "Global Fit" manufactured by Rigaku.

(Example 1)
Using the film sample fixing device 1b shown in FIG. 2, it is formed by a sputtering method on a polyethylene terephthalate film (“Lumilar” (registered trademark) U48 manufactured by Toray Co., Ltd.) having a length of 40 mm, a width of 30 mm, and a thickness of 100 μm, which is a measurement sample. The density, film thickness, and surface roughness of the TiO ₂ film obtained were measured. A film sample is placed on a sample table 2 (silicon wafer manufactured by Silicon Technology Co., Ltd., Si (100), CZ-N type, thickness 525 μm) having Ra: 0.2 nm and a resistance: 3 Ω · cm. , The film sample was fixed to the sample table 2 by operating the piezoelectric effect charging mechanism 6 (“Zerostat” manufactured by Milty). Next, the density, film thickness, and surface roughness of the TiO ₂ film formed on the polyethylene terephthalate film were measured by the above-mentioned X-ray reflectivity method. In addition, every time the film was measured by the X-ray reflectivity method, the film sample on the sample table was reattached, and the measurement was repeated 5 times (n: 1 to 5). The results are shown in Table 1.

(Example 2)
The density, film thickness, and surface roughness of the TiO ₂ film formed on the polyethylene terephthalate film were measured in the same manner as in Example 1 except that the film sample fixing device 1a shown in FIG. 1 was used. For the film sample fixing device 1a, the charging mechanism 3 used a corona discharge type charging mechanism (Corona charging bar B-500 manufactured by Green Techno Co., Ltd.), and the film sample was fixed to the sample table 2. In addition, every time the measurement was performed by the X-ray reflectivity method, the film sample was reattached, and the measurement was repeated 5 times. The results are shown in Table 1.

(Example 3)
Performed except that a sample table (Silicon wafer manufactured by Silicon Technology Co., Ltd., Si (100), CZ-N type, thickness 525 μm) having Ra: 0.2 nm and resistivity: 100 Ω · cm was used for the sample table 2. In the same manner as in Example 1, the density, film thickness, and surface roughness of the TiO ₂ film formed on the polyethylene terephthalate film were measured. The results are shown in Table 1.

(Example 4)
Example 1 except that a sample table (silicon wafer manufactured by Silicon Technology Co., Ltd., Si (100), CZ-N type, thickness 525 μm) having Ra: 10 nm and resistivity: 3 Ω · cm was used for the sample table 2. In the same manner as above, the density, film thickness, and surface roughness of the TiO ₂ film formed on the polyethylene terephthalate film were measured. The results are shown in Table 1.

(Example 5)
TiO on the cycloolefin polymer film in the same manner as in Example 1 except that a cycloolefin polymer film having a thickness of 50 μm (“Zeonoa film” (registered trademark) ZF-14 manufactured by Nippon Zeon Co., Ltd.) was used as the film substrate. The density, film thickness, and surface roughness of the _two films were measured. In addition, every time the measurement was performed by the X-ray reflectivity method, the film sample was reattached, and the measurement was repeated 5 times. The results are shown in Table 1.

(Example 6)
The density and film thickness of the TiO ₂ film on the polyethylene terephthalate film were the same as in Example 1 except that a polyethylene terephthalate film having a thickness of 30 μm (“Lumilar” (registered trademark) U48 manufactured by Toray Co., Ltd.) was used as the film substrate. The thickness and surface roughness were measured. In addition, every time the measurement was performed by the X-ray reflectivity method, the film sample was reattached, and the measurement was repeated 5 times. The results are shown in Table 1.

(Example 7)
TiO on the cycloolefin polymer film in the same manner as in Example 1 except that a cycloolefin polymer film having a thickness of 28 μm (“Zeonoa film” (registered trademark) ZM-14 manufactured by Nippon Zeon Co., Ltd.) was used as the film substrate. The density, film thickness, and surface roughness of the _two films were measured. In addition, every time the measurement was performed by the X-ray reflectivity method, the film sample was reattached, and the measurement was repeated 5 times. The results are shown in Table 1.

(Comparative Example 1)
As shown in FIG. 7, the TiO ₂ film formed on the polyethylene terephthalate film in the same manner as in Example 1 except that the film sample 28 was placed on the sample table 40 without using the film sample fixing device. The density, film thickness, and surface roughness of the sample were measured. In FIG. 7, 28a indicates an analysis surface, and 28b indicates an analysis surface that is actually used for analysis. In addition, the density, film thickness, and surface roughness were repeatedly measured 5 times by repositioning the polyethylene terephthalate film each time the measurement was performed by the X-ray reflectivity method. The results are shown in Table 1.

(Comparative Example 2)
As shown in FIG. 8, the density and thickness of the TiO ₂ film formed on the polyethylene terephthalate film are the same as in Example 1 except that the film sample 28 is fixed on the sample table 40 with the double-sided adhesive tape 29. , The surface roughness was measured. In addition, every time the measurement was performed by the X-ray reflectivity method, the film sample was reattached, and the measurement was repeated 5 times. The results are shown in Table 1.

(Comparative Example 3)
As shown in FIG. 9, the density and film of the TiO ₂ film formed on the polyethylene terephthalate film are the same as in Example 1 except that both ends of the film sample 28 are fixed on the sample table 40 with the adhesive tape 30. The thickness and surface roughness were measured. In addition, every time the measurement was performed by the X-ray reflectivity method, the film sample was reattached, and the measurement was repeated 5 times. The results are shown in Table 1.

(Comparative Example 4)
As shown in FIG. 10, the density and film thickness of the TiO ₂ film formed on the polyethylene terephthalate film are the same as in Example 1 except that both ends of the film sample 28 are fixed on the sample table 40 with magnets 31. , The surface roughness was measured. In addition, every time the film was measured by the X-ray reflectivity method, the film sample was repositioned, and the measurement was repeated 5 times. The results are shown in Table 1.

As a result of comparing the measurement results of the X-ray reflectivity methods carried out in Examples 1 to 7 and Comparative Examples 1 to 4, as shown in Table 1, in Examples 1 to 7, the film thickness, the film density and the surface roughness are all. It can be seen that the standard deviation value is small, the repeatability is very good, and the measurement can be performed accurately and accurately. On the other hand, in Comparative Examples 1 to 4, it is often the case that the measurement could not be performed. The case where the measurement cannot be performed is a case where the sample surface cannot be accurately positioned when the sample position is adjusted as a step before the X-ray reflectance measurement is performed. That is, as a flow of sample position adjustment, first, the z-axis scanning and the ω-axis scanning of the sample table are repeated a plurality of times to optimize the sample front-back position (z-axis). Then, the reflected X-ray is measured by performing ω-axis scanning, and the ω-axis is arranged at the center of the obtained peak. This procedure is also performed for the z-axis and the χ-axis, and the ω-axis → z-axis → χ-axis are repeatedly adjusted a plurality of times in this order to determine the position of the axis. When adjusting the position of the axis of the reflected X-ray, the peak cannot be detected, or when the position of the axis changes each time when the adjustment is repeated, the accurate sample surface position cannot be obtained. This is the case when it is not possible to accurately position the. If the sample position cannot be adjusted accurately, the total reflection X-ray intensity profile that can be analyzed cannot be obtained or the correct total reflection X-ray intensity profile cannot be obtained when measuring the X-ray reflectance. May be done.

In Comparative Example 1, the cause is that the flatness of the sample surface could not be ensured due to the influence of the original swell of the film sample only by placing the film sample. In Comparative Example 2, as a result of fixing the back surface of the analysis surface with the double-sided tape, the waviness of the double-sided tape itself affected the film sample, and the flatness of the analysis surface could not be ensured. In Comparative Example 3, the cause is that the film sample is slightly lifted or wavy due to the force applied when both ends of the film sample are fixed with the tape. In Comparative Example 4, as in Comparative Example 3, the cause is that the film sample is slightly lifted or wavy due to the force applied when fixing both ends of the film sample with the tape.

As is clear from the comparison of the measurement results of the X-ray reflectivity method, the analysis results of the film thickness, the film density, and the surface roughness of Examples 1 to 7 are significantly larger than those of Comparative Examples 1 to 4. It can be seen that the repeatability is high and the measurement can be performed accurately and accurately.

The film sample fixing device according to the present invention can be used for measuring and analyzing various film characteristics, and in particular, by applying it to an X-ray analyzer and method having the same, and a film manufacturing device and method using the same, various types can be used. It can be effectively used for measurement and analysis of film thickness, film density, surface roughness, etc.

1a, 1b Film sample fixing device 2, 15, 40 Sample stand 3, 19 Charging mechanism 4 Movable mechanism 5 Voltage application power supply 6 Piezoelectric effect charging mechanism 7 Piezoelectric charging mechanism voltage applying part 8 Power supply 9, 20, 28 Film sample 10 X-ray analyzer 11 X-ray source 12 Radial surface multilayer film mirror 13 Solar slit 14 Emission width limiting slit 16 Solar slit 17 Light receiving width limiting slit 18 X-ray detector 21a Emission beam 21b Parallel beam 22, 25 Voltage Applying part 23 Trigger 24, 27 Ion or electron 26 Power cable 28a Analytical surface 28b Analytical surface 29 that is actually used for analysis Double-sided adhesive tape 30 Adhesive tape 31 Magnet 101 X-ray irradiation mechanism 102 X-ray analysis film sample fixing device 103 X-ray detection mechanism

Claims (10)

It has a charging mechanism for charging the film sample and a sample table for holding the charged film sample, and the center line average surface roughness Ra of the surface of the sample table is 50 nm or less and the resistance is 100 Ω · cm or less. , A film sample fixing device characterized in that a total reflection X-ray intensity profile can be obtained 5 times when repeated measurements by the X-ray reflectance method are performed 5 times. The film sample fixing device according to claim 1, wherein the charging mechanism and the surface of the sample table face each other. The film sample fixing device according to claim 1 or 2, wherein the charging mechanism is either a charging mechanism based on a piezoelectric effect method or a charging mechanism based on a corona discharge method. The film sample fixing device according to any one of claims 1 to 3, wherein the charging mechanism is either a gun type charging mechanism or a bar type charging mechanism. The present invention according to any one of claims 1 to 4, wherein the sample table includes a voltage application mechanism, and the voltage application mechanism comprises a mechanism capable of applying a voltage having a polarity opposite to the voltage applied by the charging mechanism. The film sample fixing device described. The film sample fixing device according to any one of claims 1 to 5, wherein the charging mechanism, the sample table, or both of them has a movable mechanism capable of changing the distance between the charging mechanism and the sample table. An X-ray analyzer having an X-ray irradiation mechanism, an X-ray analysis mechanism, and a film sample fixing device according to any one of claims 1 to 6 . The X-ray analyzer according to claim 7 comprises an X-ray irradiation mechanism for irradiating a sample with X-rays, an X-ray detection mechanism for detecting reflected X-rays, and a charging mechanism on a sample table. An X-ray analysis method in which a sample fixing device for X-ray analysis for holding a sample by utilizing charging is provided, and an X-ray incident angle is incident on a sample in a range of 0.01 to 8 °. A film manufacturing apparatus having the X-ray analyzer according to claim 7. A film manufacturing method using the film manufacturing apparatus according to claim 9, wherein an X-ray analyzer is provided after a film forming step of a single film or a laminated film or before a film sample winding step.

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