JP5222322B2 - Surface analysis method and apparatus - Google Patents

Description

  The present invention relates to a surface analysis method and apparatus, and more particularly to a surface analysis method and apparatus capable of analyzing a surface sample in situ.

  Conventionally, there are various methods for analyzing a sample surface. When this is classified by depth resolution and spatial resolution, FIG. 14 (Source: Toshio Ogawa, “New Development of Surface Modification and Analysis of Polymers”, page 167, published by CMC Publishing Co., Ltd. in February 2007. The arrow A is added for the sake of explanation.). In this figure, techniques often used for polymer surface analysis are summarized briefly with respect to the area spread of the sample to be detected and the depth direction from the surface. For example, it can be grasped two-dimensionally that TOF-SIMS / SIMS is used at a depth of 10 nm from the surface layer, and that ESCA (XPS) is applicable at 10-100 nm. Furthermore, in 0.5-10 micrometers, microscopic IR and FT-IR ATR are applied. Here, while the depth resolution is in the same range, the spatial resolution (that is, area spread) is different, and the features of both methods using the same infrared light for analysis are directly expressed. . In other infrared light analysis, Johnson method (measured by rubbing KBr fine powder on the surface and applying a few drops of solvent and rubbing) and high sensitivity reflection measurement method (IR-RAS) can be used. It does not deviate from the range defined by the depth resolution and the spatial resolution. Further, from around 10 nm to around 100 μm, analysis by X-ray diffraction can be applied, and it seems that all analysis methods are covered, but information obtained by X-ray diffraction is limited. . Therefore, it is considered that an appropriate analysis method is lacking in the depth resolution range indicated by the arrow A.

  On the other hand, in surface analysis, the surface is usually peeled off and collected and measured. For example, a sharp cutting edge is formed on the safety razor-like thin blade 1, and a highly reflective metal film is provided on the blade forming surface to form a cutting blade as a sampling tool. An invention is disclosed in which the attached object is subjected to infrared spectroscopic analysis while being attached to the sampling surface with the cutting edge, and the attached object is identified and analyzed (Patent Document 1). Here, not only a special coating is required, but also the information collected on the blade from which the deposit has been scraped is analyzed, so that only information on the entire collected sample can be obtained.

  In addition, a cutting blade made of a material that transmits measurement light is attached to a cutting drive means, the cutting blade is cut into a sample, the cutting piece is shaved and placed on the rake face of the cutting blade, and the cutting piece is placed thereon. Disclosed is a sample analysis method characterized in that the cutting blade is separated from the cutting driving means, and the cutting piece is analyzed by applying measurement light while the cutting piece is placed on the cutting blade. (Patent Document 2). In this method, since the cutting blade is separated from the cutting drive means and analyzed, it is difficult to place the cutting blade on the cutting blade depending on the method of separating the cutting piece. Furthermore, the cutting piece may be lost during the movement of the cutting blade, and the productivity is lowered as a measuring method.

  Then, in order to measure the data on the inner surface of the cutting just at the same time as cutting the sample surface, the measurement light enters the diamond cutting blade from the light source through the light incident / exit surface of the diamond cutting blade. Is irradiated at the tip of the diamond cutting edge, is reflected at the cutting point of the sample, is incident on the diamond cutting edge through the tip of the diamond cutting edge, and enters from the light incident / exit surface of the diamond cutting edge. An analysis method is disclosed in which the light is received by a photodetector and disclosed (for example, Patent Document 3). In this method, information on the cutting point can be measured while cutting, but measurement light is introduced through the cutting edge, and reflected light from the cutting point is detected through the cutting edge. For this reason, the design of the path through which light passes tends to be complicated, and the design of the cutting edge is not easy.

  Further, an analysis method is disclosed in which a sample of the order of several hundreds of nanometers is cut from the surface, the cutting blade on which the sample is placed is moved to an FT-IR measuring apparatus, and measurement is performed (for example, Non-Patent Document 1). . In this method, since the analysis cannot be performed unless the cutting blade is moved to a predetermined position, measurement while cutting cannot be performed.

JP-A-11-44616 JP 2005-114679 A JP 2005-195438 A

APPLIED SPECTROSCOPY, "Infrared SurfaceAnalysis Using a Newly Developed Thin-Sample Preparation System", Volume 63, Number 1, pp. 66-72 (2009)

  As described above, it is desired to obtain information on the submicron depth from the surface, and in particular, it is desired to obtain information on the portion while changing the depth from the surface. However, with conventional analysis techniques, it is not always easy to obtain specific information on the depth of submicrons from the surface using infrared light or the like. In particular, it is difficult to analyze the structure and characteristics of the sample while changing the depth. On the other hand, it is not easy to obtain information on a cutting piece having a certain area while cutting.

  In view of such circumstances, when the analysis method has been intensively studied, it is considered that the submicron order region from the surface to about 100 to 500 nm cannot be analyzed by microscopic IR or FT-IR ATR. However, it was found that there was a problem with sampling and these analytical methods were not applied. That is, if a sample having a submicron depth can be prepared, analysis using infrared light is possible. In particular, by performing cutting and analysis in an integrated manner, the analysis of the surface layer can be performed while cutting by applying analysis using infrared light that does not require high vacuum, such as SIMS or ESCA. Furthermore, analysis in the depth direction is possible by cutting while changing the depth. Further, by devising the optical path of the measuring light, it is possible to analyze the cut piece separated from the surface layer.

  In the present invention, it is possible to provide an analysis method and an analysis apparatus that enable analysis even when a cutting blade is inserted from the surface of a sample and the state is maintained. For example, a cutting blade that cuts the surface of a target sample, a cutting piece cut from the sample, a light source that can irradiate the cutting blade with analysis light, and an optical path that allows light from the cutting piece to pass therethrough. It is possible to provide a surface analysis apparatus capable of changing the depth from the surface by relatively moving the sample or the cutting blade. Further, the sample and a cutting edge for cutting the surface thereof are arranged so that the surface and the rake face of the cutting edge are at a predetermined angle, the sample or the cutting edge is relatively moved, and the cutting edge is cut. In a state where the cutting piece is cut out from the surface by the blade, the analysis light that can be analyzed is irradiated to the cutting piece, the light (reflected light and / or transmitted light) from the cutting piece is received and analyzed, and the analysis is performed. It is possible to provide a surface analysis method for obtaining a change in position from a surface on which the cutting piece is cut from relative movement.

Specifically, the following can be provided.
(1) A cutting blade for cutting a surface sample of a sample to be analyzed, a fixing means for fixing the sample, a light source capable of irradiating analysis light to a surface sample obtained by cutting the cutting blade, and the analysis A surface on which light is irradiated to reach the surface sample, and a backup surface that backs up the surface sample; and an optical path through which data light from the surface sample irradiated with the analysis light can be analyzed. An average depth of the surface sample from the surface of the sample can be adjusted by relatively moving the fixing means and / or the cutting blade.

  Here, the surface sample is a sample obtained from the surface or surface layer of the sample, and is related to the depth from the surface (including the arithmetic average depth, the average volume by the sample volume or weight percentage, etc.). This is what you can do. The surface sample is a sample in which the influence from the inside of the sample (that is, the bulk portion; the same applies hereinafter) is limited in some way. For example, in the analysis by infrared light, A sample that can be analyzed on the basis of infrared light emitted from the sample (that is, the surface sample) without being affected, and includes at least the surface or surface layer of the sample. Here, the surface layer can mean a portion in the vicinity of the surface that can be limited so as to reduce the influence of contamination, oxide film, and the like on the outermost surface. Therefore, it is not always necessary to separate the surface sample from the sample.

  Here, the fixing means may include a fixing jig capable of fixing the sample. The cutting blade described above may have the same shape as a so-called bite used as a normal cutting tool. The cutting blade is preferably made of a material that can transmit or reflect the analysis light and the data light. The analysis light may include light irradiated for analysis, and may include indoor and outdoor light as so-called environmental light. The tip of the cutting blade that enters (or is inserted) into the sample is provided with a predetermined edge angle. The cutting edge angle is preferably 60 ° or less, more preferably 45 ° or less, and still more preferably 20 ° or less, considering the ease of penetration into the sample surface and the ease of making a surface sample. On the other hand, in consideration of the difficulty in machining the cutting edge and the ease of chipping of the cutting edge, 1 ° or more is preferable, 5 ° or more is more preferable, and 10 ° or more is more preferable.

(2) The surface analysis apparatus according to (1) above, wherein the analysis light is infrared light.

  The analysis light is not particularly limited from a short wavelength to a long wavelength, but infrared light or infrared light is preferred when measuring infrared absorption. Infrared rays are electromagnetic waves that have a longer wavelength (lower frequency) than visible red light and a shorter wavelength than radio waves. Therefore, it refers to all electromagnetic waves having a wavelength shorter than that of millimeter-wave radio waves, and the wavelength is distributed in the range of about 0.7 μm to 1 mm. That is, it can be said that the electromagnetic wave belongs between visible light and radio waves.

(3) The surface analysis apparatus according to (1) or (2) above, wherein the relative movement trajectory of the cutting blade is inclined at a predetermined angle with respect to the surface of the sample. it can.

  Here, the movement trajectory may mean a line or a surface virtually drawn by the tip of the cutting edge by moving. The cutting edge may have a straight leading edge with a predetermined edge angle, and when moving in a direction perpendicular to the leading edge (including relative movement), the movement locus draws a line in a side view. become. The relative movement may include a case where the cutting blade appears to move relatively as the sample moves even though the cutting blade is stationary when viewed from the entire system.

(4) The surface analysis apparatus according to any one of (1) to (3), wherein the backup surface is a rake face of the cutting edge.

  Here, backing up the surface sample may mean that the surface sample is located on the back side of the surface sample and is separated from the inside of the sample. Moreover, it may mean that it is in a state where it can contact the surface sample. The surface sample may be attached (or contacted or adhered) to the backup surface, or may be separated. Then, it may be behind the surface sample as viewed from the analysis light to be irradiated so that the analysis light does not reach the inside of the sample. Alternatively, analyzable light from within the sample may not reach the surface sample. The rake face may be a face on which a cut piece cut by the cutting blade is placed. For example, it can mean a surface that plays a role of scooping cutting pieces (or chips) generated in the traveling direction of the cutting edge.

(5) The surface analysis apparatus according to any one of (1) to (4), wherein the optical path is provided inside the cutting blade. At this time, the cutting blade is preferably made of a material that can transmit data light, which is light emitted from the surface sample.

  Here, the data light is light for analyzing a sample to be analyzed (for example, a surface sample). After interaction with the sample (for example, absorption, amplification, reflection, transmission, etc.), a detector is used. Or light that should be sent to the analytical instrument. That is, the data light may be polarized, absorbed, amplified, etc. due to the influence of the sample.

(6) The surface analysis apparatus according to (5), wherein the cutting blade reflects the data light on at least one surface so that the optical path can be formed therein. Further, the shape of the cutting edge can further increase reflection so that the data light can be reflected so as to be confined in at least two surfaces. Here, confining the data light may mean that the light entering the cutting blade is reflected so as not to go out of the cutting blade. The one or two surfaces are at least one of the inner surfaces of the cutting blade and that form a boundary (or interface) with the outside (for example, an open space) of the cutting blade (hereinafter referred to as “the inner surface of the cutting blade”). May include a surface. For example, data light that has once entered the inside of the cutting blade is reflected by the inner surface of the first cutting blade, travels inside the cutting blade, is reflected by the second inner surface of the cutting edge at the rear end side of the cutting blade, and is reflected. It may be subjected to analysis by passing through another cutting blade inner surface (boundary). If the reflectivity is low, it is attenuated each time it is reflected, so it is preferable that the number of reflections is small.

(7) An arrangement step in which a sample to be subjected to surface analysis and a cutting blade capable of entering from the surface of the sample are arranged to be relatively movable, and the sample and / or the cutting blade are relatively moved. An intrusion step for intruding the cutting blade from the surface of the sample, an irradiation step for irradiating an analysis light that can be analyzed from the surface of the sample and reaching a surface constituting the cutting blade, and the cutting blade It is possible to provide a surface analysis method comprising: an analysis step of receiving and analyzing light reaching the surface to be configured; and a calculation step of calculating a position from the surface from the relative movement.

(8) The surface analysis method according to (7) above, wherein the analysis light is infrared light.

(9) In the intrusion step, the rake face that is the surface constituting the cutting blade and the surface of the sample are intruded so as to form an intrusion angle of less than 90 degrees, and in the irradiation step, the analysis light The surface analysis method according to (7) or (8), wherein the surface of the rake is irradiated substantially perpendicularly to the rake face.

  Here, the penetration angle can also mean an angle formed by the surface and the rake face of the cutting edge. The cutting blade can also move relative to the rake face in a direction parallel to the rake face and enter the surface of the sample.

(10) Any one of the above (7) to (9), wherein the light irradiated from the surface and reaching the surface constituting the cutting blade passes through the inside of the cutting blade and travels to the analysis means The surface analysis method described in the above can be provided.

  Thus, a method is provided in which a cutting blade is inserted from a sample surface, and analysis light is applied from the sample surface toward the cutting blade while maintaining the inserted state, and the reflected light and / or transmitted light is analyzed. be able to. Further, the cutting blade can be coated with at least an analysis light blocking material. Then, it is possible to provide a method of analyzing from the sample cross section while inserting the cutting blade and maintaining the inserted state. At this time, the cutting edge can also be used as an analysis light blocking material. The cutting blade can be made of diamond, and the surface of the diamond can be coated with a metal film, nitride, carbide or oxide.

  According to the present invention, it is possible to analyze a state having a depth of about 100 nm or more and about 1 μm or less from the surface. In particular, the state of the part can be analyzed while changing the depth from the surface. And while cutting, the cutting piece itself can also be measured. For such analysis, it is also possible to utilize infrared absorption data accumulated so far. In addition, if the irradiation probe is devised, state analysis in a narrow area corresponding to the microscopic IR is also possible as a function in the depth direction. Further, by setting the path through which light from the sample passes within the cutting blade, the degree of freedom of the space around the sample can be increased. And since it analyzes on the spot, it is not necessary to prepare the sample for analysis separately.

It is a schematic diagram of the surface analysis system which is one example of the present invention. It is the partial expansion schematic diagram which expanded the part of the cutting blade of FIG. It is the elements on larger scale which expand further the cutting-blade part of FIG. 2, and show a mount part. It is a partial schematic diagram which shows the state which operated the surface analyzer of FIG. It is a schematic diagram explaining the main structures of the surface analyzer of another Example of this invention. It is a schematic diagram which shows the state which actuated the surface analysis apparatus of FIG. It is a schematic diagram which shows the relative positional relationship of a sample and a cutting blade. It is a schematic diagram explaining the main structures of the surface analysis apparatus of another Example of this invention. It is a schematic diagram explaining the main structures of the surface analyzer of another Example of this invention. It is the (a) partially broken perspective view and (b) BB sectional drawing of the cutting blade which may be used in another Example. In the surface analysis apparatus of another Example of this invention, it is a schematic schematic diagram which shows the state which the cutting blade penetrate | invaded into the sample. In the surface analysis apparatus of another Example of this invention, it is a schematic schematic diagram which shows the state which the cutting blade penetrate | invaded into the sample. It is a schematic diagram which shows the transition of an infrared absorption spectrum when the surface degradation of a sample is measured using the surface analysis apparatus of the Example of this invention. It is a graph showing the spatial and depth resolution of various surface analysis methods (Source: supervised by Toshio Ogawa, “New Developments in Surface Modification and Analysis of Polymers”, page 167, issued by CMC Publishing Co., Ltd. in February 2007). It is a schematic diagram of the surface analysis system which is another Example of this invention. It is a schematic diagram of the surface analysis system which is another Example of this invention. It is a schematic diagram of the surface analysis system which is another Example of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the embodiments are described for understanding the present invention and do not limit the scope of the present invention. The same or related elements are denoted by the same reference numerals, and redundant descriptions are omitted.

1 to 4 schematically show a surface analysis system according to one embodiment of the present invention. The analysis system 10 including a surface analysis device (the analysis device itself is not shown) mainly includes an optical system device 12, a cutting system device 14, and a sample holding system device 16. The optical system device 12 is provided with a CCD camera 18 and can observe a sample with its own illumination light or ambient light. Further, the analysis light 21 collected by the objective lens 20 is irradiated by being bent vertically downward by an elbow 22 formed by bending the probe. It is introduced from. As the light source 26, for example, regions of 12500～3800Cm ^-1 tungsten-iodine lamps may be to use a high intensity ceramic light source region of 7800~240cm ^-1. A mid-infrared PIR fiber system manufactured by Systems Engineering Co., Ltd. can be applied to such an analysis light probe 24.

  The cutting system device 14 includes a cutting blade 32, a cutting blade fixing jig 34 that fixes the cutting blade 32, a cutting system main body 36 that fixes the cutting blade 32, and an optical connector 38. The cutting blade 32 has an interface (or a surface different from the cutting blade 32 (including a fluid such as air and a solid) (or a solid) including a top surface 32a corresponding to a rake surface on which a cutting piece is placed and a cutting blade fixing jig 34. And a tip side 32c having a predetermined cutting edge angle. The cutting blade 32 is bonded and fixed at an edge portion 32d that defines the opening 32e of the mount plate 34a fixed to the cutting blade fixing jig 34. The cutting blade 32 should just be a hard thing which can cut a sample. However, when light is transmitted for analysis, it needs to be light transmissive. In this embodiment, the cutting edge 32 is made of diamond, and the tip side 32 c extends straight over the entire width of the cutting edge 32. However, as an option, it is possible to provide a protruding portion 32f that partially protrudes like a partially enlarged view surrounded by a circle on the upper side. At this time, the end side 32g which is a base line corresponds to the front end side 32c. With such a shape, the portion of the cutting blade that enters the sample becomes narrower, and entry can be performed more easily. On the other hand, if the protrusion 32f is too small, there is a possibility that a sufficient area (area) as a surface sample cannot be obtained. The cutting edge 32 has a parallelogram in the longitudinal section, and when the upper surface and the lower surface are arranged horizontally, when the entire size is 6 in the width direction in the figure, the cutting blade 32 is divided into two parts each in three parts. Half of the top surface on the part side is exposed to diamond. On the other hand, a half of the rear end side is provided with a reflective material coating 33 (for example, a metal such as gold or a ceramic such as TiN), and the side surface on the rear end side is also provided with the same reflective material coating 33. As such a coating material, a material having a high reflectance is preferable. For example, Spectralon (registered trademark), Spectrafect (registered trademark), Durafect (registered trademark), Infragold (registered trademark) and the like sold by Optocilius Corporation can be given as examples. Further, the clearance angle (or clearance surface) side of the tip of the cutting edge 32 is also exposed in the longitudinal (or front-rear) direction p, and the same side surface and the edge 32d of the lower surface 32b are coated with the same reflective material coating 33. ing. The cutting edge 32 has a cutting edge angle of 45 degrees, and the upper surface 32a corresponding to the rake face is disposed horizontally.

Here, as the material of the cutting blade 32, diamond that can cut a hard sample is used as an example, but other ceramics, metals, and the like can be appropriately selected and used. When analyzing using the reflected infrared light, it is not necessary for the cutting blade material to have translucency, and a material excellent in reflection is preferable. On the other hand, when analysis is performed using transmitted infrared light, it is preferable to use a material that has little reflection and excellent translucency. For example, translucent alumina or single crystal alumina (or sapphire) is expected to transmit light having a wavelength of 6.5 μm from visible light, MgF ₂ has a wavelength of 0.1 to 7.5 μm, and LiF has a wavelength of 0.1 to 7.5 μm. The translucency of light having a wavelength of 0.1 to 9 μm and CaF _{2 having} a wavelength of 0.1 to 12 μm is expected. Moreover, you may use the thing which can permeate | transmit infrared light with a wavelength of 1.2-15 micrometers although it cannot permeate | transmit visible light like Si. In particular, diamond is expected to have translucency in a wide range of 0.25 to 80 μm. However, since diamond absorbs around 4 to 5.5 μm, it is preferable to correct appropriately. Analysis using cutting blades of different materials can be performed in parallel and compensated. In addition, by measuring with different cutting edge materials, it is possible to compensate for a decrease in accuracy in a wavelength range where the material absorbs. Hereinafter, the same applies to the material of the cutting blade.

  When the cutting blade fixing jig 34 transmits light for analysis similarly to the cutting blade 32, at least a portion corresponding to the opening 32e needs to be light transmissive. For example, it may be in a hollow state. In particular, when the material is not hollow but is clogged with a translucent material, the light is guided from the cutting blade 32 to the cutting blade fixing jig 34, so that a material having a refractive index substantially equal to the material of the cutting blade 32 is more suitable. preferable. For example, quartz can be used. Further, a liquid for adjusting the refractive index can be interposed in the interface 32b in order to prevent irregular reflection on the surface. A similar reflector coating 33 is formed on the surface of the cutting blade fixing jig 34. The cutting blade fixing jig 34 is fixed to the cutting system main body 36 together with the optical connector 38, and the analysis light (data light) passing through these is guided to the optical analyzer 40 through the fiber. The cutting system main body 36 is placed on the goniometer 42 and is rotationally fixed at a preferred position. Further, the goniometer 42 is placed on an XY stage and can be moved in the horizontal direction by a servo motor or a step motor (not shown).

  The sample holding system device 16 includes a sample fixing jig 52 that fixes the sample 51 so that the surface of the sample 51 is at a predetermined angle with respect to the upper surface of the cutting blade 32. The sample fixing jig 52 fixes the sample 51 by a vacuum chuck, but this fixing can also be performed using an adhesive such as hot melt. A hand 54 for inclining and fixing the sample fixing jig 52 at a predetermined angle is fixed to a piezoelectric element stage 56 driven in the Z-axis direction by a piezoelectric element, and the piezoelectric element stage 56 is further fixed by a piezoelectric element. Fixed to the piezoelectric element stage 58 driven in the X-axis direction. These piezoelectric element stages 56 and 58 are used for adjusting the depth direction and the like in cutting with a cutting blade 32 described later. The piezoelectric element stage 58 is further placed on an X stage 62 that can be moved in the horizontal direction by a servo motor or a step motor (not shown). The cutting system device 14 and the sample holding system device 16 described here are both fixed on the base 64 and the relative position is determined.

  Next, an analysis method performed while cutting will be described with reference to FIG. In FIG. 4, it can be seen that the tip of the cutting edge 32 is inserted at a predetermined depth from the surface of the sample 51, and the cutting piece 51 a serving as the surface sample is attached to the rake face of the cutting edge 32. The remaining material 51b is on the side of the flank that ensures a certain clearance angle. The analysis light 21 is applied to the cutting piece 51 a from the analysis light probe 24 through the objective lens 20. Here, when the analysis is performed with the reflected light of the analysis light 21, the light reflected from the cutting piece 51 a may be analyzed by going back through the analysis light probe 24 as it is, and thus the detailed description is omitted. As an example of this, there is a case where a mid-infrared PIR fiber system manufactured by Systems Engineering Co., Ltd. is used with the analysis optical probe 24.

  The analysis light 21 applied to the cutting piece 51a enters the diamond cutting blade 32, and is reflected by the reflecting material coating 33 (21a) on the front side surface in the figure (21a). Is reflected by the reflecting material coating 33 in the same manner on the side surface on the rear end side (21b), and enters the lower surface 32b at a substantially right angle. Here, since the blade edge angle is 45 degrees, light incident vertically from the rake face is reflected almost horizontally. When this angle is changed, it is preferable to secure a light reflection path including securing an optical path in the cutting blade fixing jig 34 described below. The light emitted from the inside of the cutting blade beyond the lower surface 32b is similarly reflected by the reflecting material coating 33 on the wall surface in front of the hollow portion of the cutting blade fixing jig 34 (21c) and proceeds to the optical connector 38 ( 21d). This is because the front side surface of the cutting blade fixing jig 34 also has an angle of approximately 45 degrees with respect to the horizontal.

Here, the reflection of light when the optical path is in the cutting edge 32 will be considered. When light exits from the inside of the cutting blade 32, so-called incident light i travels through the refractive index n1 of the cutting blade 32 and enters the interface at an incident angle θ1. Assuming that there is air outside the cutting edge 32, the refractive index n2 is substantially equal to 1 and if it has a refraction angle θ2, the following equation holds from Snell's law.
n1 × sin (θ1) = n2 × sin (θ2)
For example, when using diamond, if n1 = 2.42 and the refraction angle θ2 = 90 degrees, the critical angle θ1 is θ1 = sin ⁻¹ (1 / 2.42 × sin (90)) = 24.4. Degree. Therefore, since the total reflection occurs at an incident angle of 25 degrees or more (for example, 45 degrees), it may not be necessary to coat the reflector. In this case, since the reflection angle θ3 = θ1, it is preferable to design the optical path appropriately.

  Here, the movement of the sample 51 that relatively moves will be described. Since the sample 51 is fixed to the sample fixing jig 52 by the vacuum chuck, when the sample fixing jig 52 moves to the arrow 52a, it moves in the same manner. Since the surface of the sample 51 having a substantially parallel surface and back surface is substantially parallel to the arrow 52a of the sample fixing jig 52, the tip of the cutting blade 32 can be moved even if the sample fixing jig 52 is moved in the direction of the arrow 52a. The position (depth from the surface of the sample 51) does not change. Therefore, the depth of the cutting piece 51a adhering to the rake face does not change. The movement in the direction of the arrow 52a can be realized by moving the piezoelectric element stage 56 in the Z-axis direction and the piezoelectric element stage 58 in the X-axis direction in cooperation. Here, in order to change the depth, the surface of the sample 51 and the rake face of the cutting edge 32 are set to a predetermined angle (in order to analyze the very surface layer, it is preferably 60 ° or less, more preferably 45 °. Or less, more preferably 30 ° or less, and considering the ease of penetration (or insertion), 3 ° or more is preferable, 5 ° or more is more preferable, and 7 ° or more is more preferable. If the movement is more rearward (or upward) than the direction parallel to the surface (for example, moving horizontally toward the tip of the cutting edge 32), the distance from the surface becomes deeper and the deeper position A cutting piece 51a made of the above material can be obtained. On the other hand, if the movement is more forward (or downward) than the direction parallel to the surface (for example, the sample 51 is moved vertically downward as it is), the distance from the surface becomes shallower, and the shallower position A cutting piece 51a made of a material can be obtained. Since the details of these movements can be precisely and freely performed by the piezoelectric element, the cutting piece 51a can be obtained freely in the depth direction. Profiling in the depth direction is also possible by linking the analysis result and this depth data. Such a relationship between movement and depth will be described later with respect to another aspect.

  FIGS. 15 to 17 each show a surface analysis system according to another embodiment. Since the basic configuration is the same as that in FIG. 1, overlapping portions are omitted. In FIG. 15, the cutting edge 31 of the cutting system device 14 ′ is different from the cutting edge 32 of FIG. 1 in that the rear end portion is a vertical surface (rear end surface). Further, the rear end surface of the rear end portion is not coated with a reflecting material. Light from the light source 26 (especially infrared light) passes through the probe 24, passes through the sample on the rake face, enters the cutting blade 31, and the light reflected by the lower left reflective material coating 33 is converted into the cutting blade. The probe 31 is arranged so as to pass through the probe 25 from a cross section of the probe 25 that passes through the probe 31 and directly contacts the rear end surface. The probe 25 is fixed to the cutting system main body 36 and guides light for analysis to the optical analyzer 40. On the other hand, in FIG. 16, the cutting blade 31 of the cutting system device 14 ″ has the same shape as the cutting blade 31 of FIG. 15, but a reflector coating 33 is formed on the rear end surface. Light (especially infrared light) from the light source 26 passes through the probe 24, passes through the sample on the rake face, enters the cutting blade 31, passes through the cutting blade 31, and directly contacts the lower left side surface. It arrange | positions so that the inside of the probe 25 may be passed from a cross section. The probe 25 guides light for analysis to the optical analyzer 40.

  In FIG. 17, the optical system of FIGS. 15 and 16 is combined, and the cross section of the probe 25 is in direct contact with the rear end surface and the lower left side surface of the cutting blade 31 of the cutting system device 14 ′ ″. The light reflected by 25 and the light not reaching the reflection are guided to the optical analyzer 40. In such a complex system, even with the same sample, the amount of insertion of the cutting blade 31 can be increased to perform analysis with reflected light and non-reflected light. In such a system, unlike the case of FIG. 1, it is not necessary to make two or more reflections in the cutting blade, and attenuation of light for analysis can be reduced. Therefore, the accuracy is expected to be improved.

5 and 6 are schematic diagrams for explaining the main configuration of a surface analysis apparatus according to another embodiment. Both the cutting blade 140 and the sample 150 are fixed 160 and moved 170 by a fixing device (not shown). The infrared light 120 that is the analysis light is applied to the rake face of the cutting blade 140, and the cutting piece 152 can be analyzed. In this embodiment, since the edge angle is very acute, it is more preferable to perform analysis using reflected light of the infrared light 120. First, as described above, the cutting blade 140 and the sample 150 are arranged in a predetermined positional relationship, and the tip of the cutting blade 140 bites into the surface of the sample 150 and is separated into the cutting piece 152 and the remaining material 154. At this time, the sample 150 is moved in the direction of the arrow 170 by the piezoelectric element stage in the same manner as described above, and the cutting edge enters deeper from the surface of the sample 150. Therefore, analysis by infrared light is analysis of material at a deeper position. This relationship will be described with reference to the schematic diagram of FIG. The rescue surface of the cutting blade 140 is horizontal, and the surface of the sample 150 is inclined at an angle α. Here, if the distance moving in the direction of the arrow 170 is d, in the figure, the distance along the surface from the biting position of the tip of the cutting blade 140 is X, and the distance from the surface of the tip of the cutting blade 140 is Y. , D = X · cos (α), and Y = X · tan (α). From these, Y = d · sin (α) / cos ² (α) is obtained. Here, if α is approximately 1 °, it is assumed that cos (α) = 1, and Y = d · sin (α). That is, the deepest place in the cutting piece 152 is Y = d · sin (α), and if the average depth is an arithmetic average, the depth <Y> = d · sin (α) / 2. .

  FIG. 8 is a schematic diagram illustrating a main configuration of a surface analysis apparatus according to still another embodiment. Here, the cutting edge 140 has a rake face fixed horizontally (arrow 160), and the infrared light 120 is irradiated toward the rake face. The surface of the sample 150 is also horizontal, and the sample 150 moves substantially horizontally (170). Therefore, the cutting blade 140 inserted from the side surface of the sample 150 scrapes off the cutting piece 152 whose depth does not change. Therefore, it is possible to analyze the cutting piece 152 having the same depth. However, in this case, since there is substantially no clearance angle, the remaining material 154 may damage the cutting blade 140. Therefore, as shown in FIG. 9, if the right side surface of the sample 156 fixed on the substrate 158 to be fixed is cut downward, the influence of the remaining material is reduced.

  FIG. 10 shows (a) a partially broken perspective view and (b) a BB cross-sectional view of a cutting blade 260 that can be used in a surface analysis apparatus of another embodiment. The cutting blade 260 is provided with a sharp portion 262 having a protruding portion 32f protruding at the tip, and has a cutting edge angle γ. When the tip of the cutting edge enters the sample, the sharp portion 262 places the surface sample of the sample on the upper surface. The sharpened portion 262 extends to the boundary 264 and continues to the main body of the cutting blade 260 having an upper surface 266 that serves as a rake face. Here, the lower surface 268 serving as a reference for the clearance angle is common, and forms a so-called rake angle (45 degrees in this embodiment) that is larger than the blade edge angle γ. The lower surface 268 and the rake surface 266 form an angle of 45 degrees. Therefore, when the analysis light entering perpendicularly to the rake face 266 is incident into, for example, a diamond cutting blade, the lower surface 268 is irradiated at an incident angle of 45 degrees and reflected by the coating. Then, the cutting blade 260 can travel parallel to the rake face 266 with a reflection angle of 45 degrees.

  FIG. 11 schematically shows a state in which the cutting blade has entered the sample in the surface analysis apparatus of another embodiment. The cutting blade 240 enters the sample 150 in the direction of the arrow 200 that is parallel to the rake face 242. At this time, the penetration angle formed by the surface 150a of the sample 150 and the rake face 242 (or the arrow 200) is α1. The cutting edge angle of the cutting blade 240 is 45 degrees. As shown in the drawing, when the surface sample of the sample 150 is placed on the rake face 242 (or the surface sample is backed up by the rake face 242) and irradiated with the analysis light 120, the surface sample is transmitted through the cutting edge 240. Break into. At this time, the analysis light 120 is incident on the rake surface 242 substantially perpendicularly, so that the light (that is, the data light) 122 entering the cutting blade 240 hits the lower surface 248 at 45 degrees and has a reflection angle of 45 degrees. Reflected and travels in the cutting blade 240 substantially parallel to the rake face.

  FIG. 12 schematically shows a state in which a cutting blade has entered a sample in a surface analysis apparatus of still another embodiment. The cutting blade 250 enters the sample 150 in the direction of an arrow 202 that is parallel to the rake face 252. At this time, the penetration angle formed by the surface 150a of the sample 150 and the rake face 252 (or arrow 202) is α2. Further, the cutting edge angle of the cutting edge 250 is γ. As shown in the figure, when the surface sample of the sample 150 is placed on the rake face 252 due to intrusion (or the surface sample is backed up on the rake face 252) and irradiated with the analysis light 120, the surface sample passes through the rake face. The light is reflected at 252 and proceeds as data light 124 in the opposite direction of the analysis light 120. The reason for this is that the edge angle γ of the cutting edge 250 is considerably smaller than 45 degrees compared to FIG. 11, and it is not always easy for data light to pass through the cutting edge 250. However, since the edge angle γ is small, it is easy to enter the sample at the tip of the cutting edge, and it is possible to provide a surface sample with higher accuracy at a distance from the surface.

  FIG. 13 shows a graph in which infrared absorption spectra are vertically arranged when the surface degradation of the sample is measured using the surface analysis system 10 (which may include a surface analysis device) described above. The vertical axis represents arbitrary intensity, and the horizontal axis represents wave number. Sample C is taken from the inside of the sample, Sample B is taken from a deep portion of the surface sample, and Sample A is a surface sample closer to the surface. The most prominent peak in sample A is attributed to the stretching vibration of the compound bond representing the degree of deterioration of the sample, and it can be seen that the deterioration is most advanced in sample A. Here, for example, assuming that the inclination angle α is 10 °, the sample A is moved by the relative distance d from the start of insertion by 3 μm, and the sample B is further moved by the additional relative distance d by 8 μm. Since the average depth of each is 0.26 μm and 0.69 μm, the degree of degradation due to the depth can be grasped at least qualitatively. Can be compensated for (for example, internal standard method), so qualitative understanding is also possible.

  As described above, in the surface analysis apparatus and the surface analysis system of the present invention, it is possible to perform sequential analysis while cutting, and to take the depth direction from the surface as a variable. In addition, using a cutting blade with a special shape and reflection structure for transmitted light, it is possible to evaluate the depth direction region of submicron order by infrared analysis, and any material that can be cut can be analyzed. Can be a target. For example, 1) Analysis of organic material films as electronic materials such as low-k films, resist films, and organic EL, and foreign substances attached to them, 2) Analysis of surface layers and depth directions of various plastics and coatings 3) It is possible to perform analysis in the depth direction of stabilizers such as ABS, PC, PP, PVC, and antioxidants. Furthermore, 4) It is possible to examine changes in the elapsed time of materials from the surface to the interior and changes in internal additives from durability tests such as weather resistance tests, and 5) structural changes due to thermal degradation of these materials, and water resistance tests. Not only can structural changes be confirmed, but 6) analysis in the depth direction from the surface of plants and biomaterials is also possible, so 7) food surface layer additives can be examined in detail.

10 analysis system, 12 optical system device, 14 cutting system device,
16 Sample holding system device, 21 Analytical light,
21a, 21b, 21c, 21d measurement light, 24 analysis light probe,
26 light source, 32, 140 cutting edge, 32a rake face,
33 Reflector coating, 51, 150 samples,
51a, 152 Cutting piece, 52 Sample holding jig

Claims (4)

A cutting edge for cutting a surface sample of a sample to be analyzed;
Fixing means for fixing the sample;
A light source capable of irradiating analysis light to a surface sample obtained by cutting the cutting blade;
A back-up surface for backing up the surface sample, which is a surface that the analysis light is irradiated to reach the surface sample;
Provided inside of the cutting edge, and an optical path for analyzable pass data light from the surface sample which the analysis light is irradiated,
The cutting blade reflects the data light on at least one surface so that the optical path can be formed therein,
The surface analysis apparatus characterized in that an average depth of the surface sample from the surface of the sample can be adjusted by relatively moving the fixing means and / or the cutting blade.   The surface analysis apparatus according to claim 1, wherein the analysis light is infrared light.   The surface analysis apparatus according to claim 1, wherein the relative movement trajectory of the cutting blade is inclined at a predetermined angle with respect to the surface of the sample.   The surface analysis apparatus according to claim 1, wherein the backup surface is a rake face of the cutting edge.

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