JP2008038198A - Method and device for measuring metal oxidation degree of metal vapor-deposited film, and method and device for measuring film thickness - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable the oxidation degree of a metal vapor-deposited film to be measured independently of a film thickness. <P>SOLUTION: In a metal vapor-deposited film forming device, a film (3) for vapor deposition uncoiled from an uncoiling roll (2) is coiled around a cooling roll (4) at a predetermined angle, vapor-deposited with a metal vapor, and coiled around a coiling roll (5), and oxygen is fed to the metal vapor from upstream and downstream sides. A surface reflectance sensor (10) and a transmittance sensor (11) are arranged between the coiling roll (5) and the cooling roll (4) close to the surface of the film (3) for vapor deposition, and the oxidation degree of the metal in the metal vapor-deposited film is calculated from the detected values of the surface reflectance sensor (10) and the transmittance sensor (11) without depending on the thickness of the metal vapor-deposited film. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for measuring a metal oxidation degree of a metal vapor-deposited film, a metal oxidation degree measuring apparatus, a film thickness measuring method, and a film thickness measuring apparatus, for example, a method for measuring the oxidation degree and film thickness of cobalt oxide deposited on a film for vapor deposition. And an apparatus.

  Conventionally, various studies have been made on the characteristics of metal vapor deposition films formed on vapor deposition films. For example, in Japanese Patent Application Laid-Open No. 61-9575 (Patent Document 1), an apparatus for detecting a change in vapor deposition film composition during the production of a vapor deposition film by installing two sensors between the vapor deposition position and the film winding position. Is disclosed. That is, the transmittance and reflectance values obtained from the two sensors maintain a certain relationship. Therefore, the composition deviation of the deposited film in the deposition process can be determined by causing an error in the relative relationship between the transmittance and the reflectance.

Japanese Patent Laid-Open No. 63-473 (Patent Document 2) measures the film thickness of a thin film formed on a substrate and the reflectance and transmittance of the thin film and the substrate in-process. After calculating the refractive index n and extinction coefficient k of the thin film according to the signal, the thin film is formed so that at least one of the calculated values n and k approaches the preset refractive index n ₀ and extinction coefficient k _0. By controlling the conditions, in-process composition control can be realized, and a desired thin film composition can be obtained.
JP 61-9575 A JP-A 63-473

  In the above Patent Document 1, the composition change of the deposited film is detected, and the degree of metal oxidation of the deposited film is not measured. Also, it does not measure the film thickness.

  In Patent Document 2, the composition of the thin film is controlled, and the degree of oxidation of the metal in the thin film is not measured. Also, it does not measure the film thickness.

  On the other hand, when measuring the degree of oxidation of a cobalt oxide layer formed on a film for vapor deposition, for example, currently using Auger Electron Spectroscopy (hereinafter referred to as AES), a sample is extracted after production and measured on a desk. Is going. Therefore, there is a delay in feedback to the manufacturing process when an abnormality is detected, and product yield is deteriorated.

  Furthermore, since AES is a destructive measurement and it is difficult to reduce the size, in-line measurement is difficult.

  The fluctuation in the degree of oxidation is monitored simply by measuring the fluctuation in the reflectance on the film surface in-line, but the reflectance on the film surface depends on the fluctuation in the film thickness of the cobalt oxide layer and is accurately oxidized. It has not led to a degree. Furthermore, the present situation is that the degree of oxidation at the interface between a film such as PET and the magnetic layer cannot be measured.

  In addition, the film thickness of the cobalt oxide layer inline is calculated from the change in transmittance. However, the transmittance of the film depends on the change in the degree of oxidation, and the film thickness can be measured accurately. There is no current situation.

  As described above, the problem of the present invention is that the degree of metal oxidation or film thickness of the deposited film formed on the film for vapor deposition is always accurately measured without depending on the film thickness or the degree of oxidation, respectively. An object of the present invention is to provide a metal oxide film measuring method, a metal oxide film measuring apparatus, a film thickness measuring method, and a film thickness measuring apparatus for a metal deposited film.

  The above-mentioned problems are that the vapor deposition film unwound from the unwinding roll is wound around the cooling roll at a predetermined angle, the metal vapor is deposited from below, wound on the winding roll, and upstream and downstream of the metal vapor. In a metal vapor deposition film forming apparatus in which oxygen is supplied from the side, a surface reflectance sensor and a transmittance sensor are disposed between the winding roll and the cooling roll in proximity to the surface of the vapor deposition film. The metal oxidation degree in the metal vapor deposition film is calculated from the detection values of the surface reflectance sensor and the transmittance sensor without depending on the film thickness of the metal vapor deposition film. This is solved by a method for measuring the degree of metal oxidation of a deposited film.

Further, the above-described problem is that the vapor deposition film unwound from the unwinding roll is wound on the cooling roll at a predetermined angle and wound, and the metal vapor is deposited from below and wound on the take-up roll. In the metal vapor deposition film forming apparatus that supplies oxygen from the downstream side, a surface reflectance sensor and a transmittance sensor are disposed between the vapor deposition roll and the take-up roll in proximity to the vapor deposition film surface. And a calculation unit for calculating the metal oxidation degree in the metal vapor deposition film from the detection values of the surface reflectance sensor and the transmittance sensor without depending on the film thickness of the metal vapor deposition film. It solves by the metal oxidation degree measuring apparatus of the metal vapor deposition film characterized.

In addition, the above-mentioned problems are that the vapor deposition film unwound from the unwinding roll is wound on the cooling roll at a predetermined angle, wound with metal vapor from below, wound on the winding roll, and upstream of the metal vapor. And a metal vapor deposition film forming apparatus configured to supply oxygen from the downstream side, and a surface sensor and a transmittance sensor are disposed between the cooling roll and the take-up roll in proximity to the surface of the vapor deposition film. The metal vapor deposition is characterized in that the film thickness of the metal vapor deposition film is calculated from the detection values of the surface reflectance sensor and the transmittance sensor without depending on the fluctuation of the oxidation degree of the metal vapor deposition film. This is solved by a film thickness measuring method.

In addition, the above-described problems are that the vapor deposition film unwound from the unwinding roll is wound on the cooling roll at a predetermined angle and wound, and metal vapor is deposited from below, wound on the take-up roll, and upstream of the metal vapor. And a metal vapor deposition film forming apparatus configured to supply oxygen from the downstream side, and a surface sensor and a transmittance sensor are disposed between the cooling roll and the take-up roll in proximity to the surface of the vapor deposition film. In addition, a calculation unit is provided that calculates the film thickness of the metal vapor deposition film from the detection values of the surface reflectance sensor and the transmittance sensor without depending on the variation in the degree of oxidation of the metal vapor deposition film. This is solved by a device for measuring the thickness of a metal vapor-deposited film.

  The metal oxidation degree of the deposited film can be measured in-line without depending on the film thickness. Further, the film thickness can be measured in-line without depending on the metal oxidation degree.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 1 is an overall schematic view of a cobalt deposited film forming apparatus according to an embodiment of the present invention, but the inside of the vacuum chamber 1 is evacuated by an evacuation system, not shown. The vapor deposition film 3 (made of PET, for example) that is sequentially unwound from the unwinding roll 2 is mounted on the cooling roll 4 at about 180 degrees as shown in the figure, and is wound on the winding roll 5.

  A crucible 6 is disposed obliquely below the cooling roll 4 and the crucible 6 is filled with cobalt metal. Electrons e are irradiated to the cobalt metal in the crucible 6 from the electron gun 7 disposed obliquely above, and the metal material is heated and melted. Cobalt metal vapor m rises from the crucible 6 toward the cooling roll 4 as shown in the figure.

  Oxygen is blown toward the steam m from an upstream oxygen introduction pipe 8 disposed on the upstream side in the film traveling direction. Furthermore, oxygen is also blown from the downstream oxygen introduction pipe 9 disposed on the downstream side.

  In this way, cobalt oxide is deposited on the deposition film 3, and as shown in FIG. 2, the film layer 23 (that is, the deposition film 3) and the interfacial cobalt layer are sequentially formed from the upper layer of the cobalt oxide deposition film 20. 22 and a cobalt oxide layer 21 in the film. The surface reflectance sensor 10 is disposed in the vicinity of the surface side of the cobalt oxide vapor-deposited film 20, that is, the cobalt oxide layer 21 side in the film, and the back surface reflectance sensor 12 is disposed on the back surface side. Note that the thickness of the interfacial cobalt oxide layer 22 is about 15 to 20% of the entire cobalt oxide layer 21 in the film.

  Further, the light emitting portion 11a of the transmittance sensor 11 is similarly disposed in the vicinity of the downstream side of the surface reflectance sensor 10. Opposite to the light emitting portion 11a, the light receiving portion 11b of the transmittance sensor 11 is disposed on the back side of the cobalt oxide vapor deposited film 20, that is, in the vicinity of the vapor deposition film layer 23 (FIG. 2). Has been. Thus, the surface reflectance sensor 10, the transmittance sensor 11, and the back surface reflectance sensor 12 are disposed between the cooling roll 4 and the take-up roll 5.

  The input lines to the surface reflectance sensor 10, the transmittance sensors 11a and 11b, and the back surface reflectance sensor 12 and the output lines therefrom are arranged in the atmosphere via a seal member R that is airtightly attached to the opening of the vacuum chamber 1. The reflectance / transmittance measuring device 13 is electrically connected. Here, the ratio of the standard reflectance to the detection value of the front surface reflectance sensor 10 or the back surface reflectance sensor 12 is calculated, and the reflectance y graduated on the vertical axis Y of the graph of FIG. 3 is supplied to the arithmetic device 14 as data. Is done. Further, the transmittance x with respect to the transmittance reference ND filter and the detected value of the transmittance sensor 11 are scaled on the horizontal axis X of the graph of FIG.

  In the first embodiment of the present invention, the film thickness under standard conditions (determined according to actual manufacturing conditions) is set as the standard film thickness.

  The increase / decrease of the film thickness can be changed by the traveling speed of the vapor deposition film 3 and the evaporation speed of the cobalt metal vapor m in the crucible 6, but in this embodiment, as shown in FIG. %, -10%, and -20% of the film thickness, and each film thickness is increased or decreased by + 10%, + 20%, -10%, -20% of the oxidation degree under the standard conditions. , Transmittance x and reflectance y are measured. In the graph of FIG. 3, the degree of interface oxidation is constant. That is, the amount of oxygen introduced from the upstream oxygen introduction pipe 8 is constant.

In FIG. 3, approximate curves y _1, y _2, y _{3, and} y ₄ are measurement points determined by reflectance y and transmittance x with respect to an oxidation degree of −20%, −10%, a standard oxidation degree, and an oxidation degree of + 10%, respectively. It is an approximate curve connecting four points, four points, three points, and four points of (x, y). However, when the degree of oxidation was + 20%, only two points of measurement data were obtained, so an approximate curve could not be obtained. The degree of oxidation is determined by the amount of oxygen 0 L / min derived from the downstream oxygen introduction pipe 9, but the standard degree of oxidation is assumed to be the amount of oxygen under actual manufacturing conditions, for example, 1.0 L / min.

The logarithmic curve functions for the approximate curves y _1, y _2, y _3, y ₄ are as described in the corners of FIG.

For example, y ₁ = 3.557Ln (x) +45.849.
R ² = 0.9725 R is a multiple correlation coefficient. A good correlation close to 1 is obtained. The same applies to the other y ₂ , y ₃ and y ₄ .
In the above equation, y ₁ is a reflectance and x is a transmittance, but 3.557 and 45.849 are constants at an oxidation degree of −20%.

In the graph of FIG. 3, the transmittance of the deposited film 20 is taken as the X axis, and the reflectance of the film is taken as the Y axis. The data (x, y) plotted on the graph is ± 10% from the in-film oxidation degree under the standard condition, ± 10%, ± 10% from the film thickness under the standard condition, and ± 10% from the film thickness under the standard condition. It is each result which measured the transmittance | permeability of the film 20 of the sample of which the film thickness was changed with% and +/- 20%, and the reflectance of the film 20 surface. A sample in which the oxidation degree in the film is constant and the film thickness condition is changed is approximated to the natural logarithmic function of curves y _1, y _2, y _{3, and} y ₄ in FIG. 3, and a good correlation is obtained. The natural logarithm function of each approximate curve is expressed as y = a * Ln (x) + b (Equation 1)
FIG. 4 is a graph in which the coefficients a and b are extracted as the Y axis and the in-film oxidation degree as the X axis. The X axis in FIG. 4 represents the standard in-film oxidation degree as 100. The coefficients a and b of the natural logarithmic function in FIG. 3 are linearly approximated with respect to the variation in the oxidation degree in the film, and a good correlation is obtained. From FIG. 4, a linear linear function for obtaining the relationship between the in-film oxidation degree s and the coefficients a and b: a = 0.0425 * s + 0.2558 (Formula 2)
b = −0.6891 * s + 100.62 (Formula 3)
Is obtained. Here, s indicates the degree of oxidation in the film.

The numerical values in (Expression 2) and (Expression 3) are the values obtained in this study. When the reflectance / transmittance reference is changed, the data in FIG. ) (Equation 3) must be obtained. However, this can be done simply by changing the reference in the reflectance / transmittance measuring device 13. Here, the reference refers to an object that needs to be measured in advance before measurement in order to calibrate the reflectance / transmittance. For example, the reflectance is a reflector having a constant reflectance, and the transmittance is an ND filter having a constant transmittance.

Substituting the functions (Equation 2) and (Equation 3) in FIG. 4 into (Equation 1) in FIG.
y = (0.0425 * s + 0.2558) * Ln (x) + (− 0.6891 * s + 100.62) (Formula 4)

Furthermore, when the in-film oxidation degree s of (Equation 4) is taken to the left side,
s = (y−100.62 + 0.2558 * Ln (x)) / (0.0425 * Ln (x) −0.6891) (Formula 5) From FIG. 3, since x is the transmittance and y is the reflectance of the surface, by substituting the measurement results of the transmittance and the surface reflectance of the film into x and y in (Equation 5), the degree of oxidation in the film s can be obtained.

The change in the degree of interface oxidation changes the reflectance and transmittance on the back surface, but does not affect the reflectance on the front surface side. When the degree of interfacial oxidation varies, the variation in transmittance exhibits the same behavior as the variation in film thickness, and therefore does not affect the method for measuring the degree of oxidation in the film.

In addition, since the reflectivity of the back surface is less dependent on the film thickness variation, it is not necessary to use a derivation method for the degree of interface oxidation such as the degree of oxidation in the film. it can.

FIG. 5 and FIG. 6 show a second embodiment of the present invention, which is a case where the film thickness is obtained from the reflectance and transmittance without depending on the degree of oxidation. The approximate curve y ₁ represents the relationship between the reflectance and transmittance when the oxidation degree is −20%, −10%, standard, + 10%, + 20% with respect to the film thickness of −20% with respect to the standard film thickness.

The approximate curve y ₂ represents the relationship between the reflectance and the transmittance when the oxidation degree is −20%, −10%, + 10%, + 20% with respect to the film thickness of −10% with respect to the standard film thickness.

Similarly, the approximate curve y ₃ represents the relationship between the reflectance and the transmittance when the oxidation degree is −20%, −10%, + 10%, + 20% with respect to the film thickness of + 10% with respect to the standard film thickness. Natural logarithmic functions are described in FIG.
For example,
y ₁ = -21.592 Ln (x) +124.57
R ² = 0.9973
Again, R is close to 1 and the correlation is good.

Although the constants −21.592 and 124.57 are different in y ₂ y ₃ , these are represented as a and b, and the vertical axis represents the film thickness t. Three spots can be obtained from the numerical data in FIG. These are linearly approximated.
That is,
a = 0.0787t−27.748
b = -1.4733t + 241.57
R ² is 0.9974 and 0.9775, respectively, and the correlation is good. t is the film thickness. The above numerical values are obtained in this study. When the reflectance and transmittance standards are changed, it is necessary to re-acquire the data in FIG. 5 and obtain the expressions a and b. However, as in the first embodiment, if the previous reference reflectance in the reflectance / transmittance measuring device 13 and the relationship between the reference transmittance and the new one can be specified, only the previous calculation can be performed. It is possible to change the data.

Substituting the above-mentioned a and b into the general formula y = a * Ln (x) + b,
y = (0.0787t−27.748) * L (x) + (− 1.4733t + 241.57).
If you bring the film thickness t in this formula to the left side,
t = (y−241.57 + 27.748 * Ln (x) / (0.0787 * Ln (x) −1.4733) Equation (1)
Since x is the transmittance and y is the reflectance from FIG. 5, the film thickness t can be obtained by substituting the measured results of the transmittance and reflectance of the deposited film into x and y in the above equations.

  The above equation (1) is stored in the memory in the arithmetic unit 14 in FIG. 1, and when the reflectance y and the transmittance x are measured, the film thickness t can be obtained by immediately substituting into the above equation (1). . A display representing this numerical value may be connected to the arithmetic unit 14. The same applies to the degree of oxidation in the first embodiment.

FIG. 7 shows the relationship between the measured back surface reflectance x and the interface oxidation degree y. The degree of interfacial oxidation was determined by setting the oxygen supply amount from the upstream oxygen introduction pipe 8 to 0.5 L · min. (◯), 1 L / min. (△), and 1.5 L · / min. (×). .
Linear relationship can be expressed as y = −306.57x + 254.51.
The correlation is good at R ² = 0.9998.

  The graph of FIG. 3 is obtained under the condition that the degree of interface oxidation is constant. If the back surface reflectance sensor 12 detects that the degree of interface oxidation fluctuates from this constant value, this fluctuation is obtained. The transmittance of the minute is corrected. For example, the (x, y) value Δ at the standard oxidation degree at the time of measuring the standard film thickness is moved in the direction of the X axis in FIG. If this correction is not performed, the standard film thickness appears to have increased or decreased. Of course, the same applies to other film thicknesses.

As described above, the degree of cobalt oxidation s can be calculated from the reflectance measurement value y and the transmittance measurement value x without depending on the film thickness, and the deposition thickness t of cobalt oxide can be oxidized. Regardless of the degree, it can be obtained by calculation from the reflectance measurement value y and the transmittance measurement value x. The arithmetic expressions for obtaining the oxidation degree s and the film thickness t are set as described above and stored in the memory in the arithmetic unit 14.

In order to obtain the graphs of FIGS. 3 and 5, the traveling speed of the vapor deposition film 3, the evaporation speed of cobalt from the crucible 6, the oxygen supply amount from the upstream oxygen introduction pipe 8, and the downstream oxygen introduction pipe 9 Although the oxygen supply amount was changed, during the deposition of cobalt oxide onto the deposition film 3 during actual production, the traveling speed of the deposition film 3 and the crucible 6 were adjusted so as to obtain the standard oxidation degree and the standard film thickness. The cobalt evaporation rate, that is, the electron irradiation intensity of the electron gun 7, the supply amount of oxygen from the upstream oxygen introduction tube 8, and the supply amount from the downstream oxygen introduction tube 9 are constant.

Next, a method for measuring the degree of oxidation of cobalt oxide and the film thickness with respect to the cobalt oxide vapor deposition film forming apparatus in the manufacturing process will be described with reference to FIG. 1 again.

The unwinding roll 2, the winding roll 5, and the cooling roll 4 are driven so that the vapor deposition film 3 travels in the direction of arrow ⇒. The peripheral surface of the cooling roll 4 is cooled, and the cobalt vapor m from the crucible 6 is oxidized by being blown with oxygen from the upstream oxygen introduction pipe 8 and the downstream oxygen introduction pipe 9 and immediately deposited on the deposition film 3. The

The interfacial cobalt oxide layer 22 shown in FIG. 2 is formed, and then the in-film cobalt oxide layer 21 is formed by blowing oxygen from the downstream oxygen introduction pipe 9. In the vicinity of separation from the cooling roll 4 to the take-up roll 5, the front surface reflectance sensor 10, the light emitting portion 11 a of the transmittance sensor 11, and the rear surface reflectance sensor 12 and the transmittance sensor 11 receive light on the back surface side. The part 11b is disposed in proximity.

The light from the light source in the reflectance / transmittance measuring device 13 is reflected from the surface reflectance sensor 10-the light projecting portion 11a of the transmittance sensor 11 and the light projecting fiber of the back surface reflectance sensor 12, and the cobalt oxide deposited film of the film 3 for deposition. And projected on the film. The reflected light and transmitted light are incident on the spectroscopic element in the reflectance / transmittance measuring device 13 through the light receiving fiber of the light receiving portion 11 of the surface reflectance sensor 10 and the transmittance sensor 11, and are decomposed and measured for each wavelength. Is done. Note that the same configuration is used when obtaining the graphs of FIGS. 3 and 5 described above. The description is partially omitted. The measurement data is supplied to the arithmetic unit 14 and substituted into the above-described equations for the degree of oxidation s and the film thickness t set inside. Thus, these are found online independently. If these indicate abnormal values, the crucible 6, the electron gun 7, the upstream oxygen introduction pipe 8, the downstream oxygen introduction pipe 9 and the like are adjusted. Of course, these may be automatically adjusted in comparison with normal values.

The effects of the above embodiment are summarized as follows.

Even if the film thickness of the cobalt oxide layer varies due to variations in deposition rate and line speed, the degree of oxidation can be made accurate.

At the same time, the thickness of the cobalt oxide layer can be measured, and the cost of the measuring apparatus can be reduced.

  By measuring the degree of oxidation in-line, if the measurement result deviates from the target value, the desired amount of oxidation can be obtained in real time by changing the amount of oxygen introduced during production, improving quality and yield. Can be expected.

As mentioned above, although embodiment of this invention was described, of course, this invention is not limited to these, A various deformation | transformation is possible based on the technical idea of this invention.

For example, a plurality of front surface reflectance sensors 10, back surface reflectance sensors 12, and transmittance sensors 11 are provided in the width direction of the deposition film 3 or the deposition film 20, and the oxidation degree distribution in the width direction of the deposition film 3 and The film thickness distribution may be measured.

Alternatively, the front surface reflectance sensor 10, the back surface reflectance sensor 12, and the transmittance sensor 11 are continuously or intermittently moved in the width direction of the deposition film 3 or the deposition film 20 to correspond to the corresponding deposition film 3 or deposition. You may make it measure the oxidation degree or film thickness of the part of the film 20. FIG.

Moreover, although cobalt was demonstrated as a metal in the above embodiment, it is not restricted to these, For example, it is applicable also to thin film oxides of magnetic materials, such as iron, chromium, and nickel. Further, the present invention can be applied to any metal as long as the transmittance varies by oxidizing the thin film metal.

The schematic side view which shows the metal vapor deposition film forming apparatus with which this invention is applied with the measuring apparatus by embodiment. The partial expanded sectional view of the cobalt oxide layer formed on the film for vapor deposition. Each measurement graph of transmittance-reflectance to determine the degree of oxidation independent of film thickness. The graph with respect to the oxidation degree s which plotted the coefficients a and b based on each measured value in FIG. Each measurement graph of transmittance-reflectance for determining film thickness without depending on the degree of oxidation. The graph with respect to the film thickness which plotted the coefficients a and b based on each measured value in FIG. The graph which shows the relationship between the back surface reflectance by measurement, and an interface oxidation degree.

Explanation of symbols

2 ... unwinding roll, 3 ... film for vapor deposition, 4 ... cooling roll, 5 ... take-up roll, 6 ... crucible, 8 ... upstream oxygen inlet tube, 9 ...・ Downstream oxygen introduction pipe, 10... Surface reflectance sensor, 11... Transmittance sensor, 12 .. back surface reflectance sensor, 13... Reflectance / transmittance measuring device, 14. Equipment, 20 ... deposition film

Claims (24)

  The vapor deposition film unwound from the unwinding roll is wound around the cooling roll at a predetermined angle, and metal vapor is deposited from below, wound on the take-up roll, and oxygen is supplied from the upstream and downstream sides to the metal vapor. In the metal vapor deposition film forming apparatus, a surface reflectance sensor and a transmittance sensor are disposed between the winding roll and the cooling roll in the vicinity of the surface of the vapor deposition film, and the surface reflectance The metal oxidation of the metal vapor deposition film is characterized in that the metal oxidation degree in the metal vapor deposition film is obtained by calculation from the detection value of the sensor and the transmittance sensor without depending on the film thickness of the metal vapor deposition film. Degree measurement method. The calculation is a step of obtaining the detection values (x, y) of the transmittance sensor and the reflectance sensor at each film thickness by varying the film thickness of the metal vapor deposition film at each of a plurality of predetermined degrees of oxidation. When,
Connecting a plurality of the detected values (x, y) to approximate a curve to obtain a natural logarithmic function, and setting the natural logarithmic function to y = a * Ln (x) + b;
(Where x is transmittance, y is reflectance, and a and b are constants)
A linear approximation of the relationship between the predetermined degree of oxidation s and the constants a and b
obtaining a linear function of a = c * s + d, b = e * s + f,
S = (y−f + d * Ln (x)) / (c * Ln (x) + e) is derived from the functions of y, a, and b, and the in-film oxidation degree is obtained in-line. The method for measuring a metal oxidation degree of a metal deposited film according to claim 1.   A back surface reflectance sensor is disposed between the winding roll and the cooling roll in the vicinity of the back surface of the vapor deposition film, and an interface oxidation degree is obtained from a detection value of the back surface reflectance sensor. The method for measuring the degree of metal oxidation of a metal vapor-deposited film according to claim 1. A plurality of the surface reflectance sensors and a plurality of the transmittance sensors are disposed in the width direction of the vapor deposition film, and the degree of oxidation in the metal vapor deposition film of the vapor deposition film facing each other is determined. The method for measuring a metal oxidation degree of a metal deposited film according to claim 1. The degree of oxidation in opposing vapor deposition forms is obtained while the surface reflectance sensor and the transmittance sensor are moved continuously or intermittently in the width direction of the vapor deposition film. Item 2. A method for measuring the degree of metal oxidation of a deposited metal film according to Item 1. A plurality of back surface reflectance sensors are arranged between the winding roll and the cooling roll in the vicinity of the back surface of the vapor deposition film, and the interface between the vapor deposition films facing each other from the detection value of the back surface reflectance sensor. 2. The method for measuring the degree of oxidation of a metal deposited film according to claim 1, wherein the degree of oxidation is obtained. The said metal is cobalt, The metal oxidation degree measuring method of the metal vapor deposition film in any one of Claim 1 to 6 characterized by the above-mentioned. The vapor deposition film unwound from the unwinding roll is wound on the cooling roll at a predetermined angle and wound from below, and the metal vapor is vapor-deposited from below, wound on the winding roll, and supplied with oxygen from the upstream side and the downstream side with respect to the metal vapor. In the metal vapor deposition film forming apparatus, a surface reflectance sensor and a transmittance sensor are disposed between the vapor deposition roll and the take-up roll in the vicinity of the vapor deposition film surface, and the surface reflectance sensor. And a calculation unit for calculating a metal oxidation degree in the metal vapor deposition film without depending on a film thickness of the metal vapor deposition film from a detection value of the transmittance sensor. Metal oxidation degree measuring device. The arithmetic unit varies the film thickness of the metal vapor deposition film at each of a plurality of predetermined degrees of oxidation, and calculates the detection values (x, y) of the transmittance sensor and the rebound ratio sensor at each film thickness. Means to capture;
Means for connecting a plurality of the detected values (x, y) at each of the predetermined degrees of oxidation and approximating a curve to obtain a natural logarithmic function;
Means for setting the natural logarithm function as y = a * Ln (x) + b;
(Where x is the transmittance, y is the reflectance a, b is a constant)
A linear approximation of the relationship between the predetermined oxidation degree s and the constants a and b
means for obtaining a function of a = c * s + d, b = e * s + f,
S = (y−f + d * Ln (x)) / (c * Ln (x) + e) is derived from the functions of y, a, and b, and the in-film oxidation degree s is obtained in-line. The apparatus for measuring a metal oxidation degree of a metal deposited film according to claim 8. A back surface reflectance sensor is disposed between the winding roll and the cooling roll in the vicinity of the back surface of the vapor deposition film, and an interface oxidation degree is obtained from a detection value of the back surface reflectance sensor. The apparatus for measuring a metal oxidation degree of a vapor-deposited metal film according to claim 8. A plurality of the surface reflectance sensors and a plurality of the transmittance sensors are disposed in the width direction of the vapor deposition film, and the degree of oxidation in the metal vapor deposition film of the vapor deposition film facing each other is determined. The apparatus for measuring a metal oxidation degree of a vapor-deposited metal film according to claim 8. The degree of oxidation in opposing vapor deposition films is determined sequentially while moving the surface reflectance sensor and the transmittance sensor continuously or intermittently in the width direction of the vapor deposition film. Item 9. The apparatus for measuring the degree of metal oxidation of a deposited metal film according to Item 8. A plurality of back surface reflectance sensors are arranged between the winding roll and the cooling roll in the vicinity of the back surface of the vapor deposition film, and the interface between the vapor deposition films facing each other from the detection value of the back surface reflectance sensor. 9. The apparatus according to claim 8, wherein the degree of oxidation is obtained. The said metal is cobalt, The metal oxidation degree measuring apparatus of the metal vapor deposition film in any one of Claims 8-13 characterized by the above-mentioned. The vapor deposition film unwound from the unwinding roll is wound around the cooling roll at a predetermined angle, and metal vapor is vapor-deposited from below, wound on the take-up roll, and supplied with oxygen from the upstream and downstream sides of the metal vapor. In the metal deposition film forming apparatus, a surface sensor and a transmittance sensor are disposed between the cooling roll and the take-up roll in the vicinity of the surface of the deposition film, and the surface reflectance sensor and A method for measuring a film thickness of a metal vapor deposition film, wherein the film thickness of the metal vapor deposition film is calculated from the detection value of the transmittance sensor without depending on a variation in the degree of oxidation of the metal vapor deposition film. The calculation is a step of obtaining the detected value (x, y) of the transmittance sensor and the reflectance sensor at each oxidation degree by varying the oxidation degree of the metal deposition film at each of a plurality of predetermined film thicknesses. When,
Connecting a plurality of the measured values at the predetermined film thickness to approximate a curve to obtain a natural logarithm function;
Setting the natural logarithmic function to y = a ′ * Ln (x) + b ′;
(Where x is the transmittance and y is the reflectance)
A linear approximation of the relationship between the predetermined film thickness t and the coefficients a ′ and b ′
obtaining a function of a ′ = c ′ * t + d ′, b ′ = e ′ * t + f ′, and t = (y−f ′ + d from the function of y, a ′, b ′. 16. The method according to claim 15, wherein the film thickness is calculated as' * Ln (x)) / (c '* Ln (x) + e'). A plurality of the surface reflectance sensors and a plurality of the transmittance sensors are arranged in the width direction of the vapor deposition film, and the thickness of the metal vapor deposition film of the vapor deposition film facing each other is obtained. The method for measuring a film thickness of a metal deposited film according to claim 15. The film thicknesses of the opposing vapor deposition films are obtained sequentially while moving the surface reflectance sensor and the transmittance sensor continuously or intermittently in the width direction of the vapor deposition film. 15. The method for measuring a thickness of a metal vapor deposition film according to 15. The method for measuring a film thickness of a metal deposited film according to claim 15, wherein the metal is cobalt. The vapor deposition film unwound from the unwinding roll is wound on the cooling roll at a predetermined angle and wound from below, and the metal vapor is vapor-deposited from below, and wound on the take-up roll, and oxygen is supplied from the upstream and downstream sides to the metal vapor. In the metal deposition film forming apparatus, a surface sensor and a transmittance sensor are disposed between the cooling roll and the take-up roll in the vicinity of the surface of the deposition film, and the surface reflectance sensor and A metal vapor deposition film comprising a calculation unit that obtains the film thickness of the metal vapor deposition film by calculation from the detection value of the transmittance sensor without depending on the oxidation degree fluctuation of the metal vapor deposition film. Film thickness measuring device. The arithmetic unit varies the degree of oxidation of the metal vapor deposition film at each of a plurality of predetermined film thicknesses to obtain detection values (x, y) of the transmittance sensor and the reflectance sensor at each degree of oxidation. Means,
Means for connecting a plurality of the detected values at the predetermined film thickness and approximating a curve to obtain a natural logarithm function;
Means for setting the natural logarithmic function as y = a ′ * Ln (x) + b ′;
(Where x is the transmittance and y is the reflectance)
A linear approximation of the relationship between the predetermined film thickness t and the coefficients a ′ and b ′
means for obtaining a function of a ′ = c ′ * t + d ′, b ′ = e ′ * t + f ′, and t = (y−f ′ + d from the function of y, a ′, b ′. 21. The apparatus for measuring a thickness of a metal deposited film according to claim 20, wherein the film thickness is calculated as' * Ln (x)) / (c '* Ln (x) + e'). A plurality of the surface reflectance sensors and a plurality of the transmittance sensors are arranged in the width direction of the vapor deposition film, and the thickness of the metal vapor deposition film of the vapor deposition film facing each other is obtained. The apparatus for measuring a film thickness of a metal vapor deposition film according to claim 20. The film thicknesses of the opposing vapor deposition forms are obtained while the surface reflectance sensor and the transmittance sensor are moved continuously or intermittently in the width direction of the vapor deposition film. 20. The apparatus for measuring a thickness of a metal vapor-deposited film according to 20. 24. The apparatus for measuring a thickness of a deposited metal film according to claim 20, wherein the metal is cobalt.

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