JP3220429B2 - Glow discharge emission spectroscopy method and apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glow discharge emission spectroscopy method and apparatus for analyzing generated light with a spectroscope while sputtering a sample.

[0002]

2. Description of the Related Art When a DC or high frequency high voltage is applied between two electrodes in an argon (Ar) atmosphere at a gas pressure of about 500 to 1300 Pa, a glow discharge occurs.
Ar ions are generated. The generated Ar ions are accelerated by a high electric field, collide with the surface of the cathode, and knock out substances existing there. This phenomenon is called sputtering, and the sputtered particles (atoms, molecules, and ions) are excited in the plasma and emit light having a wavelength specific to the element when returning to the ground state. An analysis method in which the emitted light is separated by a spectroscope to identify elements is called a glow discharge emission spectral analysis method.

[0003]

By the way, in recent years, by using such an analysis method, a thin film such as SiO ₂ which transmits light is provided on a substrate such as a silicon wafer, and the substrate and the thin film are used. The analysis of a sample having a mirror-like surface is performed. However, according to the conventional light intensity integration method (see Iron and Steel Research No. 323, pp. 27 to 33 issued in 1986), the thickness of the thin film, that is, the film thickness is determined by the amount of each component of the thin film. The sum divided by each density, that is, the sum of the film thickness of each component, is obtained, but a sufficiently accurate analytical value was not obtained, and a sufficiently accurate analytical value was not obtained for the content of each component. .

Accordingly, the present invention provides a glow discharge emission spectrometer capable of performing a sufficiently accurate analysis of the film thickness and the like of a sample having a thin film that transmits light on a substrate and having a mirror-like surface of the substrate or the thin film. An object of the present invention is to provide an analysis method and an apparatus.

[0005]

According to a first aspect of the present invention, there is provided a glow discharge optical emission spectroscopy method.
For a sample having at least one thin film that transmits light on a substrate, and at least two surfaces of the substrate and the thin film having a mirror-like surface, first, a sputtering time is measured using a standard sample having a known film thickness. The correlation between the wave number, which is the number of times of the wave, and the film thickness is obtained in advance for the wave, which is a periodic change in the measured intensity with respect to the wavelength. Then, the film number of the sample to be analyzed is obtained by applying the wave number obtained from the change in the measured intensity of the sample to be analyzed to the correlation.

According to the method of the first aspect, the film thickness of the sample to be analyzed is determined not by the adhesion amount of each component, but by the wave number having a strong correlation with the film thickness, that is, the periodicity of the measured intensity with respect to the sputtering time. Since it is obtained from the number of changes, a sufficiently accurate analysis of the film thickness can be performed.

In the glow discharge optical emission spectroscopy method according to the second aspect, the film thickness of the sample to be analyzed obtained by the method of the first aspect is multiplied by a density appropriately set as a thin film of the sample to be analyzed. Obtain the amount of the thin film attached to the sample.
Then, for each of the trace components other than the main component whose content in the thin film is expected to be the maximum, the integrated intensity, which is the integrated value of the intensity obtained by removing the wave from the measured intensity, is divided by the known emission yield. Calculate the amount of trace components attached. Further, by subtracting the total amount of the respective trace components from the amount of the thin film,
Obtain the amount of the main component adhered. Further, the amount of each component is divided by the amount of the thin film to determine the content of each component.

According to the method of claim 2, since the content of each component is determined based on the film thickness sufficiently accurately obtained by the method of claim 1, the content of each component is analyzed with sufficient accuracy. Can be.

According to a third aspect of the present invention, there is provided a glow discharge optical emission spectroscopic analysis method, wherein an integral value which is an integral value of an intensity obtained by removing a wave from the measured intensity of the main component is determined by an adhesion amount of the main component obtained by the method of the second embodiment. To obtain the emission yield of the main component. Then, based on the intensity obtained by removing the wave from the measured intensity of each component, the obtained luminescence yield of the main component, the known luminescence yield of each trace component, and the known density of each component, each unit depth Of each component, or the content of each component per unit depth.

According to the method of the third aspect, the content of each component at each unit depth, etc., based on the film thickness and the amount of the main component adhered sufficiently determined by the method of the first and second aspects. Is obtained, a sufficiently accurate analysis can also be performed on the content of each component at each unit depth.

According to a fourth aspect of the present invention, there is provided a glow discharge optical emission spectrometer for use in the method of the first aspect, wherein the glow discharge tube having an anode tube and a film thickness calculating means for obtaining a film thickness of a sample to be analyzed are provided. Have. According to the device of the fourth aspect, the same operation and effect as those of the method of the first aspect can be obtained.

A glow discharge optical emission spectrometer according to a fifth aspect is an apparatus used in the method according to the second aspect, and further includes a content calculating means for calculating the content of each component. According to the device of the fifth aspect, the same operation and effect as the method of the second aspect can be obtained.

A glow discharge optical emission spectrometer according to a sixth aspect is an apparatus used in the method according to the third aspect, and further comprises a depth characteristic calculating means for determining the content of each component at a unit depth. . According to the apparatus of claim 6, the third aspect is also provided.
The same operation and effect as those of the method are obtained.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A glow discharge optical emission spectroscopy method according to one embodiment of the present invention will be described below with reference to the drawings.
First, an apparatus used in this method will be described. In this apparatus, as shown in FIG. 1, light S emitted from a grim glow discharge tube 1 that generates light having a wavelength specific to an element by sputtering using a glow discharge and transmitted through a window plate 13 is spectrally separated. Incident on the vessel 22. The spectroscope 22 includes an entrance slit 24 and a diffraction grating 2 that diffracts the light S incident from the entrance slit 24 at different diffraction angles according to the wavelength.
6. It has an exit slit 27 for passing the diffracted light and a photomultiplier tube 28 for measuring the intensity of the diffracted light.

[0015] Further, this device is used as a glow discharge tube.
A hollow anode type grim glow discharge tube 1 as shown in FIG. 2 is used. The grim glow discharge tube 1 includes a support block (a support portion with which the samples 6 and 16 are brought into contact, and in the present embodiment, an insulating portion at the same time) 2 and an anode block 3 formed of a sealing member such as an O-ring. 11 are connected. A hollow anode tube 3d is integrally formed with the anode block 3, and this anode tube 3d is inserted into the support block 2 and is close to the analysis surfaces (surfaces) 7a and 17a of the samples 6 and 16.

Here, the samples 6 and 16 are formed on a substrate 8 or 18 such as a silicon wafer by a BPSG film (S
_{i O 2, B 2 O 3} , and has a thin film 7, 17 for transmitting light, such as P ₂ O ₅ consists glassy membrane).
The surfaces 8a and 18a and the surfaces 7a and 17a of the substrates 8, 18 and the thin films 7, 17 are mirror surfaces. The samples 6 and 16 are pressed against the support block 2 in an airtight state mainly by the cathode block 4 via a sealing member 11 such as an O-ring having an annular shape surrounding a portion to be analyzed on the analysis surfaces 7a and 17a. .

Thus, the opening of the inner space (glow discharge space) V of the support block 2 accommodating the hollow anode tube 3d is closed by the samples 6 and 16, and this inner space V is evacuated by a vacuum exhaust device (not shown). Decompression means), the first and second
Vacuum is drawn from the vacuum exhaust holes 3b and 3c. Further, the anode block 3 is provided with an argon gas supply hole 3.
a, and V in the tube is a rare gas atmosphere of argon (5
00 to 1300 Pa).

The grim glow discharge tube 1 has a power supply (power supply means) 12 between the anode block 3 and the cathode block 4.
To generate a glow discharge by applying a high-frequency or direct-current voltage to the sample 6, 1 through the cathode block 4.
A negative voltage is applied to the sample 6, and argon cations generated by the generation of glow discharge collide with the analysis surfaces 7a and 17a of the sample, thereby sputtering the samples 6 and 16. In addition, the coolant is introduced into the jacket from a coolant introduction passage (not shown) of the cathode block 4 and is fed to the coolant discharge passage.
6 and the hollow anode tube 3d are cooled.

As shown in FIG. 1, the apparatus includes an analyzer 15 comprising the following film thickness calculating means 19, content rate calculating means 20, and depth characteristic calculating means 21. First, the film thickness calculating means 19 calculates the number of times of a wave (hereinafter referred to as a wave), which is a periodic change in the measured intensity with respect to the sputtering time, using a standard sample 16 having a known film thickness. The correlation between a certain wave number and the film thickness is stored. Then, the wave number of the sample 6 to be analyzed is determined from the change in the measured intensity, and the wave number is applied to the stored correlation to determine the film thickness of the sample 6 to be analyzed.

The content ratio calculating means 20 multiplies the film thickness of the sample 6 to be analyzed obtained by the film thickness calculating means 19 by a density appropriately set as the sample 6 to be analyzed, and calculates the thin film of the sample to be analyzed. Determine the amount of adhesion. Then, for each of the trace components other than the main component whose content in the thin film is expected to be the maximum, the integrated intensity, which is the integrated value of the intensity obtained by removing the wave from the measured intensity, is divided by the known emission yield. Calculate the amount of trace components attached. Further, the sum of the amounts of the respective trace components is subtracted from the amount of the thin film to obtain the amount of the main component.
Further, the amount of each component is divided by the amount of the thin film to determine the content of each component.

The depth characteristic calculating means 21 divides the integrated intensity, which is the integrated value of the intensity obtained by removing the wave from the measured intensity of the main component, by the amount of the main component obtained by the content calculating means 20, The emission yield of the main component is determined. Then, based on the intensity obtained by removing the wave from the measured intensity of each component, the obtained luminescence yield of the main component, the known luminescence yield of each trace component, and the known density of each component, the unit depth ( The adhesion amount of each component per unit sputtering depth) or the content of each component per unit depth is determined.

Next, a method of this embodiment using this apparatus will be described. First, as described below, using a standard sample 16 having a known film thickness, a correlation between the wave number, which is the number of periodic changes in the measured intensity with respect to the sputtering time, and the film thickness is obtained in advance, and the film thickness is calculated. It is stored in the means 19. Here, the standard sample 16 is of the same type as the sample 6 to be analyzed later, and as described above, for example, the BP is placed on the silicon wafer substrate 18 as shown in FIG.
It has a thin film 17 which is an SG film, and the surfaces 18a and 17a of the substrate 18 and the thin film 17 are mirror surfaces.

First, the analysis surface 17a of the standard sample is brought into contact with the support block 2, and the cathode block 4 is pressed against the back surface 16e of the standard sample from below by a robot hand or the like (not shown) to make conductive contact, and the standard sample 16 is held. . When the inner space V of the support block 2 is evacuated to a rare gas atmosphere of argon (500 to 1300 Pa) by a depressurizing means (not shown), the analysis surface 17a of the standard sample is moved by the atmospheric pressure applied to the back surface 16e. Is also pressed against the support block 2 via the sealing member 11,
In close contact.

Then, the anode block 3 and the cathode block 4
When a high-frequency or direct-current voltage is applied between the anode tube 3d and the standard sample 16 by the power supply unit (feeding means) 12, glow discharge is generated, and argon cations are generated. The standard sample 16 is sputtered by the Ar ions, and the generated light S passes through the window plate 13 and
Of the diffraction grating 2 of the spectroscope 22 through the entrance slit 24 of
Go to 6. The diffraction grating 26 diffracts light of a predetermined wavelength, passes through an exit slit 27, and a photomultiplier tube 28
Incident on The photomultiplier tube 28 measures the intensity of the incident light.

Thus, for example, as shown in FIG.
A change in the measured intensity for each element with respect to the sputtering time is obtained. Here, Japanese Patent Application No. Hei 04-218503
As described in the above, due to the interference of the reflected light in the thin film, the measured intensity of the elements other than O changes periodically with the sputtering time, that is, forms a waveform. It has been found that there is a strong correlation between the number of waves, that is, the wave number, and the known thickness of the standard sample. In the present invention, the component of the thin film of the sample may be an element or a compound constituting the thin film, but in the present embodiment, the Si constituting the BPSG film 17 of FIG.
Each compound of O ₂ , B ₂ O ₃ and P ₂ O ₅ is used as a component, and the measured intensity of main elements Si, B and P in each component is used as the measured intensity of each component, and O is not treated as an independent component. .

The wave number is obtained as follows. First,
After the periodic change, the measured intensity of B and P not included in the substrate 18 decreases sharply because the thin film 17 is completely sputtered in the measurement portion.
Until the sputtering time, which is reduced to half of the average of the peak intensity of the peak of the waveform and the average of the intensity of the valley, the thin film 17
Is assumed to exist, and this is called a thin film sputtering time. In the present embodiment, the thin film sputtering time is determined from the measured intensity of B, which is larger, but may be determined from the measured intensity of P or O.

Next, during the thin film sputtering time, the sputtering time from the peak to the peak of the adjacent peak of the waveform at the measured intensity of Si is measured as the period of each wave, the average is calculated, and the average of the wave is calculated. By dividing the thin film sputtering time by the cycle, the wave number is calculated to, for example, two decimal places. Here, the average period of the wave is Si,
It may be determined from any of the measured intensities of B and P, but is preferably determined from the measured intensity of Si, which has the highest content and in which the wave is likely to appear clearly. Further, each sputtering time from the peak to the peak of the adjacent peak of the waveform is defined as the cycle of each wave. However, each sputtering time from the valley bottom to the adjacent valley of the waveform may be defined as the cycle of each wave.

Then, a plurality of standard samples 16 having different thicknesses are prepared.
When the wave number is obtained, a strong correlation between the Si wave number and the known film thickness of the standard sample 16 as shown in FIG. 4 can be obtained. It is stored in the means 19. In addition,
The work of obtaining this correlation from the measured intensity of the standard sample 16 may also be performed by the film thickness calculating means 19. Alternatively, the correlation may be obtained by using an apparatus of the same type different from the apparatus for analyzing the sample 6 to be analyzed, and the correlation may be stored in the film thickness calculating means 19 of the apparatus.

Next, an analysis target sample 6 of the same kind as the standard sample 16, that is, a thin film 7 which is a BPSG film on a silicon wafer substrate 8 as shown in FIG. As in the case of the standard sample 16, the intensity of light emission by glow discharge is measured for the sample 6 to be analyzed whose surfaces 8a and 7a of the 7 are mirror surfaces, and a change in the measured intensity of each element with respect to the sputtering time is obtained. Based on this, the film thickness calculating means 19 in FIG. 1 performs the same procedure as that for obtaining the Si wave number for the standard sample 16 described above,
The Si wave number is determined for the sample 6 to be analyzed, and the film thickness d of the sample 6 to be analyzed is determined by applying the Si wave number to the stored correlation (FIG. 4). According to the method of the present embodiment,
Since the film thickness d of the sample 6 to be analyzed is obtained not from the amount of each component adhered but from the wave number having a strong correlation with the film thickness as shown in FIG. 4, sufficiently accurate analysis can be performed on the film thickness d.

In the method according to the present embodiment, each of the components SiO ₂ , B ₂ O ₃ , P ₂ of the thin film 7 of the sample 6 to be analyzed is continuously calculated by the content calculating means 20 of FIG. O ₅
Of the contents C _Si , C _B , and C _P are determined. First, for example, in the present embodiment, since the analysis target sample 6 has the BPSG film 7 and the approximate density of the thin film 7 is known, the density ρ is appropriately set as the thin film 7 of the analysis target sample 6. And Specifically, for example, after the thin film 7 is melted, the adhesion amount of the thin film 7 is determined by ICP emission spectrometry, and the thin film 7 is measured by an ellipsometer or by measuring the step at a portion where a part of the thin film 7 is removed by etching. Is obtained, and a value obtained by dividing the obtained adhesion amount by the film thickness can be set as the density ρ appropriately set as the thin film 7. Then, the film thickness d of the sample 6 to be analyzed determined by the film thickness calculating means 19 is multiplied by the density ρ to obtain the attached amount (mass per unit area) W of the thin film 7 of the sample 6 to be analyzed. That is,

W = ρd (1)

[0032] Then, trace components other than the main components Si O ₂ of thin film content is expected to be the maximum B ₂ O _3, P ₂ O
₅ for each of the integrated intensity I _B from the measured intensity is the integral value of the intensity of the removal of the waves, emission of I _P known yield R _B, is divided by R _P, coating weight W _B of the minor components j, W _P
Ask for. That is,

W _j = I _j / R _j (j = B, P) (2)

Here, from the measured intensity of each element with respect to the sputtering time shown in FIG. 3, various methods can be considered for removing a wave (wave component). The method described in Japanese Patent Application No. 04-218503 can be used. That is, according to the same article, the relative intensity with respect to the sputtering depth is calculated, and the measured intensity with respect to the sputtering depth is obtained by correcting the waveform of the measured intensity with respect to the sputtering time so as to match the change, that is, the waveform. Further, then, by removing the intensity of the reflected light in consideration of the interference of the reflected light in the thin film, the exact intensity of the direct light with respect to the sputtering depth, that is, the wave was removed from the measured intensity with respect to the sputtering depth. Strength can be obtained. Moreover, according to the same publication, since the sputtering depth and the sputtering time are related by a function, the intensity obtained by removing the wave from the measured intensity with respect to the sputtering time is further obtained.

In the present invention, the main component refers to only one component whose content in the thin film is expected to be the maximum, and the other components have a particularly low content in comparison with the main component. Even if they are not, they are called minor components, and each component includes both the main component and the minor component. Further, in the present embodiment, as the measured intensity of the components _{Si O 2, B 2 O 3} , P 2 O 5, main elements Si in each component, B, so using the measured intensity of P, the components Si O ₂ , B ₂ O ₃ , P ₂ O ₅
The luminous yields R _Si , R _B , and R _P of the respective elements Si,
Not only the luminescence yield of B and P itself, but also each component Si
It is converted as the luminescence yield for O ₂ , B ₂ O ₃ , and P ₂ O ₅ .

Next, the sum of the adhering amounts W _B and W _P of the trace components j is subtracted from the adhering amount W of the thin film to obtain the main component Si.
The amount of O ₂ deposited W _Si is determined. That is,

W _Si = W−ΣW _j (j = B, P) = W− (W _B + W _P ) (3)

Further, these components SiO ₂ , B ₂ O
_3, coating weight W _Si of P ₂ O _5, W _B, by dividing the W _P in coating weight W of the thin film to determine the content of C _i of each component i. That is,

C _i = W _i / W (i = Si, B, P) (4)

As described above, according to the method of the present embodiment,
Based on the film thickness d which sufficiently accurately determined from the wave number, so obtaining the content C _i of each component i, content C _i of each component i
Can be analyzed with sufficient accuracy.

In the method of the present embodiment, the depth
The characteristic calculation means 21 calculates the sample to be analyzed as follows.
For each unit depth (unit sputtering depth) of thin film 7 of 6
Of each component i^dΔW_i, Each component i per unit depth
Content of^dΔC_iAsk ( ^dΔ is the number per unit depth
Value). First, the main component SiO 2_TwoMeasurement
The integral value of the intensity after removing the wave from the constant intensity as described above
Some integral intensity I_SiWas determined by the content ratio calculating means 20.
Main component SiO_TwoAmount of adhesion W_SiDivided by_Two
Luminescence yield R_SiAsk for. That is,

R _Si = I _Si / W _Si (5)

Then, the intensity obtained by removing the wave from the measured intensity of each component i, the above-mentioned luminescence yield R _{Si of} the main component SiO ₂ ,
The known emission yield R _j of each trace component j, and based on the known density [rho _i of each component i, adhesion amount ^d [Delta] W _i of each component i per unit depth (unit sputtering depth), the unit The content ^d ΔC _i of each component i at each depth is determined. For this, the above-mentioned conventional light intensity integration method is used.

Specifically, for example, the following formulas (6) to (6)
According to (10). Incidentally, ^t delta is meant to be a numerical value per unit time (unit sputtering time).

^T ΔW _i = ^t ΔI _i / R _i (6)

^T Δd = Σ ( ^t ΔW _i / ρ _i ) (i = Si, B, P) (7)

^D ΔW _i = ^t ΔW _i / ^t Δd (8)

^D ΔW = Σ ^d ΔW _i (i = Si, B, P) (9)

^D ΔC _i = ^d ΔW _i / ^d ΔW (i = Si, B, P) (10)

That is, first, according to the equation (6), the intensity ^t Δ obtained by removing the wave from the measured intensity of each component i per unit time.
I _i is divided by the determined luminescence yield R _Si of the main component SiO ₂ or the known luminescence yield R _j of each minor component j,
The attached amount ^t ΔW _i of each component i per unit time is determined. Next, the depth (sputtering depth) ^t Δd per unit time is calculated as the sum of the values obtained by dividing ^t ΔW _i by the known density ρ _i of each component _{i according} to equation (7). Thereby, time and depth are related. For example, according to equation (8), the adhesion amount ^t ΔW _i of each component i per unit time is divided by the depth ^t Δd per unit time, and the adhesion amount ^d ΔW _i of each component i per unit depth. Is required.

From equation (9), the sum of
Since the adhesion amount ^d ΔW of the thin film for each unit depth is obtained,
The equation (10), which ^d [Delta] W by dividing the coating weight ^d [Delta] W _i of each component i per unit depth at each component i per unit depth
Content ^{d ΔC} _i of is required. By repeating such a procedure for each unit time, the so-called depth profile can be obtained from the characteristics of the strength with respect to time and the characteristics of the amount of adhesion and the content with respect to the depth.

As described above, according to the method of the present embodiment,
Since it is based on the film thickness d and the main component adhesion amount W _{Si, which} are sufficiently accurately obtained from the wave number, the content of each component i per unit depth
^A sufficiently accurate analysis can be performed for ^d ΔC _{i and the} like. In addition,
The present invention can be applied not only to a BPSG film but also to other transparent films such as a PSG film and a PZT film, and can also be applied to a case where the thin film is a multilayer.

[0053]

As described above, according to the glow discharge optical emission spectroscopy method or apparatus of the present invention, at least one light transmitting thin film is provided on a substrate, and at least one of the substrate and the thin film is provided. For a sample whose two surfaces are mirror-finished, the thickness of the sample to be analyzed is determined not by the amount of each component attached, but by the wave number having a strong correlation with the film thickness, that is, the periodic change of the measured intensity with respect to the sputtering time. From the number of times, sufficiently accurate analysis of the film thickness and the like can be performed.

[Brief description of the drawings]

FIG. 1 is a front view showing an apparatus used for a glow discharge optical emission spectroscopy method according to an embodiment of the present invention.

FIG. 2 is a longitudinal sectional view showing a glow discharge tube of the analyzer according to the first embodiment.

FIG. 3 is a diagram showing a change in measured intensity of each element with respect to a sputtering time.

FIG. 4 is a diagram showing a correlation between a Si wave number and a film thickness.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Glow discharge tube, 3d: Anode tube, 6, 16 ... Sample (analysis target sample, standard sample), 7, 17 ... Thin film, 8, 18 ...
Substrate, 19: thickness calculating means, 20: content calculating means, 2
1: depth characteristic calculating means, S: light generated by sputtering.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-6-43101 (JP, A) JP-A-6-43100 (JP, A) JP-A-60-185143 (JP, A) JP-A-55-185 149004 (JP, A) JP-A-8-261712 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 21/62-21/74 G01B ⁷ /00-7/34 JICST File (JOIS)

Claims (6)

(57) [Claims] 1. A light-transmitting thin film on a substrate having at least one layer, and at least two of the substrate and the thin film.
In a glow discharge emission spectroscopy method in which a sample is analyzed based on the measured intensity of light generated while sputtering a thin film of a sample having two mirror-like surfaces, using a standard sample with a known film thickness, the sputtering time For a wave that is a periodic change in measured intensity, the correlation between the wave number, which is the number of waves, and the film thickness is obtained in advance, and the wave number obtained from the change in the measured intensity for the sample to be analyzed is calculated as the correlation. A glow discharge emission spectroscopy method characterized in that the thickness of a sample to be analyzed is obtained by applying the method to the above. 2. The method according to claim 1, wherein the adhesion amount of the thin film of the sample to be analyzed is obtained by multiplying the obtained thickness of the sample to be analyzed by a density appropriately set as a thin film of the sample to be analyzed. For each of the trace components other than the main component whose content in the thin film is expected to be the maximum, the integrated intensity, which is the integral value of the intensity obtained by removing the wave from the measured intensity, is divided by the known emission yield,
The amount of each trace component is obtained, and the total amount of each of the trace components is subtracted from the amount of the thin film to obtain the amount of the main component, and the amount of each of these components is divided by the amount of the thin film. Glow discharge emission spectroscopy for determining the content of each component. 3. The method according to claim 2, wherein the luminous yield of the main component is obtained by dividing the integral intensity, which is the integral value of the intensity obtained by removing the wave, from the measured intensity of the main component by the amount of the main component attached. Based on the intensity obtained by removing the wave from the measured intensity of each component, the obtained luminescence yield of the main component, the known luminescence yield of each trace component, and the known density of each component, for each unit depth. A glow discharge emission spectroscopy method for determining the amount of each component attached or the content of each component per unit depth. 4. A thin film of a sample, comprising: a glow discharge tube having an anode tube; at least one layer of a light-transmitting thin film on a substrate; and at least two surfaces of the substrate and the thin film having a mirror-like surface. In a glow discharge optical emission spectrometer that analyzes a sample based on the measured intensity of light generated while sputtering, a standard sample with a known thickness is used for waves that are periodic changes in measured intensity with respect to sputtering time. The correlation between the wave number, which is the number of waves, and the film thickness, which was obtained in advance, is stored, and the wave number is obtained from the change in the measured intensity for the sample to be analyzed.
A glow discharge emission spectrometer comprising a film thickness calculating means for applying the wave number to the stored correlation to obtain a film thickness of a sample to be analyzed. 5. The thin film of the sample to be analyzed according to claim 4, wherein the film thickness of the sample to be analyzed obtained by the film thickness calculating means is multiplied by a density appropriately set as a thin film of the sample to be analyzed. For each of the trace components other than the main component whose content in the thin film is expected to be the largest, the integrated intensity, which is the integrated value of the intensity after removing the wave from the measured intensity, is divided by the known emission yield. do it,
The amount of each trace component is obtained, and the total amount of each of the trace components is subtracted from the amount of the thin film to obtain the amount of the main component, and the amount of each of these components is divided by the amount of the thin film. And a glow discharge emission spectrometer equipped with content calculating means for calculating the content of each component. 6. The apparatus according to claim 5, wherein an integral intensity, which is an integral value of the intensity obtained by removing the wave from the measured intensity of the main component, is divided by the amount of the main component obtained by the content calculating means. Determine the luminescence yield of the component, based on the intensity obtained by removing the wave from the measured intensity of each component, the determined luminescence yield of the main component, the known luminescence yield of each trace component, and the known density of each component. A glow discharge optical emission spectrometer provided with depth characteristic calculating means for determining the amount of each component attached per unit depth or the content of each component per unit depth.