JP2010107277A - Method for measuring film thickness of organic thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for measuring the film thickness of an organic thin film which can measure the film thickness that contains inorganic elements with high accuracy. <P>SOLUTION: On the basis of the concentration C<SB>A</SB>of the inorganic element within the organic thin film 40, which is formed on the surface of a base, the organic element is included; and has a density of 2 g/cm<SP>3</SP>or less and the characteristic X-rays intensity K<SB>S</SB>of the organic element in a standard sample, characteristic X-rays intensity K<SB>1</SB>, when the organic thin film is irradiated with an electron beam is detected; and the film thickness &Delta;Z of the organic thin film is measured through Equation 1, where &rho; is the dry density (g/cm<SP>3</SP>) of the organic thin film, E<SB>0</SB>the energy of one incident electron, E<SB>j</SB>(A) is the excitation energy of the K shell of the inorganic element, R<SB>A</SB>the atomic number correction constant of the inorganic element, S'<SB>A</SB>is the stopping power of the standard sample, U<SB>0</SB>=E<SB>0</SB>/E<SB>j</SB>(A), and K<SB>A</SB>=(K<SB>1</SB>/R<SB>0</SB>)/(K<SB>S</SB>/f(x)), with R<SB>0</SB>being the generating function for the characteristic X-rays of the thin-film surface, and f(x) the absorption correction factor of the standard sample. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for measuring a film thickness of an organic thin film containing a silicone resin or the like.

Conventionally, as a paper container for beverages such as a milk carton, a so-called gable roof type paper container (gable top type) in which a rectangular cylindrical body is sealed with a heat seal is widely used (see Patent Document 1). . In these paper containers, the consumer peels off the heat seal part and opens the container to use as a spout for the contents.
By the way, when peeling the pieces of paper sealed together by heat sealing, if the adhesive force of the heat seal is too strong, the opening is not easy, and the opening is not peeled off cleanly and damaged, and the spout There is a problem that the contents are spilled without being formed neatly and become unsanitary.

Therefore, a technique for applying an anti-adhesive (abhesive agent) to a bonding surface of a piece of paper that becomes a heat seal portion has been developed (see Patent Document 2). For example, such anti-adhesives include mold release agents such as silicone resin, polyethylene wax, soybean lecithin and higher fatty acid amide; base polymers such as ethyl cellulose and cyclized rubber; and solvents such as ethyl acetate and alcohols; Are prepared in combination.
The anti-adhesion degree (adhesion strength) of the anti-adhesive is adjusted by the type of the release agent and the coating amount of the anti-adhesive.

JP-A-5-162748 JP-A-3-217480

However, since the anti-adhesive is generally colorless and transparent, it is difficult to visually determine the coating amount. Therefore, the iodine amount is usually applied to the application part of the anti-adhesive, and the coating amount is determined by the degree of color development, but the amount of anti-adhesive coating and film thickness are quantified from the color development state. It was difficult.
As a general method for measuring the thickness of the coating layer, there is a method of observing the cross section with an optical microscope or an electron microscope. However, the coating layer of the anti-adhesive is very thin, and the anti-adhesive is organic. Since it is a thin film, it is not projected clearly with a microscope, and it is difficult to measure the film thickness.
Accordingly, an object of the present invention is to provide a method for measuring a film thickness of an organic thin film that can accurately measure a film thickness containing an inorganic element.

（ρは前記有機薄膜の乾燥密度（g／cm^３）；Ｅ_０は入射電子１個のエネルギー；Ｅ_ｊ(Ａ)は前記無機元素のＫ殻の励起エネルギー；Ｒ_Ａは前記無機元素の原子番号補正定数；Ｓ’_Ａは前記標準試料の阻止能；ｅは電荷量；Ｎ_０はアボガドロ数；Ｕ_０＝Ｅ_０/Ｅ_ｊ(Ａ) ；Ｋ_Ａ＝（Ｋ_１/Ｒ_０）/（Ｋ_Ｓ/ｆ（ｘ））、但し、Ｒ_０は薄膜表面の特性Ｘ線の発生関数、ｆ（ｘ）は前記標準試料の吸収補正係数）によって前記膜厚ΔＺを測定する。 The method for measuring the film thickness of an organic thin film of the present invention measures the film thickness ΔZ of an organic thin film that is formed on the surface of a substrate that does not contain a specific inorganic element and that contains the inorganic element and has a density of 2 g / cm ³ or less. A method,
And concentration C _A of the inorganic element of the organic thin film in terms of mass ratio, based on the characteristic X-ray intensity K _S of the inorganic element according to a standard sample consisting of a single said inorganic element, the electron beam to the organic thin film The characteristic X-ray intensity K ₁ when irradiated is detected and the equation 1

(Ρ is the dry density of the organic thin film (g / cm ³ ); E ₀ is the energy of one incident electron; E _j (A) is the excitation energy of the K shell of the inorganic element; R _A is the atom of the inorganic element Number correction constant; S ′ _A is the stopping power of the standard sample; e is the charge amount; N ₀ is the Avogadro number; U ₀ = E ₀ / E _j (A); K _A = (K ₁ / R ₀ ) / ( K _S / f (x)), where R ₀ is the generation function of characteristic X-rays on the surface of the thin film, and f (x) is the absorption correction coefficient of the standard sample).

  The inorganic element may be silicon, and the inorganic element may be contained as an organic silicon compound in the organic thin film.

  According to the present invention, the film thickness of an organic thin film containing an inorganic element can be accurately measured.

Embodiments of the present invention will be described below. The organic thin film thickness measuring method of the present invention measures the thickness of an organic thin film formed on the surface of a substrate. First, as an example of an object to which the present invention can be preferably applied, a paper container for beverages such as a milk carton will be described.
FIG. 1 is a perspective view showing a paper container 50, and FIG. 2 is a development view showing a carton blank (base material) before assembly of the paper container 50. The paper container 50 is a known gable roof type (gable top type) paper container, and is formed by folding a paperboard material in which a thermoplastic resin is laminated on the front and back surfaces.

  The paper container 50 has a substantially square bottomed rectangular tube shape composed of four body panels 4, 5, 6 and 7, and the base material is folded back along the body vertical folding lines 1, 2 and 3, respectively. The corners of the part panels 4, 5, 6, and 7 are formed. In addition, a vertical seal panel 9 is formed on one side of the body panel 7 via vertical ruled lines 8, and the vertical seal panel 9 is overlapped with the edge of the body panel 4 and sealed, The body panel 4 is connected to form a cylinder, and a square cylinder body 10 is formed as a whole.

A pair of gable roof forming panels 13, 14 facing each other are connected to the upper ends of the body panels 4, 6 facing each other through the top horizontal folding lines 11, 12. Outer top seal panels 17 and 18 are connected to upper portions of the pair of gable roof forming panels 13 and 14 via seal horizontal folding lines 15 and 16. In addition, a pair of wife walls are formed at the upper ends of the other opposite body panel 5 and 7 of the cylindrical body 10 so as to face each other through the top horizontal ruled lines 19 and 20 and one is opened as a spout. Panels 21 and 22 are connected. Inner top seal panels 25, 26 are connected to the upper portions of the pair of end wall forming panels 21, 22 via seal horizontal folding lines 23, 24.
The pair of end wall forming panels 21 and 22 have seal horizontal fold lines that serve as boundaries with the inner top seal panels 25 and 26 from both ends of the top horizontal fold lines 19 and 20 that serve as boundaries with the body panels 5 and 7. Two folding lines 27 and 28 connected to the centers of 23 and 24 are provided. The end wall forming panel 21 is folded at two folding lines 27 and is folded between the gable roof forming panels 13 and 14. Similarly, the end wall forming panel 22 is folded at two folding lines 28 and folded between the gable roof forming panels 13 and 14. In this manner, a gable roof-type top portion 29 is formed on the upper portion of the body portion 10 of the paper container 50.

Furthermore, the outer top seal panels 17 and 18 and the inner top seal panels 25 and 26 are sealed to form the top seal portion 30.
Here, a part of the top seal portion 30 located on the side of the end wall forming panel 21 is peeled off and opened to serve as a spout for the contents. Therefore, the anti-adhesive agent that adjusts the adhesive strength of the heat seal to a predetermined position of the heat seal portion of the outer top seal panels 17 and 18 and the inner top seal panel 25 and peels easily as a spout and facilitates peeling. The (abhesive agent) layer 40 is applied.

The present invention can be used, for example, for measuring the film thickness of the anti-adhesive layer 40 (organic thin film) described above.
The said paperboard raw material is the paperboard which laminated | stacked the thermoplastic resin on the front and back, and can use the acid-resistant base paper for liquid paper containers with a basic weight of about 30-400 g / m < ² > as a paperboard. Examples of the thermoplastic resin include heat-sealable resins such as low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, and modified polyester.
Although described in detail later, the term "base" in the present invention, when measuring the characteristic X-ray intensity K ₁ is irradiated with the primary electron beam to the organic thin film, the primary electron beam penetrates the organic thin film This refers to the base when it enters the base. Therefore, when the primary electron beam enters the thermoplastic resin layer of the paperboard material, the “base material” indicates the thermoplastic resin layer.
Further, the base material (thermoplastic resin in the above example) does not contain an inorganic element contained in the organic thin film described later. For example, as a base material, when polyethylene (about 20 μm thickness) is laminated on paperboard and the primary electron beam enters the polyethylene layer, the elements included in the polyethylene layer to emit characteristic X-rays are C, O, and H. Does not contain inorganic elements.

As the organic thin film formed on the surface of the substrate, the above-mentioned anti-adhesive layer is exemplified. In the above embodiment, the anti-adhesive layer includes a silicone resin that serves as a mold release agent and a cellulose-based resin such as ethyl cellulose that is a base polymer. An agent or the like may be included, and Si in the silicone resin corresponds to the “inorganic element” of the present invention.
Moreover, polyethylene wax other than silicone resin, soybean lecithin, higher fatty acid amide, or the like can be used as a release agent. Furthermore, a cyclized rubber can be used as the base polymer.
The anti-adhesive layer can be formed by applying a paint containing, for example, ethyl acetate or alcohol as a solvent in addition to the above-described mold release agent and base polymer, and then drying.

In addition, when using components other than a silicone resin as a mold release agent, Si (inorganic element) resulting from a silicone resin does not exist in an anti-adhesive agent layer. In such a case, a substance containing an inorganic element (for example, alumina or silica) is blended in the anti-adhesive layer so that the characteristic X-ray intensity derived from the inorganic element can be detected.
The inorganic element in the organic thin film is contained so that the density of the whole organic thin film is 2 g / cm ³ or less. This is because the present invention penetrates the organic thin film and irradiates the base material with primary electrons to detect the characteristic X-ray intensity generated from the inorganic elements in the entire organic thin film, and the density of the organic thin film is 2 g / If it exceeds cm ³ , the characteristic X-rays cannot pass through the organic thin film, and the film thickness cannot be measured accurately.
The concentration of the inorganic elements of the organic thin film described above is a representation of the C _A to be described later as a percentage (%).

Next, details of the measurement method will be described.
First, the above-described organic thin film is irradiated with primary electrons, and the generated characteristic X-ray intensity is detected. This method is called energy dispersive X-ray spectroscopy, and can be measured by EPMA (Electron Probe Microanalyzer).
Here, the present invention detects the characteristic X-ray intensity generated from the inorganic elements in the entire organic thin film by irradiating the base film with the primary electrons through the organic thin film. Therefore, the acceleration voltage of the primary electrons is adjusted so that the primary electrons enter the underlying base material. For example, the film thickness of the anti-adhesive layer is considered to be about 2 to 3 μm, and the density of the base material (polyethylene) is 0.9 g / cm ^3. Electrons will penetrate to a depth of about 10 μm. For this reason, the acceleration voltage is preferably 15 kV.

In the present invention, in advance, a concentration C _A of the inorganic elements of the organic thin film in terms of mass ratio, we obtain as a known value. The present invention, for example, when used in process control of the coating amount of the organic thin film, the composition of the coating material of the organic thin film is known, it is possible to know the concentration C _A in advance.
Here, C _A = (mass of inorganic element in organic thin film) / (mass of organic thin film).
Further, in the present invention, in advance by measuring the standard sample comprising a single pre above-mentioned inorganic elements in energy dispersive X-ray spectroscopy, we should give a characteristic X-ray intensity K _S inorganic elements with standard samples.

によって前記膜厚ΔＺを求める。
ここで、ρは有機薄膜の乾燥密度（g／cm^３）；Ｅ_０は入射電子１個のエネルギー；Ｅ_K(Ａ)は前記無機元素のＫ殻の励起エネルギー；Ｒ_Ａは前記無機元素の原子番号補正定数；Ｓ’_Ａは前記標準試料の阻止能；ｅは電荷量；Ｎ_０はアボガドロ数；Ｕ_０＝Ｅ_０/Ｅ_ｊ(Ａ) ；Ｋ_Ａ＝（Ｋ_１/Ｒ_０）/（Ｋ_Ｓ/ｆ（ｘ））、但し、Ｒ_０は有機薄膜表面の特性Ｘ線の発生関数、ｆ（ｘ）は前記標準試料の吸収補正係数である。
又、得られたΔＺの単位はcmである。 Then, the characteristic X-ray intensity K ₁ when the organic thin film is irradiated with the electron beam is detected, and the formula 1

To obtain the film thickness ΔZ.
Here, [rho the dry density of the organic thin film ^{(g / cm 3); E} 0 is incident electrons one energy; E _K (A) is the excitation energy of the K shell of the inorganic element; R _A is the inorganic element Atomic number correction constant; S ′ _A is the stopping power of the standard sample; e is the charge amount; N ₀ is the Avogadro number; U ₀ = E ₀ / E _j (A); K _A = (K ₁ / R ₀ ) / (K _S / f (x)), where R ₀ is a generation function of characteristic X-rays on the surface of the organic thin film, and f (x) is an absorption correction coefficient of the standard sample.
The unit of ΔZ obtained is cm.

Equation 1 describes ΔZ by modifying a known equation (Philbert-Tixier method). Here, the Philbert-Tixier method is an equation for obtaining the relative concentrations of elements A and B in EPMA analysis of a thin film. Usually, in the Philbert-Tixier method, the above formula 1 is established for each of the elements A and B, and the ratio between the two is used to eliminate the unknown ρ and ΔZ, thereby obtaining the relative concentrations of the elements A and B (Japanese surface (Science Society, “Electron Probe Microanalyzer” Maruzen, p. 94, published in 1998).
On the other hand, in the present invention are as described above ρ is known, also, by utilizing the concentration C _A is also known, seeking to reverse the [Delta] Z. In addition, the organic thin film to which the present invention is applied contains an inorganic element whose characteristic X-ray intensity is measured, and the density of the thin film is 2 g / cm ³ or less, so the primary electron beam penetrates the organic thin film, The amount of inorganic elements in the entire organic thin film can be measured. Therefore, a known concentration C _A, and a characteristic X-ray intensity of the resulting inorganic element, can be calculated back [Delta] Z. On the other hand, a metal material or the like generally measured by conventional EPMA contains 100% inorganic elements and has a density exceeding 2 g / cm ³ (for example, a silicon plate when the inorganic element is silicon). Only the characteristic X-ray intensity can be obtained, and the film thickness cannot be measured accurately.
The density of the organic thin film can be calculated by measuring the weight and volume of the material material of the organic thin film. Further, substantially, the density of the substance (for example, the above-described base polymer) constituting the organic thin film may be regarded as the density of the organic thin film, and there is almost no difference in the obtained density value.

で表される。ここで、Ｚ_Ａは対象とする無機元素の原子番号；Ａ_Ａは対象とする無機元素の原子量；Ｗ_Ａ ^ｊ＝１．１１６×Ｅ_ｊ(Ａ)／（１１．５×Ｚ_Ａ）である。 In the present invention, by leaving measuring the characteristic X-ray intensity K _S in advance by a standard sample, and to allow calculation of the coefficients of the various included in Formula 1.
For example, S ′ _A indicates the stopping power of the standard sample,

It is represented by Here, Z _A is the atomic number of the target inorganic element; A _A is the atomic weight of the target inorganic element; W _A ^j = 1.116 × E _j (A) / (11.5 × Z _A ) .

R ₀ is a generation function of characteristic X-rays on the surface of the organic thin film (coefficient of backscattering effect of electron beam).
R ₀ = 1 + 2.8 (1−0.9 / U ₀ ) × η (3)
(Reuter formula) Where η = −0.0254 + 0.016Z−0.000186Z ² + 8.3 × 10 ⁻⁷ × Z ³ ; Z is the atomic number of the substance constituting the substrate directly under the organic thin film; provided that the substrate is a compound In this case, it is represented by η = ΣC _i η _i , and is a weighted average of η _{i of} each compound by the molar fraction C _i .
For example, as in the above embodiment, when the organic thin film substrate is polyethylene, polyethylene is represented by C _n H _{2n + 2} , so the weight composition ratio of C and H is about 12: 2 (n is If large). Accordingly, η _i is obtained for C and H, and the weighted average of the molar fraction C _i gives polyethylene η.
The R _0, depending on the material contained in the substrate directly under the organic thin film, K _A is corrected.

で表される。ここで、ｈ＝１．２（定数）×Ａ_Ａ/｛（Ｚ_Ａ）^２｝；σ＝４．５×１０⁵／（Ｅ_O ^1.65−Ｅ_C ^1.65）；χ＝μ／ρcosecφで表される。なお、μ／ρは質量吸収係数で、物質固有の値である。φはＸ線取り出し角度、σはレナード常数、Ｅ_O は加速電圧、Ｅ_C は最小励起電圧である。 f (χ) is an absorption correction coefficient of the standard sample. When the Philbert method or the φ (ρz) method is applied, Equation 4

It is represented by Here, h = 1.2 (constant) × A _A / {(Z _A ) ² }; σ = 4.5 × 10 ⁵ / (E _O ^1.65− E _C ^1.65 ); χ = μ / ρcosecφ The Note that μ / ρ is a mass absorption coefficient and is a value unique to a substance. φ is the X-ray extraction angle, σ is the Leonard constant, E _O is the acceleration voltage, and E _C is the minimum excitation voltage.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. “Part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Manufacture of gable-top paper containers>
When viewed from the outer surface of the container, a laminate composed of a polyethylene resin layer 20 μm / bleached kraft paper 330 g / m ² / polyethylene resin layer 60 μm is used as a paperboard material, which is punched out to form a paper container shown in FIG. A plurality of blanks were prepared. Next, using an anti-adhesive (H141, manufactured by Toyo Ink Manufacturing Co., Ltd., solid content: 18% by mass; including silicone resin and cellulose resin and indicating these solid contents), a predetermined place of the blank (reference numeral in FIG. 1) 40 position) was applied by flexographic printing.
Next, this blank is bent with a box making machine, and the side seal processing is performed to form a carton blank, and then the outer top seal panels 17 and 18 and the inner top seal panels 25 and 26 are heat sealed to form a top. The seal part 30 was formed, and the paper container 50 shown in FIG. 1 was manufactured.

<Measurement of opening force>
Of the top seal portion 30 of the paper container 50, the unsealing force of the portion sealed with the anti-adhesive layer 40 (on the side of the wife wall forming panel 21) is JIS-S-0022 (“Aged / Disabled” Measured according to “Consideration design guideline—Packaging / container—Opening test method, roof-type paper pack peeling test”.

<Preparation of measurement sample for EPMA>
Blanks 1 to 3 in which the application amount of the anti-adhesive layer 40 was adjusted by changing the printing pressure of flexographic printing were manufactured at the time of manufacturing the above-described blank for paper containers. Without blanking these blanks 1 to 3, a measurement sample having a size of about 5 mm × 5 mm was cut out together with the paperboard material from the portion where the antiadhesive layer 40 was formed for each of the blanks 1 to 3. It was.
For each blank 1 to 3, 6 measurement samples 1 to 3 were collected.

<Measurement of characteristic X-ray intensity>
First, a silicon standard substance (manufactured by JEOL Ltd.) was set in a measurement chamber of an electron microscope (scanning electron microscope JSM5610LV, elemental analyzer JED2200, both manufactured by JEOL Ltd.), and the characteristic X-ray intensity of silicon was measured. The incident voltage was 15 kev. If the incident voltage is 15 kev, primary electrons will penetrate to a depth of about 10 μm, but since the polyethylene resin layer (density 0.9 g / cm ³ ) has a thickness of 20 μm, the primary electrons are polyethylene resin. Invade to the layer. Therefore, polyethylene was considered as the substrate.
The measured value of the X-ray intensity was a net value obtained by subtracting the background. The silicon standard material used was a standard material (silicon) embedded in the tip of a pipe having a diameter of 2 mm and a length of 1 cm.
Next, the measurement samples 1 to 3 were set in the measurement chamber of the electron microscope, and the characteristic X-ray intensity of silicon was measured in the same manner. The characteristic X-ray intensity of silicon of measurement samples 1 to 3 was an average value obtained by measuring six samples.

And the film thickness ((DELTA) Z) of the anti-adhesive agent layer 40 in each measurement sample 1-3 was calculated by Formula 1.
In Formula 1, ρ = 1.1 g / cm ³ ; E ₀ = 15 × 10 ³ × 1.6022 × 10 ⁻¹⁹ × 10 ⁷ erg; E _j (A) = 1.848 kev = 1.828 × 10 ³ × 1.6022 × 10 ^{− 19} × 10 ⁷ erg (excitation energy of silicon K-shell); R _A = 0.91; S ′ _A = 0.2074; e = 1.6022 × 10 ⁻¹⁹ C = 4.8032 × 10 ⁻¹⁰ esu; N ₀ = 6.02 × 10 ²³ ; U ₀ = E ₀ / E _j (A) = 15 / 1.838 = 8.1610.
However, R _A = was determined from a predetermined graph (Values of R a a function of z and 1 / U) based on the relationship between the value of 1 / U ₀ = 0.123 and the atomic number of silicon. Also, S ′ _A was calculated from Equation 2 with W _A ^j = 13.22.

On the other hand, in calculating R ₀ , the base material was polyethylene (C _n H _{2n + 2} ), and the weight composition ratio of C and H was 12: 2. And η _C = −0.0254 + 0.016 (6) −0.000186 (6) ² + 8.3 × 10 −7 (6) ³ = 0.061, η _H = −0.0254 + 0.016 (1) −0.000186 (1) ² + 8.3 × 10 −7 (1) ³ = −0.0096, and η _polyethylene = 12/14 η _C +2/14 η _H = 0.0509 was obtained. This value was substituted into Equation 3, and R ₀ = 1 + 2.8 (1−0.9 / U) η = 1 + 2.8 (1−0.9 / 8.161) × 0.0509 = 1.127.
In calculating f (χ), h = 1.2 × 28.09 / {14 ² } = 0.172; σ = 4.5 × 10 ⁻⁵ × (E ₀ ^1.65 −E _j (A) ^1.65 ) = 5.9269 × 10 ³ ; χ = 655.8. From Equation 4, f (χ) = 0.8746.

が得られるので、式５の値と、Ｃ_Ａ及びρの実測値を式１に入れ、ΔＺを算出した。 The obtained results are shown in Table 1. Incidentally, C _A is the solid content of the anti-adhesive (H141) containing a silicone resin and a cellulose resin and elemental analysis to measure the silicon relative concentration, the content of silicon in the anti-adhesive from the result Was measured.
The density ρ of the anti-adhesive layer was determined by drying and solidifying the anti-adhesive and measuring its weight and volume.
Then, from the measured value of the X-ray intensity, a value indicating ΔZ × ρ × C _A by modifying Equation 1 (Equation 5)

Since is obtained, it placed the value of the expression 5, the measured value of C _A and ρ in Equation 1, to calculate the [Delta] Z.

  From Table 1, the smaller the ΔZ calculated by the method of the present invention is, the larger the opening force is. That is, it is shown that the film thickness of the anti-adhesive layer 40 can be calculated without removing the base material by the method of the present invention.

It is a perspective view which shows the paper container which is an example of the object to which this invention is applied. It is an expanded view which shows the carton blank (base material) before the assembly process of a paper container.

Explanation of symbols

30 Top seal part 40 Anti-adhesive layer (organic thin film)
50 paper containers

Claims (2)

A method of measuring a film thickness ΔZ of an organic thin film formed on the surface of a substrate not containing a specific inorganic element, containing the inorganic element, and having a density of 2 g / cm ³ or less,
And concentration C _A of the inorganic element of the organic thin film in terms of mass ratio, based on the characteristic X-ray intensity K _S of the inorganic element according to a standard sample consisting of a single said inorganic element, the electron beam to the organic thin film The characteristic X-ray intensity K ₁ when irradiated is detected and the equation 1

(Ρ is the dry density of the organic thin film (g / cm ³ ); E ₀ is the energy of one incident electron; E _j (A) is the excitation energy of the K shell of the inorganic element; R _A is the atom of the inorganic element Number correction constant; S ′ _A is the stopping power of the standard sample; e is the charge amount; N ₀ is the Avogadro number; U ₀ = E ₀ / E _j (A); K _A = (K ₁ / R ₀ ) / ( K _S / f (x)), where R ₀ is the function of generating characteristic X-rays on the surface of the thin film, and f (x) is the absorption correction coefficient of the standard sample). Measuring method.   The method for measuring a film thickness of an organic thin film according to claim 1, wherein the inorganic element is silicon, and the inorganic element is contained as an organic silicon compound in the organic thin film.

Images