JP2001004534A - Method and apparatus for evaluating molecular orientation of thin film and recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the accuracy of the direct data related to the molecular orientation of a thin film in a method and apparatus for measuring the orientation of molecules constituting the thin film. SOLUTION: The molecular orientation state of a thin film 111 is determined by measuring the incident azimuth dependence of the deflection state of the reflected light of infrared rays 108 incident on the thin film 111 and the reflected light of visible light 107. Infrared rays and visible light are incident on the surface of the sample at the same position at the same time. When the plane azimuth dependence of reflected infrared rays and reflected visible light is measured, the sample is rotated in-plane centering around a measuring region. When in-plane distribution is measured, a two-azimuth parallel moving stage is arranged on a stage 112 rotated centering around the axis passing a position where infrared rays and visible light impinge against.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the evaluation of the molecular alignment state of a thin film having anisotropic molecular alignment, such as a liquid crystal alignment film for giving initial alignment to liquid crystal molecules.

[0002]

2. Description of the Related Art As an evaluation method of an anisotropic thin film, a method of measuring the incident angle dependence of the intensity of reflected light generated when a plurality of wavelengths are incident using visible light (Isobe, "Refraction of anisotropic thin film"). JP-A-5-5699, Isobe, "Method for Measuring Refractive Index and Film Thickness of Anisotropic Thin Film", JP-A-5-3699
29333) and a method of measuring from the dependence of the reflected light intensity on the incident angle and the incident azimuth (Isobe “Method of measuring the refractive index and thickness of thin films”)
JP-A-3-65637), linearly polarized incident light is condensed using a lens, and the dependence of the intensity of the reflected light by the incident light having only the S-polarized component and only the P-polarized component on the incident angle and the incident azimuth can be efficiently determined. The method of measurement (Ukawa "Method and apparatus for measuring optical constants", JP-A-8-152307), the dielectric constant, the film thickness and the main dielectric constant of the oriented part are determined by rotating the sample in-plane and determining the polarization direction of the reflected light from the incident azimuth. A method of determining the direction of the coordinates, the dielectric constant and the film thickness of the non-aligned portion (Hirosawa, "Method and Apparatus for Evaluating Anisotropic Thin Films", Japanese Patent Application No. 8-49320) A method for efficiently measuring the incident angle and incident azimuth dependence of the intensity of reflected light by incident light having only an S-polarized component and a P-polarized component (Ukawa, "Optical Constant Measurement Method and Measurement Apparatus", JP-A-8-152307). ) Has been proposed.

On the other hand, infrared absorption spectroscopy using linearly polarized infrared light is widely performed to evaluate the molecular orientation state of an organic thin film (eg, Arafune et al., Applied Physics Letters, Vol. 71, p. 2755, 1997). R. A
rafune et al., Appl. Phys. Lett. 71, 2755 1998). These measures the amount of change in the intensity of the infrared light transmitted through the sample with respect to the relative angle between the polarization direction and the sample direction. That is, this is a method of detecting dichroism in which the amount of infrared absorption varies depending on the molecular orientation and evaluating the orientation. This method can be applied only to a film formed on a substrate such as silicon or calcium fluoride (fluorite: CaF ₂ ) that transmits infrared rays.

In recent years, infrared ellipsometry for measuring the wavelength dispersion of the polarization state of reflected light generated when infrared light is applied to a thin film surface has been developed, and the bonding state between a silicon substrate and a carbon film (Heights et al., Applied Physics Letters, Ltd.) has been developed. 72 volumes
780 pages, 1998 T. Heitz et al., Appl. Phy
s. Lett. 72, 780 1998) and the evaluation of the film thickness and composition of borophosphosilicate glass (BPSG) on a silicon substrate (Haoshikovsky et al., Applied Physics Letters 65, 1236, 1994 R. Ossikovski et al., Appl. Phys. L
ett. 65, 12361994). This method also provides a significant change in the polarization state at a specific infrared absorption wavelength reflecting the molecular orientation, so that knowledge about the chemical composition similar to infrared absorption spectroscopy can be obtained, but it is used only for isotropic films. It is a technique that is.

Recently, a method for evaluating the molecular orientation of a thin film by the above-mentioned infrared spectroscopic ellipsometry has been proposed (Hirosawa, "Method for evaluating molecular orientation of thin film, evaluation apparatus and recording medium", Japanese Patent Application No. 10-2).
52662). This method uses infrared light as a light source to enter the sample, and measures the incident azimuth dependence of the polarization state of reflected infrared light.By measuring at a wave number corresponding to the energy of molecular vibration, a specific structure that constitutes a thin film Although knowledge about the orientation state of the unit can be obtained, it is difficult to improve the measurement accuracy.

[0006]

As a method for evaluating an anisotropic thin film, a method using visible light (Isobe, "Method for Measuring Refractive Index and Film Thickness of Anisotropic Thin Film", JP-A-5-5699; Method for measuring refractive index and thickness of thin film "
29333, Isobe "Method for measuring refractive index and thickness of thin film"
-65637, Ukawa "Optical constant measuring method and measuring device"
Japanese Patent Application Laid-Open No. 8-15230 and Hirosawa, "Method and apparatus for evaluating anisotropic thin film" (Japanese Patent Application No. 8-49320) have been proposed. In many of these methods, the correlation between the crystal structure and the optical anisotropy of inorganic thin films with high crystallinity has been clarified. Therefore, it is possible to quantitatively evaluate the crystal orientation equivalent to the molecular orientation. is there. In particular, the “Method and apparatus for evaluating anisotropic thin film” of Japanese Patent Application No. 8-49320 can determine not only the optical anisotropy but also the thickness of a sample.

On the other hand, since the organic thin film has extremely poor crystallinity, it is difficult to determine the molecular orientation from the optical anisotropy of the film. Furthermore, in polymer thin films, such as liquid crystal alignment films, it is expected that the molecular chains are entangled with each other, and the optical characteristics of the basic units that make up the polymer chains accurately reflect the optical characteristics of the polymer chains. Not expected. That is, by measuring optical anisotropy by visible light, it is not possible to determine the molecular orientation of a thin film having poor crystallinity or a polymer organic thin film such as a liquid crystal alignment film.

On the other hand, infrared absorption spectroscopy using linearly polarized infrared light has been widely performed to evaluate the molecular orientation state of an organic thin film (eg, Arafune et al. Applied Physics Letters, Vol. 71, p. 2755, R. Arafune et al. a
l., Appl. Phys. Lett. 71, 2755 etc.). However, since infrared light does not pass through the glass substrate, it is not possible to measure the molecular alignment state of a film formed on a glass substrate such as a liquid crystal alignment film.

In addition to measuring infrared absorption, the use of infrared spectroscopic ellipsometry, which is a technique for measuring the polarization state of reflected infrared light, enables a sample on a glass substrate to be measured and forms a film. The orientation state of a specific structural unit can be determined. However, when the thickness of the sample is extremely small, the logarithm log (ρ / ρ) of the ratio of the polarization density ρ of the reflected infrared light from the sample to the polarization density ρs of the reflected infrared light from the substrate is obtained.
s) and the product εd of the dielectric constant ε of the film and the film thickness d has a proportional relationship. It should be noted that the polarization density ratio log (ρ
/ Ρs) corresponds to the phase difference component Δ of the polarization state,
The imaginary part corresponds to the amplitude component ψ. Also, the dielectric constant ε of the film
Is approximately the following equation 1 near the molecular vibration wave number ω ₀

(Equation 1) Often represented by Here, γ is a value corresponding to the lifetime of molecular vibration. The absolute value of the imaginary part of the dielectric constant becomes maximum near ω ₀ , and the incident azimuth anisotropy is also most clearly observed. On the other hand, near the wave number ω ₀ , the anisotropy is not observed because the real part of the dielectric constant becomes almost zero.

The extreme value of the real part of the dielectric constant is given by the following equation (2).

(Equation 2) The absolute value of the imaginary part of the permittivity is given by the wave number ω
_Since the value is smaller than the value at ₀ , the anisotropy is hardly observed. That is, when measured at the wave number ω ₀ , anisotropy is clearly observed in the amplitude ratio component の of the polarization state, but almost no anisotropy is observed in the phase difference component Δ of the polarization state. On the other hand, at the position of the formula 2, anisotropy is observed in both Δ and ψ, but the anisotropy of ψ is not as large as that of the formula 2. For the above reasons, it is possible to determine the molecular orientation state by infrared ellipsometry, but it is difficult to improve the accuracy. In particular, since the product of the dielectric constant and the film thickness is approximately proportional to the logarithm of the polarization density, it is difficult to determine each polarization state independently and accurately.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method and an apparatus for measuring the orientation of molecules constituting a thin film to improve the accuracy of direct information on the molecular orientation of the thin film. And

[0012]

In order to achieve the above object, the present invention provides a thin film molecular orientation evaluation method and evaluation apparatus and a recording medium described in the following (1) to (21).

(1) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared ray is determined. A method for evaluating the molecular orientation of a thin film, comprising measuring by changing the incident azimuth of light and infrared light by in-plane rotation to determine the optical anisotropy and the molecular orientation state of the sample thin film.

(2) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared ray is determined. An apparatus for evaluating the molecular orientation of a thin film, wherein the optical anisotropy and molecular orientation of a sample thin film are determined by changing the incident directions of light and infrared light by in-plane rotation.

(3) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared ray is determined. A thin film molecular orientation evaluation apparatus characterized by automatically performing measurement by changing incident directions of light and infrared light by in-plane rotation and determining the optical anisotropy and molecular orientation state of a sample thin film.

(4) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the incident azimuth dependency of the polarization state of the reflected light from the sample and the reflection infrared ray is determined. A recording medium in which a computer program for automatically controlling measurement by changing incident directions of light and infrared light by in-plane rotation is recorded.

(5) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light ray are used. By rotating the polarization measurement unit around the sample normal passing through the measurement point as an axis, the dependence of the polarization state of the reflected light from the sample on the incident direction is measured, and the optical anisotropy and molecular orientation state of the sample thin film are measured. A method for evaluating the molecular orientation of a thin film, comprising:

(6) An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light ray are used. By rotating the polarization measurement unit around the sample normal passing through the measurement point as an axis, the dependence of the polarization state of the reflected light from the sample on the incident direction is measured, and the optical anisotropy and molecular orientation state of the sample thin film are measured. A thin film molecular orientation evaluation device characterized by determining:

(7) An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light ray By rotating the polarization measurement unit around the sample normal passing through the measurement point as an axis, the dependence of the polarization state of the reflected light from the sample on the incident azimuth is automatically measured, and the optical anisotropy of the sample thin film is measured. An apparatus for evaluating the molecular orientation of a thin film, wherein the molecular orientation is determined.

(8) An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light ray are used. A recording medium on which a computer program for automatically measuring the incident azimuth dependence of the polarization state of reflected light from a sample by rotating a polarization measurement unit around a sample normal passing through the measurement point is provided.

(9) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the reflected light from the sample and the polarization direction of the reflected infrared ray have an incident direction dependent plane. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the distribution of light and infrared rays is changed by in-plane rotation of the sample, and the distribution is measured by parallel movement of the sample A method for evaluating the molecular orientation of a thin film, comprising selecting a position and determining an in-plane distribution of an optical anisotropy and a molecular orientation state of a sample thin film.

(10) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the distribution of light and infrared rays is changed by in-plane rotation of the sample, and the distribution is measured by parallel movement of the sample Select a position and measure,
An apparatus for evaluating the molecular orientation of a thin film, which determines an optical anisotropy and a molecular orientation state of a sample thin film.

(11) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the reflected light from the sample and the polarization direction of the reflected infrared ray have an incident direction dependent plane. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the incident direction of light and infrared is automatically changed by in-plane rotation of the sample, and the distribution of the sample is automatically adjusted. An apparatus for evaluating the molecular orientation of a thin film, wherein a measurement position is selected and measured by a parallel movement to determine an optical anisotropy and a molecular orientation state of a sample thin film.

(12) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and the reflected light from the sample and the polarization state of the reflected infrared ray have an incident direction dependent plane. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the incident direction of light and infrared is automatically changed by in-plane rotation of the sample, and the distribution of the sample is automatically adjusted. A recording medium storing a computer program for selecting and measuring a measurement position by parallel movement.

(13) An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light ray are used. The polarization measurement unit is rotated about the sample normal passing through the measurement point as an axis to measure the incident azimuth dependence of the reflected light and reflected infrared polarization state at the measurement position, and parallelized in two different directions orthogonal to the rotation axis. The measurement position is selected by moving the sample in parallel using a sample stage equipped with a movement function, the in-plane distribution of the incident azimuth of the reflected light and reflected infrared light is measured, and the optical anisotropy of the sample thin film and molecular A method for evaluating the molecular orientation of a thin film, comprising determining an orientation state.

(14) An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and the incident infrared light source, the incident visible light source, the reflected infrared polarization measuring section, and the reflected visible light ray The polarization measurement unit is rotated about the sample normal passing through the measurement point as an axis to measure the incident azimuth dependence of the reflected light and reflected infrared polarization state at the measurement position, and parallelized in two different directions orthogonal to the rotation axis. The measurement position is selected by moving the sample in parallel using a sample stage equipped with a movement function, the in-plane distribution of the incident azimuth of the reflected light and reflected infrared light is measured, and the optical anisotropy of the sample thin film and molecular An apparatus for evaluating the molecular orientation of a thin film, which determines an orientation state.

(15) An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and the incident infrared light source, the incident visible light source, the reflected infrared polarization measuring section, and the reflected visible light ray The polarization measurement unit is rotated about the sample normal passing through the measurement point as an axis to automatically measure the incident azimuth dependence of the reflected light and reflected infrared polarization state at the measurement position, and in two different directions orthogonal to the rotation axis. The measurement position is selected by automatically translating the sample using the sample stage equipped with a parallel translation function, and the in-plane distribution of the incident direction dependence of the reflected light and reflected infrared light is automatically measured. For determining the molecular anisotropy and molecular orientation state.

(16) An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light ray are used. The polarization measurement unit is rotated about the sample normal passing through the measurement point as an axis to automatically measure the incident azimuth dependence of the reflected light and reflected infrared polarization state at the measurement position, and in two different directions orthogonal to the rotation axis. A computer program was recorded to automatically select the measurement position by automatically translating the sample using a sample stage equipped with a parallel movement function, and to automatically measure the incident azimuth-dependent in-plane distribution of reflected light and reflected infrared light. recoding media.

(17) (1), (5), (9) or (1) characterized in that the measurement is performed in an inert gas or vacuum.
3) Method for evaluating molecular orientation of thin film.

(18) The apparatus for evaluating the molecular orientation of a thin film according to (2), (6), (10) or (14), wherein the measurement is carried out in an inert gas or in a vacuum.

(19) The measurement is performed using an aspherical lens, an aspherical reflecting mirror, or an elliptical aperture so that the area on the sample surface to which light and infrared light are applied is circular. ), (5), (9) or (13).

(20) The measurement is performed by using an aspherical lens, an aspherical reflecting mirror, or an elliptical stop so that the area on the sample surface to which light and infrared light are applied becomes circular. ), (6), (10) or (14).

(21) The optical structure and molecular orientation state of the thin film are determined from the incident orientation dependence of the polarization state of the reflected visible light ray and the reflected infrared ray generated when visible light rays and infrared rays having a certain polarization state are incident on the thin film sample. Recording medium recording a computer program for determining

The present invention measures the incident azimuth dependence of the polarization state of reflected infrared light generated when infrared light is incident on the sample surface and the polarization state of visible light reflected light. The purpose of the present invention is to improve the accuracy of direct information on the molecular orientation of a thin film. In measuring the polarization state of reflected light and the incident azimuth dependence of reflected infrared light at the same measurement point, the sample is held on a rotating stage that is perpendicular to the sample surface and passes through the measurement point, and the sample is rotated using this stage. At this time, there are a method of measuring the infrared ray and the visible light ray at different incident directions, and a method of measuring the incident angle at the same incident angle but changing the incident angle. It is also conceivable that light from a light source having a continuous spectrum is incident and the wavelength dispersion of the polarization state of the reflected light is measured.

However, there is no optical element that can simultaneously handle light in the infrared region to the visible light region corresponding to the molecular vibration energy, so that it is difficult at present to realize this. As a method of changing the incident directions of visible light and infrared light to the sample, besides the method of rotating the sample while fixing the light source as described above, the normal of the sample surface passing through the light source and the measurement point with the fixed light source There is a method of rotating around an axis. Further, when measuring the in-plane distribution of the molecular orientation, a stage that translates in two different directions is set on the rotating stage, and the sample is held thereon. Scanning of the measurement position on the sample surface is performed by this translation stage.

By analyzing the dependence of the polarization state of the reflected light of visible light on the incident azimuth based on the 4 × 4 matrix method, the optical structure of the film including the information on the film thickness can be determined. The dependence of the polarization state of the reflected infrared light on the incident direction is also analyzed based on the 4 × 4 matrix method. At this time, since the information about the film thickness is obtained from the measurement result of visible light,
The dielectric constant in the infrared region can be determined with high accuracy, and the determination accuracy of the molecular orientation state of the film is also improved.

The polarization state of the reflected light is represented by a 4 × 4 matrix (Bellman et al., Physical Review Letters, Vol. 25, p. 577, 1970). DW Berrman and TJ Scheffer,
Physcal Review Letters, 25, 577 1970). According to this method, when light enters the sample at an incident angle β, Φ _I , Φ _r , and Φ _t represent the states of the incident light, reflected light, and transmitted light to the substrate, which are established between the respective cases. The relationship is 4 in the film when the molecular orientation is uniaxially anisotropic.
The following equation is obtained using the × 4 matrix L film thickness d and the frequency ω of the incident infrared ray. i is an imaginary unit. Φ _t = exp
(IωdL) (Φ _I + Φ _r )

In L, Δ ₁₄ , Δ ₂₄ , Δ ₃₁ , Δ ₃₂ ,
Δ _33, Δ _41, Δ ₄₂ and delta ₄₄ is 0, the remainder is represented by the following formula. _{Δ 11 = - (ε e -ε} o) sinβsinθcosθsinφ / (ε e cos
² θ + ε _o sin ² θ) Δ ₁₂ = 1−sin ² β / (ε _e cos ² θ + ε _o sin ² θ) Δ ₁₃ = (ε _e −ε _o ) sin β sin θ cos θ cos φ / (ε _e cos ²
θ + ε _o sin ² θ) Δ ₂₁ = ε _o [ε _e − (ε _e −ε _o ) sin ² θ cos ² φ] / (ε _e c
^{_{os 2 θ + ε o sin 2}} θ) Δ 22 = -ε e (ε e -ε o) sin 2 θcos 2 φ / (ε e cos 2 θ +
ε _o sin ² θ) Δ ₂₃ = −ε _o (ε _e −ε _o ) sin θ cos φ sin φ / (ε _e cos ²
θ + ε _o sin ² θ) Δ ₃₄ = 1 Δ ₄₃ = ε _o [ε _e − (ε _e −ε _o ) sin ² θsin ² φ] / (ε _e c
os ² θ + ε _o sin ² θ) −sin ² β

In the above equation, ε _e and ε _o are the permittivity expressed in the main permittivity coordinate system, θ is the inclination angle of the main permittivity coordinate with respect to the film surface, and φ is the in-plane azimuthal angle of the incident light. When the polarization state of the reflected light is calculated according to this equation, it is shown that an anisotropy occurs in the polarization state of the reflected light if there is a difference between ε _e and ε _o in the equation. Further, since the difference in the angle of the principal dielectric constant coordinate with respect to the film surface is reflected on the incident azimuth dependence, the anisotropic dielectric constant and the inclination of the principal axis are determined from the measured value of the incident azimuth dependence of the polarization state. In particular, an organic thin film typified by a liquid crystal has a very small absorption in the visible light region, and the dielectric constant ε can be treated as a pure real number, so that these optical structures can be accurately determined. On the other hand, the dielectric constant is a complex number in the infrared region due to the presence of absorption due to molecular vibration. Furthermore, since the anisotropic part of the dielectric constant is considered to be a pure imaginary number at the frequency corresponding to the energy of the molecular vibration, more accurate measurement is possible.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings. (Embodiment 1) As an embodiment of the present invention, a configuration of an apparatus for incident infrared light and visible light from the same direction will be described with reference to FIG. In the figure, 101 is an FT-IR unit comprising an infrared detector and a movable mirror, 102 is an infrared analyzer, 103
Is a photomultiplier tube, 104 is an analyzer, 105 is a quarter-wave plate, 106 is a polarizer, 107 is a He-Ne laser light source, 108 is an infrared light source, 109 is a polarizer, 110 is a photoelastic element for infrared light, Reference numeral 111 denotes a sample, and 112 denotes a sample stage, which rotates around a measurement point. The atmosphere in the FT-IR unit and the housing containing the infrared detector is replaced with nitrogen gas, but the surroundings of the sample including the stage are ordinary air.

A sample measured using this apparatus was prepared in the following procedure. A polyimide PI-B made by Nissan Chemical Co., Ltd. is spin-coated on a glass substrate (Corning 7059),
After heating at 30 ° C. for 30 minutes, heating was performed at 250 ° C. for 60 minutes. Thereafter, using a cloth roller having a diameter of 50 mm, the indentation length was set at 0.
1mm, rotation speed 800rpm, substrate moving speed 30mm
Rubbing was performed twice at / s. Using this apparatus, the incident angle of infrared rays was set to 62 °, the incident angle of visible light was set to 50 °, and the wavelength dispersion of the polarization state of reflected infrared rays near 1250 cm ⁻¹ , measured at 15 ° intervals, and 1246 cm ⁻¹ . The dependence of the polarization state of the reflected light of infrared light on the incident azimuth and the dependence of the reflected light of visible light on the incident azimuth are shown in FIGS.
The results are shown in 5, 6, and 7. 2, 3, 4, and 5 are obtained from a difference spectrum from a spectrum obtained by measuring a glass substrate as a reference sample.

At this time, 101, 102, 108,
Although 109 was in a circulating nitrogen atmosphere, the sample was exposed to the atmosphere, so that the wavelength dispersion of the polarization state of the reflected infrared light showed that the microstructure corresponding to the molecular vibration of the polyimide film was the same as the water vapor in the atmosphere. Some are not clearly captured by the microstructure corresponding to carbon dioxide. For example, 15
No vibration of phenyl having an energy of about 00 cm ^-1 could be confirmed. However, the microstructure corresponding to phenyl near 1246 cm ^-1 shown in FIGS. 2 and 3 is not affected by atmospheric water vapor or carbon dioxide.

FIGS. 4 and 5 show wave numbers 1246c at which Δ becomes minimum.
It is the incident azimuth dependence of the polarization state at m ^-1 . As shown in these figures, although a clear anisotropy is seen in Δ, the dependence of ψ on the incident azimuth is not clear, and an improvement in the accuracy of the film structure analysis cannot be expected. On the other hand, in FIGS. 6 and 7 showing the incident azimuth dependence of the polarization state of visible light, clear anisotropy is observed in both Δ and ψ, and the optical structure in the visible light range can be determined with high accuracy. In particular, the thickness of the molecular orientation region in the vicinity of the film surface, which greatly affects the anisotropy of ψ, was determined to be 32 nm. But,
This arrangement has the disadvantage that the angle of incidence of infrared or visible light cannot be arbitrarily selected due to spatial limitations.

(Embodiment 2) As an embodiment of the present invention, a configuration of an apparatus for injecting infrared light and visible light from the same direction will be described with reference to FIG. In the figure, 201 is an incident infrared light source including an infrared light source and a polarizer, 202 is a photoelastic element for infrared light,
Infrared polarization detector including analyzer and FT-IR system, 203
Is an incident light source comprising a polarizer and a He-Ne laser, 20
Reference numeral 4 denotes a polarization measuring unit including a phase shifter, an analyzer and a photoelectron image, 205 denotes a rotating stage, 206 and 207 denote translation stages, and 208 denotes a sample. In this example, the incident directions of the infrared light and the visible light are different from each other by 90 °. In order to enable measurement without the influence of water vapor or carbon dioxide in the atmosphere, a vessel covering the whole and an autocollimator used for adjusting the inclination of the sample are omitted in FIG.

FIG. 9 is a diagram showing the configuration of the apparatus including the container when viewed from the visible light detecting side. In FIG. 9, the visible light polarization measuring unit is omitted. Reference numeral 1 denotes a container for accommodating the entire apparatus including a sample and an optical element in order to allow the all-infrared light path to pass through a rare gas, a nitrogen gas, or a vacuum, and has a gas inlet 2 and a gas outlet 3. Have been. Two types of this material, an acrylic resin having a thickness of 1 cm, and a stainless steel having a viewing window were tried. The sample is introduced through the introduction door 12. Reference numeral 4 denotes an FT-IR device including an infrared ray source using a tungsten filament and an interferometer. The FT-IR unit is SPC- manufactured by Bio-rad.
The 3200 was diverted, and a mirror was arranged at the sample portion of the apparatus to guide infrared rays to the outside of the apparatus. The infrared light that has exited the device passes through the polarizer 5, and is converted into a photoelastic element 6 (modulation frequency: 40 kHz).
Changes the polarization state. The infrared light reflected from the surface of the sample 9 passes through the analyzer 7 and its intensity is measured by the detector 8. Further, an autocollimator 11 was attached to confirm the inclination of the sample surface with respect to incident infrared rays. In order to improve the efficiency of adjusting the tilt of the sample, the position of the reflected light from the sample in the autocollimator was monitored by a CCD camera and projected on the display 13 outside the container.

The arrangement of this optical system excluding the container 1 is the same as the arrangement reported so far (Dreviron et al., Shin Solid Films, Vol. 236, p. 204, 1993).
B. Drevillon et al., Thin Solid Films 236, 204 1
993) is basically the same as that of the first embodiment except that the stage 10 has a rotating stage and a two-stage for adjusting the incident direction of the infrared ray to the sample.
It consists of a combination of two translation stages.

The detailed configuration of this stage is shown in FIG. In FIG. 10, reference numeral 21 denotes a rotary stage.
This rotation axis is arranged so as to pass through a position on the sample surface where the infrared rays strike. 2 installed on a rotating stage
The two parallel movement stages 22 and 23 are arranged so that the movement direction is orthogonal to the rotation axis, and the respective parallel movement directions are orthogonal. In addition, a stage 24 for adjusting the tilt of the sample surface is provided on the translation stage,
The tilt angle of the plate 26 on which the sample is directly placed is adjusted. A stage 25 that moves parallel to the rotation axis and is mounted below the rotary stage is mounted to support measurement of samples having different thicknesses. Note that the arrows in FIG. 10 indicate the moving direction of each stage. In order to automatically measure the in-plane distribution of anisotropy, the FT-IR device 4, the photoelastic element 6,
The operation of the detector 8 and the stage 12 and the acquisition of data are controlled by the computer 14.

In assembling this apparatus, the following method was used to determine the position of the sample to be measured. First, the diameter is 10 m with the polarizer, photoelastic element and analyzer removed.
The gold-coated mirror of m is placed at the sample position, and the stage is adjusted so that the reflected infrared light intensity is maximized. Thereafter, the diameter of the gold-coated area was 5 mm, 2 mm, 1 mm on the polished optical glass.
mm, and the same adjustment was performed. The position of the autocollimator was adjusted in a state where the infrared intensity was maximized using a mirror having a gold-coated area diameter of 1 mm. Thereafter, a polarizer, an analyzer, and a photoelastic element were installed, and readjustment was performed in the same procedure. The above operation was performed in a state where the side wall of the container holding the atmosphere was partially missing, and the arrangement was confirmed again after attaching the side wall. Note that circular apertures were used for the entrance side and the reflection side aperture.

A sample measured using this apparatus was prepared in the following procedure. A polyimide PI-C manufactured by Nissan Chemical Industries is spin-coated on a glass substrate (Corning 7059),
After heating at 30 ° C. for 30 minutes, the sample was heated at 250 ° C. for 60 minutes to obtain a sample. Thereafter, rubbing was performed twice using a cloth roller having a diameter of 50 mm at a pressing length of 0.05 mm, a rotation speed of 800 rpm, and a substrate moving speed of 30 mm / s. A sample not subjected to rubbing after firing was also prepared as a reference sample.

These two samples were measured using an acrylic container. The measurement was carried out by introducing an argon gas into the container, but it took about 50 minutes until the peak caused by moisture remaining in the atmosphere became inconspicuous. The height of the sample was adjusted so that the intensity of the reflected infrared rays was maximized, and the tilt was adjusted with an autocollimator. Ψ defined by the arctangent of the amplitude ratio of the P component to the S component indicating the polarization state of the reflected infrared light of the sample without rubbing measured by this device,
FIGS. 11 and 12 show the infrared wavenumber dependence of Δ defined by the phase difference between the S component and the P component, respectively. The measurement results of the rubbed sample are also shown in FIGS.
As shown in these figures, it can be seen that measurement was possible without influence of water vapor or carbon dioxide in the air in both samples.

FIGS. 15 and 16 show the wavelength dispersion around 1500 cm ⁻¹ obtained from the measurement of the rubbed sample. In this example in which the atmosphere around the sample was also replaced, fine structures corresponding to the molecular vibration of phenyl, which were not obtained by the measurement in the atmosphere of Example 1, were clearly observed in both Δ and ψ. Further, FIG. 17 shows the incident azimuth dependence of the difference of Δ at 1504 cm ⁻¹ from the glass substrate. The same measurement was performed in a nitrogen gas atmosphere, but there was no significant difference except that the time required for purging was slightly reduced to about 40 minutes.

Based on this data, focusing on the peak at 1504 cm ^-1 corresponding to the phenyl group, the orientation of the phenyl group was determined by the following method. The incident direction dependence of the polarization state of both visible light and infrared light is determined by the procedure shown in FIG.
More specifically, as described above, the polarization state of the reflected infrared light is calculated from the 4 × 4 matrix described above. The 4 × 4 matrix corresponding to the polyimide film is the same as described above. On the other hand, the 4 × 4 matrix of incident light and reflected light that pass through the non-oriented portion (isotropic portion) of the film is as follows. _{Δ 11 = 0 Δ 12 = 1} -sin 2 β Δ 13 = 0 Δ 21 = 1 Δ 22 = 0 Δ 23 = 0 Δ 34 = 1 Δ 43 = 1-sin 2 β.

These matrices have an axis parallel to the normal to the sample surface, an X-axis parallel to the plane of incidence of infrared radiation and the X
This defines the Y axis perpendicular to the Z axis. A and B are 4 × 4 matrices of the oriented part or the non-oriented part. further,
The respective film thicknesses are d1 and d2. Incident light, reflected light,
The state of the electromagnetic field of the transmitted light in the film is represented by four electromagnetic field components Ex,
Column vectors Φ _I , Φ _r , Φ _t with elements H _y , E _y , −H _x
Then, the interval is represented by the following equation. exp (−iωBd2) exp (−iωAd1) (Φ _I + Φ _r )
= Φ _t

Specifically, exp (-iωBd2), exp (-i
In the calculation of ωAd1), Taylor expansion was performed for iωBd2 and iωAd1, and the sixth order term was considered. The calculation of the powers of A and B was speeded up using the Cary Hamilton's theorem. Since Φ _I is incident light, an arbitrary value can be used. Further, Φ _t can be calculated directly from ψi according to Snell's law. From the above, Φ _r can be uniquely determined. There is a relationship between the electric field components E _rx and E _{ry of} Φ _r, the S component E _rs parallel to the sample surface of the reflected infrared ray, and the component E _rp perpendicular to both the S component and the traveling direction of the infrared ray. . E _rs = E _ry E _rp = E _rx cosβ

That is, the polarization state of the reflected light (Δr, Δr)
Is determined by exp (iΔr) tanψr = E _rx cos β / E _ry . The above calculation is performed for each measurement direction. The flow of this calculation procedure is shown in FIG.

First, the measurement result is compared with the dependence of the polarization state of the reflected visible light calculated by the above procedure on the incident direction, and the film structure parameters are optimized so that the calculation result matches the measurement result. As shown in FIG. 17, parameter optimization was performed as follows. Assuming uniaxial anisotropy, the polarization state of the reflected light can be calculated by the 4 × 4 matrix method as described above. Since many organic thin films can be considered transparent in the visible light region, the dielectric constant is a real number. In addition, the six parameters of the inclination angle of the main dielectric constant, the thickness d1, d2 of the oriented portion and the non-oriented portion, and the non-oriented portion are parameters for determining the film structure. However, since the dielectric constant of the non-oriented portion is considered to be the average value of the anisotropic dielectric constant of the oriented portion, the actual optimization parameters are five. In this case, the measurement is performed in 24 directions, and two quantities indicating the polarization state in each direction are selected. Therefore, the quantities are sufficient to determine these five parameters indicating the film structure.

However, since each measured value includes an error, it is expected that a parameter determined analytically will include a large error. Further, since the calculation formula has high nonlinearity, it is very difficult to analytically determine six parameters. Therefore, temporary values are substituted into the five unknown parameters, and the incident direction dependence of the polarization state calculated from the measured values is compared with the measured values, and the value that minimizes the sum of squares of the difference is determined as the parameter determination value. And Here, the total residual R and the residual rj (j
R = (W1 (Δobs−Δcal) ² + W2 (ψob
s−ψcal) ² ) rj = W1 (Δobs−Δcal) ² + W2 (ψobs
−ψcal) ² Δobs, Δcal, ψobs, ψcal
Are measured and calculated values of Δ and に お け る at each incident direction. W1 and W2 are weights, and Δ,
一致 Adjust the matching priority. The sum is performed for all measurement directions. In this case, it is 6 points.

The calculation of the least squares method is mainly based on the modified Markat method, and the algorithm is referred to "Data analysis by the least squares method" by Koyanagi (Tokyo University Press). Specifically, in order to determine the parameter dependence of the total residual R, partial derivatives are calculated for each of the six parameters for determining the residual rj in each measurement direction, and a differential matrix is determined using each of the six parameters as a matrix element. I do. In this case, a matrix A of 5 rows and 5 columns
become. Further, a column vector B having the residual rj as an element is defined. A column vector P that satisfies the following equation AP = B is a parameter correction vector. This value is added to the parameters used in calculating A and B to obtain a new film structure parameter, and until the measurement result and the calculation result match. This procedure is basically used.

However, in this problem, since the nonlinearity is high, the total residual obtained from the parameters corrected by this method is not always smaller than before the correction. Therefore, the operation of halving the value of the correction vector was repeated until the total residual became smaller than the value before correction. If the total residual does not decrease even after repeating the procedure of halving the size of the correction vector four times, an operation of adding an arbitrary number (damping) to the diagonal elements of the differential matrix is performed to perform the correction vector Was calculated again. The value to be added is a quarter of the value of the determinant of matrix A.
, With respect to the correction vector obtained by each damping operation, until all residuals become smaller than the residual before correction.
The value of the correction vector was halved in less than or equal to the number of times. If all residuals did not decrease even after the addition of damping, the operation of increasing the damping value by four times was performed up to five times. As a result, the dielectric constant of the alignment portion was 2.959, 2.40.
0, the inclination angle of the main dielectric constant with respect to the film surface was 30 °, the thickness of the oriented portion was 64 nm, and the thickness of the non-oriented portion was 18 nm.

Similarly, it is possible in principle to determine the optical structure of the film in the infrared region from the polarization state of the reflected infrared light. However, due to the absorption, the dielectric constant becomes a complex number, the parameters to be determined further increase, and as shown in FIG. 5 of the first embodiment, ψ is observed at the wave number corresponding to the molecular vibration of the sample. Since the anisotropy is very small, the parameters cannot be determined with high accuracy. Therefore, the optical structure in the infrared region was determined using the data of FIG. 17 and the thicknesses of the oriented part and the non-oriented part determined from the measurement of visible light. Since the permittivity is a pure imaginary number at the wave number corresponding to the molecular vibration, the parameters to be determined are the two permittivity of the orientation part and the inclination angle of the main permittivity coordinate. As shown in FIG. 17, the incident azimuth dependence of the polarization state of the reflected light mainly includes the difference between the maximum value and the minimum value of Δ, the difference between two minimum values of Δ, and the average value of Δ. Can be characterized by quantity. Since three parameters are optimized, the parameters can be determined with high accuracy.

As a result, the film thickness d was about 54 nm, the inclination angle of the main dielectric constant coordinate was around 27 °, and εoi and εei were 1.2 and 0.9, respectively. Considering that the absorption coefficient of the phenyl group in the in-plane direction of the 6-membered ring and the normal direction of the plane is 1.1, about 60% of the total of the phenyl group ((1.0 / 1.
2) {(1/2) = 0.6) was determined to be oriented with the surface of the six-membered ring inclined 27 ° from the sample surface. The determination of the optical structure in the visible light and the optical structure in the infrared was performed by creating a computer program for executing the above procedure by fortran and automatically determining the film structure using a computer.

(Embodiment 3) Using the same apparatus configuration and sample as in Embodiment 2 and scanning the measurement position using a translation stage, a range of 10 mm in length and 10 mm in width was changed to 5 mm.
9 points were automatically measured by computer control at intervals of. That is, as shown in FIG. 19, the sample is moved to the measurement position by the parallel movement stage, and after adjusting the tilt and the like, the incident azimuth dependence of the polarization state of the reflected infrared light and the reflected visible light at each measurement position is measured. If the measurement at all the measurement points initially planned is not completed, the sample is moved to the next measurement position. This procedure is repeated until all measurements are completed.
As shown in FIG. 20, there is a method in which the determination of the film structure at each measurement point is performed immediately after the completion of the measurement by the same method as in the second embodiment, and the film structure is determined while measuring the in-plane distribution of the film structure. However, since the amount of calculation for determining the film structure is large and a computer with a low processing capacity is inefficient, the measurement was performed according to the procedure in FIG. 19 and then the film structure was separately determined. FIG.
FIG. 1 shows the distribution of the ratio (εei−εoi) / εi of the difference between the two dielectric constants of the oriented portion at 1504 cm ^{−1 and} the isotropic dielectric constant. Here, εei and εoi are the imaginary part of the anisotropic dielectric constant of the orientation part,
εi is their average value.

Embodiment 4 When measuring the reflected infrared light and the reflected visible light, the shape of the incident light and the incident infrared light is usually shaped by an aperture or a mirror so that the cross section becomes circular. However, when light or infrared light is obliquely incident on the sample surface, the region where the light or infrared light hits the sample surface is shown in FIG.
It becomes an ellipse as shown in FIG. In this case, the area on the sample surface to be measured changes with the change in the incident direction of the visible light and the infrared light. Therefore, the shape of the incident light was corrected by an aperture so that the incident light became an ellipse having a long axis in the S polarization direction. 23 and 2 show the results obtained by using the elliptical aperture and the results obtained by measuring the incident azimuth dependency of the reflected infrared light measured by the circular aperture for the sample of Example 3.
It is shown in FIG. As these figures show, the anisotropy is clearer when measured with an elliptical aperture.

(Embodiment 5) When performing distribution measurement over a wide range, it is necessary to increase the movable area of the horizontal movement stage for adjusting the measurement position. Therefore, Examples 1, 2, and 3
In such a configuration, the rotation stage below the horizontal movement stage also needs to be large. As the size of the device increases, the accuracy of the rotating shaft and the combination accuracy between the stages deteriorate, and the mechanical accuracy deteriorates due to the distortion due to the weight of the device itself. It becomes difficult. For example, when measuring the distribution over the entire surface of a 20-inch panel, the movable range of the horizontal moving stage is 1000 mm.
Becomes Since the weight of the two horizontal movement stages also increases, the size of the rotation stage also increases, and the time required for changing the incident azimuth increases. Therefore, when measuring the in-plane distribution over a wide range, it is more accurate to control the incident azimuth of the sample by rotating the visible light source and the reflected light polarization analyzer and the infrared light source and the reflected infrared polarization analyzer. It's easy to do.

FIG. 25 shows the configuration of the apparatus. In this figure, 401 is a sample, 402 is a horizontal moving stage, 403
Is an incident light source including a polarizer, 404 is a polarimeter including a phaser and an analyzer, 405 is a rotary stage, and 406 is a column for fixing the detector, and is attached to 405. 407
Is an autocollimator attached to the center of the rotation axis, 4
Reference numeral 08 denotes a support for hanging the optical system. The infrared light source and the reflected infrared polarization measuring section are omitted.
The sample measured at this time was a glass substrate and a polyimide material of the same quality as in Example 2, but the polyimide was applied by transfer instead of spin coating. FIG. 26 shows the result of measuring and measuring 20 cm square at 4 cm intervals using this apparatus.
3 shows the distribution of the ratio (εei−εoi) / εi of the difference between the two dielectric constants of the oriented portion at 4 cm ^{−1 to} the isotropic dielectric constant.

[0066]

According to the present invention, the dependency of the polarization state of the reflected visible light and the reflected infrared light generated when the infrared light and the visible light are incident on the same position on the sample surface on the incident direction is measured. The thickness of the anisotropic portion and the isotropic portion can be determined more accurately, and the accuracy of determining the optical structure of the film in the infrared region is improved, and the accuracy of determining the molecular orientation state of the film is improved. Can be improved. Further, by making the cross-sectional shapes of the incident light and the incident infrared light elliptic so that the shapes of the incident infrared light and the visible light hitting the sample surface are circular, the measurement accuracy is further improved. Further, by combining the rotating stage and the horizontal moving stage, it is possible to determine the in-plane distribution of the optical structure of the film in the infrared region.

[Brief description of the drawings]

FIG. 1 is an apparatus configuration diagram showing an example of a thin film molecular orientation evaluation apparatus according to the present invention.

FIG. 2 shows a measurement result of a difference spectrum between a sample with a film of the Δ component of reflected infrared ray and glass, which was measured from directions different from each other by about 90 ° near 1200 cm ⁻¹ .

FIG. 3 shows a measurement result of a difference spectrum between a sample with a film of the 赤 外線 component of the reflected infrared ray and the glass, which was measured from directions different from each other by about 90 cm ⁻¹ near 1200 cm ⁻¹ .

FIG. 4 is a measurement result of the incident azimuth dependence of a difference spectrum between a sample with a film and glass of a Δ component of reflected infrared light at 1246 cm ⁻¹ .

FIG. 5 shows the measurement results of the incident azimuth dependence of the difference spectrum between a sample with a film of the 赤 外線 component of reflected infrared light at 1246 cm ⁻¹ and glass.

FIG. 6 shows a measurement result of the incident azimuth dependence of the Δ component of the polarization state of reflected visible light.

FIG. 7 is a measurement result of the incident azimuth dependency of the ψ component of the polarization state of the reflected light of visible light.

FIG. 8 is a diagram illustrating the configuration of an apparatus that receives infrared light and visible light from different directions.

FIG. 9 is a diagram of a device in which an infrared ray and a visible ray entering the atmosphere control container are incident from different directions, and a description of a visible light measurement system is omitted.

FIG. 10 is a configuration diagram of a sample stage.

FIG. 11 is a diagram showing the wavelength dispersion of the ψ component of reflected infrared light obtained from measurement of a sample without rubbing in an argon atmosphere.

FIG. 12 is a graph showing the wavelength dispersion of a Δ component of reflected infrared light obtained from measurement of a sample without rubbing in an argon atmosphere.

FIG. 13 is a graph showing the wavelength dispersion of the ψ component of reflected infrared light obtained by measuring a rubbed sample in an argon atmosphere.

FIG. 14 is a graph showing the wavelength dispersion of the Δ component of reflected infrared light obtained by measuring a rubbed sample in an argon atmosphere.

FIG. 15 is a diagram of the wavelength dispersion of the Δ component near 1500 cm ⁻¹ of the Δ component of the reflected infrared ray, obtained by measuring the rubbed sample in an argon atmosphere from directions different from each other by 90 °.

FIG. 16 is a diagram showing the wavelength dispersion of a ψ component near 1500 cm ⁻¹ of a Δ component of reflected infrared light obtained by measuring a rubbed sample in an argon atmosphere from directions different from each other by 90 °.

FIG. 17 is a diagram illustrating the incident azimuth dependence of the difference spectrum of the Δ component at 1504 cm ⁻¹ between the reflected infrared ray and the glass substrate, obtained from the measurement of the rubbed sample in an argon atmosphere.

FIG. 18 is a flowchart showing a procedure of a program for determining an optical structure of a film from measurement results.

FIG. 19 is a flowchart showing a procedure of a control program for automatically measuring an incident azimuth-dependent in-plane distribution of the polarization state of reflected infrared light and reflected visible light.

FIG. 20 is a flowchart showing a procedure of a control program for simultaneously performing automatic measurement of the in-plane distribution of the polarization direction of reflected infrared light and reflected visible light, and the determination of the optical structure of the film.

FIG. 21 shows 1504 cm ⁻¹ calculated from the results of anisotropy measurement of the polarization state of reflected visible light and the measurement of the incident azimuth dependence of the polarization state of reflected infrared light at 1504 cm ^−1.
FIG. 4 is a diagram showing an in-plane distribution of anisotropy of the dielectric constant of FIG.

FIG. 22 is a diagram showing a shape of a region on a sample surface irradiated with light having a circular cross section, and an arrow indicates an incident direction.

FIG. 23 shows 150 measured using an elliptical aperture.
FIG. 4 is a diagram showing the dependence of the Δ component of 4 cm ⁻¹ on the incident azimuth, where the horizontal axis represents the sample azimuth according to the reading on the stage, the vertical axis represents the phase difference, the white circle represents the sample without rubbing, and the black circle represents the measurement of the rubbed sample. The result.

FIG. 24 illustrates a 150 measured using an elliptical aperture.
It is a diagram of the incident azimuth dependence of the ψ component of the reflected infrared ray of 4 cm ⁻¹ , the horizontal axis is the sample azimuth according to the reading value of the stage, the vertical axis is the phase difference, the white circle is a sample without rubbing, and the black circle is rubbed. It is a measurement result of a sample.

FIG. 25 is an apparatus configuration diagram of an apparatus for measuring the polarization state of visible and infrared reflected light by rotating an optical system, in which an illustration of an infrared light source and a reflected infrared polarization measuring unit is omitted.

FIG. 26 is an in-plane distribution diagram of anisotropy of a dielectric constant of 504 cm ⁻¹ obtained from a measurement result obtained by a device that measures the polarization state of visible and infrared reflected light by rotating an optical system.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Container 2 Valve for gas introduction 3 Valve for evacuation 4 FT-IR spectrometer 5 Polarizer 6 Photoelastic element 7 Analyzer 8 Infrared detector 9 Sample 10 Sample stage 11 Autocollimator 12 Container door 13 Auto Monitor for collimator 14 Computer for measurement control 21 Rotation stage 22 Parallel movement stage 23 Parallel movement stage 24 Knob for adjusting tilt angle of sample 25 Parallel movement stage 26 Plate on which sample is mounted 101 FT-IR unit 102 Infrared analyzer 103 Photomultiplier tube 104 Analyzer 105 Quarter-wave plate 106 Polarizer 107 He-Ne laser light source 108 Infrared source 109 Polarizer 110 Infrared photoelastic element 111 Sample 112 Sample stage 201 Incident infrared source 202 Infrared polarization detector 203 Incident light Source 204 polarization measurement unit 205 rotates the stage 206 translation stage 207 translation stage 208 samples. 401 Sample 402 Horizontal moving stage 403 Incident light source 404 Polarimeter 405 Rotating stage 406 Support 407 Autocollimator 408 Support

Claims (21)

[Claims] 1. An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on a sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared ray is determined on the surface of the sample. A method for evaluating the molecular orientation of a thin film, wherein the measurement is performed by changing the incident azimuth of light and infrared light by internal rotation, and the optical anisotropy and the molecular orientation state of the sample thin film are determined. 2. An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on a sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared ray is determined on the surface of the sample. An apparatus for evaluating the molecular orientation of a thin film, wherein the optical anisotropy and the molecular orientation of a sample thin film are determined by changing the incident azimuth of light and infrared light by internal rotation. 3. An infrared ray having a certain polarization state and a visible light ray having a certain polarization state are incident on the same position on the sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared light is determined on the surface of the sample. A thin film molecular orientation evaluation apparatus characterized by automatically performing measurement by changing the incident directions of light and infrared light by internal rotation, and determining the optical anisotropy and molecular orientation state of a sample thin film. 4. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on the sample surface, and the incident azimuth dependence of the polarization state of the reflected light from the sample and the reflection infrared light is determined on the surface of the sample. A recording medium on which a computer program for automatically controlling measurement by changing incident directions of light and infrared light by internal rotation is recorded. 5. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. By rotating the measurement unit about the sample normal passing through the measurement point as an axis, the dependence of the polarization state of the reflected light from the sample on the incident direction is measured, and the optical anisotropy and molecular orientation state of the sample thin film are measured. A method for evaluating the molecular orientation of a thin film, characterized in that it is determined. 6. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. By rotating the measurement unit about the sample normal passing through the measurement point as an axis, the dependence of the polarization state of the reflected light from the sample on the incident direction is measured, and the optical anisotropy and molecular orientation state of the sample thin film are measured. An apparatus for evaluating the molecular orientation of a thin film, comprising: 7. An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. By rotating the measurement unit around the sample normal passing through the measurement point as an axis, the dependence of the polarization state of the reflected light from the sample on the incident azimuth is automatically measured, and the optical anisotropy of the sample thin film and An apparatus for evaluating the molecular orientation of a thin film, which determines a molecular orientation state. 8. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. A recording medium in which a computer program for automatically measuring the incident azimuth dependence of the polarization state of reflected light from a sample by rotating a measurement unit about a sample normal passing through a measurement point as an axis is recorded. 9. An in-plane distribution of the polarization direction of reflected light and reflected infrared light from a sample, which is incident on the same position on the sample surface with infrared light having a fixed polarization state and visible light having a fixed polarization state. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the incident directions of light and infrared light are changed by in-plane rotation of the sample, and the measurement position is determined by parallel movement of the sample. And determining the optical anisotropy and the in-plane distribution of the molecular orientation state of the sample thin film. 10. An in-plane distribution of the polarization direction of reflected light and reflected infrared light from a sample, wherein the infrared light having a fixed polarization state and the visible light having a certain polarization state are incident on the same surface. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the incident directions of light and infrared light are changed by in-plane rotation of the sample, and the measurement position is determined by parallel movement of the sample. And an optical anisotropy and molecular orientation state of the sample thin film are determined. 11. An in-plane distribution of polarization direction of reflected light and reflected infrared light from a sample, which is incident on the sample at the same position on the surface of the sample. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the incident directions of light and infrared light are automatically changed by in-plane rotation of the sample, and the sample is automatically parallelized. An apparatus for evaluating the molecular orientation of a thin film, wherein the measuring position is selected and measured by movement to determine the optical anisotropy and the molecular orientation state of the sample thin film. 12. An in-plane distribution of the polarization direction of reflected light and reflected infrared light from a sample, which is incident on the same position on the sample surface with infrared light having a fixed polarization state and visible light having a fixed polarization state. Using a rotation mechanism and a sample stage equipped with a parallel movement function in two different directions perpendicular to the rotation axis, the incident directions of light and infrared light are automatically changed by in-plane rotation of the sample, and the sample is automatically parallelized. A recording medium on which a computer program for selecting and measuring a measurement position by movement is recorded. 13. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on a sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. The measuring unit is rotated around the sample normal passing through the measuring point as an axis to measure the incident azimuth dependence of the reflected light and reflected infrared polarization at the measuring position, and is translated in two different directions orthogonal to the rotation axis. The sample position is selected by moving the sample in parallel using a sample stage equipped with a function, and the in-plane distribution of the incident azimuth of reflected light and reflected infrared light is measured, and the optical anisotropy and molecular orientation of the sample thin film are measured. A thin film molecular orientation evaluation method characterized by determining a state. 14. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. The measuring unit is rotated around the sample normal passing through the measuring point as an axis to measure the incident azimuth dependence of the reflected light and reflected infrared polarization at the measuring position, and is translated in two different directions orthogonal to the rotation axis. The sample position is selected by moving the sample in parallel using a sample stage equipped with a function, and the in-plane distribution of the incident azimuth of reflected light and reflected infrared light is measured, and the optical anisotropy and molecular orientation of the sample thin film are measured. An apparatus for evaluating the molecular orientation of a thin film, characterized by determining a state. 15. An infrared ray having a predetermined polarization state and a visible light ray having a predetermined polarization state are incident on the same position on a sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. The measuring unit is rotated around the sample normal passing through the measuring point as an axis to automatically measure the incident azimuth dependence of the reflected light and reflected infrared polarization state at the measuring position, and to measure in two different directions orthogonal to the rotation axis. The sample position is selected by automatically translating the sample using a sample stage equipped with a translation function, and the in-plane distribution of the incident direction dependence of the reflected light and reflected infrared light is automatically measured, and the optical properties of the sample thin film are measured. An apparatus for evaluating the molecular orientation of a thin film, which determines anisotropy and a molecular orientation state. 16. An infrared ray having a constant polarization state and a visible light ray having a constant polarization state are incident on the same position on the sample surface, and an incident infrared light source, an incident visible light source, a reflected infrared polarization measuring section, and a reflected visible light polarization section are provided. The measuring unit is rotated around the sample normal passing through the measuring point as an axis to automatically measure the incident azimuth dependence of the reflected light and reflected infrared polarization state at the measuring position, and to measure in two different directions orthogonal to the rotation axis. A recording that records a computer program for automatically selecting a measurement position by automatically translating a sample using a sample stage having a parallel movement function and automatically measuring an incident direction dependent in-plane distribution of reflected light and reflected infrared light. Medium. 17. The method according to claim 1, wherein the measurement is performed in an inert gas or in a vacuum. 18. The apparatus according to claim 2, wherein the measurement is performed in an inert gas or in a vacuum. 19. The measurement is performed using an aspherical lens, an aspherical reflecting mirror, or an elliptical aperture so that the area on the sample surface to which light and infrared light fall is circular. 14. The method for evaluating the molecular orientation of a thin film according to any one of 5, 9 and 13. 20. The method according to claim 2, wherein the measurement is performed using an aspherical lens, an aspherical reflecting mirror, or an elliptical aperture so that the area on the sample surface to which light and infrared light fall is circular. 15. The apparatus for evaluating the molecular orientation of a thin film according to any one of claims 1, 6, 10 and 14. 21. Determine the optical structure and molecular orientation of the thin film from the dependence of the polarization state of the reflected visible light and reflected infrared light generated when visible light and infrared light of a certain polarization state are incident on the thin film sample on the incident direction. A recording medium on which a computer program to be determined is recorded.