JP2005077246A - Method and apparatus for analyzing material for forming organic electronic element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new analytic method for analyzing a membrane interface phenomenon in a case that an organic electronic element is formed using a material for forming the organic electronic element, and an analyzer therefor. <P>SOLUTION: In the analytic method of the material for forming the organic electronic element using a spectrum measuring means utilizing a slab type light waveguide and a different king of two or above analytic means, an external element for causing a change with the elapse of time is applied to the material for forming the organic electronic element to output the tracking of the state change of the interface of the material for forming the organic electronic element and the light waveguide as spectrum data. The state change is subjected to time-base development to output analytic data acquired by measuring the change caused in the material for forming the organic electronic element at every stage by a different kind of the analytic means, and the spectrum data and the analytic data for every stage are outputted so as to be capable of being compared with each other. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an organic electronic element forming material analysis method and an organic electronic element forming material analysis apparatus that are preferably used for, for example, an organic electroluminescence element, and more specifically, using a slab type optical waveguide. Analytical method to obtain new information from the time-lapse spectral data of the coating film interface obtained from the measuring means and the time-lapse analytical data of the paint film obtained from other analytical means And an analysis apparatus.

  Unlike a liquid crystal display, an organic electroluminescence display using an organic substance as a light emitter is a self-luminous display that uses fluorescence or phosphorescence emitted from an excited light emitter. For this reason, it is attracting attention as a next-generation display because it has a simple film structure and can be expected to have high-speed response that can support moving images.

  As an organic electroluminescence element (hereinafter referred to as an organic EL element) constituting such an organic electroluminescence display (hereinafter referred to as an organic EL display), an organic EL having an organic compound thin film formed by vacuum deposition or the like as a light emitting film. The device has been actively researched and partly put into practical use. However, organic compounds that can be deposited by vacuum evaporation are low molecular compounds. In organic EL devices using such low molecular compounds, the organic layers are crystallized and aggregated over time, resulting in deterioration of the device and device lifetime. There are problems such as lowering, and further research and development is continuing.

  On the other hand, an organic EL element using a high molecular material or a coating type low molecular material as a light emitting material has been proposed. Since these organic compounds can be dissolved or dispersed in a solvent to form a coating solution for forming an organic EL device, there is an advantage that a large area organic EL device can be produced very efficiently with the coating solution. . Therefore, in recent years, active research has been conducted on the development of coating-type organic electronic element forming materials that can achieve high luminous efficiency and long life, and on the study of solvents and additive substances to be blended with the organic electronic element forming materials. Yes.

  However, in the case of forming an organic EL element using the coating solution for forming the organic EL element described above, how the organic compound material, the solvent, the additive substance, and the like in the coating solution are involved in the formation of the light emitting film. Moreover, it has not necessarily been clarified as to whether or not it is involved in the luminous efficiency and lifetime of the formed light emitting film. One reason for this is that the characteristics of organic EL elements, such as luminous efficiency and lifetime, are affected by the mobility and stability of bulk carriers (electrons and holes) in the luminescent film, and the film interface (for example, light emission). It is considered that it is affected by the mobility and stability of carriers at the film-electrode interface, light-emitting film-charge transport film interface, etc., but the analysis at the film interface is more difficult than the bulk analysis. One of the factors is that this is not done sufficiently. In particular, these organic EL element forming materials contain solvents, etc., so it is extremely important to analyze changes in the film interface phenomenon during the drying process of the coating film and changes in the film interface phenomenon during the deterioration process of the formed light emitting film. There is a need for an analysis method.

  As methods for analyzing the above-mentioned film interface, multiple internal reflection infrared spectroscopy, Kelvin probe contact potential difference measurement method, and the like have been proposed. However, since these methods can only measure a specific interface, they are not versatile and have a problem of poor reproducibility, and thus cannot be said to be an effective analysis method for the above-described film interface.

By the way, an apparatus for measuring a light absorption spectrum of an interface, a surface adsorbed material, a thin film, a very small amount of sample, etc. with high sensitivity using a slab type optical waveguide is known (for example, see Patent Documents 1 and 2). reference). This light absorption spectrum measuring device collects light having a certain wavelength width, for example, white light with a lens, and enters the light from a prism set at a predetermined interval from the lens into the optical waveguide film of the slab optical waveguide, The light totally reflected in the optical waveguide film is extracted through a prism with a lens set at a predetermined distance from the prism, and the emitted light is dispersed with a spectroscope and sent to a detector, resulting in an extremely large number of reflections and high sensitivity. It is possible to measure the light absorption spectrum.
JP-A-8-75639 JP 2001-108611 A

  The present invention uses the above-described spectrum measurement means using the slab type optical waveguide and other analysis means in order to analyze the film interface phenomenon when an organic EL element is formed using an organic EL element forming material. The present invention provides a new method for analyzing the chemical state at the film interface by comparing the measurement results of both of them over time. Furthermore, it is an object to provide an analysis method effective for not only an organic EL element but also an organic element forming material for forming an organic semiconductor, a solar cell, and the like, and an analysis apparatus for the analysis object. It is.

  The invention according to the first aspect for solving the above problem is a method for analyzing an organic electronic element forming material using spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means. Applying an external element that causes a change over time to the organic electronic device forming material, and outputting the tracking of the state change of the interface between the organic electronic device forming material and the optical waveguide as spectral data Then, the state change is developed on the time axis, and the analysis data obtained by measuring the change occurring in the material for forming the organic electronic element for each step by the heterogeneous analysis means is output, and the spectrum data and the analysis for each step are output. It is characterized in that the data is output so as to be comparable.

  In the present invention, an external element is given to an organic electronic device material that is a measurement sample to perform spectrum measurement while changing the coating film over time, and one or two or more in a changed state based on the measurement result over time. Perform heterogeneous analytical measurements. And it is the method of outputting both results so that comparison is possible. Therefore, according to the present invention, when an external element is added and the coating state is changed over time, the coating interface state analysis data and the coating bulk analysis data in each scene, It is possible to capture material state change information. As a result, the state change behavior of a material over time can be clarified, and the characteristic change over time of an organic electronic device made of the material can be predicted. Knowledge for developing an optimal organic electronic device Can be used to develop more desirable organic electronic devices.

  The invention according to the second aspect for solving the above problem is a method for analyzing an organic electronic element forming material using a spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means. A process of outputting spectral data over time using a spectrum measuring means while applying an external element that causes a change over time to the organic electronic element forming material, and the organic electronic element forming material The process of outputting analysis data over time using the heterogeneous analysis means while applying the same external elements over time under the same conditions as above, and the results of the output spectrum data and analysis data And a process for enabling display on the time axis.

  In this invention, an external element is given to the material for an organic electronic device, which is a measurement sample, and the coating film is changed over time, and spectrum measurement and one or more kinds of different analysis measurements are performed. This is a method of outputting in a comparable manner. Therefore, according to the present invention, the state change information of the material is obtained from the state analysis data of the coating film interface and the analysis data of the coating film bulk when the coating state is changed with time by adding an external element. Can be captured over time. As a result, the state change behavior of a material over time can be clarified, and the characteristic change over time of an organic electronic device made of the material can be predicted. Knowledge for developing an optimal organic electronic device Can be used to develop more desirable organic electronic devices.

  In the analysis method of the first aspect or the second aspect, the change that occurs in the organic electronic element forming material is a process of forming a coating film of the organic electronic element forming material or an organic material formed from the organic electronic element forming material. It is a deterioration process of an electronic device, its aging process, its aging process, or its light irradiation process.

  According to the present invention, it can be used for state analysis in a coating film forming process, an element deterioration process, an aging process, an aging process, or a light irradiation process.

  In the analysis method of the first aspect or the second aspect, (1) the spectrum data is preferably ultraviolet-visible absorption spectrum data, and (2) the heterogeneous analysis means is a thermal analysis means, a mass analysis means, and a spectroscopy. Preferably, it is one or more means selected from analysis means, and (3) two-dimensional measurement results at the same interface of the organic electronic element forming material or the organic electronic element obtained from the organic electronic element forming material. An information processing process for analyzing information and the state change of the interface with the organic electronic element forming material or the optical waveguide using the three-dimensional data by combining the information and the time-lapse information of the measurement result, (4) The external element is preferably one or more selected from heat, light, current and magnetism applied temporarily, intermittently or continuously. Preferably it is an element (5) The organic electronic device forming material is preferably an organic electroluminescence device forming material.

  In addition, an analysis apparatus according to the present invention for solving the above-described problems is an organic electronic element forming material analysis apparatus using spectrum measuring means using a slab type optical waveguide and one or more different kinds of analysis means. Means for applying an external element that causes a change over time in the organic electronic element forming material, and an interface between the organic electronic element forming material and the optical waveguide by applying the external element A state measurement of the change in state as spectral data by the spectrum measurement means, and a time axis expansion of the state change to analyze the change occurring in the organic electronic element forming material as analysis data by the heterogeneous analysis means at each stage. And means for measuring, and means for displaying the spectrum data and the analysis data at each stage so as to be comparable.

  From the analysis data of the coating film interface and the analysis data of the coating film bulk in each scene when the coating state was changed over time by adding external elements by the analysis device configured in this way It is possible to capture information on the state change of materials. As a result, the state change behavior of a material over time can be clarified, and the characteristic change over time of an organic electronic device made of the material can be predicted. Knowledge for developing an optimal organic electronic device Can be used to develop more desirable organic electronic devices.

  In addition, an analysis apparatus according to another aspect of the present invention for solving the above-described problems is provided for forming an organic electronic device using a spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means. A method for analyzing a material, comprising: means for applying an external element to the organic electronic element forming material over time; and means for measuring spectral data over time by a spectrum measuring means while applying the external element; Means for measuring analysis data over time by the heterogeneous analysis means while applying the same external elements to the organic electronic element forming material over time under the same conditions as described above, and the spectral data and the analysis data And a means for displaying them in a comparable manner on the time axis.

  With the analysis device configured in this way, when the external state is added and the coating state is changed over time, the state change of the material from the state analysis data of the coating film interface and the analysis data of the coating film bulk Information can be captured over time. As a result, the state change behavior of a material over time can be clarified, and the characteristic change over time of an organic electronic device made of the material can be predicted. Knowledge for developing an optimal organic electronic device Can be used to develop more desirable organic electronic devices.

  In the analysis apparatus of these embodiments, (i) the spectrum measurement means is preferably a spectroscope for ultraviolet-visible absorption spectrum measurement, and (ii) the heterogeneous analysis means is a thermal analyzer, a mass spectrometer and a spectrometer. Preferably, it is one or both of one or more selected from an analyzer and one or both of mass spectrometers. (Iii) The means for applying the external element can be applied temporarily, intermittently or continuously. One or more devices selected from a heating device, a light irradiation device, a current power source and a magnetic device are preferable.

  As described above, according to the analysis method and analysis apparatus of the present invention, the state analysis data of the coating film interface and the individual scenes when the coating film state is changed over time by adding external elements. The state change information of the material can be captured from the analysis data of the coating film bulk. As a result, the state change behavior of a material over time can be clarified, and the characteristic change over time of an organic electronic device made of the material can be predicted. Knowledge for developing an optimal organic electronic device Can be used to develop more desirable organic electronic devices.

  According to the present invention, it has been impossible to select an optimal organic electronic element forming material until the element is manufactured and the characteristics are evaluated. However, according to the analysis method of the present invention, the spectrum data and the heterogeneous analysis means are used. The chemical state can be analyzed by comparing with the analyzed data, so the direction in the selection work can be clarified without performing the device fabrication and characteristic evaluation as in the past. Simplification can be expected.

  Hereinafter, the analysis method of the organic electronic element formation material of this invention and its analysis apparatus are demonstrated concretely.

(Method for analyzing materials for forming organic electronic elements)
The method for analyzing a material for forming an organic electronic element of the present invention is an analysis method using a spectrum measuring device using a slab type optical waveguide and one or more different kinds of analyzers.

  This analysis method is divided into two methods. In the analysis method of the first aspect, an external element that causes a change over time is applied to the organic electronic element forming material, and the organic electronic element forming material and The tracking of the state change at the interface with the optical waveguide is output as spectral data, the state change is developed on the time axis, and the change occurring in the organic electronic element forming material is detected by one or more different types of analysis means for each stage. In this method, the measured analysis data is output, and the obtained spectrum data and the analysis data at each stage are output in a comparable manner.

  On the other hand, the analysis method of the second aspect includes a process of outputting spectral data over time using a spectrum measuring means while applying an external element that causes a change over time to the material for forming an organic electronic element, and an organic electron A process of outputting analysis data over time using one or more different kinds of analysis means while applying the same external elements to the element forming material over time under the same conditions as described above, and output spectrum data And a process for displaying the result of the analysis data on the time axis in a possible manner.

  The analysis method of the first aspect and the analysis method of the second aspect are divided in that the measurement of one or more different kinds of analysis means causes a change in the organic electronic element forming material over time under the same conditions as the spectrum measurement. It is classified according to whether it is performed while applying an external element to be applied. That is, the analysis method of the first aspect is not performed while applying an external element that causes a change over time in the organic electronic element forming material under the same conditions as the spectrum measurement, but is measured by the spectrum measurement. This is a case where the time-dependent state change is developed on the time axis and the change occurring in the material for forming an organic electronic element is measured by a heterogeneous analysis means in a state where the change is reproduced step by step. On the other hand, the analysis method of the second aspect is a case where measurement is performed by a heterogeneous analysis means while applying an external element that causes a change with time in the organic electronic element forming material under the same conditions as the spectrum measurement.

  First, a spectrum measuring apparatus using a slab type optical waveguide will be described. Slab-type optical waveguide spectroscopy is not infrared spectroscopy that captures vibrations of molecules and functional groups, but is a method that can measure interfacial absorption characteristics in the short wavelength region related to the electronic state and energy band gap over time. Therefore, it is effective for analyzing subtle changes and differences in the film state and dynamics without any chemical bond or chemical structure changes.

  FIG. 1 is a principle diagram of slab type optical waveguide spectroscopy. In the slab type optical waveguide, when light 2 enters the optical waveguide substrate 1, the light 2 is totally reflected on the surface of the optical waveguide substrate 1 and proceeds. At this time, when the sample film 3 to be used for measurement is formed on the optical waveguide substrate, the surface wave of the light 2 that travels by being totally reflected inside the substrate soaks into the sample film slightly. This surface wave is called an evanescent wave 4 and penetrates into the sample film while being exponentially attenuated as described in FIG. The penetration depth (dp) at this time is expressed by the following equation. In the following formula, λ is the incident wave wavelength, θ is the incident angle, n1 is the refractive index of the waveguide substrate, and n2 is the refractive index of the sample film or the environment around the sample film.

  In this slab type optical waveguide, the penetration depth (dp) is very shallow, and information on only molecules existing within 1 μm from the surface of the optical waveguide substrate 1 is selectively and nondestructively analyzed by adjustment. Can do. Further, by using the thinner optical waveguide substrate 1, the number of reflections can be increased, and measurement can be performed with higher sensitivity. Examples of the spectrum measuring device using such a slab type optical waveguide include measuring devices disclosed in Japanese Patent Laid-Open Nos. 8-75639 and 2001-108611, and more specifically, system instruments. The SIS-50 type | mold apparatus by a company can be mentioned.

  FIG. 2 is a block diagram showing an example of a spectrum measuring apparatus using a slab type optical waveguide disclosed in Japanese Patent Application Laid-Open No. 8-75639. In FIG. 2, as the light source 10, a light source that emits light having an arbitrary wavelength range from far ultraviolet to far infrared is used, for example, an Xe lamp is used. The light chopper 30 turns the light from the light source 10 into intermittent light having a constant period, and is provided between the light source 10 and the incident light side optical fiber 31. The sample measuring unit includes an incident light side lens 11, an outgoing light side lens 15, an incident light side prism 12, an outgoing light side prism 14, a slab optical waveguide 13, and a position control mechanism 16. The incident light side lens 11 is provided at the distal end on the exit side of the incident light side optical fiber 31, and the outgoing light side lens 15 is provided at the distal end on the entrance side of the outgoing light side optical fiber 32. Note that, as described in JP 2001-108611 A, an optical coupling method that does not use a prism can be applied.

  FIGS. 3 and 4 are a plan view and a cross-sectional view of the slab type optical waveguide. The incident light side prism 12 and the outgoing light side prism 14 are arranged on the slab type optical waveguide 13. Each of the prisms 12 and 14 is elongated so that the sample 54 and the reference portion 53 can be measured without re-installing the prism. The slab optical waveguide 13 includes a substrate 51 for supporting the optical waveguide layer 52 and an optical waveguide layer 52. A sample 54 is placed in a strip shape on one side of the slab optical waveguide 13, and the opposite side, that is, the portion without the sample 54 becomes a reference portion 53.

  As shown in FIG. 2, the detection unit includes a spectrometer 41, a photomultiplier tube 43, an amplifier 44, and a computer 42. The white light emitted from the light source 10 is converted into intermittent light having a constant period by the light chopper 30 and then introduced into the incident light side optical fiber 31. The intermittent light introduced into the incident light side optical fiber 31 passes through the incident light side optical fiber 31 and is collected by the incident light side lens 11 provided at the tip of the light output side, and is introduced into the incident light side prism 12 at an appropriate angle. Is done. The intermittent light collected by the incident light side lens 11 is introduced into the incident light side prism 12, then enters the optical waveguide layer 52 of the slab optical waveguide 13, and the intermittent light that enters the optical waveguide layer 52. After repeating total reflection in the optical waveguide layer 52, the light exits from the optical waveguide layer 52 and is introduced into the outgoing light side prism 14. The intermittent light introduced into the outgoing light side prism 14 is extracted by the outgoing light side lens 15 provided at the light incident side tip of the outgoing light side optical fiber 32 and sent to the spectroscope 41 by the outgoing light side optical fiber 32. . The intermittent light split by the spectroscope 41 is sent to the computer 42 via the photomultiplier tube 43 and the amplifier 44, and is subjected to arithmetic processing to obtain a spectrum.

  FIG. 5 shows a spectrum measuring apparatus using a slab type optical waveguide preferably applied to the present invention. The spectrum measuring apparatus using the slab type optical waveguide shown in FIG. 5 is an apparatus capable of simultaneously performing multiple reflection type ultraviolet visible absorption spectrum measurement and fluorescence emission spectrum measurement. This measuring apparatus includes an ultraviolet-visible absorption CCD spectrometer 7 that detects a multiple reflection type ultraviolet-visible absorption spectrum between the sample film 3 and the optical waveguide substrate 1. Moreover, the fluorescence PMT spectrometer 8 which detects the fluorescence emission 9 taken out from the optical waveguide is provided. Reference numeral 5 is a prism, and reference numeral 6 is a reflection mirror.

  This multiple reflection type UV-visible absorption spectrum measurement reveals the correlation between the electronic state change at the interface and the chemical bond change, and obtains UV-visible absorption spectrum data, which is information derived from the functional groups and chemical structure of the sample film 3. In the fluorescence emission spectrum measurement, the relationship between the change in the electronic state of the interface and the emission spectrum characteristic is clarified. In particular, the fluorescence emission spectrum data which is important emission characteristic information in the organic EL element characteristic is obtained. It is effective for.

  Such a spectrum measuring device outputs spectral information with time obtained from the above spectroscopes 7 and 8 to the analyzing device 101. The analysis apparatus 101 shown in FIG. 5 is not particularly limited as long as it has a function of processing the obtained spectral information so as to be analyzable, and is an information processing apparatus or an image display apparatus incorporating a calculation function such as a personal computer, or A printer device with a built-in arithmetic element can be given. With such an analysis device 101, for example, as shown in FIG. 5, analysis information with respect to the time axis can be displayed.

  In the analysis method of the present invention, an external element that causes a change over time is applied to the organic electronic element forming material constituting the sample film, and the interface between the sample film 3 and the optical waveguide substrate 1 is applied. The state change tracking is output as spectral data. By applying an external element over time, for example, it is possible to measure the spectrum over time in the coating film formation process, such as the drying process of the coating film, and the deterioration process of the organic electronic device, the aging process thereof, It is possible to measure a spectrum over time in the aging process or the light irradiation process.

  Here, the coating film forming process means, for example, that after the organic electronic element forming material is applied on the optical waveguide substrate, the solvent contained in the material is removed or the compound reacts to form a film. It is a process of changing with time. In addition, the deterioration process is, for example, a time-dependent change process in which the function of the formed film gradually decreases. The aging process is a change over time in normal temperature storage without applying an external element of heat or light energy. The aging process is a change with time when an external element of heat or light energy is applied. The light irradiation treatment process is a change with time accompanying the application of an external element of light energy.

  The sample film is a film formed by applying an organic electronic element forming material. Examples of the organic electronic element forming material for forming the sample film include an organic EL element forming material, an organic semiconductor solution, a solar cell solution, and the like. More specifically, the organic EL element forming material is a light emitting material such as a low molecular light emitting material such as coumarin, an organic compound such as a conjugated polymer material such as polyphenylene vinylene, and an aromatic solvent such as toluene or xylene. And organic solvents such as halogen-containing solvents such as dichloroethane. The organic semiconductor forming solution and the organic solar cell forming solution also contain an organic solvent similar to the organic EL element forming material.

  The temporal change of the sample film 3 can be applied by applying an external element temporarily, intermittently or continuously.

  The external element is one or more elements selected from heat, light, current, and magnetism applied temporarily, intermittently or continuously. By applying these external factors to the sample film, it is possible to measure time-dependent information such as the coating film formation process, deterioration process, aging process, aging process, and light irradiation process of the sample film.

  Heat includes warm and cold. Light includes light with different wavelengths, such as laser (monochromatic light with uniform phase), ultraviolet light, visible light, infrared light, etc., and also includes electron beams and radiation, and radiation such as X-rays and γ-rays. Is defined by the concept that is also included. The current may be direct current or alternating current, and the current value can be applied in various values. Magnetism is a case where an arbitrary magnetic field is applied, and may be a magnetic field by a magnet or an electromagnet.

  Examples of the device for applying heat include a hot plate and a heat ray heater. Examples of the device for irradiating light include an ultraviolet exposure device and an electron beam exposure device. For example, a direct current power supply device or an alternating current power supply device can be used, and examples of the device for applying magnetism include an electromagnet and a strong permanent magnet.

  The term “temporarily” refers to an application style that is applied when the chemical information of the sample film changes with time by applying the above-described external element once. In addition, intermittent is an application style that is applied when the chemical information of the sample film changes with time by applying the above-described external elements at regular intervals. Continuously refers to an application style that is applied when the chemical information of the sample film changes over time by continuously applying the above-described external elements.

  In the present invention, an appropriate external element is selected from various external elements according to the material characteristics of the sample film or according to the relationship between the applied external element and the sample film. At this time, one type of external element may be applied, or two or more types of external elements may be applied. When two or more types of external elements are applied, the application style (temporary, intermittent, continuous) of each external element may be the same or different. For example, one external element can be applied continuously and the other external element can be applied intermittently.

  In the present invention, as the heterogeneous analysis means, one or more means selected from thermal analysis means, mass analysis means and spectroscopic analysis means can be preferably mentioned, but other means may be used, for example, nuclear magnetic resonance analysis ( NMR), different types of analysis means such as microscopic observation can be used.

  Examples of the thermal analysis means include thermal weight loss change measurement (TGA), differential thermal analysis measurement (DSC), temperature programmed desorption gas analysis measurement (TDS), and the like. Of these, information on interface weight change and energy change is obtained by linking general thermal analysis means (thermal analysis equipment) such as thermogravimetric decrease change measurement (TGA) and differential thermal analysis measurement (DSC). The relationship between the electronic state change at the interface and the thermal behavior change of the film becomes clear. In addition, as a mass spectrometry means, by linking a general mass spectrometer (MS), it is possible to obtain information on gas components generated during thermal changes and changes over time of the film interface, and outgas analysis Between the results, the relationship between the change in the electronic state of the interface and the decomposition products and outgas components generated from the film during the change process becomes clear. The spectroscopic analyzers include infrared spectroscopic measurement (IR), fluorescence emission spectroscopic measurement, Raman spectroscopic measurement, X-ray photoelectron spectroscopic measurement (XPS), sum frequency spectroscopic measurement (SFG), and second harmonic spectroscopic measurement (SHG). And the like. Of these, information on chemical bonds and chemical structure changes can be obtained by linking infrared spectroscopy (IR), and the relationship between the electronic state of the interface and the chemical structure change and alteration of the film is clear. It becomes.

  As for other heterogeneous analysis means, examples of the nuclear magnetic resonance analyzer include pulse nuclear magnetic resonance analysis and solid state nuclear magnetic resonance analysis. By linking these general nuclear magnetic resonance analyses, the relationship between relaxation time changes and chemical structure changes becomes clear. Further, by linking with microscopic observation with an electron microscope, a fluorescence microscope, or the like, the relationship with the shape and shape change becomes clear.

  In the analysis method according to the first aspect of the present invention, the measurement by such a heterogeneous analysis means develops the spectral data obtained by applying the external element on the time axis, and shows the change that occurs in the sample film as a result. It is an analysis method including a process performed in a state specified for each stage and held for each stage. In this case, it is important to perform measurement while maintaining the measurement conditions of the heterogeneous analysis means in the same state as the state of each stage of the sample film, and as a result, the obtained analysis data is, for example, notable spectral data It can be effectively used to elucidate various state changes.

  On the other hand, in the analysis method of the second aspect of the present invention, the measurement by such a heterogeneous analysis means applies the same external element to the sample film over time under the same conditions as the spectrum measurement performed by applying the external element. It is the analysis method including the process performed. In this case, since the application condition of the external element of the heterogeneous analysis means is measured in the same manner as in the case of spectrum measurement, the obtained analysis data can be easily compared with, for example, spectrum data. It can be used effectively for elucidating state changes.

  The analysis method of the present invention outputs spectrum data and analysis data so that they can be compared as shown in FIG. At this time, in the analysis method of the first aspect, the spectrum data and the analysis data at each stage are output so as to be comparable, and in the analysis method of the second aspect, the result of the output spectrum data and the analysis data is obtained. Output in a comparable manner on the time axis.

  Further, the analysis method of the present invention combines the two-dimensional information of the measurement result at the same interface of the organic electronic element forming material or the organic electronic element obtained from the organic electronic element forming material with the temporal information of the measurement result. An information processing process for analyzing the state change of the interface between the organic electronic element forming material and the optical waveguide using the three-dimensional data. Here, the two-dimensional information is the surface information (X axis-Y axis) of the coating film or element formed on the plane, and the three-dimensional data is the temporal data of the film or element in the plane. This is data of a three-dimensional state change in which the change is represented on the Z axis as a time axis. In the present invention, by analyzing with such three-dimensional data, it is possible to track the change in state over time in the in-plane distribution of the film or element.

  Moreover, the above-mentioned spectrum data and analysis data, and further their analysis results can be compared with the characteristic data of the organic electronic element formed of the organic electronic element forming material, and the relationship between them can be further analyzed. Examples of the characteristic data of the organic electronic element include energy conversion efficiency data, lifetime, stability data, and the like. For example, in an organic EL element, light emission efficiency data, light emission luminance data, light emission lifetime data, and the like can be given. Such characteristic data is input to a computer and compared with spectrum data measured by a spectrum measuring apparatus using a slab type optical waveguide and analysis data measured by a heterogeneous analysis means. As a result of comparison, when the specific result of the characteristic data corresponds to the spectral data and analytical data, and also to the analytical results, the state change of the interface behavior indicated by the spectral data has an effect on the characteristic. Becomes clear.

  FIG. 6 summarizes the analysis method of the present invention. According to such an analysis method of the present invention, when an external element is added and the state of the coating film is changed over time, the state analysis data of the coating film interface, the analysis data of the coating film bulk in each scene, Therefore, it is possible to capture information on the state change of the material. As a result, the state change behavior of a material over time can be clarified, and the characteristic change over time of an organic electronic device made of the material can be predicted. Knowledge for developing an optimal organic electronic device Can be used to develop more desirable organic electronic devices.

  The analysis method of the present invention can be applied to materials other than organic electronic element forming materials. For example, liquid phase to solid film, solid film to liquid phase, gas phase to solid film (including vapor deposition), solid film to gas phase (including sublimation), liquid phase to gas phase, gas phase to liquid phase, It is also effective for analysis of state changes including phase transition such as crystal to amorphous and amorphous to crystal. More specifically, a deposition film forming process, an adhesive bonding process, a coating film (coating containing an organic solvent, a lacquer or a lacquer or a lacquer that changes to a solid film), a functional material (plasticizer, It can be effectively used as an analytical process for analyzing in a chemical state a phase change process including a polymer resin shaping process to which an additive is added) and an orientation of liquid crystal to which a potential is applied.

(Analysis device for organic electronic element forming materials)
The organic electronic element forming material analyzing apparatus 51 of the present invention uses, for example, a spectrum measuring means 52 using a slab type optical waveguide and one or more different kinds of analyzing means 56 as shown in FIG. It is an analysis device, and is a device that realizes the analysis method of the first and second aspects of the present invention described above. The analyzer 51 is provided with means (not shown) for applying an external element that causes a change over time. In addition, means 53, 54, and 55 are provided for displaying the spectrum data and the analysis data at each stage or the analysis data with time so that the spectrum data can be compared. As such means, a computer 53 for data analysis is used, and as a device for displaying or outputting analysis data, a display device 54 or a printer device 55 is used.

  In the analysis apparatus of these embodiments, (i) the spectrum measurement means is preferably a spectroscope for ultraviolet-visible absorption spectrum measurement, and (ii) the heterogeneous analysis means is one of a thermal analysis apparatus and a mass analysis apparatus or (Iii) The external element applying means is one or more selected from a heating device, a light irradiation device, a current power source, and a magnetic device that can be applied temporarily, intermittently or continuously. An apparatus is preferred. These details are as described above.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(Example 1)
In Example 1, the organic EL element formation material was analyzed when different organic solvents were employed. As a material for forming an organic EL element, a polymer green light emitting material manufactured by ADS was used. As an organic solvent, o-xylene, m-xylene, p-xylene, ethylbenzene, general-purpose xylene (o-xylene: 25%, m-xylene: 43%, p-xylene: 18%, ethylbenzene: 14%) are used. Five types of organic EL element forming materials were prepared. The polymer green light emitting material was prepared so as to be 1% by weight in each solvent.

  Five types of solutions were used and spin-coated on a washed alkali-free glass to form a coating film having a dry thickness of 1 μm. A general ultraviolet-visible absorption spectrum after drying was measured with an ultraviolet-visible spectrophotometer (trade name: UV-2000, manufactured by Hitachi, Ltd.), and the difference in spectrum depending on the solvent type was examined. The ultraviolet-visible absorption spectrum of the organic EL element film after drying for m-xylene and o-xylene is shown in FIG. There was no difference in spectral data due to the difference in xylene isomers in the wavelength range of 200-700 nm.

  Next, the drying process of the coating film formed with the organic EL element forming material described above using an interface ultraviolet-visible spectroscopic measurement apparatus (System Instruments, SIS-50 type) using slab type optical waveguide spectroscopy The interfacial ultraviolet-visible absorption spectrum data over time was measured. The measurement is performed by dropping 0.1 mL of the above-mentioned solutions having different solvent types onto an optical waveguide substrate made of synthetic quartz (manufactured by System Instruments Co., Ltd.), and then gradually drying at room temperature to change the solvent types in the coating film. After volatilization, spectral data over time during the drying process were measured. At this time, the penetration depth of the evanescent wave was about 1 μm and was measured at intervals of about 2 seconds. FIG. 9 is an interface ultraviolet-visible absorption spectrum of the coating film in the drying process for m-xylene (A) and o-xylene (B). In FIG. 9, reference numerals 1 to 4 indicate the measurement order over time. As can be seen from the results in FIG. 9, m-xylene (A) and o-xylene (B) have different interface ultraviolet-visible absorption spectra in the drying process. In addition, what used the solution which used p-xylene and general purpose xylene as a solvent seed was the same result as o-xylene (B).

  Next, the characteristic data of the organic EL element film | membrane formed with the organic EL element formation material were measured. The characteristic data of the organic EL element film is the layer configuration of glass substrate / ITO (anode) / PEDOT / PPS (hole transport layer) / organic EL element film (electron transport layer / light emitting layer) / Ca layer / Ag (cathode). The organic EL device was analyzed and examined by measuring the voltage-luminance characteristics (see Table 1), voltage-luminescence efficiency characteristics (see Table 1), and luminescence lifetime characteristics (see Table 1). As is clear from the results in Table 1, m-xylene has a significantly shorter lifetime with a luminance one order of magnitude lower than that of other solvent types and an efficiency of 1/3.

  Next, the spectrum measurement data was compared with the characteristic data of the organic EL element film. The film formed with a solution using m-xylene as a solvent species as shown in Table 1 had inferior characteristics, but the characteristic difference cannot be explained by the general UV-visible absorption spectrum results shown in FIG. However, it can be explained by the interfacial ultraviolet-visible absorption spectrum result using the slab type optical waveguide shown in FIG. 9, and its chemical state can be considered. That is, only the organic EL element forming material using m-xylene as a solvent species showed an interface UV-visible absorption spectrum and characteristic data different from others. As a result, the following can be considered.

  First, as shown in FIG. 9, unlike the case where o-xylene was used as a solvent species, the results obtained when m-xylene was used as a solvent species dramatically decreased the absorption intensity during the drying process. This result is presumed to indicate that the π-electron layer composed of the solvent species in the drying process escapes from the coating film all at once. That is, at the initial stage of the drying process, a laminated structure of π electron plane parallel to the optical waveguide substrate surface (polymer organic compound) / parallel π electron layer (solvent) / parallel π electron plane (polymer organic compound) It is thought that it was temporarily formed, and then, as the drying progresses, the solvent volatilizes all at once, and the parallel π-electron layer (solvent) is lost, which is dramatic as shown in FIG. 9 (A). It is thought that a change in absorption intensity occurs. As a result, it is considered that a laminated structure composed of a π electron plane (polymer organic compound) parallel to the optical waveguide substrate surface / parallel π electron plane (polymer organic compound) is stabilized as it is. This can be explained by the fact that the absorption intensity does not change during the subsequent drying process.

  Such a result of the interface ultraviolet visible absorption spectrum can well explain the characteristic data of the organic EL element film. That is, in the coating type organic EL element film, crystallinity and regularity are not required, and nonuniformity and amorphousness are required. Therefore, a rule formed from a solution using m-xylene as a solvent species is required. The results shown in Table 1 that the film having a typical laminated structure is inferior in characteristics such as luminance, light emission efficiency, and lifetime can be explained without contradiction.

  Conventionally, an optimum organic EL element forming material could not be selected unless the element was manufactured and the characteristics were evaluated. However, according to the analysis method of the present invention, the interface ultraviolet-visible absorption spectrum and the characteristic data were compared and applied. By analyzing the chemical state of the membrane interface, it is possible to grasp the phenomenon that the interface UV-visible absorption spectrum change during the drying process means. As a result, by using this analysis result, the direction of the selection work can be clarified without selecting the other organic EL element forming materials and preparing the elements and performing the characteristic evaluation. Significant simplification can be expected.

(Example 2)
As a result of investigating the change of the fluorescence emission spectrum before and after drying of the light emitting layer with a fluorescence emission spectrometer, only when m-xylene is used as a solvent, the spectrum hardly changes before and after drying and the emission intensity is weak. I understood that.

  Unlike other solvent systems, the measured data of the spectrum and the characteristic data of the organic EL element are contrasted. Unlike other solvent systems, the π electron plane parallel to the optical waveguide substrate surface (polymer organic compound) / parallel π electron layer (Solvent) / Parallel π-electron plane (polymeric organic compound) layer structure is considered to be temporarily formed, and even if drying progresses and the solvent volatilizes, the π-electron plane state is not random and parallelism Is retained after drying, and it is considered that the fluorescence emission spectrum of the entire film did not change.

(Example 3)
Using an apparatus equipped with a heatable unit (heater capable of heating the entire substrate) in the optical waveguide spectrometer, the measurement was performed in the same manner as in Example 1, and as a result, the layers under conditions closer to actual production were obtained. The interface state could be investigated. Specifically, the m-xylene selectivity of Example 1 was confirmed in the same manner, but it was possible to observe a drastic film state change in which the solvent volatilizes when heat was applied.

It is a principle figure of a slab type | mold optical waveguide spectroscopy. It is a block diagram which shows an example of the spectrum measuring apparatus using the slab type | mold optical waveguide currently disclosed by Unexamined-Japanese-Patent No. 8-75639. It is a top view of a slab type | mold optical waveguide. It is sectional drawing of a slab type | mold optical waveguide. This is a spectrum measuring apparatus using a slab type optical waveguide preferably applied to the present invention. It is explanatory drawing about the analysis method of this invention. It is a block diagram which shows an example of the analyzer of this invention. It is an ultraviolet visible absorption spectrum of the organic EL element film | membrane after drying about m-xylene and o-xylene. It is an interface ultraviolet visible absorption spectrum of the coating film in the drying process about m-xylene (A) and o-xylene (B).

Explanation of symbols

1 optical waveguide substrate 2 light 3 film (sample film)
4 Evanescent Wave 5 Prism 6 Reflecting Mirror 7 UV-Visible Absorption CCD Spectrometer 8 Fluorescent Emission PMT Spectrometer 9 Fluorescence Emission 10 Light Source 11 Incident Light Side Lens 12 Incident Light Side Prism 13 Slab Optical Waveguide 14 Emission Light Side Prism 15 Out Emission side lens 16 Slab type optical waveguide position and angle control mechanism 30 Optical chopper 31 Incident light side optical fiber 32 Optical fiber 33, 34 Lens 41 Spectrometer 42 Computer 43 Photomultiplier tube 44 Amplifier

Claims (13)

  A method for analyzing an organic electronic element forming material using a spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means, wherein the organic electronic element forming material changes over time. And applying an external element to generate a trace of the state change of the interface between the organic electronic element forming material and the optical waveguide as spectral data, expanding the state change over time, Outputting analysis data obtained by measuring the change occurring in the element forming material at each stage by the heterogeneous analysis means, and outputting the spectrum data and the analysis data at each stage in a comparable manner Method for analyzing element forming material.   A method for analyzing an organic electronic element forming material using a spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means, wherein the organic electronic element forming material changes over time. A process of outputting spectral data over time using a spectrum measuring means while applying an external element that causes generation of the same, and applying the same external element to the organic electronic element forming material over time under the same conditions as above A process of outputting analysis data over time using the heterogeneous analysis means while applying, and a process of displaying the results of the output spectrum data and the analysis data so that they can be compared on a time axis. And a method for analyzing an organic electronic element forming material.   The change that occurs in the organic electronic element forming material is a coating film forming process of the organic electronic element forming material, or a deterioration process of the organic electronic element formed from the organic electronic element forming material, an aging treatment process thereof, and an aging process thereof. 3. The method for analyzing a material for forming an organic electronic element according to claim 1, wherein the method is a treatment process or a light irradiation treatment process.   The method for analyzing a material for forming an organic electronic element according to any one of claims 1 to 3, wherein the spectrum data is ultraviolet-visible absorption spectrum data.   5. The organic electronic device formation according to claim 1, wherein the heterogeneous analysis means is one or more means selected from thermal analysis means, mass analysis means, and spectroscopic analysis means. Analysis method for materials.   The two-dimensional information of the measurement result at the same interface of the organic electronic element forming material or the organic electronic element forming material obtained from the organic electronic element forming material and the time-dependent information of the measurement result are combined into three-dimensional data, and the third order The information processing process which analyzes the state change of the interface with the said organic electronic element formation material or the said optical waveguide using original data is further provided, The any one of Claims 1-5 characterized by the above-mentioned. Analysis method of organic electronic element forming material.   The external element is one or more elements selected from heat, light, current, and magnetism applied temporarily, intermittently or continuously. The analysis method of the organic electronic element formation material of description.   The organic electronic element forming material according to claim 1, wherein the organic electronic element forming material is an organic electroluminescent element forming material.   An apparatus for forming an organic electronic element forming material using spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means, wherein the organic electronic element forming material changes over time. Means for applying an external element that causes an external element, and means for measuring a change in state of an interface between the material for forming an organic electronic element and the optical waveguide as spectral data by applying the external element. And means for expanding the state change over time, measuring changes occurring in the organic electronic element forming material as analysis data by the heterogeneous analysis means for each step, the spectrum data, and the analysis for each step An analysis device for a material for forming an organic electronic element, comprising: means for displaying data in a comparable manner.   A method for analyzing an organic electronic element forming material using spectrum measuring means using a slab type optical waveguide and one or more different kinds of analyzing means, wherein an external element is added to the organic electronic element forming material. Means for applying over time; means for measuring spectral data over time by means of spectrum measurement while applying the external element; and the same external elements as described above for the organic electronic element forming material under the same conditions as described above. And means for measuring analysis data over time by the heterogeneous analysis means while being applied over time, and means for displaying the spectrum data and the analysis data so that they can be compared on a time axis. Analyzing device for organic electronic element forming material.   11. The organic electronic element forming material analyzing apparatus according to claim 9, wherein the spectrum measuring unit is a spectroscope for measuring an ultraviolet-visible absorption spectrum.   The organic electronic element formation according to any one of claims 9 to 11, wherein the heterogeneous analysis means is one or more devices selected from a thermal analysis device, a mass analysis device, and a spectroscopic analysis device. Material analysis equipment.   The means for applying the external element is one or more devices selected from a heating device, a light irradiation device, a current power source, and a magnetic device that can be applied temporarily, intermittently or continuously. Item 15. The method for analyzing an organic electronic element forming material according to any one of Items 9 to 12.

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