JPWO2013099952A1 - Non-metallic element analysis method and analysis system - Google Patents

Abstract

In order to provide an analysis method and an analysis system capable of analyzing impurities such as non-metallic elements contained in a sample such as an organic semiconductor material simply and with high sensitivity and accuracy, an organic semiconductor material and a supercritical Solid organic semiconductor material by a method comprising: contacting with water or subcritical water; and detecting a nonmetallic element contained in supercritical water or subcritical water after contact with the organic semiconductor material Analyze non-metallic elements contained in it.

Description

  The present invention relates to a non-metallic element analysis method and analysis system. More specifically, the present invention relates to an analysis method and an analysis system for a nonmetallic element contained in an organic material (for example, an organic semiconductor material).

  Various impurities are contained in the organic semiconductor material, and it is known that the impurities adversely affect the performance of a device manufactured using the organic semiconductor material.

  Impurities such as halogen adversely affect device performance even at low concentrations. Therefore, there is a need for a technique that accurately and accurately measures the total amount of impurities contained in an organic semiconductor material.

  As a technique for analyzing impurities such as halogens with high sensitivity, conventionally, after a sample is burned in a combustion furnace, an impurity released from the sample by combustion is analyzed using an ion chromatograph or the like. (For example, refer to Patent Document 1).

  The conventional method will be described with reference to FIG. In the conventional method, the sample 13 is disposed in the path 11 that penetrates the inside of the combustion furnace 15. Then, the sample 13 is heated by the combustion furnace 15. Gas is supplied from one end of the path 11 to the inside of the path 11. Note that the gas contains impurities such as halogen separated from the sample 13 by heating. The gas passes through the absorber 12 provided at the rear stage of the combustion furnace 15. At this time, impurities such as halogen contained in the gas are trapped by the absorber 12. The impurities trapped by the absorption unit 12 are introduced into a detection unit 17 that can detect the impurities based on ion chromatography, mass spectrometry, capillary electrophoresis, or the like. Then, the detection unit 17 detects the impurities and quantifies the impurities.

  In addition to the above conventional methods, attempts have been made to use supercritical water or subcritical water for analysis of specific substances, but there is no example in which these methods are applied to organic semiconductor materials (for example, (See Patent Documents 2 to 4).

Japanese Patent Publication “JP-A-8-262000 (published on Oct. 11, 1996)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2003-75406 (published March 12, 2003)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2005-283508 (published on October 13, 2005)” Japanese Patent Publication “Japanese Patent Laid-Open No. 11-156378 (published on June 15, 1999)”

  However, the conventional techniques as described above have a problem that impurities such as non-metallic elements contained in a sample such as an organic semiconductor material cannot be analyzed simply, with high sensitivity and accuracy. .

  For example, in the conventional technology as described above, when a sample is burned in a combustion furnace, impurities adhere to the surface of various structures such as the combustion furnace, and the impurities remain in the analyzer. The remaining impurities raise the measured value when analyzing the next sample from the actual numerical value, and there is a problem that an accurate amount cannot be measured. In order to remove the residual impurities described above, it is conceivable to clean the inside of the analyzer. However, in the conventional technology as described above, the analysis apparatus is complicatedly configured with a material that is difficult to dispose of. Therefore, there is a problem that it takes time for cleaning.

  The conventional techniques as described above have a problem that a deflagration phenomenon occurs depending on the type of sample, and the glass used in the apparatus is broken.

  In the conventional technology as described above, the sample may be incompletely burned, and various organic substances are generated. And the said organic substance has the problem that it has a bad influence on an ion chromatograph measurement etc. In addition, although it is possible to solve the said problem by examining combustion conditions beforehand, in this case, it has the problem that much time and labor are required for examination of combustion conditions.

  In the prior art as described above, it is necessary to use conditions different from the absorption conditions of the other three types of halogens for iodine among the four types of halogens as the absorption conditions by the absorption part after combustion. Therefore, there is a problem that four types of halogens cannot be analyzed simultaneously.

  In the prior art as described above, when an anionic substance containing halogen is contained in a sample at a high concentration, the halogen to be analyzed cannot be absorbed by the absorption part. The problem is that it is not possible to analyze the amount of water.

  In the prior art as described above, when a metal complex is contained in a sample, metal is generated during combustion. As a result, there is a problem that various components such as a combustion furnace are damaged by the metal.

  The present invention has been made in view of the above-described conventional problems, and its purpose is to analyze impurities such as non-metallic elements contained in a sample such as an organic semiconductor material simply and with high sensitivity and accuracy. It is an object of the present invention to provide an analysis method and an analysis system that can be used.

  In order to solve the above problems, the analysis method of the present invention is a method for analyzing a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting the solid organic semiconductor material. A step of contacting the organic semiconductor material or the extract with supercritical water or subcritical water, and the non-critical water contained in the supercritical water or subcritical water after contact with the organic semiconductor material or the extract. And a step of detecting a metal element.

  In order to solve the above problems, an analysis system of the present invention is an analysis system for a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting the solid organic semiconductor material. A contact means for bringing the organic semiconductor material or the extract into contact with the supercritical water or the subcritical water; and the supercritical water or the subcritical water contained in the supercritical water or the subcritical water after the contact with the organic semiconductor material or the extract. And detecting means for detecting a nonmetallic element.

  The present invention has the following effects (1) to (9).

  (1) Since a nonmetallic element can be extracted in a small amount of water, the nonmetallic element can be measured with high sensitivity.

  (2) Depending on the type of semiconductor organic material or nonmetallic element, the bond between carbon and a nonmetallic element having relatively weak binding energy (for example, carbon and halogen) without completely decomposing the semiconductor organic material. Can be selectively decomposed. As a result, in measurement using an ion chromatograph or the like, impurities derived from organic substances can be reduced, and nonmetallic elements can be measured with high sensitivity.

  (3) At the time of decomposition with supercritical water or subcritical water, the recovery rate of the desired substance can be determined by adding an internal standard substance to the reaction system of the decomposition reaction. That is, when a predetermined amount of an internal standard substance is added to the reaction system and the final recovery amount of the internal standard substance is calculated by ion chromatography or the like, the recovery rate of the desired substance can be determined. And if the quantity of the nonmetallic element measured by the ion chromatograph etc. is correct | amended based on the said recovery rate, the quantity of the nonmetallic element contained in the semiconductor organic material can be measured accurately.

  (4) Since it is possible to avoid prior examination of the combustion conditions of a wide variety of organic semiconductor materials, it is possible to reduce the trouble of analyzing nonmetallic elements.

  (5) Since batch analysis is possible for each sample, multiple types or samples of the same type and multiple samples can be analyzed simultaneously. For example, the step of bringing the organic semiconductor material into contact with supercritical water or subcritical water can be performed with a simple structure that can be sealed (for example, a container such as a metal tube that can be sealed). Therefore, if the said structure is prepared for every sample, many types of samples can be batch-analyzed. As a result, many types of samples can be analyzed simultaneously.

  (6) Even if an anionic substance is contained in the organic semiconductor material in a high concentration, the non-metallic element is extracted from the organic semiconductor material in a closed system, so that the target non-metallic element ( For example, there is no worry that halogen will break through. Therefore, it is possible to avoid the trouble of preliminary analysis or the like for grasping the concentration of the anionic substance to some extent.

  (7) For example, if the step of bringing the organic semiconductor material into contact with supercritical water or subcritical water is performed using a disposable configuration (for example, a container such as a sealable metal tube), cross contamination is prevented. In addition, it is possible to save the labor of cleaning and checking the instrument. Moreover, even if it is a metal complex sample, the effort which replaces | exchanges instruments other than the structure for performing the said process can be saved.

  (8) The capacity of the container for performing the step of bringing the organic semiconductor material into contact with supercritical water or subcritical water can be easily changed. As a result, since the amount of the organic semiconductor material used for measurement can be increased, the measurement sensitivity of nonmetallic elements can be increased.

  (9) Unlike the conventional combustion method, the organic semiconductor material and supercritical water or subcritical water are brought into contact with each other in a closed system, so that non-metallic elements are not lost as an analysis system. As a result, the amount of the nonmetallic element can be accurately measured.

It is a schematic diagram which shows an example of the analysis system of this invention. It is a schematic diagram which shows the conventional analysis system.

  Although one embodiment of the present invention is described below, these are only examples of the embodiment of the present invention, and the present invention is not limited thereto. In addition, when it describes as "AB" in this specification, the said description intends "A or more and B or less."

[1. Analysis method)
The analysis method of the present embodiment is a method for analyzing a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting a solid organic semiconductor material, the organic semiconductor material or the above A step of contacting the extract obtained by extracting the organic semiconductor material with supercritical water or subcritical water; and the nonmetal contained in the supercritical water or subcritical water after contacting the organic semiconductor material or the extract. Detecting the element.

  The organic semiconductor material is not particularly limited. The organic semiconductor material can be an organic material used in organic electronic devices such as organic EL, organic transistors, organic capacitors, organic thin film solar cells, dye-sensitized solar cells, and electronic paper, and includes raw materials and intermediates thereof. . For example, aromatic hydrocarbons, polycyclic aromatic hydrocarbons, compounds derived from heteroaromatic hydrocarbons containing heteroatoms in the skeleton or polycyclic heteroaromatic hydrocarbons, and rings linked via a covalent bond A compound, a compound having a fullerene in the skeleton, a compound having porphyrin and phthalocyanine in the skeleton, a metal complex compound having the above structure, an oligomer and a polymer having the above structure are preferable, but not limited thereto.

  The organic semiconductor material analyzed by the analysis method of the present embodiment may be one of the organic semiconductor materials described above, or a mixture including two or more of the organic semiconductor materials described above. Also good. In addition, when it is a mixture, the kind of organic-semiconductor material contained in the said mixture is not specifically limited.

  In addition, the extract analyzed by the analysis method of the present embodiment uses the above-described organic semiconductor material in water or an organic solvent (for example, alcohol such as methanol, ethanol, propanol, butanol; ethyl acetate; ethyl ether; hexane). This is the extracted liquid. These extracts can be used for analysis as they are, or those obtained by substituting the solvent used for extraction with another solvent may be used. In addition, what is necessary is just to analyze according to the conditions similar to the case where the organic-semiconductor material mentioned later is made into analysis object, when making extraction liquid into analysis object.

  In the analysis method of the present embodiment, a product (for example, an organic EL electronic paper, a display TFT / OLED, a backlight, an organic transistor, a molecular rectifier, an organic solar cell, an organic semiconductor material, instead of the organic semiconductor material) It is also possible to use organic photoconductors (copy, laser, etc., biosensors) or their product intermediates. That is, in the analysis method of the present embodiment, instead of bringing the organic semiconductor material into contact with supercritical water or subcritical water in the contacting step described later, the product (or the product of the product) produced by the organic semiconductor material is used. Or a product intermediate thereof and supercritical water or subcritical water may be contacted. In this case, the product to be brought into contact with supercritical water or subcritical water may be the entire product or a part of the product. Moreover, what is necessary is just to use the same conditions as various conditions in the case of using the organic-semiconductor material mentioned later as conditions for using the said product.

  According to the above configuration, since the nonmetallic element contained in the product made of the organic semiconductor material can be directly analyzed, the performance of the product made of the organic semiconductor material can be more accurately evaluated.

  The non-metallic element to be analyzed by the analysis method of the present embodiment is not particularly limited, and all non-metallic elements can be analyzed. In the analysis method of the present embodiment, among non-metallic elements, B, Si, P, S, F, Cl, Br or I can be analyzed, and in particular, B, Si, P or S can be an analysis target, and in particular, F, Cl, Br, or I can be an analysis target.

  As the non-metallic element, for example, an element whose binding energy between the non-metallic element and carbon is smaller than the binding energy between carbon and carbon (for example, iodine, bromine, chlorine, or fluorine) is selectively used. It is also possible to use it. In this case, the basic structure of the organic semiconductor material is unnecessarily decomposed because it is easy to cut the bond between the non-metallic element and carbon without breaking the bond between carbon and carbon. Without separation, only the desired element can be separated from the organic semiconductor material and analyzed. That is, the influence which the decomposition product of organic-semiconductor material has on subsequent analysis (for example, ion chromatograph etc.) can be suppressed. Of course, in the analysis method of the present embodiment, it goes without saying that the basic structure of the organic semiconductor material may be partially or completely decomposed.

  As described above, the analysis method of the present embodiment includes a step of bringing an organic semiconductor material or an organic semiconductor material extract into contact with supercritical water or subcritical water.

  The supercritical water is intended to be water in an environment of 374.1 ° C. or higher and 22.1 MPa or higher, and the subcritical water is less than 374.1 ° C. and lower than 22.1 MPa. Intended for water in high-temperature and high-pressure environments.

  The temperature of the supercritical water may be 374.1 ° C. or higher, or 410 ° C. or higher. The temperature of the supercritical water may be 374.1 ° C. or higher and 410 ° C. or lower, may be 380 ° C. or higher and 410 ° C. or lower, or may be 380 ° C. or higher and 400 ° C. or lower.

  The temperature of the subcritical water may be 250 ° C. or higher and lower than 374.1 ° C., or may be 365 ° C. or higher and lower than 374.1.

  As will be described later, supercritical water or subcritical water can be produced by mixing an organic semiconductor material or an organic semiconductor material extract with water and then heating the mixture.

  The specific configuration of the contacting step is not particularly limited. An example of the process will be described below.

  For example, the contacting step can be performed by putting an organic semiconductor material or an organic semiconductor material extract and water in a container and sealing it, and then heating the sealed container.

  The internal volume of the sealed container is not particularly limited, and can be set as appropriate according to the amount of organic semiconductor material (or extract) and water to be contained therein. For example, it may be 0.1 mL to 0.5 mL, 0.5 mL to 1.0 mL, 1.0 mL to 2.0 mL, 1.5 mL to 1.mL. It may be 8 mL or 1.8 mL. Of course, it is also possible to use a container having an internal volume larger than these (for example, an internal volume of the order of “L”). According to the above configuration, since a desired amount of supercritical water and subcritical water can be produced, a desired amount of organic semiconductor material or organic semiconductor material extract is treated with supercritical water or subcritical water. be able to.

  The amount of water put in the sealed container is not particularly limited, and can be appropriately set according to the internal volume of the container. For example, the amount of water can be from about 5.56% to 27.8% of the internal volume of the container, from about 27.8% to about 55.6% of the internal volume of the container, From about 27.8% to about 38.9%. For example, when the internal volume of the container is 0.1 mL to 0.5 mL, the amount of water may be 5.56 μL to 139 μL, 27.8 μL to 278 μL, 27.8 μL to It may be 195 μL. When the internal volume of the container is 0.5 mL to 1.0 mL, the amount of water may be 27.8 μL to 278 μL, 139 μL to 556 μL, or 139 μL to 389 μL. . When the internal volume of the container is 1.0 mL to 2.0 mL, the amount of water may be 55.6 μL to 556 μL, 278 μL to 1112 μL, or 278 μL to 778 μL. . When the internal volume of the container is 1.5 mL to 1.8 mL, the amount of water may be 83.4 μL to 500 μL, 417 μL to 1001 μL, or 417 μL to 700 μL. . When the internal volume of the container is 1.8 mL, the amount of water may be about 500 μL to about 1000 μL, or about 500 μL to about 700 μL.

  According to the said structure, supercritical water or subcritical can be produced easily in a container.

  The amount of the organic semiconductor material or the extract of the organic semiconductor material that is put into the sealed container is not particularly limited, and can be appropriately set according to the internal volume of the container. For example, the amount of the organic semiconductor material or the extract of the organic semiconductor material can be set to 2.78 mg to 27.8 mg with respect to 1 mL of the internal volume of the container, and the internal volume of the container is 1 mL. On the other hand, it can also be set to be 0.556 mg to 55.6 mg. For example, when the internal volume of the container is 0.1 mL to 0.5 mL, the amount of the organic semiconductor material or the extract of the organic semiconductor material can be 0.278 mg to 13.9 mg, or 55.6 μg to It can be 27.8 mg. When the internal volume of the container is 0.5 mL to 1.0 mL, the amount of the organic semiconductor material or the extract of the organic semiconductor material can be 1.39 mg to 27.8 mg, or 0.278 mg to 55.55 mg. It can be 6 mg. When the internal volume of the container is 1.0 mL to 2.0 mL, the amount of the organic semiconductor material or the extract of the organic semiconductor material can be 2.78 mg to 55.6 mg, or 0.556 mg to 111 mg. possible. When the internal volume of the container is 1.5 mL to 1.8 mL, the amount of the organic semiconductor material or the extract of the organic semiconductor material can be 4.17 mg to 50.0 mg, or 0.834 mg to 100 mg. possible. When the internal volume of the container is 1.8 mL, the amount of the organic semiconductor material or the organic semiconductor material extract may be 5.00 mg to 50.0 mg, or may be 1.00 mg to 100 mg.

  The material of the said container is not specifically limited, What is necessary is just to have heat resistance while the internal space which puts an organic-semiconductor material or the extract of organic-semiconductor material, and water can be made into high temperature. In the container, for example, the inner wall surface of the container may be made of nickel alloy, gold alloy, magnesium alloy, cobalt alloy, aluminum alloy, copper alloy, alloy steel, or iron alloy. As said container, it is possible to use the container made from SUS316 generally used.

  It is preferable that the said container is a disposable container comprised independently of the heater or combustion furnace for heating the said container. If it is the above-mentioned composition, since the next sample is not analyzed in the state where the nonmetallic element derived from the sample analyzed last time remains, it is contained in the organic semiconductor material or the extract of the organic semiconductor material. Non-metallic elements can be analyzed more accurately. In the above configuration, since the container is configured independently of the heater or the combustion furnace, a plurality of containers can be heated at one time, that is, a plurality of samples can be analyzed at a time. As a result, the analysis time can be greatly shortened.

  As described above, the contacting step can be performed by putting an organic semiconductor material or an organic semiconductor material extract and water in a container and sealing it, and then heating the sealed container. is there.

  The heating temperature of the container is not particularly limited, and the container may be heated to a temperature necessary for making the water inside the container into supercritical water or subcritical water. For example, the container may be heated so that the inside of the container is 250 ° C. or higher or 260 ° C. or higher, and the container may be heated so that the inside of the container is 374.1 ° C. or higher. More specifically, the container may be heated so that the inside of the container is 260 ° C. or higher and lower than 374.1 ° C., or the container is heated so that the inside of the container is 374.1 ° C. or higher and 400 ° C. or lower. May be. Moreover, you may heat a container so that the inside of a container may be 380 degreeC or more and 400 degrees C or less. The upper limit value of the heating temperature is not particularly limited.

  The configuration for heating the container is not particularly limited, and a known heater, combustion furnace, sand bath, or the like may be used as appropriate.

  The time for contacting the organic semiconductor material or the organic semiconductor material extract with the supercritical water or the subcritical water is not particularly limited and can be set as appropriate. For example, an organic semiconductor material or an organic semiconductor material extract and supercritical water or subcritical water are used for 1 hour or more, 4 hours or more, 8 hours or more, 12 hours or more, 16 hours or more, 20 hours or more, or 48 hours or more. It is possible to make contact. According to the above configuration, the non-metallic element contained in the organic semiconductor material or the organic semiconductor material extract is efficiently contained in the organic semiconductor material or the constituent component of the organic semiconductor material (the organic semiconductor material extract). Can be separated from

  More specifically, the organic semiconductor material or the organic semiconductor material extract can be brought into contact with supercritical water or subcritical water for 1 to 48 hours. More specifically, the organic semiconductor material can be brought into contact with supercritical water or subcritical water for 1 hour to 16 hours, 4 hours to 16 hours, 8 hours to 16 hours, or 12 hours to 16 hours. It is. Separation of most of non-metallic elements that can be separated from organic semiconductor materials or constituents of organic semiconductor materials by contacting organic semiconductor material or organic semiconductor material extract with supercritical water or subcritical water for 16 hours In addition, it is possible to avoid unnecessarily decomposing the basic structure of the organic semiconductor material or the constituent components of the organic semiconductor material.

  Of course, in this invention, you may decompose | disassemble some or all of the structural component of organic-semiconductor material or organic-semiconductor material. In this case, it can be said that a longer time is preferable for bringing the organic semiconductor material or the organic semiconductor material extract into contact with the supercritical water or the subcritical water.

  The analysis method of the present embodiment includes a step of separating the residue of the organic semiconductor material and the supercritical water or the subcritical water between the contacting step and the detecting step. Also good. In the case where the basic structure of the organic semiconductor material or the constituent components of the organic semiconductor material is not decomposed as much as possible, it can be said that the separation step is preferably used. Of course, this step may be omitted. Since supercritical water or subcritical water contains non-metallic elements separated from organic semiconductor materials or components of organic semiconductor materials, the supercritical water or subcritical water is cooled, and then the supercritical water or subcritical water is cooled. Alternatively, the subcritical water and the residue of the organic semiconductor material are separated, and the obtained supercritical water or subcritical water may be analyzed in a detection step described later.

  The separation step can be performed using a known method. For example, it is possible to separate the residue of the organic semiconductor material from supercritical water or subcritical water using a known filtration filter. Further, it is possible to separate the residue of the organic semiconductor material from the supercritical water or the subcritical water using a known centrifuge. If the amount of supercritical water or subcritical water is very small, it is preferable to use a centrifuge from the viewpoint of recovering as much supercritical water or subcritical water as possible.

  According to the above configuration, since unnecessary substances are not introduced into the detection step described later, it is possible to analyze the nonmetallic element more accurately.

  The analysis method of the present embodiment may include a step of removing the metal contained in the supercritical water or the subcritical water between the contacting step and the detecting step. In addition, the metal contained in the organic semiconductor material or the component of the organic semiconductor material may be sufficient as the said metal, and the metal originating in a container may be sufficient as it. According to the above configuration, since unnecessary substances are not introduced into the detection step described later, it is possible to analyze the nonmetallic element more accurately.

  The step of removing the metal is not particularly limited as long as it is a step capable of removing the metal. For example, the metal can be removed using an ion exchange resin or the like.

  In the detecting step, a nonmetallic element contained in the supercritical water or the subcritical water after contact with the organic semiconductor material or the organic semiconductor material extract is detected.

  The detecting step can be appropriately selected according to the type of the nonmetallic element, and the specific configuration is not particularly limited. For example, the detection step includes ion chromatography (IC), mass spectrometry (MS), capillary electrophoresis (CE), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy ( ICP-AES), atomic absorption (AAS), or a combination thereof. More specifically, the detecting step includes an IC-MS method, an IC-MS / MS method, a CE method, a CE-MS method, or a CE-MS / MS method, an ICP-MS method, and an ICP-AES method. It is possible to do so.

  The detection step includes the above-described ion chromatography (IC), mass spectrometry (MS), capillary electrophoresis (CE), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy ( Among ICP-AES and atomic absorption (AAS), detection is preferably performed based on the IC method. The reason is that the measurement component can be separated from the contaminants and separated between the measurement components, and the measurement component can be quantified with high sensitivity.

  In the detecting step, it is preferable to detect a plurality of types of nonmetallic elements (for example, halogen). According to the above configuration, the analysis efficiency can be dramatically increased.

  The ion chromatograph method (IC), mass spectrometry method (MS), capillary electrophoresis method (CE) and the like described above are methods well known to those skilled in the art, and thus detailed description thereof is omitted in this specification. .

  In the analysis method of this embodiment, the step of bringing the organic semiconductor material or the organic semiconductor material extract into contact with supercritical water or subcritical water can be performed under alkaline conditions. When the above step is performed under alkaline conditions, an alkaline substance such as sodium hydroxide or potassium hydroxide is added to a mixture of an organic semiconductor material or an organic semiconductor material extract and supercritical water or subcritical water. That's fine.

  According to the above configuration, since the organic semiconductor material or the constituent components of the organic semiconductor material can be actively decomposed, substantially the entire amount of the nonmetallic element in the organic semiconductor material or the extract of the organic semiconductor material is reduced to the following amount. It can be introduced into the detecting step. As a result, the amount of the nonmetallic element can be analyzed more accurately.

  The amount of the alkaline substance added to the mixture, in other words, the pH of the mixed solution placed in the container is not particularly limited, and can be set as appropriate. For example, pH 8.0-12.0 may be sufficient and pH 10.0-12.0 may be sufficient. It can be said that it is preferable to select a pH within a range that does not corrode the container and that can sufficiently decompose the organic semiconductor material or the constituent components of the organic semiconductor material.

  In the analysis method of the present embodiment, the step of bringing the organic semiconductor material or organic semiconductor material extract into contact with supercritical water or subcritical water can be performed in the presence of an oxidizing agent. is there. When the above step is performed in the presence of an oxidizing agent, hydrogen peroxide or the like may be added to a mixture of an organic semiconductor material or an organic semiconductor material extract and supercritical water or subcritical water.

  According to the above configuration, since the organic semiconductor material or the constituent components of the organic semiconductor material can be actively decomposed, substantially the entire amount of the nonmetallic element in the organic semiconductor material or the extract of the organic semiconductor material is reduced to the following amount. It can be introduced into the detecting step. As a result, the amount of the nonmetallic element can be analyzed more accurately.

  When the constituent component of the organic semiconductor material is an unfavorable substance for the subsequent detection step, the alkaline substance or the oxidizing agent may be added to the supercritical water or subcritical water separated by the separation step. Is possible.

  According to the said structure, the residue of the organic-semiconductor material in supercritical water or subcritical water which was not able to be isolate | separated completely at the process to isolate | separate can be decomposed | disassembled completely. As a result, it is possible to prevent clogging of the column due to the presence of undecomposed residue while minimizing the influence of the decomposed product on the subsequent detection process.

  In the analysis method of the present embodiment, an internal standard substance may be added to a mixture of an organic semiconductor material or an organic semiconductor material extract and supercritical water or subcritical water in the contacting step described above. The internal standard substance is a configuration for correcting the amount of the finally detected nonmetallic element and accurately calculating the amount of the nonmetallic element contained in the original organic semiconductor material.

  As the internal standard substance, any substance other than the element to be analyzed may be used as long as it is not contained in the sample. For example, when the analyte is F or Cl and the sample does not contain Br, it is resistant to supercritical water and subcritical water, and can be easily detected in the above-described detection step. From the viewpoint, an organic compound containing bromine (for example, 2,7-Dibromofluorene) can be selected as the internal standard substance.

For example, in the step of contacting, it is assumed that an internal standard substance of X [μg] is added to a mixture of an organic semiconductor material or an organic semiconductor material extract and supercritical water or subcritical water. Then, after passing through various steps, it is assumed that an internal standard substance of Y [μg] and a nonmetallic element of Z [μg] are detected in the detection step. At this time, the amount (W [μg]) of the nonmetallic element contained in the first organic semiconductor material or the organic semiconductor material extract is calculated by the equation (1). That means
W = (X / Y) × Z (1).

The formula for calculating W is not limited to the formula (1), and various effects (for example, the difference in heat resistance between the nonmetallic element and the internal standard substance, the adsorptivity of the nonmetallic element and the internal standard substance to the container, It may be another formula that takes into account differences). For example, a test is performed to examine the difference in heat resistance between the nonmetallic element and the internal standard substance, or the difference in the adsorptivity to the container of the nonmetallic element and the internal standard substance, and the coefficient “a” reflecting the difference. (For example, the heat resistance ratio or the adsorption ratio) is obtained. And it is also possible to rewrite said Formula (1) using the said coefficient like following Formula (2), and to calculate W by the said Formula (2). That means
W = a × (X / Y) × Z (2).

[2. Analysis system)
The analysis system of this embodiment will be described below with reference to FIG. The analysis system of the present embodiment is the above [1. This is a system for carrying out the method described in the column “Analysis method”. Therefore, the description of the overlapping configuration is omitted here.

  The analysis system of the present embodiment is a system for analyzing a nonmetallic element contained in a solid organic semiconductor material 3 or an extract of an organic semiconductor material, the organic semiconductor material 3 or an extract of an organic semiconductor material, In the supercritical water 2 or the subcritical water 2 after contacting the container 1 (contact means) for contacting the supercritical water 2 or the subcritical water 2 with the organic semiconductor material 3 or the extract of the organic semiconductor material And a detection unit 7 (detection means) for detecting the contained nonmetallic elements.

  As shown in FIG. 1, in the analysis system of the present embodiment, first, an organic semiconductor material 3 or an organic semiconductor material extract and water (corresponding to supercritical water 2 or subcritical water 2) are placed in a container 1. And put. Moreover, you may add the alkaline substance or oxidizing agent mentioned above into the said container 1 as needed at this time.

  Since the organic semiconductor material 3 or the organic semiconductor material extract and the supercritical water 2 or the subcritical water 2 have already been described in detail, the description thereof is omitted here.

  The container 1 should just be the structure which can heat, after putting the organic-semiconductor material 3 or the extract of organic-semiconductor material, and water in the inside, and sealing. Note that the container 1 shown in FIG. 1 includes an organic semiconductor material 3 or an organic semiconductor material extract, a cylindrical portion that holds water, and two caps that seal both ends of the cylindrical portion. . However, the form of the container 1 is not limited to this.

  The internal volume of the container 1 is not particularly limited, and can be appropriately set according to the amount of the organic semiconductor material 3 or the organic semiconductor material extract liquid and the water contained in the container 1. For example, it may be 0.1 mL to 0.5 mL, 0.5 mL to 1.0 mL, 1.0 mL to 2.0 mL, 1.5 mL to 1.mL. It may be 8 mL or 1.8 mL. Of course, it is also possible to use a container 1 having an internal volume larger than these (for example, an internal volume of the order of “L”). According to the above configuration, since a desired amount of supercritical water and subcritical water can be produced, a desired amount of organic semiconductor material or organic semiconductor material extract is treated with supercritical water or subcritical water. be able to.

  The amount of water put into the container 1 is not particularly limited, and can be appropriately set according to the internal volume of the container 1. For example, the amount of water can be about 5.56% to 27.8% of the internal volume of container 1, can be about 27.8% to about 55.6% of the internal volume of container 1, and container 1 From about 27.8% to about 38.9% of the internal volume of For example, when the internal volume of the container 1 is 0.1 mL to 0.5 mL, the amount of water may be 5.56 μL to 139 μL, may be 27.8 μL to 278 μL, and may be 27.8 μL. It may be ˜195 μL. When the internal volume of the container 1 is 0.5 mL to 1.0 mL, the amount of water may be 27.8 μL to 278 μL, 139 μL to 556 μL, or 139 μL to 389 μL. Good. When the internal volume of the container 1 is 1.0 mL to 2.0 mL, the amount of water may be 55.6 μL to 556 μL, 278 μL to 1112 μL, or 278 μL to 778 μL. Good. When the internal volume of the container 1 is 1.5 mL to 1.8 mL, the amount of water may be 83.4 μL to 500 μL, 417 μL to 1001 μL, or 417 μL to 700 μL. Good. When the internal volume of the container 1 is 1.8 mL, the amount of water may be about 500 μL to about 1000 μL, or about 500 μL to about 700 μL.

  According to the above configuration, supercritical water or subcritical water can be easily produced in the container 1.

  The amount of the organic semiconductor material 3 or the extract of the organic semiconductor material that is put into the container 1 is not particularly limited, and can be appropriately set according to the internal volume of the container 1. For example, the amount of the organic semiconductor material 3 or the extract of the organic semiconductor material can be set to be 2.78 mg to 27.8 mg with respect to 1 mL of the internal volume of the container 1. It is also possible to set to be 0.556 mg to 55.6 mg with respect to a volume of 1 mL. For example, when the internal volume of the container 1 is 0.1 mL to 0.5 mL, the amount of the organic semiconductor material 3 or the organic semiconductor material extract may be 0.278 mg to 13.9 mg, or 55. It can be 6 μg to 27.8 mg. When the internal volume of the container 1 is 0.5 to 1.0 mL, the amount of the organic semiconductor material 3 or the organic semiconductor material extract can be 1.39 mg to 27.8 mg, or 0.278 mg to It can be 55.6 mg. When the internal volume of the container 1 is 1.0 mL to 2.0 mL, the amount of the organic semiconductor material 3 or the extract of the organic semiconductor material can be 2.78 mg to 55.6 mg, or 0.556 mg to It can be 111 mg. When the internal volume of the container 1 is 1.5 mL to 1.8 mL, the amount of the organic semiconductor material 3 or the extract of the organic semiconductor material can be 4.17 mg to 50.0 mg, or 0.834 mg to It can be 100 mg. When the internal volume of the container 1 is 1.8 mL, the amount of the organic semiconductor material 3 or the extract of the organic semiconductor material can be 5.00 mg to 50.0 mg, or can be 1.00 mg to 100 mg. .

  The material of the container 1 is not particularly limited as long as the organic semiconductor material 3 or the extract of the organic semiconductor material and the internal space for containing water can be heated to high temperatures and have heat resistance. For example, the inner wall surface of the container 1 may be made of a nickel alloy, a gold alloy, a magnesium alloy, a cobalt alloy, an aluminum alloy, a copper alloy, an alloy steel, or an iron alloy. As the container 1, a commonly used container made of SUS316 can be used.

  As shown in FIG. 1, a container 1 in which an organic semiconductor material 3 or an organic semiconductor material extract and water are placed is heated into the heating unit 5 and then heated by the heating unit 5. And by the said heating, the water in the container 1 turns into supercritical water or subcritical water.

  The heating unit 5 may be anything as long as it can heat the internal container 1, and its specific configuration is not particularly limited. For example, as the heating unit 5, a known heater, combustion furnace, or sand bath is used. Is possible. In addition, at this time, it is preferable that the container 1 and the heating part 5 are separable separate structures. Furthermore, it is preferable that the container 1 is a disposable structure. If it is the above-mentioned composition, since the next sample is not analyzed in the state where the nonmetallic element derived from the sample analyzed last time remains, it is contained in the organic semiconductor material or the extract of the organic semiconductor material. Non-metallic elements can be analyzed more accurately. Moreover, since the container 1 is comprised independently of the heating part 5 in the said structure, the several container 1 can be heated at once by the heating part 5, That is, a several sample is analyzed at once. can do. As a result, the analysis time can be greatly shortened.

  The heating temperature of the container 1 by the heating unit 5 is not particularly limited as long as the container 1 can be heated to a temperature necessary for making the water inside the container 1 into supercritical water or subcritical water. For example, the container 1 may be heated so that the inside of the container 1 becomes 250 ° C. or 260 ° C. or higher, and the container 1 may be heated so that the inside of the container 1 becomes 374.1 ° C. or higher. More specifically, the container 1 may be heated so that the inside of the container 1 is 260 ° C. or higher and lower than 374.1 ° C., or the container 1 is 37 ° C. or higher and 400 ° C. or lower. 1 may be heated. Moreover, you may heat the container 1 so that the inside of the container 1 may be 380 degreeC or more and 400 degrees C or less. The upper limit value of the heating temperature is not particularly limited.

  The time for which the organic semiconductor material 3 or the organic semiconductor material extract is brought into contact with the supercritical water 2 or the subcritical water 2 in the heating unit 5 is not particularly limited, and can be set as appropriate. For example, the organic semiconductor material 3 or the organic semiconductor material extract and the supercritical water 2 or the subcritical water 2 are 1 hour or more, 4 hours or more, 8 hours or more, 12 hours or more, 16 hours or more, 20 hours or more or It is possible to contact for 48 hours or more. According to the above configuration, the non-metallic element contained in the organic semiconductor material 3 or during the extraction of the organic semiconductor material is efficiently contained in the organic semiconductor material 3 or the constituent component of the organic semiconductor material (the extract of the organic semiconductor material Can be separated from

  More specifically, the organic semiconductor material 3 or the organic semiconductor material extract can be brought into contact with the supercritical water 2 or the subcritical water 2 for 1 to 48 hours. More specifically, the organic semiconductor material 3 or the organic semiconductor material extract and supercritical water 2 or subcritical water 2 are contacted for 1 to 16 hours, 4 to 16 hours, 8 to 16 hours, or It is also possible to contact for 12 to 16 hours. If the organic semiconductor material 3 or the organic semiconductor material extract is brought into contact with the supercritical water 2 or the subcritical water 2 for 16 hours, the non-metallic element that can be separated from the organic semiconductor material 3 or the constituent components of the organic semiconductor material Most of the components can be separated, and unnecessary decomposition of the organic semiconductor material 3 or components of the organic semiconductor material can be avoided.

  Of course, in this invention, you may decompose | disassemble some or all of the structural component of the organic-semiconductor material 3 or organic-semiconductor material. In this case, it can be said that a longer time is preferable for bringing the organic semiconductor material 3 or the organic semiconductor material extract into contact with the supercritical water 2 or the subcritical water 2.

  As shown in FIG. 1, according to the analysis system of the present embodiment, the separation unit 6 causes the residue of the organic semiconductor material 3 and the supercritical water 2 or subcritical water 2 depending on the degree of decomposition of the organic semiconductor material 3. And may be separated. That is, when most of the organic semiconductor material 3 is decomposed to form the decomposition solution 4, the decomposition solution 4 can be introduced into the detection unit 7 without using the separation unit 6. When most of the material 3 is not decomposed, the separation unit 6 separates the residue of the organic semiconductor material 3 from the supercritical water 2 or the subcritical water 2, and then detects the supercritical water 2 or the subcritical water 2. 7 may be introduced. Of course, regardless of the degree of decomposition of the organic semiconductor material 3, the residue of the organic semiconductor material 3 and the supercritical water 2 or subcritical water 2 may be separated by the separation unit 6, The supercritical water 2 or the subcritical water 2 may not be separated.

  A known configuration can be used as the separation unit 6. For example, a known filtration filter or a centrifuge can be used as the separation unit 6. If the amount of supercritical water or subcritical water is very small, it is preferable to use a centrifuge from the viewpoint of recovering as much supercritical water or subcritical water as possible.

  According to the above configuration, since an unnecessary substance is not introduced into the detection unit 7 described later, a nonmetallic element can be analyzed more accurately.

  The analysis system of the present embodiment may have a removal unit (not shown) that removes metal contained in the supercritical water 2 or the subcritical water 2. The removal unit can be provided after the heating unit 5, can be provided after the heating unit 5 and before the separation unit 6, or can be provided after the separation unit 6. The removal unit removes the metal derived from the organic semiconductor material 3 or the metal derived from the extract of the organic semiconductor material and the metal derived from the container 1 contained in the supercritical water 2 or the subcritical water 2. According to the above configuration, since unnecessary substances are not introduced into the detection step described later, it is possible to analyze the nonmetallic element more accurately.

  The removal part may be any structure that can remove metal, and its specific structure is not limited. For example, an ion exchange resin or the like can be used as the removal unit.

  In the detection part 7, the nonmetallic element contained in the supercritical water 2 or the subcritical water 2 after contacting with the organic semiconductor material 3 or the extract of the organic semiconductor material is detected.

  The detection unit 7 can be appropriately selected according to the type of the nonmetallic element, and the specific configuration is not particularly limited. For example, the detection step includes ion chromatography (IC), mass spectrometry (MS), capillary electrophoresis (CE), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy ( ICP-AES), atomic absorption (AAS), or a combination thereof. More specifically, the detecting step includes an IC-MS method, an IC-MS / MS method, a CE method, a CE-MS method, or a CE-MS / MS method, an ICP-MS method, and an ICP-AES method. It is possible to do so.

  The detection step includes the above-described ion chromatography (IC), mass spectrometry (MS), capillary electrophoresis (CE), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy ( Among ICP-AES and atomic absorption (AAS), detection is preferably performed based on the IC method. The reason is that the measurement component can be separated from the impurities and separated between the measurement components, and the measurement component can be quantified with high sensitivity.

  The detection unit 7 is preferably capable of detecting a plurality of types of nonmetallic elements (for example, halogen). According to the above configuration, the analysis efficiency can be dramatically increased.

[3. Method for controlling the quality of organic semiconductor materials]
The method of managing the quality of the organic semiconductor material according to the present embodiment is a method of managing the quality of the organic semiconductor material using the analysis method of the present invention, wherein the non-metallic element detected in the detecting step is A step of selecting an organic semiconductor material whose amount is equal to or less than a predetermined reference amount.

  In the method for managing the quality of the organic semiconductor material according to the present embodiment, the nonmetallic element detected in the detecting step is collected and the amount of the nonmetallic element is measured. The specific method of the measurement is not particularly limited, and examples thereof include inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), and atomic absorption spectrometry (AAS). Can be mentioned.

  And the organic-semiconductor material in which the quantity of the nonmetallic element detected in the said process to detect is below a predetermined reference quantity is selected. The sorting may be performed based on the type of nonmetallic element detected in the detecting step. The reference amount is not particularly limited, and can be set as appropriate according to the required quality.

  If it is a method for managing the quality of the organic semiconductor material of the present embodiment, it is possible to accurately detect the non-metallic element contained in the organic semiconductor material, and to select the organic semiconductor material based on the detection result Thus, the quality of the organic semiconductor material can be kept constant. Therefore, the method for managing the quality of the organic semiconductor material according to the present embodiment is also suitable for the quality control of the organic semiconductor material used for manufacturing the organic electronic product, which requires more accurate quality control.

[4. Manufacturing method of organic electronics equipment]
The manufacturing method of the organic electronics device of the present embodiment is a method of manufacturing an organic electronics device using the analysis method of the present invention, wherein the amount of the nonmetallic element detected in the detecting step is determined in advance. A step of selecting an organic semiconductor material that is equal to or less than a predetermined reference amount, and a step of manufacturing an organic electronics device using an organic semiconductor material of the same quality as the organic semiconductor material selected in the step of selecting. It is characterized by that.

  In the method for manufacturing an organic electronics device of the present embodiment, the nonmetallic element detected in the detecting step is collected and the amount of the nonmetallic element is measured. The specific method of the measurement is not particularly limited, and examples thereof include inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), and atomic absorption spectrometry (AAS). Can be mentioned.

  And the organic-semiconductor material in which the quantity of the nonmetallic element detected in the said process to detect is below a predetermined reference quantity is selected. The sorting may be performed based on the type of nonmetallic element detected in the detecting step. The reference amount is not particularly limited, and can be set as appropriate according to the required quality.

  The method for manufacturing an organic electronic device of the present embodiment includes a step of manufacturing an organic electronic device using an organic semiconductor material having the same quality as the organic semiconductor material selected in the selecting step.

  The above-mentioned “organic semiconductor material having the same quality as the organic semiconductor material selected in the selecting step” may be, for example, the selected organic semiconductor material itself or in the same manner as the selected organic semiconductor. It may be a manufactured organic semiconductor material or an organic semiconductor material in the same lot as the selected organic semiconductor material.

  Although it does not specifically limit as an organic electronics apparatus manufactured by the manufacturing method of this Embodiment, For example, an organic thin film solar cell, organic EL, an organic transistor (semiconductor), etc. can be mentioned.

  If it is the manufacturing method of the organic electronics apparatus of this Embodiment, since the quantity of the nonmetallic element contained in organic-semiconductor material is below a reference amount, it is possible to manufacture a high quality organic electronics product, The yield can be improved.

  In addition, this invention can also be comprised as follows.

  In order to solve the above problems, the analysis method of the present invention is a method for analyzing a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting the solid organic semiconductor material. A step of contacting the organic semiconductor material or the extract with supercritical water or subcritical water, and the non-critical water contained in the supercritical water or subcritical water after contact with the organic semiconductor material or the extract. And a step of detecting a metal element.

  In the analysis method of the present invention, the nonmetallic element is preferably B, Si, P, S, F, Cl, Br, or I.

  In the analysis method of the present invention, in the contacting step, the organic semiconductor material or the extract and the supercritical water or the subcritical water are preferably contacted for 1 to 48 hours.

  The analysis method of the present invention preferably includes a step of separating the residue of the organic semiconductor material and the supercritical water or the subcritical water between the contacting step and the detecting step.

  In the analysis method of the present invention, the detection step is performed by ion chromatography, mass spectrometry, capillary electrophoresis, inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectroscopy, atomic absorption, or a combination thereof. Is preferably carried out by

  In the analysis method of the present invention, it is preferable that a plurality of types of the nonmetallic elements are detected in the detecting step.

  In the analysis method of the present invention, in the contacting step, the organic semiconductor material or the extract and the supercritical water or subcritical water are preferably contacted in a disposable container.

  In order to solve the above problems, an analysis system of the present invention is an analysis system for a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting the solid organic semiconductor material. A contact means for bringing the organic semiconductor material or the extract into contact with the supercritical water or the subcritical water; and the supercritical water or the subcritical water contained in the supercritical water or the subcritical water after the contact with the organic semiconductor material or the extract. And detecting means for detecting a nonmetallic element.

  In the analysis system of the present invention, the nonmetallic element is preferably B, Si, P, S, F, Cl, Br or I.

  In the analysis system of the present invention, it is preferable that the contact means is for contacting the organic semiconductor material or the extract with the supercritical water or the subcritical water for 1 to 48 hours.

  The analysis system of the present invention preferably has a separation means for separating the residue of the organic semiconductor material from the supercritical water or the subcritical water after being contacted by the contact means.

  In the analysis system of the present invention, the detection means is ion chromatography, mass spectrometry, capillary electrophoresis, inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectroscopy, atomic absorption, or a combination thereof. It is preferable to perform detection.

  In the analysis system of the present invention, it is preferable that the detection means detects a plurality of types of the nonmetallic elements.

  In the analysis system of the present invention, the contact means is preferably a disposable container.

  The method of managing the quality of the organic semiconductor material of the present invention is a method of managing the quality of the organic semiconductor material using the analysis method of the present invention, wherein the amount of the nonmetallic element detected in the detecting step is The method includes a step of selecting an organic semiconductor material that is equal to or less than a predetermined reference amount.

  The organic electronic device manufacturing method of the present invention is a method of manufacturing an organic electronic device using the analysis method of the present invention, wherein the amount of the nonmetallic element detected in the detecting step is predetermined. A step of selecting an organic semiconductor material that is equal to or less than a reference amount, and a step of manufacturing an organic electronic device using an organic semiconductor material having the same quality (for example, the same lot) as the organic semiconductor material selected in the selecting step It is characterized by having.

<1. Analysis of non-metallic elements contained in various organic semiconductor materials (examination on types of organic semiconductor materials)>
According to the analysis method and analysis apparatus of the present invention, an organic semiconductor material (specifically, 4,4′-bis (N-carbazolyl) -1, 1′-biphenyl, 5,5′-di (4-biphenylyl) is used. ) -2,2′-bithiophene or tris (4-carbazoyl-9-ylphenyl) amine) (specifically, F ⁻ , Cl ⁻ , Br ⁻ , SO _4). ^2, and, I ^- to determine the amount of). Specific test methods and test results will be described below.

  After 25 mg of organic semiconductor material and 0.7 mL of water were added to the sealed container, the container was sealed.

  After putting the said airtight container in an electric furnace, it heated at 400 degreeC for 16 hours.

  After the heating, the sealed container was cooled.

  A mixture of the organic semiconductor material residue and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the organic semiconductor material and water were taken out, 0.3 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the residue of the organic semiconductor material and water and the washing water were mixed, the mixture was diluted with water to a volume 10 times as large. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

  Note that the test described above was performed twice for each organic semiconductor material. That is, at each organic semiconductor material, two test samples were obtained (total of six test samples).

The test sample was analyzed with an ion chromatograph, and the amounts of F ⁻ , Cl ⁻ , Br ⁻ , SO ₄ ²⁻ , and I ⁻ contained in each test sample were measured. Various test conditions are shown below.
Column: Dionex IonPac AG11-HC + AS11-HC (2 mm);
Eluent: KOH gradient (1-35 mM);
-Temperature: 30 ° C;
Suppressor: AMMS 25mM H ₂ SO _4;
Injection volume: 100 μL;
Detector: electrical conductivity.

  As a control test, the amount of the nonmetallic element contained in the organic semiconductor material was pretreated by a well-known method (combustion method: see Patent Document 1) and measured by ion chromatography.

  The measurement results are shown in Tables 1 to 3 below. Table 1 shows the test results of 4,4′-bis (N-carbazolyl) -1,1′-biphenyl, and Table 2 shows 5,5′-di (4-biphenylyl) -2,2 The test results for '-bithiophene are shown, and Table 3 shows the test results for tris (4-carbazoyl-9-ylphenyl) amine.

As is clear from Tables 1 to 3, according to the analysis method and the analysis apparatus of the present invention, any non-metallic element can be measured with high sensitivity in any organic semiconductor material. In addition, with respect to Cl ⁻ and Br ⁻ , the measurement results agreed well with the known method (combustion method) in any organic semiconductor material.

<2. Analysis of non-metallic elements contained in various organic semiconductor materials (examination of the amount and processing time of organic semiconductor materials)>
According to the analysis method and analysis apparatus of the present invention, a nonmetallic element (specifically, 5,5′-di (4-biphenylyl) -2,2′-bithiophene) contained in an organic semiconductor material ( Specifically, the amount of F ⁻ , Cl ⁻ , Br ⁻ , SO ₄ ²⁻ , and I ⁻ ) was measured. Specific test methods and test results will be described below.

  After 5 mg or 25 mg of organic semiconductor material and 0.7 mL of water were added to the sealed container, the container was sealed.

  After putting the said airtight container in an electric furnace, it heated at 400 degreeC for 8 hours or 16 hours.

  After the heating, the sealed container was cooled.

  A mixture of the organic semiconductor material residue and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the organic semiconductor material and water were taken out, 0.3 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the residue of the organic semiconductor material and water and the washing water were mixed, the mixture was diluted with water to a volume 10 times as large. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

  The test described above was performed twice for each condition. As a result, six test samples were obtained.

The test sample was analyzed with an ion chromatograph, and the amounts of F ⁻ , Cl ⁻ , Br ⁻ , SO ₄ ²⁻ , and I ⁻ contained in each test sample were measured. The following test methods are <1. Since it is the same as the test method described in the column of “Analysis of non-metallic elements contained in various organic semiconductor materials (examination on types of organic semiconductor materials)>”, the description thereof is omitted here and the measurement results are shown in Table 4.

  As is apparent from Table 4, according to the analysis method and the analysis apparatus of the present invention, any non-metallic element can be measured with high sensitivity even with various amounts of organic semiconductor materials and various processing times. It was.

<3. Analysis of non-metallic elements contained in various organic semiconductor materials (examination of processing time)>
In this example, the influence of the length of the treatment time with supercritical water on the amount of nonmetallic elements detected was examined in more detail. In this embodiment, after adding a known amount of a nonmetallic element to a matrix sample (corresponding to an organic semiconductor material), the matrix sample is treated with supercritical water at various times. Details of the test method will be described below.

  First, for a matrix sample (5 mg of anthracene), a fluorine-containing compound (Octafluoronaphthalene in an amount equivalent to 2 μg of fluorine), a chlorine-containing compound (9,10-Dichloroanthracene in an amount equivalent to 2 μg of chlorine), or Then, a bromine-containing compound (2,7-Dibromofluorene in an amount corresponding to 2 μg of bromine) was added to prepare a nonmetallic element-containing sample.

According to the analysis method and the analysis apparatus of the present invention, the amount of nonmetallic elements (specifically, F ⁻ , Cl ⁻ , and Br ⁻ ) contained in the nonmetallic element-containing sample was measured.

  The non-metallic element-containing sample and 0.7 mL of water were put into the sealed container and then sealed.

  After putting the said airtight container in an electric furnace, it heated at 400 degreeC for 4 hours, 8 hours, 12 hours, 16 hours, or 20 hours.

  After the heating, the sealed container was cooled.

  A mixture of the residue of the nonmetallic element-containing sample and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the nonmetallic element-containing sample and water were taken out, 0.3 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the nonmetallic element-containing sample residue and water and the washing water were mixed, the mixture was diluted to 10 times the volume with water. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

The test sample was analyzed by an ion chromatograph, ^and the amounts of F ⁻ , Cl ⁻ and Br ⁻ contained in each test sample were measured. The following test methods are <1. Since it is the same as the test method described in the column of analysis of nonmetallic elements contained in various organic semiconductor materials (examination on types of organic semiconductor materials)>, the description thereof is omitted here and the measurement results are shown in Table 5.

As is apparent from Table 5, according to the analysis method and analysis apparatus of the present invention, any nonmetallic element could be measured with high sensitivity even at various treatment times. In particular, if 12 hours or more of processing ^time, F -, Cl ^- and Br ^- a, Cl if more than 8 hours of processing time ^- revealed that it is possible to more sensitively detect ^- and Br.

  As is apparent from Table 5, the amount of the nonmetallic element detected reaches a substantially upper limit in the processing time of 12 hours. Therefore, from the viewpoint of cutting out only nonmetallic elements from the organic semiconductor material while maintaining the basic structure of the organic semiconductor material, the treatment time is preferably 4 hours or longer and 16 hours or shorter, and more preferably 8 hours or longer and 16 hours or shorter. 8 hours or more and 12 hours or less can be said to be most preferable.

<4. Analysis of non-metallic elements contained in various organic semiconductor materials (examination on the amount of organic semiconductor materials)>
In this example, the effect of the amount of the organic semiconductor material treated with supercritical water on the amount of the nonmetallic element detected was examined in more detail. In this embodiment, after adding a known amount of a nonmetallic element to various amounts of a matrix sample (corresponding to an organic semiconductor material), the matrix sample is treated with supercritical water. Details of the test method will be described below.

  First, for a matrix sample (5 mg, 20 mg or 50 mg of anthracene), a fluorine-containing compound (Octafluoronaphthalene in an amount corresponding to 2 μg of fluorine), a chlorine-containing compound (9,10− in an amount corresponding to 2 μg of chlorine) Dichloroanthracene), a bromine-containing compound (2,7-Dibromofluorene in an amount equivalent to 2 μg of bromine) or an iodine-containing compound (4,4′-Diiodobiphenyl in an amount equivalent to 2 μg of iodine) is added to add a non-metal An element-containing sample was prepared.

According to the analysis method and analysis apparatus of the present invention, the amount of nonmetallic elements (specifically, F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ ) contained in the nonmetallic element-containing sample is measured. did.

  The non-metallic element-containing sample and 0.5 mL of water were put into the sealed container and then sealed.

  After putting the said airtight container in an electric furnace, it heated at 400 degreeC for 4 hours.

  After the heating, the sealed container was cooled.

  A mixture of the residue of the nonmetallic element-containing sample and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the nonmetallic element-containing sample and water were taken out, 0.5 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the nonmetallic element-containing sample residue and water and the washing water were mixed, the mixture was diluted to 10 times the volume with water. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

The test sample was analyzed with an ion chromatograph, and the amounts of F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ contained in each test sample were measured. The following test methods are <1. Since it is the same as the test method described in the column of analysis of nonmetallic elements contained in various organic semiconductor materials (examination on types of organic semiconductor materials)>, the description thereof is omitted here and the measurement results are shown in Table 6.

As is apparent from Table 6, according to the analysis method and analysis apparatus of the present invention, any non-metallic element could be detected with high sensitivity even when the amount of various matrix samples was different. Among these nonmetallic elements, the detection sensitivity of I ⁻ , Cl ⁻ and Br ⁻ was particularly high.

<5. Study on influence of matrix sample>
In this example, the effect of the matrix sample (anthracene) on the amount of the nonmetallic element detected was examined in more detail.

  First, for a matrix sample (5 mg of anthracene), a fluorine-containing compound (Octafluoronaphthalene in an amount equivalent to 2 μg of fluorine), a chlorine-containing compound (9,10-Dichloroanthracene in an amount equivalent to 2 μg of chlorine) or bromine A contained compound (2,7-Dibromofluorene in an amount corresponding to 2 μg of bromine) was added to prepare a non-metallic element-containing sample.

  For the control test, a fluorine-containing compound (Octafluoronaphthalene in an amount equivalent to 2 μg of fluorine), a chlorine-containing compound (9 in an amount equivalent to 2 μg of chlorine) does not contain a matrix sample (5 mg of anthracene). Non-metallic element-containing samples of only 10-Dichloroanthracene) or bromine-containing compounds (2,7-Dibromofluorene in an amount corresponding to 2 μg of bromine) were also prepared.

According to the analysis method and analysis apparatus of the present invention, the amount of nonmetallic elements (specifically, F ⁻ , Cl ⁻ , Br ⁻ ) contained in the nonmetallic element-containing sample was measured. Specific test methods and test results will be described below.

  The non-metallic element-containing sample and 0.5 mL of water were put into the sealed container and then sealed.

  After putting the said airtight container in an electric furnace, it heated at 400 degreeC for 4 hours.

  After the heating, the sealed container was cooled.

  A mixture of the residue of the nonmetallic element-containing sample and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the nonmetallic element-containing sample and water were taken out, 0.5 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the nonmetallic element-containing sample residue and water and the washing water were mixed, the mixture was diluted to 10 times the volume with water. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

The test sample was analyzed with an ion chromatograph, and the amounts of F ⁻ , Cl ⁻ and Br ⁻ contained in each test sample were measured. The following test methods are <1. Analysis of non-metallic elements contained in various organic semiconductor materials (examination on types of organic semiconductor materials)> Since this is the same as the test method described in the column, the description is omitted here, and the measurement results are shown in Tables 7 and 8. Show. Table 7 shows the test results of the nonmetallic element-containing sample not including the matrix sample, and Table 8 shows the test results of the nonmetallic element-containing sample including the matrix sample.

As is apparent from Tables 7 and 8, according to the analysis method and analysis apparatus of the present invention, it was revealed that the presence of a matrix sample tends to decrease the detection sensitivity of F ⁻ and Cl ⁻ . In this case, the detection sensitivity can be increased by increasing the treatment time with supercritical water and / or the amount of supercritical water. Further, as is apparent from Tables 7 and 8, according to the analysis method and analysis apparatus of the present invention, it was revealed that the detection sensitivity of Br ⁻ is hardly affected by the matrix material.

<6. Study on processing temperature and processing time>
Put an organic semiconductor material containing a chlorine-containing compound (9,10-Dichloroanthracene in an amount corresponding to 2 μg of chlorine) and 1.3 mL or 0.8 mL of water into a sealed container (1.8 mL capacity). And then sealed.

  After the closed container is placed in an electric furnace, various times (specifically, 1 hour, 2 hours, 4 hours, 8 hours, or 16 hours), various temperatures (specifically, 250 ° C., 365 ° C.) C. or 410 ° C.).

  After the heating, the sealed container was cooled.

  A mixture of the organic semiconductor material residue and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the organic semiconductor material and water were taken out, 0.3 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the residue of the organic semiconductor material and water and the washing water were mixed, the mixture was diluted with water to a volume 10 times as large. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

The test sample was analyzed with an ion chromatograph, and the amount of Cl ⁻ contained in each test sample was measured. Various test conditions are shown below.
Column: Dionex IonPac AG11-HC + AS11-HC (2 mm);
Eluent: KOH gradient (1-35 mM);
-Temperature: 30 ° C;
Suppressor: AMMS 25mM H ₂ SO _4;
Injection volume: 100 μL;
Detector: electrical conductivity.

  The test results are shown below. As is apparent from Table 9, this test result shows that chlorine can be detected even at various processing temperatures or even at various processing temperatures.

<7. Quality control of organic semiconductor materials>
According to the analysis method and analysis apparatus of the present invention, an organic semiconductor material (specifically, TPD (N, N′-Diphenyl-N, N′-di (m-tolyl) benzidine, which is a sublimation or unpurified product) is used. )) The amount of non-metallic elements (specifically, F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ ) contained therein was measured. Specific test methods and test results will be described below.

  After 25 mg of organic semiconductor material and 0.7 mL of water were put into a sealed container (1.8 mL capacity), the container was sealed.

  After putting the said airtight container in an electric furnace, it heated at 400 degreeC for 16 hours.

  After the heating, the sealed container was cooled.

  A mixture of the organic semiconductor material residue and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the organic semiconductor material and water were taken out, 0.3 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the residue of the organic semiconductor material and water and the washing water were mixed, the mixture was diluted with water to a volume 10 times as large. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. The aqueous phase was used as a test sample in subsequent tests (ion chromatograph).

The test sample was analyzed with an ion chromatograph, and the amounts of F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ contained in each test sample were measured. Various test conditions are shown below.
Column: Dionex IonPac AG11-HC + AS11-HC (2 mm);
Eluent: KOH gradient (1-35 mM);
-Temperature: 30 ° C;
Suppressor: AMMS 25mM H ₂ SO _4;
Injection volume: 100 μL;
Detector: electrical conductivity.

  The test results are shown below. As is clear from Table 10, the test results show that the quality of the organic semiconductor material (in other words, the presence and amount of contaminants) can be evaluated and managed.

<8. Analysis of nonmetallic elements contained in various organic semiconductor materials (examination of types of nonmetallic elements)>
In accordance with the analysis method and analysis apparatus of the present invention, a nonmetallic element (specifically, a specific element contained in an organic semiconductor material (specifically, Tris [2-phenylpyridinato-C2, N] iridium (III)) The amount of B, P, and Si) was measured. Specific test methods and test results will be described below.

  After putting 15 mg of organic semiconductor material and 0.5 mL of water into a sealed container (1.4 mL capacity SUS tube), it was sealed.

  After putting the said airtight container in an electric furnace, it heated at 300 degreeC for 3 hours.

  After the heating, the sealed container was cooled.

  A mixture of the organic semiconductor material residue and water was taken out from the sealed container. In addition, it has confirmed visually that the form of the residue of organic-semiconductor material was a solid form at this time similarly to the form of the organic-semiconductor material before a heating. This indicates that in this example, the basic structure of the organic semiconductor material was not destroyed much.

  After the residue of the organic semiconductor material and water were taken out, 0.3 mL of water was newly added into the sealed container to wash the inside of the sealed container, and then the washing water was taken out.

  After the mixture of the residue of the organic semiconductor material and water and the washing water were mixed, the mixture was diluted with water to a volume 10 times as large. The dilution was filtered using MILLEX-GP PES 0.22 μm 33 mm manufactured by MILLIPORE, and the aqueous phase was separated. After adding hydrochloric acid to the aqueous phase, it was used as a test sample in subsequent tests.

  Specifically, the test sample is analyzed by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry (manufactured by Varian Technologies Japan Limited)), and B, P, and Si contained in each test sample are analyzed. The amount was measured. In addition, the specific measuring method followed the protocol attached to the measuring apparatus.

  The measurement results are shown in Table 11 below. As is clear from Table 11, the test results show that the present invention can also analyze B, P, and Si.

  The present invention is not limited to the configurations described above, and various modifications can be made within the scope of the claims, and technical means disclosed in different embodiments and examples are appropriately used. Embodiments and examples obtained in combination are also included in the technical scope of the present invention.

  The present invention can be widely used in the field using organic semiconductor materials. For example, organic EL, electronic paper, display TFT / OLED, backlight, organic transistor, molecular rectifier, organic solar cell, organic photoconductor (copy, laser, etc.), biosensor, microfabrication, photo process, nano-imprint It can be widely used in fields related to optical communication or optical storage.

1 container (contact means)
2 Supercritical water or subcritical water 3 Organic semiconductor material 4 Decomposition solution 5 Heating part 6 Separation part (separation means)
7 Detection part (detection means)
DESCRIPTION OF SYMBOLS 11 Path | route 12 Absorbing part 13 Sample 15 Combustion furnace 17 Detection part

Claims (16)

A method for analyzing a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting the solid organic semiconductor material,
Contacting the organic semiconductor material or the extract with supercritical water or subcritical water;
And a step of detecting the nonmetallic element contained in supercritical water or subcritical water after contact with the organic semiconductor material or the extract.   The analysis method according to claim 1, wherein the nonmetallic element is B, Si, P, S, F, Cl, Br, or I.   3. The analysis method according to claim 1, wherein, in the contacting step, the organic semiconductor material or the extract and the supercritical water or the subcritical water are contacted for 1 to 48 hours.   4. The method according to claim 1, further comprising a step of separating the residue of the organic semiconductor material from the supercritical water or the subcritical water between the contacting step and the detecting step. 2. The analysis method according to item 1.   The detecting step is performed by ion chromatography, mass spectrometry, capillary electrophoresis, inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectroscopy, atomic absorption, or a combination thereof. The analysis method according to any one of claims 1 to 4.   The analysis method according to claim 1, wherein a plurality of types of the nonmetallic elements are detected in the detecting step.   In the contacting step, the organic semiconductor material or the extract and supercritical water or subcritical water are brought into contact in a disposable container. Analysis method described. An analysis system for a nonmetallic element contained in a solid organic semiconductor material or an extract obtained by extracting the solid organic semiconductor material,
Contact means for bringing the organic semiconductor material or the extract into contact with supercritical water or subcritical water;
And a detection means for detecting the nonmetallic element contained in supercritical water or subcritical water after contact with the organic semiconductor material or the extract.   9. The analysis system according to claim 8, wherein the nonmetallic element is B, Si, P, S, F, Cl, Br, or I.   The analysis according to claim 8 or 9, wherein the contact means is for bringing the organic semiconductor material or the extract into contact with the supercritical water or the subcritical water for 1 to 48 hours. system.   11. The separator according to claim 8, further comprising a separation unit configured to separate the residue of the organic semiconductor material after the contact by the contact unit and the supercritical water or the subcritical water. 2. The analysis system according to item 1.   The detection means is to perform detection by ion chromatography, mass spectrometry, capillary electrophoresis, inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectroscopy, atomic absorption, or a combination thereof. The analysis system according to any one of claims 8 to 11.   The analysis system according to any one of claims 8 to 12, wherein the detection means detects a plurality of types of the nonmetallic elements.   The analysis system according to claim 8, wherein the contact means is a disposable container. A method of managing the quality of an organic semiconductor material using the analysis method according to any one of claims 1 to 7,
A method comprising the step of selecting an organic semiconductor material in which the amount of the nonmetallic element detected in the detecting step is equal to or less than a predetermined reference amount. A method for producing an organic electronics device using the analysis method according to any one of claims 1 to 7,
Selecting an organic semiconductor material in which the amount of the nonmetallic element detected in the detecting step is equal to or less than a predetermined reference amount;
And a step of manufacturing an organic electronic device using an organic semiconductor material of the same quality as the organic semiconductor material selected in the step of selecting.

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