JP2014157797A - Test piece for evaluation, evaluation method of power generation layer, and management method of manufacture facility for dye-sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a test piece for evaluation capable of simultaneously or sequentially evaluating an adsorption amount or an adsorption state of a sensitization dye to a metal oxide film of a power generation layer and electric characteristics of the power generation layer.SOLUTION: A test piece for evaluation comprises, a substrate for evaluation in which infrared light can be propagated; a counter substrate which is disposed while being spaced apart from the substrate for evaluation and through which the light is transmitted; and an electrolyte containing a redox couple interposed between the substrate for evaluation and the counter substrate. Each of the substrate for evaluation and the counter substrate is partitioned into a first region and a second region. On a board surface in the first region of the substrate for evaluation, an electron extraction layer is provided for extracting electrons from the power generation layer. In the second region and the electron extraction layer of the substrate for evaluation, the power generation layer is provided. On a board surface in the first region of the counter substrate, a reduction layer is provided through which the light is transmitted and which has a reduction capability of the electrolyte. A portion where the first region of the substrate for evaluation and the reduction layer are mutually overlapped is used as a power generation performance evaluation part and a portion where the second region of the substrate for evaluation and the reduction layer are mutually overlapped is used as a dye evaluation part.

Description

  The present invention relates to a test specimen for evaluation, a method for evaluating a power generation layer, and a method for managing a production facility for a dye-sensitized solar cell.

  In recent years, solar cells have attracted attention as a clean power source that can directly and immediately convert light energy into electric power and does not discharge pollutants such as carbon dioxide. Among solar cells, dye-sensitized solar cells are expected as next-generation solar cells because they have high conversion efficiency, are manufactured by a relatively simple method, and have a low raw material unit price.

  A dye-sensitized solar cell generally includes a transparent substrate, a counter substrate disposed opposite to the transparent substrate, an electrolyte including iodide ions sandwiched between the transparent substrate and the counter substrate, and the like. And a transparent electrode formed on the electrolyte-side plate surface of the transparent substrate, a counter electrode formed on the electrolyte-side plate surface of the counter substrate, and a power generation layer formed on the electrolyte side of the transparent electrode. The power generation layer is composed of a metal oxide film made of titanium oxide or the like and a sensitizing dye made of a ruthenium complex or the like supported on the metal oxide film. For example, Patent Document 1 discloses a dye-sensitized solar cell having the above-described configuration and using a semiconductor such as rutile-type titanium oxide or barium titanate as a metal oxide film.

  When sunlight is irradiated to the dye-sensitized solar cell having the above configuration, the sensitizing dye absorbs sunlight and emits electrons. The electrons quickly move to the metal oxide film, reach the transparent electrode, reach the counter electrode through the wiring, and reduce the triionized ions in the electrolyte to iodide ions. The reduced iodide ion is oxidized in the electrolyte and emits electrons again. By repeating such a redox reaction repeatedly, electricity flows through the dye-sensitized solar cell. Therefore, the power generation performance of the dye-sensitized solar cell is greatly affected by the amount of the sensitizing dye supported on the metal oxide film and the adsorption state of the sensitizing dye on the metal oxide film.

  As a method for examining the amount and state of adsorption of the sensitizing dye to the metal oxide film in the power generation layer, the concentration of the sensitizing dye solution, and the structure of the sensitizing dye, for example, a N719 dye as a sensitizing dye is supported on the titanium oxide film. The power generation layer is irradiated with infrared light, and absorption characteristics in infrared light are measured using multiple internal reflection Fourier transform infrared spectroscopy (hereinafter referred to as multiple internal reflection FT-IR method). An analysis method is known (see Non-Patent Document 1).

JP 2010-140811 A

Electrochemical and Solid-States Letters, 2008, 11 (7), A109

  As a method of supporting the sensitizing dye on the surface of the metal oxide film when manufacturing the above dye-sensitized solar cell, a method of immersing the metal oxide film in the sensitizing dye solution for a predetermined time is used. When the metal oxide film is immersed in a sensitizing dye solution for a certain period of time and the sensitizing dye is supported on the surface of the metal oxide film, the adsorption amount of the sensitizing dye supported on the metal oxide film, the metal oxide film and the sensitizing dye The sensitizing dye adsorption state to the metal oxide film, such as the state of chemical bonding with the sensitizing dye, the sensitizing dye concentration in the sensitizing dye solution, the type of sensitizing dye, the surface state of the metal oxide film, and the metal oxide film are sensitized. It varies greatly depending on conditions such as temperature and humidity after being immersed in the dye solution. Further, the surface state of the metal oxide film is changed by changing the pretreatment conditions of the metal oxide film, for example, changing conditions such as the baking temperature and baking time when baking the metal oxide film. As described above, the amount and state of adsorption of the sensitizing dye to the metal oxide film are easily affected by the conditions for carrying and the surrounding environment.

  The power generation performance of the dye-sensitized solar cell is evaluated by electrical characteristics such as current-voltage characteristics (hereinafter referred to as IV characteristics). The IV characteristic can be obtained by irradiating a dye-sensitized solar cell with excitation light of a power generation layer such as sunlight and measuring the current through an additional power source from the wiring connected to the transparent electrode and the wiring connected to the counter electrode. . The maximum output of the dye-sensitized solar cell can be obtained by setting the condition that the product of the current and the voltage becomes the maximum value on the photovoltaic curve obtained by the measurement. There is a correlation between the electrical characteristics of such a dye-sensitized solar cell and the amount and state of adsorption of the sensitizing dye to the metal oxide film in the power generation layer.

  Therefore, in order to produce a dye-sensitized solar cell having excellent power generation performance with high productivity and high yield, the amount of adsorption and adsorption of the sensitizing dye to the metal oxide film of the power generation layer in the production process of the dye-sensitized solar cell It is required to evaluate both the state and the electrical characteristics of the power generation layer.

  The present invention has been made in view of the above circumstances, and an evaluation specimen capable of simultaneously or sequentially evaluating the amount and state of adsorption of a sensitizing dye to the metal oxide film of the power generation layer and the electrical characteristics of the power generation layer, It is an object to provide a method for evaluating a power generation layer and a method for managing a production facility for a dye-sensitized solar cell.

The test specimen for evaluation of the present invention is a method for measuring electrical characteristics when a power generation layer comprising a metal oxide film and a sensitizing dye carried on the metal oxide film is irradiated with light, and performing multiple internal reflection Fourier transform infrared spectroscopy. An evaluation test body for evaluating the power generation layer by structural analysis of the sensitizing dye used, and comprising an evaluation substrate comprising a high refractive index medium capable of internally transmitting infrared light for infrared spectroscopy A counter substrate disposed at a distance from the evaluation substrate and transmitting the light, and an electrolyte including a redox pair injected between the evaluation substrate and the counter substrate. A first region and a second region are defined on the evaluation substrate; an electron extraction layer for extracting electrons from the power generation layer is provided on a plate surface of the first region of the evaluation substrate; and the second region of the evaluation substrate The power generation layer on the plate surface and the electron extraction layer A reducing layer that transmits the light and has a reducing ability of the electrolyte is provided on the plate surface of the counter substrate, and the first region of the evaluation substrate and the reduction layer of the counter substrate overlap each other. The power generation performance evaluation unit for measuring the electrical characteristics of the power generation layer is used for analyzing the structure of the sensitizing dye in the portion where the second region of the evaluation substrate and the reduction layer of the counter substrate overlap each other It is characterized by being a dye evaluation section.
In the test specimen for evaluation of the present invention, it is preferable that the reduction layer is made of a metal having high conductivity.

The method for evaluating a power generation layer according to the present invention includes the step of preparing the evaluation specimen, and the evaluation specimen from the counter substrate side with the electron extraction layer and the reduction layer of the evaluation specimen as terminals. A measuring step of irradiating light to the power generation performance evaluation section of the power generation layer to measure the electrical characteristics of the power generation layer, and internally transmitting infrared light to the evaluation substrate of the test specimen for evaluation, thereby performing multiple internal reflection Fourier transform red Measuring the absorption characteristics of the evaluation sensitizing dye by external spectroscopy, and analyzing the chemical structure of the evaluation sensitizing dye, and performing the measurement step and the analysis step simultaneously or sequentially. Features.
In the power generation layer evaluation method of the present invention, the reduction layer is preferably made of a highly conductive metal.

  The method for managing the production facility for a dye-sensitized solar cell according to the present invention is the method for evaluating the power generation layer in the production facility for the dye-sensitized solar cell, and the dye-sensitized solar cell based on the evaluation result of the power generation layer. It is characterized by controlling the surrounding environment of the manufacturing facility.

  According to the test specimen for evaluation, the method for evaluating the power generation layer, and the method for producing the dye-sensitized solar cell of the present invention, the amount and state of adsorption of the sensitizing dye to the metal oxide film in the power generation layer, and the electrical characteristics of the power generation layer Can be evaluated.

It is a top view which shows the test body for evaluation which is embodiment of this invention. It is a figure which shows the test body for evaluation which is embodiment of this invention, Comprising: (a) is sectional drawing at the time of seeing by the AA line shown in FIG. 1, (b) is B shown in FIG. It is sectional drawing at the time of seeing an arrow by -B line. It is a figure which shows operation | movement of the test body for evaluation which is embodiment of this invention, Comprising: It is an enlarged view of the X area | region shown to Fig.2 (a). It is the elements on larger scale which show the measurement principle of the test body for evaluation which is embodiment of this invention. It is a figure which shows the manufacturing process of the test body for evaluation which is embodiment of this invention, Comprising: (a), (b) is a top view, (c) is an arrow view by the CC line | wire shown to (b). FIG. It is a figure which shows the manufacturing process of the test body for evaluation which is embodiment of this invention, Comprising: (a), (b) is a top view, (c) is an arrow view by the DD line | wire shown to (b). FIG. It is sectional drawing which shows the manufacturing process of the test body for evaluation which is embodiment of this invention. It is a graph which shows the IV characteristic of the electric power generation layer in the test body for evaluation of Example 1 and Example 2. FIG.

  Hereinafter, an evaluation test body and a method for evaluating a power generation layer and a method for producing a dye-sensitized solar cell, which are embodiments of the present invention, will be described with reference to the drawings. The drawings used in the following description are schematic, and the length, width, thickness ratio, and the like are not necessarily the same as actual ones, and can be changed as appropriate.

  The test specimen 41 for evaluation which is an embodiment of the present invention is used for evaluating a power generation layer in a photoelectric conversion element such as a dye-sensitized solar cell. As shown in FIG. A power generation performance evaluation unit 61 for measuring electrical characteristics such as characteristics, a dye evaluation unit 62 for performing concentration measurement and structural analysis of the sensitizing dye of the power generation layer 45 using the multiple internal reflection FT-IR method, Is a test body.

  The evaluation test body 41 includes at least an evaluation substrate 42, a counter substrate 43, an electrolyte 44, a power generation layer 45, an electron extraction layer 52, and a reduction layer 53. Further, an injection hole 49 for an electrolyte 44 is provided in the counter substrate 43 and the reduction layer 53 of the evaluation test body 41 of the present embodiment, and the evaluation test body 41 of the present embodiment includes glass plates 55 and 57, and Sealing materials 47 and 56. In addition, the evaluation test body 41 of the present embodiment includes a wiring 58 and an electrical characteristic measuring device 65. In FIG. 1, illustration of the injection hole 49, the sealing materials 47 and 56, the glass plates 55 and 57, the wiring 58, and the electrical characteristic measuring device 65 is omitted. Hereinafter, each component will be sequentially described.

  The evaluation substrate 42 is made of a high refractive index medium capable of internally propagating infrared light for infrared spectroscopy such as a multiple internal reflection FT-IR method. Examples of such a high refractive index medium include silicon and gallium arsenide. A silicon substrate (hereinafter referred to as an Fz silicon substrate) made by a floating zone method is suitable as the evaluation substrate 42 from the viewpoint of extremely low loss of infrared light propagated internally. In addition, when measuring the absorption characteristics of infrared light for infrared spectroscopy of the sensitizing dye 82 of the power generation layer 45, infrared light is propagated internally to the evaluation substrate 42. Considering the refractive index of the high refractive index medium, the incident angle of infrared light, etc., the end face 42c for introducing infrared light, the plate surfaces 42a and 42b for propagating infrared light, and the infrared light are evaluated. It is preferable that the end face 42d led out to the outside of the working substrate 42 is set so as to be positioned at an angle suitable for each other (see FIGS. 3 and 4).

  The evaluation substrate 42 is partitioned into a first region 71 for forming the power generation performance evaluation unit 61 shown in FIG. 1 and a second region 72 for forming the dye evaluation unit 62 shown in FIG. .

  The counter substrate 43 is disposed at a distance from the evaluation substrate 42 and is composed of a medium that transmits light applied to the power generation layer 45. That is, the counter substrate 43 is made of a medium that transmits the light irradiated to the counter substrate 43 from the outside of the evaluation test body 41 and reaches the power generation layer 45 as indicated by arrows in FIG. When the power generation layer 45 is used in a solar cell like the test specimen 41 for evaluation of the present embodiment, the power generation layer 45 is irradiated with sunlight, so that the counter substrate 43 is a glass substrate that transmits sunlight, A plastic substrate is preferred. Examples of such a glass substrate include common glasses such as soda lime glass, borosilicate glass, quartz glass, borosilicate glass, Vycor glass, non-alkali glass, blue plate glass, and white plate glass. Examples of the plastic substrate include polyacrylic resin, polycarbonate resin, polyester resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, and polyamide resin.

  As shown in FIGS. 1 and 2, the electrolyte 44 is injected between the evaluation substrate 42 and the counter substrate 43, and an oxidation-reduction pair that generates an oxidation-reduction reaction for causing electricity to flow in the power generation performance evaluation unit 61. Contains substances. Examples of such a redox pair include iodine redox. In the electrolyte 44 containing iodine redox, for example, lithium iodide and iodine are mixed in a non-aqueous solvent such as acetonitrile or propionitrile, or a solvent such as dimethylpropylimidazolium iodide or butylmethylimidazolium iodide. The resulting solution is used.

  The side of the electrolyte 44 is sealed with a sealing material 47. The counter substrate 43 and the reduction layer 53 described later are provided with injection holes 49 for injecting the electrolyte 44 into the internal space formed between the evaluation substrate 42 and the counter substrate 43. After the electrolyte 44 is injected into the internal space, the injection hole 49 is closed by a glass plate 55 such as a glass plate, and further sealed by a sealing material 56 and a glass plate 57 from above the glass plate 55. Yes. Examples of the sealing materials 47 and 56 include a material cured by using a mixture of a photocurable resin and a thermosetting resin.

The power generation layer 45 is a layer to be evaluated using the test specimen 41 for evaluation, and includes a metal oxide film 81 used in the dye-sensitized solar cell and a sensitizing dye 82 supported on the metal oxide film 81. (See FIG. 3). The metal oxide film 81 is made of a metal material 81P that can form a porous structure. Titanium oxide (TiO ₂ ) is preferable as the metal material 81P because it can form a nano-order porous structure and a surface area much larger than the surface area of the lower layer can be obtained.

  The sensitizing dye 82 is adsorbed on the surface of the metal material 81P, and light such as sunlight is irradiated through the counter substrate 43 from the outside of the evaluation test body 41 as shown by the arrows in FIG. At this time, electrons are emitted to the metal oxide film 81. The metal oxide film 81 made of the metal material 81P having a wide band gap and having an absorber only in the ultraviolet region like titanium oxide receives electrons from the sensitizing dye 82 in this way. Examples of the sensitizing dye 82 include organic dyes such as ruthenium complex, cyanine and chlorophyll. A ruthenium complex is preferable as the sensitizing dye 82 because it absorbs a wide wavelength range, has a long photoexcitation lifetime, and stabilizes the electrons guided to the metal oxide film 81. Di (thiocyanato) -bis (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) (sometimes referred to as N3), cis-di (thiocyanato) -bis (2,2′- Bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) bis-tetrabutylammonium salt (sometimes referred to as N719), tri (thiocyanato)-(4,4 ′, 4 ″ -tricarboxy-2, 2 ′: 6 ′, 2 ″ -terpyridine) ruthenium tris-tetrabutylammonium salt (sometimes referred to as black dye).

As shown in FIGS. 1 and 2, the electron extraction layer 52 is formed on the plate surface 42 a of the first region 71 of the evaluation substrate 42. The electron extraction layer 52 is made of a material with low electrical resistance that can reliably extract electrons transferred from the sensitizing dye 82 to the metal oxide film 81. Examples of such a low resistance material include indium oxide / tin oxide (hereinafter referred to as ITO), fluorine-doped tin oxide (hereinafter referred to as FTO), zinc oxide, tin oxide, antimony-doped tin oxide, Examples include indium oxide / zinc oxide, gallium oxide / zinc oxide, and platinum. Also include titanium tetrachloride (TiCl ₄₎ as the material of the electron extraction layer 52. The electron extraction layer 52 made of TiCl ₄ also functions as a reverse electron prevention layer of the power generation performance evaluation unit 61.

  The reduction layer 53 is formed on the plate surface 43 a of the counter substrate 43. Further, the reduction layer 53 transmits light that is transmitted from the outside of the evaluation test body 41 through the counter substrate 43 to the power generation layer 45 as indicated by an arrow shown in FIG. Has reducing ability for the pair. Accordingly, the reduction layer 53 is provided on the entire plate surface 43a, whereby the redox couple in the entire electrolyte 44 is continuously reduced.

  As shown in FIG. 2A, a wiring 58 is connected to the reduction layer 53. In view of the ability to connect the wiring 58, the reduction layer 53 is preferably made of a highly conductive metal. It is more preferable that the reducing layer 53 contains platinum from the viewpoints of high catalytic ability for oxidation-reduction reaction, stability, and high conductivity. Specifically, a platinum solution in which platinum is dissolved in a solvent such as methanol or ethanol is applied to the plate surface 43a of the counter substrate 43 and baked, thereby transmitting light irradiated toward the power generation layer 45 and electrolyte. A reduction layer 53 having a reduction ability of 44 and high conductivity is formed. Further, by using a conductive substrate provided with a thin film made of ITO or FTO (not shown) on the plate surface 43a as the counter substrate 43, the conductivity of the reducing layer 53 is improved.

  The wiring 58 is provided by connecting the electron extraction layer 52 and the reduction layer 53. The electrical characteristic measuring device 65 is disposed on the wiring 58, and includes a load power source, an ammeter, a voltmeter, and the like. The wiring 58 and the electrical property measuring device 65 send the electrons that have moved from the power generation layer 45 to the electron extraction layer 52 to the reduction layer 53, and the electrical properties when an applied voltage is applied to the power generation layer 45 are obtained as measured values. .

  As shown in FIG. 2A, the power generation performance evaluation unit 61 includes a portion where the first region 71 of the evaluation substrate 42 and the reduction layer 53 overlap each other. With the configuration shown in FIG. 2A, the power generation performance evaluation unit 61 measures electrical characteristics such as IV characteristics when the power generation layer 45 is irradiated with light. FIG. 3 is a diagram for explaining the oxidation-reduction reaction in the power generation performance evaluation unit 61. The oxidation-reduction pair of the electrolyte 44 is iodine redox, the metal material 81P of the metal oxide film 81 is titanium oxide, and the sensitizing dye. The case where 82 is a ruthenium complex is illustrated.

As shown by the arrows in FIG. 3, light such as sunlight transmitted through the counter substrate 43 of the power generation performance evaluation unit 61 is absorbed by the sensitizing dye 82 supported on the metal oxide film 81 of the power generation layer 45. . The light absorption causes the sensitizing dye 82 to change from the ground state to the excited state. Electrons of the excited state sensitizing dye 82 are injected into the conduction band of the metal material 81P, and the ruthenium complex is oxidized. The electrons injected into the metal oxide film 81 move in the metal material 81P and are extracted to the electron extraction layer 52. By providing the electron extraction layer 52 having a low electrical resistance, the oxidant of the sensitizing dye 82 or the triiodide ion of the electrolyte 44 when the electrons injected into the metal oxide film 81 move in the metal material 81P. Recombination with (I ₃ ⁻ ) can be prevented. The electrons extracted to the electron extraction layer 52 move to the reduction layer 53 through the wiring 58. On the other hand, the oxidized sensitizing dye 82 receives electrons from the iodide ion (I ⁻ ) of iodine redox and is reduced to the ground state. The iodide ions are oxidized to triiodide ions, diffused in the electrolyte 44, and move to the reducing layer 53. The triiodide ions receive electrons from the reduction layer 53 and return to iodide ions. Through such a series of cycles, electricity flows in the power generation performance evaluation unit 61 as in the dye-sensitized solar cell. Therefore, an IV characteristic is obtained by applying an applied voltage by the electrical characteristic measuring device 65 provided in the wiring 58 and sweeping the current from the power generation layer 45.

As shown in FIG. 2B, the dye evaluation unit 62 includes a portion where the second region 72 of the evaluation substrate 42 and the reduction layer 53 overlap each other. With the configuration shown in FIG. 2 (b), the dye evaluation unit 62 evaluates the initial test body immediately after creation and the test body at the time of evaluation by the multiple internal reflection method, and calculates the difference between the evaluation results by calculation. Evaluation is made.
FIG. 4 is a diagram illustrating a state in which the absorption characteristics of the sensitizing dye 82 of the power generation layer 45 using the multiple internal reflection FT-IR method are measured in the dye evaluation unit 62. The evaluation substrate 42 and the electrolytic solution The components of the test specimen 41 for evaluation other than 44, the power generation layer 45 and the sealing material 47 are not shown.

  As shown in FIG. 4, the infrared light for the multiple internal reflection FT-IR method introduced into the evaluation substrate 42 from the end face 42c is caused by the difference in refractive index between the high refractive index medium and the outside thereof. It propagates through the internal space 85 while repeating the reflection at 42a and 42b. At this time, in order for the infrared light to be totally reflected on the plate surfaces 42a and 42b with a low loss, the infrared light is made to be an evaluation substrate so as to form an angle larger than the critical angle with respect to the normal line of the plate surfaces 42a and 42b. 42 is preferably introduced.

  The power of infrared light propagating through the evaluation substrate 42 first changes in accordance with the infrared light absorption characteristics of the components outside the evaluation substrate 42 such as the electrolyte 44 every time it is reflected by the plate surface 42a. When reaching the end face 45b of the power generation layer 45 in contact with the evaluation substrate 42, the power of the infrared light changes according to the infrared light absorption characteristics of the power generation layer 45 every time it is reflected by the plate surface 42a. Thereafter, each time the light is reflected on the plate surface 42a, the power of the infrared light is derived again from the end face 42d of the evaluation substrate 42 under the influence of the infrared light absorption characteristics of the components outside the evaluation substrate 42. The Thus, the infrared light emitted from the end face 42d of the evaluation substrate 42 reflects the infrared light absorption characteristics of the electrolyte 44, the power generation layer 45, the sealing material 47, and the like. Therefore, by comparing the infrared light absorption characteristics of the components outside the evaluation substrate 42 acquired in advance with the characteristics reflected in the infrared light derived from the end face 42d of the evaluation substrate 42, the power generation layer 45 Infrared absorption characteristics can be obtained.

  According to the evaluation specimen 41 of the present embodiment described above, the electrolyte 44 and the power generation layer 45 are oxidized in the power generation performance evaluation unit 61 in which the electron extraction layer 52 is formed only in the first region 71 of the evaluation substrate 42. The reduction reaction can be continuously generated, and electrical characteristics such as the IV characteristics of the power generation layer 45 can be obtained. Further, in the second region 72 of the evaluation substrate 42, the power generation layer 45 uses the multiple internal reflection FT-IR method in the dye evaluation unit 62 in contact with the evaluation substrate 42 capable of internally transmitting infrared light. An absorption characteristic for 45 infrared light is obtained. Acquisition of the electrical characteristics of the power generation layer 45 and acquisition of the absorption characteristics may be performed simultaneously or sequentially. Thus, by obtaining both the electrical characteristics of the power generation layer 45 and the absorption characteristics with respect to infrared light using the single test specimen 41 for evaluation, a more accurate evaluation of the power generation layer 45 is performed.

  Next, an evaluation method of the power generation layer 45 using the evaluation test body 41 of this embodiment will be described. The method for evaluating the power generation layer 45 includes a step of preparing the test specimen 41 for evaluation, a measurement step of measuring the electrical characteristics of the power generation layer 45, and measuring the absorption characteristics of the sensitizing dye 82 of the power generation layer 45 to determine the chemical structure. An analysis process for analysis. Hereinafter, each process will be described sequentially.

[Step of preparing test specimen for evaluation]
As shown in FIG. 5A, for example, an Fz substrate is prepared as the evaluation substrate 42 and is divided into a first region 71 and a second region 72. Subsequently, as shown in FIGS. 5B and 5C, the electron extraction layer 52 is formed on the plate surface 42 a of the first region 71 of the evaluation substrate 42. For the electron extraction layer 52, ITO, FTO, or the like can be used. In that case, the electron extraction layer 52 can be formed by, for example, a sputtering method or a printing method. Further, by applying TiCl ₄ only to the plate surface 42 a of the first region 71 of the evaluation substrate 42, the electron extraction layer 52 can be formed.

  Next, as shown in FIG. 6A, for example, a glass substrate is prepared as the counter substrate 43, and the reduction layer 53 is formed on the plate surface 43 a of the counter substrate 43. The reduction layer 53 can be formed by applying a solution obtained by dissolving platinum in a solvent such as methanol or ethanol to the plate surface 43a of the counter substrate 43 and baking the solution. Thereafter, as shown in FIGS. 6B and 6C, an injection hole 49 for injecting an electrolytic solution between the evaluation substrate 42 and the counter substrate 43 later is formed by a method such as patterning. And it forms so that the reduction | restoration layer 53 may be penetrated.

  Next, as shown in FIG. 7A, the power generation layer 45 is formed on the electron extraction layer 52 and on the plate surface 42 a of the second region 72 of the evaluation substrate 42 (not shown). As shown in FIG. 3, the power generation layer 45 forms a metal oxide film 81 on the electron extraction layer 52 and at a predetermined position on the plate surface 42 a of the second region 72, and then a sensitizing dye 82 on the metal oxide film 81. Can be formed. The formation method of the metal oxide film 81 is not particularly limited. For example, a method of performing a heat treatment after spin-coating a solution containing the metal material 81P, an AD method or a cold spray in which the metal material 81P is powdered. Examples thereof include a method of forming a film by a powder spraying method such as a method. Further, as a method of supporting the sensitizing dye 82 on the metal oxide film 81, a method of immersing the metal oxide film 81 in a solution of the sensitizing dye 82 can be mentioned. The power generation layer 45 is used for conditions such as the concentration of the sensitizing dye 82 in the solution, the immersion time, the surface state of the metal oxide film 81 to be immersed, and the temperature and humidity after the metal oxide film 81 is immersed in the solution. What is necessary is just to determine suitably according to a use.

  Next, as shown in FIG. 7B, a sealing material 47 having an appropriate thickness is disposed so as to surround a space S into which an electrolytic solution will be injected later. Here, the appropriate thickness indicates a thickness comparable to the thickness of the electrolytic solution 44 shown in FIGS. 2 (a) and 2 (b). Subsequently, the first region 71 of the evaluation substrate 42 and the reduction layer 53 of the counter substrate 43 overlap each other, and the second region 72 of the evaluation substrate 42 and the reduction layer 53 of the counter substrate 43 overlap each other. The counter substrate 43 shown in FIG. 6C is arranged to face the evaluation substrate 42 with the reduction layer 53 of the counter substrate 43 shown in FIG. 6C facing the electron extraction layer 52 side. Thereafter, the sealing material 47 is cured by an appropriate curing process. As a curing step when a mixture of a photocurable resin and a thermosetting resin is used as the sealing material 47, for example, after irradiation with ultraviolet rays from the counter substrate 43 side, it is held and allowed to stand at a temperature of about 80 ° C. The process to do is mentioned.

Next, an electrolyte 44 is injected into the space S formed by the evaluation substrate 42, the sealing material 47, and the counter substrate 43 shown in FIG. Thereafter, as shown in FIG. 7C, the upper part of the injection hole 49 is closed with a glass plate 55. The upper portions of the counter substrate 43 and the glass plate 55 are sequentially covered with the sealing material 56 and the glass plate 57, and the sealing material 56 is cured by an appropriate curing process.
Through the above steps, an evaluation test body 41 including a power generation performance evaluation unit 61 and a dye evaluation unit 62 as shown in FIGS. 1 and 2 is completed.

[Measurement process]
In order to measure the electrical characteristics of the power generation layer 45 provided in the manufactured test specimen 41 for evaluation, first, the electron extraction layer 52 and the reduction layer 53 of the power generation performance evaluation section 61 of the test specimen 41 for evaluation are connected by the wiring 58. Then, an electrical characteristic measuring device 65 is provided on the wiring 58. Subsequently, an applied voltage is applied from the electrical characteristic measuring device 65 to the reducing layer 53 to cause an oxidation-reduction reaction (see FIG. 3) in the electrolyte 44, and the current from the power generation layer 45 is passed through the electron extraction layer 52 and the wiring 58. Via the electrical characteristic measuring device 65. By measuring the current from the power generation layer 45 while changing the applied voltage, the IV characteristics of the power generation layer 45 of the power generation performance evaluation unit 61 can be accurately measured.

[Analysis process]
In order to perform concentration measurement and structural analysis of the sensitizing dye 82 of the power generation layer 45 provided in the manufactured test specimen 41 for evaluation, first, infrared spectroscopy is applied to the evaluation substrate 42 of the dye evaluation section 62 of the test specimen 41 for evaluation. The test specimen 41 for evaluation is installed in an infrared spectrometer (not shown) that performs measurement by the multiple internal reflection FT-IR method so that infrared light for use is introduced. Subsequently, as described with reference to FIG. 4, the infrared light from the infrared spectroscopic measurement device is propagated internally by the evaluation substrate 42 of the dye evaluation unit 62 of the evaluation test body 41, and the power generation layer 45 Measure the absorption characteristics for infrared light. By comparing the measurement results with the absorption characteristics of the metal oxide film 81 and the electrolyte 44 of the power generation layer 45 measured with respect to the infrared light, the absorption characteristics of the sensitizing dye 82 with respect to the infrared light can be obtained. Then, by analyzing the absorption characteristic of the sensitizing dye 82 with respect to the infrared light, the chemical structure of the sensitizing dye 82 and its change can be analyzed.

  In the method for evaluating the power generation layer 45 described above, the measurement step and the analysis step may be performed simultaneously or sequentially.

  As described above, in the method for evaluating the power generation layer 45 of the present embodiment, the IV characteristics of the power generation layer 45 are obtained using the evaluation test body 41 including the power generation performance evaluation unit 61 and the dye evaluation unit 62. In addition, the concentration, chemical structure and change of the sensitizing dye 82 can be obtained by analyzing the measurement result of the absorption characteristic for infrared light using the multiple internal reflection FT-IR method.

  Next, a method for managing a production facility for a dye-sensitized solar cell using the test specimen 41 for evaluation of the present embodiment will be described.

  A dye-sensitized solar cell manufacturing facility (not shown) is a facility that can perform the same steps as the steps of the method for evaluating the power generation layer 45 described above. However, in the dye-sensitized solar cell, a transparent substrate such as a resin film or a glass plate is used instead of the evaluation substrate 42 of the evaluation test body 41, and the transparent substrate is partitioned into a first region and a second region. Instead, it is manufactured by forming a transparent conductive layer made of the same material as that of the electron extraction layer 52 on one whole plate surface. Further, a counter conductive layer and a reduction layer are formed on the plate surface of the counter substrate.

  In the method for managing the production facility of the dye-sensitized solar cell, the material, the formation method, and the surrounding environment of the power generation layer 45 including the metal oxide film 81 and the sensitizing dye 82 are the same in the production facility of the dye-sensitized solar cell. Except for aligning, the dye-sensitized solar cell and the test specimen 41 for evaluation are manufactured in parallel using materials suitable for each component while setting and implementing an appropriate formation method and surrounding environment. . And in the formation stage of the electric power generation layer 45 in the dye-sensitized solar cell and the test body 41 for evaluation, the evaluation method of the electric power generation layer 45 demonstrated above is implemented, and the manufacturing equipment of a dye-sensitized solar cell based on the obtained result Control the surrounding environment. Specifically, when the IV characteristics of the power generation layer 45 obtained by the evaluation method of the power generation layer 45 and the result of the structural analysis of the sensitizing dye 82 do not satisfy the predetermined conditions, the production of the dye-sensitized solar cell is performed. The surrounding environment may be changed so as to satisfy the predetermined condition by applying feedback control to the surrounding environment of the facility.

  In the method for managing the production facility of the dye-sensitized solar cell according to the present embodiment, the power generation layer 45 is subjected to a predetermined condition based on the electrical characteristics of the power generation layer 45 obtained by the evaluation method of the power generation layer 45 and the structural analysis of the sensitizing dye 82. It is possible to accurately determine whether it is manufactured, increase the productivity of the dye-sensitized solar cell, and manufacture with good yield.

  The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific embodiments, and various modifications are possible within the scope of the gist of the present invention described in the claims. Deformation / change is possible.

  Next, the present invention will be described in detail by the following examples, but the present invention is not limited only to these examples.

Example 1
First, an Fz silicon substrate was prepared as an evaluation substrate, and the center in the longitudinal direction of the substrate was defined as a second region, and both sides thereof were classified as a first region. Next, an electron extraction layer made of ITO is formed on one plate surface of the Fz silicon substrate in the first region by sputtering. Then, a TiO ₂ paste is applied by screen printing so as to straddle the electron extraction layer and the one surface of the Fz silicon substrate in the second region, and baked at 500 ° C. to oxidize the metal oxide composed of TiO _2. A film was formed. Next, the metal oxide film was immersed for 24 hours at a temperature of 30 ° C. in an immersion tank containing N719 and a sensitizing dye solution containing N719 and a 1: 1 mixed solvent of acetonitrile and t-butanol. Thus, a power generation layer in which a sensitizing dye was supported on a metal oxide film was formed.

  Next, a counter substrate (hereinafter referred to as an FTO glass substrate) made of glass with one surface coated with FTO was prepared. Next, a platinum solution in which platinum was dissolved in a solvent such as methanol or ethanol was applied on the FTO, and then fired at 500 ° C. for 120 minutes to form a reduced layer made of platinum.

  Next, in order to form a space for injecting an electrolyte between the Fz silicon substrate and the FTO glass substrate, an ultraviolet curable resin and a predetermined position on one plate surface of the Fz silicon substrate or the FTO glass substrate The sealing material which consists of sealing resin which mixed thermosetting resin was arrange | positioned. Next, the first and second regions of the Fz silicon substrate and the FTO glass substrate overlap with each other, and the Fz silicon substrate and the FTO glass substrate face each other so that one plate surface of each of the Fz silicon substrate and the FTO glass substrate faces each other. An FTO glass substrate was placed with a sealing material interposed. Then, this sealing material is hardened, and an electrolytic solution (trade name: Iodolite AN-50 (tradename: Iodolite AN-50) of acetonitrile solvent in a space formed between the Fz silicon substrate and the FTO glass substrate. An electrolyte solution made of Sola Nonix Co., Ltd. was injected, and the injection hole was sealed with a glass plate, and the sealing material made of the sealing resin and the glass plate were sequentially stacked on the glass plate and sealed. Thus, the test specimen A for evaluation shown in FIGS. 1 and 2 was obtained.

(Example 2)
By replacing the electron extraction layer made of ITO with the same material as in Example 1 except that one plate surface of the Fz silicon substrate in the first region is treated with TiCl ₄ , A test specimen B for evaluation was obtained.

(Comparative Example 1)
Other than forming an electron extraction layer made of ITO on the entire surface of the Fz silicon substrate and applying the TiO ₂ paste so as to straddle the one surface of the Fz silicon substrate in the first and second regions. Obtained the test body C for evaluation by performing the same operation using the same material as in Example 1.

(Comparative Example 2)
Except for applying the TiO ₂ paste so as to straddle the one surface of the Fz silicon substrate in the first and second regions without forming the electron extraction layer made of ITO in the first region of the Fz silicon substrate. A test specimen D for evaluation was obtained by performing the same operation using the same material as in Example 1.

(Evaluation of power generation performance of power generation layer using test specimens A to D for evaluation)
In each of the test specimens A to C obtained in Examples 1 and 2 and Comparative Example 1, as shown in FIG. 2 (a), the electron extraction layer and the reduction layer are connected by wiring, and an electrical property measuring device Arranged. Since the test sample D for evaluation obtained in Comparative Example 2 was not formed with an electron extraction layer, the Fz silicon substrate of the test sample for evaluation D and the reducing layer were connected by wiring, and an electrical property measuring device was arranged. Subsequently, the IV characteristic of the power generation layer of each of the test specimens for evaluation A to D was obtained using an electrical characteristic measuring device. FIG. 8 shows a graph of the IV characteristics of the power generation layers of the test specimens A and B for evaluation in Example 1 and Example 2. Thereafter, as shown by arrows in FIG. 2 (a), energy from a commercially available LED light (manufactured by Panasonic Corporation, illuminance: 46 k lux) is irradiated onto the test specimens A to D for evaluation from the counter substrate side. Conversion efficiency was measured. Table 1 shows the open-circuit voltage (V _oc ), short-circuit current (J _sc ), fill factor (FF), and energy conversion efficiency (PCE) in the IV characteristics of the power generation layer of each test specimen A to _D.

  As can be seen from Table 1, by providing a current extraction layer in the first region of the evaluation specimens A and B of Example 1 and Example 2 to which the present invention is applied, each evaluation specimen A, The electric characteristics such as the IV characteristic of the power generation layer of B have been acquired well. In the evaluation specimen C of Comparative Example 1, electrical characteristics such as IV characteristics were obtained well, but in the evaluation specimen D of Comparative Example 2, the electron extraction layer was not formed. Thus, it was impossible to measure the electrical characteristics.

(Evaluation of sensitizing dye of power generation layer using test specimens A to D for evaluation)
Next, the Fz silicon substrate side of each of the test specimens A to D for Examples 1 and 2 and Comparative Examples 1 and 2 is opposed to a multiple internal reflection FT-IR measuring device (trade name: MB100 (BOMEN)). Then, while irradiating the evaluation specimens A to D with the same light as when the energy conversion efficiency was measured, the multiple power generation layers of the evaluation specimens A to D were increased using the multiple internal reflection FT-IR method. The chemical structure of the dye was analyzed. Table 1 shows the evaluation results of the infrared light transmittance in each of the test specimens A to D for analysis.

  In the column of “Infrared light transmissivity” in Table 1, an evaluation test D, that is, an evaluation test in which an electron extraction layer is not formed in any of the first region and the second region of the Fz silicon substrate. The infrared light transmittance of the body was described as a reference “◎”. Although the test specimen A for evaluation has a lower infrared light transmittance than the test specimen D for evaluation, the signal-to-noise ratio of the spectrum obtained with the multiple internal reflection FT-IR measurement apparatus is good, and the chemical structure of the sensitizing dye is An analyzable spectrum could be obtained. Although the test specimen B for evaluation was barely able to obtain a spectrum, the signal-to-noise ratio of the spectrum was poor, and it was difficult to analyze the chemical structure of the sensitizing dye. The test specimen C for evaluation did not pass infrared light at all, and analysis of the chemical structure of the sensitizing dye was impossible.

  As described above, according to the present invention, in the power generation performance evaluation unit in which the electron extraction layer is formed only in the first region of the Fz silicon substrate, electrical characteristics such as the IV characteristics of the power generation layer can be obtained. It was confirmed. In addition, it was confirmed that the power generation layer absorbs infrared light with the power generation layer using the multiple internal reflection FT-IR method in the dye evaluation section formed by contacting the power generation layer with an Fz silicon substrate capable of internally transmitting infrared light. did.

  DESCRIPTION OF SYMBOLS 41 ... Test body for evaluation, 42 ... Substrate for evaluation, 43 ... Counter substrate, 44 ... Electrolyte, 52 ... Electron extraction layer, 53 ... Reduction layer, 61 ... Power generation performance evaluation part, 62 ... Dye evaluation part, 71 ... First Area, 72 ... second area

Claims (5)

Measurement of electrical characteristics of a power generation layer composed of a metal oxide film and a sensitizing dye supported on the metal oxide film, and structural analysis of the sensitizing dye using multiple internal reflection Fourier transform infrared spectroscopy A test specimen for evaluation for evaluating the power generation layer according to
An evaluation substrate made of a high refractive index medium capable of internally transmitting infrared light for infrared spectroscopy;
A counter substrate disposed at a distance from the evaluation substrate and transmitting the light;
An electrolyte containing an oxidation-reduction pair injected between the evaluation substrate and the counter substrate,
A first region and a second region are defined on the evaluation substrate;
An electron extraction layer for extracting electrons from the power generation layer is provided on the plate surface of the first region of the evaluation substrate,
The power generation layer is provided on the plate surface of the second region of the evaluation substrate and the electron extraction layer,
A reducing layer that transmits the light and has a reducing ability of the electrolyte is provided on a plate surface of the counter substrate;
A portion where the first region of the evaluation substrate and the reduction layer of the counter substrate overlap each other is a power generation performance evaluation unit for measuring electrical characteristics of the power generation layer, and the second region of the evaluation substrate and the counter A test specimen for evaluation characterized in that a portion where the reduction layers of the substrate overlap each other serves as a dye evaluation unit for analyzing the structure of the sensitizing dye.   The test specimen for evaluation according to claim 1, wherein the reduction layer is made of a highly conductive metal. Preparing a test specimen for evaluation according to claim 1;
Measurement of measuring the electrical characteristics of the power generation layer by irradiating the power generation performance evaluation section of the test body for evaluation from the counter substrate side with the electron extraction layer and the reduction layer of the evaluation test body as terminals. Process,
Infrared light is propagated internally to the evaluation substrate of the evaluation test body, and the absorption characteristics of the evaluation sensitizing dye are measured by multiple internal reflection Fourier transform infrared spectroscopy, and the evaluation sensitizing dye An analysis process for analyzing the chemical structure,
A method for evaluating a power generation layer, wherein the measurement step and the analysis step are performed simultaneously or sequentially.  The power generation layer evaluation method according to claim 3, wherein the reduction layer is made of a highly conductive metal. The method for evaluating a power generation layer according to claim 3 or 4 is carried out in a production facility for a dye-sensitized solar cell, and the surrounding environment of the production facility for the dye-sensitized solar cell is controlled based on an evaluation result of the power generation layer. A method for managing a production facility for a dye-sensitized solar cell.

Images