JP5499419B2 - Test specimen for evaluation, method for evaluating sensitizing dye, method for producing dye-sensitized solar cell - Google Patents

Description

  The present invention relates to a test specimen for evaluation, a method for evaluating a sensitizing dye, and a method for producing a dye-sensitized solar cell, and in particular, a sensitizing dye contained in a dye-sensitized solar cell in the middle of production in which an electrolytic solution is sealed. The present invention relates to a method for evaluating a sensitizing dye that can be easily evaluated with high accuracy.

In recent years, among solar cells, dye-sensitized solar cells (see, for example, Patent Document 1) have attracted attention as solar cells that have a high degree of freedom in shape, can be easily manufactured, and have excellent photoelectric conversion efficiency. .
In general, a dye-sensitized solar cell includes a transparent substrate, a counter substrate disposed opposite to the transparent substrate, an electrolytic solution sandwiched and sealed between the transparent substrate and the counter substrate, and electrolysis of the transparent substrate. A metal oxide film made of a transparent electrode formed on the liquid side surface, a counter electrode formed on the surface of the counter substrate on the electrolyte side, and titanium oxide formed on the surface of the transparent substrate facing the counter substrate And a sensitizing dye made of a ruthenium complex supported on a metal oxide film.

When such a dye-sensitized solar cell is irradiated with light, the light is absorbed by the sensitizing dye and the electrons of the sensitizing dye are excited. The excited electrons move from the sensitizing dye to the transparent electrode through the metal oxide film and contribute to power generation.
Therefore, the power generation performance such as the photoelectric conversion efficiency of the dye-sensitized solar cell is greatly affected by the adsorption amount of the sensitizing dye supported on the metal oxide film and the adsorption state of the sensitizing dye on the metal oxide film. receive.
Further, as a method of supporting a sensitizing dye on the surface of the metal oxide film, a method of immersing the metal oxide film in a sensitizing dye solution for a certain time is generally used.

JP 2010-140811 A

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

  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 or the metal oxide film The adsorption state of the sensitizing dye to the metal oxide film, such as the state of chemical bonding between the sensitizing dye and the sensitizing dye, is the concentration of the sensitizing dye in the sensitizing dye solution, the type of sensitizing dye, the surface state of the metal oxide film, the metal It varies greatly depending on conditions such as temperature and humidity after the oxide film is immersed in the sensitizing dye solution. In addition, the surface state of the metal oxide film can be changed by changing the pretreatment conditions of the metal oxide film, for example, by changing conditions such as the firing temperature and firing time when firing the metal oxide film. To do.

As described above, the adsorption amount and adsorption state of the sensitizing dye to the metal oxide film are easily affected by the conditions for loading. For this reason, in order to produce a dye-sensitized solar cell having excellent power generation performance with a high yield, it is possible to examine the amount and state of adsorption of the sensitizing dye to the metal oxide film in the production process of the dye-sensitized solar cell. It is requested.
In addition, in order to produce a dye-sensitized solar cell having excellent power generation performance, the concentration of the sensitizing dye solution used when the sensitizing dye is supported on the surface of the metal oxide film and the structure of the sensitizing dye are examined. Is required.

Methods for examining the amount and state of adsorption of the sensitizing dye to the metal oxide film, the concentration of the sensitizing dye solution and the structure of the sensitizing dye include NMR (nuclear magnetic resonance method) and Uv-vis (UV-visible spectroscopic analysis). Method), FT-IR (Fourier transform infrared spectroscopy) single reflection ATR method (attenuated total reflection method) and the like.
However, these analytical methods cannot measure the adsorption state of the sensitizing dye on the metal oxide film and the structure of the sensitizing dye in the sensitizing dye solution with high accuracy.

More specifically, for example, the present inventor tried to confirm the concentration and structure of the sensitizing dye dissolved in the sensitizing dye solution using NMR. However, ¹ HNMR (proton nuclear magnetic resonance) of an NMR measurement sample obtained by collecting a certain amount of a sensitizing dye solution and mixing with a heavy solvent for NMR measurement was accumulated 10,000 times or more. No SN (signal to noise ratio) was obtained.

  In addition, in order to confirm the concentration and structure of the sensitizing dye dissolved in the sensitizing dye solution, the present inventor collects a certain amount of the sensitizing dye solution, dilutes with a specified amount of ethanol, and then Uv-vis. Measurements were made. As a result, it was possible to determine the concentration of the sensitizing dye, but no knowledge about the structure of the sensitizing dye was obtained.

In addition, the present inventor collects a certain amount of a metal oxide film carrying a sensitizing dye and measures ¹ H solid state NMR in order to confirm the adsorption amount and adsorption state of the sensitizing dye to the metal oxide film. did. However, the dipole interaction cannot be reduced sufficiently even though the measurement is performed by rotating at a high speed of 20 [kHz] to reduce the dipole interaction and increase the resolution. Was not obtained.

  In addition, in order to confirm the adsorption amount and adsorption state of the sensitizing dye to the metal oxide film, the present inventor collects a certain amount of the metal oxide film carrying the sensitizing dye and cleans it with an alkaline aqueous solution. Then, the sensitizing dye was detached from the metal oxide film, and the detached dye was collected and subjected to Uv-vis measurement. As a result, the adsorption amount of the sensitizing dye could be obtained, but knowledge about the adsorption state and structure of the sensitizing dye could not be obtained.

As another method for examining the amount and state of adsorption of the sensitizing dye to the metal oxide film, the concentration of the sensitizing dye solution, and the structure of the sensitizing dye, it is conceivable to use the multiple internal reflection FT-IR method. .
For example, there is a method of using a multiple internal reflection FT-IR method as a method for supporting an N719 dye as a sensitizing dye on a titanium oxide film and examining the adsorption state of the N719 dye on the titanium oxide film (for example, non-patent literature). 1). In this method, the adsorption state of the sensitizing dye to the metal oxide film can be measured.
Further, the concentration of the sensitizing dye solution and the structure of the sensitizing dye are measured by dropping the sensitizing dye solution onto the high refractive index medium of the measuring apparatus and measuring the sensitizing dye solution using the multiple internal reflection FT-IR method. Can be examined.

However, the amount and state of adsorption of the sensitizing dye to the metal oxide film is the period from when the sensitizing dye is supported on the metal oxide film until the electrolyte is sealed between the transparent substrate and the counter substrate. Susceptible to the conditions of For example, the solvent contained in the sensitizing dye solution used for adsorbing the sensitizing dye to the metal oxide film evaporates before the electrolyte solution is sealed, so that the sensitizing dye deteriorates and adsorbs. The state may change.
Therefore, even if the adsorption amount and adsorption state of the sensitizing dye to the metal oxide film are measured using the multiple internal reflection FT-IR method, the adsorption amount of the sensitizing dye that actually contributes to power generation in the dye-sensitized solar cell. And the adsorption state could not be known, and the relationship between the photoelectric conversion efficiency of the dye-sensitized solar cell and the adsorption amount and adsorption state of the sensitizing dye could not be evaluated.

  In order to know the adsorption amount and adsorption state of the sensitizing dye that actually contributes to power generation in the dye-sensitized solar cell, the metal oxide film contained in the dye-sensitized solar cell in the process of being sealed with the electrolyte is used. It is necessary to examine the adsorption state of the sensitizing dye. However, when measuring the adsorption state of the sensitizing dye on the metal oxide film by using the multiple internal reflection FT-IR method, the metal oxide film is pressed against the high refractive index medium (prism) of the measuring device to sensitize it. It is necessary to bring the pigment and the prism into close contact. In a dye-sensitized solar cell that is sealed with an electrolyte and has a substrate disposed outside the metal oxide film, the metal oxide film on which the sensitizing dye is adsorbed and the prism are brought into close contact with each other. It is not possible. Therefore, it is difficult to analyze the sensitizing dye supported on the metal oxide film of the dye-sensitized solar cell in the process of being sealed with the electrolyte solution in a nondestructive manner using the multiple internal reflection FT-IR method. there were.

  The present invention has been made in view of the circumstances as described above, and facilitates the adsorption state of a sensitizing dye supported on a metal oxide film of a dye-sensitized solar cell in the middle of production sealed with an electrolyte. It is an object of the present invention to provide a test specimen for evaluation that can be evaluated with high accuracy, a method for evaluating a sensitizing dye, and a method for producing a dye-sensitized solar cell using the method for evaluating a sensitizing dye.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved, and have completed the present invention.
(1) An evaluation test body measured using multiple internal reflection FT-IR, an evaluation substrate having a base material made of a high refractive index medium that transmits infrared light, an evaluation counter substrate, An evaluation metal oxide formed on a surface of the evaluation substrate that is sandwiched between and sealed between the evaluation substrate and the evaluation counter substrate, and the evaluation substrate on the opposite surface of the evaluation substrate. A test specimen for evaluation, comprising: a film; and an evaluation sensitizing dye supported on the metal oxide film for evaluation.

(2) The test specimen for evaluation according to (1), wherein the substrate is made of GaAs or Si.
(3) The evaluation substrate has a transparent electrode on one surface of the base material, the evaluation counter substrate has a counter electrode on one surface, and the transparent electrode of the evaluation substrate. The test specimen for evaluation according to (1) or (2), wherein the test electrode is arranged with the surface on the side of the counter electrode facing the surface on the side.

(4) Sealed by being sandwiched between an evaluation substrate having a base material made of a high refractive index medium that transmits infrared light, an evaluation counter substrate, and the evaluation substrate and the evaluation counter substrate. The evaluation electrolyte solution, the evaluation metal oxide film formed on the surface of the evaluation substrate facing the counter substrate for evaluation, and the evaluation sensitizing dye carried on the metal oxide film for evaluation And an analysis for analyzing the chemical structure of the evaluation sensitizing dye using multiple internal reflection Fourier transform infrared spectroscopy with the substrate side facing the measuring device. A method for evaluating a sensitizing dye, comprising: a step; and an evaluation step for evaluating the sensitizing dye for evaluation supported on the evaluation metal oxide film using a result of the analysis step.

(5) The method for evaluating a sensitizing dye according to (4), wherein the substrate is made of GaAs or Si.
(6) The evaluation substrate of the evaluation test body has a transparent electrode on one surface of the base material, the evaluation counter substrate has a counter electrode on one surface, and the evaluation It is arranged with the surface on the opposite electrode side facing the surface on the transparent electrode side of the substrate for analysis, while the analysis step irradiates light to the test specimen for evaluation from the counter substrate for evaluation, It is a step of analyzing the chemical structure of the sensitizing dye for evaluation using multiple internal reflection Fourier transform infrared spectroscopy, and the evaluation test is performed by irradiating the evaluation test body with light from the evaluation counter substrate side. A step of measuring the photoelectric conversion efficiency of the body, wherein the evaluation step uses the result in the analysis step and the photoelectric conversion efficiency, and the evaluation sensitizing dye supported on the evaluation metal oxide film (4) or (5), characterized in that Evaluation method of the sensitizing dyes described in.

(7) The surface on the counter electrode side of the counter substrate having the counter electrode is opposed to the surface on the transparent electrode side of the transparent substrate having the transparent electrode, and is sandwiched between the transparent substrate and the counter substrate. An intermediate product comprising: the sealed electrolyte solution; a metal oxide film formed on a surface of the transparent substrate facing the counter substrate; and the sensitizing dye carried on the metal oxide film. A step of forming, an evaluation substrate having a base material made of a high refractive index medium that transmits infrared light, and an evaluation counter substrate made of the same material as the counter substrate are arranged to face each other, and the electrolytic solution It is made of the same material, and is formed on the opposite surface of the evaluation substrate and the evaluation electrolytic solution sandwiched and sealed between the evaluation substrate and the evaluation counter substrate, and the evaluation substrate. Evaluation metal oxide film made of the same material as the metal oxide film, The step of forming a test specimen for evaluation comprising the evaluation sensitizing dye made of the same material as the sensitizing dye supported on the metal oxide film for evaluation, and the substrate side facing the measuring device, Analyzing the chemical structure of the sensitizing dye for evaluation using multiple internal reflection Fourier transform infrared spectroscopy, and using the results of the analyzing step, the metal oxide film supported on the evaluation A test body evaluation process for evaluating the sensitizing dye for evaluation, and an intermediate product evaluation process for evaluating the sensitizing dye supported on the metal oxide film, using the evaluation result in the test body evaluation process. A method for producing a dye-sensitized solar cell, comprising:

(8) In the step of forming the intermediate product, the metal oxide film is immersed in a sensitizing dye solution containing a sensitizing dye for a solar cell so that the sensitizing dye is supported on the metal oxide film, In the step of forming the evaluation specimen, the evaluation metal oxide film is immersed in the sensitizing dye solution, and the evaluation sensitizing dye is supported on the evaluation metal oxide film. The manufacturing method of the dye-sensitized solar cell as described in 7).
(9) The surface on the transparent electrode for evaluation side of the evaluation substrate having the transparent electrode for evaluation made of the same material as the transparent electrode on one surface of the base material, and the counter electrode The evaluation counter substrate having the evaluation counter electrode made of the same material as that of the evaluation counter electrode side is disposed so as to face the evaluation counter substrate, and the analysis step is performed from the evaluation counter substrate side. It is a step of analyzing the chemical structure of the evaluation sensitizing dye using multiple internal reflection Fourier transform infrared spectroscopy while irradiating the evaluation test body, and the evaluation test is performed from the evaluation counter substrate side. Including the step of measuring the photoelectric conversion efficiency by irradiating the body with light, and the test body evaluation step is carried on the metal oxide film for evaluation using the result in the analysis step and the photoelectric conversion efficiency. The step of evaluating the sensitizing dye for evaluation Method for manufacturing a dye-sensitized solar cell according to (7) or (8) that there.

(10) After the metal oxide film for evaluation is immersed in the sensitizing dye solution or during the immersion, the sensitizing dye solution is measured using multiple internal reflection Fourier transform infrared spectroscopy, and the sensitization Dye solution evaluation for evaluating the adsorption state of the sensitizing dye supported on the metal oxide film of the intermediate product using the result of analyzing the concentration and / or chemical structure of the sensitizing dye contained in the dye solution A method for producing a dye-sensitized solar cell according to (8) or (9), comprising a step.
(11) A liquid feeding pipe for feeding the sensitizing dye solution is provided in a dipping tank in which the metal oxide film of the intermediate product is immersed in the sensitizing dye solution, and the sensitizing dye solution in the liquid feeding pipe is provided. Is measured using multiple internal reflection Fourier transform infrared spectroscopy, and using the result of analyzing the concentration and / or chemical structure of the sensitizing dye contained in the sensitizing dye solution in the liquid feeding tube, the intermediate The method according to any one of (8) to (10), further comprising a liquid feeding dye solution analysis evaluation step for evaluating an adsorption state of the sensitizing dye supported on the metal oxide film of a product. A method for producing a dye-sensitized solar cell.

(12) After immersing the metal oxide film for evaluation of the evaluation substrate in the sensitizing dye solution and before disposing the counter electrode for evaluation facing the evaluation substrate, multiple internal reflection Fourier transform The intermediate product is measured by using the result obtained by measuring the metal oxide film for evaluation using conversion infrared spectroscopy and analyzing the adsorption state of the sensitizing dye for evaluation carried on the metal oxide film for evaluation. A dye sensitizing method according to any one of (8) to (11), further comprising a pre-sealing evaluation step for evaluating an adsorption state of the sensitizing dye supported on the metal oxide film. A method for manufacturing a solar cell.
(13) In the pre-sealing evaluation step, the metal oxide film for evaluation is pressed against a high refractive index medium of a multiple internal reflection Fourier transform infrared spectroscopy apparatus, and multiple internal reflection Fourier transform infrared spectroscopy is used. The method for producing a dye-sensitized solar cell according to (12), wherein the metal oxide film for evaluation is measured.

  In the test specimen for evaluation of the present invention, the evaluation metal oxide film on which the sensitizing dye is adsorbed and the base material made of a high refractive index medium that transmits infrared light are in close contact with each other. Can be easily measured in a non-destructive manner using the multiple internal reflection FT-IR method, and the evaluation sensitizing dye is adsorbed. The state can be easily evaluated with high accuracy.

  Moreover, the test specimen for evaluation of the present invention is similar to a dye-sensitized solar cell in the process of being sealed with an electrolytic solution, and the adsorption state of the sensitizing dye for evaluation is sealed with the electrolytic solution. This is similar to the adsorption state of the sensitizing dye that actually contributes to power generation later. Therefore, from the evaluation result of the sensitizing dye for evaluation carried on the metal oxide film for evaluation of the test specimen for evaluation of the present invention, the metal oxide film of the dye-sensitized solar cell in the process of being sealed with the electrolytic solution The adsorption state of the sensitizing dye carried on the substrate can be predicted with high accuracy, and the dye-sensitized solar cell being manufactured can be easily evaluated with high accuracy.

  Moreover, the evaluation method of the sensitizing dye of the present invention was performed by analyzing the chemical structure of the evaluation sensitizing dye of the evaluation specimen using the multiple internal reflection FT-IR method with the substrate side facing the measuring device. Since the evaluation sensitizing dye is evaluated using the results, the evaluation sensitizing dye supported on the evaluation metal oxide film can be evaluated with high accuracy and non-destructively.

  In addition, according to the method for producing a dye-sensitized solar cell of the present invention, the evaluation sensitizing dye of the evaluation specimen similar to the dye-sensitized solar cell encapsulated with the electrolytic solution is subjected to multiple internal reflection. Using the results evaluated using the FT-IR method, the sensitizing dye of the intermediate product, which is a dye-sensitized solar cell encapsulated with an electrolytic solution, is evaluated. Can be evaluated.

FIG. 1 is a schematic cross-sectional view schematically showing an example of a test specimen for evaluation of the present invention. FIG. 2 is a graph of spectra obtained by measuring the sensitizing dye solutions of Experimental Example 1 and Experimental Example 2 using a multiple internal reflection FT-IR method. FIG. 3 is a graph of spectra obtained by measuring the metal oxide films for evaluation in Experimental Example 3-1, Experimental Example 3-2, and Experimental Example 3-3 using the multiple internal reflection FT-IR method. FIG. 4 is a graph of a spectrum obtained by measuring the metal oxide film for evaluation of Experimental Example 4 using a multiple internal reflection FT-IR method.

The present invention is described in detail below.
"Evaluation specimen"
First, the test specimen for evaluation of the present invention will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view schematically showing an example of a test specimen for evaluation of the present invention. The test specimen 1 for evaluation shown in FIG. 1 is used for evaluation of a dye-sensitized solar cell, and is measured using multiple internal reflection FT-IR.

As shown in FIG. 1, the test specimen 1 for evaluation includes an evaluation substrate 2, an evaluation counter substrate 3, an evaluation electrolytic solution 4, an evaluation metal oxide film 5, and an evaluation sensitizing dye.
The members used for the dye-sensitized solar cell are used for the members excluding the evaluation substrate 2 of the evaluation test body 1. In addition, the dye-sensitized solar cell in the middle of manufacture in which a part or all of the members of the test specimen for evaluation 1 excluding the evaluation board 2 is sealed with an electrolyte solution to be evaluated using the evaluation result of the test specimen for evaluation 1 Are preferably the same. The test specimen 1 for evaluation is dye-sensitized in the middle of production in which the electrolyte solution to be evaluated is sealed, as the number of members in common with the dye-sensitized solar cell in the middle of production in which the electrolyte solution to be evaluated is sealed is larger. It becomes similar to the solar cell, and the reliability of the evaluation result of the dye-sensitized solar cell in the process of being sealed with the electrolyte solution using the evaluation result of the evaluation specimen 1 is high.

  The evaluation substrate 2 is made of a high refractive index medium (prism) that transmits infrared light. Specifically, a prism made of GaAs or Si generally used in the multiple internal reflection FT-IR method is preferably used as the evaluation substrate 2. Moreover, the evaluation substrate 2 of the present embodiment has conductivity. For this reason, the evaluation substrate 2 also serves as an electrode on the evaluation substrate 2 side, and it is not necessary to form an electrode on the evaluation substrate 2, which is excellent in productivity and is preferable.

  In addition, although it is preferable that the evaluation board | substrate 2 is what has electroconductivity, it does not need to have electroconductivity. If the evaluation substrate 2 is not conductive, an electrode made of a transparent conductive film may be formed on one surface of the evaluation substrate 2 using a vapor deposition method or the like. The transparent conductive film used in the present embodiment is not particularly limited, and can be appropriately determined according to the type of the dye-sensitized solar cell to be evaluated using the evaluation result of the test specimen 1 for evaluation, and the reliability of the evaluation In order to improve the property, it is preferably the same as the dye-sensitized solar cell to be evaluated.

  As the transparent conductive film, any material used for the transparent electrode of the dye-sensitized solar cell may be used. Specifically, as the transparent conductive film, indium oxide / tin oxide (sometimes called ITO), fluorine-doped tin oxide (sometimes called FTO), zinc oxide, tin oxide, antimony-doped tin oxide (ATO and Indium oxide / zinc oxide (sometimes called IZO), gallium oxide / zinc oxide (sometimes called GZO), Pt, or the like can be used. Among these, ITO having high electrical conductivity and FTO excellent in heat resistance and weather resistance are particularly suitable as the transparent conductive film used for the electrode.

As shown in FIG. 1, the evaluation metal oxide film 5 is formed on the surface of the evaluation substrate 2 that faces the counter substrate 3 for evaluation. As the metal oxide film 5 for evaluation, titanium oxide or the like is used.
An evaluation sensitizing dye (not shown) is carried on the surface and inside of the evaluation metal oxide film 5. The sensitizing dye for evaluation used in the present embodiment is not particularly limited, and can be appropriately determined according to the type of the dye-sensitized solar cell to be evaluated using the evaluation result of the evaluation specimen 1.

  Specifically, as a sensitizing dye for evaluation, cis-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 dye such as ruthenium tris-tetrabutylammonium salt (sometimes called black dye) be able to.

As shown in FIG. 1, the counter substrate 3 for evaluation has a counter electrode 3b on one surface of the counter substrate 3a. The evaluation counter substrate 3 is arranged with the surface on the counter electrode 3b side facing the surface on the evaluation substrate 2 side.
As the counter electrode 3b, the same electrode as in the case where the transparent electrode is formed on the evaluation substrate 2 described above can be used.

As the counter substrate 3a, for example, a transparent material such as a glass substrate or a plastic substrate can be used.
It does not specifically limit as a glass base material, General glass, such as soda lime glass, borosilicate glass, quartz glass, borosilicate glass, Vycor glass, alkali free glass, blue plate glass, and white plate glass, is mentioned.
The plastic substrate is not particularly limited, and examples thereof include polyacrylic resin, polycarbonate resin, polyester resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, and polyamide resin.

In the present embodiment, as shown in FIG. 1, two injection holes 3 d penetrating the evaluation counter substrate 3 are provided in the evaluation counter substrate 3. The injection hole 3d is used when injecting the evaluation electrolytic solution 4 between the evaluation substrate 2 and the evaluation counter substrate 3.
A transparent plate 3c is disposed on the opposite surface of the evaluation counter substrate 3 to the evaluation substrate 2 so as to close the injection hole 3d, and the transparent plate 3c is sealed so as to cover the transparent plate 3c. A resin layer 9 is provided. Therefore, the injection hole 3d is sealed by the transparent plate 3c and the sealing resin layer 9.
The transparent plate 3c is made of a transparent material such as glass, and the same material as the counter substrate 3a can be used. The sealing resin layer 9 is made of a photocurable resin and / or a thermoplastic resin, and is mixed with spacer particles (trade name: Micropearl, manufactured by Sekisui Chemical Co., Ltd.) as necessary. Also good.

As shown in FIG. 1, the evaluation electrolyte 4 is sandwiched between the evaluation substrate 2 and the evaluation counter substrate 3 and sealed with a sealing material 7.
Examples of the electrolytic solution 4 for evaluation include non-aqueous electrolyte solutions such as acetonitrile or propionitrile. In addition, the evaluation electrolytic solution 4 may be a solution in which an electrolyte such as lithium iodide and iodine are mixed in a liquid component such as dimethylpropylimidazolium iodide or butylmethylimidazolium iodide. .
As the sealing material 7, for example, a photocurable resin and / or a thermoplastic resin can be used. Moreover, the sealing material 7 may be a mixture of spacer particles (trade name: Micropearl, manufactured by Sekisui Chemical Co., Ltd.) as necessary.

In order to manufacture the test specimen 1 for evaluation shown in FIG. 1, for example, the evaluation substrate 2 is used instead of the transparent substrate of the dye-sensitized solar cell, and the electrolytic solution in the method for manufacturing the dye-sensitized solar cell is sealed. It can manufacture by performing the process to the process to stop.
Specifically, for example, the evaluation substrate 2 is prepared, and the evaluation metal oxide film 5 is formed on the evaluation substrate 2. The formation method of the metal oxide film 5 for evaluation is not particularly limited. For example, a method using a CVD method (chemical vapor deposition method) or a titanium oxide paste is applied by a screen printing method and heated. And a method of sintering. In addition, the formation method of the metal oxide film 5 for evaluation is the formation of the metal oxide film in the dye-sensitized solar cell in the middle of the production in which the electrolytic solution evaluated using the evaluation result of the evaluation specimen 1 is sealed. The method is preferably the same.

  Next, a sensitizing dye is supported on the evaluation metal oxide film 5 formed on the evaluation substrate 2. In the present embodiment, the evaluation metal oxide film 5 formed on the evaluation substrate 2 is immersed in a sensitizing dye solution containing a sensitizing dye for solar cells, and is evaluated as the evaluation metal oxide film 5. A sensitizing dye is supported. The method for immersing the evaluation metal oxide film 5 in the sensitizing dye solution is not particularly limited, and the concentration of the sensitizing dye in the sensitizing dye solution, the immersing time, and the evaluation metal oxide film 5 to be immersed. The conditions such as the temperature and humidity after immersing the evaluation metal oxide film 5 in the sensitizing dye solution can be appropriately determined. In addition, the method for supporting the evaluation sensitizing dye on the evaluation metal oxide film 5 is a dye-sensitized solar cell in the middle of production in which the electrolytic solution evaluated using the evaluation result of the evaluation specimen 1 is sealed. The method is preferably the same as the method of supporting a sensitizing dye on the metal oxide film.

  Moreover, in this embodiment, in order to improve the surface state of the evaluation metal oxide film 5 before the evaluation metal oxide film 5 is immersed in the sensitizing dye solution, the evaluation metal oxide film 5 is used. The metal oxide film for evaluation 5 may be pretreated by baking at a predetermined temperature and time. Whether or not to perform the pretreatment is determined so as to be the same as the manufacturing process of the dye-sensitized solar cell in the process of being sealed with the electrolytic solution evaluated using the evaluation result of the test specimen 1 for evaluation. Is preferred.

Next, the counter substrate for evaluation 3 provided with the counter electrode 3b is directed to one surface of the counter substrate 3a having the two injection holes 3d, and the surface on the counter electrode 3b side is directed to the surface on the evaluation substrate 2 side. Arrange.
At this time, for example, the evaluation substrate 2, the evaluation counter substrate 3, and the sealing material 7 are placed between the evaluation substrate 2 and the evaluation counter substrate 3 using the sealing material 7 by the method described below. Form an enclosed space. First, the sealing material 7 is applied to a predetermined position on the evaluation substrate 2 using a dispenser. Next, the evaluation counter substrate 3 is overlapped with the surface on the counter electrode 3 b side facing the surface of the evaluation substrate 2 to which the sealing material 7 is applied. Thereafter, the sealing material 7 is cured by performing a curing process.

  The curing step can be appropriately determined according to the material of the sealing material 7 and the like. For example, when a mixture of a photocurable resin and a thermosetting resin is used as the sealing material 7, as a curing process, ultraviolet rays (UV) are irradiated from the evaluation counter substrate 3 side for about 2 minutes, for example. For example, there is a method in which the encapsulant 7 is cured by being held at a temperature of 80 ° C. for 30 minutes and allowed to stand.

Subsequently, the evaluation electrolytic solution 4 is injected into the space between the evaluation substrate 2 and the evaluation counter substrate 3 through the injection hole 3 d of the evaluation counter substrate 3. Thereafter, a transparent plate 3c is arranged on the counter substrate 3 for evaluation so as to close the injection hole 3d. Thereafter, for example, the same material as that of the sealing material 7 is applied on the transparent plate 3c and cured in the same manner as the sealing material 7 to form the sealing resin layer 9 and sealed.
Through the above process, the test specimen 1 for evaluation shown in FIG. 1 is obtained.

"Evaluation method of sensitizing dye"
Next, a method for evaluating a sensitizing dye of the present invention in which the sensitizing dye is evaluated using the test specimen 1 for evaluation shown in FIG. 1 will be described.
First, an evaluation specimen 1 shown in FIG. 1 is prepared. Next, in the present embodiment, as shown in FIG. 1, the electric power generated by photoelectric conversion of the evaluation specimen 1 is applied to an external circuit between the evaluation substrate 2 and the counter electrode 3 b of the evaluation counter substrate 3. The wiring 8 to be supplied is connected by a method such as soldering.

Next, the surface of the evaluation substrate 2 opposite to the evaluation counter substrate 3 is opposed to the measuring apparatus, and light is applied to the evaluation test body 1 from the evaluation counter substrate 3 side as indicated by an arrow in FIG. While irradiating, the chemical structure of the sensitizing dye for evaluation is analyzed using multiple internal reflection Fourier transform infrared spectroscopy (FT-IR) (analysis process).
In this embodiment, since the evaluation substrate 2 is made of a high refractive index medium (prism) that transmits infrared light, as shown in FIG. 1, the evaluation metal oxide on which the sensitizing dye is adsorbed is formed. The material film 5 and the prism (evaluation substrate 2) are in close contact with each other. Therefore, by making the evaluation substrate 2 face the measuring device, the evaluation carried on the evaluation metal oxide film of the evaluation specimen 1 similar to the dye-sensitized solar cell in the process of being sealed with the electrolyte is produced. The sensitizing dye can be easily measured nondestructively using the multiple internal reflection FT-IR method.

Note that the multiple internal reflection FT-IR method is a method that has a longer optical path length and a stronger spectral peak intensity than the single reflection ATR method, and thus can be measured with high sensitivity.
Thereafter, as indicated by an arrow in FIG. 1, the evaluation test body 1 is irradiated with light from the evaluation counter substrate 3 side to measure the photoelectric conversion efficiency. In addition, the measurement of photoelectric conversion efficiency may be performed before or after performing an analysis process, and may be performed simultaneously with an analysis process.
Next, the evaluation sensitizing dye supported on the evaluation metal oxide film 5 is evaluated using the result in the analysis step and the photoelectric conversion efficiency (evaluation step).

"Method for producing dye-sensitized solar cell"
Next, a method for producing the dye-sensitized solar cell of the present invention using the test specimen 1 for evaluation shown in FIG. 1 and the method for evaluating a sensitizing dye described above will be described.
First, an intermediate product, which is a dye-sensitized solar cell in the middle of production sealed with an electrolyte, is formed. In the intermediate product of the present embodiment, the surface on the counter electrode side of the counter substrate having the counter electrode is opposed to the surface on the transparent electrode side of the transparent substrate having the transparent electrode, and the transparent substrate and the counter substrate An electrolytic solution sandwiched between and sealed, a metal oxide film formed on a surface of the transparent substrate facing the counter substrate, and the sensitizing dye supported on the metal oxide film. .

  In the present embodiment, the evaluation specimen 1 shown in FIG. 1 is used as an intermediate product, except that a transparent substrate having a transparent electrode is used instead of the evaluation board 2 of the evaluation specimen 1 shown in FIG. Form a similar one. Therefore, the intermediate product is manufactured, for example, using the transparent substrate having a transparent electrode instead of the evaluation substrate 2 of the evaluation test body 1 shown in FIG. It can be manufactured by the same method as that.

  As the transparent substrate used for the intermediate product, the same substrate as the counter substrate 3a of the counter substrate 3 for evaluation can be used. Specifically, it is preferable to use a glass substrate or a plastic substrate as the transparent substrate of the intermediate product. In order to increase the photoelectric conversion efficiency of the dye-sensitized solar cell, the transparent substrate of the intermediate product is better as the visible light transmittance is higher, and the visible light transmittance is preferably 70% or more. Here, the visible light means light having a wavelength of 400 to 780 nm. The visible light transmittance of the transparent substrate can be measured with a transmittance photometer with an integrating sphere.

  Next, a test specimen for evaluation is formed. The test specimen for evaluation of the present embodiment has a conductive evaluation substrate made of a high refractive index medium that transmits infrared light, and a counter electrode for evaluation made of the same material as the counter electrode. The counter substrate for evaluation made of the same material as that of the substrate is disposed so as to face the surface on the side of the counter electrode for evaluation, and is made of the same material as the electrolyte of the intermediate product and is opposed to the substrate for evaluation. Evaluation metal oxide formed on the opposite surface of the evaluation electrolytic solution sandwiched between and sealed between the substrate and the evaluation counter substrate of the evaluation substrate and made of the same material as the metal oxide film of the intermediate product It comprises a physical film and an evaluation sensitizing dye which is supported on the evaluation metal oxide film and is made of the same material as the sensitizing dye of the intermediate product.

In the manufacturing method of the dye-sensitized solar cell of this embodiment, the test body 1 for evaluation shown in FIG. 1 is formed as the test body for evaluation.
In the method for producing a dye-sensitized solar cell according to the present embodiment, in the step of forming the intermediate product, the metal oxide film is immersed in a sensitizing dye solution containing a sensitizing dye for solar cells to obtain the sensitizing dye. In the step of forming the evaluation specimen 1 on the metal oxide film, the evaluation metal oxide film 5 is immersed in the sensitizing dye solution and the evaluation sensitizing dye is supported on the evaluation metal oxide film 5. It is preferable to make it.

  In the method for producing a dye-sensitized solar cell of the present embodiment, the sensitizing dye solution is used as a high refractive index medium of a measuring apparatus after or during the immersion of the metal oxide film 5 for evaluation in the sensitizing dye solution. And the sensitizing dye solution may be measured using a multiple internal reflection FT-IR method. In this case, using the result of analyzing the concentration and / or chemical structure of the sensitizing dye contained in the sensitizing dye solution, the adsorption state of the sensitizing dye supported on the metal oxide film of the intermediate product is predicted and evaluated. Yes (Dye solution evaluation process of test specimen).

  Further, in the method for producing a dye-sensitized solar cell of the present embodiment, the sensitizing dye solution is removed from the high refractive index of the measuring device after the metal oxide film of the intermediate product is immersed in the sensitizing dye solution or during the immersion. The sensitizing dye solution may be measured by supplying to a medium and using a multiple internal reflection FT-IR method. In this case as well, using the results of analyzing the concentration and / or chemical structure of the sensitizing dye contained in the sensitizing dye solution, the adsorption state of the sensitizing dye supported on the metal oxide film of the intermediate product is predicted. (Dye solution evaluation process for intermediate products).

  Further, in the method for producing a dye-sensitized solar cell of the present embodiment, when the metal oxide film of the intermediate product is immersed in the sensitizing dye solution, the sensitizing dye solution in which the metal oxide film is immersed is accommodated. You may use what is provided with the liquid feeding pipe which liquid-feeds a sensitizing dye solution in an immersion tank. In this case, it is preferable to measure using a multiple internal reflection FT-IR method by supplying the sensitizing dye solution in the liquid feeding tube to the high refractive index medium of the measuring apparatus. As a result, using the results of analyzing the concentration and / or chemical structure of the sensitizing dye contained in the sensitizing dye solution in the liquid delivery tube, the adsorption state of the sensitizing dye supported on the metal oxide film of the intermediate product Can be estimated and evaluated (liquid feeding dye solution analysis evaluation process).

  In addition, in order to produce a plurality of intermediate products, when the metal oxide films of the plurality of intermediate products are continuously immersed in the sensitizing dye solution, the liquid feeding dye solution analysis evaluation process is continuously performed every predetermined time. And it is preferable to carry out a plurality of times. Thereby, the adsorption state of the sensitizing dye supported on each metal oxide film of the plurality of intermediate products can be evaluated. Furthermore, by controlling the adsorption state of the sensitizing dye supported on each metal oxide film using the obtained evaluation results, a plurality of intermediate products with stable quality can be manufactured with high yield.

  In addition, when any one or more of the dye solution evaluation process of the specimen, the dye solution evaluation process of the intermediate product, and the liquid feeding dye solution analysis evaluation process is performed, the concentration of the sensitizing dye solution is determined based on the measurement result. It is possible to feedback control the conditions when the sensitizing dye is supported on the metal oxide film of the intermediate product such as the immersion time. Therefore, it is possible to suppress variations in the adsorption amount and adsorption state of the sensitizing dye to the metal oxide film due to the manufacturing conditions.

  Moreover, in the manufacturing method of the dye-sensitized solar cell of this embodiment, after immersing the metal oxide film 5 for evaluation of the evaluation substrate 2 in the sensitizing dye solution, the counter electrode 3b for evaluation is attached to the evaluation substrate 2. Prior to disposition, the metal oxide film 5 for evaluation may be measured using a multiple internal reflection FT-IR method. In this case, by using the result of analyzing the adsorption state of the evaluation sensitizing dye supported on the evaluation metal oxide film 5, the adsorption state of the sensitizing dye supported on the metal oxide film of the intermediate product is predicted. (Evaluation process before sealing).

  In the evaluation process before sealing, the evaluation sensitizing dye carried on the evaluation metal oxide film 5 is exposed on the surface of the evaluation metal oxide film 5. Therefore, the evaluation metal oxide film 5 may be measured using the multiple internal reflection FT-IR method with the base material side of the evaluation substrate 2 facing the measuring device, or the evaluation metal oxide film 5 may be measured against the high refractive index medium of the multiple internal reflection FT-IR apparatus, and the metal oxide film 5 for evaluation may be measured using the multiple internal reflection FT-IR method. Both may be done to improve.

  When the pre-sealing evaluation step is performed, the accuracy of the evaluation of the adsorption state of the evaluation sensitizing dye supported on the evaluation metal oxide film 5 is improved as compared with the case where the pre-sealing evaluation step is not performed. be able to. Moreover, the reliability of the result obtained by the test body evaluation process for evaluation can be improved by collating the result in the evaluation process before sealing, and the result in the test body evaluation process mentioned later.

  Thereafter, the chemical structure of the evaluation sensitizing dye is analyzed using the multiple internal reflection FT-IR method while irradiating the evaluation specimen 1 with light in the same manner as the above-described evaluation method of the sensitizing dye (analysis). Process). Next, in the same manner as the method for evaluating a sensitizing dye described above, the test specimen 1 for evaluation is irradiated with light to measure the photoelectric conversion efficiency. Then, the evaluation sensitizing dye supported on the evaluation metal oxide film 5 is evaluated using the result in the analysis step and the photoelectric conversion efficiency in the same manner as the above-described evaluation method of the sensitizing dye (test). Body evaluation process).

Thereafter, in the method for producing the dye-sensitized solar cell of the present embodiment, the intermediate product evaluation step of evaluating the sensitizing dye supported on the metal oxide film of the intermediate product using the evaluation result in the test body evaluation step. I do.
When the evaluation result of the intermediate product in the intermediate product evaluation process is good, the wiring for supplying the electric power generated by the photoelectric conversion to the external circuit is the transparent electrode of the transparent substrate of the intermediate product and the counter electrode of the counter substrate The dye-sensitized solar cells are connected to each other by a method such as soldering. If the evaluation result of the intermediate product in the intermediate product evaluation process is not good, the intermediate product is detected as a defective product.

  The evaluation test body 1 of this embodiment includes an evaluation substrate 2, which is a base material made of a high refractive index medium that transmits infrared light, an evaluation counter substrate 3, an evaluation substrate 2, and an evaluation counter substrate 3. And an evaluation metal oxide film 5 formed on the opposing surface of the evaluation electrolytic solution 4 sandwiched between and the evaluation counter substrate 3 of the evaluation substrate 2, and the evaluation metal oxide Since the evaluation sensitizing dye supported on the film 5 is provided, the base material is composed of the evaluation metal oxide film 5 on which the evaluation sensitizing dye is adsorbed and a high refractive index medium that transmits infrared light. Are brought into close contact with each other. Therefore, by making the substrate face the measuring device, the sensitizing dye for evaluation carried on the metal oxide film for evaluation 5 can be easily measured nondestructively using the multiple internal reflection FT-IR method. The adsorption state of the sensitizing dye can be easily evaluated with high accuracy.

  Further, in the test specimen 1 for evaluation of this embodiment, the evaluation substrate 2 has conductivity, the evaluation counter substrate 3 has the counter electrode 3b on one surface, and the evaluation substrate 2 side. Since the surface of the counter electrode 3b is directed to the surface of the sensitizing dye, light is applied to the evaluation specimen 1 from the evaluation counter substrate 3 side in the analysis step of the sensitizing dye evaluation method of the present embodiment. While irradiating, the chemical structure of the sensitizing dye for evaluation is analyzed by using multiple internal reflection Fourier transform infrared spectroscopy, and the photoelectric conversion efficiency is obtained by irradiating light to the evaluation specimen 1 from the evaluation counter substrate 3 side. In the evaluation step, the evaluation sensitizing dye carried on the evaluation metal oxide film 5 can be evaluated using the result in the analysis step and the photoelectric conversion efficiency.

  Therefore, in the evaluation method of the sensitizing dye of the present embodiment, the adsorption amount and adsorption state of the evaluation sensitizing dye that actually contributes to power generation can be known, and the photoelectric conversion efficiency of the evaluation specimen 1 and the evaluation state The relationship between the amount of sensitizing dye adsorbed and the state of adsorption can be evaluated. Therefore, according to the method for evaluating a sensitizing dye of the present embodiment, the evaluation sensitizing dye supported on the evaluation metal oxide film 5 of the evaluation test body 1 is further manufactured by sealing the electrolytic solution. It can be evaluated in a state similar to a dye-sensitized solar cell on the way.

  In the present embodiment, the case where the evaluation substrate 2 of the evaluation specimen 1 has conductivity has been described as an example, but the evaluation substrate 2 has a transparent electrode on one surface. You may have. Further, the evaluation substrate 2 may not be conductive, and the counter electrode 3b may not be provided on the counter substrate 3 for evaluation. Even in this case, the evaluation sensitizing dye supported on the evaluation metal oxide film 5 can be evaluated.

In addition, in order to obtain a more reliable evaluation result of the sensitizing dye by performing a step of measuring the photoelectric conversion efficiency, the evaluation substrate 2 of the evaluation specimen 1 is transparent on one surface of the base material. The counter substrate 3 for evaluation has a counter electrode 3b on one surface, and is disposed with the surface on the counter electrode 3b side facing the surface on the transparent electrode side of the substrate for evaluation 2. Preferably there is.
Moreover, in the evaluation method of the sensitizing dye of this embodiment, although demonstrated taking the example of the method provided with the process of measuring a photoelectric conversion efficiency, the process of measuring a photoelectric conversion efficiency does not need to be performed.

"Experiment 1"
A sensitizing dye solution having a N719 concentration of 0.3% composed of N719 and a 1: 1 mixed solvent of acetonitrile and t-butanol was obtained from Si (Fz) of a measuring apparatus (trade name: MB100 (BOMEN)). The sensitizing dye solution was measured using a multiple internal reflection FT-IR method. The result is shown in FIG.

"Experimental example 2"
When the dye concentration of the sensitizing dye solution is lowered by the following method (Experimental Example 2-1), and when the dye structure of the sensitizing dye solution is changed by the following method (Experimental Example 2-2) The sensitizing dye solution in was measured in the same manner as in Experimental Example 1 using the multiple internal reflection FT-IR method. The result is shown in FIG.

<Dye concentration reduction method>
A sensitizing dye solution similar to Experimental Example 1 was diluted with a solvent (a 1: 1 mixed solvent of acetonitrile and t-butanol) to prepare a 0.1% sensitizing dye solution.
<Method of changing the dye structure>
The same sensitizing dye powder as that contained in the sensitizing dye solution of Experimental Example 1 was washed with a 0.5 M NaOH aqueous solution and evaporated to dryness using an evaporator. A deteriorated dye was obtained. Then, using the obtained deteriorated dye as a sensitizing dye, a sensitizing dye solution containing 0.3% of the deteriorated dye was prepared in the same procedure as the sensitizing dye solution of Experimental Example 1.

FIG. 2 is a graph of spectra obtained by measuring the sensitizing dye solutions of Experimental Example 1 and Experimental Example 2 using a multiple internal reflection FT-IR method.
From the peak shape of Experimental Example 1 in FIG. 2, it was confirmed that the dye contained in the sensitizing dye solution of Experimental Example 1 contains N719. Moreover, from the peak intensity of Experimental Example 1 in FIG. 2, it was confirmed that the dye concentration (N719 concentration) of the sensitizing dye solution was 0.3%.

Moreover, it has confirmed that the pigment | dye density | concentration of the sensitizing dye solution fell as shown by the peak intensity of Experimental example 2-1 of FIG. Further, from the intensity of the reference peak (absorption position 2100 cm ⁻¹ ) of Experimental Example 2-1 in FIG. 2 and the intensity of the reference peak of Experimental Example 1, when the dye is N719, the sensitizing dye solution depends on the intensity of the reference peak. It was confirmed that the dye concentration of can be detected.
In addition, the structure of the dye contained in the sensitizing dye solution was changed by comparing the peak shape of Experimental Example 2-2 in FIG. 2 with the peak shape of Experimental Example 1 (the region circled in FIG. 2). The absorption position was confirmed.
From the results of Experimental Example 1 and Experimental Example 2, it was confirmed that the concentration and structure of the sensitizing dye contained in the sensitizing dye solution can be measured using the multiple internal reflection FT-IR method.

"Experiment 3"
A titanium oxide paste was applied on an evaluation substrate made of Si (Fz) by a screen printing method and baked at 500 ° C. to form an evaluation metal oxide film made of titanium oxide. Thereafter, the evaluation metal oxide film formed on the evaluation substrate was immersed in an immersion tank containing the same sensitizing dye solution as in Experimental Example 1 for 24 hours at a temperature of 30 ° C. A sensitizing dye was supported on the membrane (Experimental Example 3-1). Further, a sensitizing dye was supported on the metal oxide film for evaluation in the same manner as in Experimental Example 3-1, except that the N719 concentration of the sensitizing dye solution was 0.1% (Experimental Example 3-2). .

Then, the surface opposite to the metal oxide film for evaluation of the evaluation substrate of Experimental Example 3-1 and Experimental Example 3-2 was opposed to the measuring device (trade name: MB100 (made by BOMEN)), and the multiple internal The metal oxide film for evaluation was measured using a reflection FT-IR method.
Moreover, the surface opposite to the metal oxide film for evaluation of the evaluation substrate in Experimental Example 3-1 before supporting the sensitizing dye is opposed to a measuring device (trade name: MB100 (made by BOMEN)), The metal oxide film for evaluation (Experimental Example 3-3) was measured using a multiple internal reflection FT-IR method.

The measurement results of the metal oxide films for evaluation in Experimental Example 3-1, Experimental Example 3-2, and Experimental Example 3-3 are shown in FIG. FIG. 3 is a graph of spectra obtained by measuring the metal oxide films for evaluation in Experimental Example 3-1, Experimental Example 3-2, and Experimental Example 3-3 using the multiple internal reflection FT-IR method.
From the peak shapes of Experimental Example 3-1, Experimental Example 3-2, and Experimental Example 3-3 in FIG. 3, the structure of the dye supported on the metal oxide film for evaluation can be detected. Experimental Example 3-1 and Experimental Example It was confirmed that the dye supported on the metal oxide film for evaluation 3-2 contained N719. Moreover, the density | concentration of the pigment | dye carry | supported by the metal oxide film for evaluation is detected from the intensity | strength of the reference peak (absorption position 2100cm < ^-1 >) of Experimental example 3-1, Experimental example 3-2, and Experimental example 3-3 of FIG. I was able to confirm that it was possible.
Based on the results of Experimental Example 3-1, Experimental Example 3-2, and Experimental Example 3-3, the concentration and structure of the sensitizing dye supported on the metal oxide film for evaluation were measured using the multiple internal reflection FT-IR method. I was able to confirm that it was possible.

"Experimental example 4"
By the method shown below, the test specimen 1 for evaluation shown in FIG. 1 was produced, and the sensitizing dye 6 for evaluation was evaluated.
First, an evaluation metal oxide film 5 made of titanium oxide was formed by applying a titanium oxide paste onto the evaluation substrate 2 made of Si (Fz) by screen printing and firing at 500 ° C. Next, the evaluation metal oxide film 5 formed on the evaluation substrate 2 was immersed in an immersion tank containing the same sensitizing dye solution as in Experimental Example 1 for 24 hours at a temperature of 30 ° C. A sensitizing dye for evaluation was supported on the oxide film 5.

  Next, the counter substrate 3 for evaluation in which the counter electrode 3b made of Pt is formed on one surface of the counter substrate 3a made of glass by the vapor deposition method, and the surface on the counter electrode 3b side is directed to the surface on the evaluation substrate 2 side. The evaluation substrate 2 and the evaluation counter substrate 3 are arranged between the evaluation substrate 2 and the evaluation counter substrate 3 by using a sealing material 7 made of a sealing resin that is disposed and mixed with an ultraviolet curable resin and a thermosetting resin. And a space surrounded by the sealing material 7 was formed. Thereafter, in the space between the evaluation substrate 2 and the counter substrate 3 for evaluation, an electrolytic solution for evaluation comprising an electrolytic solution for a commercial dye-sensitized solar cell (trade name: Iodolite AN-50 (manufactured by Soranonics)) in an acetonitrile solvent. The liquid 4 was injected and sealed to obtain the test specimen 1 for evaluation shown in FIG.

Next, as shown in FIG. 1, the wiring 8 was connected to the evaluation substrate 2 and the counter electrode 3b of the evaluation counter substrate 3 by soldering. Thereafter, as indicated by an arrow in FIG. 1, the photoelectric conversion efficiency was measured by irradiating the evaluation test body 1 with light from the LED light (25 mW / cm ² ) from the evaluation counter substrate 3 side. As a result, the photoelectric conversion efficiency was 2%.

  Next, multiple internal reflections are performed while irradiating light similar to that when the photoelectric conversion efficiency of the test specimen for evaluation 1 is measured while the evaluation substrate 2 is opposed to a measuring device (trade name: MB100 (made by BOMEN)). The chemical structure of the evaluation sensitizing dye 6 was analyzed using the FT-IR method (analysis process).

The measurement results of the metal oxide film for evaluation 5 in Experimental Example 4 are shown in FIG. FIG. 4 is a graph of a spectrum obtained by measuring the metal oxide film for evaluation of Experimental Example 4 using a multiple internal reflection FT-IR method.
The structure of the dye supported on the evaluation metal oxide film 5 can be detected from the peak shape of Experimental Example 4 shown in FIG. 4, and the dye supported on the evaluation metal oxide film 5 of Experimental Example 4 contains N719. I was able to confirm that. Moreover, it has confirmed that the pigment | dye density | concentration carry | supported by the metal oxide film 5 for evaluation was detectable from the intensity | strength of the reference peak (absorption position 2100cm < ^-1 >) of Experimental example 4 shown in FIG.
From the results of Experimental Example 4, it was confirmed that the concentration and structure of the sensitizing dye supported on the metal oxide film 5 for evaluation can be measured using the multiple internal reflection FT-IR method.

“Experimental Example 5”
An intermediate product, which is a dye-sensitized solar cell in the process of being sealed with an electrolytic solution, was formed, and the evaluation sensitizing dye was evaluated.
As an intermediate product, instead of the evaluation substrate 2 of the evaluation specimen 1 shown in FIG. 1 of Experimental Example 4, a counter electrode 3b made of Pt formed on one surface of the counter base material 3a by vapor deposition is used. A test sample similar to the test sample 1 for evaluation shown in FIG.

  Next, the photoelectric conversion efficiency of the intermediate product was measured in the same manner as in Experimental Example 4. As a result, the photoelectric conversion efficiency was about 2%.

  Next, an analysis of the chemical structure of the sensitizing dye for evaluation was attempted using the multiple internal reflection FT-IR method. However, since the surface facing the measurement device is covered with a transparent substrate made of glass, the evaluation metal oxide film 5 on which the evaluation sensitizing dye is adsorbed and the prism of the measurement device can be brought into close contact with each other. It was not possible to measure.

DESCRIPTION OF SYMBOLS 1 ... Evaluation test body, 2 ... Evaluation substrate, 3 ... Evaluation counter substrate, 3c ... Transparent plate, 3d ... Injection hole 4 ... Evaluation electrolyte, 5 ... Evaluation metal oxide film, 9 ... Sealing resin layer.

Claims (13)

A test specimen for evaluation measured using multiple internal reflection FT-IR,
An evaluation substrate having a base material made of a high refractive index medium that transmits infrared light, an evaluation counter substrate, and an evaluation substrate sandwiched and sealed between the evaluation substrate and the evaluation counter substrate An evaluation metal oxide film formed on a surface of the evaluation substrate facing the evaluation counter substrate; and an evaluation sensitizing dye supported on the evaluation metal oxide film. A test specimen for evaluation characterized by   The test specimen for evaluation according to claim 1, wherein the base material is made of GaAs or Si. The evaluation substrate has a transparent electrode on one surface of the base material,
The counter substrate for evaluation has a counter electrode on one surface, and is disposed with the surface on the counter electrode side facing the surface on the transparent electrode side of the substrate for evaluation. Item 3. The test specimen for evaluation according to item 1 or 2. An evaluation substrate having a base material made of a high refractive index medium that transmits infrared light, an evaluation counter substrate, and an evaluation substrate sandwiched and sealed between the evaluation substrate and the evaluation counter substrate And an evaluation metal oxide film formed on a surface of the evaluation substrate facing the counter substrate for evaluation, and the evaluation sensitizing dye supported on the metal oxide film for evaluation. Preparing a test specimen for evaluation; and
An analysis step of analyzing the chemical structure of the sensitizing dye for evaluation using multiple internal reflection Fourier transform infrared spectroscopy with the substrate side facing the measuring device;
An evaluation step of evaluating the evaluation sensitizing dye supported on the evaluation metal oxide film using the result of the analysis step.   The method for evaluating a sensitizing dye according to claim 4, wherein the substrate is made of GaAs or Si. The evaluation substrate of the evaluation test body has a transparent electrode on one surface of the base material, the evaluation counter substrate has a counter electrode on one surface, and the evaluation substrate It is arranged with the surface on the counter electrode side facing the surface on the transparent electrode side,
The analysis step is a step of analyzing the chemical structure of the evaluation sensitizing dye using multiple internal reflection Fourier transform infrared spectroscopy while irradiating the evaluation specimen with light from the evaluation counter substrate side. Yes,
Irradiating the evaluation specimen with light from the evaluation counter substrate side to measure photoelectric conversion efficiency,
The evaluation step is a step of evaluating the sensitizing dye for evaluation carried on the evaluation metal oxide film using the result in the analysis step and the photoelectric conversion efficiency. Item 6. The method for evaluating a sensitizing dye according to Item 5 or Item 5. The surface on the transparent electrode side of the transparent substrate having the transparent electrode is disposed opposite to the surface on the counter electrode side of the counter substrate having the counter electrode, and is sandwiched between the transparent substrate and the counter substrate and sealed. Forming an intermediate product comprising the stopped electrolyte, a metal oxide film formed on a surface of the transparent substrate facing the counter substrate, and the sensitizing dye carried on the metal oxide film When,
An evaluation substrate having a base material made of a high refractive index medium that transmits infrared light and an evaluation counter substrate made of the same material as the counter substrate are arranged to face each other, and made of the same material as the electrolyte solution, An evaluation electrolytic solution sandwiched and sealed between the evaluation substrate and the evaluation counter substrate; and the metal oxide film formed on a surface facing the evaluation counter substrate of the evaluation substrate; Forming a test specimen for evaluation comprising the metal oxide film for evaluation made of the same material and the sensitizing dye for evaluation made of the same material as the sensitizing dye supported on the metal oxide film for evaluation; ,
An analysis step of analyzing the chemical structure of the sensitizing dye for evaluation using multiple internal reflection Fourier transform infrared spectroscopy with the substrate side facing the measuring device;
Using the result in the analysis step, a test body evaluation step for evaluating the evaluation sensitizing dye supported on the evaluation metal oxide film,
An intermediate product evaluation step for evaluating the sensitizing dye supported on the metal oxide film using the evaluation result in the test body evaluation step. In the step of forming the intermediate product, the metal oxide film is immersed in a sensitizing dye solution containing a sensitizing dye for solar cells, and the sensitizing dye is supported on the metal oxide film,
In the step of forming the evaluation specimen, the evaluation metal oxide film is immersed in the sensitizing dye solution, and the evaluation sensitizing dye is supported on the evaluation metal oxide film. The manufacturing method of the dye-sensitized solar cell of Claim 7. The evaluation test body has a transparent electrode for evaluation made of the same material as the transparent electrode on one surface of the base material, the surface on the evaluation transparent electrode side of the evaluation substrate, and the same material as the counter electrode The surface of the counter substrate for evaluation having the counter electrode for evaluation consisting of is arranged so as to face the surface of the counter electrode for evaluation,
The analysis step is a step of analyzing the chemical structure of the evaluation sensitizing dye using multiple internal reflection Fourier transform infrared spectroscopy while irradiating the evaluation specimen with light from the evaluation counter substrate side. Yes,
Irradiating the evaluation specimen with light from the evaluation counter substrate side to measure photoelectric conversion efficiency,
The test body evaluation step is a step of evaluating the evaluation sensitizing dye supported on the evaluation metal oxide film using the result in the analysis step and the photoelectric conversion efficiency. The manufacturing method of the dye-sensitized solar cell of Claim 7 or Claim 8 to do.   After immersing the metal oxide film for evaluation in the sensitizing dye solution or during the immersing, the sensitizing dye solution is measured using multiple internal reflection Fourier transform infrared spectroscopy, and the sensitizing dye solution A dye solution evaluation step of evaluating the adsorption state of the sensitizing dye supported on the metal oxide film of the intermediate product using the result of analyzing the concentration and / or chemical structure of the sensitizing dye contained The method for producing a dye-sensitized solar cell according to claim 8 or 9, wherein:   A liquid feeding pipe for feeding the sensitizing dye solution is provided in a dipping tank in which the metal oxide film of the intermediate product is dipped in the sensitizing dye solution, and the sensitizing dye solution in the liquid feeding pipe is provided in multiple interiors. Using the result of analyzing the concentration and / or chemical structure of the sensitizing dye contained in the sensitizing dye solution in the liquid delivery tube measured using reflection Fourier transform infrared spectroscopy, the intermediate product The dye-sensitized dye according to any one of claims 8 to 10, further comprising a liquid-feeding dye solution analysis and evaluation step for evaluating an adsorption state of the sensitizing dye supported on the metal oxide film. A method for manufacturing a solar cell.   After immersing the metal oxide film for evaluation of the evaluation substrate in the sensitizing dye solution, before placing the evaluation counter electrode opposite to the evaluation substrate, multiple internal reflection Fourier transform infrared The metal oxide film for evaluation was measured using a spectroscopic method, and the result of analyzing the adsorption state of the sensitizing dye for evaluation carried on the metal oxide film for evaluation was used to calculate the metal of the intermediate product. The dye-sensitized solar cell according to any one of claims 8 to 11, further comprising an evaluation step before sealing for evaluating an adsorption state of the sensitizing dye supported on the oxide film. Production method.   In the pre-sealing evaluation step, the metal oxide film for evaluation is pressed against a high refractive index medium of a multiple internal reflection Fourier transform infrared spectrometer, and the evaluation is performed using multiple internal reflection Fourier transform infrared spectroscopy. The method for producing a dye-sensitized solar cell according to claim 12, wherein a metal oxide film is measured.

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