JP6266909B2 - Method for manufacturing ionic element - Google Patents

Description

  The present invention relates to a method for manufacturing an ionic element that exhibits functionality by using a pn junction formed in an ionic layer.

  Devices having various functions have been proposed as devices (ionic elements) using an electrolyte such as an ionic liquid. An example is an electric double layer capacitor having a structure in which an electrolyte is sandwiched between a pair of electrodes. In addition, an electrochemiluminescence cell (LEC: Light-emitting Electrochemical Cells) having a structure in which a voltage can be applied from a plurality of electrodes to a mixture of an electrolyte and a conductive polymer (light-emitting polymer) (for example, Non-patent document 1).

Q.Pai, A.J.Heeger et al., Science (1996)

  By the way, in the ionic element described above, it is generally required to reduce in-plane variation (for example, variation in film thickness, variation in characteristics, variation in composition, etc.). Therefore, it is desired to propose a technique that can suppress such in-plane variation.

  The present invention has been made in view of such problems, and an object of the present invention is to provide a method of manufacturing an ionic element capable of suppressing in-plane variation in the element.

The first method for producing an ionic element of the present invention includes a step of producing a mixture by mixing a porous material, an electrolyte and an amphiphilic substance in a solvent, and a step of forming the mixture into a thin film. A step of forming an ionic layer in which the electrolyte is dispersed in the porous material by drying the thin film-like mixture and evaporating the solvent from the mixture, and applying a voltage to the ionic layer to together and a step of mounting a plurality of electrodes for, providing a starting mechanism for starting the formation of the pn junction partly by forming a temperature distribution in the ion layer when said voltage is applied It is a thing.

  In the manufacturing method of the 1st ionic element of this invention, when producing a mixture, an amphiphilic substance is mixed in a solvent with a porous material and electrolyte. Thereby, when making this mixture into a thin film form, the surface tension of a mixture falls and it becomes easy to spread a mixture uniformly.

  In the manufacturing method of the 1st ionic element of this invention, it is preferable to use a high boiling-point solvent as said solvent. When it does in this way, when drying a thin film-like mixture, a solvent will become difficult to evaporate and a mixture will dry slowly. For this reason, the effect of reducing the surface tension by the amphiphilic substance functions more effectively, and the mixture is easily dried evenly in the film. As a result, the film thickness variation in the ion layer is further suppressed. Moreover, it is preferable that content of the amphiphile in the said mixture shall be 1000 ppm or less. In such a case, excessive inclusion of the amphiphilic substance in the mixture is prevented, and the amphiphilic substance functions more effectively.

  In the first method for producing an ionic element of the present invention, it is preferable to perform stirring using ultrasonic waves when mixing the porous material, the electrolyte, and the amphiphilic substance. In this case, the porous material and the electrolyte are easily mixed uniformly, and when the mixture is made into a thin film, variation in composition within the film can be suppressed. It can be suppressed. In this case, it is more preferable to perform the stirring using the ultrasonic wave for a predetermined period of time that is not less than the lower limit time and not more than the upper limit time. In this case, the durability of the ionic element during operation can be ensured while improving the stirring efficiency (the ionic element can be prevented from being broken).

The second method for producing an ionic element of the present invention comprises a step of producing a mixture by mixing a porous material and an electrolyte in a solvent, a step of making the mixture into a thin film, and mixing of the thin film By drying the body and evaporating the solvent from the mixture to form an ion layer in which the electrolyte is dispersed in the porous material, and a plurality of electrodes for applying a voltage to the ion layer attaching step and the containing Mutotomoni, provided the starter mechanism for initiating the formation of the pn junction partly by forming a temperature distribution in the ion layer when said voltage is applied, the porous material and electrolyte When mixing these, stirring using ultrasonic waves is performed.

  In the second method for producing an ionic element of the present invention, stirring using ultrasonic waves is performed when the porous material and the electrolyte are mixed. Thereby, the porous material and the electrolyte are easily mixed uniformly, and the composition variation in the film can be suppressed when the mixture is made into a thin film.

  In the second method for producing an ionic element of the present invention, it is preferable to carry out stirring using ultrasonic waves for a predetermined period of time not less than the lower limit time and not more than the upper limit time for the reasons described above.

  In the first and second ionic element manufacturing methods of the present invention, for example, a printing technique can be used in the step of forming the mixture into a thin film.

  In the first and second ionic element manufacturing methods of the present invention, it is preferable that the electrolyte is configured using molecules having a structure for suppressing ion mobility. In this case, for example, a pn junction formed in the ion layer by applying a voltage to the ion layer from the plurality of electrodes is less likely to disappear even after the transition to the voltage non-application state. (The pn junction will be maintained for some time). Therefore, it is possible to improve the functionality of the ionic element by using a pn junction having such characteristics. In this case, for example, the molecule can be configured to have a linear structure.

  In the first and second ionic element manufacturing methods of the present invention, for example, an ionic liquid can be used as the electrolyte. Moreover, as said porous material, it is possible to use a conductive polymer (light emitting polymer), for example.

  According to the first method for producing an ionic element of the present invention, the amphiphile is mixed in the solvent together with the porous material and the electrolyte when the mixture is produced. When making it into a shape, it is possible to reduce the surface tension of the mixture to facilitate the uniform spreading of the mixture. Therefore, it is possible to suppress in-plane variation (film thickness variation in the ion layer) in the ionic element.

  According to the second method for producing an ionic element of the present invention, since stirring is performed using ultrasonic waves when the porous material and the electrolyte are mixed, when the mixture is made into a thin film, Variation in composition can be suppressed. Therefore, in-plane variation (in-plane characteristic variation) in the ionic element can be suppressed.

It is a schematic cross section showing an example of composition of an ionic element concerning a 1st embodiment of the present invention. It is sectional drawing which represents typically the state of the ion layer shown in FIG. It is a flowchart showing an example of the manufacturing method of the ionic element which concerns on 1st Embodiment in process order. It is a schematic diagram showing the state of the charge double layer formed at the time of voltage application. It is the schematic diagram which expands and represents the aspect of the charge double layer shown in FIG. It is a schematic diagram for demonstrating the formation principle of a pn junction at the time of a voltage application. It is a schematic diagram for demonstrating a pn junction and the electrical storage function using it. It is a schematic diagram for demonstrating the light emission function using a pn junction. It is a schematic diagram for demonstrating the electric power generation function using a pn junction. It is a schematic diagram for demonstrating an example of the relationship between an electrical storage function, a light emission function, and an electric power generation function. It is a schematic cross section showing the other structural example of an ionic element. It is a schematic diagram showing the state of the ion layer after transfer to the voltage non-application state in the ionic element shown in FIG. It is a schematic diagram showing the state of the ion layer after transfer to the voltage non-application state in the ionic element shown in FIG. It is a schematic diagram for demonstrating each function in the ion layer after transfer to the voltage non-application state in the ionic element shown in FIG. 6 is a diagram illustrating film thickness variation of an ion layer according to Comparative Example 1. FIG. FIG. 6 is a diagram illustrating film thickness variation of an ion layer according to Example 1. It is a figure showing the relationship between the solvent concerning Example 2-1, 2-2, a film thickness, etc. It is a figure showing the relationship between the ultrasonic stirring which concerns on Example 3, and a light emission characteristic. FIG. 10 is a characteristic diagram illustrating a relationship between an applied voltage and various currents according to Example 4; It is a characteristic view showing the relationship between the elapsed time after the applied voltage interruption | blocking which concerns on Example 4, and various electric currents. It is a characteristic view which shows the relationship between the elapsed time after the applied voltage interruption | blocking which concerns on Example 4, and various electric currents with a temperature change. It is a schematic cross section showing the example of composition of the ionic element concerning a 2nd embodiment. It is a schematic diagram showing the example of a plane structure of the ion layer shown in FIG. It is a schematic plan view for demonstrating the effect | action of the microparticles | fine-particles shown in FIG. It is another schematic plan view for demonstrating the effect | action of the microparticles | fine-particles shown in FIG. 6 is a schematic cross-sectional view illustrating a configuration example of an ionic element according to Modification 1. FIG. FIG. 26 is a schematic diagram illustrating a planar configuration example of the ion layer illustrated in FIG. 25. 10 is a schematic diagram illustrating a planar configuration example of an ion layer in an ionic element according to Modification Example 2. FIG. 10 is a schematic diagram illustrating a planar configuration example of an ion layer in an ionic element according to Modification 3. FIG. 12 is a timing chart for explaining an example of a temperature distribution formation period in ionic elements according to Modifications 2 and 3. FIG. It is a schematic diagram showing the structural example of the ionic element module which concerns on 3rd Embodiment. FIG. 31 is a timing waveform diagram illustrating an example of a waveform of a drive voltage illustrated in FIG. 30. FIG. 31 is a timing waveform diagram illustrating another example of the waveform of the drive voltage illustrated in FIG. 30. It is a timing diagram showing the example of a switching of the drive method which concerns on 3rd Embodiment. It is a schematic diagram for demonstrating an effect | action of the ionic element module shown in FIG. It is another schematic diagram for demonstrating the effect | action of the ionic element module shown in FIG. FIG. 10 is a characteristic diagram illustrating a relationship between a driving period and light emission characteristics according to Example 4. FIG. 36B is an enlarged characteristic diagram illustrating a part of FIG. 36A together with a driving voltage. FIG. 10 is a characteristic diagram illustrating a relationship between a driving period and light emission characteristics according to Example 5. FIG. 37B is a characteristic diagram illustrating a part of FIG. 37A with an enlarged drive voltage. 10 is a schematic cross-sectional view illustrating a configuration example of an ionic element according to Modification 4. FIG. It is sectional drawing which represents typically the state of the ion layer shown in FIG. It is a schematic diagram for demonstrating each function in the ion layer at the time of the voltage application in the ionic element shown in FIG. It is a schematic diagram for demonstrating each function in the ion layer after transfer to the voltage non-application state in the ionic element shown in FIG. It is a schematic diagram showing the structural example of the electronic device which concerns on the application example 1 of an ionic element and an ionic element module. It is a schematic diagram showing the structural example of the electronic device which concerns on the application example 2 of an ionic element and an ionic element module.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The description will be given in the following order.
1. First embodiment (an example in which an amphiphile or ultrasonic agitation is used when manufacturing an ionic element)
2. Second embodiment (example in which a pn junction starter mechanism made of fine particles is provided)
3. Modification Example of Second Embodiment Modification Example 1 (Example of Starter Mechanism Consisting of Irregular Structure)
Modified example 2 (example of a starter mechanism for forming a temperature distribution by a thermoelectric element)
Modified example 3 (example of a starter mechanism that forms a temperature distribution by local light irradiation from a light source)
4). Third Embodiment (Example of Driving Method of Ionic Element That Reduces Voltage Intermittently)
5. Modification common to the first to third embodiments Modification 4 (another arrangement configuration example of a plurality of electrodes)
6). Application examples (application examples of ionic elements and ionic element modules to electronic devices)
7). Other variations

<1. First Embodiment>
[Constitution]
FIG. 1 schematically shows a cross-sectional configuration example (ZX cross-sectional configuration example) of the ionic element (ionic element 1) according to the first embodiment of the present invention. This ionic element 1 has a laminated structure composed of a pair of electrodes 111 and 112 and an ion layer 12 (functional layer), and is an element capable of exhibiting various functions (multifunctionality) described later. .

(Electrodes 111, 112)
Each of the electrodes 111 and 112 is an electrode for applying a voltage to the ion layer 12. In the present embodiment, these electrodes 111 and 112 are arranged so as to sandwich the ion layer 12.

  Each of the electrodes 111 and 112 has a thickness of, for example, 30 nm. The electrodes 111 and 112 are made of various metals such as gold (Au), platinum (Pt), aluminum (Al), nickel (Ni), titanium (Ti), and indium tin oxide (ITO). Oxide) and other conductive materials such as conductive oxides, conductive polymers, carbon nanotubes, and graphite. In this ionic element 1, unlike a general organic EL (Electro-Luminescence) element or the like, an electrode is used without considering the difference in work function values between the electrodes 111 and 112 and the ionic layer 12. 111 and 112 materials can be selected. For this reason, various conductive materials can be used as the electrodes 111 and 112.

(Ion layer 12)
The ionic layer 12 is inserted between the pair of electrodes 111 and 112 as described above, and is a layer that exhibits various functions to be described later (in this example, a power storage function, a light emitting function, and a power generation function). . The ionic layer 12 includes, for example, a porous material 121 having a large number of pores 121h and the inside of the porous material 121 (specifically, the pores as shown in the enlarged schematic diagram indicated by P1 in FIG. 1). 121h) and an electrolyte (electrolyte molecule) 122 dispersed therein. In other words, the ionic layer 12 is obtained by mixing the electrolyte 122 and the porous material 121 at a predetermined mixing ratio (for example, a mixing weight ratio or a mixing volume ratio). In addition, the thickness of such an ion layer 12 is 200 nm, for example.

  Here, the mixing ratio of the electrolyte 122 and the porous material 121 in the ion layer 12 is preferably, for example, electrolyte 122: porous material 121 = 1: n (for example, n ≧ 3). This is because, when the mixing ratio (for example, the mixing weight ratio or the mixing volume ratio) of the electrolyte 122 is relatively small (when the content of the electrolyte 122 is too small), a pn junction described later is hardly formed, and the light emitting operation is performed. This is because it is expected to become difficult. In other words, the mixing ratio of the electrolyte 122 and the porous material 121 is a suitable range for maintaining the pn junction formation state (light emission operation and power generation operation) even after the transition to the voltage non-application state described later. Is expected to exist.

  The porous material 121 functions as a base material (base material) of the ion layer 12. The size (diameter) of the pore 121h in the porous material 121 may be larger than the molecule of the electrolyte 122, and is, for example, 1 nm. The porous material 121 is made of, for example, an organic material such as a conductive polymer (light-emitting polymer) or an inorganic material such as a carbon nanotube. Specifically, examples of the conductive polymer include materials such as F8T2 (poly (9,9-dioctylfluorene-co-bithio-phene)). As described above, both an organic material and an inorganic material can be used as the porous material 121, but it is desirable to use an organic material such as a conductive polymer. This is because the molecular weight is increased, so that the ion layer 12 is easily formed. In addition, the porous material 121 desirably exhibits hydrophobicity in view of the balance (compatibility) with the electrolyte 122 described below.

  As described above, the electrolyte 122 is in a state where its molecules are dispersed in the pores 121 h of the porous material 121. In other words, the electrolyte 122 is impregnated in the porous material 121 (arranged so as to penetrate).

  For example, as schematically shown in FIG. 2, the electrolyte 122 is actually dispersed mainly in an ionic state in the ion layer 12. That is, some molecules of the electrolyte 122 are ionized into the cation 122c and the anion 122a. This is because the porous material 121 functions as a solvent for the electrolyte 122.

Here, the electrolyte 122 is configured by using molecules (ions) having a structure that suppresses its own mobility (a structure for suppressing ion mobility), for example, as will be described in detail later. Examples of such a molecule having an ion mobility suppressing structure include a molecule having polarity. As a specific example of a molecule having this polarity, a molecule having an anisotropic shape (elongated shape), for example, a straight chain structure, like the electrolyte 122 in the enlarged schematic diagram indicated by reference numeral P1 in FIG. The molecule | numerator which has is mentioned. As the straight chain structure, for example, an alkyl group (general _{formula: C n H 2n + 2)} , and an aryl group.

  Here, the length of the ion mobility suppressing structure (for example, the length of the linear structure) is desirably 2 nm or more (a structure having a large molecular weight), for example. From another point of view, it is desirable that the ion mobility suppressing structure has a length that is at least twice as long as the diameter of the pore 121 h in the porous material 121. This is because, within these length ranges, the ion mobility suppressing action described later is effectively performed.

  As such an electrolyte 122, it is desirable to use an ionic liquid. This is because an electric double layer to be described later is easily formed in the ion layer 12. As such an ionic liquid, for example, a linear structure (in this example, an alkyl group) such as a compound represented by the following formula (1) (tetradecyltrihexylphosphonium (tri-fluoromethylsulfonyl) amide [P66614] [TFSA]) is used. The thing of the molecular structure which has is mentioned. The ionic liquid represented by the formula (1) is a molecule having a structure for suppressing ion mobility as described above, and a molecule in which strong polarization occurs between the cation and the anion (has polarity). It has a structure.

  Such an ionic liquid is not limited to that represented by the formula (1), and any other ion may be used as long as it is a molecule having a structure for suppressing ion mobility (for example, a molecule having polarity). A liquid may be used. Specifically, for example, an ionic liquid formed by combining the following cations and anions may be used.

(A) Cations and imidazolium cations:
1-methyl-3-methylimidazolium (MMI),
1-ethyl-3-methylimidazolium (EMI),
1-propyl-3-methylimidazolium (PMI),
1-butyl-3-methylimidazolium (BMI),
1-pentyl-3-methylimidazolium (PeMI),
1-hexyll-3-methylimidazolium (HMI),
1-Octyl-3-methylimidazolium,
1-oxyl-3-methylimidazolium (OMI),
1-hexadecyl-3-methylimidazolium,
1-Butyl-2,3-dimethulimidazolium,
1,2-dimethyl-3-propylimidazolium (DMPI);
・ Pyridinium cations:
1-methl-1-propylpiprodonium (PP13),
1-methyl-1-propylpyrrolidinium (P13),
1-methyl-1-butylpyrrolidinium (P14),
1-butyl-1-methylpyrrolidinium (BMP);
・ Ammonium cation:
trimethylpropylammonium (TMPA),
trimethyloctylammonium (TMOA),
trimethylhexylammonium (TMHA),
trimethylpentylammonium (TMPeA),
trimethylbutylammonium (TMBA);
・ Pyrazolium cations:
1-ethyl-2,3,5-trimethylpyrazolium (ETMP),
1-butyl-2,3,5-trimethylpyrazolium (BTMP),
1-propyl-2,3,5-trimethylpyrazolium (PTMP),
1-hexyl-2,3,5-trimethylpyrazolium (HTMP),
1-Buthylpyridium,
1-Hexylpyridium;
(B) Anion
bis (trifluoromethanesulfonyl) imide (TFSI),
bis (fluorosulfonyl) imide (FSI),
bis (perfluoroethylsulfonyl) imide (BETI),
tetrafluoroborate (BF4),
hexafluorophosphate (PF6);

  Such an electrolyte 122 is desirably hydrophobic because of its compatibility with the porous material 121 described above. That is, it is desirable that the porous material 121 and the electrolyte 122 are both hydrophobic. This is because when the ion layer 12 is formed, the porous material 121 and the electrolyte 122 are easily mixed uniformly.

[Production method]
The ionic element 1 can be manufactured, for example, as shown in FIG. FIG. 3 is a flowchart showing an example of the manufacturing method of the ionic element 1 in the order of steps.

(Mixture production process)
First, a porous material 121 and an electrolyte 122 made of the materials described above and an amphiphilic substance (a substance having an amphiphilic molecule; a leveling agent) are mixed with a predetermined solvent (for example, chlorobenzene, dichlorobenzene, or the like). Etc.) to produce a mixture (step S11). In addition, as an amphiphilic substance, surfactant is mentioned, for example. Moreover, as this surfactant, a fluorine-type surfactant etc. are mentioned, for example. Specific examples of the fluorosurfactant include the following. At this time, the porous material 121 and the electrolyte 122 are mixed at the predetermined mixing ratio described above, for example. In addition, the content of the amphiphilic substance in the mixture is preferably about 1000 ppm or less, and more preferably about 10 ppm, for example. This is because excessive inclusion of the amphiphilic substance in the mixture is prevented, and the function of the amphiphilic substance described later is more effectively exhibited.
・ Perfluoroalkylsulfonic acid (CF ₃ (CF ₂ ) _n SO ₃ H)
・ Perfluorooctanesulfonate (PFOS)
・ Perfluoroalkylcarboxylic acid (CF ₃ (CF ₂ ) _n COOH)
・ Perfluorooctanoate (PFOA)
・ Fluorotelomer alcohol (F (CF ₂ ) _n CH ₂ CH ₂ OH)

  Here, when the porous material 121, the electrolyte 122, and the amphiphilic substance are mixed in this way, the materials are agitated using ultrasonic waves (for example, ultrasonic waves of about 50 kHz and about 100 W) in advance. It is desirable to keep This is because these materials (for example, the porous material 121 and the electrolyte 122) are easily mixed uniformly. In addition, it is desirable to perform the stirring using such an ultrasonic wave for a predetermined period (stirring time) that is, for example, a lower limit time or more and an upper limit time or less. Although details will be described later, the durability of the ionic element 1 during operation can be ensured while improving the stirring efficiency (the ionic element 1 can be prevented from being broken). Here, examples of the above upper limit time and lower limit time include 3 minutes and 10 minutes, respectively. That is, for example, stirring using ultrasonic waves is performed in a period of 3 minutes to 10 minutes. However, the upper limit value and the lower limit value (appropriate stirring time) vary depending on the type of the porous material 121 and the electrolyte 122, the output value of ultrasonic waves, and the like. Therefore, when performing stirring using ultrasonic waves, as described above, it is preferable that the stirring efficiency is high and the output and stirring time are such that the ionic element 1 is not broken.

(Mixture thinning process)
Next, the above-described mixture is formed into a thin film using, for example, spin coating or inkjet (step S12). In other words, the mixture obtained in step S11 is thinned. At this time, when spin coating is used, for example, in air, spin coating is performed for about 1 minute at a rotation rate of about 500 rpm (rotation / minute). In addition, the method for making the mixture into a thin film in this way is not limited to the above-described spin coating and inkjet, and other printing techniques can also be used. Specifically, for example, printing techniques such as nanoimprinting, induction plasma etching, and dry etching, and printing techniques such as etching techniques can be used.

(Drying process)
Subsequently, the above-described solvent is evaporated from the mixture by drying the thin film mixture thus obtained (step S13). As a result, an ionic layer 12 composed of a porous material 121 having a large number of pores 121h and an electrolyte 122 dispersed in the pores 121h, as shown in the enlarged schematic diagram indicated by reference numeral P1 in FIG. It is formed. Incidentally, when drying is performed, for example, in a dry in a nitrogen (N ₂₎ atmosphere.

(Electrode mounting process)
After that, a plurality of electrodes 111 and 112 are attached to the ion layer 12 thus obtained (step S14). Specifically, the ion layer 12 obtained in step S13 is sandwiched between a pair of electrodes 111 and 112 separately formed using, for example, a vacuum deposition method or a coating method. Thus, the ionic element 1 shown in FIG. 1 is completed. Thus, complicated steps such as a vacuum process are not necessary, and the ionic element 1 can be manufactured by a relatively simple process because it can be manufactured in a room temperature environment.

[Action / Effect]
(A-1. Formation of pn junction)
In this ionic element 1, when a voltage is applied to the ion layer 12 using the electrodes 111 and 112, a pn junction is formed in the ion layer 12 according to the following principle.

  That is, first, as shown in FIG. 4, the electrode 111 is electrically connected to the positive (+) side of the voltage supply source PS, and the electrode 112 is electrically connected to the negative (−) side of the voltage supply source PS. A predetermined voltage is applied from the PS to the ion layer 12 through the electrodes 111 and 112. Then, for example, as shown in FIG. 2, the positive ions 122 c and the negative ions 122 a are selectively moved from the state where the positive ions 122 c and the negative ions 122 a are dispersed in the ion layer 12, respectively. A double layer is formed. Specifically, as shown in FIG. 4, the cations 122c in the ion layer 12 are aligned with the surface of the electrode 112 (surface on the ion layer 12 side) at a predetermined interval. On the other hand, the anions 122a in the ion layer 12 are aligned with the surface of the electrode 111 at a predetermined interval. In FIG. 4, “h” represents a hole and “e” represents an electron, and the same applies to the following drawings.

At this time, for example, as shown in an enlarged view in FIG. 5, the electric double layer on the electrode 111 side and the electric double layer on the electrode 112 side are each formed using a minute distance of about g = 1 nm. Therefore, in each of these electric double layers, a very large capacitance of, for example, about 10 (μF / cm ² ) is formed, and a very large electric field of, for example, about 3 (MV / cm) is generated. Become.

  When a large electric field is generated in the electric double layer in this way, for example, as shown in FIG. 6, electrons e are injected from the electrode 111 into the ion layer 12, and on the electrode 111 side in the ion layer 12. An electrically conductive region A1 is formed. In addition, holes h are injected from the electrode 112 into the ion layer 12, and the electrically conductive region A <b> 2 is formed on the electrode 112 side in the ion layer 12. This time, a charge double layer is formed between the electric conduction region A1 and the cation 122c, and a charge double layer is formed between the electric conduction region A2 and the anion 122a. .

  Then, the charge double layer and the electric conduction region are repeatedly formed in this way, and finally a pn junction is formed in the ion layer 12 as shown in FIG. 7, for example. Specifically, in the ion layer 12, an n-type region 12n in which electrons e and cations 122c are mixed and dispersed is formed closer to the electrode 111 side than the pn junction surface Sj. In addition, a p-type region 12p in which holes h and anions 122a are mixed and formed is formed closer to the electrode 112 than the bonding surface Sj. These p-type region 12p and n-type region 12n form a pn junction. Based on the above principle, a pn junction is formed in a self-organized manner when a voltage is applied in the ion layer 12.

(A-2. Power storage function)
Here, in this pn junction (p-type region 12p and n-type region 12n), a very large capacitance is formed using the electric double layer as described above. It can be said that it is the state (electric storage state) which is storing. That is, in the ionic element 1, the power storage function is exhibited in the ionic layer 12 using the electric double layer formed in the ionic layer 12.

(A-3. Light emission function)
Moreover, in the ionic element 1, for example, as shown in FIG. 8, the light emitting function is exhibited by using a pn junction formed in the ion layer 12. Specifically, in the vicinity of the junction surface Sj of the pn junction, the holes h in the p-type region 12p and the electrons e in the n-type region 12n are recombined (carrier recombination occurs), and as a result, The emitted light Lout (emitted light) is emitted from the vicinity of the joint surface Sj to the outside. Based on this principle, the ionic element 1 performs a light emission operation. In FIG. 8, for the sake of convenience, the emitted light Lout is shown as being emitted in the directions of the electrodes 111 and 112, but in actuality, the emitted light Lout can be emitted in all directions.

(A-4. Power generation function)
Furthermore, in the ionic element 1, for example, as shown in FIG. 9, a power generation function (photoelectric conversion function) is exhibited by using a pn junction formed in the ion layer 12. Specifically, when incident light Lin is incident from the outside near the junction surface Sj of the pn junction, photoelectric conversion is performed near the junction surface Sj, and a carrier pair of holes h and electrons e is generated. Using the carrier pair generated in this manner (using photoelectric conversion at the pn junction), charges are accumulated in the ionic layer 12, whereby the ionic element 1 performs a power generation operation. In FIG. 9, for convenience, the incident light Lin is illustrated as being incident from the directions of the electrodes 111 and 112, but the incident light Lin can actually be incident from all directions.

  Thus, in the ionic element 1 of the present embodiment, the ionic layer 12 exhibits multi-functionality (power storage function, light emitting function, and power generation function) by using the pn junction formed in the ionic layer 12. Is done.

  That is, for example, as shown in FIG. 10, when a voltage is first applied to the ion layer 12 using the electrodes 111 and 112, a pn junction is formed in the ion layer 12, and this pn junction is formed. Then, it will be in the electrical storage state using the electric double layer mentioned above (state S1 in FIG. 10). Then, as indicated by the broken line arrow in FIG. 10, the light emitting operation (state S2) and the power generation operation (state S3) are performed based on the above-described principle using the pn junction formed in this way. Will be made respectively. Note that such light emission operation and power generation operation can be complementarily realized as indicated by the broken-line arrows in FIG. That is, for example, in addition to carriers (holes h and electrons e) obtained by power storage, it is also possible to perform a light emission operation using carriers obtained by a power generation operation. In addition, each of the power storage operation and the power generation operation can be complementarily realized as indicated by the dashed arrows in FIG. That is, for example, it is possible to store a carrier obtained by a power generation operation.

(B. Action in production method)
Next, the effect | action in the manufacturing method of the ionic element 1 of this Embodiment is demonstrated.

  First, for example, in step S <b> 11 in FIG. 3, an amphiphile is mixed in a solvent together with the porous material 121 and the electrolyte 122 to produce a mixture. Thus, the amphiphilic substance is also mixed, so that the amphiphilic substance functions as a leveling agent (surface tension adjusting agent). As a result, when the mixture is made into a thin film in the subsequent step 12, the surface tension of the mixture decreases, and the mixture becomes thin and spreads easily (thickness variation in the ion layer 12 can be suppressed). ).

  Moreover, since the high boiling point solvent (For example, solvent whose boiling point is about 80 degreeC or more) which consists of the material etc. which were mentioned above is used as a solvent at this time, when drying a thin film-like mixture in subsequent process S13, for example. In addition, the solvent is less likely to evaporate and the mixture dries slowly. Therefore, the effect of reducing the surface tension by the above-described amphiphile functions more effectively, and the mixture is easily dried evenly in the film. As a result, the film thickness variation in the ion layer 12 is further suppressed. In addition, when a mixture is dried, for example, when a hot plate (a temperature of about 50 ° C.) is used, the mixture is dried rapidly, so that the function of the amphiphilic substance is insufficient. There is a fear. In addition, in this case, since the drying is performed at a high temperature, the porous material 121 (conductive polymer or the like) may be broken.

  Furthermore, when mixing the porous material 121, the electrolyte 122, and the amphiphile in step S11, these materials are preliminarily stirred using ultrasonic waves. Thereby, the porous material 121 and the electrolyte 122 are easily mixed uniformly, and the composition variation in the film is suppressed when the mixture is made into a thin film in step S12. As a result, in-plane characteristic variations in the ionic element 1 (characteristic variations such as the light emitting function described above) can be suppressed.

(C. Action by molecules having a structure for suppressing ion mobility)
Subsequently, an operation in the case where the electrolyte 122 of the present embodiment is configured using molecules having an ion mobility suppressing structure will be described.

(Other configuration examples)
FIG. 11 schematically shows a cross-sectional configuration example (ZX cross-sectional configuration example) of an ionic element (ionic element 101) according to another configuration example. The ionic element 101 of this other configuration example corresponds to the ionic element 1 of the present embodiment in which the ionic layer 102 is provided instead of the ionic layer 12, and the other configuration is the same.

  In this ion layer 102, for example, as shown in the enlarged schematic diagram indicated by reference numeral P101 in FIG. 11, the electrolyte 103 dispersed in the pores 121h of the porous material 121 is a molecule (ion) having an isotropic shape. It is comprised using. That is, the electrolyte 103 in the ionic layer 102 is different from the electrolyte 122 of the present embodiment indicated by the symbol P1 in FIG. 1 in that the molecule has an anisotropic shape (a molecule having a structure for suppressing ion mobility). It is not.

  Therefore, in the ionic element 101, for example, as shown in FIG. 12, after the pn junction is formed in the ion layer 102 on the same principle as the ion layer 12, the voltage supply from the voltage supply source PS is cut off. When it is done (from the voltage application state to the voltage non-application state), it becomes as follows. That is, when the voltage is no longer applied to the ion layer 12 when the voltage is not applied, the positive ions 122c and the negative ions 122a in the ion layer 12 move, for example, as indicated by arrows in FIG. It is dispersed and immediately returns to the state shown in FIG.

  Then, as the positive ions 122c and the negative ions 122a move, holes h and electrons e in the ion layer 12 (pn junction) also move and disperse, respectively. As a result, a pn junction is formed from within the ion layer 12. It will disappear. The reason why the pn junction disappears immediately after the transition to the no-voltage application state is as follows. That is, unlike the present embodiment described below, the molecules of the electrolyte 103 have an isotropic shape, so that the cation 122c and the anion 122a are easy to move (high ion mobility). . In other words, the molecule of the electrolyte 103 is different from the molecule of the electrolyte 122 of the present embodiment because it does not have a structure for suppressing ion mobility.

  In this way, in the ionic element 101, the pn junction disappears immediately after the transition to the no-voltage application state, and thus the light emitting function and the power generation function cannot be exhibited after the transition to the no-voltage application state. Therefore, the functionality of the ionic element 101 is insufficient (multifunctionality cannot be realized).

(This embodiment)
On the other hand, in the ionic element 1 of the present embodiment, the electrolyte 122 in the ionic layer 12 is configured using, for example, a molecule having a structure for suppressing ion mobility (for example, a molecule having polarity). Yes. Specifically, for example, like the electrolyte 122 shown in FIG. 1, it is configured using molecules having an anisotropic shape (for example, a linear structure).

  Thereby, in the ionic element 1, the mobility of the ions (the positive ions 122c and the negative ions 122a) in the ion layer 12 is suppressed. Specifically, in this example, since it has an anisotropic shape, ions of such shape and the pores 121h of the porous material 121 or ions easily become entangled with each other, and as a result, the ions move. Expected to be difficult. As described above, when the cation 122c and the anion 122a in the ion layer 12 become difficult to move, the pn junction in the ion layer 12 is easily maintained. When the pn junction is formed, since a large electric field is generated in the charge double layer as described above, ions and carriers are forcibly moved using the large electric field to form the pn junction.

  For this reason, for example, as shown in FIG. 13, in the ionic element 1, the pn junction formed in the ionic layer 12 is in a state in which no voltage is applied, as compared with the ionic element 101 according to the other configuration example. It becomes difficult to disappear even after the transition to. In other words, unlike the ionic device 101, the ionic device 1 forms a pn junction for a certain period of time (for example, about 1000 seconds (about 17 minutes as will be described later)) even after the transition to the no-voltage application state. State will be maintained.

  As a result, for example, as shown in FIG. 14, unlike the ionic element 101, the ionic element 1 continues to realize multi-functionality by using this pn junction even after the transition to the no-voltage application state. The That is, using the pn junction, the light emission function (the emission operation of the emitted light Lout) and the power generation operation (the photoelectric conversion operation of the incident light Lin) are exhibited.

  As described above, in the present embodiment, when the mixture is prepared, the amphiphile is mixed with the porous material 121 and the electrolyte 122 in the solvent. When the mixture is made into a thin film, the surface tension of the mixture can be reduced to facilitate the uniform expansion of the mixture. Therefore, for example, in-plane variation in the ionic element 1 (thickness variation in the ion layer 12) can be suppressed as compared with the case where the mixture is made into a thin film using only spin coating. This is because film thickness unevenness due to convection of the solvent is likely to occur only by using spin coating.

  In addition, when the porous material 121, the electrolyte 122, and the like are mixed in this way, stirring is performed using ultrasonic waves. Therefore, when the mixture is subsequently made into a thin film, the composition in the film Variation can be suppressed. Therefore, in-plane variation (in-plane characteristic variation) in the ionic element 1 can be suppressed.

As described above, in the manufacturing method of the present embodiment, in-plane variations (in-plane variations in film thickness, characteristics, etc.) in the ionic element 1 can be reduced. For example, the following effects can be obtained.
・ Low voltage drive (for example, it is possible to reduce the voltage from about 2-3V to 1.5V)
・ Longer device life (for example, from about 1 hour to 3 hours or more)
・ Large element area (for example, an area of about 1 cm × 1 cm can be realized)
- emission operation at a high luminance (e.g., from a conventional 1000 cd / m ² or less, enables high brightness to 2500 cd / m ² or more)

  In the method of manufacturing the ionic element 1 of the present embodiment, as described above, both the mixing of the amphiphile and the stirring using the ultrasonic wave are performed. Any one of the above may not be performed.

  In addition, in the present embodiment, when the electrolyte 122 is configured using molecules having a structure for suppressing ion mobility (for example, molecules having polarity), the electrolyte 122 is formed in the ion layer 12. The pn junction can be maintained to some extent even after the transition to the no-voltage application state. Therefore, it is possible to improve functionality by using a pn junction having such characteristics, and it is also possible to improve user convenience.

  Specifically, using a pn junction formed in the ion layer 12, it is possible to realize multi-functionality (such as a power storage function, a light emitting function, and a power generation function).

  In addition, since the pn junction is maintained to some extent even after the transition to the no-voltage applied state, each function (storage function, light emitting function, power generation function, etc.) using the pn junction is realized even when no voltage is applied. Is possible.

  Furthermore, in particular, the element structure of the ionic element 1 according to the present embodiment also provides the following advantages compared to the element structure of the ionic element (ionic element 1E) according to Modification Example 4 described later. That is, first, the response speed of the ionic element can be improved in the present embodiment as compared with the fourth modification. Further, in the present embodiment, compared with the fourth modification, it is less affected by an interface (for example, an interface between a substrate 10 and an ion layer 12 described later), and the functionality of each function can be further improved. It becomes.

[Example]
Next, specific examples (Examples 1 to 4) in this embodiment will be described in detail.

Example 1
FIG. 15A and FIG. 15B represent film thickness variations of the ion layers according to Comparative Example 1 and Example 1, respectively. These film thickness variations were measured with a step gauge. In Comparative Example 1 shown in FIG. 15A, an amphiphile is not mixed when the above-described mixture is manufactured. For this reason, in this comparative example 1, it turns out that the big film thickness dispersion | variation about 600 nm has arisen. On the other hand, in Example 1 shown in FIG. 15B, an amphiphile (a surfactant in this example) is mixed when the above-described mixture is produced. Therefore, in Example 1, the film thickness variation is as small as about 35 nm, and it can be seen that the film thickness variation is reduced by one digit or more as compared with Comparative Example 1 described above.

(Example 2)
Next, FIG. 16 shows the relationship between the solvent and the film thickness according to Examples 2-1 and 2-2. Specifically, for each of the solvent material, the film thickness of the ionic layer 12, the drying time required for the drying step (step S13), and the surface roughness (film thickness variation) of the ionic layer 12, Example 2-1 It is shown together for each 2-2.

  In Example 2-1, chlorobenzene (boiling point = about 130 ° C.) is used as a solvent. Therefore, when the mixture is made into a thin film, chlorobenzene as a solvent is relatively easily volatilized (evaporated), and thus the drying time is relatively short (18 minutes). Therefore, it can be seen that the surface tension of the mixture is relatively high, the mixture is difficult to spread uniformly, and the film thickness variation of the ion layer 12 is relatively large (about 130 to 300 nm).

  On the other hand, in Example 2-2, dichlorobenzene (boiling point = about 180 ° C.) is used as a solvent. Therefore, when the thin film-like mixture is dried, dichlorobenzene as a solvent is less likely to evaporate than chlorobenzene, so that the drying time is much longer than that of Example 2-1 (85 minutes), and mixing is performed. Your body dries slowly. For this reason, the effect of reducing the surface tension by the amphiphile functions more effectively. Therefore, as a result of the mixture being easily dried uniformly in the film, the film thickness variation in the ion layer 12 is very small (about 20 to 28 nm) as compared with Example 2-1. I understand.

  According to these Examples 2-1 and 2-2, it is desirable to use a solvent having a boiling point as high as possible (high boiling solvent) as the solvent used in the production step of the mixture (step S11). It can be seen that it is more desirable to use a solvent having a higher boiling point among the boiling point solvents.

(Example 3)
Next, FIG. 17 shows the relationship between the ultrasonic agitation according to Example 3 and the light emission characteristics of the ionic element. The conditions of Example 3 are as follows.
-Electrolyte: ionic liquid represented by the above-mentioned formula (1)-Porous material-Luminescent polymer-Amphiphile-Surfactant (content = 10 ppm)
-Mixing ratio of electrolyte and porous material ... electrolyte: porous material = 1: 5
-Driving voltage (operating voltage) at the time of light emission operation: Implemented at 2.5 V and 3.0 V, respectively-Ultrasonic stirring: 50 kHz, 100 W ultrasonic wave, 0 minutes (no ultrasonic stirring: none), 3 minutes, 10 For 20 minutes, 20 minutes, 30 minutes

  From FIG. 17, it can be seen that in the presence of ultrasonic agitation, in the presence of ultrasonic agitation, the material is easily mixed uniformly in the mixture, and as a result, in-plane variation in light emission characteristics is suppressed. It can also be seen that a sufficient stirring effect is obtained when the ultrasonic stirring time is 10 minutes or longer. However, when the operating voltage is 3.0 V, the durability of the ionic element deteriorates (the ionic element deteriorates) if the ultrasonic stirring time becomes too long, and no light is emitted after 30 minutes. I understand that. From these facts, as described above, it can be said that the stirring using the ultrasonic wave is desirably performed in a period of, for example, about 3 minutes to 10 minutes. This is because the durability of the ionic element during operation can be ensured (deterioration of the ionic element can be suppressed) while enhancing the stirring effect (while suppressing in-plane variation of the light emission characteristics and the like).

Example 4
Subsequently, the conditions of Example 4 are as follows.
Electrolyte: ionic liquid represented by the above-mentioned formula (1) Porous material ... Luminescent polymer- Mixing ratio of electrolyte and porous material ... Electrolyte: Porous material = 1: 5

  In the ionic element of Example 4, since the ionic liquid as the electrolyte is represented by the above-described formula (1), the molecule having a structure for suppressing ion mobility (in this example, a molecule having polarity) And an anisotropic molecule). At the same time, in the ionic element of Example 4, the ion mobility is small because the mixing ratio of the ionic liquid as the electrolyte is relatively small.

  For this reason, for example, as shown by the broken line arrow in FIG. 18, when the voltage applied to the ion layer is increased, a pn junction is formed at about 2 V or more, and the light emitting operation is performed. Unlike 1, the light emission operation continues even if the applied voltage is decreased thereafter. Specifically, even when the applied voltage is reduced to 0 V (no voltage applied state), the pn junction formation state is maintained and the light emitting operation is also maintained. Note that “light-receiving current due to emitted light” shown on one vertical axis in FIG. 18 is a light-receiving current in a photodiode arranged in the vicinity of the ionic element, and represents the intensity of the emitted light (emission intensity). Corresponding value. This also applies to the following.

  Further, for example, as shown in FIG. 19, in this Example 4, even when the applied voltage is cut off (even when the voltage is not applied), the current flowing through the element and the light receiving current due to the emitted light are about It continues to flow at a somewhat large value for about 1000 seconds (about 17 minutes). That is, it can be seen that even when the applied voltage is cut off, the pn junction formation state is maintained for some time.

  Incidentally, for example, as shown in FIG. 20, when the environmental temperature was changed to 250K, 300K, and 350K in Example 4, it was found that the following temperature characteristics were exhibited. That is, it has been found that the current flowing through the element flows for a longer time after the applied voltage is cut off as the environmental temperature decreases. This is because the ion mobility decreases as the temperature decreases, and more time is required for the discharge operation. That is, it can be said that the current flowing through this element exhibits the same behavior as a general electric double layer capacitor. On the other hand, it was found that the received current (emission intensity) by the emitted light hardly depends on the environmental temperature, and continues to flow for about 1000 seconds as described above at any environmental temperature.

  Hereinafter, other embodiments (second and third embodiments) of the present invention will be described. The ionic elements of these embodiments and the like can be basically manufactured in the same manner as the ionic element 1 of the first embodiment. However, mixing of the above-mentioned amphiphile, use of a high boiling point solvent, stirring using ultrasonic waves, etc. may not be performed. In the following, the same components as those in the first embodiment and the like are denoted by the same reference numerals, and description thereof will be omitted as appropriate.

<2. Second Embodiment>
[Constitution]
FIG. 21 schematically shows a cross-sectional configuration example (ZX cross-sectional configuration example) of the ionic element (ionic element 1A) according to the second embodiment. FIG. 22 schematically illustrates a planar configuration example (XY planar configuration example) of the ion layer 12 in the ionic element 1A.

  The ionic element 1A of the present embodiment corresponds to the ionic element 1 of the first embodiment provided with a pn junction starter mechanism having a fine structure (fine particles 14A). Is basically the same. The starter mechanism is for partially (locally) starting the formation of the pn junction described above in the ion layer 12 when a driving voltage is applied to the ion layer 12 via the electrodes 111 and 112. belongs to.

As shown in FIGS. 21 and 22, the fine structure (fine particles 14 </ b> A) functioning as such a starter mechanism is dispersedly arranged in the ion layer 12. Further, these fine particles 14A are also formed in the ion layer 12 so that pn junctions are formed at a plurality of positions in a substantially isotropic (preferably isotropic) manner in the ion layer 12 (in the XY plane). And is isotropically arranged (preferably isotropic). As will be described in detail below, the fine particles 14A partially start formation of a pn junction by causing local electric field concentration in the ion layer 12. Such fine particles 14A are made of, for example, nano-scale fine particles, specifically, nanoparticles made of silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), or the like.

[Action / Effect]
In the ionic element 1A of the present embodiment, since the starter mechanism having a fine structure (fine particles 14A) is provided, when a driving voltage is applied from the electrodes 111 and 112 to the ion layer 12, this ion Within layer 12, formation of the pn junction is partially initiated.

  Specifically, first, as indicated by a broken line in FIG. 23, for example, a pn junction (p-type region 12p and n-type region 12n) is partially (near the peripheral region) in the ion layer 12 (peripheral region) ( Locally). Next, for example, as indicated by an arrow in FIG. 24, the pn junction region (peripheral region of the fine particle 14A) that is partially formed first is used as a nucleus, and the pn junction region gradually expands around the pn junction region. It becomes an aspect.

  As described above, since the pn junction is formed such that it is partially formed in the ionic layer 12 and then gradually expands, the ionic element 1A of the present embodiment is uniform throughout the ionic layer 12. Compared with the case where the pn junction is formed, the pn junction is easily formed when the drive voltage is applied.

  As described above, in the present embodiment, since the starter mechanism for partially starting the formation of the pn junction in the ion layer 12 when the voltage is applied is provided, the pn junction is formed when the driving voltage is applied. Can be made easier. Therefore, it becomes possible to keep the operating voltage (driving voltage) of the ionic element low (for example, about 1.0 V to 1.5 V).

  In addition, since this starter mechanism forms pn junctions at a plurality of locations in the ion layer 12 in a substantially isotropic manner, the pn junction region can be easily extended to the entire ion layer 12. Therefore, the operating voltage of the ionic element 1A can be kept lower.

  In particular, in the present embodiment, the starter mechanism is configured by using a fine structure (fine particles 14A). Therefore, the starter mechanism is realized by the element structure, and dynamic control is not required when performing its function. Therefore, a low operating voltage can be realized by a simple method.

  Further, since the fine particles 14A are dispersedly arranged in the ion layer 12, the formation start region of the pn junction is easily arranged isotropically. Therefore, it can be said that the operating voltage of the ionic element 1A can be easily suppressed to a lower level.

<3. Modification of Second Embodiment>
Subsequently, modified examples (modified examples 1 to 3) of the second embodiment will be described. In addition, the same code | symbol is attached | subjected to the same component as 2nd Embodiment etc., and description is abbreviate | omitted suitably.

[Modification 1]
FIG. 25 schematically illustrates a cross-sectional configuration example (ZX cross-sectional configuration example) of an ionic element (ionic element 1B) according to Modification 1. FIG. 26 schematically shows a planar configuration example (XY plane configuration example) of the ion layer 12 in the ionic element 1B.

  The ionic element 1B of this modification is provided with a starter mechanism having a fine structure (concave / convex structure 141) instead of the starter mechanism having a fine structure (fine particles 14A) in the ionic element 1A of the second embodiment. The other configurations are basically the same.

As shown in FIGS. 25 and 26, the fine structure (uneven structure 141) functioning as such a starter mechanism has a plurality of protrusions 14B on the electrode 111 (near the interface between the electrode 111 and the ion layer 12). It is formed by being distributed. Also in the present modification, these protrusions 14B are also formed so that pn junctions are formed at a plurality of locations in the ion layer 12 (in the XY plane) in a substantially isotropic (preferably isotropic) manner. They are arranged approximately isotropic (preferably isotropic) in the ion layer 12. This concavo-convex structure 141 (protrusion 14B) is also configured to partially initiate the formation of a pn junction by causing local electric field concentration in the ion layer 12 as in the case of the fine particles 14A. Such a protrusion 14B includes, for example, various metals such as gold (Au), platinum (Pt), aluminum (Al), nickel (Ni), titanium (Ti), and indium tin oxide (ITO). ) And other conductive oxides, conductive polymers, carbon nanotubes, graphite and other conductive materials, nanoscale fine particles, specifically silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), etc. It consists of materials such as nanoparticles. In FIG. 25, for convenience, the concavo-convex structure 141 has a triangular cross-sectional shape. However, the concavo-convex structure 141 is not limited to this, and the concavo-convex structure 141 has another three-dimensional shape (for example, a three-dimensional shape having a rectangular cross-sectional shape). Etc.).

  Also in this modified example, by providing the starter mechanism having such a fine structure (uneven structure 141), basically the same effect can be obtained by the same operation as in the second embodiment. Is possible.

  In particular, in the present modification, the concavo-convex structure 141 formed in the vicinity of the interface between the electrode 111 and the ion layer 12 is used as the starter mechanism, so that a pn junction is formed according to the shape design of the concavo-convex structure 141. The starting area can be freely controlled. Therefore, the operating voltage of the ionic element 1B can be easily adjusted.

[Modifications 2 and 3]
FIG. 27 schematically illustrates a planar configuration example (XY planar configuration example) of the ion layer 12 in the ionic element (ionic element 1C) according to Modification 2. FIG. 28 schematically shows a planar configuration example (XY planar configuration example) of the ion layer 12 in the ionic element (ionic element 1D) according to Modification 3.

  In the ionic elements 1C and 1D of the modified examples 2 and 3, in the ionic element 1A of the second embodiment, the following starter mechanism is provided instead of the starter mechanism having a fine structure (fine particles 14A). It corresponds to the thing. That is, it corresponds to the one provided with a starter mechanism that partially starts the formation of the pn junction by forming a temperature distribution in the ion layer 12, and the other configuration is basically the same as that of the ionic element 1A. It has become.

  Specifically, in the ionic element 1C of Modification 2 shown in FIG. 27, a starter mechanism is configured using a thermoelectric element 14C that directly forms a temperature distribution. The thermoelectric element 14C generates heat when a voltage is supplied from a power source (not shown), and the peripheral region of the thermoelectric element 14C in the ion layer 12 can be set to a relatively high temperature. Also in this modification, the plurality of thermoelectric elements 14C are formed so that pn junctions are formed at a plurality of locations in the ion layer 12 (in the XY plane) substantially isotropically (preferably isotropically). Two-dimensionally arranged substantially isotropic (preferably isotropic) on the ion layer 12.

  On the other hand, in the ionic element 1D of Modification 3 shown in FIG. 28, the starter mechanism is configured by using the light source 15 that indirectly forms a temperature distribution by locally irradiating the ion layer 12 with light. Has been. The light source 15 is driven by a power source (not shown) to locally irradiate the irradiation light L1 to the ion layer 12, and set the irradiation region to a relatively high temperature (forms a high temperature region Aht). It is possible. Also in the present modified example, such a high temperature region Aht is formed so that pn junctions are formed at a plurality of locations in a substantially isotropic (preferably isotropic) manner in the ion layer 12 (in the XY plane). Are formed approximately isotropic (preferably isotropic) on the ion layer 12.

  Thus, in the second and third modifications, a starter mechanism is provided that partially starts the formation of a pn junction by forming a temperature distribution in the ion layer 12. As a result, a pn junction region is first formed in a relatively high temperature region (such as the high temperature region Aht), and the pn junction region expands around this region as a nucleus. Therefore, basically the same effect can be obtained by the same operation as that of the second embodiment.

  Moreover, in these modified examples 2 and 3, since the formation mode of the pn junction region can be freely controlled according to the temperature distribution, the operating voltage of the ionic elements 1C and 1D can be easily adjusted.

  Furthermore, in particular, in the ionic element 1C of the modification 2, the temperature distribution is directly formed by the thermoelectric element 14C, so that the temperature distribution is easily adjusted, and the operating voltage of the ionic element 1C is further easily adjusted. be able to. On the other hand, in the ionic element 1D of Modification 3, since the starter mechanism is realized by local light irradiation from the light source 15, it is not necessary to change the element structure itself and can be realized with a simple configuration.

  For example, as shown in FIG. 29, in these modifications 2 and 3, the starter mechanism (thermoelectric element 14C or light source 15) is operated by the starting period T1 of the ionic elements 1C and 1D and the subsequent steady operation period T2 respectively. It is desirable to form the above temperature distribution only during the starting period T1. In this case, since the starter function by the formation of the temperature distribution is selectively exhibited during the period in which the pn junction is mainly formed (starting period T1), a more effective starter function is realized. Is possible.

<4. Third Embodiment>
[Constitution]
FIG. 30 schematically shows a cross-sectional configuration example (ZX cross-sectional configuration example) of the ionic element module (ionic element module 2) according to the third embodiment, together with a block configuration of the drive unit 21 described below. It is a representation. The ionic element module 2 of the present embodiment includes any one of the ionic elements 1 and 1A to 1D described so far, and a drive unit 21 that drives the ionic element. In addition, since the driving method of the ionic element according to the present embodiment is embodied in the ionic element module 2 of the present embodiment, it will be described together below.

(Driver 21)
The drive unit 21 drives the ionic element 1 (1A to 1D) by applying a drive voltage Vd to the ion layer 12 through the electrodes 111 and 112. In the present embodiment, when the ionic element 1 (1A to 1D) is driven, the driving unit 21 performs intermittent driving that lowers the driving voltage Vd intermittently (for example, periodically). Yes.

  Specifically, the drive unit 21 intermittently decreases the drive voltage Vd using a pulse waveform, for example, like the timing waveform of the drive voltage Vd shown in FIG. Specifically, in this case, there are a high voltage period TH (normal drive period) in which the drive voltage Vd = high voltage VH and a low voltage period TL (refresh operation period to be described later) in which the drive voltage Vd = low voltage VL. The pulse waveform is alternately repeated along the time axis. That is, in this case, the drive unit 21 performs intermittent drive by intermittently reducing the drive voltage Vd = VH to Vd = VL.

  Alternatively, the drive unit 21 superimposes an AC voltage (in this example, an AC voltage made up of a sine wave) on a predetermined DC voltage Vdc, as in the timing waveform of the drive voltage Vd shown in FIG. 32, for example. The drive voltage Vd may be lowered intermittently using an AC waveform. Specifically, in this case, an AC waveform in which a high voltage period VH in which drive voltage Vd ≧ DC voltage Vdc and a low voltage period VL in which drive voltage Vd <DC voltage Vdc are alternately repeated along the time axis It has become. That is, in this case, the drive unit 21 performs intermittent drive by intermittently reducing the drive voltage Vd ≧ Vdc to Vd <Vdc.

  Here, it is preferable that the drive unit 21 instantaneously (instantaneously) perform such a decrease in the drive voltage Vd and subsequent recovery. In other words, the decrease period (low voltage period TL) of the drive voltage Vd is a relatively short period (minute period) compared to other periods (non-decrease period of the drive voltage Vd, high voltage period VH). Is preferable (for example, about 10 ms).

  Further, it is desirable that the drive unit 21 intermittently lowers the drive voltage Vd to 0V. Thereby, since the application of the drive voltage Vd is intermittently stopped, the refresh operation described later is performed more effectively, and the lifetime of the ionic element 1 (1A to 1D) is further increased. is there.

  Further, for example, as shown in FIG. 33, the driving unit 21 performs constant voltage driving with the driving voltage Vd constant during the starting period T1 of the ionic element 1 (1A to 1D), and also during the starting period T1. In the subsequent steady operation period T2, it is desirable to perform the above-described intermittent drive (drive that intermittently lowers the drive voltage Vd).

[Action / Effect]
In the ionic element module 2 of the present embodiment, when driving the ionic element 1 (1A to 1D), the driving voltage Vd applied to the ionic layer 12 via the electrodes 111 and 112 is intermittently reduced. (Intermittent driving described above is performed). Thereby, in this ionic element 1 (1A-1D), the regular (for example, periodic) refresh operation | movement of the electrolyte 122 (ionic liquid etc.) in the ion layer 12 is implement | achieved on the following principles.

  Specifically, first, as shown in FIG. 34, for example, in the low voltage period VL (refresh operation period), the drive voltage Vd decreases (in this example, Vd = VL). The following actions occur at the pn junction (p-type region 12p and n-type region 12n). That is, a part of the cation 122c and the anion 122a moves, and as a result, a part of the hole h and the part of the electron e in the ion layer 12 (pn junction) move and disperse, respectively. Some of the electrons e recombine and disappear from the ion layer 12.

  Next, for example, as shown in FIG. 35, in the subsequent high voltage period VH (normal drive period), the drive voltage Vd recovers (in this example, Vd = VL returns to Vd = VH). The following effects occur in the pn junction within 12. That is, as a result of supplying (implanting) new cations 122c and anions 122 from the electrodes 111 and 112 to the n-type region 12n and the p-type region 12p, respectively, the refresh operation of the electrolyte 122 in the ion layer 12 is performed. Thus, the lifetime of the ionic element 1 (1A to 1D) is extended.

Example 4
Here, FIG. 36A shows the relationship between the drive period and the light emission characteristics according to Example 4. FIG. FIG. 36B is an enlarged view of a part of FIG. 36A (part indicated by reference numeral P2) together with the drive voltage Vd.

  In the fourth embodiment, as in the example of FIG. 31 described above, the drive voltage Vd is intermittently reduced using a pulse waveform. Specifically, a low voltage period VL (low voltage VL = 0 V) of 0.001 seconds is provided every high voltage period VH (high voltage VH = 3.0 V) of 50 seconds. 36A and 36B, in Example 4, even when the driving time reaches 5000 seconds, the light receiving current due to the emitted light hardly decreases (converges to a substantially constant value), and the ionic element It can be seen that a long service life has been realized.

(Example 5)
On the other hand, FIG. 37A shows the relationship between the drive period and the light emission characteristics according to Example 5. FIG. 37B is an enlarged view of a part of FIG. 37A (part indicated by reference numeral P3) together with the drive voltage Vd.

  In the fifth embodiment, as in the example of FIG. 32 described above, the drive voltage Vd is intermittently decreased using an AC waveform in which an AC voltage is superimposed on a predetermined DC voltage Vdc. Specifically, a cycle along the time axis between 2.8 V and 3.0 V is obtained by superimposing a 0.2 V AC waveform with Peak-to-Peak on DC voltage Vdc = 2.9 V. Generating and using a changing alternating waveform. 37A and 37B, even in this Example 5, even when the driving time reaches 5000 seconds, the light receiving current due to the emitted light hardly decreases (converges to a substantially constant value), and the ionic element It can be seen that a longer life is realized.

  As described above, in the present embodiment, when the ionic element 1 (1A to 1D) is driven, the drive voltage Vd is intermittently decreased (intermittent drive is performed), so the electrolyte in the ionic layer 12 122 regular refresh operations can be realized. Therefore, the lifetime of the ionic element 1 (1A to 1D) can be increased. Specifically, when such intermittent driving is not performed (in the case of constant voltage driving), the element life is about 1000 to 2000 seconds, whereas this embodiment (when intermittent driving is performed). Then, it becomes possible to achieve the element lifetime of about 10,000 seconds or more.

  In addition, since the drive voltage Vd is lowered and then returned instantaneously, the following effects can be obtained. That is, since the decrease period of the drive voltage Vd becomes very short, the change in the operation of the ionic element 1 (1A to 1D) due to such a decrease in the drive voltage Vd (for example, stop of the light emitting function) is recognized by the user. (Distinguishing) is difficult (desirably, it is not recognized). That is, it is possible to reduce or avoid (preferably avoid) a decrease in user convenience.

  Furthermore, since the constant voltage driving described above is performed in the starting period T1 of the ionic element 1 (1A to 1D) and such intermittent driving is performed in the subsequent steady operation period T2, the following effects can also be obtained. Is possible. That is, in the starting period T1 in which the pn junction is formed, the formation of the pn junction is promoted by constant voltage driving, while in the subsequent steady operation period T2, the refresh operation described above is performed by intermittent voltage drop driving. It becomes possible to realize a more effective driving operation adapted to the operating situation.

  In addition, for example, as shown in FIG. 31 and the fourth embodiment, when a pulse waveform is used in such intermittent driving, a refresh operation can be performed particularly effectively. On the other hand, for example, as shown in FIG. 32 and Example 5, when an AC waveform in which an AC voltage is superimposed on a predetermined DC voltage Vdc is used during such intermittent driving, a light emitting operation is performed. It is also possible to suppress flickering of light.

  Also in this embodiment, a starter mechanism for partially starting the formation of the pn junction described in the second embodiment and its modifications 1 to 3 may be provided.

<5. Modification Common to First to Third Embodiments>
Subsequently, a modification (modification 4) common to the first to third embodiments will be described. In addition, the same code | symbol is attached | subjected to the same thing as the component in these embodiment etc., and description is abbreviate | omitted suitably.

[Constitution]
FIG. 38 schematically illustrates a cross-sectional configuration example of an ionic element (ionic element 1E) according to Modification 4. The ionic element 1 </ b> E has a laminated structure including a pair of electrodes 111 and 112, an ionic layer 12 and a protective layer 13 on a substrate 10.

  The substrate 10 is a substrate for holding the element structure of the ion element 1E. The substrate 10 is made of, for example, a glass substrate, a plastic substrate, a silicon substrate, or the like.

  Here, in this ionic element 1E, unlike the ionic elements 1 and 1A to 1D described so far, a pair of electrodes 111 and 112 are arranged in parallel on the substrate 10 at a predetermined interval. Yes. The device structure is such that the ion layer 12 uniformly covers the substrate 10 and the electrodes 111 and 112.

  However, also in this modification, the ion layer 12 has the same configuration as that of the first embodiment (FIG. 1) described above, for example. That is, the ionic layer 12 includes a porous material 121 having a large number of pores 121 h and an electrolyte 122 dispersed in the pores 121 h of the porous material 121. Further, for example, as schematically shown in FIG. 39, some molecules of the electrolyte 122 are actually ionized into a cation 122 c and an anion 122 a (ionic state). As described above, the electrolyte 122 is configured using a molecule having a structure for suppressing ion mobility (for example, a molecule having polarization).

  The protective layer 13 is a layer (passivation layer) for protecting the ion layer 12 from the outside. The protective layer 13 consists of materials, such as a polymer and an oxide, for example, and the thickness is about 10 nm-100 nm, for example. The protective layer 13 may not be provided depending on circumstances.

  Note that the ionic element 1E of the present modification can also be manufactured basically in the same manner as the ionic element 1 of the first embodiment described above. However, mixing of the above-mentioned amphiphile, use of a high boiling point solvent, stirring using ultrasonic waves, etc. may not be performed.

[Action / Effect]
Also in the ionic element 1E of the present modification, basically, the same effect can be obtained by the same operation as in the first embodiment and the like. Specifically, the ionic element 1E operates as follows.

  That is, as shown in FIG. 40, for example, when a voltage is applied to the ion layer 12 using the electrodes 111 and 112, a pn junction is formed in the ion layer 12, and in this pn junction, A storage state is established using the electric double layer described above. Then, using the pn junction thus formed, a light emission operation (emission operation of the emitted light Lout) and a power generation operation (photoelectric conversion operation of the incident light Lin) are performed according to the principle described above. It becomes like this. That is, multifunctionality (a power storage function, a light emission function, and a power generation function) is realized by using a pn junction formed in the ion layer 12. In FIG. 40 and FIG. 41 below, for convenience, the emitted light Lout and the incident light Lin are illustrated as being emitted or incident along the extending direction of the ion layer 12. However, actually, the emitted light Lout can be emitted in all directions, and the incident light Lin can be incident from all directions.

  Also in the ionic element 1E, since the electrolyte 122 is configured using molecules having a structure for suppressing ion mobility (for example, molecules having polarity), the principle is the same as in the first embodiment. Thus, the pn junction formation state is maintained to some extent even after the transition to the no-voltage application state.

  Therefore, for example, as shown in FIG. 41, even after the transition to the no-voltage application state, the multi-function is continuously realized by using this pn junction. That is, using the pn junction, the light emission function (the emission operation of the emitted light Lout) and the power generation operation (the photoelectric conversion operation of the incident light Lin) are exhibited.

  Thus, also in this modification, functionality can be improved using the pn junction formed in the ion layer 12, and convenience for the user can also be improved. In particular, in this modified example, the response speed of the ionic element is reduced as compared with the above embodiment, but the pn junction maintenance time (life time in the pn junction state) after the transition to the no-voltage application state is longer. It becomes possible to do.

<6. Application example>
Subsequently, application examples of the ionic elements (ionic elements 1 and 1A to 1E) and the ionic element module 2 according to the first to third embodiments and the first to fourth modifications will be described. .

[Application Example 1]
FIG. 42 is a perspective view schematically illustrating a configuration example of the electronic apparatus (portable lighting device 3) according to Application Example 1. The portable lighting device 3 includes one or a plurality of ionic elements 1 (or ionic elements 1A to 1E) or one or a plurality of ionic element modules 2 in a housing, and emits light. It has a function of emitting emitted light Lout from the mouth 30.

  Specifically, using the power storage function and the formation of the pn junction described above, it is possible to perform the emission operation of the emission light Lout for a certain period of time after the transition to the no-voltage application state. In this way, in the portable lighting device 3, a function such as an emergency flashlight can be realized with a very small and simple configuration.

  FIG. 42 shows an example in which the light emission port 30 is provided on the side surface of the housing. However, the present invention is not limited to this. For example, the light emission port 30 is provided on the upper surface or the lower surface of the housing. You may do it. In this case, the electrodes 111 and 112 may be transparent electrodes made of ITO or the like.

[Application Example 2]
FIG. 43 schematically illustrates a configuration example of an electronic apparatus (portable charger 4) according to Application Example 2. The portable charger 4 also includes one or a plurality of ionic elements 1 (or ionic elements 1A to 1E) or one or a plurality of ionic element modules 2 in a housing. The portable charger 4 has a function of entering the incident light Lin from the light incident port 40 and outputting the power Pout obtained by photoelectric conversion of the incident light Lin to the outside.

  Specifically, it is possible to perform a power generation operation using photoelectric conversion of incident light Lin for a certain period of time after the transition to the no-voltage application state using the above-described power storage function and formation of a pn junction. It has become. Therefore, for example, as shown in FIG. 43, it is possible to realize a use in which various mobile devices 5 are charged via the connector 41 with the electric power Pout obtained by the photoelectric conversion. Here, the case of power supply via the connector 41 (wired power supply) has been described as an example. However, for example, non-contact power supply (wireless power supply) using a magnetic field or the like may be performed. . Thus, in the portable charger 4, for example, a function like an emergency charger can be realized with a very small and simple configuration.

<7. Other variations>
Although the present invention has been described above with reference to some embodiments, modifications, and application examples, the present invention is not limited to these embodiments and the like, and various modifications can be made.

  For example, the materials and the like of each layer and each member described in the above embodiments are not limited, and other materials may be used. Specifically, for example, the molecules constituting the electrolyte are not limited to the molecules described in the above embodiments and the like as long as they have an ion mobility suppressing structure. In some cases, the molecules constituting the electrolyte may not have an ion mobility suppressing structure. Furthermore, for example, the mixing ratio of the electrolyte and the porous material in the ionic layer is not limited to the mixing ratio described in the above embodiment.

  In the above-described embodiment and the like, the element structure of the ionic element has been specifically described. However, the structure is not limited to these structures, and other element structures may be used. Specifically, for example, the number of electrodes is not limited to two, and any number of electrodes (two or more) may be provided. In addition, the configuration of the starter mechanism described in the second embodiment and the modifications thereof is not limited to that described above, and the starter mechanism may be realized by another configuration. Further, the arrangement position of such a starter mechanism is not limited to the arrangement position described in the second embodiment and the modifications thereof, and other arrangement positions (for example, not substantially isotropic or isotropic). It may be a local arrangement position). In addition, in some cases, an ionic element according to another configuration example shown in FIG. 11 may be applied to the present invention.

  Furthermore, in the above-described embodiments and the like, the manufacturing method and driving method of the ionic element have been specifically described, but the manufacturing method and driving method are not limited to these, and other methods may be used. .

  In addition, in the above-described embodiment and the like, the case where the ionic element (ion layer) has each of the power storage function, the light emission function, and the power generation function has been described, but the present invention is not limited thereto. That is, what is necessary is just to have an electrical storage function and a light emission function, for example, you may make it not have a power generation function depending on the case.

  In the above-described embodiments and the like, the portable lighting fixture and the portable charger have been described as examples of the electronic device according to the application example of the ionic element of the present invention. Is not limited. That is, the ionic element of the present invention can also be applied to various other electronic devices (electronic devices using at least the power storage function and the light emitting function).

  Furthermore, in the present invention, the contents described so far can be applied in any combination.

  DESCRIPTION OF SYMBOLS 1,1A-1E ... ionic element, 10 ... board | substrate, 111,112 ... electrode, 12 ... ion layer, 12p ... p-type area | region, 12n ... n-type area | region, 121 ... porous body, 121h ... pore, 122 ... Electrolyte (molecule), 122c ... cation, 122a ... anion, 13 ... protective layer, 14A ... microparticle, 14B ... projection, 14C ... thermoelectric element, 141 ... concave structure, 15 ... light source, 2 ... ionic device module, DESCRIPTION OF SYMBOLS 21 ... Drive part, 3 ... Portable lighting fixture, 30 ... Light exit port, 4 ... Portable charger, 40 ... Light entrance port, 41 ... Connector, 5 ... Mobile device, PS ... Voltage supply source, h ... Hall, e ... electron, g ... interval, A1, A2 ... electric conduction region, Aht ... high temperature region, Sj ... bonding surface, Lin ... incident light, Lout ... emission light (emission light), L1 ... irradiation light, T1 ... starting period, T2: Steady operation period, TH: High voltage period Driving period), TL ... low-voltage period (refresh operation period), Vd ... driving voltage, VH ... high voltage, VL ... low-voltage, Vdc ... DC voltage.

Claims (15)

Producing a mixture by mixing a porous material, an electrolyte and an amphiphile in a solvent;
Forming the mixture into a thin film; and
Drying the thin film-like mixture and evaporating the solvent from the mixture to form an ion layer in which the electrolyte is dispersed in the porous material;
Attaching a plurality of electrodes for applying a voltage to the ion layer , and
A method for manufacturing an ionic element, wherein a starter mechanism is provided for partially starting the formation of a pn junction by forming a temperature distribution in the ion layer when the voltage is applied . The method for producing an ionic device according to claim 1, wherein a high boiling point solvent is used as the solvent. The method for producing an ionic element according to claim 1 or 2, wherein a content of the amphiphile in the mixture is 1000 ppm or less. The method for producing an ionic element according to any one of claims 1 to 3, wherein stirring is performed using ultrasonic waves when mixing the porous material, the electrolyte, and the amphiphilic substance. The method for producing an ionic element according to claim 4, wherein the stirring using the ultrasonic wave is performed for a predetermined period not less than a lower limit time and not more than an upper limit time. A step of producing a mixture by mixing a porous material and an electrolyte in a solvent;
Forming the mixture into a thin film; and
Drying the thin film-like mixture and evaporating the solvent from the mixture to form an ion layer in which the electrolyte is dispersed in the porous material;
The ionic layer attached a plurality of electrodes for applying a voltage to the process and the containing Mutotomoni,
Providing a starter mechanism for partially starting the formation of a pn junction by forming a temperature distribution in the ion layer when the voltage is applied;
A method for producing an ionic element, in which stirring is performed using ultrasonic waves when mixing the porous material and the electrolyte. The method for producing an ionic element according to claim 6, wherein the stirring using the ultrasonic wave is performed for a predetermined period of time not less than a lower limit time and not more than an upper limit time. The method for manufacturing an ionic element according to any one of claims 1 to 7, wherein a printing technique is used in the step of forming the mixture into a thin film. The starter mechanism is configured using a thermoelectric element that directly forms the temperature distribution.
The manufacturing method of the ionic element of any one of Claim 1 thru | or 8. The starter mechanism is formed by locally irradiating the ion layer with a light source for indirectly forming the temperature distribution.
The manufacturing method of the ionic element of any one of Claim 1 thru | or 8. The starter mechanism forms the temperature distribution only in the starting period of the starting period of the ionic element and the subsequent steady operation period.
The manufacturing method of the ionic element of any one of Claim 1 thru | or 10. The method for manufacturing an ionic device according to any one of claims 1 to 11 , wherein the electrolyte is configured using a molecule having a structure for suppressing ion mobility. The method for producing an ionic device according to claim 12 , wherein the molecule has a linear structure. Production method of the ionic element according to any one of the electrolyte claims 1 to 1 3 is an ionic liquid. Production method of the ionic element according to any one of the porous material according to claim 1 or claims 1 to 4 which is a conductive polymer.

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