JPH10135540A - Electrochemiluminescent cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase light emission intensity by forming a container of a transparent material, constituting an electrode of a plurality of pattern-like electrodes which are divided at a fine interval formed on an insulating board and arranging an optical resonator outside a container. SOLUTION: A container 7 is formed to a structure in which exposed surfaces of a first electrode 2 and a second electrode 3 are in contact with inner solution and is formed of a transparent material to enable light to be picked up. A wiring part is coated with an insulation layer except a first electrode terminal 4 and a second electrode terminal 5, and an opening part 6 of the first electrode 2 and the second electrode 3 not to generate electrode reaction in a wiring part. Solution containing a electrochemical light emitting substance is injected into the container 7, a voltage is applied to the first electrode terminal 4 and the second electrode terminal 5, and light emitted between the first electrode terminal 4 and the second electrode terminal 5 is amplified by an optical resonator 8 and picked up. A starting substance is effectively supplied to an electrode by flow of solution, radicals become easy to mix with each other and light emission intensity is increased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-efficiency electrochemical light emitting cell which can be used for a display device and a laser device utilizing electrochemical light emission.

[0002]

2. Description of the Related Art Light emission (electrochemiluminescence: ECL) from an electrolytic solution can be observed by applying a current to an electrode of a system including an electrolytic solution containing a certain dye and an electrode. For example, when an AC potential is applied to an electrolyte containing DPA (diphenylanthracene) or [Ru (bpy) ₃ ] ²⁺ (ruthenium bipyridine complex) with one electrode, cation radicals and anion radicals are generated alternately. Both diffuse from the electrode to the offshore, but partly combine, and as a result of the electron transfer reaction, excited state molecules and ground state molecules are generated. Molecules in the excited state emit photons as they fall to the ground state. The voltage required for this light emission is the difference between the potentials required for oxidation and reduction,
CRT (cathode ray tube, cathode ray tu)
be) and EL (electroluminescence, electrolumonescence) can be driven at a lower voltage than display devices.
Also, the element structure is very simple. However, such a method using a single electrode has not been put to practical use because the luminous efficiency is generally low and the luminous intensity is weak. The reason for this is that in the single-electrode method, the electrode potential must be swept at high speed, non-Faraday current such as charging current flows, and the input current is not effectively used for the electrochemical reaction. Is unstable and has a short life,
The overlap between the diffusion layers of cation radicals and anion radicals alternately generated from the electrodes is small, and the probability of causing an electron transfer reaction is reduced.

As a method of causing electrochemiluminescence, there is a direct current method using two electrodes in addition to the above-described alternating current method using a single electrode. In the direct current method, one potential is always higher than the oxidation potential,
If the other potential is set to be equal to or lower than the reduction potential, this is a very simple method that can emit light constantly. In the direct current method, both electrodes are brought close to each other to increase luminous efficiency.
This is because the lifetime of the radical generated at the electrode is short, and the probability that the cation radical and the anion radical meet must be increased. In addition, the closer the two electrodes are, the more molecules that have emitted light are supplied to the electrodes again, and the efficiency can be increased. In the DC method, a non-Faraday current such as a charging current does not flow because the potential is not changed. For this reason, the input energy can be used more efficiently for light emission as compared with the AC method.

[0004] A thin-layer cell has been proposed as a conventionally proposed structure in which both electrodes are brought close to each other. In this method, two flat electrodes are opposed to each other, and the two are separated by a spacer, and an electrolyte containing a luminescent substance is sealed therein. At least one of the electrodes must be transparent in order to extract light.

[0005] Schaper, H., Koestli
n, H., Schnedler, E.,: J. Electrochem. Soc., 1982
129, 1289-1294), rubren (rubren) in a thin layer cell of ITO (indium tin oxide) and platinum electrode.
e) was sealed, and light emission for 500 hours or more continuously was observed.

In a thin-layer cell, the distance between electrodes is determined by the thickness of the spacer, and it is substantially difficult to reduce the distance to 10 μm or less, and there is a limit in increasing luminous efficiency. In addition, since the volume is limited, the supply of the starting material is insufficient, which is one of the causes for lowering the luminous efficiency.

[0007] Wightman (Bartelt, JE, Drew, SM, Wightma) was used as electrochemiluminescence of the direct current method using two electrodes.
n, RM ,: J. Electrochem. Soc 1992, 139, 70-7
4) use two or three band electrodes separated by a small distance, sandwich two or three metal thin films via an insulating thin film, and polish the end surface. It is a band electrode. In the electrochemiluminescence, a redox cycle in which an electrochemiluminescence product becomes a starting material of the electrochemical reaction is used again. Therefore, as the number of band electrodes increases, the rate of re-reaction increases, and the reaction efficiency can be increased.
If lithography technology is used, a large number of band electrodes (comb-shaped electrodes) with a spacing of several microns can be easily manufactured, and the luminous efficiency can be significantly improved. Also, unlike the case of a thin-layer cell, the internal volume of the cell is not limited, and the starting material whose concentration has been reduced by electrolysis can be sufficiently supplied. And the light intensity decreases due to re-absorption by the solution. Further, if the electrode spacing becomes several microns, the supporting electrolyte is no longer required.

On the other hand, one of the major factors that lowers the efficiency of electrochemiluminescence is the presence of water in the solution. Since water is a strong quencher, there is no fear of water being mixed in from the supporting electrolyte. If it disappears, a further increase in efficiency can be expected. In addition, it becomes possible to use a solvent having a low polarity with little contamination of water. Furthermore, in the case of a solvent having a low polarity, an exciplex that can be used as a light-emitting material can be easily formed stably, and the light-emitting material can have a wide range.

A dye laser utilizing light emission from an organic dye can perform pulse oscillation and CW (continuous wave) oscillation, and is a tunable laser. Another laser or flash lamp was required. For this reason, dye lasers can be powerful tools in the field of spectroscopy and analytical chemistry, but have required high cost and large installation locations. Although there is a tunable laser using a semiconductor, a laser capable of selecting a wavelength with a single element over a wide visible region has not been realized. If a laser can be realized by electrochemical light emission, the above problem can be solved, but the efficiency of electrochemical light emission is low and laser oscillation has not been achieved. Since the light emitted by electrochemiluminescence is isotropic, only about half is utilized. Since the band electrode of Wightman et al. Is not effectively used and is observed through a thick solution layer, the emission intensity is further reduced.

[0010]

As described above, the conventional display device and laser device using electrochemical luminescence have a simple structure, the materials and peripheral devices are inexpensive, and the manufacturing cost can be reduced. There is a problem that it cannot be put to practical use because of its low efficiency.

An object of the present invention is to provide an electrochemiluminescent cell which can generate electrochemiluminescence with high efficiency in order to solve the above problems.

[0012]

To achieve the above object, an electrochemiluminescent cell according to the present invention comprises a solution of an electrochemiluminescent substance, an electrode for applying a potential to the solution, and an electrode for applying a potential to the solution. A container for containing the container, the container is formed of a transparent material,
The electrodes include a plurality of patterned electrodes formed on an insulating substrate and separated by minute gaps, and an optical resonator is provided outside the container.

[0013] Further, in an electrochemiluminescent cell comprising a solution of an electrochemiluminescent substance, an electrode for applying a potential to the solution, and a container for accommodating the solution and the electrode, the container is made of a transparent material. The electrode is composed of a plurality of patterned electrodes formed on an insulating substrate and separated by a minute gap, and the patterned electrode is used as one mirror, and the electrode and the outside of the container are formed. Constitutes an optical resonator with the other mirror disposed in the optical resonator.

In these cases, a structure for supplying and discharging the solution to and from the container is provided.

In these cases, the refractive index of the solution is higher than the refractive index of the material constituting the container.

[0016]

FIG. 1 is a perspective view showing the basic structure of an electrochemical light emitting cell according to the present invention.

The electrochemiluminescent cell shown in FIG. 1 includes a first electrode 2 and a second electrode 3, which are arranged at a minute interval on the upper surface of an insulating substrate 1, a first electrode 2 and a second electrode 3, and Are respectively electrically connected to an external circuit to apply a voltage.
, A second electrode terminal 4, a second electrode terminal 5, a container 7 for accommodating a solution containing an electrochemiluminescent substance, and an optical resonator 8 disposed with the container 7 interposed therebetween. Container 7
The first electrode 2 and the second electrode 3 have a structure in which the electrode surfaces are in contact with the internal solution, and are formed of a transparent material so that light can be extracted. Except for the first electrode terminal 4 and the second electrode terminal 5 and the opening portions 6 of the first electrode 2 and the second electrode 3, the wiring portion is an insulating layer so that an electrode reaction does not occur in the wiring portion. Cover with.

In the electrochemiluminescent cell having such a structure, a solution containing an electrochemiluminescent substance is injected into the container 7,
A voltage is applied to the first electrode terminal 4 and the second electrode terminal 5, and light emission generated between the first electrode terminal 4 and the second electrode terminal 5 is amplified by the optical resonator 8. By taking out
Realize light emitting devices and lasers.

[0019]

Embodiments of the present invention will be described below in detail with reference to the accompanying drawings. Note that the present invention is not limited to the following embodiments.

(First Embodiment) FIG. 2 is a side sectional view showing the structure of an electrochemical light emitting cell according to a first embodiment of the present invention.

In this embodiment, the interdigitated platinum comb-shaped electrodes (corresponding to the patterned electrodes in claims 1 and 2) 12 and 13 are provided on the lower surface of a quartz substrate 11 which is a transparent insulating substrate. The formed electrochemiluminescent cell and its application example to a light emitting device are shown.

In order to manufacture the electrochemical light emitting cell of the present embodiment, first, a comb-shaped electrode (Claims 1 and 2) meshed with a 3 inch diameter disk-shaped quartz substrate using an exposure apparatus.
Corresponds to a patterned electrode. ) 12, 13,
A resist pattern of a reference electrode 20, an external electrode (counter electrode) 21, and a terminal portion (not shown) is formed, titanium and platinum are sputter-deposited in this order by a sputtering device, immersed in methyl ethyl ketone, and lifted off using an ultrasonic cleaner. And the interdigitated comb-shaped electrodes 12, 13, the reference electrode 20,
Metal parts other than the pattern of the external electrode 21 and the terminal part were peeled off from the substrate. The platinum film thickness was about 800 °.
In order to cover the lead portion with an insulating layer, a silicon nitride film is formed on the quartz substrate 11 by a sputtering device, and the engaged comb-shaped electrodes 12, 13 are formed by a reactive etching device.
After removing the silicon nitride film of the reference electrode 20, the external electrode 21, and the terminal, the quartz substrate 11 was cut out to a predetermined size with a dicing saw. The electrode width of the interdigitated comb-shaped electrodes 12 and 13 thus prepared was about 2 μm, the gap was about 2 μm, the length of the comb teeth was about 2 mm, and the number of the comb teeth was 2
There were 50 pairs.

A block 15 having a platinum electrode 14 mirror-polished on its upper surface so as to face the interdigitated comb-shaped electrodes 12 and 13 formed on the lower surface of the quartz substrate 11 is mounted on a Teflon spacer 16 having a thickness of about 12 μm. Arranged through. The flow path 1 for supplying and discharging the liquid is supplied to the block 15.
7 and 18 are provided, and a container 19 for accommodating a solution is constituted by the comb-shaped electrodes 12 and 13, the platinum electrode 14 and the Teflon spacer 16. In addition, the reference electrode 20
A silver deposit 20a was provided on the platinum by using a silver plating solution. The external electrode 21 provided on the lower surface of the quartz substrate 11 is used when performing an electrochemical measurement.

After injecting a DMSO (dimethyl sulfoxide) solution containing about 1 mM of ruthenium complex (mM means 10 ⁻³ mol / l, the same applies hereinafter) into the container 19 having the above structure,
Channels 17 and 18 were sealed. Using a potentiostat, one potential of the comb-shaped electrodes 12 and 13 is set to 1.6 V and the other potential to -1.6 V with respect to the reference electrode 20,
When observed from the back surfaces of the comb-shaped electrodes 12 and 13, it was possible to observe orange light emission. Comb-shaped electrodes 12, 13
The light emission intensity without the platinum electrode 14 was weaker than the case where the mirror-polished platinum electrode 14 was located at a position facing the surface. From this, it was confirmed that the emission intensity can be increased by disposing the mirror (platinum electrode 14) at the position facing the comb-shaped electrodes 12 and 13.

Further, when the light emission pattern in the presence of a mirror was examined in detail, it was found that the light emission pattern caused a diffraction pattern. This diffraction pattern coincided with the pattern when the comb-shaped electrodes 12 and 13 were formed as multiple slits and plane waves having the same phase were incident on the slits. A large number of molecules in the excited state are present in the electrochemiluminescent cell centering on the electrode gap, and in the case of spontaneous emission, each molecule emits light independently, but the density of the molecules in the excited state increases, When in the optical resonator, stimulated emission occurs, resulting in a wave with a uniform phase. Also in the configuration of the present embodiment, an optical resonator is formed by the mirror-finished platinum electrode 14 and the platinum comb-shaped electrodes 12 and 13, and the electrochemiluminescence becomes a plane wave of the same phase by stimulated emission. As a result of passing through 13 slits, a diffraction pattern was generated.

When light was emitted while the solution was flowing without sealing the channels 17 and 18, the emission intensity was increased.
This is because the starting material is efficiently supplied to the comb-shaped electrodes 12 and 13 by the flow, and the radicals are easily mixed.

Next, when the solvent was changed to acetonitrile, the luminescence became unstable and the luminescence intensity decreased. quartz,
DMSO and acetonitrile each have a refractive index of 1.4.
6, 1.48, 1.34, the quartz cell and DMS
This is because O has a configuration of an optical waveguide, so that the ratio of total reflection increases, and stimulated emission easily occurs.

(Second Embodiment) In this embodiment, the effect when two kinds of light emitting substances are mixed and an example of application to a light emitting device will be described.

A DM 19 containing about 5 mM of DPA (diphenylanthracene) and about 0.1 mM of rubrene is placed in a container 19 of an electrochemiluminescent substance solution having the same structure as that of the first embodiment shown in FIG.
Inject F (dimethylformamide) solution,
After sealing 18, a power supply was connected to the interdigitated comb-shaped electrodes 12 and 13. Light vertically emitted from the back surfaces of the comb-shaped electrodes 12 and 13 was separated by a spectroscope. When a voltage of 2.3 V was applied, light emission having a center wavelength of 550 nm was observed. When the voltage was increased to 6.0 V, emission having a center wavelength of 440 nm was observed in addition to emission of 550 nm. Further, as compared with the case where the mirror-polished platinum electrode 14 is located at a position facing the comb-shaped electrodes 12 and 13 as in the first embodiment,
The emission intensity without the platinum electrode 14 was weak. From this, it was confirmed that the emission intensity can be increased by disposing the mirror (platinum electrode 14) at the position facing the comb-shaped electrodes 12 and 13. Emission at 550 nm is due to rubrene. At a potential difference of 2.3 V, only rubrene is redox-reduced, DPA does not cause an electrode reaction, and the voltage is reduced to 6.0.
When raised to V, both rubrene and DPA cause electrolysis,
This is because both emit light. As described above, in the mixed solution of the electrochemiluminescent substances having different oxidation-reduction potentials, the emission wavelength could be controlled by controlling the electrode potential.

As described above, according to the present invention, the display color can be changed by controlling the applied voltage, and application to a device is possible.

(Third Embodiment) FIG. 3 is an exploded perspective view showing the structure of an electrochemical light emitting cell according to a third embodiment of the present invention.

The electrochemiluminescent cell shown in the figure has a comb-shaped electrode 31 formed on a transparent insulating substrate and a comb-shaped electrode (corresponding to a patterned electrode in claims 1 and 2). And a transparent quartz container 33 constituting a solution reservoir 36 below the comb-shaped electrode 31.
And an optical resonator including a first concave mirror 42 and a second concave mirror 43.

In this embodiment, in the same manner as in the first embodiment, about 5 μm of electrode width, about 5 μm of gap, about 8 mm of comb teeth, and 250 pairs of comb teeth are engaged. A comb-shaped electrode 31 is formed on a transparent quartz substrate,
X It was cut out to a size of about 9.5 mm. After attaching the electrode holder with packing 32 to the comb-shaped electrode 31, the width is about 12.5 mm, the height is about 12.5 mm, and the depth is about 35 m
m in the center of a quartz container 33. Quartz vessel 33 has channels 34, 3 for supplying and discharging the solution.
5 is provided, and a solution reservoir 36 is provided in contact with the lower surface of the comb-shaped electrode 31. This quartz container 3
3 is assembled into a metal frame 37, and flanges 38 and 39 for supplying and discharging the solution are attached to the frame 37, and a Teflon tube 4 is attached to the flanges 38 and 39.
0 and 41 were attached. A syringe pump (not shown) is provided on the supply side tube of the tubes 40 and 41,
A waste liquid reservoir (not shown) was connected to the tube on the discharge side so that the solution could flow into the quartz container 33.

Further, a pair of the first concave mirror 42 and the second concave mirror 43 are mounted on the frame 37 so that the mirror surfaces face each other. First concave mirror 42 and second concave mirror 43
Have a radius of curvature of about 5 cm, and the first concave mirror 42 is coated with a dielectric multilayer vapor-deposited film so that the reflectance of the first concave mirror 42 is almost 100% in the visible light region. The second concave mirror 43 has a transmittance of About 1% and a reflectivity of about 99% were used. The adjustment was made so that the optical axis of the biconcave mirror coincided with the direction of the teeth of the comb of the comb-shaped electrode 31.

In the electrochemiluminescence cell of the present embodiment having the above-described structure, a DMSO solution containing about 10 mM of a ruthenium bipyridine complex ([Ru (bpy) ₃ ] ²⁺ ) is supplied from a syringe pump (not shown) to a quartz vessel 33. And the potential of one comb-shaped electrode is set to 1.8 V with respect to the reference electrode and the potential of the other comb-shaped electrode is set to − with a potentiostat.
When the voltage was set to 1.8 V and the electrolysis was performed, light having a strong orange directivity and having a uniform phase was emitted from the center of the second concave mirror 43 and laser oscillation was possible. Although laser oscillation did not occur in the first and second embodiments, in this embodiment, since the optical resonator is provided in the electrode length direction, the gain is larger than the loss due to absorption of the mirror or the solution. Because he was able to. Also, because the curvature of the concave mirror is also in the stable region, the standing wave can exist stably.

(Fourth Embodiment) FIG. 4 is an exploded perspective view showing the structure of an electrochemical light emitting cell according to a fourth embodiment of the present invention.

In this embodiment, a light emitting device capable of selecting a wavelength will be described.

In this embodiment, the first concave mirror (with a reflectivity of about 100%) 42 in the third embodiment shown in FIG. 3 is replaced with a prism 51 and a diffraction grating 52, and the second concave mirror (with a reflectivity of about 99%) is used. %, Transmittance of about 1%) with respect to the optical axis of 43, the angle of the diffraction grating can be freely changed. Next, a mixed solution of DPA, rubrene, and a ruthenium bipyridine complex ([Ru (bpy) ₃ ] ²⁺ ) was prepared. The concentration ratio of each dye was determined in advance so that the emission intensity would be the same when the light was emitted alone. This mixed solution was flowed into the above-mentioned cell by a syringe pump (not shown), and a potential of about 6 V was applied between the comb-shaped electrodes 31.

The wavelength of the laser light emitted from the center of the concave mirror having a transmittance of about 1% could be freely selected over the visible region by changing the angle of the diffraction grating 52. DPA, rubrene, and the ruthenium bipyridine complex ([Ru (bpy) ₃ ] ²⁺ ) have emission center wavelengths of 4
Due to the broad spectrum at 40, 550 and 610 nm, respectively, the emission from the mixed solution can cover almost the entire range of visible light. For this reason, the wavelength required for the diffraction grating can be selected.

As described above, it has been shown that a tunable electrochemiluminescence laser can be realized by using a wavelength-selective element such as a diffraction grating in one of the optical resonators of the electrochemiluminescence cell.

In the above embodiment, the case where platinum is used for the electrode has been described as an example.
Metals such as silver, copper, palladium, chromium, titanium, and stainless steel, p-type and n-type silicon, p-type and n-type germanium, gallium phosphide, gallium arsenide, ITO (indium tin oxide), indium oxide (In ₂ O ₃₎ ), Semiconductors such as tin oxide (SnO ₂ ), cadmium oxide (CdO), and cadmium tin oxide (Cd ₂ SnO ₄ ); semi-metallic materials such as glassy carbon, conductive carbon paste, and conductive carbon film. Can be.

Although the case where quartz is used as the substrate material of the electrode has been described as an example, an insulating material such as glass, silicon whose surface is oxidized, aluminum oxide, Tempax, or plastic can be used.

Although the case where quartz is used as the material of the container for accommodating the electrodes and the solution has been described as an example, highly transparent glass, Tempax, plastic, silicon oxide and the like can be used.

As the electrochemiluminescent substance, DPA (9,10-diphenylanthracene, 9,10-diphenylanthracene), rubrene, ruthenium and the like, which are redox at the electrode to generate both cation radicals and anion radicals, Bipyridine complex ([Ru (bpy) ₃ ] ²⁺ ),
ADMA ((p-9-anthryl) -N, N-dimethylaniline, (p-9-anthryl) -N, N-dimethylaniline), Py-D
MA (p- (1-pyrenyl) -N, N-dimethylaniline, p- (1-
pyrenyl) -N, N-dimethylaniline). In addition, as a material that produces either a cation radical or an anion radical and mixes with a substance that produces the other,
Pyrene, TH (cyanthren, thianthren
e), TPTA (tri (p-dimethylaminophenyl) amine, tris (p-dimethylaminophenyl) amine), TMPD
(Tetramethyl-p-phenylenediamine, tetramethyl-p
-phenylenediamine), 10-MP (10-methylphenothiazine, 10-methylphenothiazine), FA (fluoranthene, fluoranthene), luminol and the like. In addition, dye coumarin-2 (coumarin-2), coumarin-30 (coumarin-30), oxazine-1 (oxazine-1) for dye laser
Rhodamine-B, rhodamine-6G (rhodamine-B)
damine-6G) can also be used.

As the solvent, a solvent having a wide potential window, ACN
(Acetonitrile, acetonitrile), BZ (benzene,
benzene), BZN (benzenenitrile, benzonitril)
e), DME (dimethoxyethane),
TOL (toluene, toluene), THF (tetrahydrofuran), N, N-DMF (N, N-dimethylformamide, N, N-dimethylformamide), D
MSO (dimethylsulfoxide)
Etc. can be used. Further, in order to adjust the refractive index and the solubility, they may be mixed and used.

As a method of manufacturing by arranging a plurality of electrodes in minute gaps on the order of microns or submicrons, a photolithography and dry etching method, a lift-off method, or a fine processing technique such as an ion milling method is combined on a substrate. There is a method of manufacturing, a method of bringing a microelectrode close to a conductor using a piezo element such as a scanning tunneling microscope (STM), and the like.

[0047]

As described above, according to the present invention,
There is an effect that an electrochemiluminescent cell that can generate electrochemiluminescence with high efficiency can be realized. Details of the effects are as follows.

In the present invention, a comb-shaped electrode (working electrode)
The distance between them is close to the micron order or less, and DC driving is performed, so that cations and anions can be constantly generated, the probability of collision between radicals having a short life can be increased, and there is no loss of charging current. There is an effect that high-efficiency light emission can be constantly generated.

In addition, since the electrodes are arranged so that the redox cycle can be realized with high efficiency, there is an effect that the emission intensity can be remarkably increased.

Further, the distance between the electrodes can be made narrower than that of the parallel plate type thin layer cell, so that there is an effect that the light emitting region can be widened.

In the thin-layer cell type, at least one electrode must be transparent in order to extract light, but there is an effect that the electrode in the present invention does not have such a material limitation.

Further, since a supporting electrolyte which acts as a quencher and lowers the luminous intensity is not required, luminescence loss is small, a wide variety of solvents can be selected, and a solvent having a low polarity can be used. By using a solvent having a higher refractive index than the material, luminous efficiency can be increased, and there is an effect that an exciplex or the like can be used as a luminescent material.

Further, in the present invention, it is possible to emit light while flowing a solution, so that there is no limitation on the supply amount of the starting material to the electrode. Since they are easily mixed with each other, there is an effect that the emission intensity can be increased.

In the thin-layer cell configuration of the present invention in which a mirror is arranged at a position facing the comb-shaped electrode, an optical resonator is formed by the comb-shaped electrode and the mirror. In other words, it is possible to obtain a structure in which a plane wave having a uniform phase is formed, the gain exceeds the absorption, and laser oscillation can be performed.

Further, if a mirror is arranged so as to face the electrode formed on the transparent substrate, and observation is made from the back surface of the electrode, light that is away from the observer can be effectively used.
A thin cell structure with the mirror and electrode close to each other can reduce the loss due to re-absorption in the solution, so if the electrode itself is a mirror surface, it will be an optical resonator configuration and perform laser oscillation. There is an effect that can be.

In a parallel plate type thin-layer cell, the medium layer is thin and sufficient gain cannot be expected. However, if the structure is such that resonance occurs in the longitudinal direction of the cell, the gain of the optical resonator can exceed the loss. This makes it possible to oscillate.

Further, since the emission wavelength can be selected by mixing a plurality of luminescent dyes and controlling the applied voltage, a display device or a tunable laser can be realized very easily at low cost, and downsizing is easy. There is an effect that there is.

Also, separate luminescent dyes are accommodated in a plurality of syringes, and a merging circuit is provided. By changing the liquid sending speed of each syringe pump, the concentration ratio of the dyes is changed to increase the light intensity at a specific wavelength. There is an effect that it is also possible to do.

As described above, according to the present invention, an electrochemiluminescent cell which can generate electrochemiluminescence with high efficiency and is extremely useful in various fields such as a display device and a laser device is realized. There is an effect that it becomes possible.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a basic structure of an electrochemical light emitting cell of the present invention.

FIG. 2 is a side sectional view showing a structure of an electrochemiluminescent cell according to a first embodiment of the present invention.

FIG. 3 is an exploded perspective view showing the configuration of an electrochemical light emitting cell according to a third embodiment of the present invention.

FIG. 4 is an exploded perspective view showing the configuration of an electrochemical light emitting cell according to a fourth embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Insulating substrate 2 ... 1st electrode 3 ... 2nd electrode 4 ... 1st electrode terminal 5 ... 2nd electrode terminal 6 ... Opening part 7, 19, 33 ... Container 8 ... Optical resonator 11 ... Quartz Substrate 12, 13, 31 Comb electrode 14 Platinum electrode 15 Block 16 Spacer 17, 18, 34, 35 Flow path 20 Reference electrode 20a Electrodeposition 21 External electrode 32 Electrode holder 36 Solution storage 37 ... Frame 38, 39 ... Flange 40, 41 ... Tube 42 ... First concave mirror 43 ... Second concave mirror 51 ... Prism 52 ... Diffraction grating

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C09K 11/06 H01S 3/20 B (72) Inventor Masao Morita Nippon Telegraph and Telephone Nishi Shinjuku 3-chome 19-2 Shinjuku-ku, Tokyo Telephone Co., Ltd.

Claims (4)

[Claims] 1. An electrochemiluminescent cell comprising a solution of an electrochemiluminescent substance, an electrode for applying a potential to the solution, and a container for accommodating the solution and the electrode, wherein the container is made of a transparent material. Wherein the electrodes are a plurality of patterned electrodes formed on an insulating substrate and separated by minute gaps, and an optical resonator is provided outside the container. cell. 2. An electrochemiluminescent cell comprising a solution of an electrochemiluminescent substance, an electrode for applying an electric potential to the solution, and a container for accommodating the solution and the electrode, wherein the container is made of a transparent material. The electrode is a plurality of patterned electrodes formed on an insulating substrate and separated by a minute gap, and the patterned electrode is used as one mirror, and is disposed outside the container and the electrode. An electrochemiluminescent cell comprising an optical resonator constituted by the other mirror provided. 3. The electrochemical light emitting cell according to claim 1, further comprising a structure for supplying and discharging the solution to and from the container. 4. The electrochemical light emitting cell according to claim 1, wherein a refractive index of the solution is higher than a refractive index of a material forming the container.