JPH10270169A - Solid-state optical function device and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid-state optical functional element which is a self light emitting type and has a fast responding speed and its manufacture by outputting a light emitted from an organic pigment excited by applying a voltage between a transparent electrode and a needle-like electrode through the transparent electrode to the outside. SOLUTION: A solid-state optical functional element comprises a first electrode section 10 including a silicon wafer 1 and a needle-like electrode 2 and a second electrode section 20 placed oppositely to the first electrode section 10 and including a transparent electrode plate having a transparent conductive layer 4b stacked in a glass board 4a. A light emission layer 5 is provided between these sections, and a gap part is filled with an electric insulating organic high polymer 6 to be sealed. The light emission layer 5 is formed by dispersing an organic pigment in the conductive or carrier transport type organic high polymer in a single molecule form and/or in the form of super-particles of a diameter 5O nm or lower. A voltage is applied to a transparent electrode plate 4 and the needle-like electrode 2 having a height of 20 nm or more and a tip curvature of 10 nm or lower, and then a light emitted from the organic pigment placed in an excited state is taken out to the outside. Thus, a solid-state optical functional element fast in a responding speed and suited for a display means.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a solid-state optical device which can be used for a display device for displaying image information and the like in an electronic device such as a portable personal computer and a method of manufacturing the same. More specifically, the present invention relates to a solid-state optical functional device having a light-emitting layer in the form of ultrafine particles composed of a single molecule of an organic dye and an aggregate or aggregate thereof in a thin film, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a CRT display has been used as an image display device. CRT (cathode ray tube)
Needless to say, it is excellent in resolution and corresponding speed. However, flat panel displays are being replaced by flat panel displays in terms of size, weight, manufacturing cost and the like.

[0003] Flat panel displays are used as image display means especially for portable word processors and personal computers. Recently, there has been an increasing tendency to use a flat panel display as an image display means for a desktop personal computer for the purpose of securing a space on a desk or the like. As such a flat panel display, a liquid crystal display using a liquid crystal and a plasma display using a minute plasma discharge tube have been put to practical use.

[0004] For example, a liquid crystal display includes two substrate glasses sandwiching liquid crystal, and a transparent electrode provided on one of the glass plates and formed by finely processing an electronic drive circuit such as a thin film transistor. A liquid crystal display having such a configuration is widely used because of its low power consumption and excellent lightness. However, since it is not a so-called self-luminous type, an illumination light source such as a backlight is required. In addition, there are also problems such as a restriction on the viewing angle that it is difficult to see if the line of sight deviates from the direction perpendicular to the screen of the liquid crystal display, and a slow response.

As a new component of the image display device, a vacuum micro device such as a field emission display (FED), which is a self-luminous display device, has been receiving attention. This vacuum micro device is an all-solid-state display device with a cold cathode made by using micromachining and vacuum technology to perform metallization (metal coating) on the tip of a silicon needle of several microns. is there. Therefore, the manufacturing of the vacuum micro device is entirely performed by a dry process without a step of handling a liquid like the above-described liquid crystal manufacturing process. In addition, the response time of the vacuum micro device is as fast as several microseconds, and the speed is sufficient for reproducing moving images. Therefore, research is being conducted as a next-generation flat panel display.

[0006]

However, such a vacuum micro device has a vacuum portion and a narrow range of choice of luminous material, and is not sufficient for luminous materials mainly on the short wavelength side such as blue. There is a problem to be solved that there is no one having an excellent performance. In addition, the electrode of the display element has a conical or needle-shaped field emission emitter, and AC-driven thin-film electroluminescence (EL) is realized by a donor / acceptor pair emission type phosphor film such as ZnS (Ag, Al). A proposal has been made. For example, in a field emission type solid state light emitting device disclosed in Japanese Patent Application Laid-Open No. 6-13186, a conical or needle-shaped electrolytic radiation emitter 72 is formed in a two-dimensional array on a Si substrate 71 as shown in FIG. And the donor /
Acceptor pair emission type phosphor film 73, transparent insulating film 74,
And the transparent electrode 75 are sequentially laminated. However, the phosphor film 73 has low luminous efficiency and insufficient luminance.

Further, an electro-optical device having a multilayer structure using an organic compound which is advantageous from the viewpoint of compound selection.
Luminescence research and development is continuing toward commercialization. However, there are various problems to be solved, such as difficulty in a process of bonding a plurality of layers, deterioration of a bonded portion due to current injection, and the like. As a method for solving these problems, a process in vacuum has been adopted to improve the production of high-quality junctions and the removal of residual impurities. However, such problems have not been solved.

Accordingly, an object of the present invention is to solve the problems to be solved by the prior art display device as described above, and to provide a self-luminous solid-state optical device having a high response speed and a method of manufacturing the same. It is.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, a solid-state optical functional device according to the present invention comprises a plate-like transparent electrode, a needle-like electrode provided so as to face the transparent electrode, and A polymer thin film disposed between a transparent electrode and the needle-shaped electrode and containing an organic polymer medium and an organic dye dispersed in the form of a single molecule or / and ultrafine particles in the organic polymer medium; A light-emitting layer, and further, when a voltage is applied between the transparent electrode and the needle electrode, the organic dye is in an excited state, and light emitted from the excited organic dye is externally transmitted through the transparent electrode. Is output to

Preferably, the ultrafine particles have a diameter of 50 nm or less.

Preferably, the organic polymer medium is a conductive or carrier-transporting organic polymer.

Preferably, a conductive or carrier transporting organic polymer layer is provided between the light emitting layer and the transparent electrode.

[0013] Preferably, the size of the needle electrode is height 20
It is 0 nm or more and the tip curvature radius is 100 nm or less.

Preferably, a capacitance is connected between the power supply and the electrode, a DC current is cut off, and only a DC voltage is applied to the electrode.

Preferably, the void in the element is filled with an electrically insulating organic polymer.

Preferably, the residual amount of the nonvolatile component of the organic polymer in the device is 10 ^-6 Pa or less.

Further, in the method for manufacturing a solid-state optical function element according to the present invention, the light-emitting layer of the solid-state optical function element is deposited on a substrate by spraying a material in a solution or dispersion state into a high vacuum container. It is characterized by being formed by an organic thin film forming method of heat treatment.

Preferably, the substrate is a plate-shaped transparent electrode.

Preferably, an electrically insulating organic polymer layer is formed on the light emitting layer, and an electrode substrate having a needle electrode formed on the organic polymer layer is joined by hot pressing.

Preferably, an electrically insulating organic polymer layer is formed by the above-mentioned organic thin film forming method.

Preferably, the steps of forming the light emitting layer and the organic polymer layer and performing the hot pressing are performed in a high vacuum atmosphere of 10 ⁻⁶ Pa or less, and the residual amount of the nonvolatile component is reduced to 10 ⁻⁶ Pa.
^-6 Pa or less.

As described above, the solid state optical function device of the present invention
A light-emitting layer composed of a polymer thin film in which an organic dye is dispersed in the form of a single molecule or / and ultrafine particles in an organic polymer medium is arranged between a plate-like transparent electrode and a needle-like electrode, and a voltage is applied between the two electrodes. Is applied to generate an excited state of the organic dye, and light emitted from the excited state is extracted to the outside through a transparent electrode. The organic dye is excited by hot carriers generated by a strong electric field from the electrode in the vicinity of the electrode to emit light.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION A solid-state optical device according to the present invention comprises a plate-like transparent electrode, a needle-like electrode, and a polymer thin film light emitting layer disposed between the plate-like transparent electrode and the needle-like electrode. With
The light-emitting layer is formed by dispersing an organic dye in the form of a single molecule and / or ultrafine particles in an organic polymer medium. Light emission of the solid-state optical function element having such a configuration is achieved by applying a voltage between the plate-shaped transparent electrode and the needle-shaped electrode,
The excitation state of the organic dye is generated by the hot carrier from the needle-like electrode, and light emission from the excitation state is extracted to the outside through the transparent electrode.

Therefore, the positional relationship between the needle electrode and the light emitting layer is only required that the hot carrier from the tip of the needle electrode is injected into the light emitting layer, and the tip does not need to directly contact the light emitting layer. There may be an insulating thin film layer that can pass through without disappearing.

The above-mentioned needle-like electrode is formed of a minute needle-like electrode. Specifically, it is a needle-shaped protruding electrode used for an electrode such as an FED, the size of which is preferably 200 nm or more in height and 100 nm or less in tip curvature, more preferably 500 nm or more in height, and 50 nm in tip curvature. It is as follows. A structure may be employed in which a gate electrode is provided to assist generation of hot carriers from the needle-like electrode, and a voltage is applied to the gate electrode. The electrode material of the needle-shaped electrode may be any material that can easily generate hot carriers, and examples thereof include Mo and W. Such a needle-shaped electrode can be manufactured by fine processing, but a known electrode such as the above-mentioned FED electrode can also be used.

The transparent electrode facing the needle electrode may be a transparent and conductive plate-like body, and its material is not limited. However, preferably, on a transparent substrate, a semiconductor film such as indium tin oxide (ITO) or tin oxide,
Alternatively, a transparent electrode laminate in which a transparent electrode film such as a metal thin film of gold or the like is laminated is applied.

The substrate for supporting the transparent electrode is not particularly limited as long as it is a transparent support. Preferably, glass, a polymer film, a sheet or the like is used.

The organic dye constituting the light emitting layer may be any organic dye that emits light when excited by hot carriers. Examples of such an organic dye include the following, but are not limited thereto. The selection is made in consideration of the purpose of use of the solid-state optical function device and the like.

Oxazole dyes emitting blue light such as p-bis [2- (5-phenyloxazole)] benzene (POPOP); coumarin 2, coumarin 6, coumarin 7,
Coumarin dyes emitting green light, such as coumarin 24, coumarin 30, coumarin 102, and coumarin 540; rhodamine 6
G, rhodamine B, rhodamine 101, rhodamine 11
0, rhodamine-based (red) dyes such as rhodamine 590 and rhodamine 640; and light that emits light in the near infrared region such as oxazine 1, oxazine 4, oxazine 9, and oxazine 118, and is particularly suitable for optical communication. Oxazine-based dyes suitable for the functional element are exemplified. Furthermore, cyanine dyes such as phthalocyanine and cyanine iodide compounds are also included. When these dyes are selected, it is preferable to select a dye that is easily soluble in a polymer such as an acrylic resin for the purpose of forming a thin film. Such pigments include POPOP, Coumarin 2, Coumarin 6, Coumarin 3
0, rhodamine 6G, rhodamine B, rhodamine 101
And the like.

Further, organic molecules used in an organic electroluminescence (EL) film, for example, 8-hydroxyquinoline aluminum (AlQ ₃ ), 1,4-bis (2,2)
2 Diphenylvinyl) biphenyl, polyparaphenylene vinylene (PPV) derivative, distyryl arylene derivative, styryl biphenyl derivative, phenanthroline derivative, or the like, or a medium in which an additive is added to the organic molecule may be used.

These are used alone, and / or mixed, and / or laminated, and / or in a two-dimensional arrangement of multiple colors in a film plane corresponding to pixels or the like. Needless to say, the form is not limited, such as mixing with a medium that does not hinder these effects.

The organic dye of the present invention may be dispersed as a single molecule in a polymer medium, or may be dispersed as ultrafine particles formed by agglomeration of organic dye molecules including coexistence with the single dye molecule. is necessary. When the organic dye molecules are aggregated in the form of ultrafine particles, it is possible to suppress the quenching effect and generate strong light emission. In order to obtain such an effect, the diameter of the ultrafine particles should be 50 nm or less, especially 30 nm.
m or less. Further, a method for dispersing an organic dye in a polymer medium or a method for dispersing the organic dye in the form of the ultrafine particles is known to those skilled in the art, and a method of providing a polymer thin film having such a configuration is also available. There is no particular limitation, and any chemical and / or physical method known to those skilled in the art such as wet coating and dry coating may be used. Specifically, a method according to a conventional method such as a spin coater may be used. Examples of a method for obtaining a preferable film include, for example, JP-A-7-252661, JP-A-7-252670, and JP-A-6-306181. The organic thin film forming method disclosed in the above, that is, the organic material in a solution or dispersion state is sprayed into a high vacuum container and deposited on a substrate, and the fine structure control without causing thermal decomposition by performing a heat treatment can be performed. A method of forming an organic thin film thus made may be more preferably used.

The organic polymer medium applied to the light emitting layer of the solid-state optical function device of the present invention is a conductive polymer or carrier which removes the charge of the organic dye caused by applying a voltage and does not impair the excitation of the organic dye. It is preferable to use a transportable polymer. Incidentally, the prevention of the charging of the organic dye by such a polymer may be any form that can prevent the charging,
In addition to the above-described medium, the light-emitting layer may be in the form of being close to or directly laminated to a polymer thin film containing an organic dye. As the suitable conductive or carrier-transporting polymer in the present invention, a polymer having an effect of removing charge generated upon excitation by a hot carrier is preferable. In order to have such an effect, the specific electric resistance of the conductive polymer is 10 ¹⁵ Ω · cm or less, preferably 10 ¹² Ω · cm or less.
Ω · cm or less, more preferably 10 ⁹ Ω · cm or less. Therefore, the conductive polymer of the present invention may be any conductive polymer as long as it has a specific electric resistance within the above range that does not impair the excitation of the organic dye. As such a conductive polymer, for example, a polymer having an ionized nitrogen element in the main chain (JP-A-3-255)
139, JP-A-4-288127, JP-A-6-172562) and polystyrene sulfonate (JP-A-5-320390). Further, a semiconductor filler such as tin oxide or a conductive filler such as carbon or metal may be included. Particularly preferably, in order to obtain uniformity of the medium, a polymer having a phosphate ester group in the molecule (Japanese Patent Laid-Open No. 8-134244) and the change in conductivity due to humidity is substantially small, and the light emitting display characteristics are improved. Conductive polymers such as polypyrrole, polythiophene, polyaniline and derivatives thereof, and polyparaphenylenevinylene (PPV) derivatives to be stabilized are preferable. In addition, in order to facilitate film formation and conductivity adjustment, a configuration in which these conductive polymers are further dispersed in a polymer serving as another medium, for example, a high-density polymer such as an acrylic or polyester resin is used. It is preferably in a state of being dispersed in molecules.

Here, the carrier-transporting polymer is a hole-transporting polymer that has a high hole-transporting function but hinders electron transport, or a hole-transporting polymer that has a high electron-transporting function. Refers to an electron transporting polymer that blocks. Generally, a hole-transporting polymer is characterized by a small ionization potential, and an electron-transporting polymer is characterized by a high electron affinity. The carrier-transporting polymer preferably has a carrier mobility of 10 ⁻⁷ cm ² / (V · s) or more, and more preferably has a carrier mobility of 10 ⁻⁵ cm ² / (V · s) or more. . As such a carrier-transporting polymer,
Polyvinyl carbazole, polymethylphenylsilane,
Examples include polydihexylsilane, polytetraphenylamine methacrylamide, polytetraphenyldiamine methacrylamide, and derivatives thereof.

The solid-state optical functional device having the above-described configuration emits light when driven by a method and means known to those skilled in the art. That is, a voltage is applied between the electrodes (plate-shaped transparent electrode and needle-shaped electrode) of the solid-state optical function element. As a result, the organic dye molecules and / or the organic dye ultrafine particles in the light emitting layer of the light emitting layer are excited by the hot carriers generated by the strong electric field near the electrode from the needle-shaped electrode to emit light. At this time, since a microstructured electrode is used, the response speed as a display element is significantly higher than that of a conventional liquid crystal or the like. The organic dye is selected according to the purpose of use when manufacturing the solid-state optical functional device. Further, when driving the solid-state optical function device according to the present invention, when a direct current is cut off by connecting a capacitance between a power supply and the device, and when a voltage is applied between a cathode and an anode, Only an electric field may be applied to the element.

Next, a method of manufacturing a solid-state optical functional device according to the present invention will be described.

This manufacturing method includes a step of providing a needle-like electrode on a substrate and a step of providing a plate-like transparent electrode. Further, a light emitting layer is provided between the needle-like electrode and the plate-like transparent electrode.
This light emitting layer is composed of a polymer thin film in which an organic dye is dispersed in the form of a single molecule and / or ultrafine particles in an organic polymer medium. As a method for forming the needle-like electrode, a micro-machining technique known to those skilled in the art can be employed. In addition, as a method for providing a plate-shaped transparent electrode on a substrate, a vapor deposition method known to those skilled in the art can be employed. Here, as a method of forming the polymer thin film of the light emitting layer, the above-mentioned method known to those skilled in the art is applied. However, among such known methods, Japanese Patent Laid-Open No.
It is preferable to apply the organic thin film forming method disclosed in JP-A-2525271, JP-A-7-252670, or JP-A-6-306181. This method is characterized in that an organic material of two or more components is sprayed into a high vacuum vessel from a spray nozzle provided for each component in a solution or dispersion state, deposited on a substrate, and subjected to heat treatment. More preferably, pressure molding is performed after the heat treatment.
As the heat treatment means, an electric heater, infrared irradiation, or the like can be employed, and as the pressure treatment means, a known means such as a hot rolling treatment can be employed.

In the method for manufacturing a solid-state optical function device according to the present invention, all the steps of treating an organic compound such as a light-emitting layer are preferably performed under an ultra-high vacuum of 10 ⁻⁶ Pa or less, so that the device remains in the device. It is preferable that the amount of non-volatile components such as a solvent is 10 ^-6 Pa or less.

Further, the above problems can be solved and the object can be realized by filling a space existing in the device of the present invention with a polymer compound which has been subjected to ultra-high vacuum processing under ultra-high vacuum, and generating a volatile component in the device. It is preferable to prevent a decrease in purity.

Hereinafter, the present invention will be described in detail with reference to embodiments with reference to the drawings. The present invention is not limited to the following embodiments, and various modifications based on the technical idea of the present invention are possible.

Embodiment 1 FIG. 1 is a schematic side sectional view for explaining a schematic configuration of an example of a solid-state optical function device according to the present invention.

The solid-state optical function device of this embodiment is provided with a first electrode portion 10 comprising a silicon wafer 1 and a needle-like electrode 2 provided on the silicon wafer 1, and provided opposite to the first electrode portion 10. And a second electrode portion 20 comprising a transparent electrode plate 4 in which a transparent conductive layer 4b is laminated on the glass substrate 4a and the substrate 4a, and a light emitting layer 5 is provided therebetween. The configuration is such that the polymer 6 is filled and sealed with the sealant 7.

The needle-like electrode 2 constituting the first electrode portion 10 of the solid-state optical function element is made of molybdenum. For the first electrode unit 10, a cathode electrode 21 for FED manufactured by Stanford Research Institute (SRI) in the United States shown in FIG. 2 was used. As shown in FIG.
Reference numeral 1 denotes a silicon wafer 22, a conical electrode (needle electrode) 23 made of molybdenum provided on the silicon wafer 22 and formed by micromachining, and provided around the needle electrode 23. SiO ₂ film 24 and the SiO _2
2 and a gate electrode 25 made of a conductive material. In this embodiment, the gate electrode 25 of the electrode 21 of FIG. 2 is removed by etching, the needle electrode 2 tips of (electrode 23 in FIG. 2) is a SiO ₂ film 3 shown in FIG. 1 (2
The first electrode portion 10 having a structure protruding about 0.1 μm from the surface of the SiO ₂ film 24) was obtained (see FIG. 3). The first
The size and shape of the needle electrode 2 constituting the electrode unit 10 are as follows:
Specifically, it is a cone having a height of 2 μm, a tip radius of curvature of 10 nm, and a vertex angle of 10 degrees. Note that the SiO ₂ film 3 may be omitted irrespective of the present invention.

The second electrode portion 20 provided opposite to the needle electrode 2 of the first electrode portion 10 has a glass substrate 4a having a thickness of 1 mm and an indium thin film having a thickness of 100 nm on the glass substrate 4a. Transparent conductive layer 4b made of tin oxide (ITO)
Are formed by a known transparent electrode plate 4 laminated by vacuum evaporation.

Further, on the transparent electrode plate 4, a light emitting layer 5 made of a dye-containing polymer thin film was provided. At this time,
No. 252670, etc.,
A method of spraying an organic material having at least the components in the form of a solution or dispersion from a spray nozzle provided for each component into a high-vacuum vessel, depositing it on a substrate, and performing a heat treatment was applied.

FIG. 4 is a schematic configuration diagram for explaining a schematic configuration of an apparatus used for manufacturing the solid-state optical function device of the present embodiment. This apparatus is disclosed in Japanese Patent Laid-Open No. 7-25 / 1990.
No. 2671, etc., a vacuum spray chamber 30 having the same basic configuration as that disclosed in Japanese Patent Application Publication No. 2671, a hot press chamber 40 communicating with the vacuum spray chamber 30, and a mold communicating with the hot press chamber 40 and for taking in and out the substrate. A chamber 44, and a transfer means 42 for transferring a substrate among the vacuum spray chamber 30, the hot press chamber 40, and the mold chamber 44 are provided. The vacuum in each chamber is provided by a trap exhaust system 35 or a turbo pump exhaust system 36 using a turbo molecular pump. Reference numeral 41 in the drawing denotes an opening / closing unit that shuts off the space between the respective rooms. With this configuration, it is possible to manufacture the solid-state optical functional device in an integrated manner.

In this device, the organic polymer layers such as the light emitting layer 5 are formed as follows. As shown in FIG. 4, a solution 31 of a material of a film to be formed is sent to a nozzle 33 of a vacuum spray chamber 30 via a liquid sending pump 32. The vapor ejected from the nozzle is sprayed on a substrate (not shown). This substrate is set in the substrate mounting portion 29 of the substrate rotating mechanism 34 having a heating mechanism, and rotates during spraying.
As a result, the polymer solution is uniformly deposited on the substrate, and a polymer thin film is formed.

The light emitting layer 5 was formed as follows. The transparent electrode plate 4 is set on the substrate mounting part 29 facing the spray nozzle 33 of the vacuum spray chamber 30. The spray solution for forming the light emitting layer 5 sprayed from the spray nozzle 33 was prepared as follows. That is, rhodamine 6G is used as a dye, and polypyrrole, a conductive polymer, is used as a polymer medium at 70% by weight.
Using polymethacrylic acid methacrylate (PMMA), the mixture was mixed so that the pigment concentration became 8% by weight. Next, this mixture was dissolved in a solvent (acetone) to prepare a spray solution having a PMMA concentration of 10 ^-2 mol / L.

The spray solution thus obtained is applied at 1 / min.
The light emitting layer 5 having a thickness of about 1 μm was formed on the ITO film 4b of the transparent electrode plate 4 which was sprayed from the spray nozzle at a rate of 00 μl and heated to 40 ° C. The light-emitting layer 5 is a film containing the conductive polypyrrole and in which the dye rhodamine 6G is dispersed in PMMA in which a single molecule and ultrafine particles having a diameter of about 20 nm coexist, and then electrically insulating organic polymer. Layer 6 was formed on light emitting layer 5 as follows. Spraying the PMMA solution from another spray nozzle while heating the substrate to 40 ° C.
Similarly to the light emitting layer 5, an electrically insulating organic polymer layer 6 made of only PMMA was formed to a thickness of about 2 μm. In this case, a spray solution having a PMMA concentration of 10 ⁻² mol / l was prepared using acetone as a solvent.

Next, the obtained second electrode section 20 having the light emitting layer 5 and the organic polymer layer 6 laminated thereon is placed on a press table 3 of a hot press machine 38 provided in an ultra-high vacuum hot press chamber 40.
The needle-like electrode 2 of the first electrode unit 10 previously set in the counter substrate mounting part 39 of 7b was transferred to the press table 37a and set so that the organic polymer layer 6 faced. Under a high vacuum atmosphere at a pressure of 10 ⁻⁶ Pa, the pressing temperature is higher than the glass transition temperature of the organic polymer layer 6 and lower than the decomposition temperature of the light emitting layer 5 and the organic polymer layer 6;
Specifically, pressing was performed at 150 ° C. and a pressing pressure of 10 kg / cm ² . As a result, the organic polymer 6 of the organic polymer layer 6
Is filled in a gap generated when both electrodes such as the periphery of the needle-shaped electrode 2 face each other by heating and melting, and all the gaps between the two electrodes are filled with the organic polymer 6 as shown in FIG. Obtained.

After the laminate was cooled to room temperature, it was transferred to a mold chamber 44 connected to the hot press chamber 40. The gap was shut off by an opening / closing means 41, and the pressure was increased to atmospheric pressure with nitrogen gas. 7, the side surface was sealed, and an element sample of FIG. 1 was obtained. In this example, Epicoat 828 (made by Yuka Shell) was used as the sealant 7.

The evaluation of the solid-state optical element thus obtained was performed using an evaluation apparatus in which a condenser lens system, a spectroscope, and a photodetector were arranged in a dark box. That is, the measurement was performed by setting the solid-state optical function element on the front surface of the condenser lens system and detecting the light emission and the wavelength distribution thereof.

FIG. 5 is a graph showing an emission spectrum of the solid-state optical device obtained according to the present example.

When the voltage applied to the solid-state optical functional device was set to 500 V, that is, after applying a voltage of 5 × 10 ⁸ V / m to the light-emitting layer 5, light emission from the solid-state optical functional device was observed. The emission spectrum at that time was shown as curve A in the figure. On the other hand, curve B in the figure is an emission spectrum observed when the same dye used in the solid-state optical function device is excited by light irradiation. This shows that the emission spectrum A of the solid-state optical function device is slightly shifted to a shorter wavelength side than the photoexcitation spectrum B of the dye. This is considered to be because the electron level of the dye was changed by the application of a strong electric field.

Next, a rectangular wave pulse voltage was applied to evaluate the responsiveness of the solid-state optical functional device. FIG. 6 shows a response when a rectangular wave pulse C having an applied voltage of 500 V and a time width of 2.5 μs is applied. As shown, the light emission D of the solid-state optical function device exhibited a time response of decay having a relaxation time of about 5 microseconds. The device of the present invention is a direct transition from the excited state of the organic dye of the organic dye dispersed in a single molecule and an organic fine particle which is an aggregate of the organic dye molecule dispersed and coexisted with the single dye molecule, and an indirect transition. It was found that the response was much faster than that of the inorganic light emitting material that emits light.

(Embodiment 2) In the first embodiment, when the first electrode portion 10 and the second electrode portion 20 are joined together,
A solid-state optical functional device having the same configuration as in Example 1 was prepared, except that the test was performed in the air instead of the nitrogen atmosphere.

In the evaluation of the solid-state optical function device, a voltage of 0.47 farad was connected between the device and a power source in order to prevent damage to the device. When a DC voltage of 500 V was applied in the same manner as in Example 1, light emission with stable light intensity was observed.

As described above, according to the above embodiment,
An organic dye is selected as the illuminant so that the illuminant can be selected in a wide range from the ultraviolet to the infrared region, and a luminous mechanism by applying an electric field is adopted, preferably avoiding direct current, which is a severe condition for organic dyes. Also, preferably, the treatment of the organic compound is performed in an ultra-high vacuum, thereby realizing a solid-state optical device in which damage caused by application of an electric field or light emission is reduced. In addition, the response speed of the display device has been reduced by using ultra-fine particles composed of an electrode with a microstructure and an organic dye dispersed in a single molecule, or an organic dye molecule dispersed together with the dye. It is possible to realize a solid-state optical function element suitable for a display element or the like which is sufficiently higher than liquid crystal or the like.

[0059]

As described above, the solid-state optical function device and the method of manufacturing the same according to the present invention provide a polymer thin film in which an organic dye is dispersed in the form of a single molecule or / and ultrafine particles in an organic polymer medium. Is disposed between the plate-shaped transparent electrode and the needle-shaped electrode, and by applying a voltage between the two electrodes, an excited state of the organic dye is generated, and light emission from the excited state is extracted to the outside through the transparent electrode. With this configuration, it is possible to provide a self-luminous solid-state functional element suitable for display means having a high response speed and a method for manufacturing the same.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view for explaining a schematic configuration of an example of a solid-state optical function element according to the present invention.

FIG. 2 is a sectional view showing a configuration of an SRI field emission cathode electrode applied to a solid-state optical function device according to the present invention.

FIG. 3 is a schematic perspective view showing a first electrode portion of a configuration of an example of the solid-state optical functional device according to the present invention.

FIG. 4 is a configuration diagram for explaining a configuration of a manufacturing apparatus for performing an organic thin film forming method applied to a method of manufacturing a solid-state optical function element according to the present invention.

FIG. 5 is a graph showing an emission spectrum of the solid-state optical functional device according to the present invention.

FIG. 6 is a graph showing the light emission intensity of the solid-state optical function device according to the present invention.

FIG. 7 is a schematic cross-sectional view for explaining a schematic configuration of an example of a conventional solid-state optical function element.

[Explanation of symbols]

1 silicon substrate 2 Needle electrodes 3 SiO ₂ film 4 transparent electrode plate 4a glass substrate 4b transparent conductive layer 5 light-emitting layer 6 organic polymer layer 7 sealant 10 first electrode 20 second electrode portion 21 FED for the cathode electrode 22 Silicon substrate 23 Needle electrode 24 SiO ₂ film 25 Gate electrode 29 Substrate mounting part 30 Vacuum spray chamber 31 Dye / polymer solution 32 Liquid feed pump 33 Nozzle 34 Substrate rotating mechanism 35 Trap exhaust system 36 Turbo pump exhaust system 37a Anvil / heating Heater 37b Anvil / Heating heater 38 Pressurizing mechanism 39 Counter substrate mounting part 40 Hot press chamber 41 Gate valve 42 Substrate transport mechanism 43 Sample entrance 44 Load lock / mold chamber

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Takashi Hiraga 1-1-4, Umezono, Tsukuba, Ibaraki Pref. Electronic Technology Research Institute (72) Inventor Kiyoshi Chiba 2-1-1 Uchisaiwaicho, Chiyoda-ku, Tokyo No. Teijin Limited (72) Inventor Shinichiro Kim 4-2-2 Asahigaoka, Hino City, Tokyo Teijin Limited, Tokyo Research Center

Claims (13)

[Claims] A transparent electrode having a plate shape, a needle electrode provided to face the transparent electrode, an organic polymer medium disposed between the transparent electrode and the needle electrode, and an organic polymer medium. A single molecule or / in an organic polymer medium
And a light emitting layer composed of a polymer thin film containing an organic dye dispersed in the form of ultrafine particles, and, further, by applying a voltage between the transparent electrode and the needle electrode. A solid-state optical element, wherein the organic dye is in an excited state, and light emitted from the organic dye in the excited state is output to the outside through the transparent electrode. 2. The size of the ultrafine particles is 50 n in diameter.
2. The solid-state optical function device according to claim 1, wherein m is equal to or less than m. 3. The solid-state optical device according to claim 1, wherein the organic polymer medium is a conductive or carrier-transporting organic polymer. 4. The solid-state optical element according to claim 1, wherein an organic polymer layer having a conductive property or a carrier transport property is provided between the light emitting layer and the transparent electrode. 5. The needle-shaped electrode has a height of 200 nm.
The solid-state optical element according to any one of claims 1 to 4, wherein the radius of curvature is 100 nm or less. 6. The apparatus according to claim 1, wherein a capacitance is connected between a power supply and said electrode, a DC current is cut off, and only a DC voltage is applied to said electrode. 9. The solid-state optical function device according to claim 1. 7. The solid-state optical function device according to claim 1, wherein a void portion in the solid-state optical function device is filled with an electrically insulating organic polymer. . 8. The solid-state optical device according to claim 1, wherein a residual amount of a nonvolatile component of the organic polymer in the solid-state optical function device is 10 ⁻⁶ Pa or less. Functional element. 9. In producing the solid-state optical function device according to any one of claims 1 to 8, the light-emitting layer is formed by spraying a material in a solution or dispersion state into a high vacuum container and spraying the material on a substrate. A method for manufacturing a solid-state optical functional device, comprising forming an organic thin film by depositing and heating. 10. The method according to claim 9, wherein the substrate is a plate-shaped transparent electrode. 11. An electrically insulating organic polymer layer is formed on the light emitting layer, and an electrode substrate having a needle electrode formed on the organic polymer layer is joined by hot pressing. Item 10. The method for producing a solid-state optical function device according to item 9 or 10. 12. The method according to claim 11, wherein an electrically insulating organic polymer layer is formed by the organic thin film forming method. 13. The formation of the light-emitting layer and an organic polymer layer, and the step of hot pressing is performed under high vacuum atmosphere below 10 ^-6 Pa, the residue of the nonvolatile components, 10 ^-6 Pa
The method for manufacturing a solid-state optical function device according to claim 9, wherein: